JPH04345614A - Crosslinked polyurethanepolyurea particle - Google Patents

Abstract

PURPOSE:To obtain the title particles which are tough, excellent in solvent resistance, flow and handleability in packaging, storage, etc., and lowly agglomerate by selecting crosslinked polyurethanepolyurea particles each of which contains a specified compound in its inside. CONSTITUTION:Crosslinked polyurethanepolyurea particles each of which contains a finely divided inorganic compound, desirably sparingly water-soluble one, more desirably one selected between finely divided silica and finely divided aluminum oxide in its inside are selected.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention provides novel and useful
The present invention relates to crosslinked polyurethane polyurea particles containing a finely powdered inorganic compound inside the particles. More specifically, the present invention provides a method for obtaining particles through both a urethanization reaction and a ureaization reaction, respectively, in the particle formation step using the essential three components of a polyisocyanate compound, a polyhydroxy compound, and a polyamine compound. The present invention relates to crosslinked polyurethane polyurea particles which contain a finely powdered inorganic compound inside the particles, have excellent agglomeration resistance among particles, and have extremely excellent particle fluidity.

0002

[Prior Art] A so-called interfacial polymerization method in which microparticles are formed by dispersing a hydrophobic substance in an aqueous medium and growing an organic polymer substance (polymer compound) at the interface of the dispersed droplets. is already well known.

Many of them involve dispersing isocyanate prepolymers with isocyanate end groups in water;
Next, a polyamine or the like is added to the thus obtained dispersion to form stable polyurethane polyurea particles.

By the way, a feature of such an interfacial polymerization reaction is that the material forming the outer wall of the particles is supplied only from the outside of the particles, but this feature is also a drawback of this type of interfacial polymerization reaction.

That is, according to the conventional technology, the formation of the outer wall of the particle is a urea reaction between amines and isocyanates, and once the outer wall is formed by this urea reaction, the inside of the particle is formed. The remaining isocyanate groups are separated from the amino groups in the water by this formed outer wall, and further reactions can no longer proceed easily, thus preventing further growth of the outer wall. As a result, the migration of the amine in water into the particles is significantly slowed down, and as a result, the reaction reaches an apparent saturation state, leaving unreacted isocyanate groups inside the particles. It happens.

As a result, there are also problems in that the reproducibility of basic particle properties deteriorates and resources are wasted in the form of retention or accumulation of unreacted substances.

On the other hand, polyurethane polyurea particles obtained by such an interfacial polymerization reaction are generally used in a wide variety of fields due to their excellent mechanical properties and chemical resistance. dry the particles;
When used in the form of a fine powder, the dry particles tend to aggregate together due to static electricity, resulting in decreased fluidity as a powder, and in extreme cases, it may become cake-like.

[0008] Therefore, handling of such particles, such as classification, transportation, packaging, and storage, is always accompanied by difficulties.

[0009] As a method for preventing such agglomeration of particles, a fluidity improver such as finely powdered silica is mixed with the powder.
Although a method of improving the fluidity of particles is generally adopted, although this method certainly improves the fluidity of particles, it is difficult to mix the particles with fine powder silica. Further steps are required, and further homogeneous mixing usually causes unevenness in particle fluidity due to localization of fine powder silica, resulting in poor reproducibility of basic particle characteristics. The problem is that it gets worse.

0010

[Problems to be Solved by the Invention] However, in view of the various drawbacks in the prior art as described above, the present inventors have decided to add the polyurethane polyurea crosslinked particles to the polyurethane polyurea crosslinked particles rather than just physically adding them to the polyurethane polyurea crosslinked particles. If so-called immobilization can be achieved inside the urea cross-linked particles, the step of mixing the polyurethane polyurea particles and the so-called fluidity improver becomes unnecessary, and therefore, complicated operations such as such a mixing step can be avoided. In search of extremely useful polyurethane polyurea crosslinked particles, which will free up the flow of particles, and in particular will not cause problems such as uneven particle fluidity and worsening of the reproducibility of basic particle properties, we have worked hard to find , started research.

[0011] Therefore, the problem to be solved by the present invention is to provide a method that is free from complicated operations such as a mixing process, has uniform fluidity of particles, and has excellent reproducibility of basic particle characteristics. It is an object of the present invention to provide extremely useful polyurethane polyurea crosslinked particles that do not cause the problem of deterioration.

0012

[Means for solving the problem] Therefore, the present inventors
As a result of intensive studies aimed at the problems to be solved by the invention as described above, it has been found that the outer and inner walls of the particles are sufficiently formed, and in particular, the agglomeration resistance of the particles is improved. Having discovered that it is possible to obtain crosslinked polyurethane polyurea particles having a finely powdered inorganic compound immobilized inside the particles and having extremely excellent particle fluidity, the present invention has been completed. Ta.

That is, the present invention, as a means to solve these problems, firstly involves mixing a polyisocyanate compound with a stoichiometric excess of isocyanate groups and a polyhydroxy compound; Moreover, the interfacial polymerization reaction between the organic phase, which can form a three-dimensional crosslinked structure through reaction, and the polyamine, which is less than the equivalent amount of the stoichiometrically excess isocyanate groups, and the urethanization reaction inside the particles are prevented. By carrying out this process, the desired form of a finely powdered inorganic compound immobilized inside the particles can be obtained, which has particularly excellent agglomeration resistance between the particles, and
The present invention aims to provide crosslinked polyurethane polyurea particles that have extremely excellent particle fluidity.

[0014] Here, only representative examples of the above-mentioned fine powder inorganic compounds are listed.
aSO4, CaSO4, BaCO3, CaCO3, Mg
various inorganic salts such as CO3 or Ca3(PO4)2; various inorganic polymers such as talc, bentonite, silica, alumina, diatomaceous earth or clay; or powders of metals or metal oxides, which may be used alone. Of course, they may be used or two or more types may be used in combination.

When selecting the fine powder inorganic compound, considering the agglomeration resistance of the particles and the so-called matting effect when the particles are used as a matting agent for paint, it is necessary to select the above-mentioned various inorganic compounds. Among the compounds, there are compounds that are poorly soluble in water, especially hydrophobic silica (SiO2) and alumina (
The use of inorganic polymers such as Al2O3 is recommended.

The amount of the compound to be used is 0.1 to 20% based on the constituent components of the polyurethane polyurea crosslinked particles.
Within the range of 1% to 10% by weight, preferably within the range of 1 to 10% by weight, and by immobilizing it inside the particles within this range, extremely excellent agglomeration resistance and extremely excellent fluidity of the particles can be achieved. The objective polyurethane polyurea crosslinked particles having the following properties are obtained.

[0017] If the content of the finely powdered inorganic compound inside the particles is less than 0.1% by weight, it will inevitably be impossible to improve the agglomeration resistance and the fluidity of the particles. If it exceeds 20% by weight, the elasticity and toughness of the particles, which are characteristics of polyurethane polyurea, inevitably decrease, and the particles tend to become brittle, which is not preferable in any case.

Next, as the above-mentioned polyisocyanate compound, any of those known per se can be used, but among them, only the most representative ones are exemplified. Isocyanate, hydrogenated tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hydrogenated diphenylmethane-4,4'-diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, cyclohexyl-1,4-disocyanate, isophorone diisocyanate 1 , 4-tetramethylene diisocyanate, 1,
6-hexamethylene diisocyanate, naphthalene-1
, 5-diisocyanate, p-phenylene diisocyanate, dibenzyl diisocyanate, diphenyl ether diisocyanate, m- or p-tetramethylxylene diisocyanate or triphenylmethane triisocyanate. Monomers, etc.

Various modified polyisocyanates such as trifunctional or higher functional polyisocyanurate type polyisocyanates or billet type polyisocyanates based on these various monomers; or various monomers and modified polyisocyanates as listed above; A urethane containing a terminal isocyanate group obtained by urethanizing one or more of the following and one or more of various polyhydroxy compounds such as polyhydric alcohol, polyester polyol, polycarbonate polyol, polybutadiene polyol or polypentadiene polyol. These include modified polyisocyanate prepolymers, and these may be used alone or in combination of two or more.

In order for the resulting polyurethane polyurea crosslinked particles (hereinafter also referred to as polymer particles) to have particularly excellent toughness, the number average molecular weight of the polyisocyanate compound should be 200 to 10. ,000
The appropriate range is preferably 300 to 7,000, more preferably 500 to 5,000.

When designing the polyisocyanate compound, the type of isocyanate monomer units should be limited to aliphatic and/or alicyclic types when weather resistance etc. are taken into consideration, and such usage is recommended. be done.

On the other hand, the polyhydroxy compound, which is an essential component constituting the organic phase together with the polyisocyanate compound, compensates for the lack of internal crosslinking accompanying the formation of the walls of the polymer particles, and also improves the mechanical properties of the polymer particles. This polyhydroxy compound is an extremely important component for further improving the strength, and any known polyhydroxy compound can be used.

Among them, to exemplify only the most representative ones, they belong to one of the following groups.

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

0
b) Various polyols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol. Ether glycols;

c) Various polyhydric alcohols as listed above and various (cyclic ) Modified polyether polyols obtained by ring-opening polymerization with an ether bond-containing compound;

d) Polyester polyols obtained by co-condensation of one or more of the various polyhydric alcohols listed above with polyhydric carboxylic acids, including succinic acid, adipic acid, sebacic acid, azelaic acid, etc. Acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,
4-cyclohexanehycarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid or 2
, 5,7-naphthalenetricarboxylic acid and the like, polyols obtained using polyhydric carboxylic acids;

e) by polycondensation reaction of one or more of the various polyhydric alcohols as listed above and various lactones such as -caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone. Obtained lactone-based polyester polyols;

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

003
0] f) Bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and/or polyhydric alcohols, or
Epoxy-modified polyester polyols obtained by using one or more of various epoxy compounds such as glycidyl esters of monobasic acids and/or polybasic acids in combination during the synthesis of polyester polys;

Furthermore, g) polyester polyamide polyols, polycarbonate polyols, polybutadiene polyols, polypentadiene polyols, castor oil, castor oil derivatives,
Examples include hydrogenated castor oil, hydrogenated castor oil derivatives, hydroxyl group-containing acrylic copolymers, hydroxyl group-containing fluorine-containing compounds, and hydroxyl group-containing silicone resins.

It goes without saying that the polyhydroxy compounds shown in (a) to (g) may be used alone or in combination of two or more types, but their number average molecular weight is 2 or more.
00-10,000, preferably 300-7,000
, more preferably within the range of 500 to 5,000, which is also suitable for sufficient crosslinking inside the polymer particles.

[0033] In order to obtain tough polymer particles, it is desirable to use polyester polyols, especially
-caprolactone, δ-valerolactone or 3-
It is desirable to use lactone-based polyester polyols obtained by polycondensation reaction with lactones such as methyl-delta-valerolactone.

In the present invention, the ratio of the isocyanate group equivalent of the polyisocyanate compound to the hydroxyl group equivalent of the polyhydroxy compound is 1:0.1 to 1:0.
．． 9. Mix these two components preferably in a range of 1:0.1 to 1:0.8, more preferably 1:0.2 to 1:0.7, and It is important that the composition is such that the mixture itself can be three-dimensionally crosslinked.

That is, if such a mixture is to be completely converted into urethane, it is necessary to formulate the mixture in such a way that it becomes gel-like and fluidity can no longer be obtained even by heating or diluting the true solvent.

The above two conditions in designing the hydrophobic organic phase described above are essential for obtaining an internal crosslinked state that cannot be obtained only by interfacial polymerization reaction by adding polyamines, which will be described later. This is a basic requirement.

At this time, in order to carry out the interfacial polymerization reaction smoothly, it is necessary to have an excess of isocyanate groups in the above range, and this range is designed so that the outer wall of the particles can be formed quickly.

Furthermore, in the present invention, by allowing the urethanization reaction between the polyisocyanate compound and the polyhydroxy compound to proceed three-dimensionally within the particles,
Relying on conventional technology, it would be impossible to achieve this goal.
Efforts are being made to improve the toughness and solvent resistance of the entire particle.

[0039] Due to the design of the three-dimensional urethanization reaction inside the particles, a trifunctional or higher functional polyisocyanate compound and/or a polyhydroxy compound is added to the total amount of the polyisocyanate compound and polyhydroxy compound contained in the organic phase. In it, 0.1 mol% or more, preferably 0.2
By containing it in an amount of mol % or more, more preferably 0.3 mol % or more, a good three-dimensional crosslinked state inside the particles can be obtained.

[0040] As the isocyanate groups of the polyisocyanate compound in the organic phase are consumed as the interfacial polymerization reaction with the polyamine compound described below progresses, the equivalent ratio of isocyanate groups to hydroxyl groups in the particles approaches. The crosslinking density inside the particles increases as the urethanization reaction progresses, and various properties such as toughness and durability of the crosslinked polyurethane polyurea particles of the present invention are further improved.

The organic phase mixed based on such a design concept is finely dispersed in an aqueous phase, and the amount of polyamine is 0.2 to 1. 0 equivalent, preferably 0.3 to 1.0 equivalent, more preferably 0.4 to 0.9 equivalent, to perform the urea reaction at the particle interface, and also to perform the urethane reaction inside the particle. As a result, extremely tough polyurethane polyurea crosslinked particles can be obtained.

[0042] Examples of the polyamines suitably used in the present invention include well-known and commonly used diamines, polyamines, and mixtures thereof, among which only the most representative ones are mentioned. ,1
, 2-ethylenediamine, 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,
Tolylene diamine, 2,4,6-triaminotoluene hydrochloride, 1,3,6-triaminonaphthalene, isophorone diamine, xylylene diamine, hydrogenated xylylene diamine, 4,4'-diaminodiphenylmethane or hydrogenated 4,4'-diaminodiphenylmethane or various derivatives of these polyamine monomers listed above.

In the present invention, the hydrophobic organic phase dispersed in water is non-reactive, and the hydrophobic organic solvent is
If necessary, it can be added to lower the viscosity and improve the dispersibility in the aqueous phase.

In this case, the appropriate amount of the organic solvent used is 50% by weight or less, preferably 30% by weight or less, based on the total organic phase.

Suitable organic solvents are aromatic or aliphatic hydrocarbons, esters, ethers, or ketones, particularly benzene, toluene, xylene, cyclohexane, methylcyclohexane, diphenyl ether, and minerals. Spirit etc. are suitable.

These organic solvents may be distilled off by heating, reduced pressure, or the like during or after particle formation, if necessary.

Next, when dispersing the organic phase thus prepared in the aqueous phase, the polyurethane polyurea crosslinked particles of the present invention are obtained using a polyisocyanate compound, so the operation is extremely simple. So,
Although it is possible to obtain polymer particles,

0
To further stabilize the dispersion, various protective colloids such as polyvinyl alcohol, hydroxyalkylcellulose, carboxyalkylcellulose, gum arabic, polyacrylate, polyacrylamide, polyvinylpyrrolidone or ethylene-maleic anhydride copolymer are added. One or more selected from
．． 1 to 20% by weight, preferably 0.2 to 20% by weight
It is appropriate to use within a range of 20% by weight.

The aqueous phase also contains 0.1 to 10% by weight, preferably 0.2 to 20% by weight of various known and commonly used nonionic, anionic or cationic surfactants. There is absolutely no problem even if it is contained.

In the present invention, inside the particle,
The urethanization reaction between a hydroxyl group and an isocyanate group is particularly effective when the isocyanate group is an aliphatic or alicyclic group. In the case of a urea reaction with an amino group, the reaction rate tends to be lower than that of a urea reaction with an amino group.

As is well known, the reactivity of water with isocyanate groups is extremely small compared to the reactivity of water with hydroxyl groups, and due to the isolation effect of the outer wall formed by the addition of polyamines, moisture is trapped inside the particles. Of course, the purpose of the present invention is to carry out the urethanization reaction in the particles by increasing the reaction temperature and taking a long time, while the penetration into the isocyanate is negligible. In order to very effectively promote the reaction between the group and the hydroxyl group,

Cobalt naphthenate, zinc naphthenate, stannous chloride, stannic chloride, tetra-n-butyltin, tri-
One or two of various organometallic catalysts such as n-butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin acetate, dibutyltin dilaurate, tin octenoate or potassium oleate. more than seeds,

0054
] It is desirable to add the organometallic catalyst in an amount of 5 to 10,000 ppm, preferably 10 to 5,000 ppm, based on the hydrophobic organic phase. can be formed.

In other words, these organometallic catalysts extremely effectively promote the reaction between isocyanate groups and hydroxyl groups.

[0056] As a method for adding the above catalyst, water dispersion (
be added to the organic phase prior to fine dispersion) or
Alternatively, it is most appropriate to carry out the process between the step of dispersing the organic phase in water and the step of adding the polyamines.

[0057] When the catalyst is added after polyamines are added, the catalyst becomes difficult to be incorporated into the particles due to the state in which the outer wall of the particles is being formed, and as a result, the ability to promote the urethanization reaction inside the particles is reduced. It is not desirable because it tends to decrease.

As detailed above, as long as the basic requirements of the present invention are satisfied, it is possible to use an extremely simple method, especially,
It is possible to obtain crosslinked polyurethane polyurea particles that have excellent agglomeration resistance and extremely good particle fluidity, but the use of resins constituting the organic phase, protective colloids and/or surfactants in the dispersion process The particle diameter of crosslinked polyurethane polyurea particles can be freely designed and adjusted by appropriately selecting the types and amounts used, as well as various conditions such as stirring speed and reaction temperature in the dispersion process. can.

The average particle diameter of the crosslinked polyurethane polyurea particles of the present invention is usually 0.1 to 500 microns (μm).
Although the standard of the particle size varies depending on the application, particles within the range of 1 to 300 μm are particularly preferable because they are excellent in various performances such as mechanical properties.

The polyurethane polyurea crosslinked particles of the present invention contain and immobilize various finely powdered inorganic compounds as described above within a range of 0.2 to 20% by weight inside the particles. However, if necessary, the polyurethane polyurea crosslinked particles of the present invention may contain various materials as a core material.

[0061] Such a core substance for encapsulation is made to exist in a hydrophobic organic phase and incorporated into the particle, but the range and type of such core substance are not particularly limited and can be used over a wide range. It extends to.

[0062] To cite only typical examples of the core material for inner packaging, it can be used for various drugs or medicines such as herbicides, fungicides, and insecticides, as well as fragrances,
These include colorants, coloring agents, enzymes, detergents, catalysts, rust preventives, adhesives, chemical products, and foods.

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

The preparation of the crosslinked polyurethane polyurea particles of the present invention is generally carried out as follows. (a) First, the step of dispersing the aqueous phase in the organic phase is 1.
It is preferable to carry out the reaction at around room temperature of 0 to 35° C. from the viewpoint of stabilizing the dispersion system.

Such dispersion of the organic phase into the aqueous phase can be easily carried out using a dispersing means such as a homogenizer, a homodisper, or a propeller-type general-purpose stirrer, or by conventional operations.

(b) In many cases, after the above-mentioned dispersion step is completed, it is more preferable to use a propeller-type stirrer to gently stir the dispersion system in order to form the particles into spheres.

(c) To the mildly stirred dispersion, before and after adding the polyamines, especially before adding the above-mentioned organometallic catalyst for the urethanization reaction, such as dibutyltin dilaurate, it is completely added. 5-10,0 of the organic phase
It is added in an amount within the range of 0.00 ppm.

(d) Then, to such dispersion, 10
The polyamines are added at a temperature of ~35°C, preferably diluted with water to give an active ingredient content of 5 to 70%.

(e) After several tens of minutes to several hours, the reaction temperature is increased to 40 to 95°C, preferably 50 to 95°C.
By raising the temperature to 90°C and keeping it at that temperature for 1 to several hours, crosslinked polyurethane polyurea particles having a particle size in the range of 0.1 to 500 ppm can be obtained. .

(f) The polymer particles thus obtained can be used depending on the purpose and use, but they can be made into a fine powder by spray drying, centrifugal drying, filtration drying, or fluidized bed drying. It can also be used.

[0071] Thus, in the particle formation step using the essential three components of a polyisocyanate compound, a polyhydroxy compound, and a polyamine compound, the particles can be obtained through both the urethanization reaction and the urea formation reaction, respectively. Polyurethane polyurea crosslinked particles containing a finely powdered inorganic compound inside the particles and having excellent agglomeration resistance among particles and extremely excellent particle fluidity can be obtained.

[0072]

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, Comparative Examples, Applied Examples, and Comparative Applied Examples. In the following, all parts and percentages are based on weight unless otherwise specified.

First, each raw material used will be outlined. (A): Polyisocyanate compound■ "Burnock DN-950" [hexamethylene diisocyanate adduct type polyisocyanate manufactured by Dainippon Ink & Chemicals Co., Ltd.; solid content equivalent isocyanate group content = 16.8%]; , this is PI-1
shall be.

■ "Burnock DN-980S" manufactured by the same company, isocyanurate ring-containing polyisocyanate obtained using hexamethylene diisocyanate; solid content equivalent isocyanate group content = 21.0%];
This will be referred to as PI-2.

■ 1,000 parts of a polycaprolactone polyester triol having a hydroxyl value of 168.5, obtained by the polycondensation reaction of trimethylolpropane and ε-caprolactone, and 666 parts of isophorone diisocyanate were subjected to a urethane reaction. The obtained polyisocyanate resin has an isocyanate group concentration of 7.5%; hereinafter, this will be referred to as PI-3.

(B): Polyhydroxy compound ■ Polycaprolactone polyester diol with a hydroxyl value of 187, obtained by the polycondensation reaction of neopentyl glycol and ε-caprolactone; hereinafter referred to as PO-1
shall be.

(1) A polycaprolactone polyester triol having a hydroxyl value of 168.5 obtained by the polycondensation reaction of trimethylolpropane and ε-caprolactone; hereinafter, this will be referred to as PO-2.

(1) A polycaprolactone polyester triol having a hydroxyl value of 112.2 obtained by the polycondensation reaction of trimethylolpropane and ε-caprolactone; hereinafter, this will be referred to as PO-3.

(C): Polyamine compound (1) Ethylenediamine; hereinafter abbreviated as EDA. ■ Isophorone diamine; hereinafter abbreviated as IPDA.

Example 1 In a 1,000 ml flask, add “Fuji Chemi HEC A
An aqueous phase was prepared by dissolving 19 parts of "L-15F" (hydroxycellulose manufactured by Fuji Chemical Co., Ltd.) in 356 parts of water.

In a separate container, 19.6 parts of PI-1 and P
54.9 parts of I-2, 23.5 parts of PO-1, 2 parts of "AEROSIL R-972" [hydrophobic fine powder silica manufactured by Nippon Aerosil Co., Ltd.], and toluene. 25 parts of the organic phase was mixed to form an organic phase.

[0082] At 20°C, using a homomixer,
While stirring the aqueous phase at 7,000-7,500 rpm,
The organic phase prepared in advance was charged into this and stirred for 1 minute to obtain a dispersion.

Next, this dispersion was transferred to another flask, and while stirring at 200 rpm using a paddler-type stirring blade, 0.0% of dibutyltin dilaurate (DBTDL) was added.
1 part was added, and after 2 minutes, an additional 5.8 parts of a 50% aqueous solution of EDA were charged.

After being kept at room temperature (approximately 25°C) for 2 hours, 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 infiltrate the target particles inside the particles. A suspension of crosslinked polyurethane polyurea particles on which a finely powdered inorganic compound was fixed was obtained. The average particle diameter of this product was 25 μm. Example 2 A suspension of crosslinked polyurethane polyurea particles having a finely powdered inorganic compound fixed inside the particles was obtained in the same manner as in Example 1, except for changing the formulation as shown below.

[0085] That is, as the aqueous phase, "P
9 parts of "VA-205" [partially saponified polyvinyl alcohol manufactured by Kuraray Co., Ltd.], 10 parts of "PVA-217" (same as above) and 356 parts of water were used, while as the organic phase, 29.2 parts of PI-1, 28.0 parts of PI-3, 41.8 parts of PO-3 and 2 parts of toluene.
In addition, as the finely powdered inorganic compound, "Aluminum Oxide" was used.
e) 2 parts of "C" [fine powder aluminum oxide manufactured by Nippon Aerosil Co., Ltd.], 0.18 parts of DBTDL as a urethanization catalyst, and 25% of EDA as a polyamine. By using 6.9 parts of the aqueous solution, a fully crosslinked suspension of polymer particles was obtained. The average particle diameter of this product was 23 μm. Example 3 A suspension of crosslinked polyurethane polyurea particles having a finely powdered inorganic compound fixed inside the particles was obtained in the same manner as in Example 1, except for changing the formulation as shown below.

[0086] That is, as the aqueous phase, "P
9 parts of ``VA-205'', 10 parts of ``PVA-217'' and 273 parts of water were used, while as the organic phase, 17.4 parts of PI-1 and 32.3 parts of PI-2 were used, respectively. ,
Using 46.3 parts of PO-2 and 25 parts of toluene,
In addition, 4 of "AEROSIL R-200" (same as above)
Furthermore, as the urethanization catalyst, 0.18 parts of DBTDL was used, and as the polyamine, IP
By using 24.9 parts of a 30% aqueous solution of DA,
A suspension of completely crosslinked polymer particles was obtained. The average particle diameter of this product was 25 μm. Comparative Example 1 A sample containing no fine powder inorganic compound was prepared in the same manner as in Example 1, except that the use of fine powder inorganic compounds was completely omitted, and the formulation was changed to the one shown below. A control suspension of polyurethane polyurea crosslinked particles was obtained.

That is, as the aqueous phase, 19 parts of "Fuji Chemi HEC AL-15F" and 3 parts of water were used.
56 parts of PI were used as the organic phase, while PI
20 parts of PI-1, 56 parts of PI-2, 24 parts of PO-1 and 25 parts of toluene were used, and as the urethanization catalyst, 0.1 part of DBTDL was used, and as the polyamine, EDA A fully crosslinked suspension of polymer particles was obtained by using 5.8 parts of a 50% aqueous solution of . The average particle diameter of this product was 22 μm. Application Examples 1 to 3 and Comparative Application Example 1 The respective suspensions of polyurethane polyurea crosslinked particles obtained in each of the Examples and Comparative Examples were dried using a spray dryer to form a fine powder, and a 200 mesh Polymer particles larger than 75 μm were removed through a sieve.

[0088] Next, various properties and performance of each polymer particle were compared and studied, and the results are summarized in Table 1. Note 1) Measured using a powder tester (manufactured by Horikawa Micron Co., Ltd.) 2) Put 20 grams of polymer particles through a 200-mesh sieve with a diameter of 20 cm, and pass through the vibrating sieve for 1 minute using a vibrating sieve machine. However, as is clear from the results in Table 1, which are expressed in weight percent of the polymer particles that passed, the fine powder inorganic compound-fixed polyurethane polyurea crosslinked particles of the present invention have a particularly small angle of repose, and moreover, It can be seen that it is extremely practical because the passage rate is high, the agglomeration of the particles is extremely low, and the fluidity of the particles is also excellent.

[0089]

[Effects of the Invention] The polyurethane polyurea crosslinked particles of the present invention contain a finely powdered inorganic compound inside, and furthermore, the reaction has been sufficiently completed to the extent that no trace of unreacted isocyanate groups can be observed. It is something that

[0090] Therefore, the polymer particles of the present invention are extremely tough and have excellent solvent resistance, and furthermore, there is extremely little aggregation among particles, and the particles also have excellent fluidity. from the place, particle classification, transport,
Various handling aspects such as packaging and storage have been greatly improved.

Moreover, when the present invention is utilized to encapsulate various core materials, the core material itself can be protected against external damage such as mechanical destruction, organic solvents, natural environment such as water and sunlight, etc. It is effective for protecting the external environment, such as industrial wastewater, which leads to the destruction of the natural environment, and it is also effective for protecting the external environment, such as industrial wastewater, which is a core material with active residual isocyanate groups, which has been a concern until now. This makes it possible to avoid chemical changes.

Therefore, the present invention has excellent practicality in various industrial fields.

Claims (4)

[Claims] 1. Polyurethane polyurea crosslinked particles containing a finely powdered inorganic compound inside the particles. 2. The polyurethane polyurea crosslinked particles include a polyisocyanate compound in which isocyanate groups are stoichiometrically excessive, and a polyhydroxy compound;
An interfacial polymerization reaction between an organic phase that is mixed with a finely divided inorganic compound and which can form a three-dimensional crosslinked structure through the reaction, and this stoichiometrically excess polyamine having an equivalent amount of isocyanate groups or less, and particles. The polyurethane polyurea crosslinked particles according to claim 1, which are obtained through an internal urethanization reaction. 3. The polyurethane polyurea crosslinked particles according to claim 1, wherein the fine particle inorganic compound is poorly soluble in water. 4. The polyurethane polyurea crosslinked particles according to claim 1, wherein the finely powdered inorganic compound is selected from the group consisting of finely powdered silica and finely powdered aluminum oxide.