CN103119101A - Aqueous dispersion of fine resin particles - Google Patents

Abstract

Disclosed is an aqueous dispersion of fine resin particles, which is characterized by containing fine resin particles that are formed of a copolymer containing 10-90% by mass of an aliphatic polyether unit and have a melting point of not less than 120 DEG C and an average particle diameter of 1-100 [mu]m (inclusive). The aqueous dispersion of fine resin particles is especially effective in cases where less than 1 part by mass of a dispersant is contained per 100 parts by mass of the copolymer or no dispersant is contained. In addition, it is preferable that the fine particles have a particle size distribution index of 1-3. The present invention is capable of providing an extremely practical aqueous dispersion which contains fine resin particles that are formed of a highly heat-resistant copolymer that contains an aliphatic polyether unit.

Description

The resin particle aqueous dispersions

Technical field

The present invention relates to there is thermotolerance and be suitable as the tackiness agent of coating, caking agent etc. and the resin particle aqueous dispersions of coating material.

Background technology

The dispersion liquid of the resin particle that thermotolerance is high, be used to coating, caking agent, tackiness agent or field, coating agent as high function dispersion liquid.

The resin that the thermotolerance such as polyarylene sulfide, polyamidoimide is high, the tendency low with the affinity of water arranged usually, obtain their dispersion liquid, proposed to using organic solvent as medium, or the method (patent documentation 1,2) of using the dispersion agent such as tensio-active agent that it is dispersed in water.

In recent years, from the viewpoint of environment protection and labor safety, consider, the organic solvent that more and more urgent hope will be used as dispersion medium in the past becomes safe water.

On the other hand, disclose the resin particle formed by thermoplastic elastomers such as ether-ether segmented copolymers in patent documentation 3, put down in writing it and used in thermosetting resin, photo-curable resin or varnish etc.

The resin particle dispersion liquid of epithelium formation use is disclosed in addition, in patent documentation 4.In this patent documentation 4, particularly from the viewpoint of appearance of film, storage stability, consider, disclose suitable particulate, suitable particle diameter is below median size 250nm.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2007-154166 communique

Patent documentation 2: TOHKEMY 2009-67880 communique

Patent documentation 3: TOHKEMY 2008-239638 communique

Patent documentation 4: TOHKEMY 2007-277497 communique

Summary of the invention

The problem that invention will solve

In the aqueous dispersions of resin particle, use tensio-active agent in order to disperse, but in subsequent handling, the situation that mix with coating or varnish etc. as using this dispersion liquid, the dispersiveness that this tensio-active agent makes to become the situation of mixture state when mixing worsens, and sometimes can not give full play to the function of mixture.Do not mix tensio-active agent etc. in the dispersion liquid of resin particle is advisable as far as possible.

In addition, although according to environment for use and different, but at particle diameter hour, can guarantee dispersiveness, but because particle diameter diminishes, so occur that specific surface area becomes large, the problem that the viscosity of its dispersion liquid improves, in order to alleviate this impact, needing particle diameter is that 500nm is above and then be that 1 μ m is above, the aqueous dispersions of the resin particle of favorable dispersity.The stable on heating raising of resin particle in recent years plays a significant role in the novel material exploitation of every field, and then the improvement of this dispersion liquid is an important topic.

Under this situation, problem of the present invention is, the resin particle favorable dispersity that makes to have high heat resistance is provided is dispersed in the resin particle aqueous dispersions of the practicality excellence formed in water medium.

Solve the means of problem

The inventor conducts in-depth research, and found that by copolymerization the heat stable resin particulate of aliphatic poly ether unit, can realize above-mentioned purpose, completes the present invention.

, the present invention has following inventive point.

[1]. a kind of resin particle aqueous dispersions, it is characterized in that, contain resin particle,

Described resin particle is formed by the multipolymer of the aliphatic poly ether unit that contains 10～90 quality %, and fusing point is more than 120 ℃, and median size is below the above 100 μ m of 1 μ m.

[2]. resin particle aqueous dispersions as described as [1], it is characterized in that, the resin particle aqueous dispersions does not contain dispersion agent, or

When containing dispersion agent, this dispersion agent with respect to copolymer 1 00 mass parts for being less than 1 mass parts.

[3]. resin particle aqueous dispersions as described as [1] or [2], it is characterized in that, be the particulate that the size distribution index is 1～3.

[4]. resin particle aqueous dispersions as described as any one of [1]～[3], it is characterized in that, the multipolymer of the aliphatic poly ether unit that contains 10～90 quality % is the multipolymer formed by aliphatic poly ether unit and crystallinity polyester unit.

The invention effect

By the present invention, can access and contain resin particle, the very practical aqueous dispersions formed by thering is aliphatic poly ether unit, multipolymer that thermotolerance is high.In addition, the resin particle that the multipolymer used in the present invention forms, even, in fact not containing dispersion agent, also can disperse well, so, even do not use dispersion agent, also can obtain the aqueous dispersions of excellent dispersion in water.The resin particle aqueous dispersions obtained by the present invention, can be flexibly for coating, caking agent, tackiness agent or field, coating agent, cosmetic use, and be applicable to these purposes be reduced to the Water-borne modification of purpose with carrying capacity of environment.In addition, even owing to not using dispersion agent also can form the aqueous dispersions of good dispersity, so can provide in this case the inhibition dispersion agent to cause painted and water suction, high heat stable resin particulate aqueous dispersions.

Embodiment

Below be described more specifically the present invention.

Resin in resin particle aqueous dispersions in the present invention, is characterized in that, is the multipolymer that fusing point is, contains the aliphatic poly ether unit more than 120 ℃.Particularly found, by copolymerization aliphatic poly ether unit, even heat stable resin common and that the water affinity is low also than the good dispersity in organic solvent, can obtain the aqueous dispersions of excellent dispersion in water.Because dispersion medium is water, thus organic solvent can be avoided, preferred aspect environment protection, aspect labor safety, can realize the improvement of operating environment etc.In addition, although aqueous dispersions of the present invention has high heat resistance, the excellent dispersion in water, so, even do not use dispersion agent, also have good dispersiveness.Therefore, in the situation of not using dispersion agent, painted, the stable on heating reduction that can avoid dispersion agent to cause and the deterioration of water tolerance, with the close attachment reduction of base material, lip-deeply separate out, be clamminess, can become very practical aqueous dispersions.

The multipolymer used in the present invention, be contain the aliphatic poly ether unit, fusing point is the multipolymer more than 120 ℃.The state of the copolymerization of aliphatic poly ether unit can be arbitrary forms such as random copolymerization, block copolymerization, graft copolymerization, but segmented copolymer owing to can suppressing stable on heating reduction preferably.

Stating general formula (1) below aliphatic poly ether unit of the present invention means.

R means the aliphatic alkyl of divalent, specifically can list straight chain saturation alkane base, branched saturated hydrocarbon group, straight chain unsaturated alkyl, side chain unsaturated alkyl.N means number of repeat unit, is positive number.As above-mentioned straight chain saturation alkane base, branched saturated hydrocarbon group, straight chain unsaturated alkyl, side chain unsaturated alkyl, from the viewpoint of excellent dispersion water, preferably carbonatoms is 1～20, and particularly preferably carbonatoms is 1～10.

Concrete example as the aliphatic poly ether unit of copolymerization, can list polyoxyethylene glycol, polypropylene glycol, poly-1, ammediol, poly-1, multipolymer, the ethylene oxide adduct of polypropylene glycol and the multipolymer of oxyethane and tetrahydrofuran (THF) etc. of 4-butyleneglycol, poly-1,6-hexylene glycol, oxyethane and propylene oxide.Especially, owing to can giving wetting ability, easily disperseing in water, the aliphatic poly ether unit that particularly preferably carbonatoms of the R such as polyoxyethylene glycol, polypropylene glycol, poly-1,3-PD, poly-BDO is 1～10.

As the amount of aliphatic poly ether unit, in multipolymer, be the scope of 10～90 quality %, be preferably 15～90 quality % and then be preferably 20～80 quality %, 20～70 quality % more preferably.When the aliphatic poly ether unit is less than 10 quality %, the dispersiveness of resin in water worsens, so not preferred.When being greater than 90 quality %, the thermotolerance of resin reduces, so not preferred.

Weight-average molecular weight as aliphatic polyether, be not particularly limited, but be generally 500～20,000, be preferably 500～10,000.It should be noted that, weight-average molecular weight refers to by using dimethyl formamide to be measured as the gel permeation chromatography (GPC) of solvent, the weight-average molecular weight that converts and obtain with polystyrene standard.

Melting point resin in the present invention is more than 120 ℃, is preferably more than 140 ℃ and then is preferably more than 150 ℃, is particularly preferably more than 160 ℃.When fusing point is less than 120 ℃, the thermotolerance of filming etc. reduces, so not preferred.The upper limit is not particularly limited, but, from aspect dispersed water, is preferably below 300 ℃, and then is preferably below 280 ℃.It should be noted that, fusing point refers to and uses differential scanning calorimetric measurement device with 10 ℃ of/minute fusing points that determine of heat-up rate.

The multipolymer of the aliphatic poly ether unit in the present invention, as long as fusing point is more than 120 ℃, also can be not particularly limited with other multipolymer composition copolymerization.Other copolymer composition as can copolymerization, specifically can list polyester unit, polyamide units, polycarbonate unit, polyarylene sulfide ether unit, polyether-ether-ketone unit, polyimide unit or form monomeric unit of these polymkeric substance etc.Especially preferred block copolymer, the unit as forming segmented copolymer, be preferably polyester unit, polyamide units.Because even the ratio of polyether units increases, also can keep thermotolerance, so the preferred polyester unit is particularly preferably the polyester unit as the polymer unit of aromatic dicarboxylic acid and glycol.

Polyester unit, get final product so long as have ester bond on main chain or side chain, is not particularly limited, and can be obtained by sour composition and diol component polycondensation.

As the sour composition that forms polyester unit, can use terephthalic acid, m-phthalic acid, phthalic acid, 2, the 5-dimethyl terephthalic acid, 1, the 4-naphthalic acid, biphenyl dicarboxylic acid, 2, the 6-naphthalic acid, 1, the two phenoxy group ethane-p of 2-, p '-dioctyl phthalate, the phenyl indan dioctyl phthalate, succsinic acid, hexanodioic acid, sebacic acid, nonane diacid, dodecanedioic acid, dimeracid, 1, 3-pentamethylene dioctyl phthalate, 1, the 2-cyclohexane cyclohexanedimethanodibasic, 1, 4-cyclohexane cyclohexanedimethanodibasic etc., and their ester formative derivative etc., in addition as the sour composition that contains sulfonic group or its alkali, for example can use, the sulfo group terephthalic acid, the 5-sulfoisophthalic acid, the 4-sulfoisophthalic acid, 4-sulfo group naphthalene-2, the 7-dioctyl phthalate, sulfo group-terephthalyl alcohol, 2-sulfo group-1, the an alkali metal salts such as two (hydroxyl-oxethyl) benzene of 4-, alkaline earth salt, with ammonium salt etc., they can a kind or two or more copolymerization.

As the diol component that forms polyester unit, can make spent glycol, glycol ether, polyoxyethylene glycol, propylene glycol, polypropylene glycol, 1, ammediol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 7-heptanediol, 1, the 8-ethohexadiol, 1, the 9-nonanediol, 1, the 10-decanediol, 2, 4-dimethyl-2-ethyl hexane-1, the 3-glycol, neopentyl glycol, 2-ethyl-2-butyl-1, ammediol, 2-ethyl-2-isobutyl--1, ammediol, the 3-methyl isophthalic acid, the 5-pentanediol, 2, 2, 4-trimethylammonium-1, the 6-hexylene glycol, 1, the 2-cyclohexanedimethanol, 1, the 3-cyclohexanedimethanol, 1, the 4-cyclohexanedimethanol, 2, 2, 4, 4-tetramethyl--1, the 3-cyclobutanediol, 4, 4 '-sulfo-biphenol, dihydroxyphenyl propane, 4, 4 '-methylene biphenol, 4, 4 '-(2-norborneol fork base) biphenol, ring penta-1, the 2-glycol, hexamethylene-1, the 2-glycol, and hexamethylene-1, 4-glycol etc., they can use copolymer-1 kind or two or more.These resins can be used one or two or more kinds.

In the present invention, in above-mentioned resin, aspect the thermotolerance of resin, the glycol polycondensate of optimization aromatic dicarboxylic acid.Especially from the intensity aspect, preferably polyethylene terephthalate, polybutylene terephthalate etc.

Weight-average molecular weight as the multipolymer that contains aliphatic polyether of the present invention, be not particularly limited, but be generally 1,000～100,000, is preferably 10,000～80,000, and then be preferably 10,000～50,000.It should be noted that, weight-average molecular weight refers to by using hexafluoroisopropanol to measure as the gel permeation chromatography (GPC) of solvent, the weight-average molecular weight that converts and obtain with polystyrene standard.

The above-mentioned multipolymer that contains aliphatic polyether can be manufactured by known method.

As concrete example, for example can take any in following methods: make the lower alcohol diester of dicarboxylic acid, low molecular weight diols and the low melting point polymer chain segment components of excess quantity carry out transesterification reaction under the existence of catalyzer, the method that the resultant of reaction that makes to obtain carries out polycondensation; Make glycol and the low melting point polymer chain segment components of dicarboxylic acid and excess quantity carry out esterification under the existence of catalyzer, make method of the resultant of reaction polycondensation that obtains etc.

Below the resin particle in resin particle aqueous dispersions of the present invention is explained.

Resin particle aqueous dispersions in the present invention refers to, resin particle take in the dispersion medium that water is medium the dispersion liquid existed.

Now, this resin particle aqueous dispersions, it is optimum regime that resin particle swims consistently in the water as dispersion medium.According to circumstances different, have along with time lapse, the situation of resin particle sedimentation, in resin particle aqueous dispersions of the present invention, although, by resin particle generation sedimentation, by carrying out the mechanicalness redispersion, just process the dispersion liquid of redispersion like a cork and be also contained in the resin particle dispersion liquid.

The number average bead diameter of the resin particle in the resin particle dispersion is generally 1～100 μ m, is preferably 1～50 μ m and then is preferably 1～20 μ m.When number average bead diameter is less than 1 μ m, particulate easily condenses, and when being greater than 100 μ m, sedimentation in water, so not preferred.It should be noted that, the number average bead diameter of resin particle is, uses stereoscan photograph, observes 100 Arbitrary Particles and measures diameter, the value that substitution following formula (1) calculates.It should be noted that, be not the situation of circle at particle, refers to the value of measuring major diameter.The size distribution index of resin particle is in 1.0～3.0 scope, is preferably 1.0～2.0 and then be preferably 1.0～1.5.The size distribution index is greater than at 3.0 o'clock, and when using as coating agent, coating worsens, not preferred.It should be noted that, the size distribution index refers to according to following formula (3), by volume average particle size, with respect to the ratio of number average bead diameter, calculates.Volume average particle size is observe 100 Arbitrary Particles and measure diameter with stereoscan photograph, and substitution following formula (2) calculates.It should be noted that, be not the situation of circle at particle, is the value of measuring major diameter.

$\mathrm{Dn}=\frac{\underset{i=1}{\overset{n}{\mathrm{\Σ}}}\mathrm{Di}}{n}---\left(1\right)$

$\mathrm{Dv}=\frac{\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{\mathrm{Di}}^4}{\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{\mathrm{Di}}^3}---\left(2\right)$

$\mathrm{PDI}=\frac{\mathrm{Dv}}{\mathrm{Dn}}---\left(3\right)$

It should be noted that Di: the particle diameter of each particle, n: measure quantity 100, Dn: number average bead diameter, Dv: volume average particle size, PDI: size distribution index.

The shape of resin particle is preferably spherical shape, but also can be the ellipsoid shape.

As the method that obtains resin particle, can be obtained by known any method, but, especially preferably by making macromolecular solution be separated, form emulsion, add the method (No. 2009/142231st, International Publication) that poor solvent obtains particulate.

Can for example obtain by the following method; will micronized above-mentioned resin (hereinafter referred to as " polymer A ") and the polymer B of dissolving in the poor solvent of polymer A and organic solvent dissolution mix; formation is separated into take the system of this 2 phase of solution phase (hereinafter sometimes being called " polymer B solution phase ") that the solution phase (hereinafter sometimes being called " polymer A solution phase ") that polymer A is principal constituent and the polymer B of take be principal constituent; make it form emulsion; then contact with the poor solvent of polymer A, polymer A is separated out.

Aforesaid method is further specifically illustrated.

In above-mentioned, " polymer A and polymer B and organic solvent dissolution mix; form to be separated into and take the system of this 2 phase of solution phase that the solution phase that polymer A is principal constituent and the polymer B of take be principal constituent " refers to, after polymer A and polymer B and organic solvent mixing, be separated into the system of the solution phase that mainly contains polymer A and this two-phase of solution phase that mainly contains polymer B.

By using this system be separated, under the condition that can be separated, mix, make it emulsification, can form emulsion.

It should be noted that, above-mentioned in, about polymer dissolution whether, can by the temperature implementing present method, polymer A and polymer B are dissolved mix to carry out at 2 temperature when being separated, whether dissolve and be greater than 1 quality % and judge with respect to organic solvent.

This emulsion, the polymer A solution phase is disperse phase, the polymer B solution phase is external phase, and, by this emulsion is contacted with the poor solvent of polymer A, can separate out polymer A, the resin particle that obtains consisting of polymer A by the polymer A solution phase in emulsion.

In present method, at the poor solvent that can use polymer A, polymer B, the organic solvent that can dissolve them and polymer A, obtain under the prerequisite of resin particle of present method, combination is not particularly limited, but in present method, polymer A refers to high molecular polymer, be preferably natural in non-existent synthetic polymer, more preferably non-soluble polymer.

In present method, as polymer A, due to present method, using while contacting with poor solvent particulate is separated out as main points, so preferably insoluble in poor solvent, preferably undissolved polymkeric substance in the aftermentioned poor solvent, be particularly preferably non-soluble polymer.

As the non-soluble polymer here, be with respect to water, solubleness be 1 quality % following, be preferably that 0.5 quality % is following, the following polymkeric substance of 0.1 quality % more preferably.

As polymer B, can list thermoplastic resin, thermosetting resin, in the organic solvent of the polymer A of preferably using in solubilized the present invention and the polymkeric substance dissolved in the poor solvent of polymer A, wherein in above-mentioned organic solvent, dissolve, and the polymer industry operability excellence of also dissolving in pure series solvent or water, so more preferably, and then particularly preferably in dissolving in organic solvent, and the polymkeric substance dissolved in methyl alcohol, ethanol or water.

If specifically enumerate polymer B, can list poly-(vinyl alcohol) (can be also poly-(vinyl alcohol) of fully saponified type or partly-hydrolysed type), poly-(vinyl alcohol-ethene) multipolymer (can be also poly-(vinyl alcohol-ethene) multipolymer of fully saponified type or partly-hydrolysed type), Polyvinylpyrolidone (PVP), PEG, sucrose fatty ester, poly-(oxygen ethene fatty acid ester), poly-(oxygen ethene lauric fats acid esters), poly-(ethylene glycol fatty acid ester), poly-(oxygen vinyl alkyl phenyl ether), poly-(oxygen base alkyl oxide), polyacrylic acid, sodium polyacrylate, polymethyl acrylic acid, sodium polymethacrylate, polystyrolsulfon acid, sodium polystyrene sulfonate, polyvinyl chlorination tetramethyleneimine

poly-(styrene-maleic acid) multipolymer, amino poly-(acrylamide), poly-(4-Vinyl phenol), PAH, polyvingl ether, polyvinyl formal, poly-(acrylamide), poly-(Methacrylamide), poly-(oxygen vinyl-amine), PVP, poly-(vinyl pyridine), poly-amino sulfone, the synthetic resins such as polymine, maltose, cellobiose, lactose, the disaccharides such as sucrose, Mierocrystalline cellulose, chitosan, Natvosol, hydroxypropylcellulose, methylcellulose gum, ethyl cellulose, the ethyl hydroxylated cellulose, carboxymethylethylcellulose, carboxymethyl cellulose, Xylo-Mucine, the derivatived celluloses such as cellulose ester, amylose starch and its derivative, starch and its derivative, dextrin, cyclodextrin, the polyose or derivatives thereofs such as sodium alginate and its derivative, gelatin, casein, collagen protein, albumin, fibroin, Keratin sulfate, scleroproein, carrageenin, chondroitin sulfate, Sudan Gum-arabic, agar, protein etc., be preferably poly-(vinyl alcohol) (can also be poly-(vinyl alcohol) of fully saponified type or partly-hydrolysed type), poly-(vinyl alcohol-ethene) multipolymer (can also be poly-(vinyl alcohol-ethene) multipolymer of fully saponified type or partly-hydrolysed type), polyoxyethylene glycol, sucrose fatty ester, poly-(oxygen vinyl alkyl phenyl ether), poly-(oxygen base alkyl oxide), poly-(vinylformic acid), poly-(methacrylic acid), carboxymethyl cellulose, Natvosol, hydroxypropylcellulose, methylcellulose gum, ethyl cellulose, the ethyl hydroxylated cellulose, carboxymethylethylcellulose, carboxymethyl cellulose, Xylo-Mucine, the derivatived celluloses such as cellulose ester, Polyvinylpyrolidone (PVP), more preferably poly-(vinyl alcohol) (can also be poly-(vinyl alcohol) of fully saponified type or partly-hydrolysed type), poly-(vinyl alcohol-ethene) multipolymer (can also be poly-(vinyl alcohol-ethene) multipolymer of fully saponified type or partly-hydrolysed type), polyoxyethylene glycol, carboxymethyl cellulose, Natvosol, hydroxypropylcellulose, methylcellulose gum, ethyl cellulose, the ethyl hydroxylated cellulose, carboxymethylethylcellulose, carboxymethyl cellulose, Xylo-Mucine, the derivatived celluloses such as cellulose ester, Polyvinylpyrolidone (PVP), particularly preferably poly-(vinyl alcohol) (can also be poly-(vinyl alcohol) of fully saponified type or partly-hydrolysed type), PEG, carboxymethyl cellulose, Natvosol, hydroxypropylcellulose, methylcellulose gum, ethyl cellulose, the derivatived celluloses such as ethyl hydroxylated cellulose, Polyvinylpyrolidone (PVP).

The molecular weight of polymer B, in weight-average molecular weight, be preferably 1,000～100,000,000 and then be preferably 1,000～10,000,000, more preferably 5,000～1,000,000, be particularly preferably 10,000～500,000 scope, most preferred range is 10,000～100,000 scope.

Here said weight-average molecular weight refers to and uses gel permeation chromatography (GPC), and water is measured as solvent, the weight-average molecular weight converted with polyoxyethylene glycol.

In the not measurable situation of water, use dimethyl formamide to be measured, using dimethyl formamide still in not measurable situation, to use tetrahydrofuran (THF), using tetrahydrofuran (THF) still in not measurable situation, to use hexafluoroisopropanol.

As the organic solvent that polymer A and polymer B are dissolved, be the polymer A that can use, the organic solvent that polymer B is dissolved, select according to the kind of each polymkeric substance.

As concrete example, can list pentane, hexane, heptane, octane, nonane, n-decane, n-dodecane, n-tridecane, the tetradecane, hexanaphthene, the aliphatic hydrocarbon series solvents such as pentamethylene, benzene, toluene, dimethylbenzene, the aromatic hydrocarbons series solvents such as 2-methylnaphthalene, ethyl acetate, methyl acetate, butylacetate, butyl propionate, the ester series solvents such as butyl butyrate, chloroform, bromofom, methylene dichloride, tetracol phenixin, 1,2-ethylene dichloride, 1，1，1-trichloroethane, chlorobenzene, 2,6-DCT, the halohydrocarbon series solvents such as hexafluoroisopropanol, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), the ketone series solvents such as methyl butyl ketone, methyl alcohol, ethanol, n-propyl alcohol, the pure series solvent such as Virahol, METHYLPYRROLIDONE (NMP), methyl-sulphoxide (DMSO), DMF (DMF), N,N-dimethylacetamide (DMA), Texacar PC, trimethyl phosphite 99, 1,3-dimethyl-2-imidazolidone, the non-proton property such as tetramethylene sulfone polar solvent, formic acid, acetic acid, propionic acid, butyric acid, the carboxylic acid solvents such as lactic acid, methyl-phenoxide, ether, tetrahydrofuran (THF), Di Iso Propyl Ether, two

ether series solvent, the 1-butyl-3-Methylimidazoles such as alkane, diglyme, glycol dimethyl ether

acetate, 1-butyl-3-Methylimidazole

hydrosulfate, 1-ethyl-3-imidazoles

acetate, 1-ethyl-3-methylimidazole

thiocyanate-isoiony liquid or their mixture, suitably select according to the kind of used polymer A composition, polymer B composition.Be preferably the aromatic hydrocarbons series solvent, the aliphatic hydrocarbon series solvent, the halohydrocarbon series solvent, the alcohol series solvent, the ether series solvent, non-proton property polar solvent, the carboxylic acid solvent, as preferred solvent, it is the pure series solvent as water-soluble solvent, non-proton property polar solvent, the carboxylic acid solvent, as particularly preferred solvent, it is non-protic polar solvent, the carboxylic acid solvent, from obtaining easily, and can dissolve the polymkeric substance that kind is wider, and applied widely to polymer A, can with water, the solvent homogeneous phase mixing aspect that alcohol series solvent etc. is preferably used as the poor solvent of narrating is later considered, METHYLPYRROLIDONE most preferably, methyl-sulphoxide, N, dinethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, Texacar PC, formic acid, acetic acid.

These organic solvents both can have been used multiple, also can mix use, but consider from the particle aspect that obtains the less and narrow diameter distribution of particle diameter, and avoid solvent in the troublesome operation of using the separation circuit while recycling later, reduce aspect the operation burden on manufacturing and consider, preferred single organic solvent, and then preferably can be by the single organic solvent of polymer A and the two dissolving of polymer B.

In the present invention, the poor solvent of polymer A refers to the not solvent of dissolve polymer A.By dissolution with solvents, do not referred to that polymer A is below 1 quality % with respect to the solubleness of poor solvent, more preferably below 0.5 quality %, and then be preferably below 0.1 quality %.

Will use the poor solvent of polymer A in manufacture method of the present invention, be preferably the poor solvent of polymer A as this poor solvent, is also the solvent of soluble polymeric thing B.Can make like this polymer particles formed by polymer A effectively separate out.In addition, make polymer A and the solvent of polymer B dissolving and the poor solvent of polymer A be preferably the solvent that can evenly mix.

As the poor solvent in the present invention, according to the kind of the polymer A of using, the polymer A of desired use, both kinds of B are carried out various changes, if concrete example can list and be selected from pentane, hexane, heptane, octane, nonane, n-decane, n-dodecane, n-tridecane, the tetradecane, hexanaphthene, the aliphatic hydrocarbon series solvents such as pentamethylene, benzene, toluene, dimethylbenzene, the aromatic hydrocarbons series solvents such as 2-methylnaphthalene, ethyl acetate, methyl acetate, butylacetate, butyl propionate, the ester series solvents such as butyl butyrate, chloroform, bromofom, methylene dichloride, tetracol phenixin, 1,2-ethylene dichloride, 1，1，1-trichloroethane, chlorobenzene, 2,6-DCT, the halohydrocarbon series solvents such as hexafluoroisopropanol, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), the ketone series solvents such as methyl butyl ketone, methyl alcohol, ethanol, n-propyl alcohol, the pure series solvent such as Virahol, methyl-sulphoxide, DMF, N,N-dimethylacetamide, trimethyl phosphite 99, METHYLPYRROLIDONE, 1,3-dimethyl-2-imidazolidone, the non-proton property such as tetramethylene sulfone polar solvent, formic acid, acetic acid, propionic acid, butyric acid, the carboxylic acid solvents such as lactic acid, methyl-phenoxide, ether, tetrahydrofuran (THF), Di Iso Propyl Ether, two

at least one solvent in ether series solvent, the water such as alkane, diglyme, glycol dimethyl ether etc.

From effectively making polymer A become the particle aspect, consider, poor solvent is preferably aromatic hydrocarbons series solvent, aliphatic hydrocarbon series solvent, pure series solvent, ether series solvent, water, and most preferably pure series solvent, water, be particularly preferably water.

In the present invention, by suitable selective polymer A, polymer B, dissolve their organic solvent and the poor solvent of polymer A, they are combined, can make polymer A efficiently separate out, thereby obtain resin particle.

Now by the liquid after their organic solvent mixed dissolution of polymer A, polymer B and solubilized, need to be separated into and take this two-phase of solution phase that the solution phase that polymer A is principal constituent and the polymer B of take be principal constituent.

Now, the organic solvent of the solution phase that the organic solvent of the solution phase that the polymer A of take is principal constituent and the polymer B of take are principal constituent can be identical, also can be different, but the preferred identical solvent of essence.

Become the condition of two phase-separated state according to the enforcement temperature of the concentration of the kind of the molecular weight of the kind of polymer A, B, polymer A, B, organic solvent, polymer A, B, present method, pressure and difference.

In order to obtain easily becoming the condition of phase-separated state, the difference of the solubility parameters of preferred polymers A and polymer B (hereinafter sometimes being called " SP value ") is larger.

Now the difference as the SP value is 1 (J/cm ³) ^1/2above, more preferably 2 (J/cm ³) ^1/2above, and then preferred 3 (J/cm ³) ^1/2above, 5 (J/cm particularly preferably ³) ^1/2above, especially preferred 8 (J/cm ³) ^1/2above.The SP value, when this scope, easily is separated.

As long as polymer A and polymer B are both dissolved in organic solvent, be not particularly limited, be preferably 20 (J/cm as the upper limit of the difference of SP value ³) ^1/2below, more preferably 15 (J/cm ³) ^1/2below, and then preferred 10 (J/cm ³) ^1/2below.

Here said SP value is the value of calculating according to the Fedor predication method, and what be based on cohesion energy density and molar volume calculating (hereinafter is called " computing method " sometimes.) (apparatus of information of Co., Ltd., put down into distribution on March 31st, 17 for " と Meter calculation method for SP value base Foundation ying ", Yamamoto show tree work).

In situation about can not calculate by present method, can be by judging that the experimental technique whether dissolved in the solvent known at solubility parameters calculates the SP value and (hereinafter sometimes is called " experimental technique ".), use it to replace (" Polymer Handbook ", the 4th edition, J.Brand work, the distribution in 1998 of Wiley company).

Select to become the condition of phase-separated state, can change the ratio of polymer A, polymer B and this 3 composition of their organic solvent of dissolving, thereby the viewing duration state be made 3 composition phasors by with easy preliminary experiment, judge by it.

While making phasor, by polymer A, B and solvent with the arbitrary proportion mixed dissolution, then standing, more than at least 3, preferably more than 5, more preferably the point more than 10 judges whether to generate interface, be divided into the zone and the zone that is 1 phase of two-phase by identification, thereby understand the condition that becomes phase-separated state.

Now, in order to judge whether it is phase-separated state, temperature, pressure that in the time of be with the invention process, wish is used are adjusted to the ratio of polymer A, B and solvent arbitrarily by polymer A, B, polymer A, B are dissolved fully, fully stir after dissolving, then place 3 days, naked eyes are confirmed whether to be separated.

But, in the situation that becomes fully stable emulsion, even sometimes place can not be observed visually in 3 days, be separated.Can be separated on microcosmic by whether observing with opticmicroscope phase contrast microscope etc. in this case, thereby judge and be separated.

Being separated is take polymer A as main polymer A solution phase and take polymer B as main polymer B solution phase by being separated in organic solvent, thereby form.Now the polymer A solution phase is the phase that mainly is assigned polymer A, and the polymer B solution phase is the phase that mainly is assigned polymer B.Now polymer A solution phase and polymer B solution phase have kind and the corresponding volume ratio of usage quantity with polymer A, B.

As obtaining phase-separated state and industrial enforceable concentration, the concentration of polymer A, the relative organic solvent of B is what to take in the scope that can dissolve in organic solvent be prerequisite, but be preferably more than 1 quality % and be less than or equal to 50 quality %, be less than or equal to 30 quality % more preferably greater than 1 quality %, and then preferred 2 quality %～20 quality %.

In the present invention, interfacial tension that the polymer A solution phase is alternate with polymer B solution phase two, because two-phase is all organic solvent, so this interfacial tension is little, the emulsion can stable maintenance generated based on this character, so can make size distribution narrow down.Particularly when the organic solvent of polymer A phase and polymer B phase is identical, this successful.

Two alternate interfacial tensions in the present invention, because interfacial tension is too small, so can not directly measure by the methods such as sessile drop method that add different types of solution to be measured in normally used solution, but can the interfacial tension with air calculate by each, estimate thus interfacial tension.By each, the interfacial tension with air is denoted as r ₁, r ₂the time, their interfacial tension r ₁₂can pass through r ₁₂=r ₁-r ₂absolute value calculate.This r now ₁₂preferable range for being greater than 0, being less than or equal to 10mN/m, more preferably greater than 0, be less than or equal to 5mN/m, more preferably greater than 0, be less than or equal to 3mN/m, particularly preferably be greater than 0, be less than or equal to 2mN/m.

In the present invention, two alternate viscosity can affect median size and size distribution, and viscosity is smaller, and often size distribution is narrower.When viscosity ratio being defined as to wish and implementing polymer A solution phase under temperature condition of the present invention/polymers soln phase B, as preferable range, be 0.1～10, as more preferably scope, be 0.2～5, as so preferable range be 0.3～3, as scope particularly preferably, being 0.5～1.5, is 0.8～1.2 as preferable range especially.

Manufacture resin particle by the phase-separated system obtained like this.When carrying out micronize, with common reactive tank, implement.Suitable enforcement temperature of the present invention, consider from the realization property aspect of industry, is the scope of-50 ℃～200 ℃, be preferably-20 ℃～150 ℃, more preferably 0 ℃～120 ℃, and then preferably 10 ℃～100 ℃, particularly preferably 20 ℃～80 ℃, the scope of most preferably 20 ℃～50 ℃.Suitable enforcement pressure of the present invention, consider from the industrial realization aspect, for decompression state～100 an atmospheric scope, is preferably 1～5 atmospheric scope, more preferably 1～2 normal atmosphere, particularly preferably normal atmosphere.

Mixed phase separate stage under this condition, thus emulsion formed.

That is, to the solution that is separated obtained above, give shearing force, thereby generate emulsion.

When forming emulsion, the mode that becomes granular drop with the polymer A solution phase forms emulsion, but the general situation that often volume of polymer B solution phase is greater than the volume of polymer A solution phase when being separated easily forms the emulsion of this form, particularly the volume ratio of polymer A solution phase is preferably below 0.4 with respect to the total volume 1 of two-phase, more preferably between 0.4～0.1.Can measure in advance the volume ratio under each constituent concentration by when making above-mentioned phasor simultaneously, determine thus suitable scope.

The particulate obtained by this manufacturing process is the particulate of narrow diameter distribution, and this is owing to having obtained the cause of emulsion very uniformly at the emulsion formation stages.This trend is more remarkable when using both single solvent of soluble polymeric thing A, B.For this reason, obtain sufficient shearing force to form emulsion, use present known method to stir enough, can be by the liquid phase paddling process stirred by agitating vane, the paddling process stirred by continuous 2 screw mixer, the hybrid system stirred by clarifixator, by generally well-known methods such as ultrasonic irradiation are stirred, mix.

Particularly in situation about being stirred by agitating vane, stirring velocity is according to the difference of the shape of agitating vane and difference, but is preferably 50～1200rpm, more preferably 100～1000rpm, and then preferably 200～800rpm, particularly preferably 300～600rpm.

In addition, as agitating vane, specifically can list propeller-type, paddle type, flat oar type, Scroll-type, bicone, single tapered, monozonal, bizonal, screw type, ribbon type etc., as long as the system of can giving, with sufficient shearing force, is not particularly limited them.In addition, in order effectively to be stirred, baffle plate etc. can also be set in groove.

In addition, form emulsion, not only can use stirrer, the device that can also use mulser, dispersion machine etc. generally to be widely known by the people.If concrete example can list, the intermittent type mulser such as clarifixator (IKA society system), polytron refiner (キ ネ マ テ ィ カ society system), the automatic clarifixator of TK (special machine chemical industry society system), Ebara Milder mixing machine (ebara corporatlon society system), T.K.Filmics mulser, T.K.Pipeline Homomixer line-blending machine (special machine chemical industry society system), colloidal mill (refreshing Steel パ Application テ ッ Network society system), Slusher slusher, triangle wet type pulverising mill (Mitsui three pond chemical industry machine society systems), ultrasonic homogenizer, static mixer etc.

The emulsion so obtained is supplied with to the operation that the target particulate is separated out of postorder.

In order to obtain the resin particle of target, the poor solvent of polymer A is contacted with the emulsion produced by above-mentioned operation, thereby separate out the target resin particle with diameter corresponding to emulsion drop footpath.

The method that poor solvent contacts with emulsion can be both the method that adds emulsion in poor solvent, can be also the method that adds poor solvent in emulsion, but preferably in emulsion, added the method for poor solvent.

Now, as the method that adds poor solvent, as long as can obtain the resin particle that the present invention will manufacture, be not particularly limited, it can be any method in continuous dripping method, portion-wise addition method, disposable additive process, for when adding poor solvent, do not occur due to emulsion cohesion, fusion, merge the situation that makes size distribution become large or generate the block that is greater than 1000 μ m, preferably continuously dripping method, dripping method in batches, for industry is effectively implemented, continuous dripping method most preferably.

In addition, as the joining day of poor solvent, be more than 10 minutes in 50 hours, more preferably more than 30 minutes in 10 hours, more preferably more than 1 minute in 5 hours.

If implement, cohesion, fusion, merging along with emulsion are arranged, the situation generation that size distribution broadens or produces block within the time shorter than above-mentioned scope.In addition, if, with the time enforcement longer than above-mentioned scope, when considering industrial implementation, be unpractical.

By carrying out in this time range, when by emulsion, becoming resin particle, can suppress interparticle cohesion, obtain the resin particle of narrow diameter distribution.

The amount of the poor solvent added also can be according to the difference of the state of emulsion and difference, but with respect to emulsion gross weight 1 mass parts, be preferably 0.1～10 mass parts, more preferably 0.1～5 mass parts, and then preferred 0.2～3 mass parts, particularly preferably 0.2 mass parts～1 mass parts, most preferably 0.2～0.5 mass parts.

The duration of contact of poor solvent and emulsion, so long as be enough to make the sufficient time that particulate is separated out to get final product, in order to cause fully, separate out, and obtain efficient productivity, for at poor solvent, adding and finish latter 5 minutes～50 hours, more preferably 5 minutes～10 hours, more preferably 10 minutes～5 hours, particularly preferably 20 minutes～4 hours, especially be preferably 30 minutes～3 hours.

The resin particle dispersion liquid of producing like this, can be by filtration, decant, filtration under diminished pressure, pressure filtration, centrifugation, centrifuging, spraying drying, acid-precipitation method, salting-out process, freeze the generally well-known method such as freezing method and carry out solid-liquid separation, thereby reclaim fine-particle powder.

The resin particle that solid-liquid separation obtains, cleaned with solvent etc. as required, with except attachment removal or the impurity that contains etc., thereby carries out purifying.Now, as preferred solvent, be above-mentioned poor solvent, more preferably be selected from the one kind or two or more mixed solvent in water, methyl alcohol, ethanol.

The resin particle of gained can be removed residual solvent by drying.As drying means now, can list air-dry, heat drying, drying under reduced pressure, freeze-dried etc.Temperature during heating, preferably lower than second-order transition temperature, specifically is preferably 50～150 ℃.

Method of the present invention has the following advantages: can carry out flexible utilization by separating the organic solvent and the polymer B that obtain in the solid-liquid separation process carrying out in order to obtain resin particle, recycle.

The solvent obtained in solid-liquid separation is the mixture of polymer B, organic solvent and poor solvent.Remove poor solvent from this solvent, the solvent that forms use with regard to can be used as emulsion reuses.As the method for removing poor solvent, by generally well-known method, undertaken, specifically can list simple distillation, underpressure distillation, precise distillation, thin film distillation, extraction, membrane sepn etc., but the method for preferably simple distillation, underpressure distillation, precise distillation.

When carrying out the distillation procedure such as simple distillation, underpressure distillation, system is heated, and just likely can promote the thermolysis of polymer B, organic solvent, so preferably carry out under the state that there is no oxygen as far as possible, more preferably under inert atmosphere, carries out.Specifically, under the condition of nitrogen, helium, argon gas, carbonic acid gas, implement.

Below the method for manufacturing the resin particle aqueous dispersions in the present invention is explained.

The resin particle that will be obtained by aforesaid method is dispersed in the method in dispersion medium water, can be to use any in the method for habitual blending dispersion machine (such as planet mixing machine, 3 rollers, machine mixer, from revolution type mixing machine, homogeneous mixer, ball mill, ball mill, sand mill, roller mill, clarifixator, runner milling, mixing and blending machine, colo(u)rant dispersion device etc.), also several method can be combined to prepare.In addition, also can heat as required, add decompression.

Resin particle in the present invention is with respect to the addition of water, preferably according to the use of this resin particle aqueous dispersions, adjust, but be preferably below 80 quality %, and then be preferably below 50 quality %, more preferably, below 30 quality %, be particularly preferably below 20 quality %.When being greater than 80 quality %, there is resin particle to be difficult to the tendency of disperseing, need to disperse by dispersion agent etc.Under be limited to and be not particularly limited, as long as design according to purpose.

The resin particle used in the present invention, due to excellent dispersion in water, so as long as in above-mentioned preferable range, just can be not in the situation that use especially dispersion agent to be dispersed in water.

Therefore, in the present invention, owing to can not using in fact dispersion agent just to obtain the dispersion liquid of resin particle, so can be in the impact by dispersion agent self, the deterioration of painted generation, stable on heating reduction, water tolerance, with the close attachment reduction of base material, lip-deeply separate out and be clamminess etc. while becoming problem, also can use in practice.The aqueous dispersions that contains dispersion agent, particularly in the purposes of using the resin particle that the such thermotolerance of the present invention is high, heat-treat condition is that high temperature is normal conditions, so the painted grade caused by the decomposition of dispersion agent becomes more obvious, and the very large situation of the detrimentally affects such as reduction of aesthetic property is arranged.Therefore, containing dispersion agent, this is not very large advantage when using the resin particle aqueous dispersions in fact.

The content of dispersion agent, with respect to resin particle 100 mass parts, be less than 1 mass parts, preferably is less than 0.2 mass parts, does not most preferably use.

As long as dispersion agent can make resin particle be dispersed in water, just be not particularly limited, if enumerate, can list macromolecule dispersing agent, anion surfactant, cats product, zwitterionics, nonionic surfactant etc.

Concrete example as macromolecule dispersing agent, can list poly-(vinyl alcohol) (can be also poly-(vinyl alcohol) of fully saponified type or partly-hydrolysed type), poly-(vinyl alcohol-ethene) multipolymer (can be also poly-(vinyl alcohol-ethene) multipolymer of fully saponified type or partly-hydrolysed type), Polyvinylpyrolidone (PVP), PEG, sucrose fatty ester, poly-(oxygen ethene fatty acid ester), poly-(oxygen ethene lauric fats acid esters), poly-(ethylene glycol fatty acid ester), poly-(oxygen vinyl alkyl phenyl ether), poly-(oxygen base alkyl oxide), polyacrylic acid, sodium polyacrylate, polymethyl acrylic acid, sodium polymethacrylate, polystyrolsulfon acid, sodium polystyrene sulfonate, polyvinyl chlorination tetramethyleneimine poly-(styrene-maleic acid) multipolymer, amino poly-(acrylamide), poly-(4-Vinyl phenol), PAH, polyvingl ether, polyvinyl formal, poly-(acrylamide), poly-(Methacrylamide), poly-(oxygen vinyl-amine), PVP, poly-(vinyl pyridine), poly-amino sulfone, the synthetic resins such as polymine, maltose, cellobiose, lactose, the disaccharides such as sucrose, Mierocrystalline cellulose, chitosan, Natvosol, hydroxypropylcellulose, methylcellulose gum, ethyl cellulose, the ethyl hydroxylated cellulose, carboxymethylethylcellulose, carboxymethyl cellulose, Xylo-Mucine, the derivatived celluloses such as cellulose ester, amylose starch and its derivative, starch and its derivative, dextrin, cyclodextrin, the polyose or derivatives thereofs such as sodium alginate and its derivative, gelatin, casein, collagen protein, albumin, fibroin, Keratin sulfate, scleroproein, carrageenin, chondroitin sulfate, Sudan Gum-arabic, agar, protein etc., be preferably poly-(vinyl alcohol) (can also be poly-(vinyl alcohol) of fully saponified type or partly-hydrolysed type), poly-(vinyl alcohol-ethene) multipolymer (can also be poly-(vinyl alcohol-ethene) multipolymer of fully saponified type or partly-hydrolysed type), polyoxyethylene glycol, sucrose fatty ester, poly-(oxygen vinyl alkyl phenyl ether), poly-(oxygen base alkyl oxide), poly-(vinylformic acid), poly-(methacrylic acid), carboxymethyl cellulose, Natvosol, hydroxypropylcellulose, methylcellulose gum, ethyl cellulose, the ethyl hydroxylated cellulose, carboxymethylethylcellulose, carboxymethyl cellulose, Xylo-Mucine, the derivatived celluloses such as cellulose ester, Polyvinylpyrolidone (PVP), more preferably poly-(vinyl alcohol) (can also be poly-(vinyl alcohol) of fully saponified type or partly-hydrolysed type), poly-(vinyl alcohol-ethene) multipolymer (can also be poly-(vinyl alcohol-ethene) multipolymer of fully saponified type or partly-hydrolysed type), polyoxyethylene glycol, carboxymethyl cellulose, Natvosol, hydroxypropylcellulose, methylcellulose gum, ethyl cellulose, the ethyl hydroxylated cellulose, carboxymethylethylcellulose, carboxymethyl cellulose, Xylo-Mucine, the derivatived celluloses such as cellulose ester, Polyvinylpyrolidone (PVP).

Be the concrete example of tensio-active agent as negatively charged ion, can list sodium soap, lipid acid potassium, sodium alkyl benzene sulfonate, sodium alkyl naphthalene sulfonate, alkyl sulfuric ester sodium, alkyl sodium sulfonate, alkyl ether sulphate sodium, monoalkyl phosphoric acid esters, Voranol EP 2001 phosphoric acid ester sodium, fatty acid ester sodium sulfonate, fatty acid ester sodium sulfovinate, fatty acid alkyl amide sodium sulfovinate, fatty acid amide sodium sulfonate etc.

Be the concrete example of tensio-active agent as positively charged ion, can list alkyl methyl ammonium chloride, alkyl trimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, alkyl dimethyl benzyl ammonium chloride, alkyl-pyridiniums chloride etc.

As the concrete example of zwitterionics, can list alkyl amino carboxylate, carboxybetaine, alkyl betaine, sultaine, phosphino-trimethyl-glycine etc.

Concrete example as nonionic surfactant, can list sucrose fatty ester, polyoxyethylene fatty acid ester, the Wool wax alcohols,ethoxylated fatty acid ester, the polyoxyethylene sorbitan fatty acid ester, the polyoxyethylene glycol mono fatty acid ester, polyoxyethylene alkyl phenyl ether, polyoxyethylene monobenzyl phenyl ether, polyoxyethylene dibenzyl phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene list styryl phenyl ether, polyoxyethylene diphenylethyllene phenyl ether, polyoxyethylene triphenylethylene base phenyl ether, the polyoxyethylene diphenyl ether, polyoxyethylene Phenoxyphenyl ether, polyoxyethylene cumyl phenyl ether, Voranol EP 2001, fatty acid alkyl amide, fatty monoethanol amide, fatty diglycollic amide, lipid acid triglycolyl amine, the polyoxyethylene fatty acid acid amides, isopropanol amide, alkyl amine oxide, polyoxyethylene amine etc.It should be noted that, if enumerate said alkyl here, can list straight chain type saturated hydrocarbyl or the branched chain type saturated hydrocarbyl of carbonatoms 1～30.Also can replace alkyl but straight chain type unsaturated alkyl or branched chain type unsaturated alkyl.

Resin particle aqueous dispersions of the present invention, in the limit of not damaging purpose, can also add pigment or the dyestuffs such as the various medicaments such as flow agent, defoamer, mould inhibitor, pigment dispersing agent, UV light absorber, titanium oxide, zinc, carbon black as required.

Resin particle aqueous dispersions of the present invention, although thermotolerance is high, even but do not use in fact dispersion agent, also in water, disperse well, thus can automobile inside with exterior with in coating purposes, caking agent purposes, printing ink purposes, tackiness agent or coating agent purposes, the water system cosmetic uses such as coating, household electrical appliances material of construction, giving high heat resistance.Particularly substantially do not use in the situation of dispersion agent; can suppress deterioration that dispersion agent causes painted, stable on heating reduction and water tolerance, with the close attachment reduction of base material, lip-deeply separate out, be clamminess; and then; because dispersion medium is water; so can, by avoiding organic solvent, realize the improvement of the deteriorated improvement of base material, environment protection and processing environment etc.

Embodiment

Next, be described more specifically the present invention based on embodiment.But the present invention is not restricted to these embodiment.In embodiment, being determined as follows of employing.

(1) mensuration of weight-average molecular weight

Weight-average molecular weight is by gel permeation chromatography, with the calibration curve of polystyrene, compares, and calculates molecular weight.

Device: Shimadzu Scisakusho Ltd's LC-10A series processed

Post: the HFIP-806M processed of Showa Denko K. K * 2

Mobile phase: hexafluoroisopropanol

Flow velocity: 0.5ml/ minute

Detect: differential refraction rate meter

Column temperature: 25 ℃

(2) computing method-1 of number average bead diameter, volume average particle size, size distribution index

Observe particle by scanning electron microscope (the scanning electron microscope JSM-6301NF processed of NEC company), determine number average bead diameter.It should be noted that, be not bowlder at particle, and the major diameter of usining is measured as its particle diameter.

Number average bead diameter (Dn), volume average particle size (Dv), be by the mean value of any 100 particles, according to mathematical expression (1) and (2), calculates.Size distribution index (PDI) calculates according to mathematical expression (3).

$\mathrm{Dn}=\frac{\underset{i=1}{\overset{n}{\mathrm{\Σ}}}\mathrm{Di}}{n}---\left(1\right)$

$\mathrm{Dv}=\frac{\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{\mathrm{Di}}^4}{\underset{i=1}{\overset{n}{\mathrm{\Σ}}}{\mathrm{Di}}^3}---\left(2\right)$

$\mathrm{PDI}=\frac{\mathrm{Dv}}{\mathrm{Dn}}---\left(3\right)$

It should be noted that Di: the particle diameter of each particle, n: measure number 100, Dn: number average bead diameter, Dv: volume average particle size, PDI: size distribution index.

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

Be modulated in ion exchanged water the slurries that particulate 0.1% is arranged, then sent hyperacoustic ultrasonication 1 minute of 25kHz, about 100W, it is used to sample as measuring, use laser diffraction formula size-grade distribution meter (SALD-2100: Shimadzu Scisakusho Ltd's system) measured, calculate volume average particle size, number average bead diameter.

(4) mensuration of fusing point

Use the セ イ コ ー イ Application ス Star ロ ボ processed ッ ト DSC RDC220 of Le Co., Ltd., be determined under stream of nitrogen gas atmosphere the top temperature at the melting peak while heating with the heat-up rate of 10 ℃/minute.

(5) dispersed evaluation

(disperseing to estimate 1)

The aqueous dispersions of embodiment and comparative example is filled in glass sample plasma bottle processed, places 1 hour under 40 ℃, then the separate stage of visual observation composition, estimated according to following benchmark.

Zero: do not find to separate.

*: separated.

(disperseing to estimate 2)

The aqueous dispersions of embodiment and comparative example is filled in glass sample plasma bottle processed, sample after 1 minute kind of ultrasonication is almost found to be designated as " zero " who separates, will find be designated as " * " separated.

(6) evaluation of appearance of film

(coating estimates 1)

The outward appearance of filming according to following benchmark evaluation.

◎: do not find painted.

Zero: find painted slightly.

*: find that there is painted.

(coating estimates 2)

In addition, form and film simultaneously, estimate as follows its outward appearance.

Use excellent painting machine to be applied to polyester film (Dongli Ltd.'s system, 210mm * 297mm * 0.1mm) resin particle aqueous dispersions 5g obtained above, then in the fan drying machine of 150 ℃ dry 30 minutes, filmed.The outward appearance that the Visual Confirmation gained is filmed.By good being designated as " zero ", by bad be designated as " * ".

(7) use resin

East レ デ ィ Port Application Co., Ltd. system: " Ha イ ト レ Le (registered trademark) " 7247

デ ュ Port Application Co., Ltd. system: " Ha イ ト レ Le (registered trademark) " 8238

Use resin about other, carry out polymerization by following reference example.

[reference example 1]

By 16.0 parts of terephthalic acids, 1,14.0 parts of 4-butyleneglycols and weight-average molecular weight approximately 3000 poly-1,70.0 parts of 4-butyleneglycols, 0.01 part of four titanium butoxide and single normal-butyl-0.005 part, monohydroxy stannic oxide joins in the reaction vessel with ribbon type agitating wing, under 190～225 ℃, heating is 3 hours, on one side reaction water is distilled outside system, Yi Bian carry out esterification.Add 0.06 part of four titanium n-butoxide in reaction mixture, add 0.02 part of " イ Le ガ ノ ッ Network ス " 1098 (チ バ ジ ャ パ Application (strain) system resistance phenol is antioxidant), then be warmed up to 245 ℃, then last the decompression that the pressure in system was become in 50 minutes to 30Pa, under this condition, 2 hours 50 minutes kinds of polymerization, obtain aliphatic polyether-polyester copolymer.Fusing point is 160 ℃, and weight-average molecular weight is 23,000.

[reference example 2]

By 37.3 parts of terephthalic acids, 1,32.7 parts of 4-butyleneglycols and weight-average molecular weight approximately 3000 poly-1,30.0 parts of 4-butyleneglycols, 0.01 part of four titanium butoxide and single normal-butyl-0.005 part, monohydroxy stannic oxide joins in the reaction vessel with ribbon type agitating wing, under 190～225 ℃, heating is 3 hours, on one side reaction water is distilled outside system, Yi Bian carry out esterification.Add 0.06 part of four titanium n-butoxide in reaction mixture, add 0.02 part of " イ Le ガ ノ ッ Network ス " 1098 (チ バ ジ ャ パ Application (strain) system resistance phenol is antioxidant), then be warmed up to 245 ℃, then last the decompression that the pressure in system was become in 50 minutes to 30Pa, under this condition, 2 hours 50 minutes kinds of polymerization, obtain aliphatic polyether-polyester copolymer.Fusing point is 221 ℃, and weight-average molecular weight is 26,000.

[reference example 3]

By 42.7 parts of terephthalic acids, 1,37.3 parts of 4-butyleneglycols and weight-average molecular weight approximately 3000 poly-1,20.0 parts of 4-butyleneglycols, 0.01 part of four titanium butoxide and single normal-butyl-0.005 part, monohydroxy stannic oxide joins in the reaction vessel with ribbon type agitating wing, 190～225 ℃ of heating 3 hours, on one side reaction water is distilled outside system, Yi Bian carry out esterification.Add 0.06 part of four titanium n-butoxide in reaction mixture, add 0.02 part of " イ Le ガ ノ ッ Network ス " 1098 (チ バ ジ ャ パ Application (strain) system resistance phenol is antioxidant), then be warmed up to 245 ℃, then last the decompression that the pressure in system was become in 50 minutes to 30Pa, under this condition, 2 hours 50 minutes kinds of polymerization, obtain aliphatic polyether-polyester copolymer.Fusing point is 228 ℃, and weight-average molecular weight is 25,000.

(8) manufacture of resin particle

Each resin particle is based on the manufacture of following Production Example.

[Production Example 1]

Add aliphatic polyether-polyester copolymer (weight-average molecular weight 23 of producing in reference example 1 in 4 mouthfuls of flasks of 100ml, 000) 3.5g, the METHYLPYRROLIDONE 43g as organic solvent, polyvinyl alcohol (the Nippon Synthetic Chemical Industry Co., Ltd's ‘ ゴ ー セ ノ ー Le (registered trademark) ' GL-05) 3.5g, join 90 ℃, be stirred to polymer dissolution.The temperature of system is returned to 80 ℃, then stirred with 450rpm on one side, on one side will as the 50g ion exchanged water of poor solvent, via infusion pump, the speed with 0.41g/ minute is dripped.After all water all adds, stir 30 minutes, resulting suspension liquid is filtered, with ion exchanged water 100g, clean, carry out vacuum-drying 10 hours at 80 ℃, obtain white solid 3.1g.With the resulting powder of scanning electron microscopic observation, be the particulate of spherical shape, be volume average particle size is the polyether-polyester copolymer particle that 15.4 μ m, size distribution index are 1.17.

[Production Example 2]

To adding polyester elastomer " Ha イ ト レ Le (registered trademark) " 7247 as aliphatic polyether-polyester copolymer (eastern レ デ ュ Port Application Co., Ltd. system in the withstand voltage glass autoclave of 1000ml (withstand voltage nitre industry (strain) Ha イ パ ー グ ラ ス タ ー TEM-V1000N), weight-average molecular weight 29, 000) 28g, METHYLPYRROLIDONE (Kanto Kagaku K. K.'s system) 304.5g, polyvinyl alcohol (the PVA-1500 processed of Wako Pure Chemical Industries, Ltd., weight-average molecular weight 29, 000, by using washed with methanol, sodium acetate content is reduced to the polyvinyl alcohol of 0.05 quality %) 17.5g, carry out nitrogen replacement post-heating to 180 ℃, stir 4 hours to polymer dissolution.Then, will as the 350g ion exchanged water of poor solvent, via infusion pump, the speed with 2.92g/ minute be dripped.After all water all adds, stir borehole cooling, resulting suspension liquid is filtered, add ion exchanged water 700g, slurries are cleaned, the material that filters out, 80 ℃ of lower vacuum-dryings 10 hours, is obtained to white solid 26.5g.With this white solid of scanning electron microscopic observation, median size is that 5.5 μ m, size distribution index are 1.12 as a result.Analyze this white solid with Laser particle-size distribution meter (SALD-2100 processed of Shimadzu Seisakusho Ltd.) in addition, result is that volume average particle size is the polyether-polyester copolymer particle that 5.5 μ m, size distribution index are 1.12 simultaneously.

[Production Example 3]

To adding polyester elastomer " Ha イ ト レ Le (registered trademark) " 7247 as aliphatic polyether-polyester copolymer (eastern レ デ ュ Port Application Co., Ltd. system in the withstand voltage glass autoclave of 1000ml (withstand voltage nitre industry (strain) Ha イ パ ー グ ラ ス タ ー TEM-V1000N), weight-average molecular weight 29, 000) 28g, METHYLPYRROLIDONE (Kanto Kagaku K. K.'s system) 308g, polyvinyl alcohol (the PVA-1500 processed of Wako Pure Chemical Industries, Ltd., weight-average molecular weight 29, 000, by using washed with methanol, sodium acetate content is reduced to the polyvinyl alcohol of 0.05 quality %) 14g, carry out nitrogen replacement, then be heated to 180 ℃, stir 4 hours to polymer dissolution.Then, will as the 350g ion exchanged water of poor solvent, via infusion pump, the speed with 2.92g/ minute be dripped.After all water all adds, stir borehole cooling, resulting suspension liquid is filtered, add ion exchanged water 700g, slurries are cleaned, the material that filters out, 80 ℃ of lower vacuum-dryings 10 hours, is obtained to white solid 25.5g.With this white solid of scanning electron microscopic observation, median size is that 8.6 μ m, size distribution index are 1.22 as a result.With Laser particle-size distribution meter (SALD-2100 processed of Shimadzu Seisakusho Ltd.), analyzed in addition, result is that volume average particle size is the polyether-polyester copolymer particle that 8.6 μ m, size distribution index are 1.22 simultaneously.

[Production Example 4]

To adding polyester elastomer " Ha イ ト レ Le (registered trademark) " 7247 as aliphatic polyether-polyester copolymer (eastern レ デ ュ Port Application Co., Ltd. system in the withstand voltage glass autoclave of 1000ml (withstand voltage nitre industry (strain) Ha イ パ ー グ ラ ス タ ー TEM-V1000N), weight-average molecular weight 29, 000) 28g, METHYLPYRROLIDONE (Kanto Kagaku K. K.'s system) 301g, polyvinyl alcohol (the PVA-1500 processed of Wako Pure Chemical Industries, Ltd., weight-average molecular weight 29, 000, by using washed with methanol, sodium acetate content is reduced to the polyvinyl alcohol of 0.05 quality %) 10.5g, after carrying out nitrogen replacement, be heated to 180 ℃, stir 4 hours to polymer dissolution.Then, will as the 350g ion exchanged water of poor solvent, via infusion pump, the speed with 2.92g/ minute be dripped.After all water all adds, stir borehole cooling, resulting suspension liquid is filtered, add ion exchanged water 700g, slurries are cleaned, the material that filters out, 80 ℃ of lower vacuum-dryings 10 hours, is obtained to white solid 26.0g.With this white solid of scanning electron microscopic observation, result is median size 12.6 μ m, size distribution index 1.22.Analyzed in addition the polyether-polyester copolymer particle that result is volume average particle size 12.5 μ m, size distribution index 1.28 with Laser particle-size distribution meter (SALD-2100 processed of Shimadzu Seisakusho Ltd.) simultaneously.

[Production Example 5]

Add polyester elastomer " Ha イ ト レ Le (registered trademark) " 8238 (the デ ュ Port Application Co., Ltd. system as aliphatic polyether-polyester copolymer in the withstand voltage glass autoclave (withstand voltage nitre industry (strain) Ha イ パ ー グ ラ ス タ ー TEM-V1000N) of 1000ml, weight-average molecular weight 27, 000) 17.5g, METHYLPYRROLIDONE (Kanto Kagaku K. K.'s system) 315g, polyvinyl alcohol (the PVA-1500 processed of Wako Pure Chemical Industries, Ltd., weight-average molecular weight 29, 000, by using washed with methanol, sodium acetate content is reduced to the polyvinyl alcohol of 0.05 quality %) 17.5g, after carrying out nitrogen replacement, be heated to 180 ℃, stir 4 hours to polymer dissolution.Then, will as the 350g ion exchanged water of poor solvent, via infusion pump, the speed with 2.92g/ minute be dripped.After all water all adds, stir borehole cooling, resulting suspension liquid is filtered, add ion exchanged water 700g, slurries are cleaned, the material that filters out, 80 ℃ of lower vacuum-dryings 10 hours, is obtained to white solid 14.9g.With the resulting powder of scanning electron microscopic observation, the polyether-polyester copolymer particle that result is median size 4.3 μ m, size distribution index 1.25.With Laser particle-size distribution meter (SALD-2100 processed of Shimadzu Seisakusho Ltd.), analyzed in addition, result is the polyether-polyester copolymer particle of volume average particle size 5.4 μ m, size distribution index 1.25 simultaneously.

[Production Example 6]

Add polyester elastomer " Ha イ ト レ Le (registered trademark) " 8238 (the デ ュ Port Application Co., Ltd. system as aliphatic polyether-polyester copolymer in the withstand voltage glass autoclave (withstand voltage nitre industry (strain) Ha イ パ ー グ ラ ス タ ー TEM-V1000N) of 1000ml, weight-average molecular weight 27, 000) 33.25g, METHYLPYRROLIDONE (Kanto Kagaku K. K.'s system) 299.25g, polyvinyl alcohol (the PVA-1500 processed of Wako Pure Chemical Industries, Ltd., weight-average molecular weight 29, 000, by using washed with methanol, sodium acetate content is reduced to 0.05 quality %'s) 17.5g, after carrying out nitrogen replacement, be heated to 180 ℃, stir 4 hours to polymer dissolution.Then, will as the 350g ion exchanged water of poor solvent, via infusion pump, the speed with 2.92g/ minute be dripped.After all water all adds, stir borehole cooling, resulting suspension liquid is filtered, add ion exchanged water 700g, slurries are cleaned, the material that filters out, 80 ℃ of lower vacuum-dryings 10 hours, is obtained to white solid 28.3g.With the resulting powder of scanning electron microscopic observation, the polyether-polyester copolymer particle that result is median size 12.0 μ m, size distribution index 1.23.With Laser particle-size distribution meter (SALD-2100 processed of Shimadzu Seisakusho Ltd.), analyzed in addition, result is the polyether-polyester copolymer particle of volume average particle size 14.7 μ m, size distribution index 1.23 simultaneously.

[Production Example 7]

To adding the aliphatic polyether that obtains in reference example 2-polyester copolymer 17.5g, METHYLPYRROLIDONE 315.0g, polyvinyl alcohol (PVA-1500 processed of Wako Pure Chemical Industries, Ltd., weight-average molecular weight 29 in the withstand voltage glass autoclave of 1000ml (withstand voltage nitre industry (strain) Ha イ パ ー グ ラ ス タ ー TEM-V1000N), 000, by using washed with methanol, sodium acetate content is reduced to the polyvinyl alcohol of 0.05 quality %) 17.5g, after carrying out nitrogen replacement, be heated to 180 ℃, stir 4 hours to polymer dissolution.Then, will as the 350g ion exchanged water of poor solvent, via infusion pump, the speed with 2.92g/ minute be dripped.After all water all adds, stir borehole cooling, resulting suspension liquid is filtered, add ion exchanged water 700g, slurries are cleaned, the material that filters out, 80 ℃ of lower vacuum-dryings 10 hours, is obtained to white solid 17.0g.With the resulting powder of scanning electron microscopic observation, the polyether-polyester copolymer particle that result is median size 11.4 μ m, size distribution index 1.29.

[Production Example 8]

To adding the aliphatic polyether that obtains in reference example 3-polyester copolymer 17.5g, METHYLPYRROLIDONE 350.0g, polyvinyl alcohol (PVA-1500 processed of Wako Pure Chemical Industries, Ltd., weight-average molecular weight 29 in the withstand voltage glass autoclave of 1000ml (withstand voltage nitre industry (strain) Ha イ パ ー グ ラ ス タ ー TEM-V1000N), 000, by using washed with methanol, sodium acetate content is reduced to the polyvinyl alcohol of 0.05 quality %) 17.5g, after carrying out nitrogen replacement, be heated to 180 ℃, stir 4 hours to polymer dissolution.Then, will as the 350g ion exchanged water of poor solvent, via infusion pump, the speed with 2.92g/ minute be dripped.After all water all adds, stir borehole cooling, resulting suspension liquid is filtered, add ion exchanged water 700g, slurries are cleaned, the material that filters out, 80 ℃ of lower vacuum-dryings 10 hours, is obtained to white solid 17.0g.With the resulting powder of scanning electron microscopic observation, the particulate that result is spherical shape, it is the polyether-polyester copolymer particle of median size 4.3 μ m, size distribution index 1.30.

[Production Example 9]

To adding the aliphatic polyether that obtains in reference example 3-polyester copolymer 28.0g, METHYLPYRROLIDONE 308.0g, polyvinyl alcohol (PVA-1500 processed of Wako Pure Chemical Industries, Ltd., weight-average molecular weight 29 in the withstand voltage glass autoclave of 1000ml (withstand voltage nitre industry (strain) Ha イ パ ー グ ラ ス タ ー TEM-V1000N), 000, by using washed with methanol, sodium acetate content is reduced to the polyvinyl alcohol of 0.05 quality %) 17.5g, after carrying out nitrogen replacement, be heated to 180 ℃, stir 4 hours to polymer dissolution.Then, will as the 350g ion exchanged water of poor solvent, via infusion pump, the speed with 2.92g/ minute be dripped.After all water all adds, stir borehole cooling, resulting suspension liquid is filtered, add ion exchanged water 700g, slurries are cleaned, the material that filters out, 80 ℃ of lower vacuum-dryings 10 hours, is obtained to white solid 26.0g.With the resulting powder of scanning electron microscopic observation, the particulate that result is spherical shape, it is the polyether-polyester copolymer particle of median size 12.3 μ m, size distribution index 1.31.

The preparation evaluation of [embodiment 1～10, comparative example 1～4]<resin particle dispersion liquid>

Use the resin particle obtained in Production Example 1～9, use following exemplary embodiment preparation resin particle dispersion liquid, and estimate its characteristic.

In addition, as a comparative example, except use ethyl acetate as medium, also with the resin particle shown in following, prepare the resin particle dispersion liquid, contrasted with the dispersion liquid obtained in embodiment.

<for the contrast resin particle>

Nylon 12 particulates (the オ Le processed ガ ソ of ア Le ケ マ company Le, 170 ℃ of fusing points)

[embodiment 1]

Polyether-polyester block copolymer resin particulate 20 mass parts of producing in Production Example 1 are dropped in water 80 mass parts, carry out the 25kHz ultrasonication 1 minute, thereby obtain aqueous dispersions.Estimate water dispersible, result is not almost found to separate.

[embodiment 2]

Polyether-polyester block copolymer resin particulate 20 mass parts of producing in Production Example 1 are dropped in water 80 mass parts, add ト リ ト Application X-100 (ア Le De リ ッ チ company system) 0.15 mass parts as dispersion agent, carry out similarly to Example 1 ultrasonication, thereby obtain aqueous dispersions.Estimate water dispersible, result is not almost found to separate.

[embodiment 3]

The aqueous dispersions of 40 quality % of the polyether-polyester block copolymer resin particulate of producing in preparation Production Example 2, result fully scatter.With respect to these aqueous dispersions 50 mass parts, add water 50 mass parts, carry out the 25kHz ultrasonication 1 minute, thereby obtain aqueous dispersions.Estimate water dispersible, result is not almost found to separate.

[embodiment 4]

The aqueous dispersions of 40 quality % of the polyether-polyester block copolymer resin particulate of producing in preparation Production Example 3, result fully scatter.With respect in these aqueous dispersions 50 mass parts, adding water 50 mass parts, carry out the 25kHz ultrasonication 1 minute, thereby obtain aqueous dispersions.Estimate water dispersible, result is not almost found to separate.

[embodiment 5]

The aqueous dispersions of 40 quality % of the polyether-polyester block copolymer resin particulate of producing in preparation Production Example 4, result scatter.With respect to these aqueous dispersions 50 mass parts, add water 50 mass parts, carry out the 25kHz ultrasonication 1 minute, thereby obtain aqueous dispersions.Estimate water dispersible, result is not almost found to separate.

[embodiment 6]

The aqueous dispersions of 40 quality % of the polyether-polyester block copolymer resin particulate of producing in preparation Production Example 5, result scatter.With respect to these aqueous dispersions 50 mass parts, add water 50 mass parts, carry out the 25kHz ultrasonication 1 minute, thereby obtain aqueous dispersions.Estimate water dispersible, result is not almost found to separate.

[embodiment 7]

The aqueous dispersions of 40 quality % of the polyether-polyester block copolymer resin particulate of producing in preparation Production Example 6, result scatter.With respect to these aqueous dispersions 50 mass parts, add water 50 mass parts, carry out the 25kHz ultrasonication 1 minute, thereby obtain aqueous dispersions.Estimate water dispersible, result is not almost found to separate.

[embodiment 8]

The aqueous dispersions of 40 quality % of the polyether-polyester block copolymer resin particulate of producing in preparation Production Example 7, result scatter.With respect to these aqueous dispersions 50 mass parts, add water 50 mass parts, carry out the 25kHz ultrasonication 1 minute, thereby obtain aqueous dispersions.Estimate water dispersible, result is not almost found to separate.

[embodiment 9]

The aqueous dispersions of 40 quality % of the polyether-polyester block copolymer resin particulate of producing in preparation Production Example 8, result scatter.With respect to these aqueous dispersions 50 mass parts, add water 50 mass parts, carry out the 25kHz ultrasonication 1 minute, thereby obtain aqueous dispersions.Estimate water dispersible, result is not almost found to separate.

[embodiment 10]

The aqueous dispersions of 40 quality % of the polyether-polyester block copolymer resin particulate of producing in preparation Production Example 9, result scatter.With respect to these aqueous dispersions 50 mass parts, add water 50 mass parts, carry out the 25kHz ultrasonication 1 minute, thereby obtain aqueous dispersions.Estimate water dispersible, result is not almost found to separate.

[comparative example 1]

Polyether-polyester block copolymer resin particulate 20 mass parts of producing in Production Example 1 are dropped in ethyl acetate 80 mass parts, carry out similarly to Example 1 ultrasonication, thereby obtain dispersion liquid.Estimate dispersiveness, result has been separated.

[comparative example 2]

The particulate of commercially available nylon 12 (170 ℃ of the オ Le processed ガ ソ of ア Le ケ マ company Le fusing points) 20 mass parts are dropped in water 80 mass parts, add ト リ ト Application X-100 (ア Le De リ ッ チ company system) 0.15 mass parts as dispersion agent, carry out similarly to Example 1 ultrasonication, thereby obtain aqueous dispersions.Estimate water dispersible, result has been separated.

[comparative example 3]

2 particulates of commercially available nylon 1 (170 ℃ of the オ Le processed ガ ソ of ア Le ケ マ company Le fusing points), 20 mass parts are dropped in water 80 mass parts, add ト リ ト Application X-100 (ア Le De リ ッ チ company system) 1 mass parts as dispersion agent, carry out similarly to Example 1 ultrasonication, thereby obtain aqueous dispersions.Estimate water dispersible, result is not almost found to separate.

[comparative example 4]

Commercially available nylon 12 particulates (170 ℃ of the オ Le processed ガ ソ of ア Le ケ マ company Le fusing points) 20 mass parts are dropped in ethyl acetate 80 mass parts, carry out similarly to Example 1 ultrasonication, thereby obtain dispersion liquid.Estimate dispersiveness, result, almost find to separate.

The result of above-described embodiment and comparative example is as shown in table 1.

Comparative example 1, using ethyl acetate as dispersion medium, do not scatter, dispersed bad.

In addition, comparative example 2, be the resin without aliphatic poly ether unit, but this resin particle does not scatter yet.

Table 1

The evaluation of<dispersiveness>

From embodiment 1～10 and comparative example 1, copolymerization has the resin particle of aliphatic poly ether unit, even also can disperse well in water under non-dispersant condition.On the other hand, from embodiment 2 and comparative example 2～4, the resin particle of not fatty adoption ether unit only disperses in organic solvent or the water that contains more dispersion agent.

<film ocular estimate>

From embodiment 1～10 and comparative example 3, the resin particle aqueous dispersions of the application of the invention, can be prevented dispersion agent cause painted, outward appearance is good films.

Claims (4)

1. a resin particle aqueous dispersions, is characterized in that, contains resin particle,

Described resin particle is formed by the multipolymer of the aliphatic poly ether unit that contains 10～90 quality %, and fusing point is more than 120 ℃, and median size is below the above 100 μ m of 1 μ m.

2. resin particle aqueous dispersions as claimed in claim 1, is characterized in that, the resin particle aqueous dispersions does not contain dispersion agent, or

When containing dispersion agent, this dispersion agent with respect to copolymer 1 00 mass parts for being less than 1 mass parts.

3. resin particle dispersion liquid as claimed in claim 1 or 2, is characterized in that, is the particulate that the size distribution index is 1～3.

4. resin particle dispersion liquid as described as any one of claim 1～3, is characterized in that, the multipolymer of the aliphatic poly ether unit that contains 10～90 quality % is the multipolymer formed by aliphatic poly ether unit and crystallinity polyester unit.