JPH0717735B2 - Manufacturing method of fine resin particles - Google Patents

Description

Description: BACKGROUND OF THE INVENTION The present invention relates to a method for producing fine resin particles comprising a polymer or copolymer of ethylenically unsaturated monomers.

It is well known in the paint field to use fine resin particles made of a polymer or copolymer of an internally crosslinked ethylenically unsaturated monomer for the purpose of high solidification and rheology control. Further, such fine resin particles are also used as a carrier for catalysts, ultraviolet absorbers, biocides, and other functional substances, as paints, plastic materials, electrical materials, and medical and biological materials.

The applicant's Japanese Patent Application Laid-Open No. 57-187302 discloses that Polymerizing a monomer having two or more ethylenically unsaturated groups in the molecule and another ethylenically unsaturated monomer in an aqueous catalyst by an emulsion polymerization method using an amphoteric aqueous resin having An emulsion resin obtained by the above is described.

Further, JP-A-58-129066 of the present applicant is obtained by removing the dispersion medium of the emulsion by a method such as filtration, spray drying or freeze drying, or by replacing the emulsion with a solvent. It is proposed to add the fine resin dispersion to a coating composition containing a film-forming resin and a crosslinking agent.

These fine resin particles, as a result of supporting the zwitterionic aqueous resin on the surface thereof, fine resin particles produced by emulsion polymerization using a general emulsifier or dispersant,
It is not found in the fine resin particles obtained by the polymerization method in a non-aqueous solvent known as the NAD method. It has unique surface chemical and electrochemical properties.

The present invention has an anionic, cationic or zwitterionic hydrophilic group at the end of the main chain, emulsion polymerization in the presence of a modified epoxy group resin having a structure in which a hydrophobic linear polymer block is grafted as a side chain. Provided is a method of producing fine resin particles by polymerizing an ethylenically unsaturated monomer by a suspension polymerization method.

SUMMARY OF THE INVENTION The present invention comprises an epoxy resin having an epoxy equivalent of 100 to 6000.
A formula with at least one main chain derived(In the formula, R₁And R₂Means hydrogen or a methyl group, A
Is an ether bond or ester bond, or active hydrogen
Generated by the reaction between the containing group and the diisocyanate compound
Means a divalent organic group, and B is a line having a molecular weight of 100 to 7,000.
-Like polymer block, Y is hydroxyl group, amino group
Or carboxyl groups, or bound to these groups
It means a half-blocked diisocyanate residue. )so
At least one of the end groups of the main chain contains a side chain binding block represented by the formula(In the formula, R₁And R₂Is the same as above, and X is epoxy
A polyfunctional carboxylic acid having active hydrogen that reacts with a group,
Means the residue of a rufonic acid or phosphoric acid compound. )
Is an anionic group or its salt(In the formula, R₁And R₂Is the same as above and R₃Is a substituent
I may have C₂~ C₂₀Means an alkyl group of R_FourIs R
₃Same as or means hydrogen atom or benzyl group
To do. ) Becomes a cationic group or its salt
Or expression (In the formula, R₁And R₂Is the same as above and R_FiveIs hydrogen,
Or alkyl having 1 to 20 carbon atoms which may have a substituent
Base, R₆Is a straight chain having 1 to 12 carbon atoms which may have a substituent
Alternatively, it may have a branched alkylene group or a substituent.
A phenylene group, which has an ester bond or ether
R bond may be included, Z Is −COO ，-SO₃ , -OSO₃ ，Or represents a partial ester residue of an organic polybasic acid, R₇Is water
Alkyl having 1 to 12 carbon atoms which may have a substituent
Group, or phenyl group which may have a substituent
To do. ) As a zwitterionic group or salt thereof
Ethylene in an aqueous medium in the presence of modified epoxy resin
Of emulsion or suspension polymerization of water-soluble unsaturated monomers
A method for producing fine resin particles is provided.

The fine resin particles according to the present invention carry the modified epoxy resin on the surface thereof. The modified epoxy resin has a hydrophilic group at the end of the main chain and has a hydrophobic polymer block as a side chain, so that it has surface activity, and therefore the micro resin of the present invention carrying this resin on the surface thereof. Since the particles are amphipathic, they have good dispersion stability in both hydrophilic and lipophilic media, and the modified epoxy resin that they carry has cross-linking points at the ends of the side chain polymer blocks, so curing reactivity is good. It has the feature. The fine resin particles can be used as a stable emulsion resin that forms a film when the inside of the particles is not gelled,
The obtained film is excellent in water resistance, corrosion resistance, weather resistance and physical properties.

Further, the fine resin particles can be used as a filler having good dispersibility for the purpose of improving physical properties of the film, and also as a rheology control agent when the inside of the particles is gelled.

In particular, those having a relatively large particle size can be used as a carrier for various substances, as a paint, a plastic material, an electric material, and a biological material.

Detailed Discussion Modified Epoxy Resin Derived from epoxy resin with an epoxy equivalent of 100-6000,
Modification in which the main chain has at least one side chain polymer block represented by the above formula (I), and at least one of the end groups of the main chain is an anionic hydrophilic group of the above formula (II-1) Epoxy resin, described in detail in the applicant's patent application entitled "Anion Modified Epoxy Resin" filed on January 30, 1987.

Such a resin is prepared by using, as a raw material, a resin containing at least one alcoholic hydroxyl group produced by ring opening of an epoxy group in the main chain derived from an epoxy resin having an epoxy equivalent of 100 to 6000. At least one side chain of a linear polymer block having a hydroxyl group, an amino group or a carboxyl group having a molecular weight of 100 to 7,000 is introduced by a reaction with a reactive hydroxyl group, and if necessary, an herb block diisocyanate is bonded to the terminal group of the side chain. Step (b) opening at least one main chain terminal epoxy group by reaction with a polyfunctional carboxylic acid, sulfonic acid or phosphoric acid compound having active hydrogen, or reacting the terminal epoxy group with a hydroxycarboxylic acid The precursor obtained by ring-opening is acylated with a polybasic acid anhydride to introduce an acid group, and if necessary a salt It is manufactured by carrying out the steps of forming a.

A modified epoxy resin (cationic modified epoxy resin) having a cationic hydrophilic group instead of an anionic hydrophilic group at the main chain terminal and a main chain terminal having a group represented by the formula (II-2) is Obtained by ring-opening the terminal epoxy group of the epoxy resin by reaction with an amine of formula NH (R ₃ ) (R ₄ ) in step (b) above. As the amine, dimethylaminopropylamine, diethanolamine, diisopropanolamine, di-2-hydroxybutylamine, di-2-hydroxyoctylamine, N-
Methylethanolamine, N-methylisopropanoamine, N-ethylethanolamine, N-benzylethanolamine and the like are used. The production of such a cationic modified epoxy resin is described in JP-A-61-233068.

At the end of the main chain, the formula (II-3) or (II-3 ')
The modified epoxy resin having a zwitterionic hydrophilic group is
Applicant's "Amphoteric ion" filed on January 30, 1987
Described in a patent application entitled "Type-Modified Epoxy Resin"
There is. These resins are mainly derived from epoxy resins with an epoxy equivalent of 100-6000.
Alcoholicity formed by ring opening of epoxy groups in the chain
A resin containing at least one hydroxyl group is used as a raw material, and (a) a terminal is formed by a reaction with the alcoholic hydroxyl group.
Molecules having hydroxyl group, amino group or carboxyl group
At least 100-7000 linear polymer block side chains
Introduce one, and if necessary, half block to the end group of the side chain.
(B) at least one main chain terminal epoxy group of the formulaOr NHR₆-Z )₂2M  [In the formula, the symbols are the same as above. ) Reaction with the compound represented by
Depending on the reaction, the terminal epoxy group is(In the formula, R_FiveAnd R₆Is the same as above. ) Amino alcohol
The precursor obtained by ring-opening by reaction with
Acylation with anhydride to introduce zwitterionic groups, if necessary
It can be produced by carrying out the steps of treating with an acid or forming a salt in any order.

The anion-type, cation-type, and zwitterion-type modified epoxy resins preferably have these hydrophilic groups at both ends of the main chain (α, ω-swelling type), and the main chain has a molecular weight of 200 to 10,000 bisphenol. It is preferable that the side chains are polycaprolactones each having a molecular weight of 100 to 7,000, derived from a type epoxy resin, and the main chain molecular weight / side chain molecular weight = 1 / 0.1 to 5.0.

Synthesis of Fine Resin Particles The fine resin particles of the present invention use the modified epoxy resin having the above structure as an emulsifier or dispersant, and are subjected to a known emulsion polymerization method or suspension polymerization method to obtain an ethylenically unsaturated monomer in an aqueous medium. It can be produced by polymerizing a monomer. The amount of the modified epoxy resin used is 0.01 to 50% of the monomer weight in emulsion polymerization and 0.01 to 10% in suspension polymerization.
% Is preferred.

When the monomer is used as a film-forming resin for an aqueous paint, such as the fine resin particles described in Japanese Patent Application Laid-Open No. 57-187302 of the present applicant, only a monofunctional monomer or a polyfunctional compound of up to 3% is used. Alternatively, a mixture with a monofunctional monomer including a crosslinkable monomer may be used. Further, when the internally crosslinked fine resin particles are used as the filler of the coating as in the applicant's JP-A-58-129066, the monomer mixture contains 3 to 50% of a polyfunctional or crosslinkable monomer. be able to.

As the monofunctional ethylenically unsaturated monomer, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate,
(Meth) acrylic acid such as 2-ethylhexyl alkyl ester of acrylic acid or methacrylic acid, and other monomer having an ethylenically unsaturated bond which can be copolymerized therewith, for example, styrene, α-methylstyrene, vinyltoluene,
Examples include t-butyl styrene, ethylene, propylene, vinyl acetate, vinyl propionate, acrylonitrile, methacrylonitrile, and dimethylaminoethyl (meth) acrylate. Two or more kinds of these monomers may be used.

The crosslinkable copolymerizable monomer is a monomer having two or more radically polymerizable ethylenically unsaturated bonds in the molecule and / or two kinds of ethylenic monomers each carrying a group capable of reacting with each other. Including an unsaturated group-containing monomer.

Examples of the monomer having two or more radically polymerizable ethylenically unsaturated groups in the molecule include polyhydric alcohol polymerizable unsaturated monocarboxylic acid esters, polybasic acid polymerizable unsaturated alcohol esters, and 2 There are aromatic compounds substituted with one or more vinyl groups, and examples thereof include the following compounds.

Ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol dimethacrylate Acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol dimethacrylate , Glycerol diacry , Glycerol allyloxydimethacrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,1,1-trishydroxymethylethane triacrylate, 1,1,1-trishydroxymethylethane dimethacrylate, 1, 1,1-trishydroxymethylethane trimethacrylate, 1,1,1-trishydroxymethylpropane diacrylate, 1,1,1
-Trishydroxymethylpropane triacrylate,
1,1,1-Trishydroxymethylpropane dimethacrylate, 1,1,1-Trishydroxymethylpropane dimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate and divinylbenzene .

Examples of the monomer having two kinds of ethylenically unsaturated groups each carrying a group capable of reacting with each other include epoxy group-containing ethylenically unsaturated monomers such as glycidyl acrylate and glycidyl methacrylate, and acrylic acid and methacrylic acid. Acid, the carboxyl group-containing ethylenically unsaturated monomers such as crotonic acid are the most typical, but the mutually reactive groups are not limited to these,
For example, various compounds such as amine and carbonyl, epoxide and carboxylic acid anhydride, amine and carboxylic acid chloride, alkyleneimine and carbonyl, organoalkoxysilane and carboxyl, hydroxyl and isocyanato have been proposed, and the present invention broadly includes these. To do.

The fine resin particles produced in an aqueous medium or a non-aqueous organic medium are isolated by a method such as filtration, spray drying, freeze drying, etc. It can be used by pulverizing, or the synthesized dispersion can be used by substituting the solvent for the medium.

Generally, it is desirable to control the particle size of particles obtained by the polymerization method. The emulsion polymerization method is suitable for particles of 0.01 to 20 μm, and the suspension polymerization method is suitable for particles of 1 to 50 μm. If necessary, the rheology can be controlled by adjusting the particle size distribution by a polymerization process or an operation such as mixing particles after the polymerization. Further, it is of course possible to carry on the surface or inside of the resin particles a promoter substance that accelerates the reaction during curing and a functional substance that allows the composition to exhibit high functionality after curing.

The fine resin particles of the present invention in which the proportion of the polyfunctional or crosslinkable monomer is 3% or less are water-dispersed liquids, either alone or in combination with other resins, which are normally dry or thermosetting water-based paints. Can be used as

The internally crosslinked fine resin particles containing 3 to 50% of a polyfunctional or crosslinking monomer are obtained as an aqueous dispersion as it is, in a powder state obtained by drying after polymerization, filtration, or by solvent substitution. As an organic solvent dispersion liquid, it can be used in a normally dry or thermosetting coating material in combination with another resin capable of forming a film. In this case, the fine resin particles can be added in an amount of 0.1 to 50 parts by weight per 100 parts by weight of the film-forming resin.

Hereinafter, the present invention will be described in more detail with reference to Examples and Examples. "Parts" and "%" in these Reference Examples and Examples are based on weight.

Reference Example 1 350 parts of an epoxy resin having an equivalent weight of 950 and a number average molecular weight of 1900, which was obtained by the reaction of Kolben, bisphenol A and epichlorohydrin, which were equipped with a stirrer, a thermometer, a nitrogen introducing tube and a reflux cooling tube, and charged with methyl isobutyl ketone. 212 parts were added and dissolved, and under a nitrogen stream, 22 parts of hydroxybivalic acid, 25 parts of dimethylolpropionic acid and 0.400 parts of benzyldimethylamine were added and reacted at a temperature of 120 ° C until an acid value of 1 or less and an epoxy value of 0 were reached. Then, 28 parts of hexahydrophthalic anhydride and 70 parts of trimellitic anhydride
Was added and reacted at 100 ° C. for 2 hours, then 1105 parts of ε-caprolactone and 0.80 of tetraisopropoxy titanate were added.
0 part was added and the reaction was carried out at 120 ° C. for 8 hours. Next, 188 parts of methyl isobutyl ketone was added to give a nonvolatile content of 80% and an acid value of 33.
Α, ω type swell structure resin (A) having 0 anion group
was gotten.

Reference Example 2 Using the same reactor as in Reference Example 1, 3325 parts of an epoxy resin having a number average molecular weight of 900 and an epoxy equivalent of 475 obtained by the reaction of bisphenol A and epichlorohydrin was charged, and ethylene glycol monoethyl ether acetate was added.
After 928 parts were added and dissolved, the temperature was raised to 80 ° C under a nitrogen stream,
A mixture of 337 parts of dimethylaminopropylamine and 200 parts of diethanolamine was added dropwise over 1 hour. Then 1
The temperature was raised to 00 ° C. and the reaction was carried out until the epoxy value became 0.

Next, 387 parts of ε-caprolactone and 15 parts of dibutyltin dilaurate were added, the temperature was raised to 140 ° C., and the reaction was carried out for 3 hours to obtain an α, ω swelling structure resin (B) having a cationic group with a nonvolatile content of 81%. It was

Reference Example 3 Using the same reaction apparatus as in Reference Example 1, 363 parts of an epoxy resin having an epoxy equivalent of 950 and a number average molecular weight of 1900 obtained by the reaction of bisphenol A and epichlorohydrin were charged, and 235 parts of methyl isobutyl ketone were added and dissolved. Then, 40 parts of diethanolamine was added and reacted under a nitrogen stream at a reaction temperature of 80 ° C. until the epoxy value became 0. Thereafter, 117 parts of hexahydrophthalic anhydride was added and reacted at 100 ° C. for 2 hours, 514 parts of ε-caprolactone and 0.547 parts of tetraisopropoxy titanate were added, and the reaction was carried out at 120 ° C for 8 hours. Then, after cooling to 50 ° C, a half-blocked isocyanate obtained from 636 parts of isophorone diisocyanate and 446 parts of 2-ethylhexyl alcohol.
04 parts were added, and the reaction was carried out until the absorption of isocyanate group was lost in the infrared absorption spectrum.

Next, 165 parts of methyl isobutyl ketone was added to give a nonvolatile content of 8
An α, ω type swelling structure resin (C) having a zwitterionic group of 0.2% and an acid value of 27.2 was obtained.

Reference Example 4 Using the same reaction apparatus as in Reference Example 1, charged with 590 parts of the same epoxy resin as used in Reference Example 2 and 932 parts of ε-caprolactone, dissolved at 80 ° C. under a nitrogen stream, and then tetraisopropoxy titanate. 0.800 parts was added and reacted at 120 ° C for 8 hours, then 400 parts of methyl cellosolve and 78 parts of sodium N-methylalanine were added and reacted until the epoxy value became 0 at 100 ° C, nonvolatile content 80.5%, acid value 22.8. As a result, an α, ω type swelling structure resin (D) having a zwitterionic group of

Reference Example 5 Production of Film Forming Acrylic Resin Varnish A reactor similar to that used in Reference Example 1 was charged with 710 parts of toluene and 200 parts of n-butanol. Next, 200 parts of a solution having the following composition was added and heated with stirring to raise the temperature.

Methacrylic acid 12 parts Styrene 264 parts Methyl methacrylate 264 parts n-Butyl acrylate 860 parts 2-Hydroxyethyl acrylate 100 parts Azobisisobutyronitrile 10 parts While refluxing, the remaining 810 parts of the above solution are added dropwise over 2 hours. , Then azobisisobutyronitrile 3 parts and toluene
A solution consisting of 100 parts was added dropwise over 30 minutes. The reaction solution was further stirred and refluxed for 2 hours to increase the rate of conversion to resin, and then the reaction was terminated to obtain an acrylic resin varnish having a nonvolatile content of 50%.

Reference Example 6 According to Reference Example 1, an α, ω type swelling structure resin (E) having an anion group having exactly the same structure except that it does not have a side chain.
Was synthesized. The resin obtained has a nonvolatile content of 80.2% and an acid value of 10
It was 5.0.

Example 1 and Comparative Example 1 In the reaction vessel used in Reference Example 1, the α, ω type swelling structure resin (A) having an anion group obtained in Reference Example 1 was added.
2.5 parts were taken and the solvent was removed by adding a pressure reducing device at 50 ° C. After removing the solvent, 2.6 parts of dimethylethanolamine was added,
After stirring well, 370 parts of deionized water was further added and dissolved while maintaining the temperature under stirring at 80 ° C, and 4.5 parts of azobiscyanovaleric acid was dissolved in 45 parts of deionized water and 4.3 parts of dimethylethanolamine. The liquid was added. Then, a mixed solution of 65 parts of methyl methacrylate, 90 parts of n-butyl acrylate, 70 parts of styrene, 5 parts of 2-hydroxyethyl acrylate and 15 parts of ethylene glycol dimethacrylate was added dropwise over 60 minutes. After dropping, add 1.5 parts of azobiscyanovaleric acid dissolved in 15 parts of deionized water and 1.4 parts of dimethylethanolamine and add 60 parts at 80 ° C.
Continue stirring for 4 minutes, nonvolatile content 40.5%, pH 7.2, particle size 0.07
An aqueous dispersion of fine resin particles of μ was obtained. Such an aqueous dispersion of resin particles was specific and did not cause aggregation or sedimentation even after being left for one month.

This aqueous dispersion of fine resin particles was azeotropically substituted with a xylol solution to obtain a xylol dispersion containing 20% by weight of fine resin particles in the solution. Such a resin particle xylol dispersion was also stable and did not cause aggregation or sedimentation even when left for 1 month.

Next, materials having the following compositions were weighed in a stainless steel container and stirred with a laboratory stirrer to prepare a coating composition.

The fine particles dispersed in the composition of this example did not show sedimentation even after standing for 72 hours.

Ford cup No. 4 by diluting each composition with a mixed solvent of xylene / ethylene glycol monobutyl ether = 1/1
When the viscosity of the composition of this example was adjusted to 25 seconds, the nonvolatile content of the composition of this example was 42.3%, while the nonvolatile content of Comparative Example 1 was 3%.
It was 7.6%. In addition, the sagging during spray coating of the present example was far better than that of the comparative example.

Comparative Example 2 Except that the α, ω type resin (E) having an anion group obtained in Reference Example 6 was used as an emulsifier instead of the α, ω type swelling structure resin (A) having an anion group used in Example 1. In exactly the same manner, a dispersion liquid of fine resin particles having a nonvolatile content of 40%, pH = 7.9 and a particle diameter of 0.07μ was obtained. This resin particle dispersion was stable even after standing for 1 month and did not cause aggregation or sedimentation. However, the xylol dispersion containing 20% by weight of fine resin particles obtained by substituting the xylol solution by utilizing azeotrope was used. It was found that storage stability was poor when left for one month to cause sedimentation.

Example 2 370 parts of deionized water was charged in the same reaction vessel as in Example 1, and 7.5 parts of the α, ω type swelling structure resin (C) having a zwitterionic group obtained in Reference Example 3 was added with 0.3 part of dimethylethanolamine. The neutralized product was added, and the mixture was dissolved while maintaining the temperature at 80 ° C. under stirring, and a solution prepared by dissolving 4.5 parts of azobiscyanovaleric acid in 45 parts of deionized water and 4.3 parts of dimethylethanolamine was added thereto. 90 parts of methyl methacrylate, n-
Butyl acrylate 120 parts, styrene 75 parts, and 2-
9 parts of hydroxyethyl acrylate was added dropwise over 60 minutes. After dropping, add 1.5 parts of azobiscyanovaleric acid dissolved in 15 parts of deionized water and 1.4 parts of dimethylethanolamine and continue stirring at 80 ° C for 60 minutes to remove the nonvolatile content.
An aqueous dispersion (emulsion) of fine resin particles having a particle size of 41.0%, pH 7.5 and a particle size of 0.22μ was obtained. The resulting emulsion was rubbed between fingers and checked for stability, which was good. Further, even if left for 3 months, there was no aggregation or sedimentation and it had good storage stability.

Preparation and Evaluation of Permanently Dry Paint A solution prepared by removing 2 parts of the α, ω type swelling structure resin (C) having a zwitterionic group obtained in Reference Example 3 and then neutralizing it by adding 0.1 part of dimethylethanolamine to 30 Part of deionized water was added and well dissolved. Next, 45 parts of titanium dioxide pigment and 5 parts of copper phthalocyanine blue pigment were added and dispersed for 30 minutes with a paint conditioner to obtain a blue pigment paste. It was found that the obtained pigment paste had no aggregation or color separation, the particle size measured by the grind gauge was 10 μm or less, and that the α, ω type swelling structure resin had a good pigment dispersion function. Next, 250 parts of the emulsion of this example was added to the paste of the present pigment, and the mixture was thoroughly stirred to obtain a normally dry paint.

This paint was applied to a 0.7 mm iron plate so that the film thickness would be 20 μ, and dried at room temperature. Such a coating has sufficient adhesion to the substrate, and even after a test of immersing it in warm water at 80 ° C for 3 days, there is no deterioration in the gloss of the coating and no abnormalities such as blistering and peeling, and sufficient water resistance. Had.

Example 3 The same reaction vessel as in Example 1 was charged with 200 g of deionized water,
A mixture solution A consisting of 60 parts of methyl methacrylate, 50 parts of styrene, 80 parts of n-butyl acrylate and 10 parts of 2-hydroxyethyl acrylate, and Reference Example 2 was added to the temperature of 80 ° C. while sufficiently purging with nitrogen gas. 25 parts of the obtained α, ω type swelling structure resin (B) having a cation group was desolvated, and 0.71 part of acetic anhydride was added to neutralize the resin and V
A mixed solution B obtained by dissolving 4 parts of -50 (water-soluble azo initiator manufactured by Wako Pure Chemical Industries, Ltd.) in 100 parts of deionized water was added dropwise over 2 hours, and then at 80 ° C. Stirring was continued for 60 minutes to obtain a fine resin particle dispersion emulsion with a nonvolatile content of 42% and a particle size of 0.4μ. The obtained emulsion was rubbed between fingers and checked for stability, but no abnormality was found. Again 1
There was no aggregation or sedimentation even after standing for a month.

Next, this emulsion was coated on an asbestos slate plate so that the dry coating amount was 30 g / m ^{2 and} dried at 50 ° C. for 6 hours to obtain a coated slate plate. This slate board has 10
No peeling or peeling occurred even when immersed in warm water at 40 ° C for one day.

Example 4 25 parts of the α, ω swelling structure resin (D) having the zwitterionic group obtained in Reference Example 4 was desolvated in 1000 parts of deionized water in a reaction vessel, and neutralized with 0.73 part of dimethylethanolamine. Resin and polyvinyl alcohol with an average molecular weight of 1500
After charging 20 parts, while stirring at 1000 rpm and sufficiently purging with N ₂ gas to a temperature of 60 ° C., 10 parts of styrene, 30 parts of methyl methacrylate, 20 parts of n-butyl acrylate
Part, acrylonitrile 10 parts, ethylene glycol dimethacrylate 20 parts and Elsan (dimethyldithiophosphorylphenyl ethyl acetate manufactured by Nissan Chemical Industries, Ltd.) 10 parts and 2,2'-azobis- (2,4-dimethylvaleronitrile) ) (Brand name V-65, Wako Pure Chemical Industries, Ltd.)
The mixture obtained by stirring 2 parts of (manufacturing, polymerization initiator) was added dropwise over 1 hour. After finishing the dropping, change the temperature in the reaction vessel.
The temperature was raised to 70 ° C., and the reaction was further performed for 5 hours to obtain a suspension of fine resin particles. The suspension is subjected to a centrifuge to disperse the supernatant liquid and the resin particles, and then only the resin particles are dispersed in deionized water. This method is repeated 3 times to obtain a fine resin particle powder having an insecticidal effect. It was The average particle size of this resin powder was 29μ.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hirotoshi Umemoto 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (72) Inventor Ryuzo Mizuguchi 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint (56) References JP 57-187302 (JP, A) JP 58-129066 (JP, A) JP 57-164116 (JP, A) JP 58-21416 (JP, A) A)

Claims (5)

[Claims] 1. An epoxy resin having an epoxy equivalent of 100 to 6000.
From at least one main chain(In the formula, R₁And R₂Means hydrogen or a methyl group, A
Is an ether bond or ester bond, or active hydrogen
Generated by the reaction between the containing group and the diisocyanate compound
Means a divalent organic group, and B is a line having a molecular weight of 100 to 7,000.
-Like polymer block, Y is hydroxyl group, amino group
Or carboxyl groups, or bound to these groups
It means a half-blocked diisocyanate residue. )so
Including a side chain binding block represented, at least one of the end groups of the main chain is represented by the formula(In the formula, R₁And R₂Is the same as above, and X is epoxy
A polyfunctional carboxylic acid having active hydrogen that reacts with a group,
Means the residue of a rufonic acid or phosphoric acid compound. )
Is an anionic group or its salt(In the formula, R₁And R₂Is the same as above and R₃Is a substituent
I may have C₂~ C₂₀Means an alkyl group of R_FourIs R
₃Same as or means hydrogen atom or benzyl group
To do. ) Becomes a cationic group or its salt
Or expression (In the formula, R₁And R₂Is the same as above and R_FiveIs hydrogen,
Or alkyl having 1 to 20 carbon atoms which may have a substituent
Base, R₆Is a straight chain having 1 to 12 carbon atoms which may have a substituent
Alternatively, it may have a branched alkylene group or a substituent.
A phenylene group, which has an ester bond or ether
R bond may be included, Z Is −COO ，-SO₃ , -OSO₃ ，Or represents a partial ester residue of an organic polybasic acid, R₇Is water
Alkyl having 1 to 12 carbon atoms which may have a substituent
Group, or phenyl group which may have a substituent
To do. ) As a zwitterionic group or salt thereof
Ethylene in an aqueous medium in the presence of modified epoxy resin
Of emulsion or suspension polymerization of water-soluble unsaturated monomers
A method for producing fine resin particles. 2. The method for producing fine resin particles according to claim 1, wherein the epoxy resin having an epoxy equivalent of 100 to 6000 is a diglycidyl ether type epoxy resin, a diglycidyl ester type epoxy resin, or a diglycidyl amine type epoxy resin. 3. The method for producing fine resin particles according to claim 1 or 2, wherein the linear polymer block is selected from polylactone, polyether, polyester and polylactam. 4. The method for producing fine resin particles according to any one of claims 1 to 3, wherein the particle diameter is 0.01 to 50 μm. 5. An ethylenically unsaturated monomer is a monofunctional monomer.
50 to 100% by weight, and polyfunctional or crosslinkable monomer 0 to 50
5. The method for producing fine resin particles according to any one of items 1 to 4, which contains the resin in a weight percentage.