JPS6225150A - Flame-retardant and heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To provide a composition composed of an alcohol-modified polyamide imide resin, an epoxy resin containing brominated epoxy resin, and a curing assistant, and having excellent heat-resistance and flame-retardancy, high workability and processability and excellent economicity. CONSTITUTION:The objective resin composition can be produced by compounding (A) an alcohol-modified polyamide imide resin produced by polymerizing a tricarboxylic acid anhydride and 1.0-2.0 equivalent ratio of a polyisocyanate in a state dispersed in a nonaqueous dispersion medium and reacting the produced granular polyamide imide resin with an alcohol of general formula of CnH2n+1OH (n is 1-4) with (B) an epoxy resin containing 20-50wt% brominated epoxy resin and (C) a curing assistant. The amounts of the components A and C are 30-300pts.(wt.) and 0.1-5pts. per 100pts. of the component B. The brominated epoxy resin of the component B has a bromine-content of 18-50wt% and an epoxy equivalent of 330-550.

Description

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

(Prior art) As electronic devices, especially computers, become more widespread and become smaller, faster, and larger in capacity, there is an increasing demand for improved heat resistance and flame retardancy in laminated materials used in circuit boards, etc. . Various materials have been developed to meet this demand, but no resin composition has been found that is well-balanced in terms of heat resistance, flame retardance, cost, moldability, etc.

For example, there is a method of making flame retardant by introducing bromine into a heat-resistant novolac-type epoxy resin composition. It is necessary to add 20% by weight or more of the total organic component, which leads to a decrease in heat resistance (glass transition temperature: 'rg), making it impossible to achieve both flame retardancy and heat resistance.

Furthermore, the heat resistance of the resin obtained by reacting an epoxy resin and a polyfunctional incyanate with an excess of incyanate to form an isocyanurate ring and an oxazolidone ring in the molecule can be reduced by adding a small amount of bromine. However, it is difficult to put it into practical use because it has the disadvantage that the remaining unreacted isocyanate reacts with moisture in the atmosphere and deteriorates in a short period of time.

Furthermore, polyamide-imide resin, which is known as a typical heat-resistant resin, has excellent heat resistance and flame retardancy, but because the resin has a high melt viscosity, it requires high temperatures for molding.

There are processing problems, such as the need for high pressure and expensive special molding equipment.

(Problems to be Solved by the Invention) The present BA provides a resin composition that has excellent heat resistance and flame retardancy, is easy to work with, is easy to process, and is highly economical.

The resin composition of the present invention contains a polyamide-imide resin that is flame retardant by itself, so it can be flame retardant (
It is a flame-retardant, heat-resistant resin composition that has a UL rating of 94'V-0) and does not suffer from deterioration in heat resistance due to bromine content.

(Means for Solving the Problems) The present invention provides tricarboxylic acid anhydride (i) and polyisocyanate (i1) in an equivalent ratio of +1)/+++ of 1.
．． Particulate polyamideimide resin obtained by non-aqueous dispersion polymerization in the range of 0-ZO and the general formula CnHzn+tO
Alcohol-modified polyamide-imide resin (
I).

Epoxy resin (II) and curing aid (III) fff/
It is a resin composition containing F, and 30 to 300 parts by weight of the above +1) per 100 parts by weight of the above (I[), and the above (n) 1
0.1 to 5 parts by weight of the above [) per 00 parts by weight, and brominated epoxy resin (20 to
It relates to a flame-retardant and heat-resistant resin composition containing 50% by weight.

The particulate polyamide-imide resin used in the present invention is obtained by non-aqueous dispersion polymerization of polyisocyanate and tricarboxylic anhydride. For example, a first non-aqueous organic liquid that is insoluble in the particulate polyamide-imide resin to be produced, a dispersion stabilizer that is soluble in the first non-aqueous organic liquid, and a dispersion stabilizer that is soluble or insoluble in the particulate polyamide-imide resin to be produced. The tricarboxylic anhydride (i) and the polyisocyanate (II) are combined in the presence of a second non-aqueous organic liquid that is swellable and essentially immiscible with the first non-aqueous organic liquid.
)/(II+) by non-aqueous dispersion polymerization in the range of 1.0-ZO.

According to this non-aqueous dispersion polymerization, the two-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 solution polymerization, which has a limit to high solid content due to the insolubility of polyamide-imide resin in solvents, non-aqueous dispersion polymerization allows a high solid content of 50% by weight or more to be obtained in a non-aqueous organic liquid.

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

For example, n-hexane, octane, dodecane.

l5OPAR-E, l5OPA 几-H, l5OPA
几-K (The above is a product name manufactured by Esso Standard Oil Co., Ltd.)

Aliphatic or alicyclic hydrocarbons such as petroleum-based saturated aliphatic or alicyclic hydrocarbons having a boiling point of 40 to 300° C. are preferably used.

The dispersion stabilizer is soluble in the first non-aqueous organic liquid, and
Any material can be used as long as it forms a stabilizing layer on the surface of the resulting particulate polyamide-imide resin and at least has the function of stabilizing the dispersion state of particles during the polymerization process, and there are no particular restrictions on such dispersion. Two examples of the stabilizer are obtained by radical polymerization in an aliphatic or alicyclic hydrocarbon, which 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 with the particulate polyamide-imide resin used in the present invention and is essentially immiscible with the first non-aqueous organic liquid is 9
It is a non-aqueous organic liquid having inert properties that does not inhibit the polymerization reaction, is soluble or swellable with respect to at least one of the two reactants, and is capable of contacting the reaction between the end groups in the process of the two-polymerization reaction. A solvent is used that acts as a solvent to increase the molecular weight of the imide resin.

For example, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, γ-butyrolactone, N-
Vinylpyrrolidone and the like are preferred.

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 incyanate group to form an amide bond and an imide bond.

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

If necessary, a part of polycarboxylic acid or polycarboxylic anhydride other than the tricarboxylic anhydride may be used in combination with the above-mentioned tricarboxylic anhydride. For example, polycarboxylic acids such as adipic acid, sebacic acid, dodecanedicarboxylic acid, 3,3. Polycarboxylic acid anhydrides such as '4.4'-bensophenonetetracarboxylic dianhydride and 2.2-bis(4-(a4-dicarboxyphenoxy)7enyl)propane dianhydride are preferred.

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.

1. Aliphatic diisocyanates such as 12-dodecane diisocyanate, cyclobutene 1,3-diisocyanate,
Cyclohexane 1,3-diincyanate.

Cyclohexane 1,4-diisocyanate, cycloaliphatic diisocyanate such as yne7olone diisocyanate 1. lJ
phenylmethane-4,4,4"-triincyanate,
Used are polyphenylmethyl polyisocyanate, for example, polyincyanate obtained by converting a condensate of aniline and formaldehyde to 7-osgen, and isocyanurate ring-containing polyisocyanate obtained by trimerization reaction of these polyisocyanates. Considering heat resistance etc., tolylene diisocyanate, 44
Aromatic diisocyanates such as '-diphenylmethane diincyanate and isocyanurate ring-containing polyisocyanates obtained by trimerization of these aromatic diiso/anates are used.

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

If you wish to further improve the compatibility of alcohol-modified polyamide-imide resin with bisphenol-type epoxy resin and thereby increase the blending ratio of alcohol-modified polyamide-imide resin to improve the heat resistance of the composition,
Aromatic polyisocyanate as polyisocyanate,
For example, it is preferable to use 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, a mixed polyisocyanate of an incyanurate ring-containing polyincyanate obtained by trimerization thereof, and a non-aromatic polyisocyanate, such as in7olone diisocyanate. . In this case, the amount of non-aromatic polyinsyanate used is preferably 50 equivalents or less based on the total polyinsyanate, considering cost and heat resistance.

In the present invention, the m/(II) equivalent ratio of tricarboxylic anhydride (i) and polyisocyanate (i1) is 1.0-2.
．． Used in the range 0. If this equivalent ratio is less than 1.0, the amount of the carboxyl group, acid anhydride group, or Hafester group of the acid anhydride group at the terminal of the alcohol-modified polyamideimide resin, which contributes to the acid curing reaction of the epoxy resin, will decrease. If there are many free incyanate groups, the storage stability of the alcohol-modified polyamide-imide resin will decrease. If this ratio exceeds zO, unreacted acid components with poor compatibility with the epoxy resin increase, resulting in impaired molding workability.

Considering the curing reaction with epoxy resin, (+1/(I+
An acid-terminated particulate polyamide-imide resin synthesized with an equivalent ratio of 1 to 1 in the range of 1.02' to 1.5 (equivalent ratio) is preferred.

Considering the compatibility of the particulate polyamide-imide resin with the molecular tFi epoxy resin and the melt flowability of the composition (!-G
The number average molecular weight (polystyrene equivalent value) in the PC chromatogram is 30,000 or less, especially 15. It is preferable that it is OOO or less.

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

As a synthesis method, 1. For example, a homogeneous solution of all components except the acid component 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 preferred method is to add a finely powdered acid component to the resulting heterogeneous solution. According to this method, the polymerization reaction can proceed at a relatively low reaction temperature, and undesirable side reactions can be suppressed.

The particulate polyamideimide resin obtained as described above is further reacted with an alcohol represented by the general formula CnHzn++ OH (n is an integer of 1 to 4) to obtain an alcohol-modified polyamideimide resin.

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

The amount of alcohol used may be at least a sufficient amount to halfesterize the acid anhydride groups of the particulate polyamideimide resin.

For example, how to react with alcohol.

A predetermined amount of alcohol may be added to the particulate polyamideimide resin dispersed in the first non-aqueous organic liquid obtained by the production method of the present invention to cause a reaction, or particles recovered by PM or decantation may be used. Alternatively, a predetermined amount of alcohol may be added to the polyamideimide resin to cause the reaction.

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

The polyamide-imide resin obtained by purifying the nine-particulate polyamide-imide resin using a conventional purification method such as washing with water without reacting with alcohol is particularly incompatible with bisphenol-type epoxy resin.

Further, polyamide-imide resin purified using a ketone organic liquid 9 such as acetone instead of water is also not compatible with bisphenol-type epoxy resin. However, the general formula CnHz
An alcohol-modified polyamide-imide resin obtained by reacting with an alcohol represented by n + t OH (n = an integer of 1 to 4), for example, methanol, and a bisphenol-type epoxy resin are compatible.

Removal of the first non-aqueous organic liquid and dispersion stabilizer.

There are methods such as boiling with an organic liquid having a boiling point of 100° C. or less, such as n-hexane, and using a Soxhlet extractor.

The second non-aqueous organic liquid removal method button is not limited in percentage, and methods such as boiling with a polar liquid and a method using a Soxhlet extractor can be used.

Boiling with a relatively large amount of alcohol, such as methanol, is effective for removing the second non-aqueous organic liquid at the same time as the halfesterization.

Also, it is industrially effective to use water to reduce costs and to use acetone to facilitate drying.

When obtaining an alcohol-modified polyamide-imide resin for use as a molding material, the obtained alcohol-modified polyamide-imide resin preferably does not substantially contain a second non-aqueous organic liquid, but contains an auxiliary agent compatible with the epoxy resin. 2 The amount (i0
(weight i% or less).

Drying of the alcohol-modified polyamide-imide resin is carried out by the usual method of heating at 50 to 150°C under reduced pressure or normal pressure, and there is no particular restriction, but the first non-aqueous ig form, the alcohol used for halfesterization, or the second Drying is necessary to such an extent that the liquid used to remove the non-aqueous organic liquid is not present.

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

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

Product name), Ebikuron 840, 850, 855, 857
゜860.1050 (manufactured by Dainippon Ink Chemical Co., Ltd., trade name), FEB-10, PE-10, PE-100 (manufactured by Dainippon Shikizai Kogyo Co., Ltd., trade name L AER330R).

There are bisphenol epoxy 7 resins such as 331R, 334R, and 337R (trade names manufactured by Asahi Kasei Corporation).

Also ECN1235, 1273, 1280. ECN12
35 (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 Dainippon Ink Chemical Co., Ltd., trade name), PE2010. PE2020(
Manufactured by Inu Nihon Shikizai Kogyo Co., Ltd. (product name), EOCN-102
, 103, 104 (manufactured by Nippon Kaisha, trade names), etc., novolak type epoxy resins, CY175, 177°179
(Manufactured by Ciba Geigy, product name L ERL-420
Cycloaliphatic epoxy resins such as 6,4221 (manufactured by UCC, trade name), CY350. XB2615 (manufactured by Ciba Geigy, product name).

A heterocyclic epoxy resin such as TEP I C (trade name, manufactured by Nichiwa Kagaku) is used.

Considering the heat resistance of the resulting resin composition, it is preferable to use an epoxy resin having at least two epoxy groups in one molecule.

Furthermore, in consideration of impregnability into fibrous substances, heat resistance, and cost, bisphenol type epoxy resins are preferred, and when good impregnability is required, those that are liquid and have low viscosity at room temperature are preferred.

Examples of the brominated epoxy resin used include Y
DB-340, YDB-715 (manufactured by Tobu Kasei Co., Ltd., trade name) Araldai) 8011 (manufactured by Ciba Geigy Co., Ltd.,
Product name), ESB-340, ESB-400, ESB-
500 (manufactured by Sumitomo Chemical Co., Ltd., trade name), etc. are used.

The brominated epoxy resin to be used can be a normal commercially available epoxy resin, but considering workability and heat resistance, the epoxy equivalent should be 330 to 550. Preferably, the bromine content is 18 to 50% by weight, and the epoxy equivalent is 330 to 380.
Particularly preferred is one having a bromine content of 46 to 50% by weight.

The usage ratio of brominated epoxy resin (Foundation) in epoxy resin (U) is related to the amount of alcohol-modified polyamide-imide resin to be blended.
The amount of Iv) used may be small.

Epoxy resin (n
) should contain 20 to 50% by weight of the brominated epoxy resin (fV).

20 to 50 of the epoxy resin (If) used in the present invention
% by weight is considered to be brominated epoxy resin, but the rest is
It is an epoxy resin other than brominated epoxy resin, and there are no particular restrictions on the type thereof.

Examples of the curing aid (III) in the present invention include trimethylamine, triethylamine, triethylenediamine, N,N-diethylaniline, N,N-dimethylaniline, tris(dimethylaminomethyl)phenol,
N-methylmorpholine, N-ethylmorpholine, 1.8
Tertiary amines such as -diaza-bicyclo(5,4,0)undecene-7 (or its organic salt), quaternary amines such as cetyltrimethylammonium bromide, dodecyltrimethylammonium iodite, hensyldimethyltetradecylammonium acetate, etc. grade ammonium salt, 2-methylimidazole, 2-ethylimidazole, 2-methyl-4-ethylimidazole, 1-cyanoethyl-2-
Imidazole compounds such as methylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-azine-2-methylimidazole are used.

The combination of alcohol-modified polyamide-imide resin and epoxy resin in the present invention is not particularly limited, but combinations that are compatible at least during curing are preferred.

Here, being compatible at least during curing means that the alcohol-modified polyamide-imide resin, which does not substantially contain a solvent, and the epoxy resin are uniformly compatible in the temperature range from room temperature to around 250°C, which is usually used as the curing temperature. do. For example, aromatic tricarboxylic acid anhydride 9 as an acid component.
For example, particulate polyamideimide obtained from trimellitic anhydride and an aromatic polyisocyanate as an isocyanate component, such as 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, or an isocyanurate ring-containing polyisocyanate obtained by trimerization thereof. Alcohol-denatured resins and bisphenol-type epoxy resins (e.g. Ebico) 828. Cycloaliphatic epoxy resins such as CY179. Novolak type epoxy resin such as EOCN-103, heterocyclic type epoxy resin such as CY350. There is a combination with XB2615 etc.

The blending ratio of alcohol-modified polyamide-imide resin (i), epoxy resin (n) and curing aid (ml) is (I) (
The amount ranges from 30 to 300 parts by weight, preferably from 50 to 200 parts by weight, per 100 parts by weight of II). If the alcohol-modified polyamide-imide resin (I) is less than 303 parts, the heat resistance will be lowered and the physical properties will also be lowered.

Alcohol-modified polyamide-imide resin (if i1 exceeds 300 parts by weight, impregnating properties into fibrous substances decreases).

The curing aid @) is used in an amount of 0.1 to 5 parts by weight, preferably 0.3 to 3 parts by weight, per 100 parts by weight of the epoxy resin (II). If the curing aid (III) is less than 0.1 parts by weight, the reaction between (i), (II) and the brominated epoxy resin (IV) will be slow, and productivity will decrease, and if it exceeds 5 parts by weight, In this case, the reaction of the above-mentioned components becomes rapid, making the molding operation difficult.

When impregnating the flame-retardant heat-resistant resin composition of the present invention with a fibrous material, the composition must be heated and thoroughly mixed before being impregnated with the fibrous material in order to obtain a laminated material without void defects. It is preferable.

There are no restrictions on the fibrous material used, and for example, rovings, chops, chopped mats, woven fabrics, etc. made of glass fibers, carbon fibers, aromatic polyamide fibers, carbon silicon fibers, etc. can be used.

The laminated material is made of several layers of fibrous material impregnated with the flame retardant heat-resistant resin composition obtained in this manner.

It can be used in a wide range of applications such as electrical insulation parts and heat-resistant structural materials.

Further, this laminated material can be made into a B stage to improve moldability.

(Effects of the Invention) The resin composition of the present invention contains a flame-retardant polyamide-imide resin, and makes a laminate flame-retardant (UL 94V- 0
) and is a flame-retardant, heat-resistant resin composition that does not have a decrease in heat resistance due to bromine content.

(Example) Comparative examples and examples of the present invention will be explained.

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 two-ball condenser, l5OPA II, -H (fat oil manufactured by Esso Standard Oil Co., Ltd.) was placed. Add group hydrocarbon, trade name) 1529, 1
The temperature was raised to 20°C. While passing nitrogen gas, a previously prepared mixture of lauryl methacrylate 1839, 17 g of 2-hydroxyethyl methacrylate, and benzoyl peroxide paste (benzoyl peroxide content: 50 weight*) toH 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 was 14.000.

(i1) Synthesis of particulate polyamide-imide resin 4.4'-diphenylmethane diiso 7
75 g of anate, 19 g of the dispersion stabilizer solution obtained in (i) (nonvolatile content 50.5% by weight).

l5OPAR-H (aliphatic hydrocarbon manufactured by Esso Standard Oil Co., Ltd., trade name) 1509. N-methylpyrrolidone 3
3gt was added, and the temperature was raised to 100°C while stirring.

In this state, these mixtures became a homogeneous solution. Add finely powdered trimellitic anhydride 729 and heat at 100'C for 1 hour.

The reaction was continued at 115°C for 1 hour, and then raised to 125°C for 3 hours. A continuous phase of l5OPAR-1 (brown particulate polymer dispersed in it) was obtained which was recovered by filtration.

The number average molecular weight of this particulate polymer is 5.100 (polystyrene equivalent value), 1780 cm-11c imide bond, 1650 cm-', 1540 cm-'
Absorption of amide bonds was observed. The main particle diameter of the particulate polyamideimide resin was about 10 to 150 microns.

This particulate polyamide-imide resin was repeatedly boiled with methanol three times, separated from the oven, and then dried under reduced pressure at 80° C. for 8 hours.

The methanol-modified polyamideimide resin powder produced in N was white-yellow in color and substantially free of solvent.

(2) Preparation of laminated material The methanol-modified polyamide-imide resin powder obtained above (2) Pulverized product 289. Epicoat 828 (manufactured by Shell Kagaku Co., Ltd., trade name 'I 33.69. )0.
3369 was left in a dryer at 120° C. for 5 minutes to heat it, then taken out and mixed evenly to obtain a resin composition. A polypropylene film (
Manufactured by Toshisha, Tone No. 40, Type 2505. (product name) and cut a glass cloth WF350-ioonv (manufactured by Nittobo Co., Ltd., product name) into a 12 cm square.
After heating for 5 minutes, 5 g of the above resin composition was uniformly applied to a glass cloth to prepare a fiber-containing resin composition, and 8 sheets of this were stacked to form a laminated material.

Example 2 Example 1. (28 g of crushed alcohol-modified polyamide-imide resin powder obtained with Il+, Epicoat 828°29
．． 49. Example 1: YDB-340, 12, 69 and 2PZ-CN, 0.2949 as a curing aid
In the same manner as in 2), a W1 cloth was mixed and 8 sheets were stacked to create a laminated material.

Example 3 (i) Synthesis of particulate polyamideimide resin Example 1,
Using the same equipment as in (i) and (II), while passing nitrogen gas, influoron diincyanate 34.49
．． 4.4'-diphenylmethane diinocyanate 38.
89. Example 1. (i), (Dispersion stabilizer solution obtained in +1 (non-volatile content 5011jt%) 19 g, 15O
33 g of PA-H1509, N-methylbiridone was added, and the temperature was raised to 100°C while stirring. 73.89% of trimellitic anhydride, which had been pulverized in advance, was added and heated at 100°C for 1 hour, then at 115°C for 1 hour, and further [130
The temperature was raised to ℃ and the reaction proceeded for 2 hours. Continuous phase l5OPA
Since we obtained a brown particulate polymer dispersed in R, -H,
This was collected by filtration.

The number average molecular weight of this particulate polymer is 4.900 (polystyrene equivalent value), and the infrared absorption spectrum is as follows:
1780cm-' K imide bond + 1650cm-
Absorption of amide bond was observed at 1,1540 mark -1.

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

This particulate polyamide-imide resin was repeatedly boiled with methanol three times; after being separated from the oven, it was 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) Adjustment of laminated material 36 g of pulverized methanol-modified polyamideimide resin powder obtained above, Epicoat 828, 309, YDB-3
40,69 and 2PZ-CN as curing aid, 0.39
were mixed and applied in the same manner as in Example 1i21, and 8
A laminated material was created.

Comparative Example I Example 1 except that YDB-340 was not blended. (An 8-ply laminated material was created using the same two formulation conditions as No. 21.

Comparative Example 2 (i) Preparation of resin composition Epicoat 828. 359. YDB-340,15
9 and BF3MEA (manufactured by Hashimoto Kasei Co., Ltd.) 1.59 were blended, left in a dryer at 100° C. for 10 minutes, heated, taken out and mixed uniformly to obtain a resin composition.

(2) Preparation of laminated material Example 1 was prepared using the resin composition obtained above. An 8-layer laminated material was created using the same method as in (2).

The laminated materials produced as described above were used in Examples 1 to 3. For Comparative Examples 1 and 2, press conditions were 130°C.

The resulting laminate was molded at a pressure of 40 kgf/cm'' for 90 minutes and was then cured at 200° C. for 1 hour.

The heat resistance (glass transition temperature) is 5×5×1.
A 6 mm sample was cut out, a load of 5 g was applied to it, and a thermophysical testing machine (TMA:PE) was run at a heating rate of 10°C/min.
(manufactured by RKIN-BLMER).

The flame retardancy test was carried out according to UL94, and the sample size (
i27X IZ7X 1.6mm) Each set of 5 sheets was measured. Further, a laminate plate having a resin content of 45 to 46 m was used as a sample.

Table 1 shows the results.

Table 1 Evaluation results of laminates According to the results in Table 1, the laminates obtained with the compositions of Examples 1 to 3 have improved flame retardancy compared to the laminates obtained with the compositions of Comparative Examples 1 to 2. It is shown that heat resistance is also maintained.

Claims (1)

[Claims] 1. The tricarboxylic acid anhydride (i) and the polyisocyanate (ii) have an equivalent ratio of (i)/(ii) of 1.0 to 2.
．． Particulate polyamideimide resin obtained by non-aqueous dispersion polymerization in the range of 0 and general formula C_nH_2_n_+_1OH
(n is an integer of 1 to 4) alcohol-modified polyamide-imide resin (I) obtained by reacting with alcohol
, a resin composition containing an epoxy resin (II) and a curing aid (III), in which the above (II) is added to 100 parts by weight of the above (II).
30 to 300 parts by weight of I), 0.1 to 5 parts by weight of the above (III) per 100 parts by weight of the above (II), and further the above (
A flame-retardant heat-resistant resin composition containing 20 to 50% by weight of brominated epoxy resin (IV) in II). 2. Brominated epoxy resin (IV) has a bromine content of 1
The flame-retardant and heat-resistant resin composition according to claim 1, which is a brominated epoxy resin having an epoxy equivalent of 8 to 50% by weight and 330 to 550.