JPH01188520A - Minute resin particle - Google Patents

Abstract

PURPOSE:To obtain the subject particle having high resistance to water, corrosion and weather and useful as a carrier for functional substance, etc., by polymerizing an unsaturated monomer in an aqueous medium in the presence of a specific modified epoxy resin having an ionic terminal group and a block bonded to side chain and containing a side chain functional group. CONSTITUTION:The objective particle can be produced by the emulsion polymerization or suspension polymerization of an ethylenic unsaturated monomer in an aqueous medium in the presence of a modified epoxy resin induced from an epoxy resin having an epoxy equivalent of 100-6,000, containing one or more side chain bonded blocks of formula I (R1 and R2 are H or methyl; A is ether bond, ester bond, etc.; B is a linear polymer block having a molecular weight of 100-7,000; Y is OH, COOH, etc.) in the main chain and having an anionic group (salt) of formula II (X is polyfunctional carboxylic acid, sulfonic acid, etc.) or a cationic group (salt) of formula III (R3 is 2-20C alkyl; R4 is H or R3) or an amphoteric ion group (salt) of formula IV (R5 is H or 1-20C alkyl; R6 is 1-20C alkyl, etc.; Z is COO, SO3, etc.), etc.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to microscopic resin particles made of polymers or copolymers of ethylenically unsaturated monomers.

In the field of paints, it is well known to use microscopic resin particles made of internally crosslinked polymers or copolymers of ethylenically unsaturated monomers for the purpose of high solids formation and rheology control. Furthermore, such fine resin particles can be used as carriers for catalysts, ultraviolet absorbers, biocides, and other functional substances, such as paints, plastic materials, electrical materials, and medical and biological materials.

In JP-A-57-187302 filed by the present applicant, a monomer having two or more ethylenically unsaturated groups in the molecule and another ethylenically unsaturated It describes an emulsion resin obtained by polymerizing monomers in an aqueous medium by an emulsion polymerization method.

Furthermore, Japanese Patent Application Laid-Open No. 58-129066 filed by the present applicant discloses fine resin particles obtained by removing the dispersion medium from the emulsion by filtration, spray drying, freeze drying, etc., or by replacing the emulsion with a solvent. It is proposed to add a microscopic resin dispersion to a coating composition containing a film-forming resin and a crosslinking agent.

As a result of supporting the above-mentioned amphoteric aqueous resin on the surface of these micro resin particles, micro resin particles produced by emulsion polymerization using general emulsifiers and dispersants,
It has unique surface chemical and electrochemical properties not found in microscopic resin particles obtained by polymerization in non-aqueous solvents known as the NAD method.

The present invention involves emulsion polymerization or suspension polymerization in the presence of a modified epoxy resin having an anionic, cationic, or amphoteric hydrophilic group at the end of the main chain and a hydrophobic linear polymer block grafted as a side chain. Provided are minute resin particles produced by a turbidity polymerization method.

The present invention is derived from an epoxy resin having an epoxy equivalent of 100 to 6000, and has a main chain of at least one formula% (wherein R1 and R2 represent hydrogen or a methyl group. , A means an ether bond or ester bond, or a divalent organic group produced by the reaction of an active hydrogen-containing group with a diisocyanate compound, and B has a molecular weight of 100 to 7.
000 linear polymer block, and Y means a hydroxyl group, an amino group, a carboxyl group, or a half-block diisocyanate residue bonded to these groups. ), at least one of the terminal groups of the main chain is a polyfunctional compound having the formula (wherein R1 and R2 are the same as above, and X has an active hydrogen that reacts with an epoxy group). carboxylic acid,
means the residue of a sulfonic acid or phosphoric acid compound. ) or a salt thereof, or the formula (wherein R1 and R2 are the same as above, and R3 means an alkyl group of 02 to IJ which may have a substituent, R4 is the same as R3, or is a cationic group represented by a hydrogen atom or a benzyl group, or a salt thereof;
is the same as above, R5 is hydrogen or an alkyl group having 1 to 20 carbon atoms which may have a substituent, and R6 is a linear or branched chain having 1 to 12 carbon atoms which may have a substituent. An alkylene group, a phenylene group that may have a substituent, and may contain an ester bond or an ether bond, Zo is -COO°, -C)IcO
O8■ CH2C0OH.

-303°, -05Oa°, -o -p-oo or organic R7 represents a partial ester residue of a polybasic acid, R7 is hydrogen, an alkyl group having 1 to 12 carbon atoms that may have a substituent, or a substituted It means a phenyl group which may also have a group.

) Provides fine resin particles obtained by emulsion polymerization or suspension polymerization of an ethylenically unsaturated monomer in an aqueous medium in the presence of a modified epoxy resin that is a zwitterionic group represented by () or a salt thereof. do.

The fine resin particles according to the present invention carry the modified epoxy resin on their surfaces. The modified epoxy resin has a hydrophilic group at the end of the main chain and a hydrophobic polymer block as a side chain, so it has surface activity. Therefore, the micro resin of the present invention with this resin supported on the surface Because the particles are amphiphilic, they have good dispersion stability in both hydrophilic and lipophilic media, and the modified epoxy resin supported has crosslinking points at the ends of the side chain polymer blocks, so it has good curing reactivity. It has the following characteristics.

When the inside of the particles is not gelled, the fine resin particles can be used as a stable emulsion resin that forms a film, and the resulting film has excellent water resistance, corrosion resistance, weather resistance, and physical properties.

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

In particular, those with relatively large particle sizes can be used as carriers for various substances, such as paints, plastic materials, electrical materials, and biological materials.

It is derived from an epoxy resin having an epoxy equivalent of 100 to 6000, the main chain has at least one side chain polymer block represented by the above formula (I), and at least one terminal group of the main chain has the above formula (II- The modified epoxy resin having the anionic hydrophilic group in 1) is described in detail in the patent application filed by the present applicant on January 30, 1988 entitled "Anionic Modified Epoxy Resin". .

Such a resin is made from a resin containing at least one alcoholic hydroxyl group generated by ring opening of an epoxy group in the main chain derived from an epoxy resin having an epoxy equivalent of 100 to 6000, and (a) the above-mentioned alcohol. At least one linear polymer block side chain with a molecular weight of 100 to 7,000 having a hydroxyl group, amino group or carboxyl group at the end is introduced by reaction with a hydroxyl group, and if necessary, a half-bronocyclodiisocyanate is bonded to the terminal group of the side chain. (bl) ring-opening at least one terminal epoxy group of the main chain by reaction with a polyfunctional carboxylic acid, sulfonic acid or phosphoric acid compound having active hydrogen, or reaction of the terminal epoxy group with a hydroxycarboxylic acid; It is produced by acylating the precursor obtained by ring-opening with a polybasic acid anhydride to introduce an acid group and, if necessary, performing the steps of forming a salt in any order.

A modified epoxy resin having a cationic hydrophilic group instead of an anionic hydrophilic group at the end of the main chain (cationic modified epoxy resin) has a group represented by the above formula (II-2) at the end of the main chain. , is obtained by ring-opening the terminal epoxy group of the epoxy resin in step (b) by reacting with an amine of formula 11N (Ra) CR4). Examples of amines include dimethylaminopropylamine, jetanolamine, diisopropanolamine, di-2
-Hydroxybutylamine, di-2-hydroxyoctylamine, N-methylethanolamine, N-methylisopropanolamine, N-ethylethanolamine,
N-hensylethanolamine and the like are used. The production of such cationic modified epoxy resin was disclosed in Japanese Patent Application Laid-open No. 1983
-233068.

The modified epoxy resin having an amphoteric hydrophilic group represented by the formula (II-3) or (■-3'') at the end of the main chain is the Described in a patent application entitled "Zwitterionic Modified Epoxy Resins". These resins have an epoxy equivalent of 100 to 60
A resin containing at least one alcoholic hydroxyl group generated by ring opening of an epoxy group in the main chain derived from the epoxy resin No. 00 is used as a raw material, a step of introducing at least one linear polymer block side chain having a molecular weight of 100 to 7,000 and having a carboxyl group, and optionally bonding a half-block diisocyanate to the terminal group of the side chain, (bl at least one main chain terminal epoxy Formula %
Formula %) [In the formula, the symbols are the same as above. ), or the terminal epoxy group is ring-opened by reaction with an amino alcohol of formula % (wherein R6 and R6 are the same as above). It can be produced by acylating the obtained precursor with a polybasic acid anhydride to introduce a zwitterionic group, and if necessary, performing the steps of treating with an acid or forming a salt in any order.

It is preferable that the anionic, cationic and amphoteric modified epoxy resins have these hydrophilic groups at both ends of the main chain (α, ω Sudare type), and the main chain has a molecular weight of 200 to 10,000. Derived from bisphenol type epoxy resin, each side chain has a molecular weight of 100~
7000 polycaprolactone, main chain molecular weight/
It is preferable that the molecule of the side chain portion is ff1-110.1 to 5.0.

The fine resin particles of the present invention are produced by polymerizing ethylene in an aqueous medium by a known emulsion polymerization method or suspension polymerization method using a modified epoxy resin having the above structure as an emulsifier or dispersant. It can be produced by polymerizing polyunsaturated monomers.The amount of modified poxy resin used is 0.01 to 50% of the monomer weight in emulsion polymerization, and 0.01 to 50% of the monomer weight in suspension polymerization. 0.
01 to 10% is preferred.

When used as a film-forming resin for water-based paints, such as the fine resin particles disclosed in JP-A-57-187302 by the present applicant, the monomers may be monofunctional monomers only or up to 3% polyfunctional monomers. Alternatively, a mixture with a monofunctional monomer containing a crosslinking monomer may be used.

Furthermore, when internally crosslinked fine resin particles are used as a paint filler as in JP-A-58-129066 by the present applicant, the monomer mixture contains 3 to 50% of polyfunctional or crosslinkable monomers. be able to.

Monofunctional ethylenically unsaturated monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate,
Alkyl esters of acrylic acid or methacrylic acid such as 2-ethylhexyl (meth)acrylate, and other monomers having ethylenically unsaturated bonds that can be copolymerized with the same, such as styrene, α-methylstyrene, vinyltoluene,
Examples include t-butylstyrene, ethylene, propylene, vinyl acetate, vinyl propionate, acrylonitrile, methacrylate trile, dimethylaminoethyl (meth)acrylate, and the like. Two or more types of these monomers may be used.

Crosslinkable comonomers are monomers and/or monomers having two or more radically polymerizable ethylenically unsaturated bonds in the molecule.
Alternatively, it contains two types of ethylenically unsaturated group-containing monomers each carrying groups that can react with each other.

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

Ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ■, 3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol dimethacrylate Acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol dimethacrylate, glycerol dimethacrylate Acrylate, glycerol allyloxy dimethacrylate, LLI-trishydroxymethylethane diacrylate, LLI
-trishydroxymethylethane triacrylate, 1
, 1,1-trishydroxymethylethane dimethacrylate, LLI-) lis-hydroxymethylethane trimethacrylate, 1,Ll-) lis-hydroxymethylpropane diacrylate, Ll,1-) lis-hydroxymethylpropane triacrylate, 1,1. 1
-) Lishydroxymethylpropane dimethacrylate-1
., 1, Ll-) lishydroxymethylpropane trimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl tucrate and divinylhenyne.

In addition, examples of monomers having two types of ethylenically unsaturated groups each carrying mutually reactive groups include epoxy group-containing ethylenically unsaturated monomers such as glycidyl acrylate and glycidyl methacrylate, and acrylic acid and methacrylic acid. Carboxyl group-containing ethylenically unsaturated monomers such as acid and crotonic acid are the most representative, but mutually reactive groups are not limited to these.
For example, various compounds have been proposed, such as amine and carbonyl, epoxide and carboxylic acid anhydride, amine and carboxylic acid chloride, alkyleneimine and carbonyl, organoalkoxysilane and carboxyl, hydroxyl and isocyanate, etc., and the present invention broadly encompasses these. It is something to do.

Micro resin particles produced in an aqueous medium or a non-aqueous organic medium can be isolated by a method such as filtration, spray drying, or freeze drying, and then cut into appropriate particle sizes by using a mill or the like. It can be used after being pulverized, or a synthesized dispersion can be used by replacing the medium with the solvent.

- It is desirable to control the particle size of particles obtained by boat fishing by the polymerization method. Emulsion polymerization is used for particles of 0.01 to 20μ, and suspension polymerization is used for particles of 1 to 50μ.

In addition, rheology control is possible by adjusting the particle size distribution by the polymerization process or by mixing the particles after polymerization, if necessary. Furthermore, it is naturally possible to carry and include on the surface or inside of the resin particles a promoter substance that promotes 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 polyfunctional or crosslinkable monomers is 3% or less, can be used alone or in combination with other resins in the form of an aqueous dispersion to form air-drying or thermosetting water-based paints. It can be used as

The internally crosslinked micro resin particles containing 3 to 50% of polyfunctional or crosslinking monomers are dried after polymerization while remaining as an aqueous dispersion.
It can be used in air-drying or thermosetting paints in powder form obtained by filtration or as an organic solvent dispersion obtained by solvent substitution, in combination with other resins that have film-forming ability. .

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.

The present invention will be explained in more detail below using reference examples and examples. "Parts" and "%" in these Reference Examples and Examples are based on weight.

Reference example 1 Stirrer, 7! In a Colchen equipped with an A-degree meter, a nitrogen inlet tube, and a reflux condenser, an epoxy compound obtained by the reaction of bisphenol A and epichlorohydrin [950,
Charge 350 parts of epoxy resin with a number average molecular weight of 1900, add and dissolve 212 parts of methyl isobutyl ketone, and under a nitrogen stream, mix 22 parts of hydroxypivalic acid, 25 parts of dimethylolpropionic acid, and 0.40 parts of benzyldimethylamine.
After adding 0 parts of hexahydrophthalic anhydride and reacting at a temperature of 120°C until acid + i151 or less and epoxy (illiO), 28 parts of hexahydrophthalic anhydride and 7 parts of trimerisolic anhydride were added.
After adding 0 part of ε-
1105 parts of prolactone and 0 and soo parts of tetraisopropoxy titanate were added, and the reaction was carried out at 120°C for 8 hours. Next, 188 parts of methyl isobutyl ketone was added to obtain α having an anionic group with a nonvolatile content of 80% and an acid value of 33.0.
, ω-type drooping structure resin> was obtained.

Reference Example 2 Epoxy resin 332 with a number average molecular weight of 900 and an epoxy equivalent of 475 obtained by reacting bisphenol A and epichlorohydrin using the same reaction apparatus as in Reference Example 1.
After adding and dissolving 928 parts of ethylene glycol monoethyl ether acetate,
Raise the temperature to 0'C and dimethylaminopropylamine 337
A mixture of 1 part and 200 parts of jetanolamine was added dropwise over 1 hour. Next, the temperature was raised to 100°C, and the reaction was carried out until the epoxy value reached O.

Next, 387 parts of ε-caprolac and 15 parts of dibutyltin dilaurate were added, the temperature was raised to 140'C, and the mixture was reacted for 3 hours. B) was obtained.

Reference Example 3 Using the same reaction apparatus as in Reference Example 1, an epoxy equivalent of 950. Epoxy resin 36 with number average molecular weight 1900
3 parts were charged, 235 parts of methyl isobutyl ketone was added and dissolved, 40 parts of jetanolamine was added, and the reaction was carried out at a reaction temperature of 80° C. under a nitrogen stream until the epoxy value reached O.

Then add 117 parts of No. K hydrophthalic anhydride,
After reacting at 00℃ for 2 hours, ε-caprolactone 51
4 parts, 0.547 parts of tetraisopropoxy titanate) were added, and the reaction was carried out at 120°C for 8 hours. Then 50℃
After cooling to , 504 parts of half-block isocyanate obtained from 636 parts of isophorone diisocyanate and 446 parts of 2-ethylhexyl alcohol were added, and the reaction was carried out until no absorption of isocyanate groups was observed in the infrared absorption spectrum.

Next, 165 parts of methyl isobutyl ketone was added to obtain α, which has a zwitterionic group with a nonvolatile content of 80.2% and an acid value of 27.2.
A resin with an ω-type sagging structure was obtained.

Reference Example 4 Using the same reaction apparatus as Reference Example 1, 590 parts of the same epoxy resin as used in Reference Example 2, and 93 parts of ε-caprolactone.
After dissolving 2 parts at 80°C under a nitrogen stream, add 0°800 parts of tetraisopropoxy titanate and dissolve at 120°C.
The reaction was carried out for 8 hours, and then 400 parts of methyl cellosolve and 78 parts of sodium N-methylalanine were added, and 100 parts of
The reaction was carried out at ℃ until the epoxy value reached 0, and the non-volatile content was 80.
5%.

A resin D) having an .alpha., .omega.-type sagging structure with an acid zwitterion group of 22.8 was obtained.

Reference Example 5 Flume 3 I Acrylic Varnish 1 710 parts of toluene and 200 parts of n-butanol were placed in the same reaction vessel as Reference 1.
I prepared a section. Next, 200 parts of a solution having the following composition was added and heated while 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 Abbisisobutyronitrile 10
While partially refluxing, the remaining 810 parts of the above solution was added dropwise over 2 hours, and then a solution consisting of 3 parts of azobisisobutyronitrile and 100 parts of toluene was added dropwise over 30 minutes. The reaction solution was further stirred and refluxed for 2 hours to increase the conversion rate to resin, and then the reaction was terminated to obtain an acrylic resin face with a non-volatile content of 50%.

Reference Example 6 α, ω-type Sudesudare structure resin with anionic group having exactly the same structure as Reference Example 1 except that it does not have a side chain)
was synthesized. The obtained resin had a nonvolatile content of 80.2% and an acid value of 105.0.

Example 1 and Comparative Example 1 In the reaction vessel used in Reference Example 1, 6 α, ω type sudare structure resin (A) having anionic groups obtained in Reference Example 1 was placed.
2.5 parts were taken and the solvent was removed at 50°C by adding a pressure reducing device. After removing the solvent, add 2.6 parts of dimethylethanolamine, stir, then add 370 parts of deionized water and dissolve while maintaining the temperature at 80°C with stirring. To this, 4.5 parts of azobiscyanovaleric acid A solution prepared by dissolving 1 part in 45 parts of deionized water and 4.3 parts of dimethylethanolamine was added.

Next, a liquid mixture consisting 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 the dropwise addition, 1.5 parts of azobiscyanovaleric acid dissolved in 15 parts of deionized water and 1.4 parts of dimethylethanolamine was added, and stirring was continued at 80°C for 60 minutes.
Non-volatile content 40.5%, pH 7.2, particle size 0.07μ
An aqueous dispersion of minute resin particles was obtained. This aqueous resin particle dispersion was stable and did not cause aggregation or sedimentation even after being left for one month.

This aqueous dispersion of fine resin particles was replaced with a xylol solution using azeotropy to obtain a xylol dispersion containing 20% by weight of fine resin particles in the solution. This dispersion of resin particles in Kijiroru was also stable, and did not cause aggregation or sedimentation even after being left for one month.

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

, Polymer fine particles on the basis of the tip
25 parts □ The fine particles dispersed in the composition of this example showed no sedimentation even after being left for 72 hours.

Each composition was diluted with a mixed solvent of xylene/ethylene glycol monobutyl ether-1/1 and Ford Cup N
o. When the viscosity was adjusted to 25 seconds with 4, the non-volatile content of the composition of this example was 42.3%, while the non-volatile content of Comparative Example 1 was 37.6%. Furthermore, the coatings of this example exhibited much better sagging during spray coating than those of the comparative examples.

Comparative Example 2 Instead of the α, ω, ω resin (A) having an anionic group used in Example 1, the α, ω, ω resin (E) having an anionic group obtained in Reference Example 6 is used as an emulsifier. Everything else was the same, non-volatile content 40%.

A fine resin particle dispersion having a pH of 7.9 and a particle size of 0.07 μm was obtained. This resin particle dispersion was stable even after being left for one month and did not cause aggregation or sedimentation.
It was found that the kijirole dispersion containing 0% by weight caused sedimentation after being left for one month, and had poor storage stability.

Example 2 370 parts of deionized water was charged into the same reaction vessel as in Example I, and 7.5 parts of the α, ω type resin with a zwitterionic group obtained in Reference Example 3 was mixed with 0% dimethylethanolamine.
．． Add 3 parts of neutralized and dissolve while stirring while maintaining the temperature at 80°C, and add 4 parts of Abhiscyanovaleric acid.
5 parts to 45 parts deionized water and 4 parts dimethylethanolamine.
．． Three parts of the molten liquid were added. Next, 90 parts of methyl methacrylate, 120 parts of n-butyl acrylate, 75 parts of styrene, and 9 parts of 2-hydroxyethyl acrylate were added dropwise over 60 minutes. After the dropwise addition, 1.5 parts of abviscyanovaleric acid dissolved in 15 parts of deionized water and 1.4 parts of dimethylethanolamine was added to give 8 parts of dimethylethanolamine.
Stirring was continued for 60 minutes at 0°C, and the non-volatile content was 41.0% and the pH was
7,5, Aqueous dispersion of micro resin particles with a particle size of 0.22μ (
Emulsion) was obtained.

The stability of the resulting emulsion was checked by rubbing it between the fingers, and it was found to be good. Moreover, even after being left for 3 months, there was no aggregation or sedimentation, and the product had good storage stability.

14-year-old chef! After desolventizing 2 parts of the α, ω-type dull structure resin with amphoteric ionic groups obtained in Reference Example 3, 0.1 part of dimethylethanolamine was added to neutralize the resulting product, and 30 parts of the deionized Add to water and dissolve well.

Then add 45 parts of titanium dioxide pigment and 5 parts of copper phthalocyanine blue pigment and apply 3 parts of paint conditioner.
A blue pigment paste was obtained by dispersing for 0 minutes. The obtained pigment paste had no agglomeration or color separation, and the particle size measured by a grind gauge was 10 μm or less, indicating that the α, ω, ω structure resin had a good pigment dispersion function. Next, add 25% of the emulsion in this example to the paste of this pigment.
0 parts was added and thoroughly stirred to obtain an air-dry paint.

This paint was applied to a 0.7+n iron plate to a film thickness of 20 μm and dried at room temperature. This coating film has sufficient adhesion to the substrate, and even after being immersed in hot water at 80°C for 3 days, there was no abnormality such as loss of gloss, blistering, or peeling of the coating film, and it had sufficient water resistance. It had

Example 3 200 g of deionized water was charged into the same reaction vessel as in Example 1, and the temperature was brought to 80°C while thoroughly purging with nitrogen gas, and 60 parts of methyl methacrylate and 50 parts of styrene were added.
A mixed solution A consisting of 80 parts of n-butyl acrylate and 10 parts of 2-hydroxyethyl acrylate and 25 parts of the α,ω sagging structure resin (B) having a cationic group obtained in Reference Example 2 were desolventized, Mixture B obtained by dissolving the resin neutralized by adding 0.71 parts of acetic anhydride and 4 parts of V-50 (manufactured by Wako Pure Chemical Industries, water-soluble azo initiator) in 100 parts of deionized water. After dropping for 2 hours in parallel, add 8 more drops.
After stirring at 0°C for 60 minutes, a fine resin particle dispersion emulsion with a nonvolatile content of 42% and a particle size of 0.4 μm was obtained. The resulting emulsion was rubbed between the fingers to check its stability, but no abnormalities were found. Further, even after being left for one month, there was no aggregation or sedimentation.

Next, this emulsion was applied to an asbestos slate board at a dry coating weight of 30 g/m, and the emulsion was dried in the shade at 50°C for 6 hours to obtain a coated slate board. This slate board did not peel or peel even after being immersed in 40°C hot water for 10 days.

Example 4 In a reaction vessel, 1000 parts of deionized water was mixed with α,ω sagging structure resin (D) 25 having amphoteric ionic groups obtained in Reference Example 4.
After removing the solvent and charging the resin neutralized with 0.73 parts of dimethylethanolamine and 20 parts of polyvinyl alcohol with an average molecular weight of 1500, the temperature was raised to 60°C while stirring at 11000 rpm and thoroughly purging with N2 gas. 10 parts styrene, 3 parts methyl methacrylate
0 parts, n-butyl acrylate, 20 parts, acrylonitrile, 10 parts, ethylene glycol dimethacrylate, 20 parts, and 10 parts of EL (dimethyldithiophosphorylphenyl ethyl acetate manufactured by Nissan Chemical), and 2,2゛-azobis- A mixture obtained by stirring 2 parts of (2,4-dimethylvaleronitrile) (trade name V-65. 1 polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 1 hour. After the completion of the dropwise addition, the temperature inside the reaction vessel was raised to 70°C, and the reaction was further carried out for 5 hours to obtain a fine resin particle suspension. The suspension was centrifuged and dispersed into supernatant liquid and resin particles, and then only the resin particles were dispersed in deionized water. After repeating this process three times, a fine resin particle powder with an insecticidal effect was obtained. Ta. The average particle size of this resin powder is 2
It was 9μ.

Claims (5)

[Claims] (1) Derived from an epoxy resin with an epoxy equivalent of 100 to 6000, with at least one main chain ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, R_1 and R_2 mean hydrogen or methyl group However, A means an ether bond or an ester bond, or a divalent organic group produced by the reaction of an active hydrogen-containing group with a diisocyanate compound, and B means a molecular weight of 100.
~7000 linear polymer blocks, and Y means a hydroxyl group, an amino group, or a carboxyl group, or a half-block diisocyanate residue bonded to these groups. ), and at least one of the terminal groups of the main chain has the formula ▲ has a mathematical formula, chemical formula, table, etc. ▼ (II-1) (In the formula, R_1 and R_2 are the same as above. , and X means the residue of a polyfunctional carboxylic acid, sulfonic acid, or phosphoric acid compound having an active hydrogen that reacts with an epoxy group. , chemical formulas, tables, etc.▼(II-2) (In the formula, R_1 and R_2 are the same as above, and R_
3 means an alkyl group of C_2 to C_2_0 which may have a substituent, and R_4 is the same as R_3 or means a hydrogen atom or a benzyl group. ) or its salt, or the formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II-3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II-3') ( In the formula, R_1 and R_2 are the same as above, and R_
5 is hydrogen, or has 1 to 1 carbon atoms and may have a substituent
20 alkyl group, R_6 is a straight or branched alkylene group having 1 to 12 carbon atoms that may have a substituent,
It is a phenylene group that may have a substituent, and may contain an ester bond or an ether bond.
■ is -COO^■, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
-SO_3^■, -OSO_3^■, ▲mathematical formula, chemical formula,
There are tables, etc. ▼ or represents a partial ester residue of an organic polybasic acid, R_7 means hydrogen, an alkyl group with 1 to 12 carbon atoms that may have a substituent, or a phenyl group that may have a substituent. do. ) Fine resin particles obtained by emulsion polymerization or suspension polymerization of an ethylenically unsaturated monomer in an aqueous medium in the presence of a modified epoxy resin that is a zwitterionic group represented by () or a salt thereof. (2) The fine resin particles according to item 1, wherein the epoxy resin having an epoxy equivalent of 100 to 6,000 is a diglycidyl ether-based epoxy resin, a diglycidyl ester-based epoxy resin, or a diglycidyl amine-based epoxy resin. (3) The fine resin particles according to item 1 or 2, wherein the linear polymer block is selected from polylactone, polyether, polyester, and polylactam. (4) The fine resin particles according to any one of items 1 to 3, having a particle size of 0.01 to 50μ. (5) The ethylenically unsaturated monomer is a monofunctional monomer of 50 to
100% by weight and 0 to 50 polyfunctional or crosslinkable monomers
% by weight of the fine resin particles according to any one of paragraphs 1 to 4.