JP3161939B2 - Crosslinked polyurethane colloid, method for producing the same, and dispersion stabilizer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is intended for use as a modifier for paints, adhesives and varnishes for inks, or as a modifier for polymers such as resins and elastomers, as well as dispersion stabilizers such as pigments, emulsifiers and suspensions. The present invention relates to a polyurethane colloid useful as a dispersion stabilizer for suspension polymerization and the like, a method for producing the same, and a dispersion stabilizer comprising a polyurethane colloid.

[0002]

2. Description of the Related Art As a method for producing a polymer colloid,
A non-aqueous dispersion polymerization method and an aqueous emulsion polymerization method using a radical reaction are known. As a method for producing an aqueous polyurethane colloid, a method described in Japanese Patent Application Laid-Open No. 1-110506 is known. Non-aqueous polyurethane urea colloids can be produced by using a large amount of emulsifiers, or by using a large amount of emulsifiers in a polyol or resin solution, because stable colloidal particles are difficult to obtain due to aggregation and fusion of particles in the synthesis process. A method for preventing aggregation of particles by synthesizing the particles is known.

[0003]

The polyurethane colloids and colloidal particles obtained by the above-described method contain or remain emulsifiers, polyols, resins and the like. There is a problem in that it has an adverse effect on the product, the products using them are limited, and the application range is narrow. Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and to use organic or inorganic powders as modifiers for paints, adhesives, varnishes for inks, or for polymers such as resins and elastomers. Provided is a crosslinked polyurethane colloid useful as a dispersion stabilizer such as a surface modifier, a filler or a pigment, as a dispersion stabilizer for emulsion and suspension polymerization, and also as an oil-absorbing resin, and a method for producing the same. That is.

[0004]

The above object is achieved by the present invention described below. That is, the present invention, in a non-aqueous solvent containing no dispersion stabilizer, the average particle size is 0.01 ~ 0.5μ
solvated crosslinked polyurethane particles m is Ri Na stably dispersed and crosslinked polyurethane particles, polybutadiene Po
Obtained by reacting riol with an isocyanate compound.
And isocyanate over preparative group-containing polybutadiene prepolymer that
Crosslinked polyurethane colloid, wherein the reaction product der Rukoto of polyisoprene polyol, a functional group ratio and two or more polybutadiene polyol and a diisocyanate compound functional groups is reacted under conditions such that a 1 <NCO / OH ≦ 2 The isocyanate group-containing polybutadiene prepolymer obtained and the polyisoprene polyol having a functional group number of 2 or more are obtained in these soluble non-aqueous solvents in the absence of a dispersion stabilizer, and the functional group ratio is 0.8 ≦ NCO / O
A method for producing a crosslinked polyurethane colloid, wherein the reaction is performed under the condition of H ≦ 1.2, and a dispersion stabilizer comprising the above crosslinked polyurethane colloid.

[0005]

According to the present invention, when a polybutadiene prepolymer having an isocyanate group and a polyisoprene polyol having a functional group number of 2 or more are reacted in a non-aqueous solvent not containing a dispersion stabilizer to form crosslinked polyurethane particles, By reacting both so as to balance the molecular weight of the polymer chain between the crosslinking density and the crosslinking point, the crosslinked polyurethane colloid particles do not aggregate and become large,
A crosslinked polyurethane colloid stably present in a non-aqueous solvent is easily provided.

[0006] The reason that the crosslinked polyurethane particles are stably present in the nonaqueous solvent to which no dispersion stabilizer is added is that the polybutadiene chain and the polyisoprene chain constituting the polyurethane chain do not crystallize in the nonaqueous solvent. In addition, in order to control the reaction so that the molecular weight between crosslinks does not decrease, in the crosslinked particles generated as the reaction proceeds, the crosslinked portion and the polymer chain between the crosslinks are solvated with the solvent and have a large degree of freedom of movement. Since the polymer chains between the crosslinks are oriented in the solvent, it is considered that aggregation between the formed crosslinked particles is prevented and a stable colloid is formed. The stabilizing action of this colloid is fundamentally different from the conventionally known stabilizing action of a colloid in which colloid particles are composed of a solvated portion and an unsolvated portion with respect to a solvent.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. The crosslinked polyurethane colloid of the present invention is obtained by reacting a polybutadiene polyol and a diisocyanate with an isocyanate group-containing prepolymer and a polyisoprene polyol in a non-aqueous solvent in which these are dissolved in the absence of a dispersion stabilizer. It is synthesized by reacting.

[0008] The polybutadiene polyol used in the present invention is a polyol having two or more functional groups, and preferably has a molecular weight of 1,000 to 5,000. In the present invention, the polybutadiene polyol is used as a polybutadiene prepolymer having an isocyanate group obtained by reacting the polybutadiene polyol with a diisocyanate compound without or in a solvent. The reaction between the polybutadiene polyol and the diisocyanate compound is such that the functional group ratio between the isocyanate group (NCO) and the hydroxyl group (OH) is 1 <NCO
/ OH ≦ 2 to control the molecular weight of the resulting prepolymer. Polyb synthesized in this way
The molecular weight of Tajien prepolymer is important in controlling the molecular weight between crosslinks caused by reaction with the polybutadiene prepolymer and polyisoprene polyol,
Preferred molecular weights range from 1,000 to 15,000.

The diisocyanate compound used for synthesizing the polybutadiene prepolymer in the present invention includes, for example, 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-)-
Those having two isocyanate groups such as diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylhexamethylene diisocyanate, and dimer acid diisocyanate are exemplified.

The polyisoprene polyol used in the present invention is a polyol having two or more functional groups, and the preferred molecular weight is in the range of 1,000 to 30,000.

[0011] The cross-linked polyurethane colloid of the present invention, port
It is produced by reacting a butadiene prepolymer and an isoprene polyol in these soluble non-aqueous solvents in the absence of a dispersion stabilizer. Polybutadi
Reaction of the ene prepolymer and polyisoprene polyols may, for example, using a reaction vessel such as a jacketed synthesis reactor equipped with a stirrer, by adjusting the concentration of both the non-aqueous solvent to about 40-60 wt%, a reaction temperature of 60 It is preferable to carry out the stirring at a temperature of about to 120 ° C. When the reaction is performed while gradually increasing the temperature to a predetermined temperature, the viscosity of the reaction solution gradually increases. Therefore, it is preferable to perform the reaction while further adding a non-aqueous solvent to the reaction solution. In particular, it is desirable to carry out the reaction while controlling the concentration, stirring power, and the like so that the entire reaction solution does not become a gel due to an increase in viscosity due to progress of crosslinking. The reaction concentration and the reaction temperature are not limited to the above ranges, and the form of the reaction vessel and the stirrer, the stirring power, and the like are not particularly limited.

The crosslinked polyurethane colloid of the present invention obtained by reacting a polybutadiene prepolymer with a polyisoprene polyol has a crosslinked polyurethane particle having an average particle size of 0.01 to 0.5 μm in a non-aqueous solvent containing no dispersion stabilizer. Is a colloid that is stably present in In order for the crosslinked polyurethane particles to have an average particle diameter in the above range and to be stably present in the solvent, it is important to balance the crosslink density of the crosslinked particles and the molecular weight of the polymer chain between crosslinks. Po
Libutadiene prepolymer and isoprene polyol are
It is preferable to carry out the reaction under the condition that the functional group ratio satisfies 0.8 ≦ NCO / OH ≦ 1.2, since the resulting crosslinked polyurethane particles are stably present in the solvent. Functional group ratio is 0.8
If it is less than 1, the crosslinked polyurethane formed due to a small degree of crosslinking has difficulty in its existence as particles. The functional group ratio is 1.
If it exceeds 2, the whole reaction solution will be in a gelled state,
It is difficult to obtain a stable colloid. Moreover, preferred molecular weight of the polymer chains between crosslinks is in the range of 1,000 to 20,000, the molecular weight is less than 1,000, aggregation occurs between crosslinked polyurethane particles child, colloidal stability is obtained When the molecular weight exceeds 20,000, the spread of the crosslinked particles becomes large, and it becomes difficult to obtain a target particle size.

As described above, in the present invention, since the formation of a stable colloid involves the crosslinking density and the molecular weight of the polymer chain existing between the crosslinking points, the crosslinked polyurethane colloid of the present invention is dispersed in a solvent. The crosslinked polyurethane colloid particles have a crosslinked portion and a polymer chain between the crosslinking points solvated with a solvent, and the polymer chain between the crosslinking points is oriented in the solvent to obtain a stable colloid. Seem. Accordingly, the crosslinking density is increased, the molecular weight of the polymer chains between crosslinks is aggregated and crosslinked polyurethane particles child less than 1,000, believed to insufficient orientation of the polymer chains in a solvent between crosslinks Can be Accordingly, the molecular weight of the polybutadiene polyol used in the present invention, the functional group ratio between the polyol and the diisocyanate compound, the molecular weight of the polyisoprene polyol and
Adjust the functional group ratio of the polybutadiene prepolymer and polyisoprene polyol, by balancing the molecular weight of the polymer chains between crosslinks and crosslink density, rack Hashipo polyurethane particles child in a non-aqueous solvent containing no dispersion stabilizer
It is possible to control the average particle size and stability.

The non-aqueous solvent used in the present invention includes all non-aqueous solvents having no active hydrogen that dissolve the polyisoprene polyol, polybutadiene polyol and diisocyanate compound used as raw materials, and the polybutadiene prepolymer which is a reaction product thereof. Solvents can be used. Particularly preferred solvents are, for example, hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, toluene, xylene, petroleum spirit, petroleum naphtha and the like. The raw materials are dissolved in these solvents, and the dissolution includes dissolution at ordinary temperature and high temperature.

In the present invention, a stable crosslinked polyurethane colloid is produced by reacting a polybutadiene prepolymer with isoprene polyol in the absence of a dispersion stabilizer using the above-mentioned non-aqueous solvent. various surfactants commonly used for stably dispersing the particles child in a dispersion medium, dispersing agent used in the suspension polymerization or dispersion polymerization and the like, may not use a dispersion stabilizer such as a suspension stabilizer It is a feature.

The crosslinked polyurethane colloid of the present invention obtained as described above, in order that consists of solvated crosslinked polyurethane <br/> grain child, high heat resistance by using this colloid, the performance Excellent coating film can be obtained. For example, a crosslinked polyurethane colloid synthesized by reacting a polyisoprene polyol with a polybutadiene prepolymer having an isocyanate group (NCO group) at a molar ratio such that the functional group ratio is NCO / OH = 1.0,
By adjusting the concentration to 10% and applying the coating on a glass plate so as to have a thickness of 8 μm and drying, a coating excellent in transparency and having a melting temperature of 200 ° C. or higher can be obtained.

Further, polyisoprene and polybutadiene have excellent water resistance, hydrolysis resistance, heat resistance, insulation, low-temperature embrittlement resistance, impact absorption, and the like. The crosslinked polyurethane colloid of the present invention has a paint or ink vehicle, various coating agents,
It is useful as a modifier for resins and elastomers. For example, a colloid obtained by reacting a polyisoprene polyol with a polybutadiene prepolymer under the condition that the functional group ratio is NCO / OH> 1 is useful as an adhesive or as a modifier for an adhesive. . Particularly as an application of the crosslinked polyurethane colloid of the present invention, emulsification such as emulsification and suspension polymerization in a non-aqueous medium, as a dispersion stabilizer such as a suspension dispersion stabilizer, or as a particulate stabilizer such as a pigment or a filler. As a dispersant, it has an excellent performance not found in conventional dispersion stabilizers, such as a wide range of particle size control and a product with a narrow particle size distribution.

The morphology of the particles of the crosslinked polyurethane colloid of the present invention consists of the crosslinked particles 1 as shown in FIG. 1 and the polymer chains 2 between the crosslinked particles oriented in the solvent on the surface of the particles. It is supposed to be. The particle diameter of the crosslinked polyurethane colloid of the present invention is the diameter of the circle in FIG. The average particle size of the colloid particles in the present invention is measured by a particle size distribution analyzer (Microtrac X-100 manufactured by Nikkiso Co., Ltd.).
And UPR).

[0019]

Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the text, “part” or “%” is based on weight unless otherwise specified.

Synthesis Example 1 (NCO group-containing polybutadiene prepolymer: PP-1) 100 parts of a polybutadiene polyol having a hydroxyl value of 74.9 and a functional group number of 2 was charged into a synthesis kettle equipped with a stirrer and stirred. The temperature was controlled at 50 ° C., and 29.66 parts of isophorone diisocyanate were added so that NCO / OH = 2. After the addition, the reaction was continued at this temperature for 6 hours.
The temperature was raised to, to complete the synthesis of the polybutadiene prepolymer performed 3 times Mahan response. The concentration of the reaction solution is adjusted to 50% by adding nonane, and contains 2.1% of NCO groups.
A solution of polybutadiene prepolymer (PP-1) was obtained. The molecular weight of the polybutadiene prepolymer is 1939.

Synthesis Example 2 (NCO group-containing polybutadiene prepolymer: PP-2) 100 parts of a polybutadiene polyol having a hydroxyl value of 53.4 and a functional group number of 2 were charged into a synthesis kettle equipped with a stirrer, and stirred. The temperature was controlled at 40 ° C., 15.9 parts of isophorone diisocyanate was added so that the NCO / OH became 1.5, the reaction was continued for 3 hours, and the temperature was raised to 80 ° C. and the reaction was carried out for 8 hours to obtain polybutadiene. The synthesis of the prepolymer was completed. n-Octane was added to the reaction solution to adjust the concentration to 50% to obtain a solution of polybutadiene prepolymer (PP-2) containing 0.86% of NCO groups. Polybut Jie
The molecular weight of emissions prepolymer is 4860.

Synthesis Example 3 (NCO group-containing polybutadiene prepolymer: PP-3) 100 parts of a polybutadiene polyol having a hydroxyl value of 53.4 and having 2 functional groups was charged into a synthesis kettle equipped with a stirrer, and the temperature was stirred. Is controlled at 50 ° C., 21.15 parts of isophorone diisocyanate are added so that NCO / OH = 2.0, the reaction is continued for 4 hours at this temperature, and the temperature is further raised to 80 ° C. for 4 hours. Thus, the synthesis of the polybutadiene prepolymer was completed. The concentration of the reaction solution was adjusted to 50% with nonane to obtain a solution of a polybutadiene prepolymer (PP-3) containing 1.65% of NCO groups. The molecular weight of the polybutadiene prepolymer is 2541.

Synthesis Example 4 (NCO group-containing polybutadiene prepolymer: PP-4) 100 parts of a polybutadiene polyol having a hydroxyl value of 31.8 and a functional group number of 2 was charged into a synthesis kettle equipped with a stirrer and stirred. The temperature was controlled at 60 ° C., and 12.59 parts of isophorone diisocyanate was added so that NCO / OH = 2.0, and the reaction was carried out at this temperature for 5 hours to complete the synthesis of the polybutadiene prepolymer. did. The concentration of the reaction solution was adjusted to 50% with n-heptane to obtain a polybutadiene prepolymer (PP-4) solution containing 1.06% of NCO groups. The molecular weight of the polybutadiene prepolymer is 3966.

Synthesis Example 5 (NCO group-containing polybutadiene prepolymer: PP-5) 100 parts of a polybutadiene polyol having a hydroxyl value of 46.6 and a functional group number of 2.3 were charged into a synthesis kettle equipped with a stirrer and stirred. While controlling the temperature to 65 ° C., NCO / OH = 2.
13.9 hexamethylene diisocyanate
6 parts were added and the reaction was continued at this temperature for 3 hours.
And the reaction was carried out for 7 hours to complete the synthesis of the polybutadiene prelimer. The concentration of the reaction solution was adjusted to 50% with isooctane, and a polybutene containing 1.36% of NCO groups was used.
To obtain a solution of Tajien prepolymer (PP-5). Poly
The molecular weight of the butadiene prepolymer is 3530.

[0025] Example 1 A solution 47.19 parts of Synthesis Example 1 was made created the PP-1 were charged in a stirrer with synthesis reactor to control the temperature to 30 ° C. with stirring, a hydroxyl value of 13.2, functional After adding 200 parts of a 50% solution of nonane of polyisoprene polyol having a group number of 5.9 and 0.13 part of a 10% solution of toluene of stannas octate, the temperature is gradually raised to 90 ° C. The reaction was carried out for 6 hours to complete the reaction. The reaction solution was diluted by adding 988.76 parts of nonane to a concentration of 10%.
Of a stable crosslinked polyurethane colloid was obtained. The average particle size of the colloid particles is 0.0234 μm, and has the particle size distribution shown in FIG.

Example 2 115.2 parts of the PP-2 solution prepared in Synthesis Example 2 was charged into a synthesis kettle equipped with a stirrer, the temperature was controlled at 50 ° C. while stirring, the hydroxyl value was 13.2, and the number of functional groups. Of a 50% solution of polyisoprene polyol in n-octane 200
Part and stannase octate 10% toluene solution 0.4
7 parts were added. Thereafter, the temperature of the reaction solution is gradually increased to 95.
C., and the reaction was carried out at this temperature for 10 hours to complete the reaction. The reaction solution was diluted by adding 1260.0 parts of n-octane to obtain a stable crosslinked polyurethane colloid having a concentration of 10%. The average particle size of the colloid particles is 0.1.
0875 μm, showing the particle size distribution shown in FIG.

Example 3 60.06 parts of the solution of PP-3 prepared in Synthesis Example 3 was charged into a synthesis kettle equipped with a stirrer, the temperature was controlled at 40 ° C. with stirring, the hydroxyl value was 13.2, and the number of functional groups. Are added, and 200 parts of a 50% solution of nonane of polyisoprene polyol and 0.12 parts of a 10% solution of stannas octate in toluene are added, and the temperature is gradually raised to 90 ° C., and at this temperature for 8 hours. The reaction was allowed to complete. The reaction solution was diluted by adding 1040.2 parts of nonane to obtain a stable crosslinked polyurethane colloid having a concentration of 10%. The average particle size of the colloid particles was 0.0425 μm. FIG. 4 shows the particle size distribution.

Example 4 93.89 parts of the solution of PP- 4 prepared in Synthesis Example 4 was charged into a synthesis kettle equipped with a stirrer, the temperature was controlled at 50 ° C. while stirring, the hydroxyl value was 13.2, and the functional group was 50% solution of n-heptane of polyisoprene polyol having 5.9 radicals 20
0 part and 0.11 part of a 10% toluene stannate octate solution were added, and the temperature was gradually raised to 90 ° C. The reaction was carried out at this temperature for 12 hours to complete the reaction. The reaction solution was diluted by adding 1175.5 parts of n-heptane to obtain a stable crosslinked polyurethane colloid having a concentration of 10%. The average particle size of the colloid particles is 0.0465.
μm. FIG. 5 shows the particle size distribution.

Example 5 72.7 parts of the PP-5 solution prepared in Synthesis Example 5 was charged into a synthesis kettle equipped with a stirrer, the temperature was controlled at 50 ° C. while stirring, the hydroxyl value was 13.2, and the number of functional groups. 200 parts of a 50% solution of isooctane in polyisoprene polyol having a ratio of 5.9 and 0.15% solution of stannas octate in 10% toluene.
And the temperature was gradually raised to 90 ° C. After the reaction was completed at this temperature for 15 hours, the reaction solution was diluted by adding 1090.8 parts of isooctane to obtain a stable crosslinked polyurethane colloid having a concentration of 10%. The average particle size of the colloid particles was 0.0298 μm. FIG. 6 shows the particle size distribution.

Example 6 From this example, it is shown that the crosslinked polyurethane colloid of the present invention is useful as a dispersion stabilizer or a modifier. 47.5 parts of the crosslinked polyurethane colloid obtained in Example 4 and anhydrous silica 5 having a primary particle size of 40 nm
Parts and 47.5 parts of nonane were charged into a vessel, mixed for 15 minutes with a propeller-type stirrer, and further dispersed with anhydrous silica for 20 minutes while controlling the temperature at 85 ° C. with an ultrasonic disperser. This dispersion had an average dispersed particle size of silica of 0.37.
It was a stable dispersion of 0 μm. FIG. 7 shows the particle size distribution.

Example 7 In a 500 cc separable flask, 20.0 parts of the crosslinked polyurethane colloid of Example 2 and 120 parts of n-heptane were charged and mixed. Next, while mixing this solution with a homomixer, 100 parts of a polycaprolactone polyol having a hydroxyl value of 137.1 and a functional group number of 3 preliminarily heated to 70 ° C. was added to the mixed solution, and the mixture was emulsified. A good emulsion was obtained. Next, while maintaining the emulsion at 90 ° C., 44.7 parts of hexamethylene diisocyanate adduct polyisocyanate having an NCO content of 23% was gradually added, and an emulsification reaction was performed for 2 hours. 4.3 parts of a 1% toluene solution of tate was added, and the mixture was further reacted for 8 hours to obtain a dispersion of polyurethane gel fine particles. The average particle size of the dispersed fine particles was 4.99 μm. FIG. 8 shows the particle size distribution. This dispersion was vacuum-dried under reduced pressure of 100 Torr to remove the solvent, and a spherical white powder was obtained. This product was useful as a matting agent having an excellent feel for paint and a modifier for resin.

Example 8 In a 3,000 cc separable flask, 128.8 parts of the silica dispersion of Example 6 and 543.1 parts of nonane were charged and mixed. Next, while mixing with a homomixer, 126 parts of a polycaprolactone polyol having a hydroxyl value of 136.3 and a functional group number of 3 was added to the mixture, and a hydroxyl value of 85.
3, polycaprolactone polyol having 3 functional groups
4 parts, 65 parts of a polycaprolactone polyol having a hydroxyl value of 307.8 and a number of functional groups of 3 and cyanine blue 35
And a mixture obtained by heating and mixing at 42 ° C. a pigment dispersion obtained by dispersing the mixture with 3 parts by a three-roll mill, and gradually adding and suspending the mixture. This was a stable suspension. Next, while maintaining the suspension at 90 ° C.,
After gradually adding 126.1 parts of hexamethylene diisocyanate adduct polyisocyanate having an NCO group content of 23% and reacting for 2 hours, 0.13 parts of stannas octate is added, and further reacted for 10 hours. Thus, a dispersion of colored polyurethane gel fine particles was obtained. The average particle size of the dispersed fine particles was 62.04 μm. FIG. 9 shows the particle size distribution. This dispersion was vacuum-dried under reduced pressure of 100 Torr to remove the solvent, and a spherical white powder was obtained.
FIG. 4 shows a micrograph of the fine particles. These fine particles were useful as a matting agent having excellent three-dimensional feeling for paints.

[0033]

According to the present invention described above, the following effects can be obtained. (1) A crosslinked polyurethane colloid having a controlled particle size can be produced. (2) Since the crosslinked polyurethane particles in the colloid are solvated in a solvent, the crosslinked polyurethane colloid has an excellent coating film forming ability and the crosslinked portion has an effect of enhancing the coating film properties, Wide application can be expected. (3) It is possible to produce a crosslinked polyurethane colloid having an isocyanate group, and this colloid can be expected to be used for utilizing the strong polarity of the isocyanate group. (4) The obtained crosslinked polyurethane colloid particles have a small surface tension and a high surface activity, and therefore have excellent adsorption ability of other particles to the surface. From the above effects, the crosslinked polyurethane colloid of the present invention is used for coatings, modifiers such as ink vehicles and adhesives, viscosity control agents, suspension / dispersion stabilizers for the production of non-aqueous dispersions, pigments and various It can be used for a wide range of applications such as a dispersant for particulate matter.

[0034]

[Brief description of the drawings]

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

FIG. 2 shows a histogram (left vertical axis) and a cumulative distribution curve (right vertical axis) showing the particle size distribution of the colloid particles of Example 1.

FIG. 3 shows a histogram (left vertical axis) and a cumulative distribution curve (right vertical axis) showing the particle size distribution of the colloid particles of Example 2.

FIG. 4 shows a histogram (left vertical axis) and a cumulative distribution curve (right vertical axis) showing the particle size distribution of the colloid particles of Example 3.

FIG. 5 shows a histogram (left vertical axis) and a cumulative distribution curve (right vertical axis) showing the particle size distribution of the colloid particles of Example 4.

FIG. 6 shows a histogram (left vertical axis) and a cumulative distribution curve (right vertical axis) showing the particle size distribution of the colloid particles of Example 5.

7 shows a histogram (left vertical axis) and a cumulative distribution curve (right vertical axis) showing the particle size distribution of silica in the silica dispersion liquid of Example 6. FIG.

FIG. 8 is a histogram showing the particle size distribution of the polyurethane gel fine particles in the dispersion of Example 7 (left vertical axis).
And a cumulative distribution curve (right vertical axis).

FIG. 9 is a histogram showing the particle size distribution of the polyurethane gel fine particles in the dispersion liquid of Example 8 (left vertical axis).
And a cumulative distribution curve (right vertical axis).

FIG. 10 is an electron micrograph of the dried polyurethane gel fine particles of Example 8.

[Explanation of symbols]

 1: polymer chains between crosslinking points oriented in the solvent 2: solvated crosslinked particles Hist. (%): Frequency (%) Cum. (%):Accumulation(%)

Continuation of the front page (72) Inventor Tokuyuki Miyamoto 1-7-6, Nihonbashi Bakurocho, Chuo-ku, Tokyo Inside Dainichi Seika Kogyo Co., Ltd. (56) References JP-A-08-200992 (JP, A) JP-A-6 −279531 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 75/04-75/12 B01J 13/00 C08G 18/00-18/87

Claims (6)

(57) [Claims] 1. A non-aqueous solvent containing no dispersion stabilizer,
Ri average particle diameter of the name stably dispersed crosslinked polyurethane particles solvated 0.01 to 0.5 [mu] m, crosslinking Poriu
The urethane particles are composed of polybutadiene polyol and isocyanate
Containing isocyanate groups obtained by reacting
Polybutadiene prepolymer and polyisoprene polio
Crosslinked polyurethane colloid, wherein the reaction product der Rukoto with Lumpur. 2. A polybutadiene polyol having two or more functional groups and a diisocyanate compound having a functional group ratio of 1 <
An isocyanate group-containing polybutadiene prepolymer obtained by reacting under conditions of NCO / OH ≦ 2 and a polyisoprene polyol having a functional group number of 2 or more are dissolved in these soluble non-aqueous solvents in the absence of a dispersion stabilizer. A method for producing a crosslinked polyurethane colloid, wherein the reaction is performed under the condition that the functional group ratio is 0.8 ≦ NCO / OH ≦ 1.2. 3. The polybutadiene polyol has a molecular weight of 1,000 to 5,000, and the polyisoprene polyol has a molecular weight of 1,000 to 30,000.
3. The method for producing a crosslinked polyurethane colloid according to 2 . 4. The method for producing a crosslinked polyurethane colloid according to claim 2 , wherein the polybutadiene prepolymer has a molecular weight of 1,000 to 15,000. 5. A dispersion stabilizer comprising the crosslinked polyurethane colloid according to claim 1. 6. The crosslinked polyurethane colloid according to claim 2,
The dispersion stabilizer according to claim 5 , which is obtained by the method described in (1).