JPH0889789A - Production of hollow particle - Google Patents

Abstract

PURPOSE: To obtain hollow particles which can develop high coloring power and shielding power by producing microcapsule particles from a hydrophobic material and then extracting with using an org. solvent which does not dissolve the self-water dispersible resin which constitutes the particles but permeates through the resin and dissolves the hydrophobic material in the particles. CONSTITUTION: The resin particles having vacancy inside (hollow particles) which can be used for various kinds of coating materials such as coating liquid, paper, fiber, leather, and cosmetic products are produced by the following method. A self-water dispersion resin (A) and a hydrophobic material (B) which is insoluble with the resin (A) are mixed in an org. solvent (C) which can dissolve the resin (A). The obtd. mixture soln. I is phase inversed in water and emulsified to produce particles of the self-water dispersion resin (A) including the hydrophobic material (B) inside. Then an org. solvent (D) which does not dissolve the self-water dispersion resin (A) but permeates through the resin (A) and can dissolve the hydrophobic material (B) is used to extract the hydrophobic material (B) included in the particles. Then the particles are dried to complete the production of desired hollow particles.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention provides a method for producing resin particles (hollow particles) having voids (hollow parts) inside the particles. The hollow particles produced by the production method exhibit high coloring power and hiding power, and the most typical application is, for example, a substitute for titanium oxide which is a white pigment (plastic pigment), a paint,
It can be used as various coating agents for paper, textiles, leather, cosmetics, etc.

[0002]

2. Description of the Related Art Today, titanium oxide is the most typical white pigment and is widely used. However, particles having voids (hollow parts) inside due to their high specific gravity and environmental damage. That is, the replacement of white pigments with hollow particles has been attracting attention. The replacement of the white pigment by the hollow particles is based on the fact that the voids inside the resin particles cause a hiding power due to diffused reflection of light and a high white coloring power is developed.

For example, by continuous emulsion polymerization, a shell polymer is formed on a core particle containing a carboxylic acid group and then neutralized with ammonia or an amine to swell the core polymer and form voids inside the particle. A method for producing a thickener aqueous dispersion using a water-insoluble core / shell pigment-like polymer particle is disclosed in JP-B-3-7688.
It is introduced in the Gazette.

[0004]

However, in such a production method, the core polymer is not always completely enclosed by the shell polymer, and therefore many small holes communicating with the inner voids are observed on the surface of the obtained particles. It When the hollow particles having such a surface state are used as a colorant or the like, for example, when kneaded with an oily binder, the oily binder penetrates into the hollow portion, the hiding power is reduced, and the coloring power is likely to be reduced. There are challenges.

[0005]

Means for Solving the Problems The inventors of the present invention have made extensive studies to solve the above problems, and as a result, have focused on a method for producing microcapsules using phase inversion emulsification (Japanese Patent Laid-Open No. 3-221137), After forming a microcapsule particle by using a hydrophobic substance instead of the colorant used here, the self-water-dispersible resin forming the particle does not dissolve but permeates, and When extracted using an organic solvent that dissolves the volatile substance, the obtained hollow particles show a hiding power equivalent to that of the conventional technique, and a high coloring power, and the hiding power does not decrease, and the coloring power is retained and the coloring power is maintained. The inventors have found that they can be used as agents and the like to have excellent effects, and have completed the present invention.

That is, according to the present invention, the self-water-dispersible resin (A) and the self-water-dispersible resin (A) are mixed with the hydrophobic substance (B) which is not compatible with the self-water-dispersible resin (A). After mixing in an organic solvent (C) that dissolves the compound (I) to form a mixed solution (I), the mixed solution (I) is phase-inverted and emulsified in water to make the hydrophobic substance (B) a self-water dispersible resin ( A) to form particles encapsulated therein, and then self-dispersible resin (A)
The organic solvent (D) which does not dissolve but permeates the hydrophobic substance (B) is used to extract the hydrophobic substance (B) encapsulated in the particles, and then the particles are dried. The present invention provides a method for producing a characteristic hollow particle.

The self-water-dispersible resin (A) in the present invention is a resin having the ability to form a stable water dispersion without using an emulsifier under the action of an aqueous medium due to the action of a hydrophilic group in the molecule. As expected.

The hydrophilic group may be either ionic or nonionic, but the ionic hydrophilic group is preferable because the hydrophilicity of the resin can be appropriately adjusted as necessary regardless of the resin design. .

Ionic (cationic or anionic)
In the case of anionic self-water dispersible resin, the acidic group introduced into the resin has a salt structure in which a part or all of the acidic groups are neutralized with a base. In the case of a self-water-dispersible resin, some or all of the basic groups introduced into the resin are neutralized with an acid to form a salt structure. Due to the neutralized hydrophilic group having a salt structure, it can be stably dispersed in a granular form in an aqueous medium.

Examples of such an acidic group include a carboxyl group, a phosphoric acid group, a sulfone group, a sulfuric acid group and the like. Among them, the carboxyl group is a weakly acidic group, and therefore it is hydrophilic when neutralized to form a salt structure. It is preferable because the sex can be easily adjusted. Examples of the basic group include tertiary amino groups such as dimethylamino group and diethylamino group. Such acidic group or basic group is introduced into the resin through a chemical bond.

The amount of the hydrophilic group is 10 to 500 mg equivalent per 100 g of resin solid content, preferably 10 resin solid content.
20 to 400 mg equivalent per 0 g, more preferably 30 to 300 mg equivalent per 100 g of resin solids. Further, the amount of neutralized acidic group or basic group (neutralization amount, neutralization rate) is 10 to 400 mg equivalent per 100 g of resin solid content, preferably 20 to 250 per 100 g of resin solid content.
mg equivalent, more preferably 3 per 100 g of resin solids
It has 0 to 200 mg equivalent.

The neutralizing agent for neutralizing the acidic group or basic group of the self-water-dispersible resin (A) may be any of commonly used organic bases, inorganic bases, organic acids and inorganic acids. In the case of an anionic self-water-dispersible resin in which, for example, the self-water-dispersible resin (A) has a neutralized acidic group, a tertiary amine such as triethylamine or dimethylethanolamine; sodium hydroxide, Inorganic bases such as potassium hydroxide; ammonia and the like, and, in the case of a cationic self-water-dispersible resin, which has a neutralized basic group of the self-water-dispersible resin (A), acetic acid, etc. Inorganic acids such as organic acids and hydrochloric acid can be mentioned. The hydrophilicity of the self-water-dispersible resin (A) can be controlled by the neutralization amount (neutralization ratio) at this time, which facilitates the dispersion, that is, the particle size of particles to the order of several tens nm to μm. Can be controlled to a desired value and a free particle size can be obtained according to the purpose.

The resin used as the self-water-dispersible resin (A) may be any resin produced by any method as long as it is a resin containing an acidic group or a basic group as described above. An acrylic resin , Urethane resin, polyester resin, etc. are used.

When the self-water-dispersible resin is an acrylic resin, for example, a polymerizable vinyl monomer and / or oligomer containing an acidic group or a basic group as described above and another polymerizable resin It is obtained by radical polymerization of a vinyl monomer and / or oligomer in the presence of a radical initiator.

Specific examples of the acidic group-containing polymerizable monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, monobutyl itaconate and the like.

Examples of the basic group-containing polymerizable monomer include dimethylaminoethyl acrylate and diethylaminoethyl methacrylate. Furthermore,
Examples of the acidic group- or basic group-containing oligomer include vinyl modified polyester, vinyl modified urethane, vinyl modified epoxy compound and the like.

On the other hand, as the polymerizable monomer other than the polymerizable monomer containing an acidic group or a basic group, various styrene-based monomers such as styrene and vinyltoluene; vinyl acetate, acrylonitrile, methyl acrylate, ethyl acrylate, Isopropyl acrylate, acrylic acid n
Various acrylates such as hexyl butyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate; methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, etc. Methacrylic acid ester and the like can be mentioned, of which styrene is particularly preferably used.

When the self-water-dispersible resin (A) is a urethane resin, for example, polyisocyanates such as tolylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate, and polyether polyols such as polyethylene glycol and polyesters. Urethane prepolymer having an isocyanate group at the terminal which has been previously reacted with various polyols such as polyols, acrylic polyols, polybutadiene polyols, etc., containing acidic groups or basic groups such as dimethylolpropionic acid and 2,2-methylaminodiethanol Polymerization of urethane prepolymers having terminal isocyanate groups with hydroxyl groups containing hydroxyethyl methacrylate, hydroxyethyl acrylate, etc. Obtained by polymerizing an acidic group or a basic group-containing polymerizable monomer in the addition reaction product of an Nomar.

When the self-water-dispersible resin (A) is a polyester resin, for example, a polyhydric alcohol such as ethylene glycol, diethylene glycol, glycerin or trimethylolethane and phthalic anhydride,
Anionic self-water dispersible resin (A) and cationic self-water dispersible resin (A) by condensation with polybasic acids such as isophthalic acid, adipic acid, maleic anhydride, itaconic acid, trimellitic anhydride, etc. ), Together with the above components, 2,2-
Examples thereof include a method obtained by condensing a polyhydric alcohol containing a basic group such as methylaminodiethanol.

The self-water-dispersible resin (A) has a weight average molecular weight of 3,000 to 300,000, preferably 5,000 to 150,0.
The range of 00 is preferable because it forms stable particles during phase inversion emulsification and particles with a desired particle size can be obtained with a good particle size distribution.

As the hydrophobic substance (B) in the present invention, any substance may be used as long as it is incompatible with the self-water-dispersible resin (A) and soluble in the following organic solvent (D).
Among them, it is preferably liquid at room temperature rather than solid, and examples thereof include higher hydrocarbons such as liquid paraffin, soybean oil, and paraoctyl phthalate, oils and fats, and plasticizers.

The organic solvent (C) may be any as long as it dissolves the self-water-dispersing resin (A), but in consideration of drying and powdering in the subsequent step, one having a low boiling point is used. Preferably, among general-purpose organic solvents, for example,
It is preferable to use alcohols such as isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, and organic solvents such as tetrahydrofuran alone or in combination of two or more kinds.

The organic solvent (D) may be any one as long as it does not dissolve the self-water-dispersible resin (A) but permeates it and dissolves the hydrophobic substance (B). A resin that does not dissolve the resin (A) but swells is used. Of these, higher hydrocarbons having 6 to 18 carbon atoms are preferable because they are poorly soluble in the self-water-dispersible resin (A) and can be easily removed during drying. For example, acrylic resin or urethane. Hexane to resin
Examples include heptane and octane.

In the present invention, the self-water-dispersible resin (A) and the hydrophobic substance (B) which is incompatible with the self-water-dispersible resin (A) are combined with the self-water-dispersible resin (A). First step of mixing in an organic solvent (C) to be dissolved to form a mixed solution (I), and phase inversion emulsification of this mixed solution (I) in water to disperse the hydrophobic substance (B) in self-water dispersibility Second step of forming particles encapsulated in the resin (A) and permeation of the self-water-dispersible resin (A), which does not dissolve, and a hydrophobic substance (B)
It comprises a third step of extracting the hydrophobic substance (B) encapsulated in the particles using an organic solvent (D) which dissolves, and a fourth step of drying and pulverizing the particles.

In the first step, the solid content ratio of the self-water-dispersible resin (A) and the hydrophobic substance (B) controls the void ratio of the hollow particles, and this void ratio is hollow. It affects the hiding power, coloring power and mechanical strength of the particles. The ratio of self-water-dispersible resin (A) / hydrophobic substance (B) is usually used within a solid content weight ratio range of 30/70 to 90/10, and among them, 40/60 to 75 /.
The range of 25 is preferable in order to increase the porosity in the particles and to exhibit high coloring power and hiding power, and further preferably 5
Within the range of 0/50 to 70/30, the mechanical strength is further increased, which is preferable.

Any method may be used for mixing the self-water-dispersible resin (A), the hydrophobic substance (B) and the organic solvent (C). For example, the self-water-dispersible resin may be dispersed at room temperature or under heating. The resin (A) is dissolved, and the hydrophobic substance (B) is dissolved, or even if it is not dissolved, it is stirred until a uniform state is obtained.

In the second step, any method may be used as the method of phase inversion emulsification of the mixed solution (I) of the self-water-dispersible resin (A), the hydrophobic substance (B) and the organic solvent (C). Examples thereof include a method in which water is gradually added with stirring, or the mixed solution (I) is dropped into water with stirring.

In the third step, the method for extracting the hydrophobic substance (B) encapsulated in the particles by using the organic solvent (D) is not particularly limited. For example, the organic solvent (D) may be added to the system.
After adding, there is a method of stirring.

The hydrophobic substance (B) can be more efficiently extracted by removing the organic solvent (C) in advance by evaporation or the like and then adding the organic solvent (D). This method is particularly effective when the organic solvent (D) and the organic solvent (C) are compatible with each other.

In addition, particles containing the hydrophobic substance (B) in advance are separated from the aqueous medium by means such as filtration, and then the separated substance is treated with the organic solvent (D) to obtain the hydrophobic substance (B). ), The extraction efficiency is better. In this case, the particles separated from the aqueous medium are extracted with the hydrophobic substance (B) by a method of immersing or agitating in the organic solvent (D), a method of leaving the particles in a flow of the organic solvent (D), or the like. be able to. Among them, the method of removing the particles from the aqueous medium, immersing in the organic solvent (D), and stirring is preferable because the extraction efficiency is good.

In the fourth step, when the obtained hollow particles are dried and pulverized, any pulverization method may be used, and a commonly used pulverization method may be used, for example, a freeze-drying method, an air stream. A method such as a dry method is used.

When the self-water-dispersible resin forming the particles is an anion type having a neutralized acidic group at any stage from phase inversion emulsification to drying, an acid is used to When the self-water-dispersible resin is a cation type having a neutralized basic group, when treated with a base, the hydrophilic moiety which is neutralized to form a salt structure has a free acidic group or It is preferable because it becomes a basic group, the hydrophilicity of the resin is reduced, the particles are easily separated from the aqueous medium, and the subsequent steps can proceed more smoothly.

The obtained hollow particles have voids (hollow portions) inside.
It can be easily confirmed by observing the cross section with a transmission electron microscope, and by observing the surface with a scanning electron microscope whether there are significantly few voids communicating with the outer surface of the particle.

[0034]

EXAMPLES The present invention will be described in more detail based on examples. Originally, the present invention is not limited to such embodiments.

The particle size, the retention of the coloring power, and the particle surface were observed by the following methods. (1) Particle size Submicron particle size distribution meter CHDF-1100 (US M
It was measured using ATEC APPLIED SCIENCES. (2) Retention of tinting strength 1 g of the hollow particles was well mixed and dispersed in 2 g of liquid paraffin, and then a part of it was picked up and kneaded well with a fingertip. This was applied onto a black coating plate, and the change in each coloring power was visually evaluated according to the following criteria.

◯: No decrease in coloring power was observed. Δ: Some decrease in coloring power was observed. X: The coloring power was remarkably reduced. (3) Observation of particle surface and internal void The obtained particle surface was observed with a scanning electron microscope (SEM). The voids inside the particles were embedded in the resin, the resin pieces were sliced into thin pieces, and the cross section of the particles in this section was observed with a transmission electron microscope (TEM). The maximum diameter of the void inside the particle was measured from the photograph.

All parts and% are based on weight unless otherwise specified. Example 1 400 parts of methyl ethyl ketone (ME
K) was heated to 80 ° C. for reflux, and the mixture in the following proportions was added dropwise over 2 hours.

Methacrylic acid 90 parts 2-Ethylhexyl acrylate 66 parts Methyl methacrylate 90 parts Styrene 354 parts Perbutyl O (manufactured by NOF Corporation) 6 parts 1 hour and 2 hours after the end of dropping the above mixture,
After that, 0.5 parts of perbutyl O was added to the reaction solution every 4 hours for aging for 22 hours. The reaction temperature was kept at 80 ° C. MEK was added at the end of the reaction to adjust the nonvolatile content to 40%. An acrylic resin having a weight average molecular weight of 40,000 was obtained.

3.40 g of triethylamine (TEA) was added to 175 g of the acrylic resin, and the mixture was stirred until it became uniform to obtain a self-water-dispersible resin. The neutralization amount of the self-water-dispersible resin is 47.1 m based on 100 g of resin solid content.
It was g equivalent. 30 g of liquid paraffin was mixed with the self-water-dispersible resin, and water was added while stirring at 350 rpm.
00 g was slowly added dropwise. After removing the organic solvent by vacuum distillation, the solid content and the aqueous medium are separated by filtration, the obtained solid content is dispersed again in water, and the pH is adjusted to 3 with 1N hydrochloric acid aqueous solution under stirring for 30 minutes. It was stirred. The aqueous medium and the solid content were separated by filtration, the solid content was washed with water, the washing liquid was filtered off, and the obtained solid content was immersed in 400 g of heptane and stirred to extract liquid paraffin. The particles were separated from the extract by filtration, washed twice with 300 g of heptane, the washing solution was removed, and the particles were dried under reduced pressure and pulverized.

The obtained particles had an average particle size of 0.5 μm and showed high coloring power. Further, it was confirmed that the obtained particles had extremely few voids communicating with the outer surface of the particles.
Table 1 shows the maximum diameter of the inner void of the obtained particles and the result of the retention of the coloring power.

Example 2 125 g of an acrylic resin obtained in the same manner as in Example 1.
1.60 g of triethylamine was added to the mixture, and the mixture was stirred until it became uniform to obtain a self-water-dispersible resin. The neutralization amount of the self-water-dispersible resin was 48.8 mg equivalent based on 100 g of resin solid content. 50 g of para-octyl phthalate (POP) was mixed with the self-water-dispersible resin, and 500 g of water was slowly added dropwise while stirring at 350 rpm. After removing the organic solvent by vacuum distillation, the solid content and the aqueous medium were separated by filtration, and the obtained solid content was immersed in octane and stirred to extract POP. The particles were separated from the extract by filtration, washed several times with octane, the washing solution was removed, the obtained solid content was dispersed again in water, and the pH was adjusted to 3 with 1N hydrochloric acid aqueous solution with stirring. Stir for 30 minutes. The aqueous medium and the solid content were filtered off, the solid content was washed with water, the washing liquid was filtered off, and the obtained solid content was dried under reduced pressure to give powder. The obtained particles had an average particle size of 0.6 μm and showed high coloring power.

It was also confirmed that the obtained particles had extremely few voids communicating with the outer surface of the particles. Table 1 shows the maximum diameter of the inner void of the obtained particles and the result of the retention of the coloring power.

Example 3 "Unisafe PT-200" (polytetramethylene glycol manufactured by NOF CORPORATION); number average molecular weight of about 200
0) 293 parts and 77 parts of isophorone diisocyanate were placed in a flask and stirred under a nitrogen shield for 12 hours.
The temperature was raised to 0 ° C. and kept at the same temperature for 30 minutes, 0.05 part of tin octenoate was added, and 1 hour later, the temperature was lowered to 80 ° C., and 210 parts of methyl ethyl ketone and 20 parts of dimethylolpropionic acid were added. Was added and the reaction was continued at 75 ° C. for 5 hours, no increase in viscosity or decrease in the content of isocyanate groups was observed, and the acid value of the solution was 13 and the content of isocyanate groups was A urethane resin having a content of 0.9% was obtained.

2.30 g of triethylamine (TEA) was added to 162.5 g of the urethane resin and stirred until uniform to obtain a self-water-dispersible resin. The neutralization amount of the self-water-dispersible resin was 35.5 mg equivalent based on 100 g of resin solid content. Soybean oil (35 g) was mixed with the self-water-dispersible resin, 500 g of water was slowly added dropwise while stirring at 350 rpm, and then dimethylethanolamine (DME) was added.
A) was added. After removing the organic solvent by vacuum distillation,
The solid content and the aqueous medium were separated by filtration, and the obtained solid content was immersed in octane and stirred to extract soybean oil. The particles were separated from the extract by filtration, washed several times with octane, the washing solution was removed, and the particles were dried under reduced pressure and pulverized.

The obtained particles had an average particle size of 0.5 μm and showed high coloring power. Further, it was confirmed that the obtained particles had extremely few voids communicating with the outer surface of the particles.
Table 1 shows the maximum diameter of the inner void of the obtained particles and the result of the retention of the coloring power.

Comparative Example 1 A 5 liter flask equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser was used and deionized water (2900) was used.
g) and sodium dodecylbenzene sulfonate 2.
0 g in a flask with stirring under a nitrogen atmosphere at 78 ° C
Heated to.

Into the flask was added 266 g of deionized water, 0.40 g of sodium dodecylbenzene sulfonate, 416 g of butyl acrylate, 374 g of methyl methacrylate and 50 g of a monomer emulsion prepared from 10.4 g of methacrylic acid, and then water. 3.0 g ammonium persulfate dissolved in 10 ml was added and after 15 minutes the remaining monomer emulsion was fed at 16 g / min, the temperature was raised to 85 ° C. and kept at that temperature throughout the monomer addition. 15 minutes after the monomer addition was complete, the reaction mixture was cooled and at 55 ° C. 1.0 ml t-butyl hydroperoxide (70%) and sodium formaldehyde sulfoxylate dissolved in 20 g water were added. Further, at 25 ° C., 28% aqueous ammonia was added.

Then, using a 5 L round bottom flask equipped with a paddle stirrer, a thermometer, a nitrogen inlet and a reflux condenser, deionized water 2 heated to 84 ° C. in a flask under a nitrogen atmosphere was used.
115 g, sodium persulfate dissolved in 25 g water 4.
2 g was added, and the above-mentioned acrylic resin dispersion 62 was continuously added.
g was added.

A monomer emulsion consisting of 235 g of deionized water, 0.8 g of sodium dodecylbenzene sulfonate, 490 g of methyl methacrylate, 210 g of methacrylic acid and 3.5 g of ethylene glycol diacrylate was placed in the flask at 85 ° C. for 3 hours. Added to kettle. After the completion of the monomer supply, the dispersion liquid was kept at 85 ° C. for 30 minutes, cooled to 25 ° C., filtered to remove coagulated matter, and the filtered dispersion liquid was neutralized to pH 10 with ammonia.
It was freeze-dried under reduced pressure and pulverized. The obtained particles had an average particle size of 0.8 μm, and a decrease in coloring power was observed.

Further, it was confirmed that the obtained particles had many small holes communicating with the outer surface of the particles. Table 1 shows the maximum diameter of the inner void of the obtained particles and the result of the retention of the coloring power.

[0051]

[Table 1]

[0052]

The hollow particles obtained by the production method of the present invention are characterized by excellent retention of coloring power.

Claims (12)

[Claims] 1. A self-water-dispersible resin (A) and a hydrophobic substance (B) which is incompatible with the self-water-dispersible resin (A) are dissolved in the self-water-dispersible resin (A). After mixing in an organic solvent (C) to prepare a mixed solution (I), the mixed solution (I) is phase-inverted and emulsified in water to form a hydrophobic substance (B).
Organic solvent (D) capable of forming particles in which the self-water-dispersible resin (A) is encapsulated and then permeating the self-water-dispersible resin (A) but not permeating it and dissolving the hydrophobic substance (B). Is used to extract the hydrophobic substance (B) encapsulated in the particles, and then the particles are dried, to thereby produce hollow particles. 2. The production method according to claim 1, wherein a hydrophobic organic solvent is used as the organic solvent (D). 3. After forming particles in which a hydrophobic substance (B) is included in a self-water-dispersible resin (A), the organic solvent (C) is removed, and then the organic solvent (D) is added to water. The production method according to claim 1, wherein the hydrophobic substance (B) is extracted by a method. 4. The production method according to claim 3, wherein a hydrophobic organic solvent is used as the organic solvent (D). 5. After forming particles in which the hydrophobic substance (B) is included in the self-water-dispersible resin (A), the organic solvent (C) is removed, and then the particles are separated from water, followed by organic The production method according to claim 1, wherein the hydrophobic substance (B) is extracted by immersing it in the solvent (D). 6. The self-water-dispersible resin (A) contains 10 or more neutralized acidic groups or basic groups per 100 g of resin solids.
The manufacturing method according to any one of claims 1 to 5, wherein the manufacturing method has an amount of ~ 400 mg equivalent. 7. The self-water-dispersible resin (A) contains 20 or more neutralized acidic or basic groups per 100 g of resin solids.
The method according to any one of claims 1 to 5, wherein the production method has about 250 mg equivalent. 8. The method according to claim 6, wherein the self-water-dispersible resin (A) is an acrylic resin or a urethane resin. 9. The manufacturing method according to claim 1, wherein the hydrophobic substance (B) is a hydrophobic liquid substance. 10. The hydrophobic substance (B) is a higher hydrocarbon,
The method according to any one of claims 1 to 9, wherein the method is any one of oils and fats and plasticizers. 11. The production according to claim 6, wherein the weight ratio of the solid content of the self-water-dispersible resin (A) to the hydrophobic substance (B) is 30/70 to 90/10. Method. 12. The self-water dispersibility of forming the particles at any stage from the formation of the particles containing the hydrophobic substance (B) contained in the self-water dispersible resin (A) to the drying. When the resin (A) is an anion type having a neutralized acidic group, an acid is used and when the self-water dispersible resin (A) is a cation type having a neutralized basic group. Is a process using a base, The manufacturing method as described in any one of Claims 1-11.