JPS6060127A - Production of particulate composite resin - Google Patents

Abstract

PURPOSE:To obtain the titled resin in which the constituent resins intermingled with each other uniformly on a molecular level, by reacting a polyisocyanate with a polycarboxylic acid (anhydride) in the presence of specified first and second nonaqueous organic liquids and adding a molten epoxy resin to the reaction mixture. CONSTITUTION:A polyisocyanate is reacted with an acid anhydride group-containing polycarboxylic acid and/or a polycarboxylic acid at 150 deg.C or below in the presence of (A) a first nonaqueous organic liquid (e.g., octane) of b.p. of 40-300 deg.C, in which the particulate polymer formed in insoluble, and (B) a second nonaqueous organic liquid (e.g., phenol) which is immiscible with component A and in which a component A-soluble dispersion stabilizer and the particulate polymer formed is soluble or swellable to obtain (C) a particulate polymer of number-average MW <=80,000 and average particule diameter of 0.05-2,000mum dispersed in component A. Component C is mixed with a liquid or molten epoxy resin at a high agitation speed to obtain a particulate composite resin dispersed in component A.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing a thermosetting particulate composite resin that has excellent heat resistance, heat meltability, and economic efficiency and can be applied mainly to paints, adhesives, molded products, and composite materials. Regarding.

Aromatic polyimide resins, polyamideimide resins, and polyamide resins, which are known as typical heat-resistant resins, require special molding equipment because of their rigid molecular structures and require high temperatures and pressures during molding.9 Molding equipment cannot be used. Therefore.

As a method for facilitating thermal melting of these heat-resistant resins, for example, a combination of a powdered polyamide-imide resin and an epoxy resin has been proposed (see Japanese Patent Laid-Open No. 55-48242).

In addition, a thermosetting composite resin powder has been proposed, which is a combination of a polyamide-imide resin and an epoxy resin, which has excellent heat melting properties although it has slightly less heat resistance (Japanese Patent Laid-Open No. 52-68
(See Publication No. 257).

However, conventional powdered heat-resistant resins.

Since it is obtained by removing the solvent by an industrially extremely uneconomical process from a resin solution obtained by solution polymerization using an expensive special solvent such as N-methylpyrrolidone, there is a big problem in terms of cost.

Furthermore, in order to prepare a homogeneous composite resin powder of the above-mentioned heat-resistant resin and epoxy resin, conventional methods generally use a solution mixing method or a melt mixing method. This poses a major cost problem as it requires an uneconomic process to recover the powder. In addition, the melt mixing method generally requires high temperature and pressure for mixing, so
The disadvantage is that undesirable gelation tends to occur, and the process of resin mixing, melting, coarse grinding,
Since complicated processes such as fine grinding are required, there is a big problem in terms of economic efficiency.

The present inventors have improved heat resistance over the above-mentioned problems.

As a result of repeated studies on a method for producing a particulate composite resin with excellent thermal meltability and economic efficiency, we have completed a method for producing a particulate polymer fat dispersed in a non-aqueous organic liquid.

The present invention provides a first non-aqueous organic liquid that is insoluble in the particulate polymer to be produced, a dispersion stabilizer that is soluble in the first non-aqueous organic liquid, and a dispersion stabilizer that is soluble or swellable in the particulate polymer to be produced. The polyisocyanate (1) and the polycarboxylic acid (11 ) and polycarboxylic acid (iii) to form a particulate polymer CI+ dispersed in a first non-aqueous organic liquid; A method for producing a particulate composite resin in which a liquid or molten epoxy resin (I [l) is added to a polymer (11) under stirring to obtain a particulate composite resin dispersed in a first non-aqueous organic liquid.

According to the production method of the present invention, the 9-particulate composite resin is produced.

Since it is obtained as a dispersion of relatively small particles in the first nonaqueous organic liquid, it can be easily recovered from the dispersion by a filtration operation and used as it is as a liquid paint.

Moreover, especially in the production method of the present invention, an inexpensive general-purpose solvent can be used as the first non-aqueous organic liquid.

According to the production method of the present invention, the operation and process are extremely simple without using special melting and mixing equipment.

Particulate composite resins that are homogeneously compatible at the molecular level can be obtained at low cost.

The first non-aqueous organic liquid in the present invention is:

It is insoluble in the particulate polymer produced.

A nonaqueous organic liquid is used that has inert properties that do not inhibit the polymerization reaction.

For example, n-hexane, octane, dodecane, liquid puff 7
Ia, l5OPAR-E, l5OPAR-H.

Aliphatic or alicyclic hydrocarbons such as 15OPAR-K (fFa manufactured by Esso Standard Oil Co., Ltd., ! = petroleum-based saturated aliphatic or alicyclic hydrocarbon with a boiling point range of about 40 to 300°C) , benzene, toluene, xylene, Nl
5SEKI l-ll5OL-100, Nl5SEKI
HISOL-150 (all 9 product names manufactured by Nippon Petrochemical Co., Ltd.).

An aromatic hydrocarbon fA such as a petroleum aromatic hydrocarbon having a boiling point range of about 80 to 300° C. is used.

Considering the reaction temperature, those having a boiling point of 80° C. or higher are preferred. These can be used alone or in combination.

In the present invention, the second non-aqueous organic liquid that is essentially immiscible with the first non-aqueous organic liquid is a non-aqueous organic liquid that has inert properties that do not inhibit the reaction, and the particles produced A solvent is used that is soluble or swellable with respect to the polymer and acts as a solvent for contacting the reaction between end groups in the polymerization reaction process and increasing the molecular weight of the resulting polymer. Here, the first non-aqueous organic liquid and (ri
Essentially immiscible refers to completely insoluble in the first non-aqueous organic liquid, as well as not completely insoluble, but immiscible to the extent that the two liquids phase separate at a certain mixing ratio. This means that it also includes non-aqueous organic liquids. Preferably, the second non-aqueous organic liquid is a polar liquid and has a higher affinity for the resulting polymer or reactant contained in the permissive phase than the first non-aqueous organic liquid. . Examples of such a second non-aqueous organic liquid include N-methylpyrrolidone, N-vinylpyrrolidone, dimethylformamide,
Dimethylacetamide, γ-butyrolactone, phenol, cresol, etc. are used.

These may be used alone or in combination of two or more. Preferably, a combination of an aliphatic or alicyclic hydrocarbon and N-methylpyrrolidone is used as the first non-aqueous organic liquid.

The dispersion stabilizer is soluble in the first non-aqueous organic liquid, and
There are no particular limitations, and any material can be used as long as it forms a stabilizing layer on the surface of the particulate polymer to be produced and has the function of at least stabilizing the dispersion state of particles during the polymerization process. Such a dispersion stabilizer can be obtained, for example, by radical polymerization in an aliphatic or alicyclic hydrocarbon that is the first non-aqueous organic liquid. A vinyl polymer whose main chain contains a hydroxyl group or an epoxy group formed from a long-chain alkyl ester of acrylic acid or methacrylic acid having 12 or more carbon atoms is preferably used.

Examples of the polyisocyanate used in the present invention include tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, naphthalene-1,5-diisocyanate, and 4,4'-diisocyanate.
Aromatic diisocyanates such as diphenylmethane diisocyanate, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate.

Aliphatic diisocyanates such as 1.12-dodecane diisocyanate, cyclobutene 1,3-diisocyanate,
cycloaliphatic diisocyanates such as cyclohexane 1,3- and 1,4-diisocyanate, isophorone diinozoanate, triphenylmethane-4,4:4'-triisocyanate, polyphenylmethylpolyiso/anate, e.g. Polyinocyanates such as hepta-osgenated condensates with formaldehyde and isocyanate ring-containing polyisocyanates obtained by trimerization of these polyisocyanates are used.

Considering compatibility with epoxy resin, heat resistance, cost, etc., tolylene diisocyanate is preferred.

4.4'-diphenylmethane diisocyanate, 4.4
'-Diphenyl ether diisocyanate, influorone diisocyanate, polyphenylmethyl polyisocyanate or polyisocyanate having an inocyanurate ring is used.

These polyisocyanates may be used alone or in combination depending on the purpose. For example, it is preferable to use a mixed system of isophorone diisocyanate and 4,4'-diphenylmethane diisocyanate for the particulate polymer used in combination with a bisphenol type epoxy resin.

Polyisocyanate is used to control the reaction rate during the polycondensation reaction process and to obtain a stable particulate polymer.
-Butanol, benzyl alcohol xime, phenol, cresol, etc. may be partially or completely stabilized with a suitable blocking agent having one active hydrogen in the molecule.

C is a polycarboxylic acid having an acid anhydride group.

For example, tricarboxylic anhydrides such as trimellitic anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, 3,4,4'-benzophenonetricarboxylic acid-3,4'-anhydride, 1 , 2,3.4-butanetetracarboxylic acid, cyclopenta/tetracarboxylic acid, ethylenetetracarboxylic acid, bicyclo-(2,2.2:]-]octo7)-ene-2:3,5:6-tetra Aliphatic and alicyclic tetrabasic acids such as carboxylic acids, pyromellitic acid, 3
, a; 4.4'-benzophenonetetracarboxylic acid, bis(3.4-dicarboxyphenyl)ether, 2
,3,6.7-naphthalenetetracarboxylic acid,1,2,
5.6-naphthalenetetracarboxylic acid, ethylene glycol bistrimelitate, 2.2'-bis(3.4
-Biscarboxyphenyl) Furonokun.

2, 2:3, a'- or 3, 3: 4, 4'-
Piphenyltetracarphonic acid, helylene-3. 4,
9. 1 0-tetracarboxylic acid, bis3,4-dicarboxyphenylsulfone.

2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)pronokun, 2.2-bis[4-(2.

3-dicarboxyphenoxy)phenyl]pronokun,
4-(2,3-dicarboxyphenoxy)-4'-(3
．． 4-dicarboxyphenoxy)-diphenyl-2.2
-Aromatic tetrabasic acids such as propane, thiophene-2. 3
, 4. Examples include tetrabasic acid dianhydrides or -anhydrides such as heterocyclic tetrabasic acids such as 5-tetracarboxylic acid and pyrazinetetracarboxylic acid.

A polyamideimide is obtained from a polycarboxylic acid containing an acid anhydride group having a free carboxyl group, such as tricarboxylic anhydride, and a polyisocyanate. Further, a polyimide can be obtained from a polycarboxylic acid having only an acid anhydride group such as tetracarboxylic dianhydride and a polyisocyanate. Generally epoxy 1N
Considering compatibility with fats, heat resistance, cost, etc., trimellitic anhydride and 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propanihydride are recommended.

3, 3: 4.4'-benzophenone tetracarbo/acid dianhydride or pyromellitic dianhydride is preferred.

These polycarboxylic acids/acids having an acid anhydride group may be used alone or in combination depending on the purpose. For example, it is preferable to use 2,2'-bis(3,4-biscarboxyphenyl)propanihydride alone or in combination with trimellitic anhydride for the particulate polymer used in combination with a bisphenol-type epoxy resin. .

Examples of polycarboxylic acids include terephthalic acid.

Isophthalic acid, 2.6 +, 2.5- or 3,6-
Dicarboxytoluene, 2,6-dicarboxynaphthalene.

3,3'-Also 1d 4,4'-dicarboxybiphenyl, bis(3-4id4-carboxyphenyl)ether.

Bis(3- or 4-carboxyphenyl)ketone.

Bis(3- or U4-carboxyphenyl)sulfone, bis(3- or 4-carboxyphenyl)methane, bis(
3- or 4-carboxyphenyl) dimethylmethane, trimellitic acid, trimesic acid.

Pyromellitic acid, tris(2-carboxyethyl)in cyanurate, tricarpallic acid, nitrilotriacetic acid, nitrilotripropionic acid, adipic acid, sebacic acid,
Dodecanedicarboxylic acid and the like are used.

In consideration of heat resistance, isophthalic acid or terephthalic acid, trimesic acid, tris(2-carboxyethyl)isocyanurate or nitrilotriacetic acid are preferred.

What are the amounts of polyisocyanate and polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group?

The equivalent ratio of the total carboxyl groups of the polycarboxylic acid and/or polycarboxylic acid having an acid anhydride group to the total isocyanate groups of the polyisocyanate (total carboxyl groups/total isocyanate groups) is in the range of 1.0 to 2.0. It is preferable to keep it within. Here, 1 equivalent of acid anhydride group is treated as 1 equivalent of carboxyl group. If it is less than 1.0, the amount of carboxyl group, acid anhydride group, or derivative thereof at the end of the particulate polymer that contributes to the acid curing reaction of the epoxy resin decreases, resulting in loss of heat resistance. Furthermore, as a result of the increased number of remaining free incyanate groups, the storage stability of the 9 particulate polymer is reduced. When this ratio exceeds 2.0, unreacted acid components with poor compatibility with the epoxy resin increase, resulting in poor molding workability.

Preferred particulate polymers are prepared in such a way that all of the terminal groups are carboxyl groups, anhydride groups or derivatives thereof (eg, hafester groups with alcohols).

Considering the compatibility with the epoxy resin and the melt flowability of the composition, the molecular weight of the particulate polymer is determined by the number average molecular weight (polystyrene equivalent value) in the GPC chromatogram.
, o o o or less.

The reaction temperature between the polycarboxylic acid having an acid anhydride group and/or the acid component of the polycarboxylic acid and the polyisocyanate is preferably less than 150°C.

Examples of the synthesis method include a homogeneous solution in which all components except the acid component are mixed, or a homogeneous solution of polyisocyanate and a second non-aqueous organic liquid is dispersed in the form of oil droplets in the first non-aqueous organic liquid. A method in which a finely powdered acid component is added to a homogeneous solution is preferred. According to this method, the polymerization reaction can proceed at a relatively low reaction temperature, and undesirable side reactions can be suppressed.

The stirring method used in the reaction involves high-speed shearing using an emulsifier (homomixer).

Mechanical cutting of particles with a propeller-type stirrer.

A stirring method that does not involve pulverization is used.

The emulsifier is preferably used in areas where the conversion of reactants to polymer is not very high. A desirable agitation method is to use an emulsifier to reduce the particle diameter at the beginning of the reaction, and at a point near the polymerization rate at which the dispersion stability of the particles is good, replace it with a propeller-type stirrer and proceed with the reaction further. There is. According to this method, a particulate polymer having a relatively small particle size and uniform particle size can be obtained. Depending on the synthesis system, it is also possible to use an emulsifier to form small particles before the reaction.

The particulate polymer obtained illegally has an average particle size of 0.
J1 is obtained in agglomerate particle morphology ranging from 0.05 to 2000 μIn and above. Good average particle size is 0,1~
500μ mouth 1. The most preferred is 0.5 to 100 μm
It is.

In the present invention, a liquid or molten epoxy resin is used. Liquid epoxy resin refers to an epoxy resin whose melting point is below room temperature and an epoxy resin dissolved in an organic solvent. The molten epoxy resin refers to an epoxy resin that has a melting point higher than room temperature and is made into a liquid state by heating. Epoxy resins having these properties can be used in the wood cutting. As such epoxy resin.

For example, GY250, 260, 280. CY221,23
0°CT2O0 (manufactured by Ciba Geigy, trade name), Epicote 815, 828, 1001, 1004.100
7 (manufactured by Shell Kagaku Co., Ltd., trade name), Ep-4100°4900.4340f (manufactured by Kadenka Co., Ltd., trade name).

Ebicuron 840, 850, 855, 857, 860°1050 (manufactured by Inu Nippon Ink Chemical Co., Ltd., trade name).

FEB-10, PE-10, PE-100 (trade names, manufactured by Dainippon Shikizai Kogyo Co., Ltd.), AER330R.

331B, 334R, 337L (manufactured by Mukasei Co., Ltd.)

There are bisphenol-type epoxy resins such as (trade name).

Also ECN 1235.1273.1280. EpN
1138 (manufactured by Ciba Geigy, product name), ESCN
-220 (manufactured by Sumitomo Chemical Co., Ltd., trade name), N-730°N-770, N-660, N-670 (manufactured by Inu Nippon Ingi Chemical Co., Ltd., trade name), PE2010. PE 2020
(Manufactured by Dainippon Shikizai Kogyo Co., Ltd., product name), EOCN-10
Novolak type epoxy resin such as 2,103,104 (manufactured by Nippon Kaisha, trade name), CY175,177°17
9 (manufactured by Ciba Geigy, product name), E-L-420
Cycloaliphatic epoxy resins such as 6,4221 (manufactured by UCC, trade name), CY350. Heterocyclic epoxy resins such as XB2615 (trade name, manufactured by Ciba Geigy) and TEPIC (trade name, manufactured by Nissan Chemical) are used. Considering the heat resistance of the resulting particulate composite resin, it is preferable to use an epoxy resin having at least two epoxy groups in one molecule. In consideration of heat resistance and cost, bisphenol-type epoxy resins, novolac-type epoxy resins, and trisglycidyl isocyanurates, such as TEPIC (trade name, manufactured by Nissan Chemical) are preferred.

When using a liquid epoxy resin dissolved in an organic solvent, examples of the organic solvent include methanol.

Alcohols such as ethanol, propatool, butanol, benzyl alcohol, and methylene chloride.

Carbon tetrachloride, chloroform, 1,2-dichloroethane,
MJ Clen, chlorinated hydrocarbons such as monochlorobenzene and dichlorobenzene, ketones such as acetone and methyl ethyl ketone, benzene, and toluene.

Aromatic hydrocarbons such as xylene, ethyl ether.

Ethers such as tetrahydrofuran and dioxane.

Esters such as ethyl acetate and propyl acetate, cellosolves such as methyl cellosolve and ethyl cellosolve, water, and the above-mentioned second non-aqueous organic liquid are used.

Preferred organic solvents include those having a boiling point of 100 DEG C. or higher, essentially immiscible with aliphatic or alicyclic hydrocarbons, and soluble in epoxy resins, such as methanol and 1,2-dichloroethane.

Water etc. are used.

The amount of organic solvent to be used is as follows: fil, fil) and/or fiii)/second non-aqueous organic liquid and organic solvent
The weight ratio is in the range of 10015 to 100 and is 100/1 to
It is preferable to use a ratio in the range of 100.

Considering the dispersion stability and cost of the particulate polymer, it is preferable to use it in the smallest amount possible.

In the present invention, a liquid or molten epoxy resin is added with stirring to the particulate polymer dispersed in the first non-aqueous organic liquid produced. the result.

The epoxy resin is adsorbed to or compatible with the particulate polymer to form a homogeneous particulate composite resin. Further, the particulate polymer to which the epoxy resin is added is preferably a particulate polymer that has been heated in order to form a homogeneous particulate composite resin. The heating range is from normal temperature to 180°C, preferably from normal temperature to 130°C. If the temperature exceeds 130°C, undesirable gelation of the epoxy resin and particulate polymer may occur. In order to obtain a homogeneous particulate composite resin, after the epoxy resin is added to the particulate polymer under stirring, it is preferred to continue stirring for an additional 0.1 to 5 hours, preferably 0.2 to 1 hour.

According to the present invention, a gelled particulate composite resin is obtained.

It can also be obtained intentionally. To obtain a gelled particulate composite resin, a particulate polymer and an epoxy resin are mixed in an appropriate ratio for gelation to form a particulate composite resin.

This may be heated to allow the reaction to proceed until gelation occurs.

In the present invention, the particulate polymer and the epoxy resin.

They are used in combinations that are compatible at least during curing. Here, being compatible at least during curing usually means that
This means that the particulate polymer substantially free of solvent and the epoxy resin are uniformly compatible in the temperature range from room temperature to around 250° C., which is used as the curing temperature.

The blending amounts of the particulate polymer and epoxy resin can be arbitrarily determined depending on the purpose. Considering heat resistance.

Preferably, the ratio is such that the carboxylic acid, acid anhydride group, or a derivative thereof, which is the terminal group of the particulate polymer, and the epoxy group of the epoxy resin are equivalent. In the case of heating and pressure molding, it is preferable to use 100 to 900 parts by weight of the particulate polymer per 100 parts by weight of the epoxy resin, especially in consideration of heat resistance. In particular, for low pressure transfer molding, epoxy resin 100
It is preferred to use 100-500 parts by weight of the 9 particulate polymer.

In the present invention, a curing aid (catalyst) is used as necessary.

Epoxy resin hardeners are used.

Examples of curing aids (catalysts) that may be used as needed include trimethylamine, triethylamine, triethylenediamine, N,N-diethylaniline, N,N-dimethylaniline, tris(dimethylaminomethyl)phenol, N-methylmorpholine, N-ethylmorpholine,
Tertiary amines such as 1.8-diaryl-bicyclo(5,4,0)undecene-7 (or its organic acid salt), cetyltrimethylammonium bromide, dodecyltrimebulammonium ioguite, benzyldimethyltetradecylammonium acetate Quaternary ammonium salts such as 2-methylimidazole, 2-ethylimidazole, 2-methyl-4-ethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-quenylimidazole, 1 Imidazole compounds such as -azine-2-methylimidazole and the like are used. The amount of curing aid used is 0.1 to 0.1 to epoxy resin.
It is preferable to use it in an amount of 5% by weight, preferably 0.5 to 3% by weight.

As the epoxy resin curing agent, acid anhydride curing agents and amine curing agents are used.

Examples of acid anhydride curing agents include dodecenylsuccinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, methylnadic anhydride, pyromellitic anhydride, maleic anhydride, chlorendic anhydride, and anhydride. Benzophenone tetracarboxylic acid, methyltetrahydrophthalic anhydride, tetodihydrophthalic anhydride, methylbexahydrophthalic anhydride, trimellitic anhydride.

Tetrabromophthalic anhydride and the like are used.

Examples of the amine curing agent include hexamethylene diamine, diethylene triamine, diaminodiphenylmethane, and diaminodiphenylsulfone, but in consideration of storage stability, diaminodiphenylsulfone is preferably used.

The epoxy resin curing agent is 0.5 to 1 for the epoxy resin.
It is preferable to use 00% by weight.

The curing aid and epoxy resin curing agent described above may be added before adding the epoxy resin, may be added to the particulate polymer at the same time as the epoxy resin, or may be added in advance during the production of the particulate polymer. good.

In the present invention, fillers, glass fibers,
A reinforcing material such as carbon fiber may also be used.

As a filler, for example, fused quartz powder, Fuselex RD-8 (all trade names manufactured by Ryumori Co., Ltd.).

Examples of glass fibers include FESS-005 and FES.
S-010, FESS'-015 (the above are the product names of Fuji Fiberglass Co., Ltd.) 9 Examples of carbon fibers include Ta2O, T500 (the above are the product names of Toshisha Co., Ltd.) 0.0
Those cut into pieces of about 1 nm to 1 mm are used.

The fillers, glass fibers, carbon fibers, etc. described above are preferably added to the particulate polymer under stirring at the initial stage of the reaction. As a result, a particulate composite resin containing a filler, glass fiber, carbon fiber, etc. is obtained.

The particulate composite resin obtained in this way is processed as necessary after removing the second non-aqueous organic liquid or the organic solvent used for the liquid epoxy resin directly from the dispersion, removing P, and refining the resin to form a powder. Will it be collected as a

After f is removed from the dispersion, it is washed and removed with a washing solvent such as water, methanol, acetone, etc. to obtain a powdered resin.

The particulate composite resin obtained by the production method of the present invention exhibits good heat resistance, mechanical properties, and electrical properties.

It is useful for heat-resistant paints, heat-resistant sheets, heat-resistant adhesives, heat-resistant laminated materials, heat-resistant sliding materials, heat-resistant molded products, and heat-resistant composite materials with glass fibers and carbon fibers. In particular, since a relatively stable dispersion system can be obtained in the case of a fine particle system, the dispersion solution can also be used as a dispersion paint. Further, the gelled particulate composite resin is useful as a heat-resistant thixotropic agent, a heat-resistant filler, a lubricating oil thickener, an adsorbent for inorganic elements, a separation material for organic compounds, and the like.

The present invention will be explained using Examples and Comparative Examples.

Example 1 (1) Synthesis of dispersion stabilizer In a four-bottle flask equipped with a thermometer, a stirrer, and a ball-and-tube condenser, 1529° lauryl (aliphatic hydrocarbon manufactured by Etsuo Standard Oil Co., Ltd., trade name) was added. 87.59% of methacrylate and 20.59% of 2-hydroxyethyl methacrylate were added, and the temperature was raised to 145°C. While passing nitrogen gas, lauryl methacrylate 87.09. A mixture of 2-hydroxyethyl methacrylate s, og and benzoyl peroxide paste (benzoyl peroxide content: 50% by weight) 9.69 was added dropwise over 2 hours with stirring. Subsequently, the reaction was continued at the same temperature for 4 hours. This dispersion stabilizer solution was heated to 2
The non-volatile content when dried for a period of time is 40% by weight.

The number average molecular weight of the dispersion stabilizer (determined by gel permeation chromatography using boristyrene of known molecular weight as a calibration curve; the same applies hereinafter) was 6,400.

(2) Production of particulate composite resin While passing nitrogen gas through a 500 m1 four-hole flask equipped with a thermometer, a stirrer, and a 9-ball condenser.

4.4'-diphenylmethane diisocyanate 759 (
0.3 mol), 19 g of the dispersion stabilizer solution obtained in +11 (nonvolatile content 40% by weight), 150 g of 15OPARH.

Add 733 g of N-methyl birolide, 38Q f',
The temperature was raised to 90°C while stirring at p and m. In this state, these mixtures became a homogeneous solution. Finely powdered trimellitic anhydride 729 (0,375 mol) was added in advance, and the mixture was heated at 100°C for 1 hour.

The reaction was continued at 115°C for 1 hour, and then raised to 125°C for 4 hours. A brown particulate polymer dispersed in a continuous phase of 15OPAR-H was obtained. Subsequently, the mixture was cooled to 70°C, and heterocyclic epoxy resin CY350 (manufactured by Ciba Geigy, trade name) 609 was added while stirring.
After continuing to stir at that temperature for 20 minutes, it was rapidly cooled to room temperature. A light brown particulate composite resin having a main particle diameter of 10 to 80 μm was obtained dispersed in l5OPAR-H as a continuous phase. The content of CY-350 contained in this particulate composite resin was determined to be approximately 30% by weight based on the method of quantifying epoxy groups using infrared absorption spectroscopy. This particulate composite resin was heated at 160°C for 2 hours, at 180°C for 10 hours, and then heated at 200°C for 2 hours.
When heated at ℃ for 24 hours, a uniform and transparent film-like cured product was obtained.

When the glass transition temperature of this product was measured using a thermophysical tester, it was found to be 199°C, indicating good heat resistance.

Example 2 Example 1. Using the same equipment as in (2), 34.4 g (0.0 g) of isophorone diisocyanate was added while passing nitrogen gas.
, 155 mol), 4,4'-diphenylmethane diisocyanate 38.89 (0,155 mol), Example 1. (
Dispersion stabilizer solution obtained in step 11 (nonvolatile content 40% by weight) 19
9. 150 g of 15OPAR-H and 339 g of N-methylpyrrolidone were added, and the temperature was raised to 100°C while stirring.

Pre-micronized trimellitic anhydride 73.8
9 (0,384 mol) and heated at 100°C for 1 hour.
1 hour at 115℃.

The temperature was further raised to 130°C and the reaction was continued for 2 hours.

After obtaining the brown particulate polymer dispersed in the continuous phase 15OPAR-H, it was subsequently cooled to 70°C and treated with bisphenol-type epoxy resin Epicoat 828 (manufactured by Shell Chemical Co., Ltd.).
60 g of the product name) was added with stirring, and stirring was continued at that temperature for 20 minutes, followed by rapid cooling. continuous layer l5
Main particle diameter 10-80 μm dispersed in OPAR-1-I
A light brown particulate composite resin was obtained. The content of Epicoat 828 contained in this particulate composite resin was determined in Example 1,
(As measured by the same method as No. 21, it was approximately 321 tl:%
Met. Further, when heated under the same conditions as in Examples 1 and (2), a uniform and transparent film-like cured product was obtained. When the glass transition temperature of this product was measured using a thermophysical tester, it was found to be 182°C, indicating good heat resistance.

Example 3 Heterocyclic epoxy resin TEPIC ( Manufactured by Nichiryo Kagaku Co., Ltd., product name) 609 and 2PZ
-CN (manufactured by Shikoku Kasei Co., Ltd., 1-cyanoethyl-2-phenylimidazole) 0.3 g was added to 1,2-dichloroethane 6
．． A solution of 0.09 at 80° C. was added with stirring. After further stirring at that temperature for 20 minutes, the mixture was rapidly cooled to obtain a pale brown particulate composite resin having a main particle size of 10 to 80 μm dispersed in the continuous phase of 15OPAR-H. The particulate composite resin was collected by filtration, thoroughly washed with n-hexane and then water to remove l80PA⇠-H and N-methylpyrrolidone, and then washed under reduced pressure of 31 nmHg.
It was dried at 70° C. for 10 hours to obtain a powdery particulate composite resin. This was put into a compression molding machine (mold temperature: 200℃, molding pressure: 200 Kg/cm2 + molding time: 30 minutes, mold:
When molded using a mold for producing HD T test pieces, a uniform and slightly opaque cured product was obtained. Example 1
When the glass transition temperature of the cured product obtained by heating under the same conditions as above was measured using a thermophysical tester, it was found to be 225°C, indicating good heat resistance.

Example 4 The particulate composite resin dispersed in the continuous phase 15OPAR,-II obtained in Example 3 was further heated at 160°C for 2 hours.

The mixture was heated at 180° C. for 5 hours while distilling off 1,2-dichloroethane. This particulate composite resin does not dissolve in N-methylpyrrolidone and does not melt or flow at all even when heated under the same conditions as in Examples 1 and 21, so it is a gelled spherical particulate composite resin. This was confirmed.

Example 5 (1) Synthesis of dispersion stabilizer Using the same equipment as in Example 1 and (11), 15OPAR-H1529 was placed in a flask and the temperature was raised to 120°C. Methacrylate 183g, 2-hydroxyethyl methacrylate 9g, methacrylic acid 69, benzoyl peroxide paste (benzoyl peroxide content 50% by weight) 109
The mixture was added dropwise over 2 hours while stirring. Subsequently, the temperature was raised to 140°C, and the reaction was continued at the same temperature for 5 hours.

When this dispersion stabilizer solution was baked at 170° C. for 30 minutes, the nonvolatile content was 50% by weight, and the number average molecular weight of Dispersion Stabilizer 9 was 15.000.

(2) Production of particulate composite resin 4.4'-diphenylmethane diisocyanate 257.
19 (1,03 mol), trimellitic anhydride 246.
99 (1,29 mol), N-methylpyrrolidone 113.
1 g, 180PAR, -H514, 3 g and 68.69 g of the dispersion stabilizer solution obtained in Example (1) were mixed and stirred at high speed using a homomixer at 100°C.
The time reaction proceeded. Thereafter, the reaction was transferred to the same apparatus as in Example 1゜(2), heated to 115°C for 1 hour, and further heated to 125°C for 4 hours. A polymer was obtained. Subsequently, it was cooled to 70°C, and the bisphenol type epoxy resin Epicoat 82 was added.
8 Add 206g while stirring, and at that temperature add 206g.
After continuing to stir for 0 minutes, the mixture was rapidly cooled to room temperature. A light yellow particulate composite resin having a main particle diameter of 0.5 to 2 μm was obtained dispersed in a continuous phase of IS 0PAR-1-H. The content of Epicoat 828 contained in this particulate composite resin was measured in the same manner as in Example 1 and (21) and was approximately 2.
It was 9% by weight. When this dispersion of particulate composite resin was heated as it was under the same conditions as in Examples 1 and 21, a uniform and transparent film-like cured product was obtained.The glass transition temperature of this product was measured using a thermophysical tester. Then 1
It showed good heat resistance at 80°C.

Example 6 Example 1, (4,4'-diphenylmethane diisocyanate) 479 (0,188 mol), Example 1, (11
Dispersion stabilizer solution obtained (non-volatile content: 40M)
l5OPA-H1509, N-methylpyrrolidone 33
g was added thereto, and the temperature was raised to 90'C while stirring. Pre-pulverized 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propanihydride 10
09 (0,192 mol) and 2-methylimidazole 0.
6g was added, heated at 100°C for 1 hour, and heated at 115°C for 1 hour.
2 hours at 125℃.

The reaction was further continued at 140°C for 5 hours. Continuous phase l5OP
A dark red particulate polymer dispersed in AR-H was obtained. Subsequently, the mixture was cooled to 70°C, and bisphenol-type epoxy resin Epicor) 828 aog was added while stirring.
After continuing to stir at that temperature for 20 minutes, it was rapidly cooled to room temperature. A pale yellow-red particulate composite resin having a main particle diameter of 10 to 80 μm was obtained dispersed in a continuous phase of 15OPAIL-H. Epicoat 828 contained in this particulate composite resin
The content was measured in the same manner as in Example 1, (2) and was found to be about 18M. When this particulate composite resin was heated under the same conditions as in Examples 1 and 21, a uniform and transparent film-like cured product was obtained.

Comparative Example 1 (1) Synthesis of dispersion stabilizer In a four-loop flask equipped with a thermometer, a stirrer and a 9-ball condenser, 1529 (aliphatic hydrocarbon manufactured by Esso Standard Oil Co., Ltd., aliphatic hydrocarbon, trade name) was placed. The temperature was raised to 120°C. While passing nitrogen gas.

pre-prepared lauryl methacrylate 1839,
17 g of 2-hydroxyethyl methacrylate.

Benzoyl peroxide paste (benzoyl peroxide content 5
0% by weight) was added dropwise over 2 hours while stirring. Continue to raise the temperature to 140℃, and at the same temperature
Allowed time to react. This dispersion stabilizer solution was heated to 30°C at 170°C.
The non-volatile content when baked for 50.5 minutes is 9
The number average molecular weight of the dispersion stabilizer was 14,000.

(2) Synthesis of particulate polymer While passing nitrogen gas through a fourth flask equipped with a thermometer, stirrer, and bulb/tube condenser, 4.4'-diphenylmethane diisocyanate-1.759 (0,3 mole).

Dispersion stabilizer solution obtained in (1) (non-volatile content 50.5%
) 19 g, 150 g, l5OPAR-H (x Aliphatic hydrocarbon manufactured by Standard Oil Co., Ltd., trade name) 150 g, N-
Add methylpyrrolidone 339 and add 10 while stirring.
The temperature was raised to 0°C. In this state, these mixtures became a homogeneous solution. In advance, add 72 g of powdered trimellitic anhydride (0,375 mol) and heat at 100°C for 1
Time: 1 hour at 115°C.

The temperature was further raised to 125°C and the reaction was continued for 3 hours.

A brown particulate polymer dispersed in the continuous phase 15OPA-H was obtained and recovered by one sieve.

After thorough washing with n-hexane and hot acetone.

It was dried at 80° C. for 5 hours under reduced pressure. The number average molecular weight of this powdery particulate polymer is 5,100 (polystyrene equivalent value), with an imide bond at 1780 cm-' and 16
Absorption of amide bonds was observed in 50cm"-" and 1540CI11-". The main particle diameter of this particulate polyamide-f mid resin was approximately 10 to 15.Olj. This was carried out under the same conditions as in Example 3. Compression molded with.

The particulate polyamide-imide resin was a powdery -hz that hardly melted, and no molded product was obtained.

As is clear from the above, the present invention has excellent heat resistance.

It becomes possible to produce a particulate composite resin with excellent melt flowability and economic efficiency.

Claims (1)

[Claims] 1. A first non-aqueous organic liquid that is insoluble in the particulate polymer to be produced, a dispersion stabilizer that is soluble in the first non-aqueous organic liquid, and soluble or swellable in the particulate polymer to be produced. and the polyisocyanate (1
) and polycarboxylic acid (11) having an acid anhydride group and/
or react with polycarboxylic acid +in+ to form particulate polymer (1) dispersed in the first non-aqueous organic liquid, and further disperse the particulate polymer in the first non-aqueous organic liquid. (
A method for producing a particulate composite resin, characterized in that a liquid or molten epoxy resin (It) is added to 1) with stirring to obtain a particulate composite resin dispersed in a first non-aqueous organic liquid. .