JPH04175327A - Polyurethanepolyurea particle - Google Patents

Abstract

PURPOSE:To provide the title fluorinated particle which is tough and excellent in solvent resistance, weathering resistance, etc., by reacting an organic phase containing an excess of a polyisocyanate compound and a hydroxylated fluorine compound by contact with an aqueous polyamine solution. CONSTITUTION:An organic phase comprising a polyisocyanate compound (e.g. 1,6-hexamethylene diixocyanate) in an amount to give stoichimoetrically excess isocyanate groups and a hydroxylated fluorine compound (e.g. a vinyl fluoride/2-- hydroxyethyl vinyl ether/methyl vinyl ether copolymer) and being capable of forming a three-dimensional crosslinked structure by reaction is dispersed in a water phase with a homogenizer or the like. An aqueous solution of a polyamine (e.g. 1,2-ethylenediamine) in an amount at most equivalent to the stoichimetrically excess isocyanate groups is added to the obtained dispersion, and the resulting mixture is subjected to an interfacial polymerization reaction and a urethane formation reaction within a particle to produce a polyurethanepolyurea particle having fluorine atoms in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to new and useful polyurethane polyurea particles having fluorine atoms in the molecule.

More specifically, through the reaction of a polyisocyanate compound, a hydroxyl group-containing fluorine compound, and a polyamine compound, a urethanization reaction and a ureaization reaction are performed in the particle formation process. The present invention relates to fluorine-containing polyurethane polyurea particles having the following properties.

[Prior art] A hydrophobic substance is dispersed in an aqueous medium, and the dispersed a
A so-called interfacial polymerization method in which organic polymers are grown at the droplet interface, thereby forming microparticles, is already known.

In most of these methods, a stable polyurethane polyurea is formed by dispersing an isocyanate prepolymer having an isocyanate end group in water, and then adding a polyamine or the like to the dispersion.

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

According to the conventional technology, the formation of the outer wall of the particle is a urea reaction between amines and isocyanate i, and as a result of this urea reaction, once the outer wall is formed, the isocyanate remaining inside the particle is formed. By this outer wall that has been formed, the amino groups in the water will be isolated, and subsequent reactions will no longer be able to proceed easily, therefore, as the outer wall continues to grow. As a result, the migration of the amine in water into the particles becomes extremely slow, and as a result, the reaction reaches an apparently saturated state while leaving unreacted isocyanate groups inside the particles. It happens. As a result, there are also problems in that the reproducibility of basic particle characteristics deteriorates and resources are wasted in the form of retention or accumulation of unreacted materials.

On the other hand, polyurethane polyurea particles obtained by such interfacial polymerization reactions generally have excellent mechanical properties and chemical resistance, so they have been used in many fields.
Depending on the type of raw material compound constituting the polyurethane polyurea particles, they have the disadvantage of poor weather resistance.

As a method for improving the weather resistance of particles, there is a method for producing polyurethane polyurea particles using isocyanate prepolymers using aliphatic or cycloaliphatic diisocyanates.
Even with such improved methods, it is extremely difficult to obtain polyurethane polyurea particles that have excellent long-term weather resistance.

(Problems to be Solved by the Invention) However, the present inventors have completed the present invention as a result of intensive studies in view of the various shortcomings of the prior art described above. The object of the present invention is to provide highly practical fluorine-containing polyurethane polyurea particles in which the outer and inner walls of the particles are sufficiently formed, and which have particularly excellent weather resistance.

[Means for Solving the Problems] Therefore, the present inventors focused on the problems to be solved by the invention as described above, and as a result of intensive studies, obtained the desired fluorine-containing polyurethane polyurea particles. This led to the completion of the present invention. That is, the present invention provides, as a means for solving these problems,
An interfacial polymerization reaction occurs between the organic phase, which is a mixture of a polyisocyanate compound and a hydroxyl group-containing fluorine compound, and which can form three-dimensional crosslinks through the reaction, and a stoichiometrically excess polyamine having an amount equal to or less than the isocyanate group equivalent. By carrying out the urethanization reaction inside the particles,
The purpose is to provide a fluorine-containing polyurethane polyurea.

Here, as the above-mentioned polyisocyanate compound, it is preferable to use a polyisocyanate compound consisting of an aliphatic and/or alicyclic diisocyanate in consideration of weather resistance, among which only particularly representative ones are exemplified. In particular, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane-484'-diisocyanate, 1,4-tetramethylene diisocyanate,
1,6-hexamethylene diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate,
Diisocyanate monomers such as microhexyl-1,4-diisocyanate or isophorone diisocyanate, or various types of polyisocyanurate-type polyisocyanates or billet-type polyisocyanates based on these various monomers. Modified polyisocyanates, etc., and furthermore, one or more of the various diisocyanate monomers and modified polyisocyanates listed above, polyhydric alcohols, polyester polyols, polycarbonate polyols,
These include urethane-modified polyisocyanate prepolymers having terminal isocyanate groups obtained by urethanizing one or more of various polyhydroxy compounds such as polybutadiene polyol, hydroxyl group-containing fluorine compound, or polypentadiene polyol, These may be used alone or in combination of two or more.

In order for the obtained fluorine-containing polyurethane polyurea particles (hereinafter also referred to as polymer particles) to have particularly strong toughness, the number average molecular weight of the polyisocyanate compound is within the range of 200 to 10.000, Preferably 800-7,000, more preferably 500-5
,000 is desirable.

On the other hand, the hydroxyl group-containing fluorine compound, which is a component constituting the organic phase together with the polyisocyanate compound, compensates for the lack of internal crosslinking caused by the formation of the walls of the polymer particles, and also improves the weather resistance of the particles. For example, the hydroxyl group-containing fluorinated compound may contain 15 to 75% by weight of a fluorine-containing vinyl monomer, 15 to 75% by weight of a fluorine-containing vinyl monomer, and a hydroxyl group-containing vinyl A product obtained by copolymerizing 1-80% by weight of a monomer and 5-85% by weight of another copolymerizable monomer,
Representative examples are shown.

If the amount of the fluorine vinyl monomer used is less than the above range, the weather resistance and durability of the particles will decrease, while if it exceeds the above range, the particles will deteriorate. Either case is unfavorable since it becomes difficult to form.

In addition, if the amount of the hydroxyl group-containing vinyl monomer used is less than the above range, the solvent resistance and durability of the coating film will decrease; on the other hand, if it exceeds the above range, , as the flexibility of the particles decreases,
Either case is not preferable.

Typical examples of the above-mentioned fluorinated vinyl monomers include vinyl butonide, vinylidene butonide, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, promotrifluoroethylene, pentafluoropropylene, or hexafluoropropylene. or perfluoroalkyl perfluorovinyl ethers such as trifluoromethyl trifluorovinyl ether, pentafluoroethyl trifluorovinyl ether or heptafluoroprobyl trifluorovinyl ether;
There are compounds such as fluoroalkyl vinyl ether (however, the number of carbon atoms in the alkyl group is 1-18), but among them, vinylbutylene, tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, (bar)fluoroalkyl vinyl ether (however, It is desirable to use perfluoroalkyl trifluorovinyl ethers in which the alkyl group has 1 to 18 carbon atoms or the alkyl group has C1 to CI8.

Typical examples of the hydroxyl group-containing vinyl monomer include:
2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether,
Vinyl ethers having a hydroxyl group such as 3-hydroxybutyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 5-hydroxypentyl vinyl ether, or 6-hydroxyhexyl vinyl ether; addition of the above-mentioned various vinyl ethers with ε-caprolactone Reaction product; 2-hydroxyethyl (meth)allyl ether, 3-hydroxypropyl (meth)
Allyl ether, 2-hydroxypropyl (meth)allyl ether 1,4-hydroxybutyl (meth)allyl ether, 3-hydroxybutyl (meth)allyl ether, 2-hydroquine-2-methylpropyl (meth)allyl ether, 5- Hydroxyl group-containing allyl ethers such as hydroquine pentyl (meth)allyl ether or 6-hydroxyethyl (meth)allyl ether; addition reaction products of these various allyl ethers listed above with ε-caprolactone; 2-hydroxyethyl (meth)allyl ether; ) acrylate,
2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate
Acrylate, polyethylene glycol mono (meth)
Acrylate or polypropylene glycol mono
Hydroxyl group-containing (meth)acrylates such as (meth)acrylates; these various (meth)acrylates and ε
Examples include the main component in the addition reaction of caprolactone.

Examples of the other copolymerizable monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether,
Alkyl vinyl ethers or substituted alkyls such as isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, chloromethyl vinyl ether, chloroethyl vinyl ether, hensyl vinyl ether or phenylethyl vinyl ether Vinyl ethers; cycloalkyl vinyl ethers such as cyclopentyl vinyl ether, cyclohexyl vinyl ether or methylcyclohexyl vinyl ether; vinyl-2,2-dimethylpropanoate, vinyl-2,2-
Dimethylaminoethyl, vinyl-2,2-dimethylpentanoate, vinyl-2,2-dimethylhexanoate, vinyl-2-ethyl-2-methylbutanoate, vinyl-2-ethyl-2-methylpentanoate ate, vinyl-
3-chloro-2,2-dimethylpropanoate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl iso#1 acid, vinyl caproate, vinyl caprate, vinyl caprate, vinyl laurate, C7 branched aliphatic Vinyl carboxylate, C1° branched aliphatic vinyl carboxylate, C
Il's! Vinyl aliphatic carboxylates or vinyl aliphatic carboxylates such as vinyl stearate; vinyl cyclohexanecarboxylate, vinyl methylcyclohexanecarboxylate, vinyl benzoate or trimethoxysilylpropyl vinyl ether, trimethoxysilylpropyl vinyl ether, methyljethoxysilylpropyl vinyl ether , γ-(meth)acryloyloxypropyltrimethoxysilane, r-(meth)acryloyloxypropyltriethoxysilane or r-(meth)acryloyloxypropylmethyldimethoxysilane, monomers containing hydrolyzable silyl groups, Amino group-containing amide unsaturated monomers such as N-dimethylaminoethyl (meth)acrylamide, N-diethylaminoethyl (meth)acrylamide, N-dimethylaminopropyl (meth)acrylamide or N-diethylaminopropyl (meth)acrylamide; Dimethylaminoethyl (meth)
acrylate or dialkylaminoalkyl (meth)acrylate such as diethylaminoethyl (meth)acrylate W4; tert-butylaminoethyl (
Amino group-containing monomers such as meth)acrylate, tert-bitylaminopropyl (meth)acrylate, aziridinylethyl (meth)acrylate, pyrrolidinylethyl (meth)acrylate or piperidinylethyl (meth)acrylate; or carboxyl group-containing monomers such as (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid. From the viewpoint of increasing the polymerization yield of the hydroxyl group-containing fluorine-containing vinyl compound itself, it is desirable to use alkyl vinyl ethers, cycloalkyl vinyl ethers, hydroxyl group-containing vinyl ethers, and carboxylic acid vinyl esters. The type and amount of the monomer to be used may be determined as appropriate from the viewpoints of particle formation properties, particle performance such as weather resistance, etc.

In order to prepare the hydroxyl group-containing fluorine-containing compound, a polymerization reaction may be carried out using a Rancal polymerization initiator and making full use of the known techniques such as emulsion polymerization, suspension polymerization, bulk polymerization, or solution polymerization. As the radical polymerization initiator, diacyl peroxides such as acetyl peroxide or benzoyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide or cyclohexanone peroxide; hydrogen peroxide,
- Hydroperoxides such as butyl hydroperoxide or cumene hydroperoxide;
Dialkyl peroxides such as di-L-butyl peroxide or dicumyl peroxide; alkyl peroxy esters such as t-butyl peroxyacetate or L-butyl peroxypihalate; azobisisobutyronitrile or azobis Representative examples include azo compounds such as isobutyronitrile; or persulfates such as potassium persulfate or ammonium persulfate.

As the polymerization reaction method, there are various known methods as mentioned above, but among them, bulk polymerization and solution polymerization are preferable, and from the viewpoint of particle formation, solution polymerization is more preferable. The method is particularly desirable.

Typical solvents used in preparing the hydroxyl group-containing fluorine-containing compound by solution polymerization include aromatic hydrocarbons such as henzene, toluene, or xylene; 0-pentane, n-hexane, n- aliphatic hydrocarbons such as octane or mineral spirits; alicyclic hydrocarbons such as cyclopencune, cyclohexane, methylcyclohexane or ethylcyclohexane; ethers such as dimethoxyethane, tetrahydrofuran, dioxane, diisopropyl ether or di-n-butyl ether; Acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone,
Ketones such as methyl amyl ketone, cyclohexanone or isophorone; methyl acetate, ethyl acetate, acetic acid n
- Esters such as propyl, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate or ethylene glycol monobutyl ether acetate; Examples include chlorinated hydrocarbons such as carbon chloride, trichloroethane, and tetrachloroethane, and further include N-methylpyrrolidone, dimethylformamide, dimethylacetamide, and ethylene carbonate. Of course, such organic solvents may be used alone or as a mixture of two or more.

In order to prepare the hydroxyl group-containing fluorine-containing compound from each of the monomer components listed above by a solution polymerization method, all the monomers, a polymerization initiator, and a solvent are charged into a reactor at once and polymerized, or the fluorine-containing compound is Monomers other than the fluorine-containing vinyl monomers and a polymerization initiator are added to a reactor containing vinyl monomers and a solvent, respectively, either continuously or in portions, and polymerized. Furthermore, the reactor tank containing only the solvent, all the monomers and the polymerization initiator,
Methods such as adding each component continuously or in portions and polymerizing them can be applied.

In the present invention, the ratio of the isocyanate group equivalent of the polyisocyanate compound to the hydroxyl group equivalent of the hydroxyl group-containing fluorine compound is I:0.1 to 1:0.9, preferably 1.
: 0.1 to 1:0.8, more preferably 0.2
It is important to mix both of these components by using within a range of 0.7 to I:0.7, and to create a composition in which the mixture of these two components itself can be three-dimensionally crosslinked. That is, it is necessary to formulate the mixture in such a way that it becomes gel-like when completely subjected to the urethanization reaction, and fluidity cannot be obtained even by heating or diluting the true solvent. The above two conditions in designing the hydrophobic organic phase are essential conditions for obtaining an internal crosslinked state that cannot be obtained only by the interfacial polymerization reaction by adding a polyamine, which will be described later, and are the basic requirements of the present invention. be.

In this case, in order to achieve interfacial polymerization without difficulty, an excess of iso and noanate groups in the above range is necessary.
This range is set so that two outer walls of the particles are formed quickly.

Furthermore, in the present invention, by allowing the urethanization reaction to proceed three-dimensionally within the particles, it is possible to improve the toughness and solvent resistance of the entire particles, which could not be achieved with conventional techniques. Due to the design of the three-dimensional urethanization reaction inside the particles, a trifunctional or higher functional polyisocyanate compound and/or a hydroxyl group-containing fluorine-containing compound is added to the total amount of the polyisocyanate compound and polyhydroxy compound contained in the organic phase. 0.1 mol% or more, preferably 0.2 mol% or more, more preferably 0.3 mol%
By containing the particles in the above amount, a good three-dimensional crosslinked state inside the particles can be obtained. As the polyisocyanate 4 in the organic phase is consumed as the interfacial polymerization reaction with the polyamine described below progresses, the equivalent ratio of isocyanate groups to hydroxyl groups in the particles approaches, and the degree of crosslinking inside the particles increases to that of urethane. As the chemical reaction progresses, the layer increases, and the properties such as toughness and durability of the fluorine-containing polyurea particles of the invention further improve.
improves.

The hydrophobic organic phase mixed in this way is generally
Finely disperse the polyamine in water, add 1 equivalent of excess isocyanate groups contained in the organic phase, and add O12 to the polyamine.
~1. O equivalent, preferably 0.3 to 1.0 equivalent, more preferably 0.4 to 0.3 g equivalent, is added to carry out the ureation reaction at the particle interface, and also to carry out the urethanization reaction inside the particle. By carrying out this process, extremely tough polyurethane polyurea particles are obtained.

Suitable polyamines used in the present invention include well-known and commonly used diamines, polyamines, and mixtures thereof, among which only representative ones include 1,2-ethylenediamine, bis-(3-amino propyl)-amine, hydrazine, hydrazine-2-
Ethanol, His-(2-methylaminoethyl)-methylamine, 1,41-diaminonechlorohexane, 3-amine-1-methylaminopropane, N-hydroxyethylethylenediamine, N-methyl-his-(3-aminopropyl - xamethylenediamine, 1-aminoethyl-1
, 2-ethylenediamine, his(N,IJ'-aminoethyl) = 1.2-ethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamino, phenylenediamine, tolylenediamine, 2,4.6-)riamino Toluentaihi (
・Rochloride, L3,6-triaminonaphthalene, isophorone diamine, xylylene diamine, hydrogenated xylylene cyanine, 4,4'-diaminophenylmethane or hydrogenated 4,4'-diaminodiphenylmethane, or derivatives of these polyamine monomers From the viewpoint of weather resistance, it is desirable to use an aliphatic type and/or an alicyclic type.

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

Typical organic solvents that can be used include those used in preparing the hydroxyl group-containing fluorine compounds, among others, Hensen, toluene, xylene, cyclohexane, methylcyclohexane, mineral spirit, etc. is suitable.

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

When dispersing the organic phase in the aqueous phase, polyvinyl alcohol, hydroxyalkyl cellulose, carboxyalkyl cellulose, gum arabic, polyacrylate,
It is preferable to use one or more types selected from various protective colloids such as polyacrylamide, polyvinylpyrrolidone, and ethylene-maleic anhydride copolymer within a range of 0.2 to 20% by weight. Moreover, this aqueous phase is 0.2 to 10
There is no problem even if it contains various nonionic, anionic, or cationic surfactants in the amount by weight.

The present invention is characterized by carrying out an active S:urethanization reaction inside the particles, but as is known, the urethanization reaction with hydroxyl 5a isocyanate groups is particularly difficult when the isocyanate group is a fatty acid. In the case of group-based or alicyclic-based S groups, the reaction rate tends to be lower than that of the urea reaction with an amino group. As is well known, the reactivity between water and isocyanate is extremely small compared to the reactivity with hydroxyl groups, and due to the isolation effect of the outer wall formed by the addition of polyamine, the penetration of water into the interior of the particles is negligible. Therefore, the objective of the present invention is to carry out the urethanization reaction in the particles by increasing the reaction temperature and taking a long time. Cobalt naphthenate, for the purpose of promoting very effectively
Zinc naphthenate, stannous chloride, stannic chloride, tetra-n
-butyltin, tri-n-butyltin acetate, n-butyltin trichloride, trimethyltin hydroxide, trimethyltin 7-chloride, 1-thyltin noacenanoacetate tin dilaurate, tin octenoate, or Add one or more of various organometallic catalysts, such as potassium oleate, to the hydrophobic organic phase for 5 to 10 seconds. OOOppm
, preferably in a range of 10 to 5.000 ppm, and by adding the -F organometallic catalyst, tough crosslinked particles can be formed in an extremely short time. The method for adding the above-mentioned organometallic catalyst includes adding the organometallic catalyst into the organic phase prior to water dispersion (fine dispersion), or a step of dispersing the organic phase in water and adding a polyamine. It is appropriate to add it in the middle of the process. When an organometallic catalyst is added after adding a polyamine, 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 tends to decrease. I don't like it because of some things.

The fluorine-containing polyurethane polyurea particles of the present invention can contain various substances as core substances as long as the basic requirements of the present invention are satisfied. The core substances encapsulated in this way are present in the hydrophobic organic phase and incorporated into the particles, but they are not particularly limited and can range over a wide range. Typical examples of such core materials include herbicides, fungicides, insecticides, etc.
Pharmaceuticals, fragrances, colorants, catalysts, foods, adhesives, detergents,
These include enzymes, color formers, chemical products, and rust preventives.

In addition, if necessary, various synthetic resins such as plasticizers, paraffins, animal and vegetable oils, silicone oils, or xylene resins that are inert to incyanate groups, and ketone resins are also included. You can also do that.

The manufacturing process of the fluorine-containing polyurethane polyurea particles of the present invention is generally carried out as follows.

a) In the present invention, the step of dispersing the organic phase in the aqueous phase is preferably carried out at around room temperature of 10 to 35°C from the viewpoint of stabilizing the dispersion system. Such dispersion of the organic phase into the aqueous phase can be carried out simply by suitable dispersion means such as a homogenizer, homodisper or propeller-type general purpose stirrer or by conventional operation.

b) In many cases, after the above-mentioned dispersion step is completed, it is preferable to mildly stir the dispersion using a propeller-type stirrer for the purpose of making the particles spherical.

C) To the mildly stirred dispersion, add an organometallic catalyst for promoting the urethanization reaction, such as dibutyltin dilaurate, to 5 to 10% of the total organic phase before and after adding the polyamine, and especially before adding the polyamine. , added in an amount of OOOppm.

d) Then 10% of the polyamine described above was added to the dispersion.
The polyamine is added at a temperature of ~35°C, and it is preferred that the polyamine is diluted with water to a concentration of 5 to 70% of the active ingredient.

e) After several tens of minutes to several hours, the reaction temperature is raised to 40 to 95°C, preferably 50 to 90°C,
By maintaining the same temperature for 1 to several hours, 0.1 to 50
Tough crosslinked polyurethane polyurea particles having a particle diameter of 0 μm and having a nearly spherical shape are obtained.

f) The particles thus obtained may be used for their respective purposes; they may be made into fine powders by spray drying, drying, centrifugal drying, filtration drying or fluidized bed drying. You can also use

[Example] Next, the present invention will be specifically explained using Examples, Comparative Examples, Applied Examples, and Comparative Applied Examples. Parts and % in examples
Unless otherwise specified, all are based on weight.

First, each raw material used in this example will be explained.

(A): Polyisocyanate compound (1) "Harnosoku DN-950, (hexamethylene diisocyanate adduct type polyisonoanate resin manufactured by Dainippon Ink & Chemicals Co., Ltd.; solid content equivalent isocyanate group concentration - 16.8%) Hereinafter, this will be referred to as pr-1.

(2) DN-980S (manufactured by the same company, obtained using hexamethylene diisocyanate. Isocyanurate type polyisocyanate resin; isocyanate group concentration - 21.0%) was used, but the following 1.
This is designated as Pl-2.

(3) Polycondensation reaction of 7+7 methylolpropane and ε-caprolactone, with a hydroxyl value of 16
1000 parts of polycaprolactone polyester triol of 8.5 and 666 parts of isophorone diisocyanate
A polyisocyanate resin having an isocyanate group concentration of 7.5% obtained by subjecting the polyisocyanate resin to a urethane reaction with the polyisocyanate resin was hereinafter referred to as Pf-3.

(B) Hydroxyl group-containing fluorine-containing compound - (1) Into a stainless steel autoclave sufficiently purged with nitrogen, add 250 parts of vinyl p-tert-butylbenzoate and add 9" (manufactured by Shell, Netherlands). , C9 (vinyl ester of branched aliphatic carboxylic acid)
parts, 250 parts of 4-hydroxybutyl vinyl ether,
480 parts of n-butyl acetate, 15 parts of azubisisovaleronitrile (ABVN), and 10 parts of tert-butyl peroxyoctoate (TBPO) were charged.

Then, 4 of the liquefied and collected chlorotrifluoroethylene
00 parts of xylene was press-injected and reacted at 60''C for 15 hours with stirring. When the non-volatile content (NV) reached 67%, it was cooled to room temperature and 318 parts of xylene was added, and the NV reached 55%.
A solution of the target fluorine-containing compound having a hydroxyl value of 120 was obtained. Hereinafter, this will be abbreviated as a fluorine-containing compound (PO-1).

(2) Same as in (1) above except that the monomer composition was changed to 150 parts of Heoha 9 J, 47 hydroxybutyl vinyl ether, 250 ethyl vinyl ether, 100, and chlorotrifluoroethylene 500. NV was 68%. When the temperature reaches 55%, cool to room temperature and add 60 parts of xylene until the NV is 55%.
A solution of the target fluorine-containing compound having a hydroxyl value of 120 was obtained. Hereinafter, this will be abbreviated as a fluorine-containing compound (PCI-2).

(3) The composition of the monomer is 260 parts of cyclohexyl vinyl ether 4-
Except for hydroxybutyl vinyl ether 250/chlorotrifluoroethylene 490,
Similarly to (1) above, when NV reaches 68%,
Cool to room temperature and add 346 parts of xylene until the NV is 5.
A solution of the target fluorine-containing compound having a hydroxyl value of 120 at 5% concentration was obtained. Hereinafter, this will be referred to as a fluorine-containing compound (P O-3).
It is abbreviated as

(C): Polyamine compound (1) Ethylenediamine was used, but it will be abbreviated as EDA hereinafter.

(2) 1,6-hexamethylene diamine was used, hereinafter abbreviated as HMDA.

Example 1 Into a 1,000ml flask, rPVA-217J was added.
10 parts of (partially saponified polyvinyl alcohol manufactured by Kuraray Co., Ltd.) and 9 parts of rPVA-205J (same as above)
An aqueous phase was prepared by dissolving 1 part in 273 parts of water. In a separate container, 18 parts of PI-1, 34 parts of PI-2, PO-1
and 25 parts of toluene were mixed to form an organic phase. 7,000 to 7,000 using a homomixer at room temperature.
While stirring the aqueous phase at 500 rpm, the organic phase prepared in advance was added thereto and stirred for 1 minute to obtain a dispersion. Next, transfer this dispersion to another flask and
After stirring at 200 rprn with a molded stirring blade,
Add 0.18 parts of dibutyltin dilaurate (DBTDL) and after 2 minutes, add 5 parts of a 50% aqueous solution of EDA.
．． I prepared 26 copies. After keeping at room temperature for 2 hours, 50
The temperature was raised to °C for 1 hour at the same temperature, then 2 hours at B O'C.
The reaction was allowed to continue for a certain period of time to obtain the desired suspension of fluorine-containing polyurethane polyurea particles. The average particle size of the particles was 25 microns.

Example 2 The same operations as in Example 1 were repeated, except that the substances listed below were used.

That is, as the aqueous phase, 9 parts of rPVA-205j, rpvA-217, (7) Io part, and 356 parts of water were used, and as the organic phase, 80 parts of PI-1, PI Using 28 parts of -3 and 40 parts of PO-2, as a urethane catalyst,
Using 0.18 parts of DBTDL, as the polyamine,
3.45 parts of a 50% aqueous solution of EDA was used.

As a result, a suspension of completely crosslinked particles was obtained. The average particle size of the particles was 80 microns.

Example 3 The same procedure as in Example 1 was repeated, except that the following substances were used.

That is, as the aqueous phase, [Fuji Chemical HECAL-15FJ (Fuji Chemical ■
Using 19 parts of hydroxyethylcellulose (manufactured by hydroxyethylcellulose (manufactured in Japan)) and 356 parts of water, 20 parts of PI-2, 56 parts of PI-3, and 37 parts of PO-3 were used as the organic phase, and as the urethanization catalyst. D.
0.18 parts of BTD Lo) were used, and 5.8 parts of a 50% aqueous solution of HMDA was used as the polyamine.

As a result, a suspension of completely crosslinked particles was obtained. The average particle size of the particles was 20 microns.

Comparative Example 1 Instead of a hydroxyl group-containing fluorine-containing compound, a polyester polyol with a hydroxyl value of 187 (hereinafter abbreviated as PO-4) obtained by co-condensation of opentyl glycol and adipic acid was used, In addition, a control suspension of polyurethane polyurea particles was obtained by repeating the same operation as in Example 1, except for changing the formulation as shown below.

That is, as the aqueous phase, 9 parts of rPVA-205J, 10 parts of rPVA-217J, and 356 parts of water were used, and as the organic phase, 80 parts of PI-1 and 28 parts of PI-3 were used, respectively. 25 parts of DBTDL and PO-4 were used as the urethanization catalyst.
．． 18 parts were used, and as the polyamine, E
3.45 parts of a 50% aqueous solution of DA was used. the result,
A suspension of completely crosslinked particles was obtained. The average particle size of the particles was 25 microns.

Application Examples 1 to 3 and Comparative Application Example 1 Each polyurethane polyurea particle suspension obtained in each Example and Comparative Example was made into a fine powder by a spray drying method, and then the respective polymer particles were compared. Table 1 summarizes the areas where the study was conducted.

Table 1) Each polymer particle was sealed in a quartz cell, and the appearance of the polymer particle was observed after irradiation with a fade meter for 1,000 hours.

2) The appearance of the polymer particles was visually judged using a Q-trowel.

3) Judgment was made by observing polymer particles with an electron microscope (3,500x magnification).

As is clear from the results in Table 1, the fluorine-containing polyurethane polyurea particles of the present invention have excellent weather resistance and are free from particle deterioration due to light S.

:Effect of the invention:' In this way, the fluorine-containing polyurethane polyurethane particles of the present invention obtained by straining have internal S: unreacted isocyanium-
The reaction has been sufficiently completed to the extent that no trace of the t group can be observed. Accordingly, the fluorine-containing polyurethane polyurea particles of the present invention are extremely tough and have excellent solvent resistance, and moreover, they are made by using a hydroxyl group-containing fluorine compound as an organic phase component constituting the inside of the particles. It also has the characteristics of being extremely durable and weather resistant.

When various core substances are encapsulated by making full use of the present invention,
These core materials can be protected from external environments such as mechanical destruction, organic solvents, natural environments such as water and sunlight, and chemical changes in the core materials due to active residual isone anate groups, which have been a concern up until now. It is possible to avoid this. Therefore, the present invention is extremely useful and highly practical in various industrial fields.

Agent: Patent Attorney Katsutoshi Takahashi

Claims (1)

[Claims] 1. Polyurethane polyurea particles having fluorine atoms in the molecule. 2. The polyisocyanate compound and the hydroxyl group-containing fluorine-containing compound are mixed in such a way that the isocyanate groups are stoichiometrically excessive, and the organic phase is capable of forming a three-dimensional crosslinked structure through reaction, and this stoichiometric Polyurethane polyurea particles having fluorine atoms in the molecule, obtained through an interfacial polymerization reaction with a polyamine having an excess of isocyanate group equivalent or less, and a urethanization reaction inside the particles. 3. The polyisocyanate compound is aliphatic and/or
or a cycloaliphatic diisocyanate. 4. The polyisocyanate compound is aliphatic and/or
The particles according to claim 2, which are obtained by reacting an alicyclic diisocyanate with a polyhydroxy compound having two or more hydroxyl groups in one molecule. 5. The polyisocyanate compound is aliphatic and/or
or an isocyanurate type polyisocyanate of an alicyclic diisocyanate, the particles according to claim 2. 6. The hydroxyl group-containing fluorine-containing compound contains 15 to 75% by weight of the fluorine-containing vinyl monomer, 1 to 80% by weight of the hydroxyl group-containing vinyl monomer, and 5 to 5% of the other copolymerizable monomer. 8
The particles according to claim 2, which are obtained by copolymerizing 5% by weight and 5% by weight so that the total amount is 100% by weight.