JPH08120092A - Crosslinked particle of polyurethane colloid and its preparation - Google Patents

Abstract

PURPOSE: To prepare crosslinked particles of a polyurethane colloid, which are useful as a coating compound, an adhesive, a varnish for an ink, a modifier therefor, a resin, a modifier for an elastomer, a dispersion stabilizer for a pig ment, a stabilizer for emulsion polymerization and the like. CONSTITUTION: Crosslinked particles of a colloid dispersed in a solvent comprise a portion solvated with a solvent and a crosslinked, non-solvated portion, and the particle diameter of the crosslinked and non-solvated portion is 0.01 to 1.0μμm.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a polyurethane useful as a paint, an adhesive, a varnish for inks, a modifier for these, a modifier for resins, an elastomer, a pigment dispersion stabilizer, a stabilizer for emulsion polymerization, and the like. The present invention relates to colloidal crosslinked particles and a method for producing the same.

[0002]

As a conventional method for producing colloidal particles, a non-aqueous dispersion polymerization method and an aqueous emulsion polymerization method using a radical reaction are known. Further, as a method for producing aqueous polyurethane urea colloidal particles, there is disclosed in JP-A-1-
The method described in Japanese Patent No. 110506 is known. In the above-mentioned method for producing non-aqueous polyurethaneurea colloidal particles, particles are aggregated or fused with each other during the synthesis process, and it is difficult to obtain stable colloidal particles, so it is required to use a large amount of emulsifier, or as a medium. A method of synthesizing particles in a polyol or a resin solution to prevent the particles from aggregating is known.

Of these methods, the method using a large amount of emulsifier has a bad influence on the final product by the emulsifier, while the use of the obtained colloidal particles is limited when a polyol or a resin solution is used as a medium. Is
There are problems such as narrow application range. Therefore, the object of the present invention is to solve the above-mentioned problems of the prior art and to improve the stability of paints, adhesives, varnishes for inks, modifiers thereof, resins, modifiers of elastomers, pigment dispersion stabilizers, emulsion polymerizations. The purpose of the present invention is to provide crosslinked polyurethane colloid particles useful as an agent and the like.

[0004]

The above objects can be achieved by the present invention described below. That is, the present invention, the colloidal crosslinked particles dispersed in the solvent is composed of a portion that is solvated with respect to the solvent and a crosslinked non-solvated portion,
The particle diameter of the crosslinked non-solvated portion is 0.01 μm to 1.0 μm.
m is a polyurethane colloid cross-linked particle and a method for producing the same.

[0005]

When the inventor reacts a prepolymer having an isocyanate group dissolved in a non-aqueous medium with a polyamine compound, as the reaction between the isocyanate and the active hydrogen group of the amine proceeds, the generated urea bonds are bound to each other. Due to the formation of hydrogen bonds and cross-linking structure, insoluble domains are formed in the medium, and at the same time, the oil-modified polyol chain is solvated in the medium, resulting in colloidal cross-linked particles due to aggregation of insoluble domains. It has been found that a stable polyurethane colloid cross-linked particle can be easily obtained by preventing the enlargement of the polymer.

Further, in the present invention, the fat-and-oil modified polyol to be used has a low crystallinity in a non-aqueous medium, and the fat-and-oil modified polyol is mainly used in the medium even after undergoing a polymerizing process which occurs as the reaction proceeds. The freeness of the polymer chain is maintained, and the degree of freedom of the polymer chain around it decreases due to the occurrence of hydrogen bonds between one urea bond and the crystal structure due to the cross-linking structure. The formation of a central domain facilitates microphase separation between the amorphous part and the crystalline part, and the solvated polymer chains around the crystalline part are regularly outwardly oriented. This is a fundamentally different action from the known method for producing colloidal particles obtained by polymerizing under a micelle.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the preferred embodiments. In the present invention, an oil-and-fat modified polyol and a polyisocyanate compound are reacted in a non-aqueous medium or without a solvent to synthesize a prepolymer having an isocyanate group. The reaction between the oil / fat modified polyol and the polyisocyanate compound is 1 <NCO / OH ≦ 2.
Under the conditions described above to control the molecular weight of the solvated prepolymer chain. The molecular weight of the prepolymer thus synthesized is not particularly limited, but the preferred range is about 50.
It is 0 to 15,000.

Next, the prepolymer is charged into a jacket-type synthetic kettle equipped with a stirrer, and the concentration is adjusted by adding a non-aqueous solvent so that the concentration becomes 5 to 70% by weight. While stirring this solution, a solution of a polyamine compound adjusted to a concentration of 2 to 20% by weight was gradually added to cause a reaction to synthesize polyurea, thereby producing polyurethane colloid crosslinked particles. The polyamine used at this time may be a normal polyamine or a tri- or higher functional polyurea polyamine obtained by reacting a tri- or higher functional polyisocyanate with a diamine.

The method of adding the polyamine may be a method of adding the prepolymer or the solution thereof to the polyamine solution in addition to the above method. The temperature for polymer synthesis and crosslinking reaction is not particularly limited, but the preferred temperature is 30 ° C.
~ 120 ° C. The reaction temperature for polymer synthesis and crosslinking reaction, the reaction concentration, the form of the stirrer, the stirring power, the addition rate of the polyamine solution and the prepolymer or the solution is not particularly limited, but the polyamine compound and the isocyanate group of the prepolymer Since the reaction is fast, it is preferable to control the reaction so that a rapid reaction does not occur.

The fat-and-oil modified polyol used in the present invention is a polyol having a functional group of 2 or less, and the preferable molecular weight is 1,000 ± 300, but is not limited thereto. Specific examples of the fat-and-oil modified polyol include, for example, a method of alcoholizing various fats and oils with lower alcohols and glycols, a method of partially saponifying fats and oils, a method of esterifying hydroxyl group-containing fatty acid with glycol, and the like. Those containing 2 or less hydroxyl groups, or J. H. SAUNDERS, K .; C. POLYURETHANES, CHEMISTRY by FRISCH
AND TECHNOLOGY PART 1, Che
Examples thereof include oil-and-fat modified polyols described in mistry (p48-53) (published in 1962) and the like. Examples of the above-mentioned hydroxyl group-containing fatty acid include ricinoleic acid, 12
-Hydroxystearic acid, castor oil fatty acid, hydrogenated castor oil fatty acid and the like can be mentioned.

Examples of the polyisocyanate compound used in the synthesis of the polyurethane colloid crosslinked particles of the present invention include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylene diisocyanate,
Meta-xylene diisocyanate, 1,6-hexamethylene diisocyanate, lysine diisocyanate, 4,4
′ -Methylenebis (cyclohexyl isocyanate),
Methylcyclohexane-2,4- (or -2,6-)-
Examples thereof include those having two isocyanate groups such as diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate and dimer acid diisocyanate.

Further, compounds having polyfunctional isocyanate groups such as isocyanurates, burettes, adducts, and polymers of these compounds, for example,
4,4 ′, 4 ″ -triphenylmethane triisocyanate, 2,4-tolylene diisocyanate cyclic trimer,
Cyclic trimer of 2,6-tolylene diisocyanate, mixed 3 moles of cyclic trimer of 2,4- and 2,6-tolylene diisocyanate, diphenylmethane-4,4'-
Diisocyanate trimer, reaction product of 3 moles of diphenylmethane-4,4'-diisocyanate with 1 mole of trimethylolpropane, 3 moles of 2,4-tolylene diisocyanate and 1 mole of trimethylolpropane Reaction product of 3 moles of 2,6-tolylene diisocyanate with 1 mole of trimethylol propane, reaction product of 3 moles of 2,4-tolylene diisocyanate with 1 mole of trimethylol ethane Reaction product of 3 moles 2,6-tolylene diisocyanate and 1 mole trimethylolethane, mixed 3 moles 2,4
-And 2,6-tolylene diisocyanate with 1 mol of trimethylolpropane reaction products and the like, and these polyisocyanates, methanol, ethanol, phenol, cresol, ε-caprolactam, methyl ethyl ketone oxime, acetone oxime, N, A compound obtained by reacting a compound having one active hydrogen in the molecule, such as N-dimethylhydroxyamine, diethyl malonate, and acetylacetone, with a part or all of the isocyanate groups of the polyisocyanate compound can be used.

The non-aqueous medium used in the present invention includes:
It dissolves the oil-and-fat modified polyol, the polyisocyanate compound, and the polyamine compound, which are the raw materials used, and any non-aqueous solvent having no active hydrogen can be used. Particularly preferred are hydrocarbon-based single or mixed solvent systems such as hexane, heptane, octane, nonane, decane, cyclohexane, toluene and xylene. still,
In the present invention, "dissolution" includes both dissolution at room temperature and high temperature.

Examples of the polyamine compound used in the present invention include ethylenediamine, diaminopropane, diaminobutane, hexamethylenediamine, trimethylhexamethylenediamine, N-aminoethylpiperazine,
Bis-aminopropylpiperazine, polyoxypropylenediamine, 4,4-diaminodicyclohexylmethane, isophoronediamine, thiourea, methyliminobispropylamine and other diamines alone or as a mixture, dipropylenetriamine, diethylenetriamine, triethylenetriamine and polyoxy. Trifunctional or higher functional polyamines such as propylenetriamine can be preferably used alone or as a mixture. Further, when the above diamine is used, it is used as a trifunctional or higher polyurea polyamine obtained by reacting the diamine and the trifunctional or higher polyisocyanate at a ratio of approximately NCO / NH ₂ = 1.

Fat-and-oil modified polyol used in the present invention,
The type, amount and ratio of the polyisocyanate compound, the polyamine compound and the resulting prepolymer are determined for the purpose of controlling the size and stability of the colloid crosslinked particles in the solvent used. That is, the crosslinked polyurethane colloidal particles of the present invention are formed by a domain of a crystal part which is not solvated in a solvent and a polymer chain which extends from the domain and is solvated in the solvent. It affects the properties of the colloidal crosslinked particles.

As described above, the polyurethane colloid cross-linked particles formed by the domain of the unsolvated crystal part and the solvated polymer chain are a colloidal dispersion which is stable in the solvent, and the light scattering of the dispersion is carried out. Makes it look like yellowish opalescence from blue opalescence. The particle size of the domains of the polyurethane colloid crosslinked particles in the dispersion is usually 0.01 to
1.0 μm, the molecular weight of one of the solvated polymer chains is about 500 to 15,000, and for a homogeneous solvent system the ratio of solvated to unsolvated moieties is from 99: 1. In the range of the weight ratio of 60:40, particularly preferably 9
The weight ratio is from 5: 5 to 75:25. If the ratio of the non-solvated portion is too low, the stability of the domain of the non-solvated portion is lowered, and good colloidal crosslinked particles are hard to be produced. On the other hand, when the ratio of the unsolvated portion is too high, the domain of the unsolvated portion becomes large, the stability of the obtained colloid crosslinked particles is lowered, and the colloid crosslinked particles are likely to aggregate.

Since the polyurethane colloid cross-linked particles of the present invention are heterogeneous particles formed from unsolvated crystal part domains and solvated polymer chains, their properties are unsolvated domains. It has the performance of both solvated and polymer chains. As an example, polyurethane colloid crosslinked particles synthesized by reacting a prepolymer having an isocyanate group with a polyamine compound at a molar ratio of NCO / NH ₂ = 1.0 are used as a dispersion liquid having a solid content of 5 to 10% by weight as a glass. When a dry film was applied on a plate to a thickness of 10 μm and dried to form a film, the dry film was excellent in transparency and had no tackiness, and surprisingly, the melting temperature was 200. Showed above ℃.

This is considered to be a result of the excellent film-forming ability of the polymer chain and the heat resistance of the crystal domain.
Therefore, the above colloidal crosslinked particles that do not substantially contain an isocyanate group are useful as a vehicle for non-crosslinked type paints and inks having excellent heat resistance and abrasion resistance. On the other hand,
Polyurethane colloid crosslinked particles having an isocyanate group remaining by reacting a prepolymer with a polyamine with NCO / NH ₂ > 1 can utilize the excellent reactivity of the isocyanate group in addition to the above effects. It is also useful as a vehicle for cross-linking type paints and inks, an adhesive and their modifiers.

The morphology of the polyurethane colloid crosslinked particles of the present invention in a solvent is supposed to be as shown in FIG. Regarding the control of the particle size of the colloidal crosslinked particles, it is possible to control the size including the solvation portion and the domain and the control of the solvation portion and the domain. The appearance color and particle size of the polyurethane colloid crosslinked particle dispersion described above are
It represents the domain part.

[0020]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, unless otherwise specified, "parts" and "%" in the text are based on weight.

(Synthesis of Prepolymer) Example 1 Bifunctional oil-and-fat modified polyol 10 having a hydroxyl value of 119.4
0.0 part and 100.0 parts of n-nonane are charged into a synthetic kettle equipped with a stirrer, and the temperature is controlled at 50 ° C while stirring. 47.3 parts of isophorone diisocyanate prepared in advance so that NCO / OH = 2 was gradually added over 1 hour, the reaction was continued for 3 hours under these conditions, and the reaction was further continued at 90 ° C. for 2 hours to complete the synthesis. Let Next, the non-volatile content was adjusted to 50% with n-nonane, and the isocyanate group was 3.03%.
A containing prepolymer solution was obtained. The molecular weight of this prepolymer is 1,384, and this prepolymer solution is designated as PP-1.

Example 2 Bifunctional oil-and-fat modified polyol 10 having a hydroxyl value of 119.4
0.0 part and 100.0 parts of n-decane are charged into a synthetic kettle equipped with a stirrer, and the temperature is controlled at 50 ° C while stirring. 31.5 parts of isophorone diisocyanate prepared in advance so that NCO / OH = 2 was gradually added over 1 hour, the reaction was continued for 3 hours under these conditions, and the reaction was continued at 90 ° C. for 2 hours to complete the synthesis. Let Next, the non-volatile content was adjusted to 50% with n-decane, and the isocyanate group was 1.12%.
A containing prepolymer solution was obtained. The molecular weight of this prepolymer is 3,708, and this prepolymer solution is designated as PP-2.

Example 3 Bifunctional oil-and-fat modified polyol 10 having a hydroxyl value of 119.4
0.0 part and xylol 100.0 parts are charged into a synthetic kettle equipped with a stirrer, and the temperature is controlled at 50 ° C while stirring. 26.0 parts of isophorone diisocyanate prepared in advance so that NCO / OH = 2 was gradually added over 1 hour, the reaction was continued for 3 hours under these conditions, and the reaction was continued at 90 ° C. for 2 hours to complete the synthesis. Let Next, the non-volatile content is adjusted to 50% with xylol, and the isocyanate group content is 0.70%.
A containing prepolymer solution was obtained. The molecular weight of this prepolymer is 6,032, and this prepolymer solution is designated as PP-3.

Example 4 Bifunctional oil-and-fat modified polyol 10 having a hydroxyl value of 119.4
0.0 part and 100.0 parts of toluol are charged into a synthetic kettle equipped with a stirrer, and the temperature is controlled at 50 ° C while stirring. 27.8 parts of isophorone diisocyanate prepared in advance so that NCO / OH = 1.5 was gradually added over 1 hour, the reaction was continued under these conditions for 3 hours, and the reaction was further performed at 90 ° C. for 2 hours to synthesize. Was completed. Next, the nonvolatile content was adjusted to 50% with toluene, and the isocyanate group was adjusted to 1.75.
% Prepolymer solution was obtained. The molecular weight of this prepolymer is 2,402, and this prepolymer solution is designated as PP-4.

(Synthesis of Polyurethane Colloidal Crosslinked Particles) Example 5 100.0 parts of PP-1 synthesized in Example 1 and 900.0 parts of n-nonane were charged in a synthetic kettle equipped with a stirrer and the temperature was maintained while stirring. NCO / NH in advance while controlling the temperature to 40 ° C.
A solution of 1.6 parts of diethylenetoeramine prepared so that ₂ = 1.0 was dissolved and a solution of 30.4 parts of n-nonane was gradually added over 5 hours, and the reaction was carried out at 70 ° C for 1 hour to synthesize. To complete. This dispersion was a translucent milky white stable dispersion having a solid content of 5%.

Example 6 100.0 parts of PP-1 synthesized in Example 1 and 900.0 parts of n-nonane were charged into a synthetic kettle equipped with a stirrer, and the temperature was controlled at 40 ° C. while stirring. NCO / NH in advance
A solution of 24.1 parts of n-nonane in which 1.3 parts of triethylenetetramine was prepared so that ₂ = 1.0 was gradually added over 5 hours, and the reaction was carried out at 70 ° C for 1 hour to synthesize. Complete. This dispersion was a translucent milky white stable dispersion having a solid content of 5%.

Example 7 100.0 parts of PP-2 synthesized in Example 2, 1.0 part of a trifunctional isophorone diisocyanate type polyisocyanate (isocyanurate type) and 912.3 parts of n-decane were stirred. Put in a synthetic kettle and set the temperature to 5 while stirring.
Control at 0 ° C. to dissolve. NCO / NH ₂ = 1.
A solution of 120.4 parts of n-decane in which 6.3 parts of isophoronediamine prepared so as to be 0 was gradually added over 5 hours, and the reaction was carried out at 70 ° C. for 1 hour to complete the synthesis. The dispersion was a stable reddish blue dispersion having a solid content of 5%.

Example 8 100.0 parts of PP-2 synthesized in Example 2, 5.6 parts of trifunctional isophorone diisocyanate type polyisocyanate (isocyanurate type) and 106.4 parts of n-decane were stirred. Put in a synthetic kettle and set the temperature to 5 while stirring.
Control at 0 ° C. to dissolve. NCO / NH ₂ = 1.
A solution of 150.1 parts of n-decane in which 7.9 parts of isophoronediamine prepared so as to be 0 was gradually added over 5 hours, and the reaction was carried out at 70 ° C. for 1 hour to complete the synthesis. This dispersion was a milky white stable dispersion with a solid content of 5%.

Example 9 100.0 parts of PP-2 synthesized in Example 2, 1.0 part of a trifunctional isophorone diisocyanate-based polyisocyanate (isocyanurate type) and 919.0 parts of n-decane were stirred. Put in a synthetic kettle and set the temperature to 5 while stirring.
Control at 0 ° C. to dissolve. NCO / NH ₂ = 1.
A solution of 43.7 parts of n-decane in which 2.3 parts of isophoronediamine prepared so as to be 0 was gradually added over 5 hours, and the reaction was carried out at 70 ° C. for 1 hour to complete the synthesis.
This dispersion was a stable translucent opalescent color dispersion having a solid content of 5%.

Example 10 100.0 parts of PP-2 synthesized in Example 2, 5.6 parts of trifunctional isophorone diisocyanate type polyisocyanate (isocyanurate type) and n-decane 1,006.
4 parts are charged into a synthetic kettle equipped with a stirrer, and the temperature is controlled to 50 ° C. while stirring to dissolve. Beforehand NCO / NH ₂ =
A solution of 73.7 parts of n-decane in which 3.9 parts of isophoronediamine prepared so as to be 1.0 was gradually added over 5 hours, and the reaction was carried out at 70 ° C. for 1 hour to complete the synthesis. This dispersion was a slightly yellowish semi-transparent bluish white stable dispersion having a solid content of 5%.

Example 11 100.0 parts of PP-2 synthesized in Example 2 and 900.8 parts of n-decane were placed in a synthetic kettle equipped with a stirrer and dissolved while stirring and controlling the temperature at 50 ° C. Let NC in advance
A solution of 65.7 parts of n-decane in which 3.5 parts of polyoxypropylenetriamine having a molecular weight of 440 prepared so that O / NH ₂ = 1.0 was dissolved was gradually added over 5 hours, and the mixture was heated to 70 ° C. The reaction is carried out for 1 hour to complete the synthesis. This dispersion was a transparent and stable dispersion having a solid content of 5%.

Example 12 100.0 parts of PP-3 synthesized in Example 3 and 900.0 parts of xylol were charged in a synthesis kettle equipped with a stirrer and the temperature was controlled at 50 ° C. while stirring to dissolve them. NC in advance
Molecular weight of 2,000 prepared so that O / NH ₂ = 1.0
A solution of 210.9 parts of xylol in which 11.1 parts of polyoxypropylenetriamine of 0 was dissolved is gradually added over 5 hours, and the reaction is carried out at 70 ° C. for 1 hour to complete the synthesis. This dispersion was a transparent and stable dispersion having a solid content of 5%.

Example 13 100.0 parts of PP-4 synthesized in Example 4 and 900.0 parts of toluol were charged in a synthesis kettle equipped with a stirrer and the temperature was controlled at 50 ° C. while stirring to dissolve them. NCO in advance
/ NH ₂ = 1.0 A solution of 115.9 parts of toluol prepared by dissolving 6.1 parts of polyoxypropylenetriamine having a molecular weight of 440 was gradually added over 5 hours, and at 70 ° C. for 1 hour. The reaction is carried out to complete the synthesis. This dispersion was a transparent and stable dispersion having a solid content of 5%.

(Application to Production of Polyurethane Gel Fine Particles) Example 14 20 parts of polybutylene adipate having an average molecular weight of 1,000 is dissolved at 60 ° C., and isocyanurate polyisocyanate 8.12 of hexamethylene diisocyanate is dissolved therein.
Parts were added and mixed uniformly. This was gradually added to a mixed solution of 4.0 parts of the polyurethane colloid crosslinked particles of Example 5 and 25 parts of n-decane prepared in a 1-liter stainless steel container in advance, and the mixture was stirred and emulsified with a homogenizer for 15 minutes. This emulsion has an average dispersoid particle size of 13.5.
The emulsion was stable with no separation and having a size of μm.

Then, this was placed in a reaction vessel equipped with an anchor type stirrer, the temperature was raised to 80 ° C. while rotating at 400 rpm, and the reaction for 6 hours was completed to obtain a dispersion liquid of polyurethane gel fine particles. The dispersion was vacuum dried at 100Toor to separate n-decane to obtain polyurethane gel particles. This was in the form of a true spherical white powder having an average particle diameter of 15 μm and was useful as a delustering agent for paints and resins.

Example 15 20 parts of the polyurethane colloid cross-linked particles of Example 10 and 150 parts of n-nonane were charged and mixed in a 1-liter separable flask. Next, 100 parts of a trifunctional polylactone polyol having an average molecular weight of 1,250 preheated to 70 ° C. was gradually added to this liquid while mixing with a homomixer to emulsify. This emulsion had a mean dispersoid particle size of 32 μm and was a stable emulsion without separation. Further, 44.9 parts of hexamethylene diisocyanate adduct polyisocyanate was gradually added.

Then, while rotating the homomixer, the temperature was raised to 90 ° C. and reacted for 45 minutes. Then, the temperature was raised to 90 ° C. while rotating at 200 rpm instead of the anchor type stirrer, and the reaction was carried out for 6 hours. Then, a dispersion liquid of polyurethane gel particles was obtained. The dispersion was vacuum dried at 100Toor to separate n-nonane to obtain polyurethane gel particles. This was in the form of a true spherical white powder having an average particle diameter of 35 μm and was useful as a delustering agent for paints and resins.

Example 16 A 1-liter separable flask was charged with 20 parts of the polyurethane colloid cross-linked particles of Example 10 and 150 parts of n-decane and mixed. Next, 100 parts of a trifunctional polylactone polyol having an average molecular weight of 1,250 preheated to 70 ° C. was gradually added to this liquid while mixing with a homomixer to emulsify. This emulsion had a mean dispersoid particle diameter of 9 μm and was stable without separation. Further, 44.9 parts of hexamethylene diisocyanate adduct polyisocyanate was gradually added.

Next, while rotating the homomixer, the temperature was raised to 90 ° C. and reacted for 45 minutes. Then, the temperature was raised to 90 ° C. while rotating at 200 rpm instead of the anchor type stirrer, and the reaction was carried out for 6 hours. Then, a dispersion liquid of polyurethane gel particles was obtained. The dispersion was vacuum dried at 100Toor to separate n-decane to obtain polyurethane gel particles. This was a white spherical powder having an average particle diameter of 10 μm and was useful as a delustering agent for paints and resins.

Example 17 20 parts of polybutylene adipate having an average molecular weight of 1,000 was dissolved at 60 ° C., and hexamethylene diisocyanate wasocyanurate polyisocyanate 8.12 was dissolved therein.
Parts were added and mixed uniformly. This product was gradually added to a mixed solution of 4.0 parts of the polyurethane colloid crosslinked particles of Example 10 and 25 parts of n-decane prepared in a 1-liter stainless steel container in advance, and the mixture was stirred and emulsified with a homogenizer for 15 minutes. The emulsion had a mean dispersoid particle size of 4 μm and was stable without separation.

Then, this was placed in a reaction vessel equipped with an anchor type stirrer, the temperature was raised to 90 ° C. while rotating at 400 rpm, and the reaction for 6 hours was completed to obtain a dispersion liquid of polyurethane gel fine particles. The dispersion was vacuum dried at 100Toor to separate n-decane to obtain polyurethane gel particles. This was in the form of a true spherical white powder having an average particle size of 6 μm and was useful as a delustering agent for paints and resins.

Example 18 20 parts of polybutylene adipate having an average molecular weight of 1,000 was melted at 60 ° C., and hexamethylene diisocyanate wasocyanurate polyisocyanate 8.12 was dissolved therein.
Parts were added and mixed uniformly. This product was gradually added to a mixed solution of 3.0 parts of the polyurethane colloid crosslinked particles of Example 1 and 25 parts of n-decane prepared in a 1-liter stainless steel container in advance, and emulsified with a homogenizer for 15 minutes while stirring. This emulsion had a mean dispersoid particle size of 8 μm and was a stable emulsion without separation.

Next, this was charged into a reaction vessel equipped with an anchor type stirrer, the temperature was raised to 90 ° C. while rotating at 400 rpm, and the reaction for 6 hours was completed to obtain a dispersion liquid of polyurethane gel fine particles. The dispersion was vacuum dried at 100Toor to separate n-decane to obtain polyurethane gel particles. This was a white spherical powder having an average particle diameter of 10 μm and was useful as a delustering agent for paints and resins.

[0044]

EFFECTS OF THE INVENTION The crosslinked polyurethane colloidal particles and the method for producing the same of the present invention have the following effects. 1. It is possible to produce polyurethane colloid cross-linked particles with controlled particle size and domain size. 2. Since it is composed of solvated and unsolvated domains in the solvent, it is expected to be widely used because it has the effect of enhancing the coating film forming ability of the soft solvation portion and the coating properties of the hard domain. I can. 3. It is possible to produce polyurethane colloid cross-linked particles having an isocyanate group in the solvation part, and it can be expected to be used for application of strong reactivity of isocyanate group. 4. The obtained polyurethane colloid cross-linked particles have a low surface tension and a large surface activity, and therefore have excellent adsorbability to the surface of other particles. From the above effects, the polyurethane colloid cross-linked particles of the present invention are coatings, ink vehicles, adhesive modifiers, viscosity control agents, dispersion stabilizers for the production of non-aqueous dispersions,
It has a wide range of applications such as pigment dispersants.

[0045]

[Brief description of drawings]

FIG. 1 is an imaginary view of a cross section of a polyurethane colloid crosslinked particle of the present invention.

[Explanation of symbols]

 1: Solvated polymer chain 2: Domain of unsolvated part

Claims (4)

[Claims] 1. Colloidal crosslinked particles dispersed in a solvent,
A polyurethane colloid comprising a part that is solvated with a solvent and a cross-linked non-solvated part, and the particle diameter of the cross-linked non-solvated part is 0.01 μm to 1.0 μm. Crosslinked particles. 2. The colloidal crosslinked particles are polyurethane colloidal crosslinked particles obtained by the reaction of an oil-and-fat modified polyol, a polyisocyanate and a polyamine compound, wherein the solvated portion is an oil-modified polyol and the unsolvated portion is urea. The crosslinked polyurethane colloidal particle according to claim 1, which is composed of a hydrogen bond and a crosslinked structure. 3. A fat-modified polyol is reacted with a diisocyanate compound in a functional group ratio of 1 <NCO / OH ≦ 2,
A method for producing crosslinked polyurethane colloidal particles, which comprises synthesizing a prepolymer having an isocyanate group and further reacting a part or all of the isocyanate group with a polyamine having three or more functional groups. 4. The method for producing crosslinked polyurethane colloidal particles according to claim 3, wherein the trifunctional or higher functional polyamine is a trifunctional or higher functional polyurea polyamine obtained by reacting a polyamine alone or a trifunctional or higher functional polyisocyanate with a diamine. .