JPH05155967A - Polyurethane-polyurea particle - Google Patents

Abstract

PURPOSE:To provide the subject particles having specified particle diameter and particle diameter distribution and hence suitable for applications where an excellent appearance, a good touch. and a high value added are needed, such as for a coating material, a printing ink, a toner, and a toner carrier. CONSTITUTION:Polyurethane-polyurea particles having a mean particle diameter of 1-100mum, pref. 1-60mum, and a shape parameter of Weibull distribution based on the particle diameter distribution of at least 1.5 are provided. The particles may be three-dimensionally cross-linked, may have isocyanurate rings, and may contain a pigment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to polyurethane polyurea particles having a specific particle size and particle size distribution capable of imparting excellent properties to paints, printing inks, toners, toner carriers and the like.

More specifically, the present invention is obtained through both reactions such as a urethanization reaction and a urethanization reaction, and since it has a specific particle size and particle size distribution, it is excellent in appearance and touch, and has a good design and feeling, or The present invention provides polyurethane polyurea particles suitable for applications such as paints, printing inks, toners, toner carriers, and the like, for which high added value is strongly demanded.

[0003]

2. Description of the Related Art A so-called interfacial polymerization method in which a hydrophobic substance is dispersed in an aqueous medium and fine particles are formed by growing an organic polymer substance (polymer compound) at the interface of the dispersed droplets. Is already well known for.

Many of them are prepared by dispersing an isocyanate prepolymer having isocyanate end groups in water.
Then, a method of forming stable polyurethane polyurea particles by adding a polyamine or the like to the dispersion liquid thus obtained, the polyurethane polyurea particles obtained by such an interfacial polymerization reaction,
Generally, it is used in various fields because of its excellent mechanical properties and chemical resistance.

[0005] For example, a coating material containing polyurethane polyurea particles is known as a so-called sensitive coating material which gives a high-quality coating film which is not glossy and excellent in touch.

[0006]

In recent years, it has been desired to further improve the matteness of the coating film, its uniformity, and the tactile sensation even in coating materials containing polyurethane polyurea particles. I couldn't fully answer.

[0007]

Means for Solving the Problems As a result of intensive studies, the inventors of the present invention focused on the above-mentioned problems,
It is more important than expected that the resin used has a specific average particle size range and particle size distribution, and a polyurethane polyurea having the specific average particle size range and particle size distribution is more important than expected. It has been found that such problems can be solved by producing particles, and the present invention has been completed.

[0008]

[Structure] That is, the present invention has an average particle size of 1 to 100 μm.
, And a polyurethane polyurea particle having a shape parameter of 1.5 or more when its particle size distribution is applied to a Weibull distribution, and more preferably an average particle size of 1 to 60 μm.
The polyurethane polyurea particles have a shape parameter of 1.5 or more when the particle size distribution is applied to the Weibull distribution in the range of m.

Further, the polyurethane polyurea particles are polyurethane polyurea particles which may be three-dimensionally cross-linked, and may further have an isocyanurate ring in the molecule. The above polyurethane polyurea particles are polyurethane polyurea particles which may include a pigment.

The polyurethane polyurea particles in the present invention are usually almost spherical and the particle size is also calculated based on the sphere as a basic shape, according to the manufacturing method. Since such particles are usually composed of a large number of particles having non-uniform particle sizes, it is necessary to express the composition by the average particle size and the particle size distribution.

The average particle diameter generally includes a number average, a length average, an area average, and a volume average, but the average particle diameter in the present invention is a volume average that is usually used. The average particle size of the polyurethane polyurea particles in the present invention is 1 to 100 μm, and when used as a coating resin,
The thickness is more preferably 1 to 60 μm, but if it is smaller than this, gloss appears, and when touched, the coating film feels cold, and it is difficult to call it a sensitive paint. On the other hand, if it is larger than this, a rough feeling becomes significant when touched, which is not preferable. When used as a resin for printing ink, the range of 1 to 10 μm, when used as a toner is 5 to 30 μm, and when used as a toner carrier, the range of 50 to 100 μm is preferable.

The Weibull distribution is expressed by the following equation. F (t) = 1-exp [-(t / η) ^m ] where F (t) is the Weibull distribution function, t is the particle size, η is the scale parameter, and m is the shape parameter.

The shape parameter m represents the shape of the distribution, and the larger the value, the narrower the distribution. Of course, all particle size distributions cannot be completely represented by the Weibull distribution, so the value that can be approximated to the maximum is used. The shape parameter m of the distribution of the polyurethane polyurea particles in the present invention needs to be 1.5 or more. For example, when it is used as a resin for paint, if it is smaller than this, the width of the distribution is widened and unevenness of the gloss of the coating film is generated, and the tactile sensation is compared with that of the same average particle size.
Roughness is likely to occur. Even when used for printing inks, toners, and toner carriers, if the distribution shape parameter m of the polyurethane polyurea particles is 1.5 or more, an excellent product without unevenness can be produced.

To obtain polyurethane polyurea particles, an organic layer comprising a mixture of a polyisocyanate compound and optionally a polyhydroxy compound is dispersed in water,
Then, an interfacial polymerization method in which a polyamine or the like is added to this dispersion is general.

In order to obtain the polyurethane polyurea particles of the present invention, as the polyisocyanate compound, any of the commonly used polyisocyanates can be used, but among them, particularly representative ones will be exemplified.
First, as the aliphatic isocyanate, hexamethylene diisocyanate and 2,4-diisocyanate-1-1-
Methylcyclohexane, diisocyanate cyclobutane, tetramethylene diisocyanate, o-, m- or p-xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, dimethyldicyclohexylmethane diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, dodecane diisocyanate, tetramethylxylene diisocyanate Or isophorone diisocyanate,

As the aromatic isocyanate, tolylene-2,4-diisocyanate and tolylene-2,6-
Diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyldiphenylmethane-4,4 '
-Diisocyanate, m- or p-phenylene diisocyanate, chlorophenylene-2,4-diisocyanate, naphthalene-1,5-diisocyanate, diphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenyl-1,3,5 -Isocyanate monomers such as triisopropylbenzene-2,4-diisocyanate carbodiimide-modified diphenylmetadiisocyanate, polyphenylpolymethylene isocyanate or diphenylether diisocyanate,

Further, as the modified polyisocyanate based on these various monomers, for example, an excess isocyanate monomer alone or two or more kinds is represented by various dihydric alcohols, trihydric alcohols or tetrahydric or higher polyhydric alcohols. Polyurethane polyisocyanate obtained by reacting with the above-mentioned polyhydroxy compound, or polyisocyanate containing an isocyanurate ring obtained by polymerizing various isocyanate monomers as listed above, or obtained by reacting with water A typical example is polyisocyanate containing a buret bond.

Here, in order to make the polyurethane polyurea particles easily spherical and have excellent toughness, it is preferable that the polyisocyanate compound has an isocyanurate ring in the molecule. The number average molecular weight of polyisocyanate is 200 to 10,
Those within the range of 000, preferably within the range of 300 to 7,000, and more preferably within the range of 500 to 5,000 are suitable.

On the other hand, the polyhydroxy compound, which is optionally mixed with the organic phase, compensates for the lack of internal cross-linking associated with the formation of the walls of the polymer particles, and further enhances the mechanical strength of the polymer particles. Although having an effect of improving, when such a polyhydroxy compound is used to obtain the polyurethane polyurea particles of the present invention, any of the commonly used polyhydroxy compounds can be used. However, if only representative examples are given, they belong to any of the following groups.

(A) Ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol , 1,4-bis (hydroxymethyl) cyclohesane, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, Polyhydric alcohols such as glycerin or hexanetriol;

(B) Various types such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol. Polyether glycols of;

(C) Various polyhydric alcohols such as those listed above, and various polyhydric alcohols such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether or allyl glycidyl ether. Modified polyether polyols obtained by ring-opening polymerization with a (cyclic) ether bond-containing compound;

(D) Polyester polyols obtained by cocondensation of one or more of various polyhydric alcohols as listed above with polyhydric carboxylic acids, which comprises succinic acid, adipic acid, sebacic acid, Azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,
4-cyclohexanehycarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid, etc. Polyols obtained by using representative polyvalent carboxylic acids;

(E) Polycondensation of one or more of various polyhydric alcohols as listed above with various lactones such as-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone. Lactone polyester polyols obtained by the reaction;

Alternatively, as described above, lactone-modified polyester polyols obtained by polycondensation reaction of various polyhydric alcohols, polyhydric carboxylic acids, and various lactones described above, respectively;

(F) Various types such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and / or polyhydric alcohols, or glycidyl esters of monobasic acids and / or polybasic acids Epoxy-modified polyester polyols obtained by combining one or more of the epoxy compounds of 1) during the synthesis of polyester polyols;

(G) Polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative, hydroxyl group-containing acrylic copolymer, hydroxyl group-containing fluorine-containing compound or hydroxyl group-containing compound For example, silicone resin.

In order to obtain the polyurethane polyurea particles of the present invention, when such a polyhydroxy compound is used, the polyhydroxy compounds shown in these (a) to (g) can be used alone. Two or more species may be used in combination, but the number average molecular weight is 200 to 10,000.
It is preferably 0, preferably 300 to 7,000, and more preferably 500 to 5,000 for sufficient crosslinking inside the polymer particles.

In order to obtain tough polymer particles, it is desirable to use polyester polyol.
It is preferable to use lactone-based polyester polyols obtained by polycondensation reaction with lactones such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone.

In the present invention, when a polyhydroxy compound is used, the ratio of the isocyanate group equivalent of the polyisocyanate compound and the hydroxyl group equivalent of the polyhydroxy compound is 1: 0.05 to 1: 2.0, preferably These components are mixed within the range of 1: 0.1 to 1: 1.8. In order for the polyurethane polyurea particles to be excellent in toughness, it is desirable that the mixture itself of these two components has a composition capable of three-dimensional crosslinking. That is, in that case, it is preferable that the mixture of these two components becomes a gel as the reaction progresses and the fluidity is no longer obtained even by heating or diluting the true solvent.

The mixed hydrophobic organic phase thus obtained is generally finely dispersed in water, and 0.2 to 1.0 equivalent of polyamine is added per equivalent of excess isocyanate groups contained in the organic phase. , Preferably 0.3 to 1.0 equivalents, more preferably 0.4 to 0.9 equivalents, to carry out a ureation reaction at the particle interface, and, if necessary, urethane inside the particles. The desired polyurethane polyurea crosslinked particles can be obtained by carrying out the chemical reaction as well.

The polyamines preferably used in the present invention include diamines, polyamines, and mixtures thereof which are usually used. Of these, only typical ones are mentioned.
1,2-ethylenediamine, 1,3-propanediamine, bis (3-aminopropyl) amine, hydrazine,
Hydrazine-2-ethanol, bis (2-methylaminoethyl) methylamine, 1,4-diaminocyclohexane, 3-amino-1-methylaminopropane, N-hydroxyethylethylenediamine, N-methyl-bis (3
-Aminopropyl) amine, tetraethylenediamine,
Hexamethylenediamine, bis (N, N'-aminoethyl) -1,2-ethylenediamine, 1-aminoethyl-
1,2-ethylenediamine, diethylenetriamine, tetraethylenepentamine,

Pentaethylenehexamine, phenylenediamine, toluylenediamine, 2,4,6-triaminotoluentrein chloride, 1,3,6-triaminonaphthalene, isophoronediamine, xylylenediamine, hydrogenated xylylenediamine, 4,4'-diaminodiphenylmethane or hydrogenated 4,4'-diaminodiphenylmethane, tolylenediamine, phenylenediamine,
Examples thereof include polyoxyalkylene polyamines and various derivatives of these polyamine monomers.

In the present invention, a non-reactive and hydrophobic organic solvent is added to the hydrophobic organic phase dispersed in water, if necessary, to reduce the viscosity and improve the dispersibility in the aqueous phase. Can be improved. In this case, the amount of the organic solvent used is 50% by weight or less, preferably 30% by weight or less, based on the whole organic phase. The organic solvent used is preferably an aromatic or aliphatic hydrocarbon, ester, ether, or ketone solvent, among which benzene, toluene, xylene, cyclohexane,
Methylcyclohexane, diphenyl ether or mineral spirits are suitable. These organic solvents, if necessary, during or after particle formation,
It may be distilled off by a conventional method such as heating or depressurization.

Then, the thus-prepared organic phase is dispersed in an aqueous phase. At this time, in order to stabilize the dispersion, polyvinyl alcohol, hydroxyalkyl cellulose, carboxyalkyl cellulose, gum arabic,
One or more selected from various protective colloids such as polyacrylate, polyacrylamide, polyvinylpyrrolidone or ethylene-maleic anhydride copolymer may be used.

Further, the aqueous phase may contain various known and conventional nonionic, anionic or cationic surfactants.

In the present invention, when a polyhydroxy compound is optionally used, the reactivity of water with an isocyanate group is extremely small as compared with the reactivity with a hydroxyl group, and the polyamine is used. Although the penetration effect of moisture into the inside of the particles can be neglected due to the isolation effect by the outer wall formed by the addition of the compounds, the urethanization reaction in the particles is achieved by increasing the reaction temperature and the reaction time. For the purpose of effectively promoting the reaction between the isocyanate group and the hydroxyl group in the particles, cobalt naphthenate, zinc naphthenate, stannous chloride, stannic chloride, tetra-n-butyltin, tri-n -Butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin acetate

One or more of various organometallic catalysts such as dibutyltin dilaurate, tin octenoate or potassium oleate are added to the hydrophobic organic phase in an amount of 5-1 to 5: 1.
It may be added in the range of 0000 ppm, preferably 10 to 5000 ppm, and by adding the organometallic catalyst, tough crosslinked particles can be formed in an extremely short time.

There are several methods for adjusting the polyurethane polyurea particles having the average particle size and particle size distribution according to the present invention. First, at the time of interfacial polymerization, resins constituting the organic phase, protective colloid in the dispersion step, and / or
Alternatively, the types of surfactants and their amounts, or various conditions such as stirring speed and reaction temperature in the dispersion step may be appropriately set.
By selecting or by filtering the resulting suspension,
Or wet polyurethane classifiers such as hydrogravity wet classifier, hydrocyclone, or dried polyurethane sieve, sieve, or gravity inertia type, centrifugal force-gravity-inertia type, centrifugal type, cyclone classifier, rotary wall type By dry classification such as forced vortex type, when applied to Weibull distribution, the shape parameter is 1.5 or more, and the average particle size is 1 to 100 μ.
m is a polyurethane polyurea particle, more preferably
The average particle size is 1 to 60 μm for paint resins, 1 to 10 μm for printing ink resins, and 5 to 3 for toner.
The target average particle size and distribution can be adjusted to 0 μm, and in the case of a toner carrier, 50 to 100 μm.

The polyurethane polyurea particles thus obtained are used according to their respective purposes and uses, but are used in the form of fine powder by a spray drying method, a centrifugal drying method, a filtration drying method or a fluidized bed drying method. You can also do it.

The polyurethane polyurea particles of the present invention may contain various core substances. The core substance for inclusion is present in the hydrophobic organic phase and taken into the inside of the particle, but the range and type of the core substance are not particularly limited and can be wide range. Is.

[0042] To give only a typical representative core substance for encapsulation, various drugs or pharmaceuticals such as fungicides, algaecides, herbicides, fungicides or insecticides can be used. , Fragrances, colorants, color formers, enzymes, detergents, catalysts, rust preventives, adhesives, UV absorbers, liquid crystals, magnetic materials, conductive materials such as chemicals or food additives And so on.

If necessary, plasticizers, paraffins, animal and vegetable oils or silicone oils which are inert to isocyanate groups, or various synthetic resins such as xylene resins and ketone resins may also be used. It can be included as appropriate.

[0044]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples, Comparative Examples, Application Examples and Comparative Application Examples. In the following, all parts and% are based on weight unless otherwise specified.

First, the raw materials used will be described. (A): Polyisocyanate compound (1) "Bernock DN-901S" (manufactured by Dainippon Ink and Chemicals, Inc., isocyanurate ring-containing polyisocyanate obtained using hexamethylene diisocyanate; isocyanate group content = 23. 2%);
This is designated as PI-1.

(2) The solid content of "Bernock DN-950" (manufactured by Dainippon Ink and Chemicals, Inc., hexamethylene diisocyanate adduct type polyisocyanate resin; isocyanate group concentration = 16.8% in terms of solid content) is used. However, this is hereinafter referred to as PI-2. (3) 1,6-hexamethylene diisocyanate; hereinafter abbreviated as HDI.

(B): Polyhydroxy compound (1) The hydroxyl value obtained by the polycondensation reaction of trimethylolpropane and ε-caprolactone is 168.
Polycaprolactone polyester triol 5: hereinafter referred to as PO-1. (2) A polyester diol having a hydroxyl value of 112, which is obtained by a polycondensation reaction between neopentyl glycol and adipic acid; hereinafter referred to as PO-2.

(C): Polyamine compound (1) Ethylenediamine; hereinafter abbreviated as EDA. (2) 1,6-hexamethylenediamine; hereinafter, HMD
Abbreviated as A. (D): Mill base 30 parts PO-1, 70 parts "Tipaque R-8
20 ", and 25 parts of toluene are mixed, and then kneaded by a three-roll mill to obtain a white mill base (MB-1).
Got

Example 1 In a 1,000 ml flask,
An aqueous phase was prepared by dissolving 8 parts of "PVA-205" (partially saponified polyvinyl alcohol manufactured by Kuraray Co., Ltd.) in 392 parts of water. In another container, PI-1 86.2
Parts and 13.8 parts of PO-1 were mixed to obtain an organic phase.
At room temperature, using a homomixer, 7,000-7.5
The organic phase prepared in advance was charged while stirring the aqueous phase at 00 rpm, and the mixture was stirred for 1 minute to obtain a dispersion liquid.

Then, this dispersion liquid was transferred to another flask and stirred with a paddler type stirring blade to obtain EDA.
Was charged with 6.34 parts of a 50% aqueous solution. Hold at room temperature for 2 hours, then raise to 50 ° C and keep at the same temperature for 1 hour at 80 ° C.
The reaction was allowed to continue for 2 hours to obtain a desired suspension of polyurethane polyurea particles. This suspension was directly made into a powder by a spray dry method (referred to as S-1 as a comparative example), and a slurry classification liquid cyclone device (trade name; Super Clone, manufactured by Oishi Machinery Co., Ltd.) that is wet classification. (3) Separation type was used to perform classification, and the resulting suspension was spray-dried to obtain powdery polyurethane polyurea particles (referred to as B-1).

The particle size distributions of both of them were measured by a laser analysis type particle size distribution meter (trade name; SK Laser Micron Sizer, manufactured by Seishin Enterprise Co., Ltd.). The former has an average particle size of 5.7 μm and a shape parameter of the Weibull distribution is 0. .75, the latter having an average particle size of 5.9 μm and a shape parameter of Weibull distribution of 1.6.
It was 2. However, for the shape parameter of the Weibull distribution, the data is converted by hand calculation and the quality control support system JUS is used.
It was determined using software E-QCAS (manufactured by NEC Software Co., Ltd.).

Example 2 A target suspension of polyurethane polyurea particles was obtained in the same manner as in Example 1 except that the formulation was changed as described below. That is, as the water phase, 2 parts of "PVA205" and "PVA21", respectively.
7 "[partially saponified polyvinyl alcohol manufactured by Kuraray Co., Ltd.] and 396 parts of water were used, while 42.7 parts of MB-1 and PI- were used as the organic phase, respectively.
2 of 24.0, HDI of 9.3, and PO-2 of 2
With 4.0 parts, the polyamine used is 25 parts of EDA.
% Aqueous solution, a suspension of polyurethane polyurea particles was obtained.

From this suspension, as in Example 1, polyurethane polyurea particles having an average particle size of 10.9 μm and a Weibull distribution shape parameter of 1.13 (referred to as S-2 as a comparative example) were obtained only by drying. , And wet classification followed by drying to give a mean particle size of 10.6 μm and a Weibull distribution shape parameter of 1.77 (B−
2) white polyurethane polyurea particles were obtained.

Example 3 A target suspension of polyurethane polyurea particles was obtained in the same manner as in Example 1 except that the formulation was changed as described below.

That is, as the water phase, "P
VA205 "2 parts and 398 parts of water, while the organic phase is 84.9 parts of PI-2 and PO, respectively.
-2. 15.1 parts and using ED as polyamine
A suspension of polyurethane polyurea particles was obtained by using 6.6 parts of a 50% aqueous solution of A.

From this suspension, as in Example 1, the average particle diameter was 30.7 μm, the shape parameter of the Weibull distribution was 1.03 (referred to as S-3 as a comparative example) only by drying, and after wet classification. After drying, polyurethane polyurea particles having an average particle size of 30.8 μm and a Weibull distribution shape parameter of 1.93 (referred to as B-3) were obtained.

(Application Examples 1 to 3 and Comparative Examples 1 to 3) Polyurethane polyurea particles (B-1, B-) obtained in the respective examples.
45 parts of 2 and B-3), Burnock D7-885
(Polyol manufactured by Dainippon Ink and Chemicals, Inc., nonvolatile content 80%, hydroxyl value 83), PI-116 parts,
After mixing, xylene and butyl acetate were diluted with a thinner mixed at a ratio of 1: 1 and coated on an ABS plate by air spraying so that the dry film thickness was 50 μm to prepare a test plate.

As a comparative example, the polyurethane polyurea particles (S-1, S-2, S-) of the comparative examples described in each example are described.
Except that 3) was used, the same procedure as above was carried out, and A
A test coated plate was prepared by coating a BS plate so that the dry film thickness was 50 μm. The test coated plate thus obtained was allowed to stand at room temperature for 1 week, and then evaluated.

[0059]

[Table 1]

The degree of matting and the unevenness of gloss were visually evaluated.
(Evaluation Criteria) ⊚: The gloss is completely disappeared or there is no uneven gloss. ○: The gloss is almost disappeared or there is almost no uneven gloss. Δ: Slightly glossy or slightly glossy. X: There is gloss or uneven gloss.

The feeling of roughness was judged by touching it with the hand. (Evaluation criteria) ⊚: There is no rough feeling. ○: There is no feeling of roughness. Δ: There is a slight roughness. X: There is a feeling of roughness. As is clear from the results shown in Table 1, it is clear that the polyurethane polyurea particles of the present invention are excellent in the glossiness, uniformity and tactile sensation of the coating film when used in a coating composition. Is.

B-1 to B-obtained in Examples 1, 2 and 3
3 and Comparative Examples S-1 to S-3

From Figure 1

FIG. 6 shows. The horizontal axis of the graph is the particle size (unit is μm),
The vertical axis shows the section ratio and the cumulative ratio.

[0063]

INDUSTRIAL APPLICABILITY The present invention can provide polyurethane polyurea particles suitable for paints, printing inks, toners, toner carriers, etc., which are excellent in appearance and touch, and whose designability and sensitivity or high added value are strongly required.

[0064]

[Brief description of drawings]

FIG. 1 shows a particle size distribution of B-1.

FIG. 2 shows a particle size distribution of S-1.

FIG. 3 shows a particle size distribution of B-2.

FIG. 4 shows a particle size distribution of S-2.

FIG. 5 shows a particle size distribution of B-3.

FIG. 6 shows a particle size distribution of S-3.

Claims (5)

[Claims] 1. Polyurethane polyurea particles having an average particle size of 1 to 100 μm and a shape parameter of 1.5 or more when the particle size distribution is applied to a Weibull distribution. 2. An average particle diameter of 1 to 60 μm and a shape parameter of 1. when the particle diameter distribution is applied to a Weibull distribution.
The polyurethane polyurea particle according to claim 1, which is 5 or more. 3. The polyurethane polyurea particle according to claim 1, which is three-dimensionally crosslinked. 4. The polyurethane polyurea particle according to claim 1, which has an isocyanurate ring in the molecule. 5. The polyurethane polyurea particles according to claim 1, wherein a pigment is included. [0000]