JPS60156717A - Fine epoxy based particle and production thereof - Google Patents

Abstract

PURPOSE:To obtain fine epoxy based particles having an average particle diameter within a specific range and improved heat and solvent resistance, by adding a water-soluble curing agent containing a specific amount of hydrazine (derivative) to an uncured epoxy based resin emulsion. CONSTITUTION:Fine particles obtained by emulsifying an uncured epoxy compound, preferably consisting of 80-100wt% compound having two or more epoxy groups and 0-20wt% compound having one epoxy group, adding a water- soluble curing agent containing hydrazine (derivative) expressed by the formula (R is H, >=5C alkyl, phenyl or 2-hydroxyethyl) in an amount of 20% or above of amine equivalent calculated stoichiometrically from the epoxy equivalent of the above-mentioned emulsion, and curing the resultant mixture in the particulate form. USE:Usable as fillers for rubber, plastics, etc. and chromatographic column packings, etc. since functional groups can be introduced into the surface of the particles.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to novel epoxy-based organic spherical fine particles having an average particle diameter of 05 to 50 μm and a method for producing the same.

Industrial applications Fine particles made of organic polymers, especially spherical particles, are used as fillers and reinforcing agents for rubber and plastics.

It is also used as a matting agent, filler, and reinforcing agent for paints, adhesives, etc., for almost the same purposes as inorganic fillers and inorganic pigments, but its main feature is that it is lighter in weight than inorganic materials. It has become.

This is further characterized by making the organic particles hollow or porous. Furthermore, unlike inorganic materials, it is possible to add all functional groups to the surface of organic particles, which allows them to be used as column packing materials for chromatographs, enzymes, and antigens.

It is also used as a carrier for immobilizing antibodies. spherical,,"
・ By applying □ to a spherical shape, the □ properties in each application are often significantly improved.

Prior Art Organic spherical fine particles can be produced using conventional emulsion polymerization methods. ,.

In these methods, an acrylic monomer and a radical reaction initiator are placed in water, and the acrylic monomer is polymerized into particles in the presence or absence of an emulsifier.

Polymerization and polymerization methods are generally advantageous in the production of spherical fine particles with a diameter of 0.5μ or less.However, for particles larger than 0.5μ, the production time increases rapidly, so it is not suitable for industrial use. is an unsuitable method. In addition, in the case of suspension polymerization,
Although it is convenient for obtaining much larger particles than emulsion polymerization, the particle shape is not necessarily spherical and the particle size distribution is usually extremely wide.

When using an acrylic monomer as a starting material, it is not possible to produce fine particles containing a large amount of ethylenic double bonds within the particles, as predicted from the single polymerization principle. Double bonds in the particles are preferable because their own crosslinking ability can dramatically improve their suitability as fillers and reinforcing agents.

Uncured epoxy resin Air, Le, John, water-based paint,
It has long been well known as a raw material for adhesives, cement reinforcing agents, etc. But for these purposes.

After curing, the emulsion particles become a three-dimensionally integrated resin-like material, as in the case of solvent-type or solvent-free epoxy resins, and water is always removed during or after curing. In other words, in the uncured epoxy emulsion that has been used conventionally, the emulsion particles are ultimately used in a state in which they are combined with each other. It is relatively easy to coalesce the epoxy emulsion particles in this way, and changes can occur without any particular intention unless there is a particular restriction on strength or the like.

A technique for curing uncured epoxy emulsion into fine particles is disclosed in JP-A-53-73249. In this method, an amine type curing agent, which is generally recognized as a curing agent for epoxy compounds, is also mentioned as a curing agent, but the specific type of each curing agent is not mentioned. However, according to the research conducted by the present inventor, it was found that the most important point in curing an uncured epoxy emulsion into particulate form lies in the type of curing agent.Thus, the present invention was arrived at after intensive study of three different curing agents. be.

Purpose of the Invention The present invention aims to reduce the average particle size of acrylic monomers from 0.5 to 50, which is difficult to prepare using emulsion polymerization or suspension polymerization.
The object of the present invention is to provide novel spherical particles made from epoxy resin and a method for producing the same, which are relatively uniform particles of μ. Because it can be introduced into a wide range of applications and has high heat and solvent resistance, it provides unique particles and methods for their production that are suitable for many applications.

Composition of the invention The present invention is configured as follows.

(1) Epoxy-based fine particles comprising an epoxy-based resin in which hydrazine or a hydrazine derivative represented by the following general formula has reacted with an epoxy group, and are spherical with an average particle diameter of 0.5 to 50 μm.

(R represents hydrogen, an alkyl group having 5 or less carbon atoms, or a phenyl group or a 2-hydroxyethyl group.) (2) Add a water-soluble curing agent to an uncured epoxy resin emulsion and cure it into fine particles. In this case, a water-soluble curing agent containing 15% or more of the amine equivalent calculated stoichiometrically from the epoxy value of the epoxy resin emulsion is used as hydrazine or a hydrazine derivative represented by the following general formula, , a method for producing epoxy-based fine particles.

(R represents hydrogen, an alkyl group having 5 or less carbon atoms, a phenyl group, or a 2-hydroxyethyl group.) Preferred Embodiments of the Invention The details of the present invention will be sequentially explained below.

It is important that the epoxy compound used in the uncured epoxy emulsion of the present invention has an epoxy compound having two or more epoxy groups in its nine molecules as a main component. Examples of such epoxy compounds include the following compounds.

1. As a substance having two epoxy groups, it is a glycidyl etherified product of bisphenol A type at both ends.

Diglycidyl ether of polyethylene glycol.

Diglycidyl ether of polypropylene glycol, neopentyl glycol diglycidyl ether and 1.6-
diglycidyl ethers of aliphatic alcohols such as diglycidyl ethers of aliphatic alcohols such as hexanesiol diglycidyl ether; alicyclic diglycidyl ethers such as glycidyl ethers at both ends of hydrogenated bisphenol A type; Examples include diglycidyl ethers, which are bisphenols with alkylene oxide added to both ends.

Those having six or more epoxy groups include polyglycidyl ethers of aliphatic polyhydric alcohols such as glycerin triglycidyl ether and trimethylolpropane triglycidyl ether, polyglycidyl ethers of phenol novolak type compounds, and trisepoxypropyl isocyanate. Examples include slate r Nr " + "-tetraglycidyl m-xylene diamine 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane.

In the present invention, it is necessary to emulsify these epoxy compounds in water to form an emulsion. For this reason, emulsification is generally difficult with highly water-soluble epoxy compounds such as diglycidyl ether of alkylene oxide with a high degree of monopolymerization and glycerin diglycidyl ether, so it is not preferable to use them frequently.

Epoxy compounds having two or more epoxy groups in the molecule and containing one or more ethylenic double bonds in the molecule are also preferably used in the present invention.

Examples of such compounds include partial (meth)acrylates of compounds having five or more epoxy groups in the molecule as described above, and partial esters with dicarboxylic acids having ethylenic double bonds such as maleic acid. Can be mentioned.

In the present invention, as the epoxy compound of the uncured epoxy emulsion, the above-mentioned epoxy compounds having two or more epoxy groups in the molecule are used alone or as a mixture.
Those containing 0 to 100% by weight are preferably used. On the other hand, in the present invention, as the remaining epoxy compound, one containing an epoxy compound having one epoxy group in one molecule alone or in a mixture of D to 60% by weight is preferably used.

Examples of such epoxy compounds include the following. Glycidyl ethers of aliphatic hydrocarbons such as 2-ethyl hexyl glycidyl ether and 2-methyl octyl glycidyl ether; glycidyl ethers of aromatic hydrocarbons such as phenyl glycidyl ether have two or more epoxy groups in one molecule. There are epoxy compounds in which only one epoxy group is left and the remaining epoxy group is reacted with amines or added with hydrochloric acid. It is also suitable for the present invention that an epoxy compound having one epoxy group in the molecule also has an ethylenic double bond.

Examples of such compounds include glycidyl (meth)acrylate and epoxy compounds having two or more epoxy groups in the molecule with one epoxy group remaining.

The remaining epoxy group is esterified with a dicarboxylic acid having an ethylenic double bond such as (meth)acrylic acid or maleic acid, or an alcoholic compound with an ethylenic double bond such as 2-hydroxyethyl (meth)acrylate. Examples include a reaction product of a compound with a hydroxyl group and epichlorohydrin.

In order to achieve the present invention, as described above, the epoxy compound of the uncured epoxy emulsion must contain 70 to 100% by weight, preferably 80 to 100% by weight of a compound having two or more epoxy groups in the molecule, and preferably 80 to 9% by weight of epoxy compounds in the molecule. The compound having one group must have a weight ratio of 0 to 30%, preferably D to 20% by weight. If the weight of an epoxy compound that has one epoxy group in the molecule exceeds 40%, sufficient polymerization or crosslinking cannot be carried out in the curing reaction by the curing agent, resulting in products with weak physical strength or adhesive properties. You can only get things. Generally, when an epoxy compound having only one epoxy group in the molecule is used too much, the physical strength of the cured product decreases, so it is preferable to increase the proportion of the epoxy compound having three or more epoxy groups.

The uncured epoxy emulsion particles of the present invention include.

Other additives may be included as long as they do not impair the present invention. The most typical additives are organic and inorganic pigments and dyes used to color epoxy particles. A blowing agent can also be used to make the fine particles porous and hollow. Antistatic agent.

Conductive agents, ultraviolet absorbers, etc. can also be added depending on the purpose. These additives are added before emulsifying the uncured epoxy compound.

They are usually blended by thoroughly mixing or dissolving them.

The uncured epoxy composition of the present invention is then emulsified with water. Emulsification is generally carried out with the aid of emulsifiers. The emulsifier used for this purpose is not particularly limited, and any emulsifier known as an emulsifier for epoxy compounds can generally be suitably used.

Examples of emulsifiers that can be used in the present invention include ether-type nonionic surfactants such as polyoxyethylene/phenol substituted ethers and polyoxyethylene O polyoxypropylene block polyethers, higher fatty acid esters of polyethylene glycol, etc. These include ester-type nonionic surfactants such as fatty acid esters of polyhydric alcohols, and alkoxylated rosins. Further, it is also possible to use a self-emulsifying agent such as polyamide amine, which is a reaction product of dimer acid and polyether diamine or aliphatic polyamine, and which can be used as a curing agent for epoxy compounds.

These emulsifiers are usually used in an amount of 30 weight percent or less per epoxy compound, but the amount used is not particularly limited.

The emulsifier is generally used in a mixed state in the epoxy composition, but it is also possible to add the emulsifier to water and vigorously mix it with an epoxy compound containing or not containing the emulsifier.

Generally, the difficulty of converting a compound into tetramer is affected by its viscosity. When the epoxy compound has a high viscosity or is a type of epoxy compound that solidifies at room temperature.

9 is difficult to emulsify sufficiently using mechanical force alone. In such cases, a diluent for the epoxy compound is used together with an emulsifier.

Diluents include ketones, alcohols, cellosolves,
Examples include dioxane, aromatic hydrocarbons, and esters such as ethyl vinegar.

As described above, the epoxy composition prepared using the epoxy compound and the emulsifier as its basic composition is then emulsified according to a conventional method to form an uncured epoxy emulsion. Although the emulsification method is not particularly limited, one typical method is shown below.

The above-mentioned epoxy composition containing an emulsifier is heated to room temperature to 95°C, and water having a temperature within the above temperature range is added in four portions to it while stirring at high speed. In general, it is preferable to add water intermittently rather than continuously, and it is recommended to alternate the period of addition with the period of stirring only. In this method, the initial addition of water forms a W10 emulsion, but the addition of water causes a phase inversion to a JO/W emulsion. 1. During phase inversion and after forming 0/W type emulsion. In particular, high-speed stirring is required to reduce the diameter, homogenize, and stabilize the emulsion. Alternatively, there is also a method of directly preparing an O/W type emulsion.

There is a close relationship between the concentration of an epoxy emulsion and the emulsion particle size and stability; if the concentration is too low, aggregation tends to occur and stability deteriorates.

Generally, it is considered that a condition for obtaining a good emulsion is to adjust the emulsion concentration to about 10 to 80% by weight, but the present invention does not particularly limit this range. In order to prepare an emulsion with a lower concentration than this, it is common to first prepare the emulsion with a concentration within the above range 14-1 and then dilute it with water to a predetermined concentration.

Epoxy emulsions are given stability in water by the action of emulsifiers, such as hydroxyethyl cellulose and carboxymethyl cellulose.

It is also effective to add a substance that acts as a protective colloid, such as gum arabic or polyvinyl alcohol, to water in advance to increase the stability of the emulsion.

In the present invention, epoxy fine particles are prepared by adding hydrazine or a derivative thereof to the uncured epoxy emulsion obtained as described above and curing the emulsion particles into particles.

Piperazine and its derivatives used in the present invention must have the following structure.

(R is hydrogen, an alkyl group having 5 or less carbon atoms, a phenyl group, or a 1d2-hydroxyethyl group) The present invention uses hydrazine or a derivative thereof having the above structure, which is calculated stoichiometrically from the epoxy value of the epoxy emulsion. This is achieved by adding at least 20 parts by weight of 1 equivalent of amine. Since the curing of epoxy compounds is generally carried out in the presence of chemically equivalent amounts of the epoxy compound and amine compound, it is extremely unlikely that apparent curing will be observed even with a small amount, such as 20% by weight of the equivalent amine amount. This is an interesting phenomenon.

The curing reaction of an uncured epoxy emulsion by hydrazine or its derivative can be estimated by quantifying the amount of hydrazine or its derivative remaining in water after one reaction.

That is, the apparent epoxy group reaction rate E and the reaction rate P of hydrazine and its derivatives can be calculated as follows.

eQfp fp E, Q = Epoxy value Po of epoxy compound: Amine value f6 of hydrazine or its derivative: Feeding amount of epoxy compound fp: Feeding amount r of hydrazine or its derivative: Remaining amount of hydrazine or its derivative after reaction When the amount f2 of l-"radin t or its derivative is small, P increases but E decreases. If E becomes small, the epoxy emulsion particles will not harden sufficiently,
When P is opened, the particles stick to each other and become integrated L-. This phenomenon occurs when the amount of hydrazine or its derivative charged is less than 20 weight i-% of 1 equivalent of amine calculated stoichiometrically from the epoxy value of the epoxy emulsion. On the other hand, as becomes larger, P generally decreases, but E increases.

Therefore, the larger f is, the better the hardened particles can be obtained, but if the f is too large, the stability of the emulsion is impaired, so the amount of hydrazine and its derivatives charged is preferably 400% or less of the amine equivalent.

17- The epoxy emulsion concentration when curing an uncured epoxy emulsion with hydrazine tia and its derivatives is not particularly limited, but it is preferably 5 weight percent or more from the viewpoint of emulsion stability.

However, if the concentration of the epoxy emulsion is too high, the chances of contact between particles increases and they tend to aggregate during the curing reaction, so it is desirable that the emulsion concentration during curing is 80% by weight or less.

In order to perform particulate curing of epoxy emulsion, the gist of the present invention is to use hydrazine or a derivative thereof as a curing agent, but other water-soluble curing agents may also be used in combination with hydrazine or its derivative. It is possible. Examples of compatible curing agents include aliphatic amines such as isopropylamine, and alkylene polyamines such as ethylenediamine and diethylenetriamine.

Alcohol amines such as ethanolamine, jetanolamine, triethanolamine, aliphatic tertiary amines such as triethylamine, benzyl 18-mino. Aromatic amines such as 4-aminodiphenylamine, 4,4/-diaminodicyclohexylmethane, N(
Examples include 2-aminoethyl)piperazine. These compounds coexist to realize particulate curing of the epoxy emulsion only when hydrazine or its derivative having the structure shown above is present in an amount of 20 or more by weight of the stoichiometric amine equivalent. In other words, the use of water-soluble curing agents other than hydrazine or its derivatives, alone or in combination, does not result in particulate curing of the epoxy emulsion. In other words, in order to achieve the present invention, the above-mentioned hydrazi/or derivative thereof is used as a water-soluble curing agent at a ratio of 20% by weight of the equivalent amine amount stoichiometrically calculated from the epoxy value of the epoxy emulsion. The above is used, and if necessary, other water-soluble curing agents are used in combination.

To add water-soluble hardeners containing piperazine or its derivatives to epoxy emulsions, it is common practice to mix the hardener directly into the emulsion; Another recommended method is to dissolve it in a water-soluble organic solvent such as alcohol and then add it. In particular, the presence of small amounts of alcohols serves to increase the reaction rates E and P.

Further, as methods for adding the water-soluble curing agent, there are two methods: adding the entire amount at once and adding the water-soluble curing agent in small amounts continuously or intermittently. There is no particular problem in achieving the present invention using either method, but when either or both of the epoxy emulsion concentration and curing agent solution concentration are high and when a large amount of curing treatment is performed, 9 reactions are required. Continuous or intermittent addition in small portions is recommended to control the rate and heat of reaction.

Another possible method for adding the curing agent is to add part or all of the curing agent in advance to the water used to emulsify the uncured epoxy resin, and to emulsify it using the same.

The reaction between the epoxy compound and the curing agent is generally an exothermic reaction. Since the reaction rate increases as the temperature rises, one heat generation is preferable in terms of accelerating the curing speed, but when performing particulate curing of epoxy emulsions, increasing the emulsion temperature often increases the curing rate. Decrease the stability of the emulsion inside. The reason for this is not well understood, but it is presumed that it increases the adhesion of the semi-hardened particles and promotes aggregation of the emulsion particles with each other.

For this reason, when adding human Radin or its derivatives, if necessary, other water-soluble curing agents, to an uncured epoxy emulsion and curing it into particles, the liquid temperature should be kept below 70°C for a while after the addition of the curing agent. In terms of reaction operation, it is necessary to cool the curing temperature to below this temperature and, if necessary, to add a curing agent in small amounts continuously or intermittently. However, at the end of one reaction, it is possible to raise the liquid temperature to 70° C. or higher in order to complete the reaction.

, furthermore, although this also does not limit the invention, ``
If the epoxy emulsion after adding the curing agent is continued to be stirred as it is, as the curing reaction progresses, the particles will reach a state where they tend to stick to each other21-, and at this stage the particles will collide and agglomerate to a large size. more likely to occur. In order to prevent this, it is desirable to stop stirring at this stage and restart stirring after the 9 particles no longer exhibit stickiness.

Furthermore, a method of "stirring the curing agent and the epoxy emulsion until they become uniform, and then allowing the emulsion to stand and harden" is also very effective in preventing adhesive bonding between particles.

Epoxy fine particles are prepared by curing into particulate form in one or more ways. If the hardened particles are separated from the water by filtration or centrifugation, they can be recovered in powder form. The epoxy fine particles have a particle size of 0.5 to 50 μm, depending on the curing conditions.

In some cases, they are prepared to have a smaller spherical shape, but if some agglomeration occurs during curing, they may grow into non-spherical porous particles. Such non-spherical shafts are often aggregates of millet-shaped spherical particles. Further, during static curing, the particles at the bottom may be crushed and change from their original spherical shape to a flattened spherical shape, but any shape of 9 or more is characterized as unique to the present invention.

The epoxy fine particles after curing are used in a dry state or in a dispersed state in a medium such as water or alcohol, or are subjected to surface modification treatment.

Incidentally, in order to improve the heat resistance and solvent resistance of the particles of the present invention, the particles may be heat-treated after drying. In this case, carboxylic acid hydrazide is already present in the particles. There are also unreacted residual epoxy groups in the particles.

If you want to deactivate this. This goal can be achieved by treating the particles with an acidic solution such as dilute sulfuric acid.

When using hydrazine as a curing agent, excess hydrazine can be decomposed by treating the reaction solution with an oxidizing agent such as hydrogen peroxide before collecting particles from the reaction solution after curing. In that case, the product is decomposed into a gaseous state and leaves the yarn.

The effort of cleaning particles can be significantly omitted.

Effect of the invention The effects of the present invention can be summarized as follows.

(2) New spherical particles made of epoxy resin and having an average particle diameter of 05 to 50 μm are obtained.

(2) It has been shown that hydrazine and certain hydrazine derivatives are effective as curing agents for obtaining the above particles.

■ When the curing agent is hydrazine, excess hydrazine can be decomposed in gaseous form by treatment with an oxidizing agent such as hydrogen peroxide, which greatly reduces the cleaning required when recovering particles compared to when using other amine compounds. Can be omitted.

Example 1 10g of commercially available bisphenol A diglycidyl ether type epoxy resin (Epicote 828) was added to 100cc
The mixture was placed in a polycup, and 08 g of commercially available BoIJ, Neugen EiA-157 (Daiichi Kogyo Seiyaku), which is a t-oxyethylene O phenol-substituted x-thyl emulsifier, was added.

80 O using a stirring rod with a Teflon plate blade attached to the tip.
rpm, and kneaded for 1 minute. Next, put 6cc of water into the syringe f1. 5 cc at 1 minute intervals, 800
Sequential additions were made under stirring at rpm. As a result. A milky white emulsion liquid with an epoxy value of 619 is 168 in the polycup.
B was obtained.

The curing state was observed by changing the amount of hydrazine (H, NNH, .H, 0, aminated 125) added to this uncured epoxy emulsion. Irrigation Hydrazine T Go 8c
After diluting with water in step c, the uncured epoxy emulsion was gradually added with gentle stirring. The curing reaction is 25°0,
The test was carried out in a stationary state for 10 days. The results are shown in the table below, where curing is insufficient when the amine equivalent is stoichiometrically calculated from the epoxy value of the epoxy emulsion and is less than 20.
It could not be extracted as particulate matter. The particles obtained in Examples 1-1 to 1-3 all had an average particle size of 5 to 5.
It was observed with a scanning electron microscope that it had a true spherical shape of 8 μm.

25- *　○: Particulate hardening ×: Particles are easily bonded and not sufficiently cured.

Example 2 The mixing ratio of Epicote 828 (epoxy value 190), which has two epoxy groups in the molecule, and glycidyl methacrylate (epoxy value 145), which has one epoxy group in the molecule, was changed. The surfactant Neugen EA-137 was added at 12 parts by weight to the epoxy compound mixture.

An emulsion was formed in the same manner as in Example 1, 100 equivalents of hydrazine nonahydrate was added, and the mixture was allowed to stand at 25° C. for 5 days to cure. □ As shown in the table below, when the amount of glycidyl methacrylate was low, fine spherical particles containing double bonds could be prepared, but when the amount was high, the emulsion particles bonded to each other during the curing reaction. Eventually, the entire mixture coagulated and became integrated, and the phase separated from water to oil.

Note that the average particle diameters shown in Table 9 are values measured for the slurry before drying using a centrifugal sedimentation type particle size distribution analyzer CAPA-500 manufactured by Horiba, Ltd.

Example 3 N, 'N, N/, with 4 epoxy groups in the molecule
N/-tetraglycidyl m-xylene diamine (trade name: TE'TRA D=X, epoxy value 100. Mitsubishi Gas Chemical), Epicote 828, which has two epoxy groups in the molecule, and one epoxy group in the molecule. 2-ethyl hexyl glycidyl ether (trade name Epolite y'-
800. Epoxy value 200. The mixing ratio of Kyoeisha oils and fats was changed, and 12 parts by weight of the surfactant Neugen EA'=157 was added to the epoxy compound mixture. It was emulsified in the same manner as in Example '1.

Irrigation human □ Add 50 iqb of radin, 6 at 30°0
It was allowed to stand and harden for several days.

As shown in the table below, when there is a large amount of 2-ethyl hexyl glycidyl ether, the emulsion particles bond to each other during the hardening reaction, and eventually aggregate and integrate as a whole, resulting in phase separation into an oily state. However, when the amount was small, fine spherical particles could be prepared.

=27-28 - Example 4 9 g of commercially available bisphenol A digly□cidyl ether type epoxy resin Epicor+828 and Epicort 1
Put 1 g of 002 into a 100 cc polycup, and add emulsion 49 (Daiichi Kogyo Seiyaku) using a commercially available polyoxyethylene/phenol substituted nityl emulsifier.
O, 8g was added. After heating and melting, emulsification was carried out in the same manner as in Example 1 using the same emulsifying device as in Example 1, to obtain an uncured epoxy emulsion liquid with an industrial oxygen resistance value of 400.

Curing solutions having different composition ratios of radine and ethylenediamine diluted with 10 g of water were added to this epoxy emulsion, and the mixture was allowed to stand at 30° for 4 days to cure.

The results are shown in the table below, and it was found that when the water hydrazine was 20% or more of the amine equivalent calculated stoichiometrically from the epoxy value, it could be cured into particles and one spherical fine particles could be obtained.

Example 5 1.4 g of Neugen EA-137 was added to 10 g of Ebicor 1-828 and emulsified in the same manner as in Example 1 to obtain an uncured epoxy emulsion.

Curing liquids diluted with 12 g of water and having different composition ratios of water hydrazine and triethylamine were added to this epoxy emulsion, and the mixture was allowed to stand at 55° 0 for 4 days to cure.

The results are shown in the following table, and it was found that when the water hydrazine was 2D% or more of the amine equivalent calculated stoichiometrically from the epoxy value, particulate curing was possible and 9-spherical fine particles were obtained.

Example 6 The amount of hydrazine derivative added to the uncured epoxy emulsion obtained in Example 1 was varied and the curing state was observed.

25°0, the hardening state after standing for 10 days is shown in the table below.
It has been found that within the scope of the present invention, fine spherical particles can be obtained.

Patent Applicant Toshi Co., Ltd. Procedure Ne City J, F-yama Patent Office Commissioner Manabu Shiga 1. Indication of 1982 Patent Application No. 10296 2. Title of Invention Epoxy-based fine particles and method for producing the same 5. Number of inventions increased by the amendment None 6. [Detailed description of the invention column] of the specification subject to the amendment 7. Contents of the amendment 1- In the specification (1) "Spherical shape" in the second line of page 3 ” is corrected to “shape”.

(2) ``1 acrylic hinoma'' in page 3, line 8, I'' is corrected to ``1 acrylic nanatsuma''.

(3) "15% of the amine equivalent" on page 6, line 13 is corrected to "20% of the 1-amine equivalent."

(4) Page 7, lines 15-16 [Delete diglycidircony-1 of aliphatic al-1-l such as del in 1.

(5) "IN, N', N'-tetra" in the 7th line of page 8 is corrected to "l'N, N, N', N'-tetra".

(6) "r40wt%" in the first line of page 11 is corrected to "r30wt4%".

(7) "1piperazine" on page 15, line 14 and page 19, line 17 are respectively corrected to "hydrazine."

(B) "Amination" on page 25, line 3 is corrected to "1-amine equivalent."

(9) In the table on page 32, column 1 Neugen E A-137J, reference example-7 has ro, 6'', reference example-8 has f, 1.0
J, rl in Reference Example-9, 4. Add each J.

(10) Add "uncured epoxy emulsion" in the second line of page 7 to 1 uncured epoxy resin] J Mulsion-1
and correct it.

Claims (1)

[Claims] (1) Hydrazine or human ° represented by the following general formula
Epoxy-based fine particles are made of an epoxy-based resin in which a radin derivative is reacted with an epoxy group, and are spherical with an average particle diameter of 05 to 50 microns. (R is hydrogen, an alkyl group having 5 or less carbon atoms, 1 phenyl group
-1: 2-hydroxyethyl group t. ) (2) When adding a water-soluble curing agent to an uncured epoxy resin emulsion and curing it in the form of fine particles, the hydrazi/or hydrazine derivative represented by the following general formula is added based on the epoxy value of the epoxy resin emulsion. A method for producing epoxy fine particles, characterized by using a water-soluble curing agent containing 20% or more of the stoichiometrically calculated amine equivalent. 1- (R represents hydrogen, an alkyl group having 5 or less carbon atoms, a phenyl group, or a 2-hydroxyethyl group.)