TW201219491A - Resin particles water dispersion - Google Patents

Abstract

Provided is resin particles water dispersion characterized by containing resin particles which are formed by copolymer comprising 10 to 90 % by mass of aliphatic polyether unit, have the melting point 120 DEG C or more, and have an average particle diameter of 1 μ m or more to 100 μ m or less. It is particularly efficacious that a dispersant is less than 1 mass by part per 100 mass by part of copolymer or the dispersant is not contained in copolymer. Particularly, particle diameter distribution index is 1 to 3 particles. According to the present invention, it is able to obtain a useful water dispersion containing resin particles which are formed by copolymer having high heat resistance and comprising aliphatic polyether unit.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous dispersion of resin fine particles having heat resistance and suitable as a binder or coating material for coatings, adhesives and the like. [Prior Art] An aqueous dispersion of resin particles of high heat resistance is used in the form of a coating, an adhesive, a binder or a coating agent in the form of a highly functional dispersion. A resin having high heat resistance such as polyarylsulfide or polyamidoxime generally has a tendency to lower in affinity with water. In order to obtain such a dispersion, it has been proposed to use an organic solvent as a medium. A method of dispersing in water by using a dispersing agent such as a surfactant (Patent Documents 1 and 2). In recent years, from the viewpoint of environmental protection or labor safety, the demand for changing the organic solvent used in the dispersion medium to high-safety water has become extremely high. On the other hand, Patent Document 3 discloses resin particles containing a thermoplastic elastomer such as an ether ester block copolymer, and is described as being used for a thermosetting resin, a photocurable resin, a varnish or the like. Further, in Patent Document 4, a resin fine particle-receiving liquid for forming a film is disclosed. In Patent Document 4, particularly preferred fine particles are disclosed from the viewpoints of coating film appearance and storage stability, and a suitable particle diameter is 250 nm or less in terms of an average particle diameter. CITATION LIST Patent Literature Patent Literature, Japanese Patent Application Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. 2008-. In the aqueous dispersion of the resin fine particles, the interface activity is used for the dispersion, but the next step of using the 5 liter dispersion, that is, When a paint or a varnish is mixed, the surfactant may deteriorate in dispersibility when it is in a mixed state, or the function of the mixture may not be sufficiently exhibited. It is preferable to do not contain a surfactant or the like in the dispersion of the resin fine particles. In addition, although the particle size is small, the dispersibility can be ensured. However, since the particle diameter is reduced, the specific surface area is increased, and the viscosity of the dispersion is increased. The effect is that the particle diameter is 5 〇〇 nm or more, more preferably 1 μm η or more, and the dispersibility is good = an aqueous dispersion of resin fine particles. In recent years, the improvement of 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 important issues. In view of the above, an object of the present invention is to provide an aqueous dispersion of resin fine particles which is excellent in practicality in which resin fine particles having high heat resistance are dispersed in an aqueous medium with good dispersibility. The inventors of the present invention have been able to achieve the above objective, and as a result, the inventors of the present invention have found that the heat-resistant resin microparticles obtained by copolymerizing the polyphonic unit have completed the present invention. That is, the present invention has the following constitution:

S -5-.201219491 [1] An aqueous dispersion of resin fine particles, characterized in that: the granules are obtained from a copolymer containing ruthenium to 9% by mass of a ruthenium, and have a melting point of 1 2 〇 Above °c, average above 1 ΟΟμπι. [2] The aqueous dispersion of resin fine particles according to [1], wherein the resin liquid does not contain a dispersing agent, or is contained in an amount of less than 1 part by mass relative to the copolymerized portion. [3] The water dispersion of resin particles such as [1] or [2], which is a particle of 1-3. [4] The resin fine particles of any one of [1] to [3] contain 10 to 90 masses. /. Copolymerization of aliphatic polyether unit copolymer aliphatic scaly unit and crystalline polyester unit (effect of the invention) According to the present invention, resin fine particles comprising an aliphatic south-containing heat copolymer can be obtained. In addition, the resin obtained from the copolymer which is used in the present invention is substantially free of a dispersant and can be well dispersed in water, and an aqueous dispersion excellent in dispersibility is obtained by using a knife. The obtained aqueous dispersion of the resin fine particles can be used in the field of coatings, agents or coating agents, and in cosmetic applications, and can be applied to the aqueous application of environmental loads such as ^°H. Moreover, since the knife-cross section can also be a dispersible aqueous dispersion, it is possible to suppress the coloring and water absorption of the lipid microplate dispersion due to the dispersant. The resin-containing micro-aliphatic polyether has a single particle size of 1 μm. The particulate water dispersion 100 weights is a particle size distribution dispersion, wherein the system contains a lipid. Water-dispersible fine particles for use in a polyether unit, even if the adhesive is not adhered to the object according to the present invention, even if it is not used, it can be provided in a tree having high heat resistance. - 201219491 [Embodiment] Morphology) The present invention will be described in more detail below. The invention relates to a resin in an aqueous dispersion of resin fine particles ^ Wi Λ 1 ? n ° rr, wherein the bath has a bath point of 120 C or more and contains an aliphatic-Γ A ± (early-earth copolymer). It is known that the hunting is made of an aliphatic polyether unit. /, polymerization, even a heat-resistant resin having a low affinity with water, is superior to water in the organic solvent, and is excellent in dispersibility. Since the dispersion medium is water, the organic solvent can be avoided, thereby being environmentally friendly, and the work environment can be improved in terms of labor safety, etc. Further, the aqueous dispersion of the present invention 'Despite the high heat resistance, the elongation is excellent due to the dispersibility to water', so there is still a good score even if no dispersant is used. (4) Therefore, when the dispersant is not used, it can be suppressed from coloring or heat resistance due to the dispersant. An aqueous dispersion which reduces the water resistance and deteriorates the adhesion of the crucible to the substrate, and which is excessively applied to the surface and exhibits a greasy sound. The copolymer used in the present invention is an ancient complaint. Have aliphatic polyether units and The point is 1 20. The copolymer above 〇. The fat is taken from the 〇 ～ 〜 曰 奴 聚醚 聚醚 聚醚 的 的 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共 共The copolymer is preferably from the viewpoint of suppressing the resistance to hydrazine, & / 〇 * W heat I. The aliphatic polyether unit of the present invention, wherein v = is represented by the following general formula (1): (1) -R—0- R represents a divalent aliphatic nicotine group, and in the case of a rural worker, in the case of a steroid, a linear saturated hydrocarbon group, a branched saturated hydrocarbon group, an ancient hydrazine, a linear unsaturated hydrocarbon group, and a sub-unsaturated Hydrocarbyl group. η is a repeating unit number of seven 矣 double representing a positive number. The above linear 201219491 and hydrocarbyl group, branched saturated hydrocarbon group, linear unsaturated hydrocarbon group, branched unsaturated dibasic group are carbon number 1 2 0, from the dispersibility to water It is preferable from the viewpoint of excellentness, especially the latter number 1 to 1 Å. Specific examples of the copolymerized aliphatic polyether unit include polyethylene glycol, polypropylene glycol, f trimethylene glycol, and poly Tetramethylene glycol, polyhexamethylene glycol, copolymer of ethylene oxide and propylene oxide, polypropylene An ethylene oxide adduct of a diol, a copolymer of ethylene oxide and tetrahydrofuran, etc. In particular, from the viewpoint of imparting hydrophilicity and being easily dispersed in water, polyethylene glycol, polypropylene glycol, and polytriaxene are preferred. The carbon number of R such as a diol or a polytetraethylenediyl glycol is iMO. The amount of the aliphatic polyether unit is in the range of 10 to 90 denier in the copolymer, preferably 15 to 90% by mass. More preferably, it is 2 〇 to 8 〇 in mass / 〇 is more preferably 20 to 70% by mass. () If the aliphatic polyether unit is less than ι 〇, and the dispersibility of the resin in water is deteriorated, it is not good. If the heat resistance of the resin exceeds 9 会, it is not good. Li 〇 / 〇 ' ^ This heat payment limit, s is usually 5 〇〇 ~ 20,000, preferably 500 〜 1 〇〇〇 (). Further, the amount of the mass is determined by using a dimethyl melamine, a hydrazine gel::: (GPC), and a standard polystyrene conversion: a bite amount. I averaging the present invention t, the melting point of the resin is 1 2 〇 ° C or more, more than dry soil, more preferably l5 〇 ° C or more, and particularly preferably 16 〇. 〇 Above. The second is 14 baht. 〇 1 201: The heat resistance of the coating film or the like is lowered, which is not preferable. && ‘The point is lower, but from the viewpoint of water dispersibility, A ..., special two 300 C or less is better than 280 〇 C or less. Further, the melting point refers to a bright spot measured at a temperature rising rate of 1 o ° c / minute using a differential scanning heat. ...*

S -8 - 201219491 In the present invention, the copolymer of the aliphatic polyether unit may be copolymerized with other copolymer components without limitation, as long as the melting point is 12 (TC or more). Specifically, it may be copolymerized. Other copolymerizable components may, for example, be a polyester unit, a polyamine unit, a polycarbonate unit, a poly(arylene sulfide) unit, a polyetheretherketone unit, a polyimine unit, or a single constituting the polymer. a bulk unit or the like. Among them, a block copolymer is preferred, and a unit constituting the block copolymer is preferably a polyester unit or a polyamidene unit. From the viewpoint of maintaining heat resistance even if the ratio of the polyether unit is increased, The polyester unit is preferably a polymer unit of an aromatic dicarboxylic acid and a diol, that is, a polyester unit. The polyester unit is not particularly limited as long as it has an ester bond in the main chain or the side chain. The acid component is obtained by polycondensing an acid component and a diol component. The acid component constituting the polyester unit is terephthalic acid, isophthalic acid, phthalic acid, 2,5-dimercapto terephthalic acid, 1,4-naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,2-double Phenoxyethane-p,p'-dicarboxylic acid, phenyldihydrotaphthalic acid, succinic acid, adipic acid, sebacic acid, sebacic acid, dodecanedioic acid, dimer acid, 1 , 3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc., and the ester-forming derivatives thereof, and the like, For the acid component and the acid component thereof, for example, sulfo terephthalic acid, 5-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfonaphthalene-2,7- An alkali metal salt such as a dicarboxylic acid, a sulfo-p-diethylenediphenylene glycol, a 2-sulfo-1,4-bis(hydroxyethoxy)benzene, an alkaline earth metal salt, or an ammonium salt, etc. Or two or more kinds of copolymerization. The diol component constituting the polyester unit can be used: ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, Ι^-

S 201219491 Butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9- Decylene glycol, 1,10-decanediol, 2,4-dimercapto-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-hexyl Glycol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedime, 2,2,4,4-tetradecyl-1,3 - cyclobutanediol, 4,4'-thiodiphenol, bisphenol A, 4,4'-methylene diphenol, 4,4'-(2-indenyl)diphenol, cyclopentane- 1,2-diol, cyclohexane-1,2-diol, and cyclohexane-1,4-diol can be copolymerized by using one type or two or more types. These resins may be used alone or in combination of two or more. In the present invention, in the above, the diol polycondensate of the aromatic dicarboxylic acid is preferred from the viewpoint of heat resistance of the resin. Among them, from the viewpoint of strength, polyethylene terephthalate, polybutylene terephthalate or the like is preferable. The weight average molecular weight of the aliphatic polyether-containing copolymer of the present invention is not particularly limited and is usually 1,000 to 100,000, preferably 10,000 to 80,000, more preferably 10,000 to 5,000. Further, 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 conventional method. Specific examples are, for example, a method in which a lower alcohol diester of a dicarboxylic acid, an excess of a low molecular weight diol, and a low melting point polymer segment component are subjected to a transesterification reaction in the presence of a catalyst, and the obtained reaction product is polycondensed. And a method for esterifying a s -10-.201219491 dicarboxylic acid with an excess of a diol and a low-point polymer segment component in the presence of a catalyst, and subjecting the obtained reaction product to polycondensation, etc. 0. Next, the resin fine particles in the resin fine particle aqueous dispersion of the present invention are described. In the present invention, the 9 resin fine particle aqueous dispersion means that the resin fine particles are present in a dispersion medium containing water as a medium. At this time, the resin fine particle aqueous dispersion is optimal in that the resin fine particles continue to float in the water which is a dispersion medium. However, depending on the case, the resin fine particles may settle as time passes, but the aqueous resin fine particle dispersion of the present invention may be easily redispersed by mechanical redispersion treatment in which the resin fine particles have settled. In the resin fine particle aqueous dispersion, the resin fine particles are dispersed one by one, and the paper is preferably a "paw, more preferably. The number average particle diameter is less than 1 μιη, and the particles become easy to aggregate. If it exceeds: m, it is not good because it will settle in water. Further, the resin fine particles: the number average particle diameter refers to the observation of the number of the Rensi particles by scanning electron micrograph, and the diameter is measured, and the following formula (1) Calculated. In addition, when the particles are non-circular, the long diameter of the crucible. The particle size distribution index of the resin particles is U~3. G. The range is preferably U~2.〇, more preferably 1q~15. The distribution index exceeds 3.0', and the coating property when used as a coating agent is not good. The X 'particle size distribution index' is calculated according to the following formula (7): ratio of the average particle size of the limb to the number average particle diameter Volumetric particle size, based on scanning electrons : Electronic Selective Micromirror Photographs Measure Any 100 Grains

S -1 1 - 201219491 Sub' and the diameter is measured, and the long diameter is measured. Calculate according to the following formula (2). When the particle is not a perfect circle, Σ Di (1) (2) j = i__ n 12

Dv Σ Di Σ Di Bu] (3) PDi =

Dn Further, Di: particle size of each T ^ 10, n: number of measurements 100, Dn: number average particle diameter, Dv: volume average particle size, PDI: particle size distribution index. The opening of the tree 曰 曰 曰 办 办 办 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ In the method of obtaining a resin, it is possible to use any of the conventional methods, in which a method of preferably forming an emulsion by phase separation into a molecular solution and adding a poor/mixing agent to obtain fine particles (International Publication No. 2009/ 14223 No. 1). For example, the following method can be used: the above-mentioned resin (hereinafter referred to as polymer A) to be microparticles is separated from the polymer B in a poor solvent dissolved in the polymer A, and the organic solvent is dissolved and mixed to form a polymer a. The emulsion phase of the main component (hereinafter sometimes referred to as the polymer A solution phase) and the solution phase of the polymer B as the main component (hereinafter sometimes referred to as the polymer B solution phase), the emulsion is made After the formation, the poor solvent of the polymer A is contacted, whereby the polymer A is precipitated. The above method will be more specifically described below.

The above "separates the polymer A and the polymer B and the organic solvent in a dissolved mixed phase to form a solution phase mainly composed of the polymer A and the polymer B.

• 12- S 201219491 Two-phase system of solution phase as the main component. ^ 彳糸 彳糸 When mixing polymer A with poly-β and B, it is divided into a solution phase mainly containing polymer ruthenium and mainly A two phase system of solution phase of polymer B. By using such a phase-separated system, ", π human> ^" is kneaded, emulsified, and formed into an emulsion under phase separation conditions. The solution is to dissolve the mixture in the present B and dissolve the two to exceed 1 mass. Further, in the above, the temperature at which the polymer is dissolved, that is, the temperature at which the polymer A and the polymer are separated from each other, is determined based on the % of the organic solvent. The emulsion is a polymer A, Xuanyou Zhiqi A , the liquid phase becomes the continuous phase of the human B solution phase, and the emulsion is contacted with the poor solvent of the compound I to make the polymer A from the polymer A in the hawthorn The solution phase is precipitated to obtain resin fine particles composed of the polymer A. In the method, the polymer A, the polymer B, the organic solvent for dissolving the organic solvent, and the poor solvent of the polymer A are used as long as the resin particles of the method can be obtained. 'The combination is not specific, the method towel, the polymer a refers to the high molecular polymer, preferably the non-naturally occurring synthetic polymer' is more preferably a water-insoluble polymer. In the method, the polymerization Analysis of the contact of good solvent A It is preferable that the solvent of the fine particles is insoluble in the poor bath-soluble polymer described later. In view of the above, it is preferred that the polymer is insoluble in the polymer, especially non-aqueous. Here, the water-insoluble polymer means a polymer having a water solubility of 丨 mass 0 / 〇 or less, preferably 〇 5 mass % or less, more preferably 〇 1 mass %.

S -13- 201219491 Polymer B may be a thermoplastic resin dissolved in the method used in the method, ',, a 4-type resin, but it is preferably a poor solvent of A, wherein /16 Μ organic solvent and polymer solvent or water It is better from the viewpoint of industrial/combined with the above organic solvent, soluble in alcohol, good in Goode, and excellent in benzene, especially in cold organic solvent, and soluble in yttrium--methanol , ethanol or water. To the right, a polymer yttrium, a saponified or partially saponified poly (polyvinyl alcohol) (completely saponified copolymer (completely saponified or partially VIII: available): poly(vinyl alcohol) ψ λ, . I &quot ; knife saponification poly (vinyl alcohol - ethyl coal, ruthenium polymer can also be), / poly 7 榼Α 〇 Qiu) conjugated pyrrolidone, poly (ethylene glycol), glycoside ester, poly (qi 抡 抡 庶 庶 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知 知_ ), poly(oxyethylene alkyl phenyl ether), ♦ (oxyalkyl ether), polyacrylic acid, poly field*, enamel, polyacrylic acid, polymethyl (tetra) acid, polystyrene, acid, polystyrene Ethylene continuous acid steel, polyvinylpyrrolidinium chloride, poly(styrene-maleic acid) copolymer, amine (polyacrylamide), poly(p-vinylphenol), polyallylamine, Polyethyl ether, polyvinyl acetal, poly(acrylamide), poly(mercapto acrylamide), poly(oxyethylene amine), poly(vinyl hydral ketone), poly (vinyl d ratio) Acridine) Synthetic resin such as occupational, polyethyleneimine, maltose, cellobiose, lactose, sucrose and other disaccharides, cellulose, chitosan, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, B Cellulose, ethyl hydroxy cellulose, carboxymethyl ethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, cellulose esters, cellulose derivatives, amylose and its derivatives, starch and Polysaccharides or derivatives thereof such as derivatives, dextrin, cyclodextrin, sodium alginate and its derivatives, gelatin, casein, phenylephrine, albumin, fibrinin, keratin, blood Fiber S. -1 4- •201219491 Protein (fibnn), carrageenan chondroitin sulfate, arginine, etc., compared with # * # Ah ,. Soil is poly(vinyl alcohol) (completely saponified or partially saponified poly( Ethyl alcohol) or poly(vinyl alcohol-ethylene) copolymer (completely or partially saponified poly(vinyl alcohol-ethylene) copolymer may also be) 'polyethylene glycol, strict sugar fatty acid § , poly(oxyethylene alkyl benzene (4), poly (oxyalkyl hydrazine), poly (acrylic acid) , poly(methylpropionate), thioglycolyl cellulose, phenylethyl cellulose, basal fiber, ▼ carbaryl, 6-based, fiber ^, = ketone cellulose, thiomethyl Ethyl fiber, (tetra)methylcellulose 'mercaptomethylcellulose nanofiber' (four) and other cellulose derivatives, polyvinylpyrrole, more preferably poly(vinyl alcohol) (fully saponified or partially deuterated) Poly(ethylene glycol) can also be, poly(vinyl alcohol-ethylene) copolymer (completely saponified or partially saponified poly(vinyl alcohol ethylene) copolymer, polyethylene glycol, thiomethyl cellulose , phenylethyl cellulose, M-propyl cellulose, thiol cellulose, ethyl cellulose, ethyl cellulose, methyl ethyl cellulose, buffer methyl cellulose, slow base a cellulose derivative such as methyl cellulose or cellulose ester, polyvinylpyrrolidone, preferably poly(vinyl alcohol) (completely saponified or partially saponified poly(vinyl alcohol)), poly( Ethylene glycol), carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, B Hydroxy cellulose, cellulose derivatives, polyvinyl pyrrole 0 piperidone. The molecular weight of the soil two-earth polymer B is preferably 5,000 to 1 in terms of weight average molecular weight, 〇〇〇, 〇〇〇, and particularly preferably in the range of 1 〇〇〇〇 to 5 ,, most The range is preferably 10,000 to 100,000.

S -15-201219491 The weight average molecular weight referred herein is the weight average molecular weight obtained by gel permeation chromatography (GPC) using water as a solvent. When it is impossible to measure water, dimethyl decylamine is used, and if it is not possible to measure it, tetrahydrofuran is used, and when it is not possible to measure, hexafluoroisopropanol is used. The organic solvent in which the polymer A and the polymer B are dissolved is an organic solvent which can dissolve the polymer A and the polymer B to be used, and can be selected depending on the type of each polymer. Specific examples include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, ruthenium, ketone, ruthenium, tetradecene, cyclohexane, and cyclopentan. An aromatic hydrocarbon solvent such as a solvent, benzene, toluene, diphenyl or 2-nonylnaphthalene, an ester solvent such as ethyl acetate, methyl acetate, butyl acetate, butyl propionate or butyl butyrate, or chloroform. , bromoform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene, 2,6-dichloropyrene, hexafluoroisopropanol A halogenated hydrocarbon solvent, a ketone solvent such as acetone, acetophenone, decyl isobutyl ketone or butyl ketone, an alcohol solvent such as decyl alcohol, ethanol, 1-propanol or 2-propanol, or N-methyl- 2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), hydrazine, hydrazine-dimercaptocarboxamide (DMF), N,N-dimercaptoacetamide (DMA), propylene carbonate, An aprotic polar solvent such as trimethylphosphoric acid, 1,3-didecyl-2-imidazolidinone or sulfolane; a carboxylic acid solvent such as formic acid, acetic acid, propionic acid, butyric acid or lactic acid; anisole or diethyl ether; Tetrahydrofuran, diisopropyl ether, dioxane, diethylene glycol ether, dimethoxy An ether solvent such as an alkane, 1-butyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium hydrogensulfate, 1-ethyl-3-imidazole rust acetate, 1 -ethyl-3-

-16- S .201219491 Methyl imidazole Depending on the choice used. Preferred halogenated tobacco-based agents, acid-prone polar solvents, carboxylic acid viewpoints, solvent points, and the most preferred methionine. The particle size A and the poly-polymer A are dissolved in a good solvent, and the solvent is preferably used. Use this to precipitate. Further, the poor lyophilized yam & oxoate plasma 肀 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 私 混合物 σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ σ In the aromatic hydrocarbon system, π / 糸, Fenjian, Yueshao aliphatic hydrocarbon solvent, m ^ s ^ system / preparation sword, aprotic polar solution of the current ' 'more preferably for the aqueous addition &> The alcoholic solvent, the non-quality/gluten, and the carboxylic acid solvent of the 丨 丨 / 合 合 特 特 特 特 特 特 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 β It is a wide range of polymers and is suitable for the polymer enthalpy. It can be uniformly mixed with water or alcohol, which is used as a poor solvent helmet N 吏. _2·呲 鲷 鲷 鲷, _ τ τ 飒 飒, N N — dimethyl, N, N-didecyl 醯 醯 妷 妷 、 、 、 、 、 、 、 、 、 、 便 便 便 便 便It can also be used in combination, but from the viewpoint of particles having a small ruthenium size and a small particle size distribution, from the viewpoint of the separation step at the time of avoidable solvent recovery, the trouble of 6/step is reduced, and the number of people R is reduced and The earlier organic solvent is more preferably a single organic solvent which dissolves both of the polymerization materials B. The decree, the poor solvent of polymer A, means that the polymerization cannot be made, and the solvent is =. The insoluble polymer is a polymer A having a degree of incompatibility of 1% by mass or less, preferably 5% by mass or less, of 1% by mass or less. In the method, a poor solvent of the polymer A is used, but the defect is a poor solvent of the polymer A and the dissolution of the polymer b is dissolved, so that the polymer particles composed of the polymer A are efficiently decomposed. The solvent of the substance A and the compound b and the polymer a 〖!/ are preferably a solvent which can be uniformly mixed.

S-17-201219491 In the present method, the type of the polymer A to be used is preferably changed to various types depending on the type of the polymers A and B to be used, and specific examples thereof include pentane and An aliphatic hydrocarbon solvent such as an alkane, heptane, octane, I a ketone pit, n-decane, n-dodecane, n-tridecane, tetradecane, cyclohexane or cyclodecane, benzene, toluene, Aromatic hydrocarbon solvents such as diphenylbenzene and 2_methinecae, 'ethyl acetate' methyl acetate', acetic acid, butanyl esters such as t, butyl propionate, butyl butyrate, etc., gas imitation, bromoform Gas produced carbon tetrachloride, 1,2-chloroethane, 1,1,1-three gas, ethylene, chlorobenzene, 26 gas toluene, hexafluoroisopropanol, etc. , TG @同, methyl isobutyl ketone, methyl ketone and other ketone solvents, methanol, ethanol, 1-propanol, 2-propanol and other alcohol solvents, dimethyl hydrazine (DMSO), hydrazine, hydrazine - Dimethylamine (DMF), hydrazine, hydrazine-dimethylacetamide (Dma), trimethylphosphonium N-methyl-2-pyrrolidone, ι,3·didecyl-2-imidazole Acridine II = long J stone wind calculation aprotic polar solvent, tannic acid, B , propionic acid, butyric acid, decanoic acid solvent, anisole, diethyl ether, tetrahydrofuran, diisopropyl ether, decane, dimethyl dimethyl ether, dimethoxy ethane, etc. At least one solvent is produced. The water is preferably selected from the viewpoint of efficiently polymerizing the polymer A. The hydrocarbon solvent, the aliphatic hydrocarbon solvent, the alcohol solvent, and the two-part perfume are preferably an alcohol solvent or water, and particularly preferably water. . In the present method, the polymer A is precipitated by appropriately selecting a poor solvent of the polymerization & A, the polymerization 16B, the solvent of the solvent, and the polymer A to form a resin particle. . Oh, it will be aggregated

S -18- .201219491 At this time, the organic solvent of the solution phase mainly composed of polymer A as the main component and the organic solvent of the Ft branch of the polymer may be different, but substantially It is preferably the same solvent. The conditions for the same two-phase separation state, depending on the polymer, polymer A, B, the early county, the B species B: the sound of the agricultural sound ~ knife, the type of organic agent, polymer A The exhibition and the temperature and pressure of the method are different. In order to obtain a condition that is easy to be in a phase-separated state, the solubility parameter of the input = and the polymer B (hereinafter sometimes referred to as an SP value): At this time, the difference of the SP values is 1 (J/cm 3 严 ΟΠ / ρ τ η 3 '» 1^ . Χ More preferably 5 " 31/, upper, and more... (Μ1, 2 or more, especially better) above, excellently 8 (J/cm3) 1/2 or more. If the SP value is this range It is easy to phase-separate. Values: As long as the compound A and the polymer B are soluble in the organic solvent, the upper limit of the difference between the SP values is preferably "2" (J/cm3) i&quot The following is more preferably l5 (J/cm3) i/2 or less, and more preferably ^ ι/2 or less. The SP value referred to herein is calculated according to the Fedor algorithm, based on the agglutination energy density and the molar molecule. Volume-based calculator (hereinafter referred to as the calculation method) ("SP value basic application and calculation method", Yamamoto Hideki, Information Agency Co., Ltd., issued on March 3, 2007). Based on this calculation When the method cannot be calculated, the solubility parameter is calculated according to the experimental method determined by whether or not the known solvent is dissolved (hereinafter sometimes referred to as an experimental method), and Substitute ("p〇lymer handb〇〇k

Fourth Edition, by J. Brand, Wiley, 1998).

S -19- 201219491 In order to select the conditions for the phase separation state, a simple preliminary experiment can be made by changing the ratio of the three components of the polymer A, the polymer B, and the organic solvent in which the organic solvent is dissolved. The phase diagram is discriminated. The phase diagram is produced by mixing and dissolving the polymers A, B and the solvent in an arbitrary ratio and at the time of standing, at least 3 points or more, preferably 5 points or more, more preferably 10 points or more. It is determined that the conditions for the phase separation state can be found by distinguishing the regions separated into two phases and the regions separated into phases. In this case, in order to determine whether or not the phase is separated, the polymers A and B are adjusted to the ratio of the polymer A, B and the solvent to the temperature and pressure of the present invention, so that the polymers a and B are completely Dissolved, and after stirring, the mixture was thoroughly stirred and allowed to stand for 3 days to confirm whether the phase separation was observed on the giant. ^ When you become a very stable emulsion, even if you place 3 曰, there is still no phase separation on the giant. In this case, it is determined microscopically whether or not phase separation is performed using an optical microscope, a phase contrast microscope or the like to determine phase separation. The phase cutter is formed by separating into a polymer A solution phase mainly composed of polymer A in an organic solvent and a polymer B solution phase mainly composed of polymer B. At this time, the polymer A solution phase is a phase mainly composed of polymer A, and the phase of the polymer B solution is a phase mainly composed of polymer b. At this time, the polymer A solution phase and the polymer b solution phase have a volume ratio in response to the types and amounts of the polymers A and B. The concentration of the polymers A and B relative to the organic solvent is such that the phase separation state can be obtained and the concentration which can be industrially implemented is soluble.

-20- S 201219491 Yes. Within the scope of the limit is premise - preferably more than ... /. ~50 berry / 〇 'better than "%", 2 mass% /. ~ 2 〇 mass%., and better in this method, the polymer A solution phase 蛊 interfacial interfacial tension, from two The average machine 2, the two tensions of the liquid phase of the valley are small, depending on its nature, from the point of view, its interface point, its particle size distribution will be reduced = the organic solvent that can stably maintain the same phase, the effect is obvious; : Phase A and Polymer B In this method, the two-phase bucket can not be used normally; the surface tension in the liquid-liquid boundary is directly measured due to the too small interfacial tension, but the suspension is determined by adding a heterogeneous solvent. According to the titration, it is possible to estimate the interface 茫: "When the surface tension between each phase and the air is pushed ri, r2, the interface is stretched." Let the surface tension of each phase with the air be at this time, the absolute range of ~, the absolute The value is estimated to be 0 to 5 mN/m, and t is 0 to 10 mN/m. More preferably, it is 0 to 2 mN/m. Preferably, it is greater than 0 to 3 mN/m, and more preferably greater than the two-phase cloth in the method. , the viscosity is relatively small, ^ viscosity will affect the average particle size and the particle size ratio is defined as the tendency to reduce the distribution of this hair When the viscosity/polymer B solution phase is used, the polymer A solution under the temperature condition of the month i preferably ranges from 0.2 to 5, preferably from 0 to 1 or more, more preferably more than 0.5, and more preferably A more preferable range is 〇.3 or more and 3 or less, hereinafter. 以下.5 or less 'excellent range is 〇_8 or more i.2 Use this method to select granules. When performing microparticulation, the system is manufactured by the knives. The resin microsystem is carried out in a usual reaction vessel. It is suitable for carrying out the preferred temperature of the present invention in the period of 201219491, and from the viewpoint of industrial applicability, it is in the range of -50C to 200C, preferably _2〇.〇15〇.〇 More preferably, it is 0 to 120 ° C, and more preferably 10 t: 10 (rc, particularly preferably 2 〇 < t, 8 (rc, preferably in the range of 20 C to 50 ° C. The preferred pressure is from the viewpoint of industrial applicability to the range of the reduced pressure to the atmospheric pressure, more preferably from 1 atm to 5 atm, and more preferably from argon to 2 atm. Under such conditions, the phases of the phase separation system are mixed to form an emulsion. That is, the phase separation solution obtained above is dissolved. When the shearing tfe JU It is applied to form the pore-forming liquid, it seems to be a smear-like i-day particle, but in the case of general phase separation, when the volume of the solution B solution phase is larger than the volume of the polymer A solution phase, f The tendency of the emulsion is particularly suitable for the formation of 4 people in such a form, and the volume ratio of the liquid phase of the small π-A bath is preferably 0.4 or less with respect to the volume of the two-phase δ, and more preferably between 〇4 and 〇1. It is better to measure the volume ratio of the concentration of each component at the same time, and 6 is in the proper range. The resin microparticles obtained by the production method are microscopically small in particle size distribution, but the broad cause is in the emulsion. At the stage of formation, I got the very ":" reason. This tends to be more pronounced when using dissolving polymerization 16A and sputum. Therefore, 'in order to obtain the formation of emulsification _ @ o ' use conventional methods to fall off; machine =:; liquid phase search method for missing wing search, hybrid method for continuous biaxial mixing homogenizer, ultrasonic irradiation, etc. Conventional methods are commonly used for mixing. -22- 201219491 Especially, in particular, when mixing with a stirring wing, although depending on the shape of the stirring blade, the stirring speed is preferably 50 rpm to 12 rpm, more preferably 100 rpm to 1000 rpm, and even more preferably 2 〇. 〇rpm~8〇〇rpm 300rpm~600rpm ° Further, the agitating wing is specifically, for example, propeller type, wheel blade split, plane paddle type, turbine type, double cone type, single cone type, single belt type, double belt type The screw type, the spiral belt type, and the like are not particularly limited as long as they can apply sufficient shearing force to the system. Further, in order to efficiently perform the disturbance, a disturbance plate or the like may be provided in the tank. Further, in order to produce an emulsion, it is not necessary to use only a mixer, and a generally well-known device such as an emulsifier or a disperser may be used. Specific examples No, there are a homogenizer (made by IKA) and p〇iytr〇n (five) coffee.

Batch emulsifier, such as TK automatic homogenizer (made by Special Machine Chemical Co., Ltd.), Ebara milder (manufactured by Ebara Seisakusho Co., Ltd.), τκ 'I pipelinehomomixer (COLLOIDMIL (manufactured by Kobelco Panteeh Co., Ltd.), thrasher , three-wet micro-pulverizer (manufactured by Mitsui Sanike Chemical Co., Ltd.), ultrasonic: new machine, static mixer, etc. = The emulsion obtained in this way, followed by the steps that can be provided. The magical particles are precipitated in order to obtain the purpose of the resin. The fine particles ' can be connected to the emulsion produced by the above steps by the solvent which is a poor solvent, and the target resin fine particles can be precipitated according to the diameter of the emulsion diameter. The method of contacting the poor solvent with the emulsion is: adding The method of emulsion can also be used in the method of milk =::= W 'but it is better to add a bad solvent to the emulsion: wide

S -23- 201219491 At this time, the resin particles produced by the introduction of the poor solvent are not particularly limited to the addition method, and the one-time addition method causes the emulsion to aggregate, melt, and form a mass of more than 1〇〇〇μηι. The law 'for the purpose of industrially effective addition. The method 'as long as the invention can be obtained, can be a continuous dropping method 'fractions', but in order to add a poor solvent and the particle size distribution is increased, or it is easy to be preferably a continuous dropping method, a fractional rate, The best one is a continuous drop, and the time for adding a poor solvent is '10 minutes or more and 50 hours or less', more preferably 30 minutes or more and 10 hours or less, and more preferably less than 5 hours and less than 5 hours. When the right side is shorter than the δ hai range, the emulsion is agglomerated and the particle size distribution is large, and agglomerates are formed. Further, when it is carried out for a longer period of time than this range, it is not practical when considering industrial implementation. By carrying out in this time range, when the emulsion is converted into resin fine particles, aggregation between particles can be suppressed, and resin fine particles having a small particle size distribution can be obtained. The amount of the poor solvent to be added varies depending on the state of the emulsion, but is preferably relative to the total weight of the emulsion! The mass fraction is added to the hazelnut summer portion, more preferably 0.1 to 5 parts by mass, and more preferably 2 to 3 parts by mass, '仏 is 0.2 mass 1 to 1 part by mass, preferably 0.2 to 0.5 parts by mass. Poor; the contact time of the valley d with the emulsion may be sufficient for the precipitation of the fine particles, but in order to cause sufficient precipitation and obtain efficient productivity, it is preferably 5 minutes to 5 hours after the addition of the poor solvent, More preferably, it is more than 5 minutes, less than 1 minute, and more preferably more than 1 minute.

S -24- 201219491 5 ^ Only within the range, especially better than 20 minutes and less than 4 hours, especially good for 3 minutes or more and less than 3 hours. In this way, the resin particle dispersion of the succinct clothes can be filtered, 2 'salt pressure filtration, pressure filtration, centrifugal separation, centrifugal filtration, spray drying, acid precipitation method, salting out method, A conventionally known method such as a freeze-solidification method performs solid-liquid separation to recover fine particle powder. The resin fine particles of the solid-liquid partitioning + u may be washed with a solvent or the like as needed, thereby removing impurities or the like which are adhered or contained, and purifying them. In this case, the Nujia' mixture is preferably the above-mentioned poor solvent, and more preferably selected from the group consisting of water, methanol, and ethanol, or a mixed solvent of two or more kinds. The obtained resin particles can be dried to remove residual solvent. In the day of the day, έί: Bee VL - Bu Zhiwan can be listed as air drying, heating and drying, decompression and drying 'cold freeze drying. The temperature at the time of heating, preferably lower than the glass transition temperature, is specifically 50 to 150. (:. In the method of separating the moon, the organic solvent and the poly-separation which are obtained by solid-liquid separation obtained when the resin fine particles are obtained can be recovered as a solvent obtained by solid-liquid separation, and is a mixture of a polymer ruthenium and a good solvent. 1% bauxite a organic bath and no ΛHello agent to remove bad solvents, you can Α ★丨m Ma Lihua liquid shape &> JM 冉 use the usual methods to push > knowledge method, you can use β, in particular, can be listed as 馏 Q Q Q, precision distillation, + early distillation, decompression utilization... membrane lord, stroke, membrane separation, etc., preferably Α 仃 蒸馏 single distillation, decompression Distillation and other distillation systems are heated, resulting in the promotion of polymer enthalpy or machine, and the concept of thermal decomposition which may cause the solvent of the cockroach to be combined.

S -25- 201219491 Point and in the state of anaerobic, it is better to carry out under _. Specifically, it is carried out under a nitrogen gas environment. Hurricane milk carbon monoxide strips People 5 brothers Ming made this cover in the Ming Dynasty} Day t Yang _ 丨 Make the upper, f ancient + this July tree moon 曰 particles aqueous dispersion method. Method The resin particles are dispersed in three rolls of water as a dispersion medium, two:::::=: planetary mixer, = (two machines, sand mill, roll mill, homogenizer, pulverizer, either Ve In the method of 〇, paint shaker, etc., it is heated or added under reduced pressure. & It is also necessary to 'in the present invention' resin resin particles added to the resin particles moisture water Qiu t 7 ± m in the heart of the Magang with 5 Hai, more Μ with 11 and adjusted ' should be 80% by mass for 50 The mass is below 5%, and the better is 3 〇 quality, 仏 is 2 质 晋. / ν Γ ^ The fraction exceeds 80% by mass, and the resin particles may be difficult to be dispersed in parts (4). The lower limit is not (four) limit ^$ can be set according to the purpose. w j Therefore 4: The resin particles used are excellent in dispersibility to water, and are:疋34 is a preferred range, and the resin can be dispersed without using a dispersant in particular: = ί 明 由于 由于 由于 由于 由于 由于 由于 由于 由于 由于 实质上 实质上 实质上 实质上 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、荽& t River Sweater 4 & Reduced adhesion reduction, deterioration of water quality, for substrate use. Person 8: It can also be practical when leaking to the surface and sticky. The aqueous dispersion containing the dispersant, especially in the use of the high-resistance resin particles of the high-resistance -26-201219491 according to the present invention, the heat treatment strip is thus caused by the discoloration of the dispersant: the temperature system is a general case, the degree of measurement is lowered, etc. The adverse effects can become non-private: significant sputum for the use of dispersants, the use of resin particles water = therefore, the content of substantially non-dispersant, relative to the two sides of the tree - profit point. a Berry, the best is not used. The dispersing agent may be a polymer dispersing agent, an anionic dispersing agent, or a zwitterionic interface: a surfactant, a cation agent, or the like. Specific examples of the surfactant and the nonionic interfacial polymer dispersant include poly(ethylene glycol) (completed or P-type 4 poly(ethyl alcohol)), poly ( Ethylene glycol B:) Copolymer (completely or partially polycondensed poly(ethylene glycol-ethylene), or polymer), polyethylene ketone, poly(ethylene glycol), sucrose Fat=sour vinegar, poly(oxyethylene fatty acid vinegar)' poly(oxyethylene lauryl fatty acid ester), poly(oxyethylene glycol mono-fatty acid ester), poly(oxyethylene alkyl phenyl ether) = oxane Ether, polyacrylic acid, sodium polyacrylate, polyacrylic acid, sodium polymethacrylate, % styrene, sodium styrene, polyvinylpyrrolidine chloro, poly (styrene horse) Toluene) copolymer, amine poly(propylene amide), poly(p-vinylphenol), polyallylamine 'polyvinyl ether, polyethylene methylal, poly(acrylamide), poly(fluorenyl) Acrylamide, oxyethyleneamine, poly(vinyl bromidone), poly(vinyl π-pyridine), ♦aminopurine, polyethyleneimine, etc. Synthetic resin, maltose, cellobiose, lactose, sucrose and other disaccharides, cellulose, chitosan, hydroxyethyl cellulose, hydroxypropyl cellulose, Yue cellulose, ethyl cellulose, ethyl

S -27- 201219491 Cellulose derivatives such as hydroxycellulose, carboxydecylethylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, cellulose ester, linear powder and its derivatives, starch Polysaccharides or derivatives thereof, degradants, casein, collagen, albumin Fibrin, carrageenan, chondroitin sulfate, acacia, agar, protein, etc., preferably poly(vinyl alcohol) (completely saponified or partially saponified poly(vinyl alcohol) may also be) (vinyl alcohol-ethylene) copolymer (completely saponified or partially saponified poly(vinyl alcohol-ethylene) copolymer), polyethylene glycol, sucrose fatty acid ester, poly(oxyethylene alkyl phenyl ether), Poly(oxyalkyl ether), poly(acrylic acid), poly(methacrylic acid), carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, ethyl Hydroxycellulose, carboxymethylethylcellulose a cellulose derivative such as carboxymercapto cellulose, decylmethylcellulose sodium or cellulose ester, polyvinylpyrrolidone, more preferably poly(vinyl alcohol) (fully saponified or partially saponified poly(ethylene) Alcohol), poly(vinyl alcohol-ethylene) copolymer (completely saponified or partially saponified poly(vinyl alcohol-ethylene) copolymer, polyethylene glycol, carboxymethyl cellulose, hydroxyethyl cellulose 'Hydroxypropyl cellulose, methyl cellulose, ethyl cellulose, ethyl hydroxy cellulose, carboxymethyl ethyl cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, cellulose ester, etc. Derivatives, polyvinylpyrrolidone, etc. Specific examples of the anionic surfactant include sodium fatty acid, potassium fatty acid, sodium alkylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyl sulfate, and alkane. Sodium sulfonate, sodium alkyl ether sulfate, monoalkyl phosphate, sodium polyoxyethylene alkyl ether phosphate, sodium fatty acid ester sulfonate, fatty acid ester sulfur

-28- S, fatty acid 醯 201219491 酉文鲇 sodium, sodium sulfhydryl sulfate, etc. Specific examples of the cationic surfactant include methylammonium chloride, alkyltrimethylammonium chloride, and dialkyl chloride: alkyldimethylammonium chloride, alkylpyridine chloride, and the like. Specific examples of the zwitterionic surfactant include a carboxylate, a carboxybetaine, an alkylbetaine, and a sulfobetaine betaine. Specific examples of the nonionic surfactant include 鱿s曰, polyoxyethylene fatty acid ester, polyoxyethylene lauric fat, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycol, and poly Oxyethylene alkyl phenyl ether, polyoxyethylene monodecyl phenyl ether dibenzyl phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene phenyl ether, polyoxyethylene distyryl phenyl ether, polyoxygen Vinyl phenyl ether, polyoxyethylene diphenyl ether, polyoxyethylene phenoxy oxyethylene cumene benzene, polyoxyethylene alkyl ether, fatty amine, fatty acid monoethanol decylamine, fatty acid diethanol decylamine, ethanol S&amine, polyoxyethylene fatty acid amine, isopropanol amidated amine, polyoxyethylene amine, and the like. Further, in the alkyl group exemplified herein, a linear saturated hydrocarbon group of 1 to 30, or a branched saturated hydrocarbon group may be substituted with a linear unsaturated hydrocarbon group, or a branched type unsaturated aqueous dispersion of the resin fine particles of the present invention, It is also possible to add a leveling agent, an antifoaming agent, an anti-popping agent, a pigment dispersing agent, an ultraviolet absorbing agent, or a pigment or dye such as titanium oxide, zinc or carbon black, as needed. Sodium sulfonate, chlorinated sulfonyl, chlordamine, sucrose fatty acid vinegar, mono-fatty acid, polyoxyethylene, monostyrene, trisylphenyl sulfonate, polyalkanol fatty acid Example of alkyl oxygen: carbon number. The alkyl group is also a hydrocarbon group. The purpose of the five-party bulging agent

S -29-.201219491 The aqueous dispersion of the resin fine particles of the present invention, although highly heat-sensitive, can be well dispersed in water without substantially using a dispersing agent. Coatings for interior and exterior coatings, home appliances, building materials, etc. = adhesives, inks, adhesives or coatings, and cosmetics for high heat resistance, especially without dispersion. The coloring or heat resistance caused by the dispersing agent is lowered, the deterioration of the property is deteriorated, the adhesion to the substrate is lowered, the surface is leaked, the surface is sticky, and since the dispersion medium is water, the substrate can be improved by avoiding the organic solvent. Deterioration, environmental protection, workplace environment, etc. [Examples] Hereinafter, the present invention will be described in more detail based on examples. The invention is not intended to be limited to such embodiments. The measurements used in the examples are as follows. (1) Measurement of weight average molecular weight The weight average molecular weight was calculated by using gel permeation chromatography and aligning with a calibration curve obtained from a polyolefin.

Device: LC-10A series column made by Shimadzu Corporation (share): HFIP-806M2 mobile phase made by Showa Denko Co., Ltd. Flow rate of hexafluoro-isopropanol: 0 · 5 m 1 /min Detection: Differential refractometer Column temperature: 2 5 °C (2) Number average particle size, volume average particle size, particle size distribution index method-1 Observation of particles by scanning electron microscope (Scanning microscope JSM-630 1NF, manufactured by JEOL Ltd.) When the number average particle is measured, and the particle is not round, the long diameter is measured as the particle diameter. However, due to the steam path and the hydration, the water-resistant emerging agent is limited to the stupid B calculation electronic path. -30- 201219491 The number average particle diameter (Dn)' volume average particle diameter (Dv) is the average of any 1 〇 0 particles, calculated according to the formulas (1) and (2). The particle size distribution index (PDI)' is calculated according to the formula (3). Σ Di

Dn

Dv ηΣ Di Σ Di (1) (2) PDI ^

Dv Dn (3) Determination number 100, Dn: Quantity p DI : Particle size distribution index. Further, D i · particle diameter of each particle, 犷 average particle diameter ' Dv : volume average particle diameter (3) number average particle diameter, volume "<Day. Method 2 Calculation of cumulus thousand-average particle size and particle size distribution index Generic TT q & π υ.π. In the case of the singularity of the singularity of the singularity of the singularity of the singularity of the singularity of the squirrel ° V weight) I) The measurement is performed, and the average particle diameter and the number average particle diameter are calculated. Dan basket 槚 (4) Determination of melting point Using the Seiko Instruments (DS) RDC220, the top temperature was measured under ambient conditions. Evaluation of Dispersibility of Dissolved in Nitrogen Solution (5) at 10 C/min liter/dishness heating (Dispersion evaluation 1) 201219491 /IT shell bottle, at 4 (TC placed! hour, 'fly filled in glass The sample state was evaluated according to the following criteria: ~X visual observation of the separation of the composition. 〇: No separation is considered. X: Separation. (Dispersion evaluation of the examples and comparative examples, \ water dispersion is filled in The glass sword-like bottle is rated as 〇 by one-minute ultrasonic wave different from the glass I sample, and is evaluated as x by the separator. '7 Almost no separation is considered (6) Evaluation of the appearance of the coating film (coating evaluation 1) The appearance of the coating film was evaluated according to the following criteria: ◎. Coloring was not considered. 〇: It was considered to be slightly colored. X: Coloring was considered. (Coating evaluation 2) Further, a coating film was formed, 廿#, and the appearance was evaluated as follows. 5 g of the resin micro-distribution k obtained as described above was applied to a 1 S film by a bar coater (manufactured by Toray Co., Ltd., J. J'' 2 1 〇mm X 2 9 7 mm X 0 · 1 mm), dried at 405 ° C for 30 minutes with a 徉乂 air dryer to obtain a coating film. Visually confirm the appearance of the soil pancreas in addition to the obtained coating film. The good one is rated as 〇, the bad one is rated as X 〇 (7) using resin Dongli Dubang shares) 3⁄4 八; r! # . A system:, 'HYTREL (registered trademark) 7247

S -32- .201219491 manufactured by DuPont Co., Ltd.: "HYTREL (registered trademark),, 8238 For other resins used, polymerization was carried out according to the following reference examples. [Reference Example 1] 16.0 parts of terephthalic acid, 1, 4 14.0 parts of butanediol, 70.0 parts of polytetradecyl diol having a weight average molecular weight of about 3000, 0.01 parts of titanium tetrabutoxide, 0.005 parts of mono-n-butyl monohydroxytin oxide, and placed in a spiral belt type stirring blade The reaction vessel was heated at 190 to 225X for 3 hours, and the reaction water was discharged from the outside of the system to carry out a acetification reaction. 0.06 parts of tetra-n-butyl titanate was additionally added to the reaction mixture, and "Irganox" 1 098 was added. After the 2 parts of Chiba Japan's hindered phenolic antioxidant), the temperature was raised to 245. (:, secondly, it took 50 minutes to depressurize the system internal pressure to 30 Pa, and under this condition for 2 hours and 50 minutes. Polymerization to obtain an aliphatic polyether-polyester copolymer having a melting point of 60 ° C and a weight average molecular weight of 23,000. [Reference Example 2] 37.3 parts of terephthalic acid and 32.7 parts of 1,4-butanediol and Polytetramethylene glycol 30.0 having a weight average molecular weight of about 3,000 0.01 parts of titanium tetrabutoxide and 0.005 parts of mono-n-butyl monohydroxytin oxide, placed in a reaction vessel equipped with a spiral belt type stirring wing, at 190 to 225. (: heating for 3 hours, discharging the reaction water outside the system The esterification reaction was carried out while 0.06 parts of tetra-n-butyl titanate was additionally added to the reaction mixture, and 0-02 parts of ''Irganox' 109 8 (Chiba Jap an anti-oxidation phenol-based antioxidant) was added, and then the temperature was raised to 245 ° C, secondly, it takes 50 minutes to reduce the pressure in the system to 30 Pa ' under the conditions of 2 hours and 50 minutes to obtain an aliphatic polyether-polyester copolymer. The melting point is 221 ° C, the weight average molecular weight 26,000. *33- 201219491 [Reference Example 3] 42.7 parts of terephthalic acid, 37.3 parts of ruthenium-butanediol, and polytetramethylene glycol having a weight average molecular weight of about 3000, 2 parts of tetrabutoxytitanium 〇.〇1 f, 5 parts of mono-n-butyl monohydroxytin ruthenium oxide, placed in a reaction vessel equipped with a spiral red belt type search wing, heated at 19 〇 to 225 ° t for 3 hours, one side of the reaction water The outside of the system is discharged from the surface to perform the § reaction. Addition to the reaction mixture 0.06 parts of tetra-n-butyl titanate was added, and after adding 2 parts of ''Irganox''i〇98 (Chiba Japan's hindered phenol-based antioxidant) 升温.〇, the temperature was raised to 245. 〇, secondly, cost The pressure in the system was reduced to 30 Pa in 5 minutes, and polymerization was carried out for 2 hours and 5 minutes in this condition to obtain an aliphatic polyether-polyester copolymer. The melting point was 228 < t, and the weight average molecular weight was 25,000. (8) Production of Resin Fine Particles Each of the resin fine particles was produced in accordance with the following production examples. [Production Example 1] An aliphatic polyether-polyester copolymer (weight t average molecular weight 23, 〇〇〇) 35 g prepared in Reference Example 1 was added to a 10-neck flask of 100 μm, and N as an organic solvent. - mercapto-2-pyrrolidone 43g, polyvinyl alcohol (Nippon Synthetic Chemical Co., Ltd., Gohsenol (registered trademark), GL-〇5) 3_5g' heated to 9〇C' and disturbed to dissolve the polymer until. Bring the system temperature back to 80. (: After 'in a state of stirring at 450 rPm, 5 〇g of ion-exchanged water as a poor solvent was added dropwise at a rate of 0.41 g/min by infusion pumping. After adding the whole amount of water, stirring for 30 minutes, and filtering was obtained. The suspension was washed with ion-exchanged water 1 〇〇g, and vacuum-dried at 8 (rc for 10 hours) to obtain a white solid 3.1 ge in scanning type.

S-34-201219491 The powder obtained by electron microscopy was observed to be a spherical particle, and it was a polyether-polyester particle having a volume average particle diameter of 1 5 · 4 μm and a particle size distribution index of 1. 丨7. [Manufacturing Example 2] A polyester elastomer added as an aliphatic polyether styrene copolymer among the financial pressure glass south shyness (pressure resistant glass machine (share), HipergUster TEM_V1000N) at 1 000 m L "HYTREL" (registered trademark) 7247 (manufactured by Toray DuPont Co., Ltd., weight average molecular weight 29, 〇〇〇) 28 g, N-methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.) 3〇4 5g, Polyvinyl alcohol (PVa i5 制 manufactured by Wako Pure Chemical Industries Co., Ltd., weight average molecular weight 29, _: washed with methanol 'to reduce the sodium acetate content to 〇. 〇 5 mass%) 17. Thereafter, it was heated to 18 Torr and spoiled for 4 hours until the polymer dissolved. Thereafter, 35 § of ion-exchanged water as a poor solvent was dropped through the infusion liquid f at a rate of 2.92 g/min. Complete the addition of the whole amount of water*, continue to stir to cool down, filter the obtained suspension, add 7GQg of ion-exchanged water for re-slurry washing, and dry the filter at 8 (TC vacuum drying for 1 hour to obtain white solid) 26.5 g. The white solid was observed by a scanning electron microscope, and the average particle diameter was 5-5 μm, and the particle size distribution index was 丨° 2 and 'the same

The white solid was a polyether-polyester copolymer fine particle having a volume average particle diameter of 5·5 μηι and a particle size distribution index as a result of a laser particle size distribution (manufactured by Shimadzu Corporation, MM analysis). [Production Example 3] 〇〇〇mL's resistance to broken glass high dust dad (resistant house glass industry (shares)'

Among the HlPergIaSterTEM_V1〇〇〇N), added as an aliphatic poly-poly

S-35- 201219491 Polyester elastomer of ester copolymer" hytrel, (registered trademark) 7247 (made by Toray DuPont Co., Ltd. 'weight average molecular weight 29, 〇〇〇) 28 g, N-methyl-2-pyrrole 3 〇 8g, polyvinyl alcohol (pvA_丨5〇〇 manufactured by Wako Pure Chemical Industries, Ltd.), weight average molecular weight 29,000: washed with methanol to reduce the sodium acetate content to 0 '05 mass%) i4g, after nitrogen substitution, heated to 18 〇t:, and stirred for 4 hours until the polymer was dissolved. Thereafter, it was added as a poor solvent at a rate of 2.92 g/min via an infusion pump.离子g ion-exchanged water. After the addition of the whole amount of water, continue to stir to cool down, filter the obtained suspension, add 7 〇〇g of ion-exchanged water for re-slurry washing, and filter the filter at 80 ° C was dried under vacuum for 1 hr to obtain 25.5 g of a white solid. The white solid was observed by a scanning electron microscope, and the average particle size was 8·6 μΐη, and the particle size distribution index was 122 ^, while the white solid was at a laser particle size. Distribution meter Seoda-2 100), which was obtained by Shimadzu Corporation, was a polyether-polyester copolymer fine particle having a volume average particle diameter of 8 · 6 μηι and a particle size distribution index of 丨 22. [Production Example 4] 1000 mL of pressure-resistant glass In the autoclave (pressure-resistant glass industry, HipergUster TEM-V1000N), a polyester elastomer added as an aliphatic polyether-polyester copolymer"HYTREL, (registered trademark) 7247 (Dongli Dubang Co., Ltd.) Company, weight average molecular weight 29, 〇〇〇) 28g, N_ decyl-2-pyrrolidone (made by Kanto Chemical Co., Ltd.) 3〇1叾, polyvinyl alcohol (pVA_l5〇 manufactured by Wako Pure Chemical Industries Co., Ltd.) 〇, weight average molecular weight 29,000: washed with methanol to reduce the sodium acetate content to 0. 〇 5 mass%) 10.5 §, after nitrogen substitution, heated to i8 〇t:,

-36- S 201219491 and stirred for 4 hours until the polymer dissolved. The speed drop is treated as a bad solution: ================================================================================== In an hour, 26.0 g of a white solid limb was obtained. The self-coloring solid was observed by a scanning electron microscope to have a particle diameter of 12.6 μm and a particle size distribution index of 122. In addition, the white solid was analyzed by a laser particle size distribution meter (manufactured by Shimadzu Corporation, ΜΗ(10)) as a polystitch-polyester copolymer fine particle having a volume average particle diameter of 125 μm and a particle size distribution index (3). [Manufacturing Example 5] In a 1000 mL pressure-resistant glass autoclave (pressure-resistant glass industry (share),

Among the HiPerglaster TEM-V10〇〇N), the poly-Sl elastomer "HYTREL" added as an aliphatic poly-poly-WU is used as a trademark of Yang 8 (made by DuPont Co., Ltd., weight average molecular weight 27, 〇〇〇) 17 5 §, N 曱 -2-. 2i5g, polyvinyl alcohol (PVA_丨5〇〇 manufactured by Wako Pure Chemical Industries Co., Ltd.), weight average 2 sub-quantity 29,000: washed with methanol to reduce sodium acetate content To 5 贝5 里 0/〇) 17.5 g, after nitrogen substitution, heated to 18 〇. 〇 and stir for 4 hours until the polymer dissolved. Thereafter, 35 〇g of ion-exchanged water as a poor solvent was added dropwise at 2.92 g/min via an infusion pump. After the completion of the addition of the entire amount of water, the mixture was stirred to cool down, and the obtained suspension was filtered, and 700 g of ion-exchanged water was added for re-slurry washing, and the mixture was dried under vacuum for 8 hours at TC to obtain a white solid of 14.9 g. The obtained powder was observed by a scanning electron microscope, and as a result, it was a spherical particle of the positive-37-201219491, which was a β-ether-polyester copolymer fine particle having an average particle diameter of 43 μm and a particle size distribution index. At the same time, the white solid was analyzed by a particle size distribution meter (SALD-2100, manufactured by Shimadzu Corporation), and the result was a volume: a poly-polyacetate copolymer particle having a particle diameter of 5.4 and a particle size distribution index of 25.25. Example 6] A polyester elastomer "HYTREL" added as an aliphatic polyether-polyester copolymer in a 1000 mL pressure-resistant glass autoclave (pressure-resistant glass industry (share), = Perglaster TEM_vl〇〇〇N) (registered trademark) 8238 (manufactured by DuPont Co., Ltd., weight average molecular weight 27, 〇〇〇) 33 25 Lu, N.methyl-2-pyrrolidone (manufactured by Kanto Chemical Co., Ltd.) 299 2, polyvinyl alcohol (Heguang Pure Pharmaceutical Industry Co., Ltd. Preparation pvA_15 〇〇, weight average molecular weight 29,000: washed with methanol, so that the sodium acetate content is reduced to 0,. 〇 1% by mass) 17.1 §, after nitrogen substitution, heated to i8 〇 c > c, and stirred for 4 hours After the polymer is dissolved, the 35 〇g ion as a poor solvent is added to the Kawasui water at a rate of 2.92 g/min through the infusion pump j, and then the stirring is continued to cool down, and the obtained suspension is filtered. 7 μg of ion-exchanged water was added for repolymerization: Mei' and the filter was dried in vacuo at 8 (rc for 1 hr to obtain a white solid, 28.3 g. The powder obtained by a scanning electron microscope was observed. The granule-like particles are small ether-polyester copolymer fine particles having an average particle diameter of 12 ceramsite and a particle size distribution index of 23: χ, and the white solid is distributed in a laser particle size (Shimadzu Corporation) , SALD2i〇〇) analysis, the result is a (four)-polyester copolymer fine particle having a volume average particle diameter of 14.7 μm and a particle size distribution index of 123. -38- 1 .201219491 [Production Example 7] High-pressure finishing of 1000 mL of dust glass ( Dust-resistant glass industry (shares),

Among the Hiperglaster TEM-VlOOON), 17.5 g of the aliphatic polyether-polyester copolymer obtained in Reference Example 2, N-methyl-2-pyro B, 3 15.0 g, and polyvinyl alcohol (Wako Pure Chemical Industries, Ltd.) were added. PVA-1500 manufactured by Co., Ltd., weight average molecular weight 29,000: 17.5 g by washing the knee with decyl alcohol to reduce the sodium acetate content to 0.05% by mass, after heating with nitrogen, heating to 180 ° C, and stirring for 4 hours Until the polymer dissolves. After that, by adding 350 g of ion-exchanged water as a poor solvent at a rate of 2.92 g/min through an infusion pump, the addition of the entire amount of water is continued, and the suspension obtained by reducing the pH is added to the ion-exchanged water 7 〇〇g was subjected to re-slurry washing, and the filter was subjected to vacuum drying at 80 ° C for 1 hour to obtain 1 7.0 g of a white solid. The obtained powder was observed by a scanning electron microscope to have a spherical shape, and was a polyether-polyester copolymer fine particle having an average particle diameter of η 4 μηι and a particle size distribution index of 丨.29. [Reference Example 8] In 1000 mL of pressure-resistant glass high-pressure dad (Finance Glass Industry Co., Ltd.,

Among the Hiperglaster TEM-V1000N), the aliphatic poly-polyester copolymer obtained in Reference Example 3 was added, 17.5 g of 'N-mercapto-2-pyrrolidone 3 5 0.0 g, polyvinyl alcohol (Wako Pure Chemical Industries Co., Ltd.) Co., Ltd. PVA - 1 500 0' weight average molecular weight 2 9,0 0 〇: 17.5 g by washing the strip with methanol to reduce the sodium acetate content to 0.05% by mass, after heating with nitrogen, 'heated to 180. (:, and stirred for 4 hours until the polymer was dissolved. Thereafter, 350 g of ion-exchanged water as a poor solvent was dropped by a rotary pump at a rate of 2 92 g/min. After the completion of the addition of the entire amount of water, the flow was continued.

-39- S 201219491 Stirring was carried out to cool, the obtained suspension was filtered, and ion-exchanged water was added for re-slurry washing, and the fraction was filtered at 8 (rc vacuum drying for 1 hour) to obtain a white solid 17. g. The obtained powder was observed by a scanning electron microscope, and as a result, it was a spherical microparticle, and it was a polyether-polyester copolymer fine particle having an average particle diameter of 4 3 = a particle size distribution index of 1 · 3 Å. [Production Example 9 Adding the aliphatic polyether-polyester copolymer obtained in Reference Example 3 to 1000 mL of pressure-resistant glass high pressure dad (pressure-resistant glass industry (Hip), Hiperglaster TEM-VlOOON) 28. 〇g, N-methyl _ 2_. Slightly bite 3 〇 8.0g, polyvinyl alcohol (PVA-1 500 made by Wako Pure Chemical Industries Co., Ltd., weight average molecular weight 29, 〇〇〇: washed with decyl alcohol to reduce the sodium acetate content to 0.05 mass 17.5 g, after nitrogen substitution, heated to 18 (TC, and stirred for 4 hours until the polymer was dissolved. Thereafter, 350 g of ion exchange as a poor solvent was added dropwise at 2.92 g/min via an infusion pump. Water. After adding the full amount of water, continue to stir to cool down. The obtained suspension was filtered, and 7 g of ion-exchanged water was added for re-slurry washing, and the filter was dried under vacuum at 8 ° C to obtain a white solid of 26,0 g. The obtained powder was observed under a microscope, and as a result, it was a spherical microparticle, and it was a polyether-polyester copolymer fine particle having an average particle diameter of 12 mm 3 and a particle size distribution index of 丨 31. [Examples 1 to 10, Comparative Example 1 to 4] <Preparation and evaluation of aqueous dispersion of resin fine particles> Using the resin fine particles obtained in Production Examples 1 to 9, the resin fine particle dispersion liquid was prepared using the following representative examples, and the properties thereof were evaluated.

S-40-201219491 Ethyl ester, in addition to the examples, in the comparative example, the medium was changed. The resin fine particles obtained by dispersing the resin fine particles shown below were used for comparison. '<Resin fine particles for comparison> Melting point 170°〇Nylon 12 fine particles (〇rga manufactured by Arkema Co., Ltd. [Example 1 ] ' The polyether-polyester prepared in Production Example 1 was placed in an amount of 20 parts by mass in 80 parts by mass of water. The polymer resin particle wave treatment was carried out to obtain an aqueous dispersion. The moisture was carried out: the clock was 25 KHz, and the sound was not considered to have a separation price. [Example 2] The polyether-polyester produced in Production Example 1 was embedded in 20 masses. 80 parts by mass of water, 0.15 parts by mass of the polymer resin fine particles Xl〇〇 (manufactured by Aldrich Co., Ltd.) and added Triton, ί 1 搂 搂, 隹 如 如 如 田 田 田 田 田 田 田 田 田 田 田 田 田 田 田 田The results of the sonication treatment 'obtaining water ~ political night. Evaluation of water dispersibility' were hardly considered to be separated. [Example 3] 40% by mass of water dispersion of (IV)·polyacetate block copolymer resin fine particles produced in Production Example 2 was prepared. In the case of the liquid dispersion, the amount of the aqueous dispersion was changed to 5 parts by mass of the added water, and the ultrasonic treatment was carried out for 1 minute to obtain an aqueous dispersion. When the water dispersibility was evaluated, almost no separation was considered. [Example 4] Injury manufacturing example 3 system The aqueous dispersion of 40% by mass of the polyether-polyester block copolymer resin fine particles is sufficiently dispersed. Relative to the aqueous dispersion

-4 1-S 201219491 50 parts by mass Adding 5 parts by mass of water, and performing ultrasonic treatment at 25 kHz for 1 minute to obtain an aqueous dispersion. The evaluation of the water dispersibility was carried out, and the result was that there was no separation for the old hand. [Example 5] The mass of the polyether-polyacetate block copolymer resin fine particles produced in Production Example 4 was prepared. The /Q aqueous dispersion is dispersed. 50 parts by mass of water was added to 5 parts by mass of the aqueous dispersion, and ultrasonic treatment at 25 kHz for i minutes was performed to obtain an aqueous dispersion. Evaluation of water dispersibility was carried out, and the results were hardly considered to be separated. [Example 6] When 40% by mass of the aqueous dispersion of the polyether-polyester block copolymer resin fine particles produced in Production Example 5 was prepared, it was dispersed. 50 parts by mass of water was added to 5 parts by mass of the aqueous dispersion, and ultrasonic treatment at 25 kHz for j minutes was performed. [Evaluation of water dispersibility obtained by obtaining an aqueous dispersion ’" was not considered to be separated.

[Example 7J] When 40% by mass of the aqueous dispersion of the polyether-polyester block copolymer resin fine particles produced in Production Example 6 was prepared, it was dispersed. With respect to the aqueous dispersion 5, the capsule 3 was inoculated with 50 parts by mass of water, and subjected to ultrasonic treatment at 25 kHz for 1 minute to obtain an aqueous dispersion. Evaluation of water dispersibility was carried out, and the results were hardly considered to be separated.

[Example 8] When 40% by mass of the aqueous dispersion of the polyether-polyester block copolymer resin fine particles produced in Production Example 7 was prepared, it was dispersed. 50 parts by mass of water was added to 5 parts by mass of the aqueous dispersion, and a supersonic of 25 KHz was performed for 1 minute.

S-42-201219491 Wave treatment' Obtained aqueous dispersion. Evaluation of water dispersibility was carried out, and the results were hardly considered to be separated. [Example 9] When 40% by mass of the aqueous dispersion of the mystery-polyester block copolymer resin fine particles produced in Production Example 8 was prepared, it was dispersed. 50 parts by mass of water was added to 50 parts by mass of the aqueous dispersion, and ultrasonic treatment was performed at 25 kHz for 1 minute to obtain an aqueous dispersion. Evaluation of water dispersibility was carried out, and the results were hardly considered to be separated. [Example 10] When 40% by mass of the aqueous dispersion of the polyether-polyester block copolymer resin fine particles produced in Production Example 9 was prepared, it was dispersed. 50 parts by mass of water was added to 5 parts by mass of the aqueous dispersion, and ultrasonic treatment was performed at 25 kHz for 1 minute to obtain an aqueous dispersion. Evaluation of water dispersibility was carried out, and the results were hardly considered to be separated. [Comparative Example 1] 2 parts by mass of the polyether-polyester block copolymer resin fine particles produced in Production Example 1 were placed in 80 parts by mass of ethyl acetate, and ultrasonic treatment was carried out in the same manner as in Example 1 to obtain a dispersion liquid. . The evaluation of the dispersibility was carried out, and the result was separation. .

[Comparative Example 2] Commercially available nylon 12 fine particles (Orgasol manufactured by Arkema Co., Ltd., bright point 170. 20 parts by mass of hydrazine was added to 80 parts by mass of water), and 0.15 parts by mass of Triton X.100 (manufactured by Aldrich Co., Ltd.) was added as a dispersion. In the same manner as in Example 1, ultrasonic treatment was carried out to obtain an aqueous dispersion. The evaluation of the aqueous dispersion was carried out, and the result was separation. -43- '201219491 [Comparative Example 3] Commercially available nylon 12 fine particles (Orgasol manufactured by Arkema Co., Ltd.) 20 parts by mass of 170 ° C) was added to 80 parts by mass of water, and 1 part by mass of Triton X-100 (manufactured by Aldrich Co., Ltd.) was added as a dispersing agent, and ultrasonic treatment was carried out in the same manner as in Example 1 to obtain an aqueous dispersion. When the evaluation of the aqueous dispersion was carried out, almost no separation was observed. [Comparative Example 4] 20 parts by mass of commercially available nylon 12 fine particles (Orgasol, Arkema Co., Ltd., 170 ° C) was added to 80 parts by mass of ethyl acetate. In the same manner as in Example 1, ultrasonic treatment was carried out to obtain a dispersion liquid. Evaluation of the dispersion liquid revealed almost no separation. The results of the above examples and comparative examples are shown in Table 1. In Comparative Example 1, Ethyl acetate A dispersion medium, and undispersed, dispersibility is poor. Further, in Comparative Example 2, a resin having no aliphatic polyether units of the resin fine particles are not dispersed.

-44- S 201219491 Table 1 Dispersion composition component 1 Undercoat film evaluation Resin particle production example Medium dispersant dispersant/resin fine particle (%) Dispersion evaluation 1 Dispersion evaluation 2 Coating evaluation 1 Coating evaluation 2 Example 1 Polyether- Polyester Copolymer Production Example 1 Water No 〇〇 ◎ ◎ Example 2 Polyether-Polyester Copolymer Production Example 1 Water Triton X-100 0.75 〇〇〇〇 Example 3 Polyether-Polyester Copolymer Production Example 2 Water No 〇〇〇〇 Example 4 Polyether-Polyester Copolymer Production Example 3 Water No 〇〇〇〇 Example 5 Polyether-Polyester Copolymer Production Example 4 Water No 〇〇〇〇 Example 6 Polyether-polyester copolymer production example 5 Water-free 〇〇〇〇 Example 7 Poly-mycopolymer copolymer production example 6 Water-free 〇〇〇〇 Example 8 Polyether-polyester copolymer production example 7 Water No 〇〇〇〇 Example 9 Polyether-Polyester Copolymer Production Example 8 Water No 〇〇〇〇 Example 10 Polyether-Polyester Copolymer Production Example 9 Water No 0 〇〇〇〇 Comparative Example 1 Polyether-polyester copolymer ethyl acetate without 0 XX - - Comparative Example 2 Nylon 12 Water Triton X-100 0.75 XX - - Comparative Example 3 Nylon 12 Water Triton X-100 5 〇〇 XX Comparative Example 4 Nylon 12 Ethyl acetate No 0 〇〇 - - [Evaluation of dispersibility] From implementation In Examples 1 to 10 and Comparative Example 1, it was found that the resin fine particles obtained by copolymerizing the aliphatic polyether unit were well dispersed in water even in the absence of a dispersant. On the other hand, from Example 2 and Comparative Examples 2 to 4, it is understood that the resin fine particles containing no aliphatic polyether unit are dispersed only in an organic solvent or water containing more dispersant. <Evaluation of Appearance of Coating Film> From Examples 1 to 10 and Comparative Example 3, it was found that by using the aqueous resin fine particle dispersion of the present invention, a coating film having a good appearance against coloring by a dispersing agent can be obtained. . -45- 201219491 [Simple description of the diagram] Benefit ° * »>, [Key component symbol description] Benefits #»*>

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Claims (1)

201219491 VII. Patent application scope: 1. An aqueous dispersion of resin microparticles, characterized in that the resin microparticles are composed of a copolymer containing 10 to 90% by mass, and a melting point of 1 20 ° C or more, above 1 ΟΟμηι below. 2. The resin fine particle water-based resin fine particle dispersion according to claim 1 does not contain a dispersing agent, or 100 parts by mass of the copolymer, less than 1 part by mass. 3. A particle having a water particle diameter distribution index of 1 to 3 as claimed in claim 1 of the patent scope. 4. The dispersion according to any one of claims 1 to 3, wherein the dispersion contains 10 to 90% by mass of a fatty acid comprising an aliphatic polyether unit and a crystalline copolymer. a dispersion comprising resin fine particles, an aliphatic polyether unit having an average particle diameter of 1 μm, wherein the resin particles containing the resin particles of the water-based polyether unit are copolymerized with respect to the dispersion liquid. 47- .201219491 IV. Designation of the representative representative: (1) The representative representative of the case is: None. (2) A brief description of the component symbols of this representative figure: None. 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: -3- S