JP2000313733A - Production of spherical resin particle dispersion and spherical resin particle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a spherical resin particle dispersion having a sharp particle diameter distribution in a wide particle diameter range of 0.1-500 μm. SOLUTION: A liquid dispersion phase X composed of a resin precursor A and a dispersion medium Y not dissolving the component A are fed to a cylindrical container equipped with stirring blades having end parts reaching to the vicinity of the inner peripheral surface. The stirring blades are rotated at a high speed to force the component X and the component Y to the inner peripheral surface of the container by centrifugal force. The component X is dispersed into the component Y by the rotation of the end parts of the stirring blades while rotating the components in a hollow liquid film state and the component A is reacted with a curing agent B.

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 in which a resin precursor (A) is placed in a cylindrical container provided with a stirring blade having an end reaching near the inner peripheral surface.
And a dispersion medium (Y) that does not dissolve (A) are supplied, and the stirring blade is rotated at high speed to press (X) and (Y) against the inner peripheral surface of the container by centrifugal force. While rotating in the form of a hollow liquid film, while stirring by rotation of the end of the stirring blade, (X) is dispersed in (Y),
A method for producing a spherical resin particle dispersion, which comprises reacting (A) with a curing agent (B);
A spherical resin particle dispersion having an average particle size of 10 to 500 μm and a particle size distribution ε represented by the following formula of 0 to 1.2; ε = (D90−D10) / D50 wherein , 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.

The cylindrical container used in the present invention is not particularly limited as long as it has a cylindrical shape centered on the rotation axis of the stirring blade, and may have a tapered surface upward or downward as necessary. . If necessary, a flow blocking plate can be provided on the upper part of the cylindrical container in order to obtain a liquid film having a constant thickness. The shape of the stirring blade is not particularly limited as long as it has an end near the inner peripheral surface of the cylindrical container. Specific examples include a propeller blade, a disk turbine blade, a toothed impeller blade, a paddle turbine blade, and milling. Wheel blades, wire wheel blades, and the like. Also,
The inner diameter of the cylindrical container is usually 50 to 1,000 mm, preferably 80 to 500 mm.

[0007] The gap between the end of the stirring blade and the inner peripheral surface of the cylindrical container is particularly provided that the end is in a range where the end is sufficiently in contact with the liquid film of the processing liquid formed by pressure bonding on the inner peripheral surface. Without limitation,
Usually 0.01 to 100 mm, preferably 0.1 to 10 m
m. Also, the thickness of the liquid film formed on the inner peripheral surface of the cylindrical container by pressure by the high-speed rotation of the stirring blade is usually 0.3 to 300 m.
m, preferably 0.5 to 100 mm.

The method for supplying the dispersion phase (X) and the dispersion medium (Y) into the cylindrical container is not particularly limited, but is a method in which the dispersion phase (X) and the dispersion medium (Y) are separately supplied from the upper portion of the container and dispersed in a batch system, and a continuous supply from the lower portion of the container And continuous dispersion.

The average particle diameter of the spherical resin particles is determined in consideration of conditions such as the type of the resin precursor (A), the viscosity of the dispersed phase (X), the type of the dispersion medium (Y), and the temperature during dispersion. The particle diameter can be controlled to a desired value by appropriately selecting the type of the stirring blade, the rotation speed of the stirring blade, and the supply amounts of the dispersion phase (X) and the dispersion medium (Y). Is
Usually 1 to 100 m / sec, preferably 3 to 50 m / s
ec. When the peripheral speed is less than 1 m / sec, the particle size distribution becomes broad, and when it exceeds 100 m / sec, the particle size becomes too small to obtain particles of 10 μm or more, which is the object of the present invention. The rotation speed of the stirring blade is set so that the peripheral speed is within the above range in consideration of the rotation diameter of the blade, and is usually 100 to 30.000 rpm, preferably 5 to 30.000 rpm.
It is 00 to 15,000 rpm.

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 the 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 trivalent or higher valent polyol (trimethylopropane, glycerin, etc.) may be used in combination with the above low molecular weight 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,
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 may be a 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, (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 low-molecular 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.

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

The polyetherester diol is obtained by polycondensation of at least one of the above-mentioned polyetherdiols with 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 for forming 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, ethylene diamine,
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 (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.) to form ketimines. 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, in addition to the low molecular weight diols and triols exemplified as the raw materials for the polyester polyol, 4- to 6- or higher-valent polyhydric alcohols (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 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.).

Of 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.

If necessary, a reaction terminator [monoalcohol (methanol, ethanol, propanol, butanol, etc.), monoamine (monoethylamine, monobutylamine, dibutylamine, etc.), alkanol (C2-4) amine (B1) 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 compound 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 compound 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 for forming an epoxy resin by reacting with (A2), in addition to the polyamines exemplified in the above (B1), ketiminated products thereof and polythiols, those 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.).

As the more preferable (C) when the dispersion medium (Y) is an aqueous medium, 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 20 to 100 ° C., preferably 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 dispersed 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, while (B) and (X) are continuously mixed,
This is a method of continuously dispersing in (Y).

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 as important as the temperature of the dispersion 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 dispersion phase (X) and the dispersion medium (Y) prepared as described above are introduced into a cylindrical container, and a liquid film is formed on the inner peripheral surface of the container by centrifugal force caused by high-speed rotation of the stirring blade. Is pressed into contact with the end of the rotating stirring blade and stirred to disperse (X) in (Y) and, if necessary, to carry out a heating reaction and a solvent removal, to thereby obtain spherical resin particles. A dispersion (E) is obtained.

In dispersing the dispersed phase (X) in the dispersion medium (Y) as described above, any of a batch system and a continuous system can be used as a dispersion system, but the effect of the present invention is maximized. In order to achieve the maximum effect, continuous dispersion is more preferable. As a method of continuously performing dispersion, for example, while keeping the peripheral speed of the stirring blade constant, each of (X) and (Y) is supplied with a liquid sending pump (eg, a plunger pump, a diaphragm pump, a bellows pump, etc.).
For example, there is a method in which the dispersion is continuously supplied from the lower portion of the cylindrical container, and the formed dispersion is continuously taken out from the outlet provided in the upper portion of the cylindrical container. If necessary, the dispersion may be transferred to a tank or the like and subjected to a heating reaction and solvent removal. Peripheral speed of stirring blade, dispersion time (residence time of liquid film on inner peripheral surface of container)
Etc. are appropriately selected according to the particle size of the target resin particles. Dispersion time is usually 1 to 300 seconds, preferably 1.5 to
It is 120 seconds, more preferably 2 to 30 seconds. If the dispersion time is less than 1 second, the particle size distribution becomes broad and 300
If the average particle diameter exceeds the above range, a dispersion having a desired average particle diameter may not be obtained. The supply rates of (X) and (Y) are set in consideration of the volume of the cylindrical container and the dispersion time.

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 spherical resin particle dispersion (E) of the present invention thus obtained have an average particle diameter (D) of 10 to 500 μm and a particle diameter distribution ε of 0 to 1.2. There is a feature that 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).

The average particle diameter of the resin particles of the spherical resin particle dispersion (E) obtained by the method of the present invention is usually from 0.1 to 0.1.
Although it is 500 μm, in order to sufficiently exert the effects of the present invention, a preferable average particle diameter D is 10 μm ≦ D ≦ 30.
0 μm, more preferably 100 μm ≦ D ≦ 300 μm
It is. In addition, a preferred particle size distribution is such that ε is 0 to 0.1.
5, more preferably 0 to 0.2.

The average particle size D and the particle size distribution ε here 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, D is the particle size when the cumulative amount is 50%: D
Ε is the particle diameter D9 when the cumulative amount is 90%.
0, particle diameters D10 and D50 when the cumulative amount is 10%
Is defined as: ε = (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.

[0066]

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, "parts" indicates parts by weight and "%" indicates% by weight.

[Production Example of Resin Precursor (A)] Production Example 1 A four-necked flask equipped with a stir bar and a thermometer was charged with polycaprolactone diol [Placcel L220AL] having a number average molecular weight of 2,000. Daicel]
2,000 parts are charged and 110 ° C. under reduced pressure of 3 mmHg
And dehydrated for 1 hour. Subsequently, 457 parts of isophorone diisocyanate (hereinafter referred to as IPDI) were charged, and 11
The reaction was carried out at 0 ° C. for 10 hours to obtain an isocyanate group-terminated urethane prepolymer having a free isocyanate content of 3.6%. This is referred to as a resin precursor (A-1).

[Production Example of Chain Extender (B1)] Production Example 2 A stirring rod, a cooling pipe, a nitrogen introduction pipe and a thermometer were set.
60 parts of acetone and 60 parts of isophoronediamine (hereinafter referred to as IPDA) were charged into a one-necked flask, and reacted at 40 ° C. for 12 hours under nitrogen. At this time, the reaction rate was 65%. Further, 14.0 parts of di-n-butylamine was added and mixed to obtain a chain extender solution (B1-1).

[Production Example of Dispersed Phase (X)] Production Example 3 50 parts of resin precursor (A-1) and 12.5 parts of ethyl acetate
The resulting mixture was mixed and adjusted to a temperature of 55 ° C. to prepare a dispersed phase (X-1).

Production Example 4 50 parts of the resin precursor (A-1), 12.5 parts of ethyl acetate and 5 parts of talc were mixed, the temperature was adjusted to 55 ° C., and the dispersed phase (X
-2) was prepared.

[Production Example of Dispersion Medium (Y)] Production Example 5 Polyvinyl alcohol [“PVA-23” as a dispersant
5 ", manufactured by Kuraray Co., Ltd.] was dissolved in 985 parts of water and the temperature was adjusted to 25 ° C. to obtain a dispersion medium (Y-1).

Example 1 (Y) A cylindrical vessel having an inner diameter of 80 mm and a height of 50 mm equipped with a toothed impeller blade having a rotating diameter of 76 mm and a flow shield plate (liquid film thickness of 18 mm) having a width of 18 mm was prepared. -1) 1
80 parts were charged. Next, (B-1) is added to 62.5 parts of (X-1).
1-1) After mixing 6.6 parts, immediately put into a container,
Dispersion was performed at a peripheral speed of 10 m / s for 20 seconds to obtain a dispersion. The obtained dispersion was transferred into a flask equipped with a stirrer and a thermometer, heated to 80 ° C., and the reaction was continued for 5 hours. Then, the solvent was distilled off under reduced pressure to remove the spherical resin particle dispersion ( E1) was obtained. The obtained dispersion (E-1) was separated by filtration, washed and dried to obtain spherical resin particles (F1). The evaluation results of (E1) and (F1) are shown in Tables 1 and 2.

Example 2 In Example 1, (X-2) was used as a dispersion phase in an amount of 67.5.
In the same manner as in Example 1, except that the dispersion was performed at a peripheral speed of 30 m / s for 20 seconds.
2) was obtained. From the obtained dispersion (E2), spherical resin particles (F2) were obtained in the same manner as in Example 1. This (E2)
Tables 1 and 2 show the evaluation results of (F2) and (F2).

Example 3 A dispersion medium supply port connected to a separate tank and pump at the lower part of the vessel and a dispersion phase supply port connected to an L-shaped nozzle in a cylindrical vessel were provided at the upper part of the inner peripheral surface of the vessel. In a cylindrical container having a diameter of 80 mm and a height of 50 mm provided with a toothed impeller blade (rotating diameter of 76 mm) having a discharge port, the blade is placed in a cylindrical container.
While rotating at a peripheral speed of 0 m / s, (Y-1) was changed to 67.
While supplying at a rate of 5 kg / hr to form a liquid film, (X
-2) and (B1-1) at 21.1 kg /
hr and 2.06 kg / hr, and continuously supplied to the disperse phase supply port while mixing them via a static mixer to be dispersed (residence time: about 20 seconds). Discharged continuously. The obtained dispersion was treated in the same manner as in Example 1 to obtain a spherical resin particle dispersion (E3) and a spherical resin particle (F3). Tables 1 and 2 show the evaluation results of (E3) and (F3).
Shown in

Example 4 A spherical resin particle dispersion (E) was prepared in the same manner as in Example 3 except that the peripheral speed of the stirring blade was changed to 5 m / s.
4) and spherical resin particles (F4) were obtained. This (E
Tables 1 and 2 show the evaluation results of 4) and (F4).

Comparative Example 1 180 parts of (Y-1) were charged into a beaker. Then (X
-1) Immediately after mixing (B1-1) with 62.5 parts in a beaker, the mixture was mixed for 1 minute at 9000 rpm using an ultra disperser [manufactured by Yamato Scientific Co., Ltd.] to obtain a dispersion. I got The obtained dispersion was treated in the same manner as in Example 1 to obtain a spherical resin particle dispersion (E11) and a spherical resin particle (F11). The evaluation results of (E11) and (F11) are shown in Tables 1 and 2.

Comparative Example 2 In a tank equipped with a stirrer, 67.5 parts of (X-2) and 6.6 parts of (B1-1) were mixed. Using a gear pump,
The mixture and the dispersion medium (Y-1) were mixed at a liquid ratio of 203.5: 300.
Was quantitatively supplied to a static mixer (manufactured by Noritake Company) having a diameter of 1 cm and 15 elements. The liquid sending speed at this time was adjusted so that the mixing time in the static mixer was 0.3 seconds. The mixed dispersion mixed by the static mixer was treated in the same manner as in Example 1 to obtain a spherical resin particle dispersion (E12) and a spherical resin particle (F12). The evaluation results of (E12) and (F12) are shown in Tables 1 and 2.

[0078]

[Table 1]

[0079]

[Table 2]

(Measurement Method) The average particle size and the particle size distribution were measured with a laser diffraction type particle size distribution analyzer [manufactured by Nikkiso Co., Ltd.]. The angle of repose and the angle of spatula were measured with a "Powder Tester" manufactured by Hosokawa Micron.

[0081]

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. A spherical resin particle having a sharp particle diameter distribution and having no irregular shaped particles can be easily obtained in a wide range of arbitrary target particle diameters. 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. Since the particle size distribution is sharp and spherical, the resulting powder has good powder flowability and good workability during handling. 5. 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.

Continued on the front page F term (reference) 4F070 AA46 AA53 DA33 DC01 DC12 DC13 DC14 4J034 CA01 CA03 CA04 CA05 CA13 CA14 CA15 CA16 CA24 CC03 CC12 CC45 CC52 CC53 CC61 CC62 CC65 CC67 DA01 DB04 DC02 DC35 DC37 DC43 DF01 DF02 HC03 HA HC12 HC17 HC22 HC46 HC52 HC61 HC71 HC73 JA41 JA42 QC04 RA07 RA08 RA16 4J036 AA01 AC01 AC02 AD01 AD08 AD09 AD21 AF01 AF03 AF06 AG04 AH05 AH07 AJ05 AJ08 AJ09 AJ17 AJ18 BA01 BA09 CD13 DA01 DA02 DA04 DB15 DC02 DC10 DC28

Claims (8)

[Claims] 1. A liquid dispersion phase (X) comprising a resin precursor (A) and a dispersion medium which does not dissolve (A) in a cylindrical container provided with a stirring blade having an end reaching the vicinity of an inner peripheral surface. (Y) is supplied, the stirring blade is rotated at high speed, and (X) and (Y) are pressed against the inner peripheral surface of the container by centrifugal force to rotate in the form of a hollow liquid film, while rotating the end of the stirring blade. And (A) is reacted with the curing agent (B) while stirring to disperse (X) in (Y). 2. The peripheral speed of the stirring blade is 1 to 100 m / sec.
The method according to claim 1, wherein (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 production method according to claim 1 or 2, wherein (A) is a polyepoxy compound,
The method according to claim 1 or 2, wherein (B) is at least one selected from the group consisting of polyamines or ketiminated products thereof, polycarboxylic anhydrides, polyamide polyamines, polythiols, imidazoles and polyoxazolines. 5. The temperature T1 of (X) is 30 to 75 ° C.
The temperature T2 of (Y) is in the range of TI ± 10 ° C.
1 has a viscosity of 100 to 5,000 mPa ·
The method according to claim 1, wherein s is s. 6. A particle obtained by the production method according to claim 1, having an average particle diameter of 10 to 500 μm and a particle diameter distribution ε represented by the following formula of 0 to 1.2. A spherical resin particle dispersion. ε = (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 6, 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.