JPH0867756A - Production of epoxy resin ionomer microparticle and its resin composition - Google Patents

Abstract

PURPOSE: To produce microparticles improved in storage stability by making it of a core resin comprising an epoxy resin or a cured product thereof and a carboxylic coating material resin at least part of which is in the form of an ionomer. CONSTITUTION: Methacrylic resin is reacted under heating with another vinyl monomer such as styrene in a specified ratio, and an organic solvent is added to the formed polymer solution to obtain a self-water-dispersible resin solution as a coating material. A methyl ethyl ketone solution of a bisphenol epoxy resin or a product thereof cured with an amine curing agent each having a mean particle diameter of about 1-0.05μm and serving as a core is mixed with the dispersible resin solution. Water is added to the combined solution under agitation to form an epoxy resin dispersion containing the organic solvent, and the solvent is removed in a vacuum from the dispersion to obtain an aqueous dispersion. This dispersion is dissolved again in water, and sodium ethoxide is added to the solution to neutralize the coating material resin with sodium ions to form an ionomer. The product is dried to obtain epoxy resin ionomer microparticles.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing epoxy resin ionomer fine particles and a resin composition comprising the epoxy resin ionomer fine particles and a thermoplastic resin ionomer. More specifically, the present invention uses a resin having a self-dispersing ability in water as a constituent component of an essential organic phase, and the unsaturated carboxylic acid of the outer shell (shell layer) of a microcapsule of an epoxy resin is exposed to water. Neutralize with ions,
A method for producing fine particles of an epoxy resin ionomer by removing water from an emulsion of an epoxy resin which does not use a hydrophilic substance such as a conventional emulsifier by a method for producing fine particles of an epoxy resin ionomer. Further, the present invention provides a resin composition comprising the epoxy resin ionomer fine particles and a thermoplastic resin ionomer. The epoxy resin ionomer fine particles and the resin composition of the present invention are coating materials such as paints and reinforcing materials for rubber and plastics. It is also useful as a coloring compounding agent, and also as a thermosetting resin composition having excellent heat resistance and strength.

[0002]

BACKGROUND OF THE INVENTION It is known that relatively small particles of epoxy resin are obtained by curing the epoxy resin in an emulsion system. Specifically, Japanese Examined Patent Publication No. 62-48972 and Japanese Unexamined Patent Publication No. 61-87721 disclose that an epoxy resin is emulsified with water as a dispersion and the epoxy resin is cured.

Forced emulsification using a nonionic surfactant has been widely used as a conventional method for making an epoxy resin aqueous. When the epoxy resin is dispersed, it is general that the resin is heated or dissolved in a solvent and liquefied, and then an emulsifier is added and water is added dropwise to disperse the resin. At that time, a large shear force is required to reduce the particle size of the emulsion, and a device having a large power is required as a dispersing device.

When using a low-power device, it is necessary to add a large amount of emulsifier. In either case, the emulsion particle size is often 1 μm or more, and it is difficult to obtain a stable dispersion.

Such an epoxy resin emulsion is
Even after curing, the emulsifier remains in the cured product, which causes the performance (particularly water resistance and water absorption) of the cured product to be significantly reduced.
As described above, in the emulsification in the process of producing the epoxy resin fine particles according to the conventional technique, it is the current situation that the dispersion stability is secured and the particles are made into fine particles by using the emulsifier or the organic solvent frequently.

A microencapsulation method that does not use an emulsifier has already been proposed in Japanese Patent Laid-Open No. 3-221137. In this Japanese Patent Laid-Open No. 3-221137, a mixture of a self-water-dispersible resin and a hydrophobic substance is used as an organic phase, water is injected into the organic phase, or the organic phase is introduced into an aqueous medium. By using the self-dispersing agent as a core material, the hydrophobic substance can be used as a core material, and at the same time, ultrafine particle capsules having a particle diameter of 1 μm or less can be instantaneously formed using the self-water-dispersible resin as a wall material. Can be very useful,
A method for producing ultrafine particle capsules is described. However, this publication does not specifically describe any epoxy resin as a hydrophobic substance.

[0007]

The object of the present invention is basically to provide a method for producing an epoxy resin fine particle capsule having a particle size of 1 μm or less, and to provide a hydrophobic liquid and / or a hydrophobic liquid. In producing microcapsules in which a solid substance is included in a resin, microcapsules using self-water-dispersible resins having dispersibility that self-disperse with an average particle size of 0.1 μm or less under the action of an aqueous medium. The present invention is intended to provide a method for producing an epoxy resin microcapsule, characterized in that the formation of the microcapsules and the atomization in a water medium and the capsule wall (shell layer) formation are carried out substantially at the same time.

A further object of the present invention is that it contains no hydrophilic emulsifier and organic solvent and has a particle size of 1 μm.
The object of the present invention is to provide a method for producing epoxy resin fine particles having a storage stability of m or less and good storage stability and an epoxy resin composition having an excellent balance of physical properties.

[0009]

Therefore, as a result of extensive studies on the above problems, the present inventor has found that an epoxy resin formed from a self-water-dispersible resin and an epoxy resin
After producing epoxy resin fine particles from an aqueous dispersion of self-emulsifying resin particles, the unsaturated carboxylic acid that imparts the self-water dispersibility of the shell layer is neutralized with cations and ionized to thereby use the resin. It was found that the physical properties of the obtained molded product are remarkably improved when the molded product is manufactured by the method of producing a molded product, and by blending the obtained epoxy resin ionomer fine particles with the thermoplastic resin ionomer, excellent heat resistance, strength and moldability are obtained. The present invention has been completed by finding out that such a resin composition can be obtained.

That is, according to the present invention, epoxy resin particles are produced by separating an aqueous dispersion liquid obtained by dispersing resin particles composed of a resin as a core material and a resin as a coating material in an aqueous medium and drying. In the method, the core material is an epoxy resin or a cured product thereof, and the coating material is a resin containing at least a part of an ionomerized carboxylic acid group, which provides a method for producing epoxy resin ionomer fine particles. And preferably the number average particle diameter of the epoxy resin particles is 1 to 0.05 μm,
The present invention provides a method for producing epoxy resin ionomer fine particles, characterized in that the epoxy resin has a weight average molecular weight of 150 to 10,000, and a resin composition comprising the epoxy resin ionomer fine particles and a thermoplastic resin ionomer.

Here, the carboxylic acid group-containing resin at least a portion of which is ionized is a resin solution dissolved in a solvent which is soluble in water to a certain extent, such as methyl ethyl ketone, under mild stirring conditions and an emulsifier or the like. Resin which has a carboxyl group in the molecule which can be easily phase-inverted and easily obtained with a particle size of 0.1 μm or less, and which is further neutralized with a basic compound such as amine. Say.

At least a part of the carboxylic acid group of the carboxylic acid group-containing resin may be ionomerized, but the carboxylic acid group of the carboxylic acid group-containing resin neutralized with cations is based on all carboxylic acid groups. It is preferably 30 to 100 mol%.

Examples of the carboxylic acid group-containing resins having such properties include resins containing an unsaturated carboxylic acid such as (meth) acrylic acid, maleic acid, fumaric acid, maleic anhydride as a polymerization component. Among these, a copolymer of (meth) acrylic acid and another vinyl polymerization monomer is preferable.

Examples of the carboxylic acid group-containing resins include ethylene oxide adducts of (meth) acrylic acid and known [eg, "water-soluble polymer" CMC 1 Co., Ltd.).
[Published November 992], copolymers with other acrylic resins can also be used.

Examples of other vinyl-polymerizable monomers include aromatic vinyl monomers, (meth) acrylic acid alkyl esters, acrylonitrile, butadiene, vinyl acetate and the like. These 1 type, or 2 or more types of mixtures are used. Of these, aromatic vinyl monomers such as styrene and / or (meth) acrylic acid alkyl esters such as methyl (meth) acrylate are generally used from the viewpoint of coating film performance. As the aromatic vinyl monomer, for example, styrene, α-methylstyrene, brominated styrene,
Examples thereof include α-methoxystyrene, and among these, styrene is most preferable from the viewpoint of reactivity. Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and the like, and of these, methyl methacrylate is preferable from the viewpoint of heat resistance.

The ratio of (meth) acrylic acid to other vinyl polymerizable monomers is not particularly limited, but from the viewpoint of water dispersibility, (meth) acrylic acid and other copolymerizable vinyl polymerizable monomers are used. Is preferably 100: 1 to 99 by weight.

Next, the epoxy resin of the present invention is an epoxy resin that is sparingly soluble or insoluble in water, and is a condensation reaction product of a part of alcohol and epichlorohydrin (eg, glycidyl ether of glycerin).
, Which is a known epoxy resin other than the above, and is a resin which is a core material of the epoxy resin fine particles of the present invention. Moreover, what melt | dissolved the solid epoxy resin in the solvent can also be used.

Specific examples of the epoxy resin include bisphenols such as bisphenol A, bisphenol F, bisphenol D and halogen-substituted compounds thereof: novolacs such as phenol novolac, cresol novolac and bisphenol A novolac: glycidyl amines. Examples include naphthalene skeleton epoxy: imide group-containing epoxies: trifunctional or higher polyfunctional epoxies, etc. These may be used alone or in admixture of two or more. Among these, bisphenol type epoxy resin is preferable.

Further, in the present invention, an epoxy resin cured product obtained by reacting the above epoxy resin with a curing agent can also be used. Examples of the curing agent for the epoxy resin include amine curing agents, polyaminoamides, acid anhydrides, isocyanates, melamines and phenols.
One kind or two or more kinds can be used. From the standpoint of these medium curability, amine curing agents are preferred.

The molecular weight of the epoxy resin of the present invention is not particularly limited, but the weight average molecular weight is from 150 to 10
000 epoxy resins are preferable from the viewpoint of coating strength. Further, the epoxy resin of the present invention also includes a combination of an epoxy resin with a thermoplastic resin having compatibility with this resin.

Resins that can be used in combination with such epoxy resins include acrylic resins such as polymethylmethacrylate; polystyrene, styrene-maleic anhydride copolymers, styrene-methylmethacrylate copolymers, styrene-acrylonitrile copolymers. Styrene resin such as coalesce; rubber modified polystyrene, ABS resin, MB
Rubber-containing resin such as S resin, SBR, SBS; PBT
Resin, polyester resin such as PET resin; thermoplastic resin such as ethylene-vinyl acetate, polyphenylene oxide, polyvinyl chloride, polyvinyl alcohol, AES resin, polyacetal, polyamide, fluororesin, phenol resin, urea resin, melamine resin, Examples include thermosetting resins such as unsaturated polyester resins and alkyd resins.

The resin composition of the present invention comprises the above epoxy resin ionomer and the thermoplastic resin ionomer. Examples of the thermoplastic resin include a copolymer of ethylene or an α-olefin unsaturated carboxylic acid, a copolymer of an aromatic vinyl-based monomer and an unsaturated carboxylic acid, and the like, and (meth) acrylic as a copolymerization component. Those containing an acid are preferred. The content of (meth) acrylic acid in this copolymer is preferably 3 to 20% by weight from the viewpoint of storage stability. When the content of (meth) acrylic acid is 3% by weight or less, the effect of ionomerization is small, and when it is 20% by weight or more, reactivity with an epoxy resin becomes a problem and moldability is deteriorated. Absent.

At least a part of the carboxylic acid group of the thermoplastic resin may be ionomerized, but the carboxylic acid group of the thermoplastic resin neutralized with cations is 30 to 100 moles based on all the carboxylic acid groups. % Is preferable.

In addition to the aromatic vinyl monomer and unsaturated carboxylic acid, other monomers copolymerizable with them can be used. Examples of other copolymerizable monomers include (meth) acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate: vinyl such as (meth) acrylonitrile. Cyanides: itaconic acid, maleic acid, fumaric acid,
Polymerizable unsaturated fatty acids such as crotonic acid and cinnamic acid: maleimides, unsaturated carboxylic acid anhydrides and the like.

The amount of these other monomers used is not particularly limited, but is preferably 100 parts by weight or less, and 1 to 99 parts by weight based on 100 parts by weight of the total amount of the aromatic vinyl monomer and (meth) acrylic acid. More preferably.

Specific examples of the thermoplastic resin include styrene-methacrylic acid copolymers, styrene-methacrylic acid-methyl methacrylate copolymers,
Examples thereof include a styrene-methacrylic acid-butyl acrylate copolymer, and among them, a styrene- (meth) acrylic acid copolymer is preferable from the viewpoint of solution miscibility with the epoxy resin ionomer fine particles.

This copolymerized thermoplastic resin can be produced by a commonly used production method, for example, JP-A-60-106818.
It can be easily produced by the method exemplified in JP-A-60-168710. The polymer chain structure of the copolymer resin is not particularly limited, and may be a random copolymer, a block copolymer or a graft copolymer. The weight average molecular weight of this copolymer resin is not particularly limited, but is usually 3
50,000 to 500,000 is preferable.

The ionomer in the present invention is obtained by neutralizing the epoxy resin fine particles and the copolymerized thermoplastic resin with cations. As the cation, an organic amine can be used in addition to the metal ion. As the metal ion source, metal oxides, hydroxides, carbonates, acetates and the like are used. Examples of the metal ions include alkali metal ions, alkaline earth metal ions, transition metal ions, and the like, and monovalent and divalent alkali (earth) metals such as lithium, sodium, magnesium, and calcium are preferable in terms of hue. However, the counter ion is not limited to these, and known counter ions can be used (for example, “Physical properties and industrial application of ionomer” [published by IPC Co., Ltd., described in October 1989]].

The epoxy resin ionomer fine particles, the thermoplastic resin ionomer, and the resin composition containing these ionomers as essential components are prepared by using the epoxy resin fine particles used in the present invention and / or the counter ion described as the thermoplastic resin as a solvent. After melting, the mixture is heated and stirred to react, and a method of precipitating in a poor solvent, or a solution method or a heating roll for evaporating the solvent by a casting method, a Banbury mixer,
A single-screw extruder, a twin-screw extruder, a single-screw / two-screw joint extruder, etc. are used, and the epoxy resin fine particles and / or the thermoplastic resin is melt-mixed with a counter ion and the like, and the epoxy resin fine particles are also melted. Also, it can be produced by a method of forming an ionomer in the production process of the copolymer resin.

The epoxy resin ionomer fine particles and the thermoplastic resin ionomer are mixed by mixing the above-mentioned ionomers at the time of producing the ionomer, or by heating each ionomer with a heating roll, Banbury mixer, single screw extruder, twin screw extruder, single screw extruder. It can be produced by a commonly used method such as a method of mixing with a twin-screw extruder or a method of simply dry blending.

A resin having compatibility with these resin ionomer components may be used in combination. Examples of such resins include acrylic resins such as polymethylmethacrylate; styrene resins such as polystyrene, styrene-maleic anhydride copolymer, styrene-methylmethacrylate copolymer and styrene-acrylonitrile copolymer; rubber. Rubber-containing resin such as modified polystyrene, ABS resin, MBS resin, SBR and SBS; polyester resin such as PBT resin and PET resin; ethylene-vinyl acetate, polyphenylene oxide, polyvinyl chloride, polyvinyl alcohol, AES resin, polyacetal, It may be a thermoplastic resin such as polyamide or fluororesin, or a thermosetting resin such as phenol resin, urea resin, melamine resin, unsaturated polyester resin or alkyd resin.

The resin composition of the present invention thus obtained further contains compounding agents such as antioxidants, ultraviolet absorbers, flame retardants, antistatic agents, antibacterial agents, pigments, dyes and foaming agents which are usually used. It can be blended. In addition to these, fillers such as glass fiber, carbon fiber, metal fiber, glass beads, glass powder, glass flakes, asbestos, wellanite, mica, talc, clay, calcium carbonate, titanium, calcium titanate, and barium sulfate are added. They can be used alone or in combination.

The thus obtained epoxy resin ionomer fine particles and the resin composition of the present invention are used as a raw material for coating materials and as a molding material. As a molding material, injection molding; uniaxially stretched film, biaxially stretched film, or the like,
Sheet: Board Extrusion molding, vacuum molding, profile forming, extrusion foam molding, blow molding and the like can be molded into various molded products for use.

[0034]

EXAMPLES The present invention is described below with reference to examples, but the present invention is not limited to these. Hereinafter, "parts" means "parts by weight" unless otherwise specified.

First, an epoxy resin (core material) is dissolved in a self-water-dispersible resin such as a resin containing a carboxylic acid group (hereinafter, this step is referred to as a mixing step). Then, the self-water-dispersible resin phase in which the epoxy resin is dispersed is dispersed in an aqueous medium (hereinafter, this step is referred to as a dispersion step). afterwards,
The organic solvent of the self-water-dispersible resin phase is removed by distillation (hereinafter, this step is referred to as a solvent removal step).

Reference Example 1 (Synthesis of Resin Containing Carboxylic Acid Group) 33 parts of methacrylic acid, 50 parts of styrene, 27 parts of methyl methacrylate, 100 parts of methyl ethyl ketone and 3 parts of azobisisobutyronitrile were mixed to prepare a mixture. 25% is charged into a reaction vessel and the temperature is raised to 80 ° C. The remaining 75% of the mixture is then added dropwise over 3 hours with stirring under a nitrogen atmosphere. At this time, the temperature in the reaction system is maintained at 80 ° C. After dropping, the mixture is further stirred for 3 hours and then cooled to room temperature.
To this polymer solution, 35 parts of N-methylmorpholine was added and mixed well to obtain a self-water-dispersible resin solution (hereinafter this solution is referred to as D1).

Reference Examples 2 to 4 (Synthesis of Resin Containing Carboxylic Acid Group) According to the composition shown in Table 1, reference example 2 to reference example 4 were carried out in the same manner as D1 except for the composition. , D
4).

Example 1 (Production of epoxy resin fine particles) [Mixing step] 100 parts of 50% methyl ethyl ketone solution of Epicron 1050 (BPA type epoxy resin, epoxy equivalent 470, manufactured by Dainippon Ink and Chemicals) and D of Reference Example 1
100 parts of 1 are mixed.

[Dispersion Step] 200 parts of water was poured over 1 hour while stirring the above mixed solution to obtain an epoxy resin dispersion containing an organic solvent.

[Solvent Removal Step] The above epoxy resin aqueous dispersion was stirred at 60 ° C. under reduced pressure (15 mmHg) to remove the organic solvent to obtain an aqueous dispersion containing no organic solvent.

The average particle size of the epoxy resin particles in the aqueous dispersion was 100 nm. Also, this dispersion is from 5 ° C to 80 ° C.
No separation occurred in the range of ℃ for 3 months or more, and there was no change in particle size, viscosity, etc. Fine particles were separated from water from the aqueous dispersion and dried to obtain a powder sample.

The ionization of the obtained epoxy resin fine particles is carried out by redispersing the fine particle powder in water, adding sodium methoxide in a chemical equivalent amount, and then at 60 ° C. for 4 hours to 24 hours.
The reaction was carried out with stirring for a time, and the methacrylic acid of the outer shell resin was neutralized with sodium ions. After ionization, water is separated and dried to obtain epoxy fine particle ionomer powder (hereinafter, this epoxy resin fine particle ionomer is referred to as A1).
I got

The degree of neutralization reaction was confirmed by a change in IR spectrum near 1560 cm ^-1 .

Examples 2 to 5, Comparative Examples 1 and 2 (Production of Epoxy Resin Fine Particles) The steps of each step were carried out in the same manner as in Example 1 except for the shell resin shown in Table 2, and the epoxy resin fine particle ionomer powder was used. Got the body The epoxy resin fine particle ionomers obtained in Examples 2 to 5 are referred to as A2, A3, A4 and A5, respectively.
The epoxy resin fine particle ionomers obtained in Comparative Examples 1 and 2 are referred to as A6 and A7, respectively.

Reference Example 5 (Production of Thermoplastic Resin Ionomer) 2,000 ml of distilled water was charged into a 5 liter stainless steel reactor equipped with a turbine type stirring blade, and 10 g of partially saponified polyvinyl alcohol as a suspension stabilizer and After dissolving 0.05 g of sodium dodecylbenzene sulfonate,
Styrene 900 g, methacrylic acid 100 g, liquid paraffin 10 g, peroxyhexahydroterephthalic acid di-
4 g of tert-butyl and 1 g of tert-butyl perbenzoate were sequentially charged. After replacing the inside of the container with nitrogen gas, 5
The temperature was raised under stirring at 00 rpm, suspension polymerization was carried out at 90 ° C. for 10 hours, and further reaction was carried out at 120 ° C. for 3 hours. The produced granular styrene-methacrylic acid copolymer was washed, dehydrated and dried. The obtained thermoplastic resin ionomer is hereinafter referred to as B1.

Reference Examples 6 to 9 (Production of Thermoplastic Resin Ionomer) Reference Example 5 except that each monomer was used in the composition shown in Table 3.
A copolymer was obtained in the same manner as in. The ionomers of Reference Examples 6, 7 and 9 were prepared by dissolving each copolymer in tetrahydrofuran (20 wt%), adding a chemical equivalent of sodium methoxide, and reacting at 60 ° C. for 4 hours to 24 hours. The reaction solution was added dropwise to ethyl alcohol to obtain an ionomer as a thermoplastic resin powder. The obtained thermoplastic resin powder ionomers are hereinafter referred to as B2, B3, B4 and B5.

Examples 6 to 14 and Comparative Examples 3 and 4 (Production of Resin Composition) Epoxy resin fine particle powder alone or the epoxy resin fine particle powder and the thermoplastic resin ionomer were used in a small amount of tetrahydrofuran in Tables 4 and 5. The resin composition was prepared by kneading in the proportions as described above.

After drying the above resin composition, a film having a thickness of 0.3 to 0.4 mm was obtained by melt compression molding. A strip test piece having a width of 4 mm and a length of 45 mm was prepared from the film, and a tensile test was performed using Tensilon. The change in Young's modulus with temperature was measured by a dynamic viscoelasticity measuring device. Crosshead speed of tensile test is 5mm / min
(25 ° C.), Young's modulus was measured at 1 Hz.

The components having the compositions shown in Tables 4 and 5 were mixed, molded and evaluated by the above method. The results are shown in Tables 4 and 5. <Evaluation of Moldability> ○: Good appearance of the compression molding film ×: Cracks are generated on the surface of the compression molding film,
Or the sample does not fill completely in the mold because the sample does not melt and flow sufficiently.

[0050]

[Table 1]

[0051]

[Table 2] 1: Bisphenol type epoxy resin Epicron 1050 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) Epoxy equivalent 470 2: Polyamide type epoxy curing agent Epicuron B3150 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) 3: Sodium methoki Neutralization of methacrylic acid by the side.

[0052]

[Table 3]

[0053]

[Table 4] *: The molded film is very brittle and cannot be measured.

**: Young's modulus is too small to measure.

[0055]

[Table 5] Comparative Examples 5 and 6 Test pieces were prepared and evaluated in the same manner as in Example 1 except that the components were used in the compositions shown in Table 6. The results are shown in Table 6.

The sodium methoxide used in the present invention was a reagent grade (Kanto Chemical Co., Inc.).

[0057]

[Table 6]

[0058]

EFFECTS OF THE INVENTION According to the present invention, fine particles having a particle size of 0.5 μm or less and excellent in storage stability can be obtained. With this fine particle powder, a high-strength melt-molded product can be obtained. Furthermore, since the resin composition of the present invention has an excellent balance of moldability, heat resistance, and strength, coating materials such as paints, rubber, fillers such as plastics, matting agents, and various moldings as thermoplastic resins. Used in materials.

Claims (15)

[Claims] 1. A method for producing epoxy resin particles by separating an aqueous dispersion liquid obtained by dispersing resin particles comprising a resin as a core material and a resin as a coating material in an aqueous medium and drying the dispersion. A method for producing fine particles of an epoxy resin ionomer, wherein the resin of the core material is an epoxy resin or a cured product thereof, and the resin of the coating material is a resin containing a carboxylic acid group at least a part of which is ionomerized. 2. The number average particle diameter of the epoxy resin particles is 1 to 1.
The manufacturing method according to claim 1, wherein the thickness is 0.05 μm. 3. The epoxy resin as the core material has a weight average molecular weight of 1
The epoxy resin of 50 to 10000. 3.
The manufacturing method described. 4. The method according to any one of claims 1 to 3, wherein the epoxy resin cured product of the core material is a reaction product of a bisphenol type epoxy resin and an amine curing agent. 5. A resin containing a carboxylic acid group is (meth)
The production method according to claim 1, which is a vinyl-based copolymer obtained by reacting acrylic acid with another copolymerizable vinyl-based monomer. 6. The method according to claim 5, wherein the other copolymerizable vinyl-polymerizable monomer is an aromatic vinyl monomer and / or a (meth) acrylic acid alkyl ester. 7. The method according to claim 5, wherein the weight ratio of (meth) acrylic acid to the other copolymerizable vinyl-polymerizable monomer is 100: 1 to 99. 8. The method according to claim 6, wherein the aromatic vinyl monomer is styrene. 9. The method according to claim 6, wherein the (meth) acrylic acid ester is methyl methacrylate. 10. A carboxylic acid group neutralized by cations of a carboxylic acid group-containing resin at least a part of which is ionomerized is 30 to 100 mol% based on all carboxylic acid groups.
The manufacturing method according to any one of claims 1 to 9. 11. A resin composition comprising the epoxy resin ionomer fine particles according to claim 1 and a thermoplastic resin ionomer. 12. The resin composition according to claim 11, wherein the thermoplastic resin of the thermoplastic resin ionomer is a copolymer containing (meth) acrylic acid as a copolymerization component. 13. The resin composition according to claim 11 or 12, wherein the thermoplastic resin of the thermoplastic resin ionomer is a copolymer containing styrene and (meth) acrylic acid as copolymerization components. 14. The resin composition according to claim 13, wherein the content of (meth) acrylic acid is 3 to 20% by weight based on the thermoplastic resin. 15. The resin composition according to claim 11, wherein the carboxylic acid groups neutralized by the cations of the thermoplastic resin ionomer are 30 to 100 mol% based on the total carboxylic acid groups. .