JPH06279561A - Production of fine urethane-crosslinked particle - Google Patents

Abstract

PURPOSE:To provide an excellent method for efficiently producing optionally colored fine urethane-crosslinked particles having a mean particle size of 5mum or lower and a narrow particle-size distribution and useful for various applications including coating materials and printing inks. CONSTITUTION:Optionally colored fine urethane-crosslinked particles having a mean particle size of 5mum or lower and a shape parameter of Weibull distribution of 1.5 or higher are obtd. by causing a mixture of a urethane component with a dispersion medium to collide at a high speed under pressure with a plane section in a flow passage or causing collision between the mixture itself at a high speed under pressure in the flow passage to disperse the mixture and then forming crosslinked particles by curing reaction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful method for producing urethane crosslinked fine particles. More specifically, it relates to a method for producing urethane crosslinked fine particles obtained by dispersing a urethane component in a dispersion medium with a specific dispersing device.

[0002]

2. Description of the Related Art In recent years, fine particles or ultrafine particles have attracted attention in various fields regardless of whether they are organic or inorganic. Among them, the urethane fine particles synthesized by the interfacial polymerization method, which have been developed in recent years, have been used in paints, inks, adhesives, etc. by blending a urethane component alone or a pigment-encapsulated substance with a resin.

In order for such particles to be stably present in the product, it is necessary that they are crosslinked particles so as not to be swelled by a solvent or to swell, and in order to form crosslinked particles, in the raw material components thereof, A production method is known in which a raw material having a trifunctional or higher functional isocyanate group is introduced, a crosslinking reaction based on the isocyanate group is allowed to proceed, and finally urethane crosslinked particles are obtained.

For the production of such urethane crosslinked fine particles, the dispersion polymerization or suspension polymerization method is industrially inexpensive and efficient, and compared with the emulsion polymerization which requires the addition of a large amount of a surfactant, It has an advantage that there is little concern about residual surfactant that may have an adverse effect at the time of use, and is excellent in that spherical particles are formed unlike the pulverization method.

However, conventionally, it has been considered difficult to obtain a narrow particle size distribution with an average particle size of 5 μm or less by dispersion polymerization or suspension polymerization. In particular, when urethane particles are prepolymerized beforehand and then particles are synthesized by dispersion or suspension polymerization, it is difficult to produce urethane crosslinked particles having a small average particle size and a narrow particle size distribution. It was

When a pigment is contained in these urethane crosslinked fine particles, it is generally more difficult to produce particles having a small average particle diameter, and therefore, it is possible to use industrial means.
A method for producing such colored fine particles has been desired.

[0007]

Therefore, the problem to be solved by the present invention is that urethane crosslinked fine particles having an average particle size of 5 microns or less and having a narrow particle size distribution, and an average particle size of 5 microns or less, It is intended to provide a method for producing colored urethane crosslinked fine particles having a narrow particle size distribution.

[0008]

Means for Solving the Problems The inventors of the present invention have earnestly studied in order to solve the above-mentioned problems, and as a result, have found that the urethane cross-linking has an average particle size of 5 microns or less and a narrow particle size distribution. The inventors have found a method for industrially inexpensively and efficiently producing fine particles, and urethane crosslinked fine particles colored by adding a pigment to them, and have completed the present invention.

[0009]

[Structure] That is, according to the present invention, a mixed liquid of a urethane component and a dispersion medium is made to collide with a flat surface portion in a flow path at high speed and under pressure, or
Alternatively, a urethane crosslinked fine particle characterized by forming crosslinked particles by a curing reaction after the mixed solution is dispersed by colliding a mixed solution of a urethane component and a dispersion medium in the flow path at high speed and under pressure. It is a manufacturing method.

Further, according to the present invention, a mixed liquid of a urethane component and a dispersion medium is made to collide with a flat surface portion in a flow path at high speed and under pressure to disperse the mixed liquid, and then crosslinked particles are formed by a curing reaction. A method for producing urethane crosslinked fine particles, characterized in that a mixed solution of a urethane component and a dispersion medium is caused to collide with a flat surface portion in a flow path under high speed and pressure, and then the mixed solution is further flowed in the flow path. A method for producing urethane crosslinked fine particles is characterized in that crosslinked particles are formed by a curing reaction after the mixed liquid is dispersed by colliding with each other.

The present invention is a method for producing urethane crosslinked fine particles, characterized in that the urethane crosslinked fine particles are polyurethane polyurea particles, and the urethane crosslinked fine particles have an average particle size of 5 μm or less and Weibull. The method for producing urethane crosslinked fine particles is characterized in that the distribution shape parameter is 1.5 or more.

Further, the present invention is a method for producing urethane crosslinked fine particles, characterized in that the obtained urethane crosslinked fine particles are urethane crosslinked fine particles colored by incorporating a pigment in the crosslinked particles. Is 5 microns or less and the shape parameter of the Weibull distribution is 1.5 or more, and a method for producing urethane crosslinked fine particles colored by containing a pigment is included.

More specifically, the method for producing the urethane crosslinked fine particles of the present invention is, for example, the collision of the mixed liquid of the urethane component and the dispersion medium with the flat surface portion in the flow channel at high speed and high pressure, or in the flow channel. It is characterized by using a dispersion device having a structure capable of causing collision of the mixed liquids at high speed and high pressure twice or more.

Further, in the method for producing urethane crosslinked fine particles according to the present invention, the pressure when the mixed liquid passes through the flow path of the dispersing device is 10 to 10000 kg / cm ² , and the urethane crosslinked fine particles are produced. The method also includes a method for producing urethane crosslinked fine particles, wherein the dispersion medium of the mixed solution is water.

Next, the present invention will be described in detail. In the present invention, the disperser used is important, and the disperser used in the present invention will be described first. That is, the disperser preferably used in the present invention is generally called a pressure nozzle type emulsifier, and accelerates the fluid at high speed, and the dispersed particles contained in the fluid are miniaturized by collision or impact by cavitation. High pressure homogenizer, that is, jet flow type, bubble homogenizer,
Microfluidizer (made by Microfluideck)
Etc. is also a type of disperser included in these.

In order to explain the disperser used in the present invention more clearly, the dispersion chamber of the dispersion apparatus will be specifically described with reference to the drawings. 1 to 3 are dispersion chambers of a microfluidizer (manufactured by Microfluideck Co., Ltd.) whose main purpose is dispersion due to collision of mixed solutions, and FIGS. 4 and 5 are dispersion chambers due to collision of mixed solution with wall surface. 2 shows a dispersion chamber of a high pressure homogenizer mainly composed of.

In FIGS. 1 and 2, 1 and 2 are restraining portions, and 3 and 4 are disks capable of withstanding ultra-high pressure. Each of the disks 3 and 4 is provided with two through holes and an extremely narrowed connecting groove for connecting the two holes, and the diameter of the groove is 50 to 10
00 microns is preferred. The disks 3 and 4 are 90 degrees inward so that the connecting grooves of the two disks contact each other and the connecting grooves are in a cross shape because the fluid passes from the disk 3 to the disk 4. Are combined in the position.

In FIGS. 1, 2, and 3, the mixed liquid of the premixed urethane component and the dispersion medium is added to 5 to 30 k.
Under pressure of g / cm ² , it is fed to the restraining part 1 in the chamber. The flow path of the mixed liquid that has entered the restraining portion 1 is divided into two, is introduced into the disk 3, and collides with the flat surface portions 5 and 6 of the disk 4 as it is. The liquid mixture that collided with the flat surface
In the connecting groove 7 of the disk 3 which is in contact with the disk 4, the mixed liquids collide with each other in the central portion 8 of the disk 3 by being accelerated and flowing along the central portion.

Due to the collision with the flat surface and the collision between the liquids, the urethane component is dispersed and crushed into fine particles.
Next, the mixed liquid flows from the central portion 8 toward the outside through the connecting groove 9 of the disk 4 formed in 90 degrees phase, and is taken out through the two holes in the disk 4.

Further, the dispersion chamber may have a structure in which the mixed liquid only collides with the flat surface portion. An example of a high pressure homogenizer having the structure of the dispersion chamber is shown in FIGS. In FIG. 4, the chamber has a valve 1 at the center.
0, a handle 12 for adjusting the position of the valve and adjusting the clearance with the valve seat 11.

In FIG. 5, which is a more enlarged view of the valve portion, a mixed liquid of the premixed urethane component and the dispersion medium is supplied into the chamber from the direction of the arrow on the left side of the drawing and collided with the valve. Due to this collision, the urethane component is dispersed and crushed into fine particles.

At this time, it is possible to adjust the particle size of the obtained fine particles by adjusting the valve position, and further, when troubles such as clogging of the cured product in the dispersion chamber occur. Also, maintenance such as disassembly and cleaning is easy, which is preferable in industrial production.

In the microfluidizer (manufactured by Microfluideck Co.) shown in FIGS. 1, 2 and 3, when the mixed solution passes through the two divided flow paths and the connecting groove in the chamber, and in FIGS. In the high pressure homogenizer shown, when the mixture hits the valve, the mixture is accelerated and the pressure rises. Further, the liquid passes through the narrow channel at a high speed, so-called cavitation phenomenon occurs, and the cavitation phenomenon also effectively disperses the particles in the mixed liquid.

Therefore, it is possible to accelerate the mixed liquid at high speed and collide the wall surfaces or the mixed liquid with each other at high speed and high pressure.
It is important to the present invention. The flow velocity of the mixed liquid in the flow path of the dispersing device used in the present invention is extremely fast, and generally, the fastest flow velocity in the device is said to be 460 m / sec from the speed of sound, but it is accurate when the mixed liquid is dispersed. Is difficult to measure,
Generally, the pressure in the disperser, which is proportional to the flow velocity, replaces the acceleration conditions for these fluids.

Generally, the higher the pressure, the smaller the particle size, but in the present invention, the pressure is 10 to 10,000 k.
It is preferably adjusted to g / cm ² , preferably 10 to 8000 kg / cm ² . 10 kg / cm ² was insufficient dispersion in the following, also wear of exceeds 10000 kg / cm ² substrate can not withstand violent long-term use. More specifically, the operating pressure differs slightly depending on the disperser used.

For example, in the case of Microfluidizer (manufactured by Microfluideck Co.), it is preferably 100 to 100.
5000 kg / cm ² , more preferably 500 to 30
It is 00 kg / cm ² . In the case of a high pressure homogenizer, it is generally possible to disperse at a slightly lower pressure. For example, in the case of a high pressure homogenizer manufactured by APV Gourin Co., preferably 50 to 3000 kg / cm ² , more preferably 100 to 2000 kg / cm ² .

The valves or disks need to be sufficiently resistant to impinge the fluid under these high pressures. Therefore, the material of the valve or the disk is an inorganic material such as a sintered metal, a metal oxide, a boride, a carbide, a ceramic such as a nitride, or a mixture thereof, which can withstand ultrahigh pressure.

The dispersion device used in the present invention is, of course,
The structure is not limited to that shown in FIGS. 1 to 5, and the structure allows the mixed solution to collide with a predetermined plane portion in the channel of the chamber under high pressure, or the mixed solution is mixed with each other in the channel of the chamber under high pressure. Basically, any structure may be used as long as it can collide. However, in order to sufficiently perform the dispersion and crushing of the present invention, the mixed solution is applied to the flat surface portion,
Alternatively, a structure in which the mixed liquids can collide with each other twice or more is preferable.

For this purpose, for example, as shown in FIG. 6, the structure is such that the flow path is connected by the connecting groove on the surfaces where the disk 3a having one hole and the disk 4a having one hole are in contact with each other. Alternatively, as shown in FIG. 7, the structure may be such that, after colliding at the center of the connecting groove of the disk 3b, it can be taken out through the hole 13 of the disk 4b. Also, as shown in FIG.
As described above, the structure may be such that after the liquid mixture collides, it further collides with the valve 10b.

Specific examples of the dispersing device used in the present invention include A.S. P. V. Examples include a high-pressure homogenizer manufactured by Gorin, a microfluidizer manufactured by Microfluidic, and a nanomizer manufactured by Cosmo Light Equipment Co., Ltd. of Japan.

Generally, the larger the number of collisions, the narrower the particle size distribution, but the upper limit of the number of collisions is determined by the manufacturing efficiency and other factors, and in particular, it is necessary to set the upper limit on the number of collisions when the mixed liquid passes through the disperser. There is no.

Water and / or an organic solvent can be used as the dispersion medium in the present invention. The former is generally called emulsion polymerization or suspension polymerization, and the latter is called dispersion polymerization. In general, when water is used as the dispersion medium, it is preferable because it is less dangerous in terms of disaster prevention and hygiene. When an organic solvent is used as the dispersion medium, it is necessary to select one that does not dissolve the urethane component, and examples thereof include aliphatic hydrocarbons which are generally nonpolar solvents.

Also, when water is used as the dispersion medium, it may be diluted with an organic solvent for the purpose of adjusting the viscosity of the urethane component in advance. As the organic solvent which can be used at that time, the urethane component is dissolved. Aromatic or aliphatic hydrocarbon, ester, ether, alcohol, or ketone solvents are suitable. However, industrially, it is particularly preferable to use water as a dispersion medium in terms of cost, equipment, safety, and the like.

Examples of the dispersion stabilizer necessary for stabilizing the dispersion of the urethane component in the dispersion medium include polyvinyl alcohol, hydroxyalkyl cellulose, carboxyalkyl cellulose, gum arabic, polyacrylate, polyacrylamide, polyvinylpyrrolidone, or ethylene maleic anhydride. One or more selected from copolymers, various commonly used nonionic, anionic or cationic surfactants, various protective colloids and the like may be used.

The urethane component in the present invention is
It refers to a mixture or reaction product containing a polyisocyanate compound as an essential component and having a functional group capable of reacting with an isocyanate group as necessary, a reaction catalyst and / or a polyamine compound, and the like. In order to further form crosslinked particles, at least one of these compounds is used.
One must have a trifunctional or higher functional reactive group.

In the present invention, of the urethane component, an organic phase comprising a polyisocyanate compound and, if necessary, a mixture of a polyhydroxy compound and a reaction catalyst,
Using the above-mentioned disperser, it is characterized in that it is finely dispersed in a dispersion medium, but if necessary, a general fluid stirrer, a high-speed rotating high-shear stirrer, a colloid mill, an ultrasonic emulsifier, etc. Mixing or coarse dispersion may be carried out, and then fine dispersion may be carried out by the disperser of the present invention.

Then, the dispersion liquid of the organic phase finely dispersed in this way and the dispersion medium is then heated as it is for curing reaction, or by the interfacial polymerization reaction method in which polyamine or the like is added to this dispersion liquid, urethane crosslinked fine particles are formed. can get. By the reaction of polyisocyanate with polyamine or water, not only urethane bond but also urea bond is generated, so that stronger particles can be obtained. At this time, the reaction temperature is 20
It is suitable to carry out in the range of -200 ° C, preferably 30-150 ° C.

As the above-mentioned polyisocyanate compound, any of the known and commonly used ones can be used. Among them, the representative ones will be described below. ,
Hexamethylene diisocyanate, 2,4-diisocyanate-1-methylcyclohexane, diisocyanate cyclobutane, tetramethylene diisocyanate,

O-, m- or p-xylylene diisocyanate, hydrogenated xylylene diisocyanate, dicyclohexylmethane diisocyanate, dimethyldicyclohexylmethane diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, dodecane diisocyanate, tetramethyl xylene diisocyanate or isophorone diisocyanate, etc.,

The aromatic isocyanates include tolylene-2,4-diisocyanate and tolylene-2,6.
-Diisocyanate, diphenylmethane-4,4'-diisocyanate, 3-methyldiphenylmethane-4,
4'-diisocyanate, m- or p-phenylene diisocyanate, chlorophenylene-2,4-diisocyanate, naphthalene-1,5-diisocyanate,

Diphenyl-4,4'-diisocyanate, 3,3'-dimethyldiphenyl-1,3,5-triisopropylbenzene-2,4-diisocyanate Carbodiimide-modified diphenylmetadiisocyanate, polyphenylpolymethylene isocyanate or diphenylether diisocyanate Isocyanate monomers such as

Further, as a modified polyisocyanate based on these various monomers, for example, an excess of isocyanate monomers alone or two or more of them is used with various dihydric alcohols, trihydric alcohols or tetrahydric or higher polyhydric alcohols. Polyurethane polyisocyanate obtained by reacting with a representative polyhydroxy compound,

Alternatively, a polyisocyanate containing an isocyanurate ring obtained by polymerizing various isocyanate monomers as listed above, or
A typical example is polyisocyanate containing a buret bond obtained by reacting with water. The number average molecular weight of these polyisocyanates is 200
Those of ˜10,000, preferably 300 to 7,000 are suitable.

On the other hand, the polyhydroxy compound, which is mixed if necessary, has the effect of compensating for the lack of internal cross-linking associated with the formation of the wall of the polymer particles and further improving the mechanical strength of the polymer particles. As the polyhydroxy compound, any of those known and commonly used can be used.

Of these, if only representative examples are given, they belong to any of the following groups. (A) ethylene glycol, propylene glycol,
1,3-propanediol, 1,4-butanediol,
1,3-butanediol, 1,5-pentanediol,
Neopentyl glycol, 1,6-hexanediol,

3-methyl-1,5-pentanediol,
1,4-bis (hydroxymethyl) cyclohexane, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylolethane,
Trimethylolpropane, 2,2,4-trimethyl-
Polyhydric alcohols such as 1,3-pentanediol, glycerin, or hexanetriol;

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

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

(D) Polyester polyols obtained by cocondensation of one or more of the various polyhydric alcohols listed above with polyhydric carboxylic acids, including succinic acid, adipic acid, sebacic acid, Azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid,

Glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanedicarboxylic acid,
Polyvalent carboxylic acids particularly represented by 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid Polyols obtained by using

(E) By polycondensation reaction of one or more of various polyhydric alcohols as listed above with various lactones such as caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone. Lactone-based polyester polyols obtained; or lactones obtained by polycondensation reaction between various polyhydric alcohols, polyvalent carboxylic acids, and various lactones listed above, respectively. Modified polyester polyols;

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

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

Of course, the polyhydroxy compounds shown in (a) to (g) may be used alone or in combination of two or more, but the number average molecular weight thereof is 2
00 to 1,000,000, preferably 300 to 50
10,000, more preferably 1000 to 100,000
A value of 0 is suitable for sufficient crosslinking inside the polymer particles.

In the present invention, when a polyhydroxy compound is used, the ratio of the isocyanate group equivalent of the polyisocyanate compound to the hydroxyl group equivalent of the polyhydroxy compound is 1: 0.05 to 1: 2.0, preferably These components are mixed by using within the range of 1: 0.1 to 1: 1.8.

The polyamine compound used in the present invention includes known and commonly used diamines, polyamine compounds,
Or a mixture thereof, but if only representative ones among them are given, 1,2
-Ethylenediamine, 1,3-propanediamine, bis (3-aminopropyl) amine, hydrazine, hydrazine-2-ethanol, bis (2-methylaminoethyl)
Methylamine,

1,4-diaminocyclohexane, 3-amino-1-methylaminopropane, N-hydroxyethylethylenediamine, N-methyl-bis (3-aminopropyl) amine, tetraethylenediamine, hexamethylenediamine, bis (N, N'-aminoethyl) -1,
2-ethylenediamine, 1-aminoethyl-1,2-ethylenediamine, diethylenetriamine, tetraethylenepentamine,

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

The reaction catalyst referred to in the present invention is a catalyst which effectively promotes the reaction between the isocyanate group and the hydroxyl group in the fine particles, and for example, cobalt naphthenate,
Zinc naphthenate, stannous chloride, stannic chloride, tetra-n
-Butyltin, tri-n-butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin acetate,
Dibutyltin dilaurate

One or more of various organometallic catalysts such as tin octenoate or potassium oleate are used in an amount of 5 to 10.000 ppm, preferably 10 to 5,000 ppm, and more preferably 10 ppm, based on the urethane component. -10
It is preferable to add it within the range of 00 ppm.

The urethane crosslinked fine particles produced according to the present invention are usually almost spherical, and the particle size is also required to be spherical. Since such particles are composed of a large number of particles having non-uniform particle diameters, it is necessary to express the composition by the average particle diameter and particle size distribution. The average particle size generally includes number average, length average, area average, and volume average,
The average particle diameter referred to in the present invention is a volume average that is usually used.

The urethane crosslinked fine particles produced by the present invention have an average particle size of 5 μm or less, and have a narrower particle size distribution, in other words, a sharp particle size distribution. As an index showing the sharpness of these particle size distributions,
Here, the shape parameter m of the Weibull distribution expressed by the following equation is used. f (t) = d / dt · F (t) = m / η (t / η) ^m-1
exp [-(t / η) ^m ] (where F (t) is the Weibull distribution, f (t) is the probability density function of the Weibull distribution, t is the particle size, η is the scale parameter, and m is the shape parameter. Represents.)

FIG. 9 shows the relationship between the probability density function of the Weibull distribution and the shape parameter m. The shape parameter m represents the shape of the distribution, and the larger the value, the narrower the distribution. Of course, it is not possible to completely represent all the particle size distributions with the Weibull distribution probability density function, so the value that is maximally approximated is used. According to the production method of the present invention, urethane crosslinked fine particles having a shape parameter value of 1.5 or more, and more specifically, having a particle size distribution of 1.5 to 3.0 are obtained.

The urethane crosslinked fine particles produced according to the present invention are used according to their respective purposes and uses, but they are fine powder-like particles obtained by a spray drying method, a centrifugal drying method, a filtration drying method or a fluidized bed drying method. Can also be obtained as It is also possible to disperse the resin in a binder resin depending on the application by a method such as flashing.

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

Among them, according to the manufacturing method of the present invention,
It is also possible to easily obtain colored fine particles containing a pigment in which fine particles are difficult to obtain. As the pigment to be included in the present invention, known and commonly used organic pigments, inorganic pigments, and extender pigments are used, but among them, only typical ones will be mentioned. Is an insoluble azo pigment such as Benzidin Yellow, Hansa Yellow, and Lake Red 4R, and a soluble azo pigment such as Lake Red C, Carmine 6B and Bordeaux 10.

Copper phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, basic dyed lakes such as rhodamine lake and methyl violet lake, acid dyed lakes such as quinoline lake and fast sky blue, and mordant dye pigments such as alizarin lake. , Anthraquinone series, thioindigo

And vat dye pigments such as perinone
Examples include quinacridone-based pigments such as Shincacia Red B, dioxazine-based pigments such as dioxazine / violet, and condensed azo-based pigments such as chromophthal.

Next, as inorganic pigments, chromates such as yellow lead, zinc chromate and molybdate orange, ferrocyan compounds such as dark blue, titanium white, zinc white, mapico yellow, iron black, red iron oxide, and chromium oxide green. Metal oxides, cadmium yellow, cadmium red and sulfide selenides such as mercury sulfide,

Sulfates such as barium sulfate and lead sulfate,
Silicates such as calcium silicate and ultramarine, carbonates such as calcium carbonate and magnesium carbonate, phosphates such as cobalt violet and manganese purple, metal powders such as aluminum powder, gold powder, silver powder and brass powder, pearl pigments, etc. Can be mentioned.

Further, as extender pigments, precipitated barium sulfate, barium carbonate, flour, gypsum, white alumina, clay,
It is also possible to use silica, silica white, talc, calcium silicate and precipitable magnesium carbonate, and also carbon black which does not belong to both an inorganic pigment and an organic pigment.

These pigments are preferably kneaded with one or more of the above-mentioned polyhydroxy compounds and used as a mill base. If necessary, the pigment may be chemically surfaced before use or during kneading. Two or more kinds of pigments may be combined for treatment or kneading, or an additive such as a dispersant and a color separation preventing agent which are known and commonly used in the fields of coating industry and printing ink industry may be used in combination.

The kneading is carried out by using a known conventional disperser such as a ball mill, a pebble mill, a sand mill, an attritor, a roll mill, a high speed impeller disperser and a high speed stone mill. The viscosity of the kneading system may be adjusted by adding an active organic solvent.

As these organic solvents, the organic solvents that can be used for the purpose of adjusting the viscosity of the urethane component described above can be used. The mill base thus obtained, a polyisocyanate compound, and optionally a polyhydroxyl compound, a reaction catalyst and an organic solvent are blended according to the desired application and uniformly mixed to form an organic phase, It is possible to obtain urethane crosslinked fine particles containing a pigment according to the production method.

Further, only the representative core substances for encapsulation referred to in the present invention other than pigments are exemplified, for example, various agricultural chemicals such as herbicides, fungicides or insecticides, or various food additives, Including pharmaceuticals, fragrances, coloring agents, coloring agents, enzymes, detergents, catalysts, rust preventives, adhesives, UV absorbers, liquid crystals, magnetic materials, conductive materials, etc. Substances in a very wide range of fields such as chemical products can be optionally included.

If necessary, an inert plasticizer,
Catalysts, paraffins, animal and vegetable oils or silicone oils that do not affect the formation of the urethane crosslinked fine particles of the present invention,
Alternatively, various synthetic resins such as xylene resins and ketone resins can be appropriately included.

For these substances, the solid one is adjusted by the same method as the pigment, and the liquid one is adjusted the viscosity of the above-mentioned urethane component such as polyhydroxy compound, polyisocyanate compound, polyamine compound or urethane component. Similarly, it can be included in the urethane crosslinked fine particles by a method of dissolving or dispersing it in an organic solvent.

The ratio of the pigment or the core substance for inclusion other than the pigment contained in the urethane crosslinked fine particles is 0.1 to 95 relative to the solid content of the urethane crosslinked fine particles.
%, Preferably 0.5 to 90% by weight.

[0079]

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

First, each raw material used will be outlined. (A): Polyisocyanate compound (A-1) "Bernock DN-901S" (manufactured by Dainippon Ink and Chemicals, Inc., isocyanurate ring-containing polyisocyanate obtained using hexamethylene diisocyanate; isocyanate group content = 23.2
%); Hereinafter, this is referred to as PI-1.

(A-2) "Barnock DN-950"
(Manufactured by Dainippon Ink and Chemicals, Inc., an adduct-type polyisocyanate obtained using hexamethylene diisocyanate; ethyl acetate solution, nonvolatile content = 75%, isocyanate group content = 12.5%); To P
I-2.

(B): Polyhydroxy compound (B-1) Hydroxyl value of 16 obtained by polycondensation reaction of trimethylolpropane and ε-caprolactone
A polycaprolactone polyester triol of 8.5; hereinafter referred to as PO-1.

(B-2) Hydroxyl value of 5 obtained by polycondensation reaction of 1,4-butanediol and adipic acid
A polyester diol of 6.0; hereinafter referred to as PO-
Set to 2.

(B-3) 32.6 parts of PO-1 and 6.9 parts of "Fastgen Blue FGF" (blue pigment manufactured by Dainippon Ink and Chemicals, Inc.) were kneaded with a triple roll. Blue Mill Base; hereinafter referred to as PO-3.

(C): Polyamine compound Ethylenediamine; hereinafter abbreviated as EDA.

(Example 1) In a 1,000 ml flask,
0.2 part of "PVA-420K" (partially saponified polyvinyl alcohol manufactured by Kuraray Co., Ltd.) was added to 399.
An aqueous phase dissolved in 8 parts of water was prepared. In another container, PI
68.5 parts of -1 and 31.5 parts of PO-1 were mixed to obtain an organic phase.

After mixing the aqueous phase and the organic phase with a glass rod, the mixture is an emulsifying machine having a chamber connected to a disk having an inner diameter of 100 μm, a microfluidizer (manufactured by Microfluideck). Inject the mixture with a compressor into the nozzle, and apply 300 Kg /
Dispersed at a pressure of cm ² .

Then, this dispersion was transferred to another flask and stirred with a paddler type stirring blade to obtain EDA.
Was charged with 5.7 parts of a 50% aqueous solution. 2 hours at room temperature
After the temperature was maintained, the temperature was raised to 50 ° C. and the reaction was continued at the same temperature for 1 hour and at 80 ° C. for 2 hours to obtain a target suspension of urethane crosslinked fine particles.

The obtained suspension was passed through a 200-mesh sieve for the purpose of removing defective particles, and 0.4% remained on the sieve without passing through the sieve. In addition, the particle size distribution of the particles that have passed through the sieve is measured by a laser analysis particle size distribution meter (trade name;
SK Laser Micron Sizer, manufactured by Seishin Enterprise Co., Ltd.), the average particle size was 1.8 μm,
The shape parameter when applied to the Weibull distribution was 1.7. FIG. 10 shows a particle size distribution chart of the urethane crosslinked fine particles obtained.

Example 2 A target suspension of urethane crosslinked fine particles was obtained in the same manner as in Example 1 except that the formulation was changed as described below. That is, as the aqueous phase, 1 part of "PVA205" (partially saponified polyvinyl alcohol manufactured by Kuraray Co., Ltd.) and 399 of water, respectively.
The same operation as in Example 1 was performed except that the parts were used.

The obtained suspension was passed through a 200-mesh sieve, and 0.1% remained on the sieve without passing through the sieve. The average particle size of the particles that passed through was 1.6 μm,
The shape parameter when applied to the Weibull distribution was 2.0. FIG. 11 shows a particle size distribution chart of the obtained urethane crosslinked fine particles.

Example 3 An intended suspension of urethane crosslinked fine particles was obtained in the same manner as in Example 1 except that the formulation was changed as described below. That is, as the organic phase, PI
-27.3 parts and 42.7 parts of PO-2 were mixed and it was set as the organic phase, and the same operation as Example 1 was performed.

When the obtained suspension was passed through a 200-mesh sieve, 0.3% did not pass through the sieve and remained on the sieve. The average particle size of the particles that have passed is 1.0 μm,
The shape parameter when applied to the Weibull distribution was 1.9. FIG. 12 shows a particle size distribution chart of the obtained urethane crosslinked fine particles.

Example 4 An intended suspension of urethane crosslinked fine particles was obtained in the same manner as in Example 1 except that the formulation was changed as described below. That is, the same operation as in Example 1 was performed except that a high pressure homogenizer (Model 15MR manufactured by APV Gorin Co., Ltd.) was used as a disperser and the dispersion was performed at a pressure of 500 Kg / cm ² .

When the obtained suspension was passed through a 200-mesh sieve, 0.2% remained on the sieve without passing through the sieve. The average particle size of the particles that passed through was 1.7 μm, and the shape parameter when applied to the Weibull distribution was 1.7. FIG. 13 shows a particle size distribution chart of the obtained urethane crosslinked fine particles.

Example 5 An intended suspension of urethane crosslinked fine particles was obtained in the same manner as in Example 1 except that the formulation was changed as described below. That is, PI-1 as the organic phase
Was mixed with 69.5 parts of PO-3 and 39.5 parts of PO-3 to form an organic phase, and 4 parts of a 50% aqueous solution of EDA was used, and the same operation as in Example 1 was performed.

The obtained suspension was passed through a 200-mesh sieve, and 0.1% remained on the sieve without passing through the sieve. The average particle diameter of the particles that passed through was 1.5 μm, and the shape parameter when applied to the Weibull distribution was 1.9. FIG. 14 shows a particle size distribution chart of the obtained urethane crosslinked fine particles.

Example 6 A target suspension of urethane crosslinked fine particles was obtained in the same manner as in Example 1 except that the formulation was changed as described below. That is, PI-1 as the organic phase
Was mixed with 39.5 parts of PO-3 to form an organic phase, and a high-pressure homogenizer was used as a disperser.
The same operation as in Example 1 was carried out except that the dispersion was carried out at a pressure of 00 Kg / cm ² and 4 parts of a 50% aqueous solution of EDA was used.

When the obtained suspension was passed through a 200-mesh sieve, 0.2% remained on the sieve without passing through the sieve. The average particle size of the particles that passed through was 1.4 μm, and the shape parameter when applied to the Weibull distribution was 1.9. FIG. 15 shows a particle size distribution chart of the obtained urethane crosslinked fine particles.

Comparative Example 1 An intended suspension of urethane crosslinked fine particles was obtained in the same manner as in Example 1 except that the formulation was changed as described below. That is, using a homomixer as a disperser, while stirring the aqueous phase at 7,000 to 7,500 rpm, the organic phase prepared in advance was charged.
Stirring for a minute gave a dispersion.

The obtained suspension was passed through a 200-mesh sieve, and 12.9% remained on the sieve without passing through the sieve. The average particle size of the particles that passed through was 25.6μ.
m, the shape parameter when applied to the Weibull distribution was 1.0. FIG. 16 shows a particle size distribution chart of the obtained urethane crosslinked fine particles.

(Comparative Example 2) By the same dispersion method as in Comparative Example 1, the other formulation was carried out in the same manner as in Example 2 to obtain the desired urethane crosslinked fine particles. When passed through a 200-mesh screen, 0.8% did not pass through the screen and remained on the screen. The average particle size of the particles that passed through was 12.0μ.
m, the shape parameter when applied to the Weibull distribution was 1.0. FIG. 17 shows a particle size distribution chart of the obtained urethane crosslinked fine particles.

(Comparative Example 3) By the same dispersion method as in Comparative Example 1, the other formulation was carried out in the same manner as in Example 3 to obtain the desired urethane crosslinked fine particles. When passed through a 200-mesh screen, 15.8% did not pass through the screen and remained on the screen. The average particle size of the particles that have passed is 20.8 μm,
The shape parameter when applied to the Weibull distribution was 0.9. FIG. 18 shows a particle size distribution chart of the obtained urethane crosslinked fine particles.

(Comparative Example 4) By the same dispersion method as in Comparative Example 1, the other formulation was carried out in the same manner as in Example 5 to obtain the desired urethane crosslinked fine particles. When passed through a 200-mesh screen, 15.8% did not pass through the screen and remained on the screen. The average particle size of the particles that passed through was 33.4 μm,
The shape parameter when applied to the Weibull distribution was 1.0. FIG. 19 shows a particle size distribution chart of the obtained urethane crosslinked fine particles.

As is clear from the above results, in the production method of the present invention, even under the same compounding conditions, the average particle size is very small, and the value of the shape parameter when the particle size distribution is applied to the Weibull distribution is A large and narrow distribution is obtained. Furthermore,
The same is true for a system containing a pigment, and the amount of defective particles produced is small, which is known to be an excellent method for producing particles.

[0106]

INDUSTRIAL APPLICABILITY The present invention has an average particle size of 5 microns or less and a narrow particle size distribution, and is useful for various applications such as paints and printing inks. An excellent production method capable of efficiently producing crosslinked fine particles can be provided.

[0107]

[Brief description of drawings]

FIG. 1 is an exploded perspective view of a chamber of a dispersion device used in the present invention.

FIG. 2 is a cross-sectional view of a chamber of a dispersion device used in the present invention.

FIG. 3 is an assembled perspective view of a disk of a chamber of a dispersion device used in the present invention.

FIG. 4 is a cross-sectional view of a chamber of a dispersion device used in the present invention.

FIG. 5 is a sectional view of a chamber of a dispersion device used in the present invention.

FIG. 6 is an assembled perspective view of a disk of a chamber of a dispersion device used in the present invention.

FIG. 7 is an assembled perspective view of a disk of a chamber of a dispersion device used in the present invention.

FIG. 8 is a sectional view of a chamber of a dispersion device used in the present invention.

FIG. 9 is a diagram showing a relationship between a shape parameter of a probability density function equation of a Weibull distribution and a Weibull probability distribution.

FIG. 10 shows a particle size distribution chart of the urethane crosslinked fine particles obtained in Example 1.

FIG. 11 shows a particle size distribution chart of the urethane crosslinked fine particles obtained in Example 2.

FIG. 12 shows a particle size distribution chart of the urethane crosslinked fine particles obtained in Example 3.

FIG. 13 shows a particle size distribution chart of the urethane crosslinked fine particles obtained in Example 4.

FIG. 14 shows a particle size distribution chart of the urethane crosslinked fine particles obtained in Example 5.

FIG. 15 shows a particle size distribution chart of the urethane crosslinked fine particles obtained in Example 6.

16 shows a particle size distribution chart of the urethane crosslinked fine particles obtained in Comparative Example 1. FIG.

FIG. 17 shows a particle size distribution chart of the urethane crosslinked fine particles obtained in Comparative Example 2.

FIG. 18 shows a particle size distribution chart of the urethane crosslinked fine particles obtained in Comparative Example 3.

FIG. 19 shows a particle size distribution chart of the urethane crosslinked fine particles obtained in Comparative Example 4.

[Explanation of symbols]

 1, 2: Suppression part 3, 3a, 3b, 4, 4a, 4b: Disc 5, 6: Flat part of disc 7: Disc connecting groove 8: Central portion of connecting groove 9: Disc connecting groove 10, 10a, 10b: valve 11: valve seat 12: handle 13: disc hole

Claims (9)

[Claims] 1. A high-speed liquid mixture of a urethane component and a dispersion medium.
After the mixed liquid is dispersed, the liquid mixture is dispersed by colliding the liquid mixture of the urethane component and the dispersion medium with each other in the flow passage under high pressure or at high speed under pressure, or by curing. A method for producing urethane crosslinked fine particles, which comprises forming crosslinked particles by a reaction. 2. A high speed mixed liquid of a urethane component and a dispersion medium
The method for producing crosslinked urethane fine particles according to claim 1, wherein the crosslinked particles are formed by a curing reaction after the mixed liquid is dispersed by colliding with a flat surface portion in the flow path under pressure. 3. A mixed solution of a urethane component and a dispersion medium at high speed
After being made to collide with a flat portion in the flow channel under pressure, the mixed liquid is further collided in the flow channel to disperse the mixed liquid, and then crosslinked particles are formed by a curing reaction. The method for producing urethane crosslinked fine particles according to claim 1. 4. The method for producing urethane crosslinked fine particles according to any one of claims 1 to 3, wherein the urethane crosslinked fine particles are polyurethane polyurea particles. 5. The urethane crosslinked fine particles have an average particle diameter of 5 μm or less and a shape parameter of the Weibull distribution of 1.5 or more, according to any one of claims 1 to 3. Method for producing urethane crosslinked fine particles. 6. The urethane crosslinked fine particles according to any one of claims 1 to 3, wherein the urethane crosslinked fine particles are urethane crosslinked fine particles colored by incorporating a pigment into the crosslinked particles. Method. 7. A dispersion device having a structure capable of causing collision of a mixed liquid of a urethane component and a dispersion medium with a flat surface portion in a flow channel or collision of the mixed liquids in the flow channel two or more times is used. The method for producing urethane crosslinked fine particles according to any one of claims 1 to 3, which is characterized in that. 8. The method for producing urethane crosslinked fine particles according to claim 7, wherein the pressure when the mixed liquid passes through the flow path in the dispersion device is 10 to 10,000 kg / cm ² . 9. The method for producing urethane crosslinked fine particles according to any one of claims 1 to 3, wherein the dispersion medium is water.