JP2003138015A - Polyamideimide resin paste and coating material comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamideimide resin paste having excellent flexibility, adhesion to a sealing material, solvent resistance, and chemical resistance, being soluble in a nitrogen-less polar solvent, being curable at a low temperature, and having excellent heat resistance, electric properties, moisture resistance, workability and economical efficiency, while maintaining low warpage, and to provide a coating material comprising the paste. SOLUTION: This thixotropic polyamideimide resin paste comprises (A) 100 pts.wt. of a polyamideimide resin obtained by reacting, in a nitrogen-less polar solvent, a mixture of (a) a polycarboxylic acid with an acid anhydride group, the acid having three valences or more, or a derivative of the acid, (b) a diisocyanate with a number average molecular weight of 500-10,000 that is represented by general formula (I) (wherein R's are each independently a 1-18C alkylene group; X's are each independently a 1-18C alkylene or arylene group; and m and n are each independently an integer of 1-20), and (c) an aromatic polyisocyanate, (B) 1-50 pts.wt. of an epoxy resin, and (C) 1-90 pts.wt. of inorganic and/or organic fine particles. A coating material is prepared by comprising the paste.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamideimide resin paste having thixotropic properties suitable for a coating method such as a printing machine, a dispenser or a spin coater, and a film forming material containing the same.

[0002]

2. Description of the Related Art In recent years, in the field of electronic parts, polyimide resin and polyamide-imide resin have been used instead of epoxy resin as a resin having excellent heat resistance, electrical characteristics and moisture resistance in order to respond to miniaturization, thinning and high speed. , Polyamide resin is used. These resins have a rigid resin structure, and when used as a thin film base material, the base material after curing largely warps, and the cured film lacks flexibility and is inferior in flexibility.

Therefore, various polyamide-imide resins in which the resin is made flexible and the elastic modulus is made low have been proposed. However, conventionally, N-methyl-2 has been used as a solvent for varnishing.
Since a high-boiling-point nitrogen-containing polar solvent such as pyrrolidone is used, high-temperature curing at 200 ° C. or higher is required at the time of curing, which causes a problem of thermal deterioration of electronic members. Further, when the varnish is applied to the base material and left for a long time, whitening and voids of the coating film due to moisture absorption occur, which causes a problem of complicated working conditions. On the other hand, as a resin which is soluble in a non-nitrogen-containing polar solvent and has a low warp and flexibility, for example, JP-A-7-304950 and JP-A-8-333455 disclose polyimidesiloxane. These polyimidesiloxanes use an expensive diamine having a dimethylsiloxane bond as a starting material for lowering the elastic modulus, and are inferior in economic efficiency. In addition, as the amount of modification of siloxane increases, the adhesion to the encapsulant, solvent resistance,
There is a problem that chemical resistance (solder flux resistance) decreases.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art and is excellent in low warpage, flexibility, adhesion with a sealing material, solvent resistance and chemical resistance. The present invention provides a polyamide-imide resin paste that is soluble in a non-nitrogen-containing polar solvent, has low-temperature curability, and is excellent in heat resistance, electrical characteristics, humidity resistance, workability, and economy, and a film-forming material containing the same. .

[0005]

The present invention provides (A) (a)
Tricarboxylic or higher polycarboxylic acid having an acid anhydride group or a derivative thereof, (b) general formula (I)

[0006]

[Chemical 2]

[In the formula, a plurality of R's each independently represent an alkylene group having 1 to 18 carbon atoms, and a plurality of X's each independently represent an alkylene group having 1 to 18 carbon atoms or an arylene group; m and n each independently represent an integer of 1 to 20], which is a polyamide-imide resin composition containing a polyamide-imide resin obtained by reacting diisocyanate represented by the formula as an essential component. (C) 100 parts by weight of a polyamide-imide resin characterized by reacting a mixture of aromatic polyisocyanates in a nitrogen-free polar solvent, (B) an epoxy resin of 1 to 50 parts by weight, and (C) an inorganic and / or Or organic fine particles 1-9
The present invention provides a polyamide-imide resin paste containing 0 part by weight and having thixotropy. The present invention also provides a film forming material containing the polyamide-imide resin paste.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamide-imide resin paste of the present invention comprises the above-mentioned (A) polyamide-imide resin 10
It contains 0 parts by weight, (B) 1 to 50 parts by weight of an epoxy resin, and (C) 1 to 90 parts by weight of inorganic and / or organic fine particles as essential components. Examples of the (a) tricarboxylic or higher polycarboxylic acid having an anhydride group or a derivative thereof used in the production of the polyamideimide resin of the component (A) in the present invention are represented by the general formulas (II) and (III). A compound can be used, and it is not particularly limited as long as it is a derivative of a trivalent carboxylic acid having an acid anhydride group that reacts with an isocyanate group. Considering heat resistance and cost, trimellitic anhydride is particularly preferable.

[0009]

[Chemical 3]

[0010]

[Chemical 4]

(However, in both formulas, R is hydrogen, and has 1 to 10 carbon atoms.
Represents an alkyl group or a phenyl group, Y is —CH 2 —,
-CO-, -SO2-, or -O- is shown. In addition to these, tetracarboxylic dianhydride (pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 1,2,5, 6
-Naphthalene tetracarboxylic dianhydride, 2, 3, 5,
6-pyridine tetracarboxylic dianhydride, 1,4,5,
8-naphthalenetetracarboxylic dianhydride, 3,4
9,10-perylenetetracarboxylic dianhydride, 4,
4'-sulfonyldiphthalic dianhydride, m-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride,
4,4'-oxydiphthalic acid dianhydride, 1,1,1,
3,3,3-hexafluoro-2,2-bis (2,3-
Or 3,4-dicarboxyphenyl) propane dianhydride, 1,3-bis (3,4-dicarboxyphenyl)
-1,1,3,3-tetramethyldisiloxane dianhydride, butanetetracarboxylic dianhydride, bicyclo-
[2,2,2] -Oct-7-ene-2: 3: 5: 6-
Tetracarboronic acid dianhydride, etc., aliphatic dicarboxylic acids (succinic acid, glutaric acid, adipic acid, azelaic acid,
Suberic acid, sebacic acid, decanedioic acid, dodecanedioic acid,
Dimer acid, etc.), aromatic dicarboxylic acid (isophthalic acid,
Terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, etc.) can be used. The diisocyanate represented by the general formula (I) used as the component (b) in the present invention has the general formula (IV)

[0012]

[Chemical 5]

[In the formula, plural R's each independently represent an alkylene group having 1 to 18 carbon atoms, and m is 1 to 20.
An integer] and the general formula (V)

[0014]

[Chemical 6]

[In the formula, X represents an alkylene group having 1 to 18 carbon atoms or an arylene group such as a phenylene group (which may have a lower alkyl group such as a methyl group as a substituent)] It can be obtained by reacting the represented diisocyanate with or without a solvent.
Examples of carbonate diols represented by the above general formula (IV) include, for example, a trade name PL manufactured by Daicel Chemical Industries, Ltd.
ACCEL, CD-205, 205PL, 205HL,
210PL, 210HL, 220, 220PL, 220
HL is mentioned, and these are used individually or in combination of 2 or more types.

Examples of the isocyanates represented by the general formula (V) include diphenylmethane-2,
4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3 '-Dimethyldiphenylmethane-
2,4'-diisocyanate, 3,2'- or 3,3'-
Or 4,2'- or 4,3'- or 5,2'- or 5,3 '
-Or 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,
3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4 'diisocyanate, diphenylmethane- 4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone-
4,4'-diisocyanate, diphenyl sulfone-
4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate,
Aromatic polyisocyanates such as m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate and 4,4 ′-{2,2bis (4-phenoxyphenyl) propane} diisocyanate are used. Preferably. These can be used alone or in combination of two or more.

Hexamethylene diisocyanate,
Aliphatic or fat such as 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanera, 4,4'-dicyclohexylmethane diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, lysine diisocyanate A cyclic isocyanate and a polyisocyanate having three or more functional groups may be used, or those stabilized with a blocking agent necessary for avoiding aging may be used. The blocking agent includes alcohol, phenol, oxime, etc., but is not particularly limited.

The amount of the carbonate diol represented by the general formula (IV) and the diisocyanate represented by the general formula (V) used is such that the ratio of the number of hydroxyl groups to the number of isocyanate groups is isocyanate group / hydroxyl group = 1.01. It is preferable to set it as above.

The reaction can be carried out without solvent or in the presence of an organic solvent. The reaction temperature is preferably 60 to 200 ° C., and the reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions adopted, and the like. Examples of organic solvents that can be used include ketone solvents (methyl ethyl ketone, netyl isobutyl ketone, cyclohexanone, etc.) ester solvents (ethyl acetate, butyl acetate, γ-butyrolactone, etc.), ether solvents (diethylene glycol dimethyl ether, triethylene glycol dimethyl ether). Etc.), cellosolve-based solvent (butyl cellosolve acetate, ethyl cellosolve acetate,
Methyl cellosolve acetate etc.), aromatic hydrocarbon total solvent (toluene, xylene, p-cymene etc.), tetrahydrofuran, dioxane, N-methyl-2-pyrrolidone,
Examples include N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like.

The number average molecular weight of the component (b) diisocyanate thus obtained is from 500 to 10,000.
Is preferable, 1,000 to 9,500 is more preferable, and 1,500 to 9,000 is particularly preferable. If the number average molecular weight is less than 500, the warp tends to deteriorate, and if it exceeds 10,000, the reactivity of diisocyanate tends to decrease, and it tends to be difficult to form a polyamideimide resin.

In the present specification, the number average molecular weight means gel permeation chromatography (GP).
It is a value measured by C) and converted using a calibration curve of standard polystyrene.

The polyisocyanate compound as the component (c) in the present invention is not particularly limited, and examples thereof include:
The diisocyanates or polyisocyanates represented by the general formula (V) used in the component (b) alone or in 2
Combinations of more than one type can be used.

Examples of the polyisocyanate compound as the component (c) include 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 '-[2,2- Bis (4-phenoxyphenyl) propane] diisocyanate, biphenyl-
4,4'-diisocyanate, biphenyl-3,3'-diisocyanate biphenyl-3,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 2,2'-dimethylbiphenyl-4,4 'Cyanate, 3,3'-diethylbiphenyl-4,4'-diisocyanate, 2,2'-diethylbiphenyl-4,4'
-Diisocyanates and the like can be used. These may be used alone or in combination. If necessary, a portion of this may be added to hexamethylene diisocyanate, 2,2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-
Aliphatic, alicyclic isocyanates such as dicyclohexylmethane diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, and lysine diisocyanate, and polyisocyanates having 3 or more functional groups may be used, and avoid changes over time. For this purpose, a stabilizer which is stabilized with a necessary blocking agent may be used. Examples of the blocking agent include alcohol and phenol oxime, but are not particularly limited. The total amount of component (c) is 5
It is preferable that 0 to 100% by weight is an aromatic polyisocyanate, and 4,4′-diphenylmethane diisocyanate is particularly preferable in consideration of the balance of heat resistance, solubility, mechanical properties, cost and the like.

The general formula (I) of the component (b) in the present invention is
The mixing ratio of the diisocyanate represented by and the polyisocyanate of the component (c) is preferably 1 / 0.9 to 0.9 / 0.1 in terms of an equivalent ratio of the component (b) / the component (c), The ratio is more preferably 0.2 / 0.8 to 0.8 / 0.2, and particularly preferably 0.3 / 0.7 to 0.7 / 0.3. If this equivalent ratio is less than 0.1 / 0.9, the elastic modulus cannot be lowered, and the warpage and adhesiveness tend to decrease. If it exceeds 0.9 / 0.1, the film properties such as heat resistance are reduced. Tends to decrease.

The component (a) having an acid anhydride group 3
The proportion of polycarboxylic acid having a valency or higher is (a) based on the total number of isocyanate groups in the components (b) and (c).
The ratio of the total number of carboxyl groups and acid anhydride groups of the component is 0.
6 to 1.4 is preferable, and 0.7 to
It is more preferable to be 1.3, and 0.8 to
It is particularly preferable that the ratio is 1.2. If this ratio is less than 0.6 or exceeds 1.4, it tends to be difficult to increase the molecular weight of the polyamide-imide resin.

The reaction in the method for producing the polyamide-imide resin used in the polyamide-imide resin paste of the present invention is carried out by releasing carbon dioxide gas which is liberated from the reaction system in the presence of an organic solvent, preferably a non-nitrogen-containing polar solvent. It can be carried out by heat condensation while removing.

The non-nitrogen-containing polar solvent is an ether solvent, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, a sulfur-containing solvent, for example,
Dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane, ester solvents, for example, γ
-Butyrolactone, cellosolve acetate, a ketone solvent such as cyclohexanone, methyl ethyl ketone, an aromatic hydrocarbon solvent such as toluene and xylene, etc., and these may be used alone or in combination of two or more kinds. It is preferable to select and use a solvent that dissolves the produced resin. After the synthesis, it is preferable to use a suitable solvent as the paste solvent as it is. [Gamma] -butyrolactone is most preferable because it has high volatility, low-temperature curability, and efficient reaction in a homogeneous system.

The amount of the solvent used is preferably 0.8 to 5.0 times (weight ratio) of the polyamideimide resin produced. If it is less than 0.8 times, the viscosity at the time of synthesis is too high, and it becomes difficult to stir to make the synthesis difficult. If it exceeds 5.0 times, the reaction rate tends to decrease. The reaction temperature is preferably 80 to 210 ° C., and 100 to 1
The temperature is more preferably 90 ° C, and particularly preferably 120 to 180 ° C. If it is less than 80 ° C, the reaction time becomes too long, and if it exceeds 210 ° C, a three-dimensional reaction occurs during the reaction, and gelation tends to occur. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions adopted. If necessary, the reaction may be carried out in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium and cobalt, or a metalloid compound.

The number average molecular weight of the polyamide-imide resin thus obtained is preferably 4,000-40,000, more preferably 5,000-38,000, and more preferably 6,000-. Particularly preferably, it is 36,000. When the number average molecular weight is less than 4,000, the film properties such as heat resistance tend to be deteriorated.
If it exceeds 000, it becomes difficult to dissolve in a non-nitrogen-containing polar solvent, and it tends to become insoluble during synthesis. In addition, workability tends to be poor. Further, the isocyanate group at the terminal of the resin can be blocked with a blocking agent such as alcohols, lactams and oximes after the completion of the synthesis.

The component (B) epoxy resin used in the present invention is, for example, a bisphenol A type epoxy resin such as Epicoat 828 having a trade name of Yuka Shell Epoxy Co., Ltd., or a trade name of Toto Kasei Co., Ltd. Bisphenol F type epoxy resin such as YDF-170, trade name Epicoat 152, 154 having properties of Yuka Shell Epoxy Co., Ltd., trade name EPPN-201 manufactured by Nippon Kayaku Co., Ltd., trade name DEN- manufactured by Dow Chemical Co., Ltd. Phenolic novolac type epoxy resin such as 438, trade name EOCN-12 manufactured by Nippon Kayaku Co., Ltd.
5S, 103S, 104S or other o-cresol novolac type epoxy resin, trade name Epon1031S manufactured by Yuka Shell Epoxy Co., Ltd., trade name Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd., manufactured by Nagase Chemicals Co., Ltd. Product name Denacol EX-611, EX-6
14, EX-614B, EX-622, EX-512,
EX-521, EX-421, EX-411, EX-3
Polyfunctional epoxy resins such as 21; Epikote 604, trade name, manufactured by Yuka Shell Epoxy Co., Ltd .; YH434, trade name, manufactured by Tohto Kasei Co., Ltd .; Trade name, T, manufactured by Mitsubishi Gas Chemical Co., Inc.
ETRAD-X, TERRAD-C, trade name GAN manufactured by Nippon Kayaku Co., Ltd., trade name ELM-1 manufactured by Sumitomo Chemical Co., Ltd.
20 type amine type epoxy resin, trade name Araldite PT810 manufactured by Ciba Specialty Chemicals Co., Ltd.
Heterocyclic ring-containing epoxy resin, ERL42 made by UCC
Alicyclic epoxy resins such as 34, 4299, 4221, 4206 and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

Among these epoxy resins, the amine type epoxy resin having three or more epoxy groups in one molecule is
It is particularly preferable from the viewpoint of improving solvent resistance, chemical resistance and moisture resistance. The epoxy resin (B) used in the resin composition of the present invention may contain an epoxy compound having only one epoxy group in one molecule. Such an epoxy compound is preferably used in the range of 0 to 20% by weight based on the total amount of the polyamide-imide resin. Examples of such an epoxy compound include n-butyl glycidyl ether,
Examples include phenyl glycidyl ether, dibromophenyl glycidyl ether, and dibromo cresyl glycidyl ether. Also, alicyclic epoxy compounds such as 3,4-epoxycyclohexyl and methyl (3,4-epoxycyclohexane) carboxylate can be used.

In the present invention, the amount of the component (B) epoxy resin used is 100% of the component (A) polyamide-imide resin.
The amount is preferably 1 to 50 parts by weight, more preferably 2 to 45 parts by weight, still more preferably 3 to 40 parts by weight. If the amount of the epoxy resin compounded is less than 1 part by weight,
Solvent resistance, chemical resistance, and moisture resistance tend to decrease, and
If it exceeds 0 parts by weight, heat resistance and viscosity stability tend to be lowered. As a method of adding the epoxy resin, the epoxy resin to be added may be dissolved in the same solvent as the solvent contained in the polyamideimide resin in advance and then added, or may be directly added to the polyamideimide resin.

(C) Inorganic or organic used in the present invention
As fine particles, in the polyamide-imide resin solution described above
To form a paste, and the paste is thixotropic
There is no particular problem as long as it can impart the ropy property. This
Examples of such inorganic fine particles include silica (Si
O_Two), Alumina (Al_TwoO_Three), Titania (Ti
O _Two), Tantalum oxide (Ta_TwoO₅), Zirconia (Z
rO_Two), Silicon nitride (Si _ThreeN_Four), Barium titanate
(BaO / TiO_Two), Barium carbonate (BaCO_Three),
Lead titanate (PbO ・ TiO_Two), Zirconate titanate
Lead (PZT), lead lanthanum zirconate titanate (PLZ
T), gallium oxide (Ga_TwoO_Three), Spinel (MgO
・ Al_TwoO_Three), Mullite (3Al_TwoO_Three・ 2Si
O_Two), Cordierite (2MgO / 2Al)_TwoO_Three/
5 SiO_Two), Talc (3MgO ・ 4SiO)_Two・ H2
O), aluminum titanate (TiO_Two-Al
_TwoO_Three), Yttria-containing zirconia (Y_TwoO_Three-Zr
O_Two), Barium silicate (BaO ・ 8SiO)_Two), Nitrogen
Arsenic (BN), calcium carbonate (CaCO_Three), Sulfuric acid
Lucium (CaSO_Four), Zinc oxide (ZnO), titanium
Magnesium acid (MgO ・ TiO_Two), Barium sulfate
(BaSO_Four). Organic bentonite, carbon (C)
Can be used, and one or more of these can be used
It can also be used.

The organic fine particles used in the present invention are not particularly limited as long as they can be dispersed in the above-mentioned polyamideimide resin solution to form a paste and can impart thixotropic property to the paste. As such organic fine particles, fine particles of a heat resistant resin having an amide bond, an imide bond, an ester bond or an ether bond are preferable. The heat-resistant resin is preferably a polyimide resin or a precursor thereof from the viewpoint of heat resistance and mechanical properties,
Fine particles of polyimide resin or its precursor, or polyamide resin are used. The polyimide resin can be obtained by reacting an aromatic tetracarboxylic dianhydride and an aromatic diamine compound.

Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ', 4.
4'-biphenyltetracarboxylic dianhydride, 2,2 ',
3,3′-bisphenyltetracarboxylic dianhydride,
2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) Propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane Dianhydride, bis (3,4-
Dicarboxyphenyl) sulfone dianhydride, 3,4
9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride,
Benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ', 4'-benzophenone tetracarboxylic dianhydride, 2,3,2', 3'-benzophenone tetracarboxylic dianhydride Anhydride, 2,3,3 ', 4'-benzophenone tetracarboxylic acid dianhydride, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride Anhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1,4,5,8-
Naphthalene tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-
Tetracarboxylic acid dianhydride, 2,3,6,7-telorachlornaphthalene-1,4,5,8-tetracarboxylic acid dianhydride, phenanthrene-1,8,9,10-tetracarboxylic acid dianhydride , Bis (3,4-dicarboxyphenyl) dimethylsilane dianhydride, bis (3,4-dicarboxyphenyl) methylphenylsilane dianhydride, bis (3,4-dicarboxyphenyl) diphenylsilane dianhydride, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-
Tetramethyldicyclohexane dianhydride, p-phenylene bis (trimellitic acid monoester acid anhydride), 2,
2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-
Dicarboxypheno) phenyl] hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxypheno) phenyl] propane dianhydride, 4,4-bis (3,4-dicarboxyphenoxy) ) Diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitate anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitate anhydride), 1 , 2- (ethylene) bis (trimellitate anhydride), 1,3- (trimethylene) bis (trimellitate anhydride), 1,4- (tetramethylene) bis (trimellitate anhydride), 1,5- (pentamethylene) Bis (trimellitic anhydride), 1,6- (hexamethylene) bis (no trimellitate) Things), 1,7 (heptamethylene) bis (trimellitate anhydride), 1,8- (octamethylene) bis (trimellitate anhydride), 1,9
(Nonamethylene) bis (trimellitate anhydride), 1,
10- (decamethylene) bis (trimellitate anhydride), 1,12- (dodecamethylene) bis (trimellitate anhydride), 1,16- (hexadecamethylene) bis (trimellitate anhydride), 1,18- (octadeca) Methylene) bis (trimellitate anhydride) and the like, and these may be mixed and used.

The above-mentioned aromatic tetracarboxylic dianhydride may be a tetracarboxylic dianhydride other than the aromatic tetracarboxylic dianhydride, depending on the purpose, in an amount of more than 50 mol% of the aromatic tetracarboxylic dianhydride. It can be used in a range that does not exist. As such a tetracarboxylic dianhydride,
For example, ethylene tetracarboxylic dianhydride, 1,2,
3,4-butanetetracarboxylic dianhydride, pyrazine-
2,3,5,6-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride , 4,8-Dimethyl-1,2,3,5,6,7
-Hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-
Tetracarboxylic acid dianhydride, pyrrolidine-2,3,4
5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, bis [exobicyclo (2,2,1) heptane-2,3-dicarboxylic anhydride] sulfone, Bicyclo- (2,2,2) -oct (7) -ene-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofuryl)-
Examples thereof include 3-methyl-3-cyclohexane-1,2-dicarboxylic acid anhydride and tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride.

As the aromatic diamine compound, for example,
o-phenylenediamine, m-phenylenediamine, p
-Phenylenediamine, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether,
3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3 '
-Diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone,
3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone, 4,4'-diaminodiphenyl ketone, 2,
2-bis (3-aminophenyl) propane, 2,2-bis (3,4'-diaminophenyl) propane, 2,2-
Bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,
2-bis (3,4'-diaminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenyl) benzene, 1,4-bis ( 4-aminophenyl) benzene, 3,3 '-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 3,4'-[1,4
-Phenylenebis (1-methylethylidene)] bisaniline, 4,4 '-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 2,2-bis [4-
(3-Aminophenoxy) phenyl] propane, 2,2
-Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4-
(4-Aminophenoxy) phenyl] hexafluoropropane, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy))
There are phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, and the like, and these may be used as a mixture.

As the aromatic diamine compound, a diamine compound other than the aromatic diamine compound can be used in a range not exceeding 50 mol% of the aromatic diamine compound depending on the purpose. Examples of such a diamine compound include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamino. Heptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (3-aminopropyl) tetramethyl polysiloxane etc. are mentioned.

From the viewpoint of film properties, it is preferable to react the aromatic tetracarboxylic dianhydride and the aromatic diamine compound in approximately equimolar amounts. The reaction between the aromatic tetracarboxylic dianhydride and the aromatic diamine compound is performed in an organic solvent. Examples of the organic solvent include N-methyl-2-
Pyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-3,4,5,6-tetrahydro2 (1H) -pyrimidinone, 1,3-dimethyl-2-
Nitrogen-containing compounds such as imidazolidinone, sulfur compounds such as sulfolane and dimethyl sulfoxide, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, ε
-Lactones such as caprolactone, dioxane, 1,2
-Ethers such as dimethoxyethane, diethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, triethylene glycol (or diethyl, dipropyl, dibutyl) ether, tetraethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, methyl ethyl ketone, Methyl isobutyl ketone, cyclohexanone, acetophenone ketones, butanol, octyl alcohol, ethylene glycol,
Alcohols such as glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol monomethyl (or monoethyl) ether, tetraethylene glycol monomethyl (or monoethyl) ether, phenols such as phenol, cresol, xylenol, ethyl acetate, butyl acetate, Esters such as ethyl cellosolve acetate and butyl cellosolve acetate, hydrocarbons such as toluene, xylene, diethylbenzene and cyclohexane, and halogenated hydrocarbons such as trichloroethane, tetotachloroethane and monochlorobenzene are used.

These may be used alone or in combination.
Considering solubility, low hygroscopicity, low temperature curability, environmental safety, etc., it is preferable to use lactones, ethers, ketones and the like. The reaction temperature is 80 ° C or lower, preferably 0 to 5
Perform at 0 ° C. The reaction solution gradually thickens as the reaction proceeds. In this case, polyamic acid that is a precursor of the polyimide resin is generated. This polyamic acid may be partially imidized, and this is also included in the precursor of the polyimide resin.

The polyimide resin is selected by dehydrating and ring-closing the above reaction product (polyamic acid). Dehydration ring closure is 120 ℃ ~
It can be performed by a method of heat treatment at 250 ° C. (thermal imidization) or a method of using a dehydrating agent (chemical imidization). 1
In the case of the method of heat treatment at 20 ° C. to 250 ° C., it is preferable to perform it while removing water generated by the dehydration reaction outside the system. At this time, water may be removed azeotropically by using benzene, toluene, xylene or the like. In the method of performing dehydration ring closure using a dehydrating agent, it is preferable to use an acid anhydride such as acetic anhydride, propionic anhydride, or benzoic acid, a carbodiimide compound such as dicyclohexylcarbodiimide, or the like as the dehydrating agent. At this time, a dehydration catalyst such as pyridine, isoquinoline, trimethylamine, or aminopyridineimidazole may be used if necessary. The dehydrating agent or dehydrating catalyst is preferably used in the range of 1 to 8 mol per 1 mol of the aromatic tetracarboxylic dianhydride.

The polyamide-imide resin or its precursor is
In the production of the polyamideimide resin or the precursor thereof, instead of the aromatic tetracarboxylic dianhydride, a trivalent trivalent such as trimellitic anhydride derivative such as trimellitic anhydride or chloride of trimellitic anhydride is used. It can be produced by using tricarboxylic acid anhydride or its derivative. Further, instead of the aromatic diamine compound and the other diamine compound, a diisocyanate compound whose residue other than the amino group corresponds to the diamine compound can also be used for production. As the diisocyanate compound that can be used, there is a diisocyanate compound that can be obtained by reacting the aromatic diamine compound or another diamine compound with phosgene or thionyl chloride. The polyamide resin is produced by reacting an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or phthalic acid, a derivative of these dichlorides or acid anhydrides with the aromatic diamine compound described above or another diamine compound thereof. be able to.

Examples of the heat-resistant resin having an ester bond include polyester resins. Examples of the polyester resin include aromatic dicarboxylic acids such as the above-mentioned terephthalic acid, isophthalic acid and phthalic acid, their dichlorides and acid anhydrides. Of 1,4-dihydroxybenzene, bisphenol F, bisphenol A, 4,4'-
Some are obtained by reacting an aromatic diol compound such as dihydroxybiphenyl.

As the polyamide-imide resin, a polyamide-imide resin obtained by reacting an aromatic tetracarboxylic dianhydride and an aromatic diamine compound containing isophthalic acid dihydrazide as an essential component is preferably used. As the aromatic tetracarboxylic dianhydride and the aromatic diamine compound, those mentioned above are used. The molar ratio of isophthalic acid dihydrazide in the aromatic diamine compound is preferably 1 to 100 mol%. If it is less than 1 mol%, the solubility resistance to the modified polyamideimide resin tends to decrease, and if the content of isophthalic acid dihydrazide is high, the moisture resistance of the layer formed by the paste of the present invention tends to decrease. 80 mol% is more preferable, and 20 to 70 mol% is particularly preferable. This polyamide-imide resin can be obtained in the same manner as in the synthesis of the polyimide resin, such as the compounding ratio of the aromatic tetracarboxylic dianhydride and the aromatic diamine compound, the organic solvent used, the synthetic method, and the like.

The polyamideimide resin obtained by reacting trimellitic anhydride and, if necessary, a dicarboxylic acid and a polyisocyanate easily becomes insoluble in an organic solvent when heated, and organic fine particles made of this polyamideimide resin. Can also be used. The polyamide-imide resin can be manufactured in the same manner as the above-mentioned polyamide-imide resin manufacturing method. As a method for forming fine particles, for example, a non-aqueous dispersion polymerization method (Japanese Examined Patent Publication No. 60-48531, JP-A-59-230).
No. 018, precipitation polymerization method (JP-A-59-108030).
Japanese Patent Laid-Open No. 60-212425), a method of mechanically pulverizing powder modified from a resin solution, a method of atomizing the resin solution under high shear while adding the resin solution to a poor catalyst, and drying a spray solution of the resin solution. To obtain fine particles, and a method of precipitating fine particles of a resin having temperature dependence of solubility in a solvent in a detergent or a resin solution.

In the resin paste of the present invention having thixotropy, organic fine particles which are insoluble in a solvent are used, but as a whole, a uniform layer containing a polyamideimide resin and an organic solvent is used before heating and drying. The organic fine particles are present as a non-uniform layer, and a mixture is preferably used so that a uniform layer containing the polyamideimide resin and the organic fine particles as essential components is formed after heating and drying.

As the organic solvent, one that dissolves the above-mentioned polyamide-imide resin is used. When the organic fine particles are used, it is also preferable to use one having the property that both the polyamideimide resin and the organic fine particles described above are soluble in the organic solvent at the temperature when the resin paste is dried by heating. The inorganic and / or organic fine particles in the present invention have an average particle diameter of 50 μm or less and a maximum particle diameter of 10
Those having a particle size of 0 μm or less are preferably used.
If the average particle size exceeds 50 μm, it becomes difficult to obtain a paste having a thixotropy coefficient of 1.3 or more, which will be described later, and if the maximum particle size exceeds 100 μm, the appearance and adhesion of the coating film tend to be insufficient. It is preferable to use inorganic fine particles as the fine particles.

The amount of the inorganic and / or organic fine particles used in the present invention is in the range of 1 to 90 parts by weight with respect to 100 parts by weight of the polyamideimide resin. When it is less than 1 part by weight, it becomes difficult to obtain a paste having a thixotropy coefficient of 1.3 or more, and when it exceeds 90 parts by weight, the fluidity of the paste tends to be impaired. It is particularly preferable that the amount is 2 to 50 parts by weight.

The solution of the polyamide-imide resin is inorganic and / or
Alternatively, as a method for dispersing the organic fine particles, roll kneading, mixing with a mixer and the like, which are generally performed in the field of coating materials, are applied, and there is no particular limitation as long as the method is a method in which sufficient dispersion is performed. Most preferable is kneading with three rolls a plurality of times. Polyamideimide resin paste in the present invention,
It is preferable that the thixotropy coefficient is 1.3 or more. For example, in the case where a printing machine forms a pattern by a coating method using a dispenser, if it is less than 1.3, shape retention after coating is insufficient, so that sagging or flow-out occurs, and a pattern that is practically necessary. There is a tendency that the accuracy cannot be satisfied.

Here, the thixotropy coefficient (TI value) of the paste is an E-type viscometer (manufactured by Toki Sangyo Co., Ltd. RE80U).
Type), the apparent viscosity of the paste at a rotational speed of 1 rpm and 10 rpm measured at a sample amount of 0.5 ml and a measurement temperature of 25 ° C., and is expressed as a ratio η1 / η10 of η1 and η10.
The polyamide-imide resin paste of the present invention has a viscosity of 1 to
1,000 Pa · s, thixotropic coefficient (TI value)
But. The range of 1.3 to 10 is preferable, and the viscosity is 2 to
Those having 700 Pa · s and a TI value in the range of 1.5 to 8.0 are particularly preferably used.

The polyamide-imide resin paste of the present invention contains surfactants such as organic or inorganic fillers, defoaming agents and leveling agents in order to improve workability during coating and film properties before and after film formation. , Colorants such as dyes or pigments,
A heat stabilizer, an antioxidant, a flame retardant, and a lubricant can also be added. The polyamideimide resin paste according to the present invention is combined with a base material such as an overcoat material for electronic parts, a liquid encapsulating material, a varnish for enameled wire, an impregnating varnish for electrical insulation, a casting varnish, a mica, and a glass cloth. It can be used for sheet varnish, MCL laminated board varnish, friction material varnish, interlayer insulation film, surface protection film, solder resist layer, adhesive layer, etc. in the field of printed circuit boards, etc. It is preferably used as a material.

[0052]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. Example 1 In a 5 liter four-necked flask equipped with a stirrer, a cooling tube with an oil / water separator, a nitrogen introducing tube and a thermometer, PLACCEL CD-220 (manufactured by Daicel Chemical Co., Ltd. 1,6- Trade name of hexanediol-based polycarbonate diol) 1000.0 g (0.50 mol) and 4,4'-diphenylmethane diisocyanate 25
0.27 g (1.00 mol) and γ-butyrolactone 8
33.51 g was charged and the temperature was raised to 140 ° C. 140
The reaction was carried out at 0 ° C for 5 hours to obtain diisocyanate. Furthermore,
Trimellitic anhydride 28 is added to this reaction solution as the component (a).
8.20 g (1.50 mol), 4, as the component (c),
4'-diphenylmethane diisocyanate 125.14
g (0.50 mol) and γ-butyrolactone 1361.
14 g was charged, the temperature was raised to 160 ° C., and the mixture was reacted for 6 hours to obtain a resin having a number average molecular weight of 18,000. The obtained resin is diluted with γ-butyrolactone to give a viscosity of 160
A polyamide-imide resin solution having a Pa · s and a nonvolatile content of 52% by weight was obtained. The molar ratio of component (b) / component (c) is 0.5 / 0.5.

YH-434 (Tohto Kasei Co., Ltd.) was added to 100 parts by weight of the resin content of the obtained polyamide-imide resin solution.
Product name of amine type epoxy resin, epoxy equivalent of about 12
0, 4 epoxy groups / molecule) and 10 parts by weight were added and diluted with γ-butyrolactone to obtain a polyamide-imide resin composition having a viscosity of 100 Pa · s and a nonvolatile content of 52% by weight. To 1.200 g of the obtained polyamide-imide resin composition, 34.0 g of Aerosil 380 (trade name, manufactured by Nippon Aerosil Co., Ltd., average particle diameter 0.2 μm or less, silica fine particles) was added, and coarse kneading was performed first, followed by high speed 3 This kneading was repeated 3 times using this roll to perform the main kneading to obtain a polyamideimide resin paste in which silica fine particles were uniformly dispersed. After allowing this paste to stand for 12 hours, an E-type viscometer (Toki Sangyo Co., Ltd.)
Manufactured by RE80U), and the viscosity at 25 ° C. was measured. At this time, the viscosity was 90 Pa · s and the TI value was 2.1.

Example 2 In Example 1, instead of 10 parts by weight of YH-434, Epicoat 828 (trade name of bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 189, epoxy group 2) The same operation as in Example 1 was carried out except that 10 parts by weight of (parts / molecule) was used, and the viscosity was 91P.
As a result, a paste having a TI of 2.1 was obtained.

COMPARATIVE EXAMPLE 1 In Example 1, 34.0 g of Aerosil was mixed with 0.30 g.
Except for 0 g, the same operation as in Example 1 was performed,
A paste having a viscosity of 51 pa · s and a TI value of 1.0 was obtained.

Comparative Example 2 The same operation as in Example 1 was carried out except that 10 parts by weight of YH434 and 10 parts by weight of YH434 were used, and a paste having a viscosity of 98 pa · s and a TI value of 2.0 was obtained. It was

Comparative Example 3 In a flask similar to that used in Example 1 except that the flask was 2 L, 40.0 g (0.60 mol) of 4,4'-diphenylmethane diisocyanate as the component (c) and anhydrous trihydrate as the component (a) were used. 69.1 g (0.36 mol) of meritic acid
And silicone dicarboxylic acid BY16-750 (Toray
Product name of dimethylpolysiloxane-based dicarboxylic acid manufactured by Dow Corning Silicone Co., Ltd. 335.0 g (0.2
4 mol), 277.1 g of γ-butyrolactone and 277.1 g of N-methyl-2-pyrrolidone, and 160 ° C.
After the temperature is raised to 2, the mixture is reacted for 2 hours and the number average molecular weight is 1
2,600 resins were obtained. The obtained resin was diluted with γ-butyrolactone to obtain a polyamideimide resin solution having a viscosity of 8 Pa · s and a nonvolatile content of 40% by weight. Aerosil 380 was added to 1,200 g of the obtained polyamide-imide resin solution.
34.0 g was added and the same kneading as in Example 1 was performed to obtain a paste having a viscosity of 30 Pa · s and a TI value of 2.9.

Physical properties of the polyamide-imide resin paste and the polyamide-imide resin composition obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1.

The obtained polyamide-imide resin paste was applied onto a shape-retaining polyimide film. After drying at 90 ° C for 15 minutes, 120 ° C for 120 minutes or 160 ° C for 6 minutes in an air atmosphere.
Coating film obtained by heating for 0 minutes (thickness 20 to 30 μm, 5 m
Universal projector (manufactured by Nikon Corporation, magnification: 50)
The rate of change in the shape of the coating film before and after curing was evaluated by using a double. ◯: coating film shape change rate 0 to less than 5% Δ: coating film shape change rate 5 to less than 10% ×: coating film shape change rate 10% or more

The obtained polyamide-imide resin composition was applied onto a polyimide film having a warp thickness of 50 μm, a length of 35 mm, and a width of 20 mm, dried at 90 ° C. for 15 minutes, and then at 120 ° C. for 120 minutes in an air atmosphere. Or 60 at 160 ° C
About the coating film (thickness: 20 μm) obtained by heating for a minute,
The coated surface was placed on the surface plate downward, and the warp height was evaluated.

Solvent resistance: The obtained polyamideimide resin composition was applied onto the rough surface of an electrolytic copper foil having a thickness of 35 μm and dried at 90 ° C. for 15 minutes, and then 120 ° C. at 120 ° C. in an air atmosphere.
Minute or 160 ° C. for 60 minutes, and the resulting coating film (thickness: 20 to 30 μm) is heated in acetone at room temperature for 1 minute.
The coating film was immersed for a period of time, and changes in the appearance of the coating film were evaluated according to the following criteria. : No change in appearance △: Change in appearance in part ×: Change in overall appearance

Chemical resistance (tin plating solution resistance) The obtained polyamideimide resin paste was applied onto the rough surface of an electrolytic copper foil having a thickness of 35 μm. After drying at 90 ° C for 15 minutes, in air atmosphere at 120 ° C for 120 minutes or 1
Coating film obtained by heating at 60 ° C for 60 minutes (thickness: 20 ~
30 μm), tin plating solution heated to 70 ° C (TEINPOSITE LT3 manufactured by Shipley First Co., Ltd.)
The coating film was dipped in 4) for 4 minutes, taken out, washed with warm water at 60 ° C. for 5 minutes, heated at 100 ° C. for 10 minutes and dried, and the change in appearance of the coating film was evaluated. : No change in appearance △: Change in appearance in part ×: Change in overall appearance

Adhesion to Encapsulating Material The obtained polyamideimide resin composition was applied onto a rough surface of an electrolytic copper foil having a thickness of 35 μm or a polyimide film having a thickness of 50 μm, and dried at 90 ° C. for 15 minutes, It is heated at 120 ° C. for 120 minutes or at 160 ° C. for 60 minutes in an air atmosphere, and the resulting coating film (thickness: 20 to 30 μm) is coated with an epoxy-based encapsulant [trade name of Hitachi Chemical Co., Ltd.]. CEL-
C-5020] by potting 0.06 g,
Heat at 120 ° C. for 120 minutes, then at 150 ° C. for 120 minutes. The obtained coating film is bent so that the sealing material side is on the outside,
The peeling mode was evaluated according to the following criteria. : Base material / coating interface peeling △: Coating film / sealing material interface peeling x: No adhesion

Moisture Resistance (Pressure Cooker Test) After applying the obtained polyamideimide resin composition onto the rough surface of an electrolytic copper foil having a thickness of 35 μm or a polyimide film having a thickness of 50 μm, and drying at 90 ° C. for 15 minutes The coating film (thickness: 20 to 30 μm) obtained by heating at 120 ° C. for 120 minutes or 160 ° C. for 60 minutes in an air atmosphere was subjected to a pressure cooker test (abbreviated as PCT, condition 12).
The following criteria were used to evaluate the change in the appearance of the coating film after conducting 1 ° C., 2.0265 × 10 ⁵ Pa, 100 hours). : No change in appearance △: Change in appearance in part ×: Change in overall appearance

[0065]

[Table 1]

[0066]

EFFECT OF THE INVENTION The polyamide-imide resin composition of the present invention is excellent in low warpage, flexibility, adhesion to sealing materials, solvent resistance and chemical resistance, and is soluble in non-nitrogen-containing polar solvents. It has low temperature curability, and is excellent in heat resistance, electrical characteristics, workability and economy. Further, the film-forming material of the present invention can form a film having the above-mentioned excellent characteristics, and is an overcoat material for semiconductor devices and various electronic components, an interlayer insulating film in the field of rigid or flexible substrates, a surface protective film. , Sheet varnish combined with base materials such as liquid sealing material, varnish for enameled wire, impregnated varnish for electrical insulation, cast varnish, mica, glass cloth, varnish for MCL laminate, etc. Suitable for use in varnish for friction material.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // (C08L 79/08 C08L 63:00 63:00 101: 00 101: 00) F term (reference) 4J002 CD052 CD062 CD132 CM041 CM043 DA016 DE096 DE106 DE136 DE146 DE186 DE236 DF006 DG046 DJ006 DJ016 FD013 FD016 4J038 DB001 DB002 DB281 DB282 DG262 DJ051 DJ052 JB27 KA06 KA08 MA14 MA02 MA02 MA02 MA02 MA11 MA02 MA11 MA02 XB37 ZA17 ZA24 ZA32 ZA33 ZB02

Claims (5)

[Claims] Claims: (A) (a) trivalent or higher polycarboxylic acid having an acid anhydride group or a derivative thereof, (b) general formula (I) [in the formula, plural R's each independently have 1 to 18 carbon atoms].
Of the above, a plurality of X's each independently represent an alkylene group having 1 to 18 carbon atoms or an arylene group, and m and n each independently represent an integer of 1 to 20]. A polyamide-imide resin composition containing a polyamide-imide resin obtained by reacting as an essential component. (C) 100 parts by weight of a polyamide-imide resin characterized by reacting a mixture of aromatic polyisocyanates in a non-nitrogen-containing polar solvent, (B) an epoxy resin of 1 to 50 parts by weight, and (C) an inorganic and / or Alternatively, a polyamide-imide resin paste containing 1 to 90 parts by weight of organic fine particles and having thixotropy. 2. Polyamideimide resin (a) and (b)
The compounding ratio {(a) / (b)} is 0.1 / 0.
9 to 0.9 / 0.1, and the total ratio of the isocyanate groups of (c) to the total number of carboxyl groups and acid anhydride groups of (a) and (b) is 0.6 to 1.4. Item 10. The polyamide-imide resin paste according to Item 1. 3. The polyamideimide resin paste according to claim 1, wherein the non-nitrogen-containing polar solvent is γ-butyrolactone. 4. The polyamideimide resin paste according to claim 1, wherein the epoxy resin is an amine type epoxy resin having three or more epoxy groups. 5. A film-forming material containing the polyamide-imide resin paste according to claim 1, 2, 3, or 4.