JPS62184016A - Heat-resistant molding resin composition - Google Patents

Abstract

PURPOSE:To make it possible to form a uniform cured product, by mixing a specified alcohol-modified polyamide-imide resin with an epoxy resin and, optionally, a curing aid. CONSTITUTION:This composition is formed by melt-kneading a composition containing an alcohol-modified polyamide-imide resin obtained by reacting a particulate polyamide-imide resin obtained by the nonaqueous dispersion polymerization of a tricarboxylic acid anhydride (I) and a polyisocyanate (II) of a I to II equivalent ratio of 1.0-2.0 with an alcohol of the general formula: CnH2n+1 OH (wherein n is an integer of 1-4), an epoxy resin (B) and, optionally, a curing aid (C) with a kneader. As a combination of component A with component B, a combination of components which can be kneaded into a uniform resin composition during kneading and are compatible with each other is desirable. Examples of components C include tert. amines and imidazole compounds.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a heat-resistant molding resin composition powder.

(Prior technology) Polyamide-imide resin, which is known as a typical heat-resistant resin, requires high temperature and high pressure during molding due to its rigid molecular structure, so special molding equipment is required. 1 Ordinary molding equipment cannot be used and is dangerous. stomach.

In order to solve this problem, the present inventors discovered that an inexpensive alcohol-modified polyamide-imide resin obtained by a non-aqueous dispersion polymerization method works as a curing agent for epoxy resin. We proposed a heat-resistant resin composition that uses an epoxy resin as a curing agent for resins and as a molding improver for alcohol-modified polyamide-imide resins (Japanese Patent Application Laid-Open No. 1983-1999).
204613).

(Problems to be Solved by the Invention) However, this heat-resistant resin composition has a problem in that when the epoxy resin used for fF has a high molecular weight (high softening point), it becomes difficult to knead with the alcohol-modified polyamide-imide resin. was there.

The method for mixing epoxy resin and alcohol-modified polyamide-imide resin is a simple dry blending method, static melting in a heating furnace at the time of use, or before use.

There were problems in that it was difficult to obtain a uniform cured product in the end because a heat melting method using a stirrer was not used, or gelation occurred during crosstalk.

The present invention solves these problems and provides a heat-resistant molding resin composition from which a uniform cured product can be obtained.

(Means for Solving the Problems) The present inventors have developed an alcohol-modified polyamide-imide resin obtained by non-aqueous dispersion polymerization of tricarboxylic anhydride and polyisocyanate, an epoxy resin, and, if necessary, a curing aid. By melt-kneading the resin composition using a kneader, a heat-resistant molding resin composition which can be uniformly kneaded in a short time and has improved compatibility has been obtained.

That is, in the present invention, the tricarboxylic anhydride (i) and the polyincyanate (i1) are used in an appropriate quantitative ratio (i1/<II).
The particulate polyamideimide resin obtained by non-aqueous dispersion polymerization at a ratio of 1.0 to 2.0 is added with the general formula CnHx
An alcohol-modified polyamideimide resin (I) obtained by reacting an alcohol represented by n 15OH (n is an integer of 1 to 4), an epoxy resin (If) and, if necessary, a curing aid (III). The present invention relates to a heat-resistant molding resin composition obtained by melt-kneading the resin composition containing the present invention using a kneader.

There are no particular limitations on the epoxy resin used in the present invention. For example, CY250, 260, 280°CY221,
230. CT2O0 (Chiha Geigy company name, product name)
, Epicote 815,828,1001゜1004.1
007 (manufactured by Shell Chemical Co., Ltd., trade name).

Ep-4100, 4900, 4340 (manufactured by Jiryukasha).

Product name), Ebikuron 840, 850, 855, 857
゜860.1050 (manufactured by Dainippon Ink Chemical Co., Ltd., trade name L) PEB-10, PE-10, PE-100 (manufactured by Dainippon Shikizai Kogyo Co., Ltd., trade name), AE 330R.

There are bisphenol type epoxy resins such as 331R, 334R, and 337B (trade names manufactured by Asahi Kasei Corporation).

Also ECN] 235, 1273, 1280. EpN11
38 (manufactured by CibaKey Co., Ltd., product name) e ESCN
-220 (manufactured by Sumima Kagaku Co., Ltd., product name L N-730°N-770, N-660, N-670 (manufactured by Dainippon Ink Chemical Co., Ltd., product name L PE2010.PE2020)
(Manufactured by Dainippon Shikizai Kogyo Co., Ltd., product name), EOCN-10
Novolac type epoxy resin such as 2,103,104 (manufactured by Nippon Kayaku Co., Ltd., trade name), CY175,177°17
9 (manufactured by Ciba Geigy, product name), BRL-420
Cycloaliphatic epoxy resins such as 6,4221 (hereinafter referred to as UCC company name, product name), CY350. XB2615 (manufactured by Ciba Geigy, product name).

TEPIC (Nippon Kagaku, product name), XB2615 (
A heterocyclic epoxy resin such as Ciba Geigy (trade name) is used. Considering the heat resistance of the resulting heat-resistant resin composition, it is preferable to use an epoxy resin having at least two epoxy groups in one molecule.

The particulate polyamide-imide resin used in the present invention is obtained by non-aqueous dispersion polymerization of polyisocyanate and tricarboxylic acid anhydride in the above ratio. For example, a first non-aqueous organic liquid that is insoluble in the particulate polyamideimide resin that is produced.

The dispersion stabilizer is soluble in the first non-aqueous organic liquid and the first non-aqueous organic liquid is soluble or swellable to the resulting particulate polyamide-imide resin and is essentially immiscible with the first non-aqueous organic liquid. In the presence of two non-aqueous organic liquids.

Tricarboxylic anhydride (i) and polyisocyanate (i)
) in a proportion such that +11/(II) is 1.0 to zO.

According to this non-aqueous dispersion polymerization, the 9-particulate polyamide-imide resin is obtained as a dispersion of relatively small particles in the first non-aqueous organic liquid, and therefore can be easily recovered from the dispersion by a filtration operation. Further, in this polymerization, an inexpensive general-purpose solvent that is insoluble in the particulate polyamideimide resin to be produced as the first non-aqueous organic liquid can be used. Unlike the solution polymerization method, which has a limit to high solid content due to the insolubility of the polyamide-imide resin in solvents, non-aqueous dispersion polymerization makes it possible to obtain a high solid content of 50% by weight or more in a non-aqueous organic liquid.

As the first non-aqueous organic liquid, a non-aqueous organic liquid that is insoluble in the two-particulate polyamide-imide resin and has inert properties that does not inhibit the one-polymerization reaction is used.

For example, n-hexane, octane, dodecane.

l5OPAR-E, l5OPAR-H, l80PAR
Aliphatic or alicyclic hydrocarbons such as -K (trade name manufactured by Esso Standard Oil Co., Ltd.; a petroleum-based saturated aliphatic or alicyclic hydrocarbon with a boiling point range of about 40 to 300°C) are preferably used. .

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 polyamide-imide resin 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 hydroxyl group-containing vinyl polymer whose main chain is formed from a long-chain alkyl ester of acrylic acid or methacrylic acid having 12 or more carbon atoms is preferably used.

The second non-aqueous organic liquid that is soluble or swellable in the particulate polyamide-imide resin used in the present invention and is essentially immiscible with the first non-aqueous organic liquid inhibits the double polymerization reaction. A non-aqueous organic liquid having non-inert properties and soluble or swellable with respect to at least one of the reactants.

Catalyzes the reaction between end groups during the polymerization reaction process.

A solvent is used that acts as a solvent to increase the molecular weight of the polyamide-imide resin. For example, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, r-butyrolactone, N-vinylpyrrolidone, and the like are preferably used.

The tricarboxylic anhydride used in the present invention may be any tricarboxylic anhydride having a carboxyl group and an acid anhydride group that react with an isocyanate group to form an amide bond and an imide bond.

There are no particular restrictions. For example, trimellitic anhydride is preferably used.

If necessary, a polycarboxylic acid or a polycarboxylic acid anhydride other than the tricarboxylic anhydride may be used in combination with the tricarboxylic anhydride described above.

For example, polycarboxylic acids such as adipic acid, sebacic acid, dodecanedicarboxylic acid, a, r4+'-benzophenonetetracarboxylic dianhydride, 2,2-bis(4-(3
, 4-dicarboxyphenoxy)phenyl] polycarboxylic acid anhydrides such as propane dianhydride are preferred.

Examples of the polyisocyanate used in the present invention include tolylene diinocyanate, xylylene diinocyanate, 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,
Cyclohexane 1,3- and 1,4-diisocyanates, cycloaliphatic diisocyanates such as isophorone diisocyanate, triphenylmethane-4,4:4"-triisocyanate, polyphenylmethyl polyisocyanates, e.g. condensation of aniline with formaldehyde Polyisocyanates such as phosgenated polyisocyanates and incyanurate ring-containing polyisocyanates obtained by trimerization of these polyisocyanates are used.

Considering heat resistance etc., aromatic diincyanates such as tolylene diisocyanate and 4,4'-diphenylmethane diisocyanate, and isocyanurate ring-containing polyisocyanates obtained by trimerization reaction of these aromatic diincyanates are preferably used. .

These polyisocyanates may be used alone or in combination depending on the purpose.

The particulate polymer obtained as described above has the general formula C
An alcohol-modified polyamide-imide resin is obtained by reacting an alcohol represented by nH2n+xOH (n is an integer of 1 to 4).

As the alcohol, methanol is preferable from the viewpoint of boiling point and cost.

The amount of alcohol used is sufficient as long as it is sufficient to halfesterize the acid anhydride groups of the particulate polymer.

For example, how to react with alcohol.

A predetermined amount of alcohol may be added to the particulate polymer dispersed in the first non-aqueous organic liquid obtained by the production method of the present invention for reaction, or particulate polymers recovered by filtration or decantation may be used. A predetermined amount of alcohol may be added to the polymer for reaction.

The reaction temperature is from room temperature to 200°C, preferably around the boiling point of the alcohol used.

A polyamide-imide resin purified using a normal purification method such as washing the obtained particulate polymer with water without reacting with alcohol is not compatible with a bisphenol-type epoxy resin.

Also, polyamide-imide resin purified using a ketone organic liquid 9 such as acetone instead of water.

Not compatible with bisphenol type epoxy resins.

However, the alcohol-modified polyamide-imide resin obtained by reacting with an alcohol represented by the general formula CnH+tOH (" is an integer from 1 to 4), such as methanol, and the bisphenol-type epoxy resin are compatible.

It is thought that the halfestered terminal structure of the alcohol-modified polyamide-imide resin contributes to its compatibility with the bisphenol-type epoxy resin.

There are no particular limitations on the method for removing the second non-aqueous organic liquid, and examples include boiling with a polar liquid and a method using a Soxhlet extractor. In order to remove the second non-aqueous organic liquid at the same time as halfesterization, it is effective to boil with a relatively large amount of alcohol, such as methanol. Also, it is industrially effective to use water to reduce costs and use acetone to facilitate drying.

When obtaining alcohol-modified polyamide-imide resin powder for use as a molding material, it is preferable that the obtained alcohol-modified polyamide-imide resin powder does not substantially contain the second non-aqueous organic liquid; It can also be contained as a compatibility aid in an amount of 10% by weight or less that does not cause foaming and does not affect the required physical properties.

Drying of the alcohol-modified polyamide-imide resin is carried out by the usual method of heating to 50 to 150°C under reduced pressure or normal pressure, and there are no particular restrictions, but the first non-aqueous organic liquid...-alcohol used for phesterization Alternatively, drying is necessary to such an extent that the liquid used to remove the second non-aqueous organic liquid does not remain.

For example, if you want to improve the heat resistance of the composition by increasing the compatibility of alcohol-modified polyamide-imide resin with bisphenol-type epoxy resin and increasing its blending ratio, aromatic polyisocyanate, for example 4.4 It is preferred to use a mixed polyisocyanate of '-diphenylmethane diisocyanate, tolylene diisocyanate, or an incyanurate ring-containing polyisocyanate obtained by trimerization thereof, and a non-aromatic polyisocyanate, such as influorone diinocyanate.

In this case, the amount of non-aromatic polyinsyanate used is preferably 50 equivalents or less based on the total amount of isocyanate in consideration of heat resistance and cost.

In the present invention, the tricarboxylic anhydride (i) and the polyisocyanate (i1) have an equivalent ratio (i)/(li) of 1.
It is used in a ratio of 0 to 2-0. If this ratio is less than 1.0, the amount of terminal carboxyl groups, acid anhydride groups, or acid anhydride...-wanister groups of the alcohol-modified polyamideimide resin that contribute to the acid curing reaction of the epoxy resin will decrease. As a result, heat resistance is impaired.

As a result of machining, the number of remaining free incyanate groups increases, resulting in a decrease in the storage stability of the alcohol-modified polyamide-imide resin. If this ratio exceeds 2.0, unreacted acid components with poor compatibility with the epoxy resin increase, resulting in poor molding workability.

Considering the curing reaction with the epoxy resin, the equivalent ratio (i1/
An acid-terminated alcohol-modified polyamide-imide resin synthesized with (II) in the range of 1.02 to 1.5 is preferred.

The molecular weight of alcohol-modified polyamide-imide resin is determined by the number average molecular weight (
Polystyrene equivalent value) of 30,000 or less, especially 15.
000 or less is preferable.

The reaction temperature between the tricarboxylic anhydride and the polyisocyanate is preferably less than 150°C.

Synthesis methods include 2, for example, 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.

Although the combination of alcohol-modified polyamide-imide resin and epoxy resin in the present invention is not limited to fF,
A combination in which the resin composition is uniformly kneaded and exhibits compatibility during melt mixing is preferred. Compatibility here means that particles of alcohol-modified polyamide-imide resin cannot be observed in the molten resin composition obtained in the compatibility test.

In terms of compatibility, 9 is obtained from, for example, trimellitic anhydride and an aromatic polyisocyanate, such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, or an incyanurate ring-containing polyisocyanate obtained by trimerization reaction thereof. A particulate polyamideimide resin modified with the above alcohol and a bisphenol epoxy resin 1 such as Epicoat 1001.
Novolak type epoxy resin 2 e.g. EOCN-103J
i′.

Heterocyclic epoxy resin 1 e.g. XB261
5 (manufactured by Ciba Geigy, 1,3.5-)lisepoxyprobyl isocyanurate) and the like is preferred.

The blending amounts of the alcohol-modified polyamide-imide resin and the epoxy resin can be arbitrarily determined depending on the purpose. Considering heat resistance, carvone W1. which is the terminal group of alcohol-modified polyamideimide resin. The ratio of the acid anhydride group or its derivative to the epoxy group of the epoxy resin is preferably large.

When melt-kneading the above composition using a kneader, considering the improvement in compatibility of the resin composition, the epoxy resin 10
It is preferable to use 30 to 300 parts by weight of alcohol-modified polyamide-imide resin to 0 parts by weight, and 50 to 25 parts by weight.
It is particularly preferred to use 0 parts by weight.

Further, a curing aid (catalyst) is used if necessary.

For example, trimethylamine, triethylamine.

Triethylenediamine, N,N-diethylaniline.

N, N-dimethylaniline, tris(dimethylaminomethyl)phenol, N-methylsulfoline.

N-ethylmorpholine, 1,8-diaza-bicyclo(5
, 4,0) Tertiary amines such as undecene-7 (or its organic acid salt), quaternary ammonium salts such as cetyltrimethylammonium bromide, dodecyltrimethylammonium iodite, benzyldimethyltetradecylammonium acetate.

Furthermore, 2-methylimidazole, 2-ethylimidazole, and 2-methyl-4-ethylimidazole.

1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-azine-2
- imidazole compounds such as methylimidazole; The amount of curing aid to be used is preferably 0.05 to 0.05 to 9, based on the epoxy resin from the viewpoint of gelation and molding cycle of the composition.
The range is 55 to 5 weight, preferably 0.1 to 3 weight.

When the above composition is melt-kneaded using a kneader, dry blending is performed as a pretreatment if necessary to ensure uniform kneading.The tri-blend method is not particularly limited as long as it is a dry blending method. A tabletop mixer, super mixer, etc. are used.

The kneader used for melt-kneading the above composition is not particularly limited, and examples thereof include a single-screw extruder and a co-rotating twin-screw extruder.

A bidirectional rotating twin screw extruder, a pressure kneader, a co-rotating twin screw blade type table kneader, a bidirectional rotating twin screw blade type table kneader, etc. are used. It is particularly effective to use a crosstalk machine with a large shearing force. The melt-kneading temperature of the kneader is such that the temperature of the composition is higher than the melting temperature of the epoxy resin9, usually from room temperature (i0 to 25°C) to 200°C, preferably from room temperature to 150°C.

If the resin temperature is below room temperature, the viscosity of the epoxy resin will not decrease and uniform crosstalk will not occur.

Frictional heat is generated between the inside of the mixer and the resin composition.

The heat causes the resin composition to react rapidly and gelation occurs.

Further, when the resin temperature exceeds 200°C, the action of the curing aid used as necessary becomes active rapidly, and the resin composition gels in a short time.

The kneading time is determined by the amount of alcohol-modified polyamide-imide resin, the amount of epoxy resin, the amount of curing aid used if necessary, the temperature of the cross-wire resin, and the cross-wire ability of the kneader. Preferably, the end point is when the interfering material becomes brownish and transparent.

Further, if necessary, the mixture may be melt-kneaded by pressurizing a kneader. In particular, when the blending ratio of alcohol-modified polyamide-imide resin is large, it is preferable to apply pressure to melt and cross-wire.

The resin composition thus obtained is returned to room temperature and then pulverized to form a molded powder. There are no particular restrictions on the method of pulverization, but for example, it is effective to use a coarse pulverizer, pulverize the resin composition to a certain size, and then pulverize it with a fine pulverizer (such as a hammer mill).

Furthermore, if it is desired that the particle size of the obtained molded powder be constant within a certain range, the molded powder with the desired particle size distribution can be obtained by nine classifications. There are no particular restrictions on the classification method, and a commonly used classification method may be used.

For example, it is effective to use a classifier (vibrating sieve, blower sifter), etc.

Furthermore, if the above-mentioned molding resin powder is desired to be more general-purpose and to have improved physical properties, the above-mentioned composition may be used as a filler to produce fused quartz powder, Fuselex RD-8 (manufactured by Tatsumori Co., Ltd.),
It includes inorganic powders such as (trade name), pulverized glass fibers, pulverized carbon fibers, etc., and can also be melted and mixed in a kneader to form a molded powder.

The heat-resistant molding resin composition of the present invention can be applied to a wide range of applications such as heat-resistant laminated materials, heat-resistant molded products, heat-resistant adhesives, heat-resistant composite materials, heat-resistant sealing materials, and heat-resistant powder coatings.

(Effects of the Invention) According to the present invention, the alcohol-modified polyamide-imide resin and the epoxy resin can be uniformly melted and mixed, regardless of the molecular weight of the epoxy resin, and the cross-wire state is improved compared to conventional compositions. , the appearance, heat resistance, physical properties, etc. of the cured product are improved.

(Examples) The present invention will be specifically explained below using nine comparative examples and examples.

Example 1 (i) Synthesis of particulate polyamide-imide resin (i) Synthesis of dispersion stabilizer In a four-loaf flask equipped with a thermometer, a stirrer, and a 9-ball condenser, 15OPAR-H (Esso Standard Oil Co., Ltd.) aliphatic A hydrocarbon (trade name) 1529 was added and the temperature was raised to 120°C. While passing drilling gas, pre-prepared lauryl methacrylate 1839, methacrylic acid-2
-Hydroxyethyl 179, 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 4 hours.

This dispersion stabilizer solution had a nonvolatile content of 50.5% by weight when baked at 170° C. for 30 minutes, and the number average molecular weight of the dispersion stabilizer 9 was 14,000.

(i1) Synthesis of methanol-modified polyamide-imide resin powder Stable dispersion obtained with 4,4'-diphenylmethane diisocyanate 759e (i) while passing nitrogen gas through a four-loop flask equipped with a thermometer, a stirrer, and a bulb/tube condenser. agent solution (non-volatile content 50.5 weight percent) 199,
l5OPAR-H (aliphatic hydrocarbon manufactured by Esso Standard Oil Co., Ltd., trade name) 1509. N-methylpyrrolidone 3
3 g was added, and the temperature was raised to 100°C while stirring. In this state, these mixtures became a homogeneous solution. In advance, finely powdered trimellitic anhydride 729 was added, heated at 100°C for 1 hour, then at 115°C for 1 hour, and then heated at 125°C for 1 hour.
The temperature was raised to ℃ and the reaction proceeded for 3 hours. Continuous phase l5OPA
Since a brown particulate polymer dispersed in R-H was obtained.

This was collected by filtration. The number average molecular weight of this particulate polymer is 5.000 (polystyrene equivalent value)*
Imide bond at '1780cm-'*1650cm-
Absorption of amide bond was observed at 'e1540cm-'.

The main particle diameter of this particulate polyamideimide resin is about 10~
It was 150μ.

This particulate polymer was boiled three times in methanol, and F
The side edges were dried under reduced pressure at 80°C for 8 hours.

The purified methanol-modified polyamideimide resin powder contained substantially no solvent and was white-yellow in color.

(2) Preparation of heat-resistant molding resin composition (i) Methanol-modified polyamide-imide resin powder 1009 obtained in Tl+). XB2615 (Ciba Geigy epoxy resin, 1,3.5-) lith eboxyglobil in cyanurate) 1009 and 2PZ-C as a curing aid
N (imidazole, manufactured by Shikoku Kasei Co., Ltd., trade name) 0.59
were mixed in a plastic bag and triblended by hand for about 2 minutes. This compound was heated to 120°C using a co-rotating twin-screw blade tabletop kneader P n V-0,3 type (trade name manufactured by Irie Shokai Co., Ltd., usage capacity 80 to 200 m/, full size i13
00 mr) and then pressurized using a 1 kg weighting tool to carry out melt cross-fertilization for 10 minutes. Also, the temperature of the blend at this time was FillO<0>C. After completion of the melting and mixing, the mixture was taken out from the kneader to obtain a heat-resistant molding resin composition.

(3) Preparation of heat-resistant molding resin powder The heat-resistant molding resin composition obtained in (2) was brought to room temperature and placed in the bench kneader used in (2) for coarse pulverization.

Pulverize the material using a pulverizer AP-B (manufactured by Hoiyo Ironworks, product name)
The powder was pulverized with a sieve of 75 It, and the powder that passed 75μ was used as a heat-resistant molding resin powder.

Example 2 The methanol-modified polyamide-imide resin synthesized in Example 1 (■) was converted into 1209. XB26] 5 to 809°2PZ-
A heat-resistant molding resin powder was obtained in the same manner as in Example L 1(i), (21, (31) except that CN was changed to 0.4 g.

Example 3 XB2615 1009 of Example 1 (2) was converted to EOCN-
103 (Novolac type epoxy resin manufactured by Nippon Kayaku Co., Ltd.) 10
Example 1(i), except that it was changed to 0g, +21° (
A heat-resistant molding resin powder was obtained in the same manner as in 3).

Comparative Example 1 (i) Synthesis Example 1 of particulate polyamideimide resin (i
) was synthesized in the same manner.

(2) Preparation of heat-resistant molding resin Methanol-modified polyamideimide resin 309 synthesized in the same manner as in Example 1(i). XB2615309, 2
PZ-CN0.159 with a diameter of 60. Mixed in a 70mm deep round can, left in a heating oven heated to 120°C for 15 minutes,
The mixture was mixed by stirring using a stirrer for about 10 minutes. After returning the can to room temperature, the mixture was taken out to obtain a heat-resistant molding resin composition.

+3) Preparation of heat-resistant molding resin powder The heat-resistant molding resin obtained in step (2) is pulverized using an Aica universal pulverizer M^-120 type (manufactured by Shibata Kagaku Kiki Kogyo Co., Ltd., trade name).
Heat-resistant molding resin powder was obtained in the same manner as in Example 1 (3).

Comparative Example 2 A methanol-modified polyamide-imide resin synthesized in the same manner as in Example 1(i) was used at 369. XB2615 249.
A heat-resistant molding resin powder was obtained in the same manner as in Comparative Examples 1 (2) and +31, except that the 2PZ-CN content was changed to 0.129.

Comparative Example 3 Comparative Example 112) XB2615 309 was replaced with EOCN-1
Comparative Example 1 (21°(
A heat-resistant molding resin powder was obtained in the same manner as in 3).

Examples 1 to 3 created as described above. Comparative examples 1 to 3
The compatibility of the heat-resistant molding resin powder was observed under hot conditions.

Furthermore, Examples 1 to 3. The heat-resistant molding resin powders of Comparative Examples 1 to 3 were molded using a compression molding machine under molding conditions (mold temperature 180°C).
, a molding pressure of 100 kgf/cm'' (gauge pressure), and a molding time of 15 minutes), and the appearance was observed.

This molded product was post-cured at 200° C. for 10 hours to provide a sample for glass transition temperature measurement.

The above results are summarized in Table 1.

Table 1 Evaluation results of heat-resistant molding resin powder Evaluation method Compatibility: Sample 0.19 was placed on a hot plate heated to 180°C, stirred, and visually judged.

○ for brown transparent, △ for brown translucent, brown Opaqueness was judged as ×.

Appearance of molded product: The molded product was visually evaluated.

Glass transition temperature: A sample of 5 x 5 x 1.6 ann was cut out from the molded product after post-curing at 200°C for XIO hours, a load of 5 g was applied, and heat was applied at a heating rate of 10°C/min. It is shown as a value measured using a physical testing machine (TMA: manufactured by PERKIN-ELMER).

From the results in Table 1, the compatibility of Example 1 compared with Comparative Examples 1 to 3.
-3 was improved, and the appearance of the molded product was that of Example 2,
Comparing Example 3 with Comparative Examples 2 and 3 shows that the molded product of Example 2.3 is superior.

Claims (1)

[Claims] 1. Tricarboxylic anhydride (i) and polyisocyanate (ii) in equivalent ratio (i)/(ii) of 1.0 to 2.
The general formula C_nH_2_n_+_1 is added to the particulate polyamideimide resin obtained by non-aqueous dispersion polymerization at a ratio of 0.
Contains an alcohol-modified polyamide-imide resin (I) obtained by reacting an alcohol represented by OH (n is an integer of 1 to 4), an epoxy resin (II) and, if necessary, a curing aid (III). A heat-resistant molding resin composition obtained by melt-kneading the composition using a kneader.