JP2000297156A - True-sphere resin particle dispersion and preparation thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for stably preparing a true-sphere resin particle dispersion showing a sharp particle size distribution in a wide average particle size range of from a submicron meter to several hundred micron meters. SOLUTION: In a method for preparing a resin particle dispersion (E), wherein a liq. dispersion phase (X) comprising a resin precursor (A) is dispersed into a dispersant (Y) which does not dissolve (A), followed by reaction with a curing agent (B), (X) is dispersed into (Y) through a porous body having pores with a pore size distribution ε of 0-1, the ε being described in the following equation: ε=(ϕ90-ϕ10)/ϕ50 (where the ϕ90, ϕ10 and ϕ50 are each a pore size when the cumulative amt. in the relative cumulative pore size distribution curve is 90%, 10% or 50%).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a spherical resin dispersion. More specifically, the present invention relates to a method for producing a spherical resin dispersion having a sharp particle size distribution in a wide range of particle sizes.

[0002]

2. Description of the Related Art Conventionally, methods for producing a spherical resin dispersion include a suspension polymerization method, an emulsion polymerization method, a method of mechanically dispersing or emulsifying a resin solution, and the like. Attempts have been made to obtain resin particles having the required target particle size while satisfying the required resin physical properties in the application. As the target particle diameter, a particle diameter according to the intended use is required, from a submicron fine particle region to a relatively large particle size region of several hundred μm.

The above-mentioned method is a method which has been widely used in the past for producing resin particles of submicron to several tens of microns. However, in these methods, the sharpening of the particle diameter distribution cannot be said to be sufficient, and it is particularly difficult to produce resin particles having a particle diameter of 100 microns or more and a sharp particle diameter distribution; And the usable materials are limited to radically polymerizable monomers; In order to improve these drawbacks, the present applicant previously dispersed a isocyanate group-terminated urethane prepolymer as a resin precursor in an aqueous dispersion medium, and caused this to undergo a chain extension reaction to form spherical polyurethane resin particles. A method for obtaining the same has been proposed (JP-A-8-120041).

[0004]

However, although the above method has a considerable effect on controlling the particle size and the particle size distribution, it cannot be said that it is still sufficient in terms of the sharpness of the particle size distribution. The present invention aims to sharpen the particle diameter distribution in spherical resin particles having a large particle diameter of several tens μm or more, particularly exceeding 100 μm, and further, a wide particle diameter range from submicron to several hundred microns. The object of the present invention is to provide a method for producing a spherical resin particle dispersion having a sharp particle diameter distribution.

[0005]

Means for Solving the Problems The present inventors have intensively studied a method for solving the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention provides a method of dispersing a liquid dispersed phase (X) comprising a resin precursor (A) in a dispersion medium (Y) in which (A) is not dissolved and reacting with a curing agent (B). In the method for producing the product (E), (X) is dispersed in (Y) by passing through a porous body having pores having a pore size distribution ε of 0 to 1 represented by the following formula. = (Φ90-φ10) / φ50 wherein φ90, φ10 and φ50 have a cumulative amount of 90% in the relative cumulative pore distribution curve, respectively. The pore diameter at 10% and 50%. The liquid dispersed phase (X) comprising the resin precursor (A) is
In a resin particle dispersion (E) obtained by dispersing (A) in a dispersing medium (Y) that does not dissolve and reacting with a curing agent (B), the resin particles have an average particle diameter of 0.01 to 500 μm,
And a spherical resin particle dispersion (second invention) characterized in that the particle size distribution ε1 represented by the following formula (2) is 1 or less; ε1 = (D90−D10) / D50 (2) , D90, D10 and D50 are the particle diameters when the cumulative amount in the relative cumulative particle diameter distribution curve is 90%, 10% and 50%, respectively. And spherical resin particles obtained by removing the dispersion medium (Y) from the dispersion (third invention).

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, in order to obtain a spherical resin dispersion having a sharp particle size distribution, the pore size distribution of the pores of the porous material is important. In the relative cumulative pore distribution curve of the porous body, the pore diameter distribution ε is expressed as “the pore diameter (φ1 when the cumulative amount is 10% in the relative cumulative pore diameter distribution curve).
0) "and" 9 in the relative cumulative pore size distribution curve.
The pore diameter (φ10) at 0% ”and the“ pore diameter (φ10) when the cumulative amount is 50% in the relative cumulative pore diameter distribution curve ”can be defined by the following formula. ε = (φ90−φ10) / φ50 The pore size distribution ε is usually 0 to 1, preferably 0.5 or less, more preferably 0.2 or less. When ε exceeds 1, resin particles having a sharp particle size distribution, which is the object of the present invention, cannot be obtained. The relative cumulative pore distribution curve of the porous body is usually measured with a mercury intrusion porosimeter.

[0007] As a porous body satisfying such requirements,
Examples of the through-hole include a porous nozzle, a porous plate, and a cylindrical porous membrane having a pore size distribution ε within the above range. The material is not particularly limited as long as it has mechanical strength enough to withstand the pressure when (X) is injected and does not dissolve or swell in either the dispersed phase or the continuous phase and is chemically stable. Or organic. Examples of the porous body include a metal nozzle, a Teflon cylinder having a large number of pores formed therein, such as those disclosed in JP-B-62-25618, JP-A-61-40841, and the like. Examples thereof include a porous glass formed into a film.

The average particle diameter (D1) of the resin of the spherical resin dispersion (E) of the present invention is determined by the type of the resin precursor (A), the viscosity of the dispersed phase (X), the type of the continuous phase (Y), etc. In consideration of the above conditions, the desired particle diameter can be controlled by appropriately selecting the pore diameter of the porous body. The pore diameter is usually 0.01 to 100 μm, preferably 0.01 to 100 μm.
To 30 μm, and in order to maximize the effect of the present invention, the pore diameter is more preferably 5 to 30 μm. This makes it possible to obtain spherical resin particles having a large particle diameter (average particle diameter of several tens μm to several hundred μm), which is one of the objects of the present invention. Particularly preferred as a porous body satisfying such conditions are those called SPG films or MPG films using the above-described porous glass.

The resin to which the method of the present invention is applied includes:
Resins formed by a polyaddition reaction between the resin precursor (A) and the curing agent (B), such as polyurethane resins and epoxy resins.

As a precursor of the polyurethane resin, an isocyanate group-terminated urethane prepolymer (A1) is used, and as a precursor of the epoxy resin, a polyepoxy compound (A2) is used.

The above (A1) comprises an excessively equivalent amount of the organic polyisocyanate (a1) and a number average molecular weight of 500 to 10,
Isocyanate group-terminated urethane prepolymer derived from a high molecular weight diol (a2) and, if necessary, a low molecular weight diol (a3).

As the organic polyisocyanate (a1), the number of carbon atoms (excluding carbon in the NCO group, the same applies hereinafter)
18 aliphatic diisocyanates [ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate, etc.];
15 alicyclic diisocyanate [isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), etc.]; aromatic polyisocyanate having 6 to 20 carbon atoms [1] 2,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 2,4'- and / or
Or 4,4′-diphenylmethane diisocyanate (MDI) or the like]; an araliphatic diisocyanate having 8 to 12 carbon atoms [xylylene diisocyanate (XDI),
α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI) and the like]; modified products of these diisocyanates (carbodiimide group, uretdione group, uretoimine group, urea group, buret group, isocyanurate group, urethane group) Etc.); and combinations of two or more of these. Among these, preferred are HDI, IPDI, hydrogenated MDI, XDI
And TMXDI, particularly preferred are HDI,
IPDI and hydrogenated MDI.

Examples of the polymer diol (a2) include polyester diol, polyether diol, polyether ester diol, and a mixture of two or more thereof.

Examples of the polyester polyol include a condensed polyester diol obtained by condensation polymerization of a low molecular diol and a dicarboxylic acid or an ester-forming derivative thereof; a polylactone diol obtained by subjecting a lactone monomer to ring opening polymerization using the low molecular diol as a starting material. ;
Polyester polylactone diol obtained by ring-opening polymerization of a lactone monomer with a condensed polyester diol; low molecular weight diol and carbonate (dimethyl carbonate,
Polycarbonate diol obtained by condensation polymerization with ethylene carbonate and the like; and mixtures of two or more of these.

The low molecular diols described above or in the above include aliphatic diols having 2 to 12 or more carbon atoms [linear diols (ethylene glycol, 1,4
-Butanediol, 1,6-hexanediol, 1,9
-Nonanediol), diols having a branched chain (propylene glycol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2-diethyl-
1,3-propanediol, 1,2-, 1,3- or 2,3-butanediol, etc.); polyalkylene (C2-4) glycols having a molecular weight of less than 500 (polyethylene glycol, polypropylene glycol, polyoxytetra Diols having a cyclic group (for example, those described in JP-B-45-1474, such as 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, m- or p-xylene glycol, etc.); Alkylene (2-4 carbon atoms) oxide low molar adduct (molecular weight less than 500); polyhydric phenols [monocyclic dihydric phenols (catechol, hydroquinone, etc.), bisphenols (biphenol, bisphenol A, bisphenol F, bisphenol S) Etc.] Emissions oxide low mol adduct (number 2-4 carbons) (molecular weight less than 500); and mixtures of two or more thereof.

If necessary, a polyol having a valency of 3 or more (trimethylopropane, glycerin, etc.) may be used together with the low-molecular diol. When the trivalent or higher polyol is used in combination, the amount thereof is 5 mol% or less in the low molecular weight polyol.

Examples of the dicarboxylic acid or its ester-forming derivative include aliphatic dicarboxylic acids having 2 to 12 carbon atoms (succinic acid, adipic acid, sebacic acid, and the like).
Glutaric acid, azelaic acid, maleic acid, fumaric acid, etc., aromatic dicarboxylic acids having 8 to 15 carbon atoms (phthalic acid, terephthalic acid, isophthalic acid, etc.), and ester-forming derivatives thereof [anhydrides, lower alkyl (carbon Number 1
4) Ester, etc.] and a combination of two or more of these. Preferred are adipic, terephthalic and isophthalic acids. If necessary, a trivalent or higher polyvalent carboxylic acid in an amount not exceeding 5 mol% in the carboxylic acid component may be used together with the above dicarboxylic acid. Examples of such polycarboxylic acids include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid (anhydride) and pyromellitic acid (anhydride)).

The lactone monomer described above or in the above includes lactone having 4 to 15 or more carbon atoms,
For example, γ-butyrolactone, ε-caprolactone, γ-
Valerolactone and a combination of two or more of these.

Specific examples of preferred polyester polyols include polyneopentyl adipate diol, polyethylene adipate diol, polyethylene butylene adipate diol, polybutylene hexylene adipate diol, poly-3-methylpentane adipate diol, polybutylene isophthalate diol, polybutylene isophthalate diol, and polybutylene isophthalate diol. (Diethylene glycol) terephthalate diol, polycaprolactone diol, polyhexamethylene carbonate diol, and the like.

Examples of the polyether diol include compounds having a structure in which an alkylene oxide is added to a compound having two active hydrogen atoms (for example, the above-mentioned low molecular weight diol, divalent phenols, amines, etc.).

Examples of the amines include alkyl or alkenyl amines having 1 to 18 or more carbon atoms, cyclohexylamine, aniline, piperazine and the like.

As the alkylene oxide, ethylene oxide (EO), propylene oxide (P
O), 1,2-, 1,3-, 1,4- or 2,3-
Butylene oxide, styrene oxide, carbon number 5
10 or more α-olefin oxides, epichlorohydrin and combinations of two or more thereof (block and / or random addition). Preferred are EO, PO, 1,4-butylene oxide and a combination of two or more of these.

Among the polyether diols, preferred are those obtained by adding an alkylene oxide to a low molecular weight diol and polytetramethylene ether glycol.
O is added.

The polyetherester diol can be obtained by polycondensation of at least one of the above-mentioned polyetherdiols and at least one of the dicarboxylic acids or the ester-forming derivatives thereof exemplified as the raw material of the polyeryesterdiol. Things.

The number average molecular weight of (a2) is usually from 500 to
It is 10,000, preferably 800 to 5,000, more preferably 1,000 to 3,000. If the number average molecular weight is less than 500, the properties (strength, soft feeling, etc.) of the obtained resin will be insufficient, and if it exceeds 10,000, the viscosity of the dispersed phase (X) will be too high and the dispersion will be unstable.

As the low molecular weight diol (a3) optionally used together with (a2), the compounds exemplified as the starting materials for the polyester diol can be used. Preferred as (a3) is an aliphatic diol.
When (a3) is used in combination, the amount thereof is usually 50 mol% or less, preferably 0.5 to 0.5 mol%, based on the total amount of the polyol component.
30 mol%.

When the isocyanate group-terminated urethane prepolymer (A1) is formed, the equivalent ratio of the isocyanate group of (a1) to the hydroxyl group of (a2) and (a3) (NCO
/ OH) is usually 1 to 3, preferably 1.3 to 2.5. The free isocyanate group content of (A1) is usually 1 to 10% by mass, preferably 3 to 6% by mass.

The curing agent (B1) used to form polyurethane resin particles by reacting with (A1) includes a chain extender or a crosslinking agent such as water, polyamines, ketiminated polyamines, and polyvalent polyamines. Alcohols,
Polythiols, amino alcohols, amino carboxylic acids, and combinations of two or more of these.

Examples of the polyamines include diamines [aliphatic diamines having 2 to 12 carbon atoms (eg, ethylenediamine,
Propylene diamine, 1,6-hexane diamine, etc.), alicyclic diamine having 4 to 15 carbon atoms (for example,
4'-diaminodicyclohexylmethane, 4,4'-diamino-3,3'-dimethyldicyclohexyl, 1,4
-Diaminocyclohexane, isophoronediamine, etc., and an aromatic ring-containing diamine having 6 to 15 carbon atoms (for example, phenylenediamine, diaminotoluene, diethyltoluenediamine, xylylenediamine, α, α, α ′,
α′-tetramethylxylylenediamine, etc.), heterocyclic diamines (eg, piperazine etc.) etc .; triamine or higher polyamines [polyalkylene (C 2-4) polyamines (eg, diethylenetriamine, triethylenetetramine , Dipropylenetriamine, triethylenetetramine, tetraethylenepentamine and the like), polyethyleneimine (polymerization degree 3 to 10 or more), and a combination of two or more of these.

Examples of the ketiminated polyamines include compounds obtained by reacting a part or all of the amino groups of the above polyamines with ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.). Preferred among the ketones are acetone and methyl ethyl ketone. The method for synthesizing the ketimine compound is not particularly limited, and a known method may be used. For example, a method of heating a mixture of an amine and an excess amount of a ketone and removing water generated as necessary can be exemplified. The conversion of the ketimination is usually 20% or more, preferably 50 to 100%, more preferably 80 to 100%, based on the number of moles of the amino group.

Examples of the polyhydric alcohols include low-molecular diols and triols exemplified as the raw materials for the polyester polyol, and polyhydric alcohols having 4 to 6 or more valences (for example, pentaerythritol, diglycerin, sorbitol, etc.), Alcohols having a tertiary amino group [eg, triethanolamine, triisopropanolamine, N, N, N ′, N′-tetrakis (hydroxyethyl) ethylenediamine and the like] and the like can be mentioned.

Examples of the polythiols include compounds in which the above-mentioned polyhydric alcohol is reacted with hydrogen sulfide in the presence of an alkali to substitute a hydroxyl group with a mercapto group.

As the amino alcohol, a compound having 2 to 1 carbon atoms is used.
And mono- or dialkanolamines (e.g., monoethanolamine, diethanolamine, diisopropanolamine, N-hydroxyethylaniline, etc.).

As the aminocarboxylic acid, a compound having 2 to 1 carbon atoms is used.
Examples include two or more aminocarboxylic acids (eg, aminopropionic acid, aminocaproic acid, etc.).

Among the compounds exemplified as (B1), preferred are alicyclic diamines, aliphatic diamines and ketimines thereof, and particularly preferred are isophorone diamine, 1,6-hexanediamine and ketimines thereof. It is. When a bifunctional one is used as (B1), thermoplastic polyurethane resin particles are obtained, and when a trifunctional or more is used, three-dimensionally crosslinked polyurethane resin particles are usually obtained.

In the above polyurethane resin forming reaction, the isocyanate group-terminated urethane prepolymer (A
The equivalent ratio of (B1) to 1 equivalent of isocyanate group in 1) is usually 0.5 to 2 equivalents, preferably 0.7 to 1.5 equivalents.
Equivalent, more preferably 0.8 to 1.2 equivalent.

Along with said (B1), if necessary, a reaction terminator [monoalcohol (methanol, ethanol, propanol, butanol, etc.), monoamine (monoethylamine, monobutylamine, dibutylamine, etc.), alkanol (C2-4) amine ( Monoethanolamine, diethanolamine, etc.) can be used. The amount of the reaction terminator to be used is generally 0 to 0.2 equivalent, preferably 0.05 to 0.15 equivalent, relative to 1 equivalent of the isocyanate group of (A1).

In the present invention, the polyepoxy compound (A2), which is a precursor of the epoxy resin, includes aromatic,
Alicyclic, aliphatic and heterocyclic polyepoxy compounds are included.

Examples of the aromatic polyepoxy compounds include polyglycidyl ethers of polyhydric phenols and polyglycidyl aromatic polyamines. Examples of polyglycidyl ethers of polyhydric phenols include bisphenols (bisphenol F, bisphenol A, bisphenol B, bisphenol AD, bisphenol S, tetrabromobisphenol A, tetrachlorobisphenol A, 4,4′-dihydroxybiphenyl, octachloro-4). Diglycidyl ethers of 4,4'-dihydroxybiphenyl, etc .;
Diglycidyl ethers of resorcinol, hydroquinone, etc .; triglycidyl ethers of monocyclic trihydric phenols (eg, pyrogallol); polynuclear dihydric phenols (1,5
A diglycidyl ether of phenol or cresol novolak resin; a diglycidyl ether obtained from the reaction of 2 mol of bisphenol A with 3 mol of epichlorohydrin; phenol and glyoxal, glutaraldehyde or Polyglycidyl ethers of polyphenols obtained by condensation reaction with formaldehyde; polyglycidyl ethers of polyphenols obtained by condensation reaction of resorcinol and acetone. Also included are diglycidyl urethane compounds obtained by the addition reaction of tolylene diisocyanate or diphenylmethane diisocyanate with glycidol, and diglycidyl ethers of alkylene oxide (ethylene oxide or propylene oxide) adducts of bisphenols. Examples of the polyglycidyl aromatic polyamine include N, N-diglycidylaniline and N, N-glycidylaniline.
N, N ′, N′-tetraglycidyldiphenylmethanediamine.

Examples of the alicyclic polyepoxy compound include vinylcyclohexene dioxide, limonene dioxide,
Dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxydicyclopentyl ale, 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexane Carboxylate,
Bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) butylamine and the like can be mentioned. Further, the alicyclic polyepoxy compound also includes a hydride of the aromatic polyepoxy compound.

Examples of the aliphatic polyepoxy compounds include polyglycidyl ethers of aliphatic polyhydric alcohols, polyglycidyl esters of polyhydric fatty acids, and polyglycidyl aliphatic amines. Polyglycidyl ethers of polyhydric aliphatic alcohols include polyhydric alcohols having 2 to 6 or more [ethylene glycol,
Propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, polyglycerin, and their polyoxyalkylenes (having 2 to 2 carbon atoms)
4) ethers and the like] polyglycidyl ethers; vinyl (co) polymers containing glycidyl (meth) acrylate as a constitutional unit (number average molecular weight of 500 to 10,000)
Or more). Examples of polyglycidyl esters of polyvalent fatty acids include diglycidyl esters of aliphatic polycarboxylic acids having 2 or 3 or more valences (such as succinic acid, adipic acid, azelaic acid, and dodecane diacid). Examples of the polyglycidyl aliphatic amine include N, N, N ′, N′-tetraglycidylhexamethylenediamine.

Examples of the heterocyclic polyepoxy compound include trisglycidylmelamine.

Among these, preferred are diglycidyl ethers of bisphenols and polyglycidyl ethers of aliphatic polyhydric alcohols. The epoxy equivalent of (A2) is usually from 100 to 3,000, preferably from 200 to 1,000. The number of epoxy groups is usually 2 to 6 or more.

As the curing agent (B2) used to form an epoxy resin by reacting with (A2), in addition to the polyamines exemplified in the above (B1), ketiminated products thereof and polythiols, a curing agent having 4 carbon atoms ~ 15 or more polycarboxylic anhydrides (such as succinic anhydride, phthalic anhydride, tetrahydrosuccinic anhydride, dodecenyl succinic anhydride, trimellitic anhydride, pyromellitic anhydride, methylcyclohexene dicarboxylic anhydride); polyamides Polyamines [eg polycondensates of polymerized fatty acids (dimer acids) with excess equivalents of (poly) alkylene polyamines (ethylenediamine, diethylenetriamine, etc.)];
Imidazoles (such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole); polyoxazolines [e.g., a reaction product of N-hydroxyalkyl (C1-30) oxazolidine with polyisocyanate, N Esters of hydroxyalkyl (1 to 30 carbon atoms) oxazolidine and polycarboxylic acids (succinic acid, adipic acid, phthalic acid and the like); and a combination of two or more of these.

The amount of (B2) to be used is generally 0.5 to 1.5 equivalents, preferably 0.7 to 1.2 equivalents, per equivalent of the epoxy group of (A2).

For the purpose of accelerating the reaction between (A2) and (B2), a curing accelerator commonly used for epoxy resins can be used. Examples of such a curing accelerator include phosphorus compounds (eg, triphenylphosphine, triphenylphosphite, etc.); imidazoles (eg, 2-methylimidazole, 2-phenylimidazole, etc.); tertiary amines [eg, 2- ( Dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl)
Phenol, benzyldimethylamine, 1,8-diazabicyclo (5,4,0) undecene-7] and the like. The amount of the curing accelerator used is usually 5% by mass or less, preferably 0.1% by mass based on the total mass of (A2) and (B2).
３3% by mass.

In the method of the present invention, the resin precursor (A)
May be diluted with an organic solvent (C) and / or heated and adjusted as necessary (temperature T1: corresponding to the temperature of the dispersed phase (X) during dispersion) to adjust the viscosity and the like of the dispersed phase (X). . Examples of the above (C) include ester solvents (methyl acetate, ethyl acetate, butyl acetate, etc.), ketone solvents (acetone, methyl ethyl ketone, etc.), and hydrocarbon solvents (benzene, toluene, xylene, cyclohexane, n-hexane). , N-heptane, etc.).

More preferable (C) when the dispersion medium (Y) is an aqueous medium is an organic solvent (c1) having a solubility in water of 5 g or more at a temperature T1, for example, ethyl acetate, methyl ethyl ketone, acetone, and a mixture thereof. Mixtures of more than one species. Here, the solubility is 100 g
Represents the solubility in water. In addition to (c1), an organic solvent (c2) having a solubility in water at a temperature T1 of less than 5 g, for example, toluene, xylene, n-hexane, n-heptane, etc. is used in combination to obtain a more stable spherical resin. A dispersion can be obtained.

The amount of (C) used is usually 0 to 50% by mass, preferably 10 to 40% by mass in the case of (c1), and in the case of (c2), based on the mass of the dispersed phase (X). Usually 0
It is 15% by mass, preferably 1 to 10% by mass.

In the present invention, the temperature T1 of (X) is usually from 20 to 100 ° C., preferably from 30 to 75 ° C. T
When 1 is within the above range, a stable spherical resin dispersion can be obtained while controlling the rapid reaction between (A) and (B). Further, the viscosity of the (X) at the temperature T1 is as follows:
Usually 100 to 10000 mPa · s, preferably 200
５5000 mPa · s. By setting the viscosity in the above range, a stable spherical resin dispersion can be smoothly obtained.

In the present invention, the disperse phase (X) comprises the resin precursor (A), and together with (A), if necessary, has a weight average molecular weight of from 1,000 to 1,000, which has no reactivity with (A) and (B). 50,000 or more resin (d)
Can also be contained. As (d), for example, polyester resin, modified polyester resin, polyurethane resin, epoxy resin, polyamide resin, polycarbonate resin, polyether resin, poly (meth) acrylic resin, polystyrene resin, Polyolefin resins and the like can be mentioned. When (d) is contained, the mass ratio between (d) and (A) is usually 0/100 to 95 /.
5 range. If necessary, the dispersed phase (X) further contains conventionally known additives for inorganic or organic resins (antioxidants, light stabilizers, etc.), plasticizers, pigments, fillers, antiblocking agents and the like. You can also.

In the present invention, the curing agent (B) may be present in the dispersed phase (X) in advance, or may be present in (Y). Further, (B) may be added to the dispersion after (X) is dispersed in (Y). Preferably, (B) is previously present in (X), and more preferably, (B) and (X) are continuously mixed and continuously dispersed in (Y) while being continuously mixed.

The dispersion medium (Y) used in the present invention is not particularly limited as long as it does not dissolve the resin precursor (A), but is preferably an aqueous medium. Water alone may be used as the aqueous medium, but water-miscible organic solvents,
For example, alcohols (methanol, isopropanol,
Ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (eg, methylcellosolve), and lower ketones (eg, acetone, methylethylketone) can also be used in combination. The amount of the dispersion medium (Y) to be used is usually 50 to 2 based on 100 parts by mass of the dispersion phase (X).
000 parts by mass, preferably 100 to 1000 parts by mass. When the amount of (Y) is within the above range, a stable spherical resin dispersion can be obtained more smoothly.

The dispersion medium (Y) may contain a known dispersant, if necessary, for the purpose of stabilizing the dispersion state. When (Y) is an aqueous medium, preferable dispersants include water-soluble polymers (methylcellulose, polyvinyl alcohol, polyethylene glycol, polyacrylates, polyvinylpyrrolidone, etc.) and inorganic powders (calcium carbonate powder, calcium phosphate powder, hydroxyapatite). Powder, silica powder, etc.), surfactants (sodium dodecylbenzenesulfonate, sodium lauryl sulfate, etc.). The amount of the dispersant used is (Y)
Is usually 10% by mass or less, preferably 0.0% by mass.
01 to 8% by mass, more preferably 0.01 to 5% by mass
It is. If the content exceeds 10% by mass, the physical properties of the resin may be undesirably affected.

In the present invention, from the viewpoint of controlling the reaction between (A) and (B), the temperature of the dispersion medium (Y) is important as well as the temperature of the dispersed phase (X). The temperature of (Y) is usually 20
-100 ° C, preferably 30-75 ° C. Further, the temperature T2 of (Y) is changed by T1 with respect to the temperature T1 of (X).
By setting the temperature within the range of ± 10 ° C., a more uniform dispersion can be obtained.

In the present invention, the disperse phase (X) prepared as described above is injected into the dispersion medium (Y) by press-fitting and passing through pores. To obtain a spherical resin particle dispersion (E).

In dispersing the dispersed phase (X) in the dispersion medium (Y) by passing it through the porous material, any of a batch system and a continuous system can be used as the dispersion system. In order to maximize the effect, dispersion in a continuous system is more preferable. When the dispersion is continuously performed, the supply method of (X) and (Y) may be performed by a liquid feed pump or the like, and is not particularly limited, but (Y) is continuously supplied while giving vibration or pulsation. Is preferred. More preferably, the supply is performed with pulsation. In particular, by giving pulsation, the particle size distribution of the resulting dispersion can be sharpened. Means for imparting vibration to (Y) include, for example, a vibration member (plate, blade, screw, etc.) immediately before (Y) comes into contact with the porous body.
And a method of giving a reciprocating motion to (Y).
The amplitude of the vibration is usually 1 to 200 mm, and the frequency is usually 10 to
It is 600 times / minute, preferably 30 to 400 times / minute.
As a specific example of the device for applying vibration, there is, for example, a device described in JP-A-2-149327.
As a method of giving a pulsation to (Y), for example, when supplying (Y), a plunger type pump, a diaphragm type pump, or the like is used so that (Y) has a flow in the positive direction with respect to the supply direction. A method of giving a motion that alternately repeats a state and a state in which (Y) is stationary can be given. The pulsation cycle is usually 10 to 600 times / minute, preferably 30 to 400 times / minute. Note that (Y) may be supplied while being given both vibration and pulsation.

The heating reaction after dispersion is usually carried out at 20 to 100 ° C.
It is preferably carried out in a temperature range of 40 to 95 ° C. The reaction time is generally 0-24 hours, preferably 2-12 hours.

The resin particles of the thus obtained spherical resin particle dispersion (E) of the present invention have an average particle diameter (D1).
Is 0.01 to 500 μm, the particle size distribution ε1 is 1 or less, and the particle size distribution is sharp over a wide range of particle sizes. Further, (E) does not contain irregular particles which cannot be avoided by the conventional method (such as irregular particles in which fine particles are aggregated, elliptical particles, rod-like or needle-like deformed particles).

In order to sufficiently exhibit the effects of the present invention,
Preferred average particle size is 10 μm ≦ D1 ≦ 300 μm,
More preferably, 100 μm ≦ D1 ≦ 300 μm. Further, a preferred particle size distribution is such that ε1 is 0.7 or less,
More preferably, it is 0.5 or less.

The average particle size (D1) and the particle size distribution ε1 can be measured by a laser diffraction type particle size distribution measuring device or the like. In the obtained relative cumulative particle size distribution curve, D1 corresponds to a particle size when the cumulative amount is 50%: D50, ε1 is a particle size D90 when the cumulative amount is 90%, and a particle when the cumulative amount is 10%. Diameter D10,
And D50 are defined by the following equation. ε1 = (D90−D10) / D50

In the present invention, the spherical resin particles (F) are obtained by removing the dispersion medium (Y) from the spherical resin particle dispersion (E) by a known method (filtering, washing, drying, etc.). be able to. Since (F) is a true sphere and has a very sharp particle size distribution, it exhibits excellent performance such as high powder flowability and uniform coating film formation.

The spherical resin particles of the present invention may contain, if necessary, known additives (a modifying agent such as a pigment, a dye, a release agent, a lubricant, a plasticizer, an antiblocking agent, a coupling agent, a weather-resistant stabilizer). Agents, heat stabilizers, flame retardants, etc.). The amount of these additives to be used is generally selected from the range of 0 to 40% by mass based on the mass of the resin precursor (A), and is appropriately selected in consideration of the purpose of use and effects. The additives are
It may be previously contained in the dispersion phase (X) or the dispersion medium (Y) before the dispersion, or may be added after the dispersion. The powder may be added to the obtained resin particles and mixed with the powder.

The spherical resin particle dispersion or spherical resin particles obtained by the method of the present invention may be used as an adhesive for interlining, a suede-like paint, a hot melt adhesive, a powder paint, a slush molding material, various fillers. , Spacers, toners and the like.

[0065]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. In the following description, “part” indicates “part by mass” and “%” indicates “% by mass”.

[Production Example of Resin Precursor (A)] Production Example 1 A polycaprolactone diol having a number average molecular weight of 2,000 and a hydroxyl value of 56 [“Placcel L220AL” was placed in a reaction vessel equipped with a stir bar and a thermometer. (stock)
2000 parts) and heated to 110 ° C. under a reduced pressure of 3 mmHg to perform dehydration for 1 hour. Subsequently, 457 parts of isophorone diisocyanate (IPDI) were charged, and the reaction was carried out at 110 ° C. for 10 hours to obtain a resin precursor (A-1) having a terminal isocyanate group. The free isocyanate content of the resin precursor was 3.6%.

[Production Example of Chain Extender (B)] Production Example 2 A stirring rod, a cooling pipe, a nitrogen introducing pipe, and a thermometer were set.
Methyl ethyl ketone (hereinafter MEK) 5
0 parts were charged, and the temperature was raised to 50 ° C. while stirring under nitrogen introduction. Then, isophorone diamine (hereinafter IPDA) 3
0 parts were added, the temperature was raised to 70 ° C., and the reaction was carried out for 24 hours while removing water generated under reflux. After the reaction, 70 ° C under reduced pressure
To remove MEK. The reaction had an IPDA content of 6
The conversion was 7%, and the conversion was 85%. Further di-
7.0 parts of n-butylamine was added and mixed to obtain a chain extender solution (B-1).

[Production Example of Dispersed Phase (X)] Production Example 3 150 parts of resin precursor (A-1), 37.5 parts of ethyl acetate, and 15.3 parts of a chain extender solution (B-1) are mixed. And the temperature was adjusted to 40 ° C. to obtain a dispersed phase (X-1). At this time, the viscosity of (X-1) was 1500 mPa · s.

Production Example 4 A dispersion phase (X-2) was obtained in the same manner as in Production Example 3 except that 81 parts of ethyl acetate was used. At this time, the viscosity of (X-2) was 300 mPa · s.

Production Example 5 7.5 parts of n-heptane was further added to the dispersed phase (X-1) obtained in Production Example 3 and the temperature was adjusted to 40 ° C. to obtain a dispersed phase (X-3). At this time, the viscosity of (X-3) is 1400 mPa ·
s.

[Production Example of Dispersion Medium (Y)] Production Example 5 Polyvinyl alcohol [“PVA-23” as a dispersant
5 ", manufactured by Kuraray Co., Ltd.] 20 parts were dissolved in 980 parts of water,
The temperature was adjusted to 40 ° C. to obtain a dispersion medium (Y-1).

Example 1 A membrane dispersion module (manufactured by Ise Chemical Industry Co., Ltd.) was charged with a pore diameter of 18 μm, a pore volume of 0.38 ml / g, and 10φ × 125.
mm MPG glass film (manufactured by Ise Chemical Industry Co., Ltd.). In the dispersion medium (Y-1) continuously supplied (supply speed: 75 g / min) to the inner phase of the glass membrane by the non-pulsation pump, the dispersed phase (X-1) is continuously transmitted from the outer phase of the glass membrane by the non-pulsation pump. The mixture was supplied (supply rate: 7.5 g / min) and dispersed through the pores of the glass membrane. The obtained dispersion was put into a flask equipped with a stirrer and a thermometer, heated to 80 ° C. and reacted for 10 hours, and then the solvent was removed to obtain a resin particle dispersion (E1). . When confirmed under a microscope, all particles were truly spherical. Further, (E1) is separated by filtration, washed,
After drying, true spherical resin particles (F1) were obtained. This (E1)
Table 1 shows the evaluation results of (F1) and (F1).

Example 2 In Example 1, (Y-1) was continuously supplied while giving a pulsation using a diaphragm pump (number of strokes: 12).
The operation was performed in the same manner as in Example 1 except that 0 times / minute and the supply rate: 75 g / minute) to obtain a spherical resin particle dispersion (E2). Table 1 shows the evaluation results of (E2).

Example 3 The same operation as in Example 2 was carried out except that the stroke number of the diaphragm pump was changed to 340 times / minute, and the dispersion of true spherical resin particles (E3) and the fine spherical resin particles (E3) were performed. F3) was obtained. Table 1 shows the evaluation results of (E3) and (F3).

Example 4 A spherical resin particle dispersion (E4) and a spherical resin were prepared in the same manner as in Example 3 except that the feed rate of (X-1) was changed to 15 g / min. Particles (F4) were obtained. Table 1 shows the evaluation results of (E4) and (F4).

Example 5 The same operation as in Example 3 was carried out except that (X-2) was used as the dispersed phase in Example 3, to obtain a dispersion of true spherical resin particles (E5) and a fine spherical resin particle (F5). ) Got. Table 1 shows the evaluation results of (E5) and (F5).

Example 6 A spherical resin particle dispersion (E6) was obtained in the same manner as in Example 3, except that (X-3) was used as the dispersed phase. Table 1 shows the evaluation results of (E6).

Example 7 In Example 5, the pore diameter was 9.5 μm and the pore volume was 0.4.
A spherical resin particle dispersion (E7) was obtained in the same manner as in Example 5, except that an MPG glass film of 3 ml / g and 10φ × 125 mm was used. Table 1 shows the evaluation results of (E7).

Example 8 In Example 7, a dispersion phase (X-4) obtained by adding 7.5 parts of n-heptane to (X-2) was used as the dispersion phase. 0.42ml / g, 10φ × 1
A spherical resin particle dispersion (E8) was obtained in the same manner as in Example 5, except that a 25 mm MPG glass film was used. Table 1 shows the evaluation results of (E8).

Comparative Example 1 In a beaker, 25 parts of (A-1) and 2.55 parts of (B-1) were mixed, and 250 parts of (C-1) were added.
Using an ultra disperser (manufactured by Yamato Scientific Co., Ltd.), mixing was carried out at 6000 rpm for 30 seconds to perform dispersion.
The same operation as in Example 1 was performed using the obtained dispersion to obtain a resin particle dispersion (E9) and a resin particle (F9). When confirmed by a microscope, it was confirmed that partially deformed spherical particles and rod-like particles were included.
Table 2 shows the evaluation results of (E9) and (F9).

REFERENCE EXAMPLE 1 100 parts of (F9) obtained in Comparative Example 1 was used in an opening diameter of 250 μm.
And sieved using a sieve having a pore size of 75 μm.
53 parts of resin particles (F10) having a size of 5 to 250 μm were obtained. Table 2 shows the evaluation results of (F10).

[0082]

[Table 1]

[0083]

[Table 2]

[Evaluation Method] The average particle size (D-50) and the particle size distribution (ε)
Laser diffraction particle size distribution analyzer [Nikkiso Co., Ltd.]
Was measured by ε indicates that the particle size distribution becomes sharper as it approaches 0. The angle of repose and the angle of spatula were measured with a powder tester manufactured by Hosokawa Micron.

[0085]

The method for producing a spherical resin particle dispersion and the spherical resin particle dispersion or the spherical resin particles of the present invention have the following effects. 1. In a wide range of target particle diameters, spherical resin particles having a sharp particle diameter distribution and no irregular particles can be easily obtained. 2. In particular, an average particle diameter of 50 μm, which was conventionally difficult to manufacture
As described above, it is possible to obtain spherical particles having a particle diameter distribution of 100 μm or more and a sharp particle diameter distribution. 3. Since no operation such as classification of resin particles is required, there is no loss and it is economical. 4. Compared to the conventional dead polymer film dispersion method, it is economical because there is no need to use a large amount of an organic solvent to disperse a low molecular weight resin precursor. 5. Since the particle size distribution is sharp and spherical, the resulting powder has good powder flowability and good workability during handling. 6. Since the powder fluidity is good, a coating film or a molded product having a uniform thickness can be obtained. The spherical resin particle dispersion or the spherical resin particles obtained by the method of the present invention having the above effects are hot melt adhesives, interlining adhesives, suede-like paints, powder paints,
It is useful for industrial applications such as slush molding materials, various fillers, spacers and toners.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08G 59/42 C08G 59/66 59/50 C08J 3/03 CFC 59/54 CFF 59/66 C08J 3/075 CFC CFF // C08L 63:00 75:04 101: 00 F term (reference) 4F070 AA46 AA53 CA01 CA16 CB03 GB05 4J034 CA01 CB03 CC22 CD01 DA01 DB03 DF01 DF11 DF14 DG00 DG03 DG04 DG16 DH00 HA02 JA12 JA42 QC04 SA01 RA07 SD02 SD03 4J036 AA01 DB15 DC02 DC22 DC28 DC41 DC48 DD02 HA13 JA01 JA03 JA06 KA03 KA06

Claims (8)

[Claims] 1. A liquid dispersion phase (X) comprising a resin precursor (A) is dispersed in a dispersion medium (Y) in which (A) is not dissolved and reacted with a curing agent (B) to disperse resin particles. In the method for producing the product (E), (X) is dispersed in (Y) by passing through a porous body having pores having a pore size distribution ε of 0 to 1 represented by the following formula. For producing a spherical resin particle dispersion. [epsilon] = ([phi] 90- [phi] 10) / [phi] 50 [wherein, [phi] 90, [phi] 10 and [phi] 50 are pore diameters when the cumulative amount in the relative cumulative pore distribution curve is 90%, 10% and 50%, respectively. ] 2. The method according to claim 1, wherein said porous body has a pore diameter of 0.01 to 100 μm. 3. The method according to claim 1, wherein (X) is supplied while supplying (Y) while pulsating, when (E) is continuously produced by continuously supplying (X) and (Y), respectively. 2. The production method according to 2. (A) is an isocyanate group-terminated urethane prepolymer, and (B) is at least one selected from the group consisting of polyamines or ketimines thereof, polyhydric alcohols, polythiols and amino alcohols. The method according to claim 1. 5. A method according to claim 1, wherein (A) is a polyepoxy compound,
4. The method according to claim 1, wherein (B) is at least one selected from the group consisting of polyamines or ketiminated compounds thereof, polycarboxylic anhydrides, polyamide polyamines, polythiols, imidazoles and polyoxazolines. Production method. 6. A resin particle obtained by dispersing a liquid dispersion phase (X) comprising a resin precursor (A) in a dispersion medium (Y) in which (A) is not dissolved and reacting with a curing agent (B). In the dispersion (E), the average particle size of the resin particles is 0.01 to 5
00 μm, and the particle size distribution ε1 represented by the following formula is 1
A spherical resin particle dispersion characterized by the following. ε1 = (D90−D10) / D50 [where D90, D10 and D50 are the particle diameters when the cumulative amount in the relative cumulative particle diameter distribution curve is 90%, 10% and 50%, respectively. ] 7. The dispersion according to claim 8, wherein the resin particles are thermoplastic polyurethane resin particles. 8. A spherical resin particle obtained by removing the dispersion medium (Y) from the dispersion according to claim 6 or 7.