JP2001302795A - Polyamide-imide resin composition and coating film forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyamide-imide resin composition having excellent low warpage, flexibility, adhesion to a sealing material, solvent resistance, and chemical resistance, and further, being nitrogen-free type polar solvent-soluble, and having low-temperature curing properties, and excellent heat resistance, electrical characteristics, humidity resistance, workability and economic efficiency, and to obtain a coating film forming material having the above characteristics by using the same. SOLUTION: The polyamide-imide resin composition comprises the polyamide- imide resin having a repeating unit represented by formula (I) (wherein plural Rs are each a 1-18C alkylene group; plural Xs are each a 1-18C alkylene group or arylene group; (m) and (n) are each an integer of 1-20; and Y is a tervalent organic group), and the coating film forming material gives a coating film formed by using the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyamide-imide resin composition and a film-forming material obtained using the same.

[0002]

2. Description of the Related Art In recent years, in the field of electronic components, epoxy resins have been used as resins having excellent heat resistance, electrical properties and moisture resistance in response to miniaturization, thinning and high speed.
Polyimide resin, polyamide imide resin, polyamide resin and the like are used. However, these resins have a rigid resin structure, and when used as a thin film substrate, the substrate after curing is greatly warped, and the cured film lacks flexibility and has poor flexibility.

[0003] 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 nitrogen-containing polar solvent such as pyrrolidone is used, curing at a high temperature of 200 ° C. or higher is required at the time of curing, and there has been a problem that electronic members are thermally degraded. Also,
When the varnish is applied to the base material and the standing time is prolonged, whitening and voids occur in the coating film due to moisture absorption, which causes a problem that the working conditions are complicated.

On the other hand, it is soluble in non-nitrogen-containing polar solvents,
As a resin having low warpage and flexibility, for example,
JP-A-7-304950 and JP-A-8-333455 disclose polyimide siloxane. These polyimidesiloxanes use an expensive diamine having a dimethylsiloxane bond as a starting material for lowering the elastic modulus,
Poor economics. In addition, there is a problem that the adhesion to the sealing material, the solvent resistance, and the chemical resistance (solder flux resistance) decrease with an increase in the amount of modification of the siloxane.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and is excellent in low warpage, flexibility, adhesion to a sealing material, solvent resistance and chemical resistance. Polyamide-imide resin composition which is soluble in non-nitrogen-containing polar solvent, has low-temperature curability, and is excellent in heat resistance, electrical properties, moisture resistance, workability and economy, and a coating having the above-mentioned properties using the same It is to provide a forming material.

[0006]

According to the present invention, there is provided (A) a compound represented by the following general formula (I):

Embedded image (Wherein, a plurality of Rs each independently have 1 to 18 carbon atoms)
A plurality of Xs 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, and Y is a trivalent (Indicating an organic group).

The present invention also relates to (A) (a) a tri- or higher valent polycarboxylic acid having an acid anhydride group or a derivative thereof, and (b) a compound represented by the general formula (II):

Embedded image (Wherein, a plurality of Rs each independently have 1 to 18 carbon atoms)
A plurality of Xs 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). And a polyamide-imide resin composition containing a polyamide-imide resin obtained by reacting as an essential component.

[0008] The present invention also relates to a polyamideimide resin composition wherein the component (A) is obtained by further using (c) a polyisocyanate compound as a reaction component.
The present invention also relates to the above polyamideimide resin composition containing a non-nitrogen-containing polar solvent as an organic solvent.

Further, in the present invention, the mixing ratio of the component (b) and the component (c) in the production of the polyamide-imide resin of the component (A) is 0.1 in equivalent ratio of the component (b) and the component (c).
1 / 0.9 to 0.9 / 0.1, (b) and (c)
The ratio of the total number of carboxyl groups and acid anhydride groups of component (a) to the total number of isocyanate groups in the component is from 0.6 to
1.4 relates to a polyamide-imide resin composition.

The present invention also relates to (A) 100 parts by weight of a polyamide-imide resin and (B) epoxy resins 1 to 50.
The present invention relates to a polyamideimide resin composition containing parts by weight. The present invention also relates to a polyamide-imide resin composition, wherein the epoxy resin (B) is an amine type epoxy resin having three or more epoxy groups. Furthermore, the present invention
A film-forming material comprising the polyamide-imide resin composition according to any of the above.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamide-imide resin composition of the present invention contains the above-mentioned (A) polyamide-imide resin as an essential component. In the general formula (I), Y is a trivalent organic group, but is generally a residue of a trivalent tricarboxylic anhydride which reacts with an isocyanate compound or an amine compound to form a polyamideimide resin.

In the production of the polyamide imide resin as the component (A) in the present invention, generally, a tri- or higher valent polycarboxylic acid having an acid anhydride group or a derivative thereof is used as the component (a). Examples of this include, but are not particularly limited to, those having an acid anhydride group capable of reacting with an isocyanate group. For example, general formulas (III) and (IV)

Embedded image (Wherein, R ′ represents hydrogen, an alkyl group having 1 to 10 carbon atoms or a phenyl group, and Y represents —CH ₂ —, —CO—, —SO ₂
-Or -O-)) and its derivatives. Trimellitic anhydride is particularly preferred in consideration of adhesion, cost, and the like.

In addition to the above-mentioned polycarboxylic acids or derivatives thereof, if necessary, tetracarboxylic dianhydrides (pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride) may be used. Anhydride, 3,3 ', 4,4'
-Biphenyltetracarboxylic dianhydride, 1,2,5
6-naphthalenetetracarboxylic dianhydride, 2,3
5,6-pyridinetetracarboxylic dianhydride, 1,4
5,8-naphthalenetetracarboxylic dianhydride, 3,
4,9,10-perylenetetracarboxylic dianhydride,
4,4'-sulfonyldiphthalic dianhydride, m-tert-phenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 1,1 ,
1,3,3,3-hexafluoro-2,2-bis (2
3- or 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4-
(2,3- or 3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis [4- (2,3- or 3,
4-dicarboxyphenoxy) phenyl] 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-
Tetracarboxylic dianhydride, etc.), aliphatic dicarboxylic acids (succinic acid, glutaric acid, adipic acid, azelaic acid,
Suberic acid, sebacic acid, decandioic acid, dodecandioic acid,
Dimer acid, etc.), aromatic dicarboxylic acids (isophthalic acid,
Terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, etc.) can be used.

The diisocyanate represented by the general formula (II) used as the component (b) in the present invention is, for example, a compound represented by the general formula (V)

Embedded image (Wherein, a plurality of Rs each independently represent an alkylene group having 1 to 18 carbon atoms, and m is an integer of 1 to 20) and a general formula (VI)

Embedded image [In the formula, X is an arylene group such as an alkylene group having 1 to 18 carbon atoms or a phenylene group (which may have a lower alkyl group having 1 to 5 carbon atoms such as a methyl group as a substituent). The reaction is carried out in the absence of a solvent or in an organic solvent.

The carbonate diols represented by the above general formula (V) include, for example, PLACCEL, CD-205, 205PL, trade names manufactured by Daicel Chemical Industries, Ltd.
05HL, 210, 210PL, 210HL, 220,
Those commercially available as 220PL and 220HL can be used, and these can be used alone or in combination of two or more.

The diisocyanates represented by the above general formula (VI) include, for example, 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, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenylether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylsulfone- 4,4'-diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-
Diisocyanate, m-xylylene diisocyanate,
p-xylylene diisocyanate, naphthalene-2,6
It is preferable to use aromatic polyisocyanates such as -diisocyanate and 4,4 '-[2,2bis (4-phenoxyphenyl) propane] diisocyanate.
These can be used alone or in combination of two or more.

Hexamethylene diisocyanate,
Aliphatic or alicyclic compounds such as 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, and lysine diisocyanate Isocyanates and tri- or higher functional polyisocyanates may be used, and those stabilized with a blocking agent necessary to avoid aging may be used. Examples of the blocking agent include alcohol, phenol and oxime, but there is no particular limitation.

The amount of the carbonate diol represented by the general formula (V) and the diisocyanate represented by the general formula (VI) is such that the ratio of the number of hydroxyl groups to the number of isocyanate groups is as follows: isocyanate group / hydroxyl group = 1.01. It is preferable to make the above. The reaction can be performed without a solvent or in the presence of an organic solvent. The reaction temperature is 60-
The temperature is preferably set to 200 ° C., and the reaction time can be appropriately selected depending on the scale of the batch, the reaction conditions employed, and the like.

The diisocyanate of the component (b) thus obtained has a number average molecular weight of 500 to 10,000.
Is preferred, more preferably from 1,000 to 9,500, and particularly preferably from 1,500 to 9,000. If the number average molecular weight is less than 500, the warpage tends to deteriorate, and if it exceeds 10,000, the reactivity of diisocyanate decreases, and it tends to be difficult to form a polyamideimide resin. In addition,
In the present specification, the number average molecular weight is a value measured by gel permeation chromatography (GPC) and converted using a calibration curve of standard polystyrene.

In the present invention, it is preferable to use a polyisocyanate compound other than the component (b) as the component (c) from the viewpoint of heat resistance. Such a polyisocyanate compound is not particularly limited. For example, the diisocyanate represented by the general formula (VI) or the tri- or higher polyisocyanate used in the component (b) may be used alone or in combination of two or more. They can be used in combination.

As the polyisocyanate compound of the component (c), it is preferable that 50 to 100% by weight of the total amount is an aromatic polyisocyanate.
Considering the balance between mechanical characteristics and cost,
4'-Diphenylmethane diisocyanate is particularly preferred.

The general formula (II) of the component (b) in the present invention
The mixing ratio of the diisocyanate represented by the formula (c) and the polyisocyanate of the component (c) is 0.1 / 0.9 to 0.9 / 0.1 in the equivalent ratio of the component (b) / the component (c). It 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 the equivalent ratio is less than 0.1 / 0.9, the elastic modulus cannot be reduced, and the warpage and adhesion tend to decrease. Tends to decrease.

The component (a) having an acid anhydride group having 3
The blending ratio of the 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 components is 0.
6 to 1.4, preferably 0.7 to 1.4.
1.3 is more preferable, and 0.8 to
It is particularly preferred that the ratio be 1.2. When this ratio is less than 0.6 or more than 1.4, it tends to be difficult to increase the molecular weight of the polyamide-imide resin.

The reaction in the method for producing a polyamide-imide resin of the present invention is carried out by heat-condensing in the presence of an organic solvent, preferably a non-nitrogen-containing polar solvent, while removing the carbon dioxide gas liberated from the reaction system. Can be performed. Ether solvents as the non-nitrogen-containing polar solvent,
For example, diethylene glycol dimethyl ether, diethylene glycol, diethyl ether, triethylene glycol, dimethyl ether, triethylene glycol, diethyl ether, a sulfur-containing solvent such as dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane, an ester solvent such as γ-butyrolactone , Cellosolve acetate, ketone solvents, for example,
Cyclohexanone, methyl ethyl ketone, aromatic hydrocarbon solvents, for example, toluene, xylene and the like,
These can be used alone or in combination of two or more. 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 for the paste as it is. Γ-butyrolactone is most preferred for being highly volatile, capable of imparting low-temperature curability, and efficiently performing a homogeneous reaction.

The amount of the solvent used is preferably 0.8 to 5.0 times (by weight) the polyamideimide resin to be produced. If the ratio is less than 0.8, the viscosity at the time of synthesis tends to be too high and the synthesis tends to be difficult due to inability to stir. If the ratio exceeds 5.0, the reaction rate tends to decrease. The reaction temperature is preferably from 80 to 210 ° C, and from 100 to 1
The temperature is more preferably 90 ° C, particularly preferably 120 to 180 ° C. If the temperature is lower than 80 ° C., the reaction time becomes too long. If the temperature exceeds 210 ° C., a three-dimensional reaction occurs during the reaction and gelation is likely to occur. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed. If necessary, the reaction may be performed 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 polyamideimide resin thus obtained has a number average molecular weight of preferably 4,000 to 40,000, more preferably 5,000 to 38,000, and more preferably 6,000 to 38,000. Particularly preferred is 36,000. When the number average molecular weight is less than 4,000, film properties such as heat resistance tend to decrease,
If it exceeds 000, it is difficult to dissolve in a non-nitrogen-containing polar solvent, and it is easily insolubilized during synthesis. Also, the workability tends to be poor. Further, after the completion of the synthesis, the isocyanate group at the terminal of the resin can be blocked with a blocking agent such as alcohols, lactams, and oximes.

Examples of the epoxy resin (B) used in the present invention include bisphenol A type epoxy resins such as Epicoat 828 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.) and trade names (trade name, manufactured by Toto Kasei Co., Ltd.) Bisphenol F type epoxy resin such as YDF-170, Yuka Shell Epoxy Co., Ltd.
Phenol novolak type epoxy resin such as Epicoat 152, 154 (trade name), EPPN-201 (trade name, manufactured by Nippon Kayaku Co., Ltd.), DEN-438 (trade name, manufactured by Dow Chemical Co., Ltd.), products manufactured by Nippon Kayaku Co., Ltd. Name EOCN-125S, 10
O-cresol novolak type epoxy resin such as 3S, 104S, etc., trade name Epon1 manufactured by Yuka Shell Epoxy Co., Ltd.
031S, trade name Araldite 0163 manufactured by Ciba Specialty Chemicals Co., Ltd., trade name Denacol EX-611, EX-614, EX-61 manufactured by Nagase Kasei Co., Ltd.
4B, EX-622, EX-512, EX-521, E
Multifunctional epoxy resins such as X-421, EX-411, EX-321, etc., trade name Epicoat 604 manufactured by Yuka Shell Epoxy Co., Ltd., trade name YH-434 manufactured by Toto Kasei Co., Ltd., Mitsubishi Gas Chemical Co., Ltd. Brand names TETRAD-X, TETRA
DC, trade name GAN manufactured by Nippon Kayaku Co., Ltd., Sumitomo Chemical Co., Ltd.
Amine type epoxy resin such as ELM-120, trade name
Epoxy resin containing heterocycle such as Araldite PT810 (trade name, manufactured by Ciba Specialty Kelkars Co., Ltd.), UC
ERL4234, 4299, 4221, 420 manufactured by Company C
And alicyclic epoxy resins such as No. 6 and the like, and these can be used alone or in combination of two or more. Among these epoxy resins, an amine type epoxy resin having three or more epoxy groups in one molecule is particularly preferable in terms 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 used in an amount of 0 to 2 with respect to the total amount of the polyamideimide resin.
It is preferable to use it in the range of 0% by weight. Examples of such epoxy compounds include n-butyl glycidyl ether, phenyl glycidyl ether, dibromophenyl glycidyl ether, dibromocresyl glycidyl ether, and the like. 3,4-epoxycyclohexyl,
An alicyclic epoxy compound such as methyl (3,4-epoxycyclohexane) carboxylate can be used.

In the present invention, the amount of the epoxy resin used as the component (B) is 100
The amount is preferably 1 to 50 parts by weight, more preferably 2 to 45 parts by weight, and still more preferably 3 to 40 parts by weight with respect to parts by weight. If the amount of the epoxy resin is less than 1 part by weight,
Solvent resistance, chemical resistance, and moisture resistance tend to decrease.
If it exceeds 0 parts by weight, heat resistance and viscosity stability tend to decrease. 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 before addition, or may be directly added to the polyamideimide resin.

The polyamide-imide resin composition of the present invention may contain an organic or inorganic filler, if necessary, in order to improve the workability during coating and the film properties before and after the film is formed.
Surfactants such as antifoaming agents and leveling agents, coloring agents such as dyes or pigments, curing accelerators, heat stabilizers, antioxidants, flame retardants, lubricants and the like can be added.

The polyamide-imide resin composition of the present invention comprises:
As a film forming material, for example, an overcoating agent for a semiconductor element or various electronic components, an interlayer insulating film in a rigid or flexible substrate field, a surface protective film, a solder resist layer, an adhesive layer, etc., a liquid sealant, an enamel wire varnish,
It can also be used as a varnish for sheets, a varnish for MCL laminates, and a varnish for friction materials in combination with substrates such as impregnated varnishes for electrical insulation, cast varnishes, mica, and glass cloth. The film forming material in the present invention has a film formed using the composition, a semiconductor element, a flexible circuit board,
Refers to laminates, enameled wires and the like.

The polyamide-imide resin composition of the present invention can use a polyamide-imide resin obtained by using the above-mentioned component (b) diisocyanate or further obtain an intended effect by using an epoxy resin. it can.

[0033]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.

Example 1 PLACCEL CD-220 as a component (b) was placed in a 5-liter four-necked flask equipped with a stirrer, a condenser equipped with an oil-water separator, a nitrogen inlet tube and a thermometer.
1000.0 g (0.50 mol) of 1,6-hexanediol-based polycarbonate diol manufactured by
4'-diphenylmethane diisocyanate 250.27
g (1.00 mol) and γ-butyrolactone 833.5
1 g was charged and the temperature was raised to 140 ° C. The reaction was carried out at 140 ° C. for 5 hours to obtain a diisocyanate [in the general formula (I), R represents a hexamethylene group, X represents a diphenylmethane group, and m = 13 and n = 1].

Further, 288.20 g (1.50 mol) of trimellitic anhydride was added to the reaction solution as the component (a).
As the component (c), 125.14 g (0.50 mol) of 4,4'-diphenylmethane diisocyanate and 136.14 g of γ-butyrolactone were charged, the temperature was raised to 160 ° C., and the mixture was reacted for 6 hours to give a number average molecular weight of 18 , 0
00 resin was obtained. The obtained resin was diluted with γ-butyrolactone to obtain a polyamideimide resin solution having a viscosity of 160 Pa · s and a nonvolatile content of 52% by weight. The component (b)
The molar ratio of the component (c) is 0.5 / 0.5.

Example 2 YH-434 (trade name of an amine type epoxy resin manufactured by Toto Kasei Co., Ltd., epoxy equivalent of about 120, based on 100 parts by weight of the resin component of the polyamideimide resin solution obtained in Example 1)
10 parts by weight (4 epoxy groups / molecule) were added, and the mixture was diluted with γ-butyrolactone to obtain a polyamideimide resin composition having a viscosity of 100 Pa · s and a nonvolatile content of 52% by weight.

Example 3 In Example 2, 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 of about 189, epoxy group 2 Except for using 10 parts by weight of each (molecule / molecule), the same operation as in Example 1 was performed to obtain a viscosity of 95 Pa ·
s, a resin composition having a nonvolatile content of 52% by weight was obtained.

Comparative Example 1 288.2 g of trimellitic anhydride was used as the component (a) in the same flask as in Example 1 except that the flask was changed to 2 L.
(1.50 mol), 382.9 g (1.53 mol) of 4,4'-diphenylmethane diisocyanate and 1006.7 g of N-methyl-2-pyrrolidone were charged as components (c), and heated to 130 ° C., Let it react for 3 hours,
A resin having a number average molecular weight of 16,000 was obtained. The obtained resin was diluted with N, N'-dimethylformamide to obtain a polyamideimide resin solution having a viscosity of 17 Pa · s and a nonvolatile content of 38% by weight.

Comparative Example 2 10 parts by weight of YH-434 was added to 100 parts by weight of the resin component of the polyamideimide resin solution obtained in Comparative Example 1, and diluted with N-methyl-2-pyrrolidone.
A polyamide-imide resin composition having a Pa · s and a nonvolatile content of 38% by weight was obtained.

Comparative Example 3 In the same flask as in Comparative Example 1, 4,4 'was added as the component (c).
-Diphenylmethane diisocyanate 150.0 g
(0.60 mol), 69.1 g (0.36 mol) of trimellitic anhydride as component (a) and silicone dicarboxylic acid BY16-750 (a dimethylpolysiloxane dicarboxylic acid manufactured by Dow Corning Toray Silicone Co., Ltd.) (Trade name) 335.0 g (0.24 mol), γ-butyrolactone 277.1 g and N-methyl-2-pyrrolidone 27
After charging 7.1 g, the temperature was raised to 160 ° C., and the mixture was reacted for 2 hours to obtain a resin having a number average molecular weight of 12,600.
The resulting resin was diluted with γ-butyrolactone to give a viscosity of 8
A polyamide imide resin solution having a Pa · s and a nonvolatile content of 40% by weight was obtained.

Comparative Example 4 10 parts by weight of YH-434 was added to 100 parts by weight of the resin component of the polyamideimide resin solution obtained in Comparative Example 3, and diluted with γ-butyrolactone. 39% by weight of a polyamide-imide resin composition was obtained.

The physical properties of the polyamideimide resin solution and the polyamideimide resin composition obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1.

Warpability The obtained polyamide-imide resin composition was applied on a polyimide film having a thickness of 50 μm, a length of 35 mm and a width of 20 mm, dried at 90 ° C. for 15 minutes, and then dried under an air atmosphere.
The coating film (thickness: 20 μm) was heated at 120 ° C. for 120 minutes or at 160 ° C. for 60 minutes and placed on a surface plate with the coated surface facing down, and the warpage height was evaluated.

Solvent Resistance The obtained polyamideimide resin composition is applied on the rough surface of an electrolytic copper foil having a thickness of 35 μm, dried at 90 ° C. for 15 minutes, and then dried at 120 ° C. for 120 minutes in an air atmosphere. Heated at 160 ° C. for 60 minutes, and obtained coating film (thickness: 20 to 30 μm)
About, dipped the coating film in acetone at room temperature for 1 hour,
Changes in the appearance of the coating film were evaluated according to the following criteria. ○: no change in appearance △: some change in appearance ×: change in overall appearance

Adhesion to Sealing Material The obtained polyamide-imide resin composition was applied on a rough surface of an electrolytic copper foil having a thickness of 35 μm or on a polyimide film having a thickness of 50 μm, and dried at 90 ° C. for 15 minutes. Under air atmosphere, heat at 120 ° C for 120 minutes or 160 ° C for 60 minutes,
On the obtained coating film (thickness: 20 to 30 μm), an epoxy-based sealing material [CEL-C-50, trade name, manufactured by Hitachi Chemical Co., Ltd.]
20] and potted at 120 ° C. for 120
And further heated at 150 ° C. for 120 minutes. The obtained coating film was bent so that the sealing material side was on the outside, and the mode of peeling was evaluated according to the following criteria. ：: Interfacial peeling of substrate / coating film △: Interfacial peeling of coating film / sealing material ×: No adhesion

Moisture Resistance (Pressure Cooker Test) The obtained polyamideimide resin composition was applied on a rough surface of a 35 μm-thick electrolytic copper foil or on a 50 μm-thick polyimide film, and dried at 90 ° C. for 15 minutes. Heating in an air atmosphere at 120 ° C. for 120 minutes or 160 ° C. for 60 minutes,
About the obtained coating film (thickness: 20 to 30 μm), a pressure cooker test (abbreviated as PCT, conditions: 121 ° C.,
(2.0265 × 10 ⁵ Pa, 100 hours), the change in the appearance of the coating film was evaluated according to the following criteria. ○: no change in appearance △: some change in appearance ×: change in overall appearance

[0047]

[Table 1]

[0048]

Industrial Applicability The polyamideimide resin composition of the present invention has low warpage, flexibility, excellent adhesion to sealing materials, solvent resistance and chemical resistance, and is soluble in non-nitrogen-containing polar solvents. And has low-temperature curability, and is excellent in heat resistance, electrical properties, workability and economy.

The polyamide-imide resin composition of the present invention has the above-mentioned excellent properties as a film-forming material, and can be used as an interlayer insulating film in the field of overcoats for semiconductor devices and various electronic parts, rigid or flexible substrates, and the like. , Surface protective film, solder resist layer, adhesive layer, liquid sealing material, varnish for enameled wire, impregnated varnish for electrical insulation, casting varnish, mica, sheet varnish combined with glass cloth, etc., MCL It is suitably used for varnishes for laminated boards and varnishes for friction materials. Film forming materials such as various electric parts and electronic parts obtained by forming a film are excellent in reliability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // (C08L 79/08 (C08L 79/08 63:00) 63:00) AF term (Reference) 4J002 CD012 CD022 CD042 CD122 CM041 FD010 FD090 FD310 GH01 GH02 GJ01 GJ02 GQ05 4J038 DB062 DB072 DB152 DB262 DB282 DJ051 JA03 JA20 JA26 JA33 JA62 JA70 JC11 JC12 JC18 KA06 MA07 MA09 NA04 NA11 NA12 NA04 RA21 PA03 PA04 SA12 SA42 SA43 SA72 SB01 SB02 SB03 TA11 TA12 TA21 TA22 TB01 TB02 UA082 UA111 UA121 UA122 UA131 UA132 UA142 UA151 UA152 UA222 UA252 UA261 UA262 UA362 UA422 UA662 UA672 UB1 UB1 UB1 UB211 UB211 VA022 VA031 VA032 VA041 VA051 VA061 VA062 VA072 VA081 VA082 VA091 VA102 WA02 WA04 WA17 XA03 XA14 X A15 XA18 XA19 XB12 XB14 XB19 ZB01 ZB02 ZB03 ZB50

Claims (8)

[Claims] (A) General formula (I) (Wherein, a plurality of Rs each independently have 1 to 18 carbon atoms)
A plurality of Xs 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, and Y is a trivalent A polyamide-imide resin having a repeating unit represented by the following formula: 2. (A) (a) a tri- or higher valent polycarboxylic acid having an acid anhydride group or a derivative thereof, and (b) a general formula (II): (Wherein, a plurality of Rs each independently have 1 to 18 carbon atoms)
A plurality of Xs 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. 3. The polyamide-imide resin composition according to claim 2, wherein the component (A) is obtained by further using (c) a polyisocyanate compound as a reaction component. 4. The polyamide-imide resin composition according to claim 1, comprising a non-nitrogen-containing polar solvent as an organic solvent. 5. The compounding ratio of the component (b) and the component (c) in the production of the polyamide-imide resin of the component (A) is 0.1 / 0.0 in equivalent ratio of the component (b) and the component (c). 9 ~
0.9 / 0.1, and the ratio of the total number of carboxyl groups and acid anhydride groups of the component (a) to the total number of isocyanate groups in the components (b) and (c) is 0.6 to 1.4. The polyamide-imide resin composition according to claim 3, wherein 6. The polyamide-imide resin composition according to claim 1, comprising (A) 100 parts by weight of a polyamide-imide resin and (B) 1 to 50 parts by weight of an epoxy resin. 7. The epoxy resin (B) has three epoxy groups.
The polyamide-imide resin composition according to claim 6, which is an amine-type epoxy resin having at least one epoxy resin. 8. A film forming material having a film formed by using the polyamide-imide resin composition according to claim 1.