JP2000095997A - Polyamideimide resin paste and film-forming material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamideimide resin paste excellent in softness, adhesion to sealants, solvent resistance and chemical resistance while retaining low warpage and, in addition, soluble in non-nitrogen-containing polar solvents, having low temperature curability and excellent in heat resistance, electrical characteristics, resistance to moisture, workability, shape retention and economy, and a film-forming material containing the same. SOLUTION: A polyamideimide resin paste comprises (A) 100 pts.wt. polyamideimide resin obtained by reacting (a) a tri- or higher-valent polycarboxylic acid having an acid anhydride group or a derivative thereof, (b) a dicarboxylic acid having a number average molecular weight of 1,000-10,000 represented by the formula (a plurality of R are each independently a 1-12C alkylene group; a plurality of X are each independently a 1-12C alkylene group or an arylene group; and n and m are each independently an integer of 1-20) and (c) a polyisocyanate compound, (B) 1-50 pts.wt. epoxy resin, and (C) inorganic fine particles and/or organic fine particles, and a film-forming material comprises this polyamideimide resin paste.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyamide-imide resin paste and a film-forming material containing the same.

[0002]

2. Description of the Related Art In recent years, in the field of electronic components, in order to respond to miniaturization, thinning, and high speed, polyimide resins and polyamide imides have been used instead of epoxy resins as resins having excellent heat resistance, electrical characteristics and moisture resistance. Resin and polyamide resin are used. These resins have a rigid resin structure and, when used as a thin film substrate, have a problem that the substrate after curing is greatly warped, 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, a high-boiling nitrogen-containing polar solvent such as N-methyl-2-pyrrolidone has been used as a solvent for varnishing.
There is a problem that thermal degradation of the electronic member occurs. In addition, when the varnish is applied to the base material and then left for a long time, there is a problem in that whitening and voids occur in the coating film due to moisture absorption, which complicates working conditions.

On the other hand, it is soluble in non-nitrogen-containing polar solvents,
As a resin having low warpage and flexibility, for example, polyimide siloxane is disclosed in JP-A-7-304950 and JP-A-8-333455. These polyimide siloxanes use an expensive diamine having a dimethyl siloxane bond as a starting material in order to reduce the modulus of elasticity, and are inferior in economic efficiency. In addition, there is a problem that the adhesion to the sealant, the solvent resistance, and the chemical resistance (tin plating liquid resistance, solder flux resistance) decrease as the amount of modification of the siloxane increases.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and retains low warpage while maintaining flexibility, adhesion to a sealant, solvent resistance and chemical resistance. Excellent,
Moreover, it is soluble in non-nitrogen-containing polar solvents, has low-temperature curability, and is excellent in heat resistance, electrical properties, moisture resistance, workability, shape retention and economy, and a film-forming material containing the same. Is provided.

[0005]

The present invention provides (A) and (a)
A trivalent or higher polycarboxylic acid having an acid anhydride group or a derivative thereof, (b) a compound represented by the general formula (I):

Embedded image [Wherein, a plurality of Rs each independently have 1 to 12 carbon atoms.
A plurality of X each independently represents an alkylene group having 1 to 12 carbon atoms or an arylene group,
m and n each independently represent an integer of 1 to 20], and 100 parts by weight of a polyamideimide resin obtained by reacting a dicarboxylic acid having a number average molecular weight of 1,000 to 10,000 and (c) a polyisocyanate compound. ,
The present invention relates to a polyamideimide resin paste containing (B) 1 to 50 parts by weight of an epoxy resin and (C) 1 to 90 parts by weight of inorganic fine particles and / or organic fine particles.

[0006] The present invention also relates to the polyamideimide resin paste containing a non-nitrogen-containing polar solvent as an organic solvent. Further, in the present invention, the mixing ratio of the component (a) and the component (b) constituting the polyamide imide resin of the component (A) is 0.1 / 0.9 in an equivalent ratio of the component (a) / the component (b). ~
0.9 / 0.1, and the ratio of the total number of isocyanate groups of the component (c) to the total number of carboxyl groups and acid anhydride groups in the components (a) and (b) is 0.6 to 1.4. The present invention relates to the above-mentioned polyamideimide resin paste. The present invention also relates to the polyamide-imide resin paste, wherein the epoxy resin is an amine-type epoxy resin having three or more epoxy groups. Further, the present invention has a viscosity at 25 ° C. of 1 to 1000 Pa · s and a thixotropic coefficient of 1.3 to 1
The present invention relates to any of the above-mentioned polyamideimide resin pastes in the range of 0. The present invention also relates to a film forming material containing any of the above-mentioned polyamideimide resin pastes.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamide-imide resin paste of the present invention comprises the above-mentioned (A) polyamide-imide resin 1
00 parts by weight, (B) 1 to 50 parts by weight of an epoxy resin, and 1 to 90 parts by weight of inorganic fine particles and / or organic fine particles as essential components.

In the present invention, the trivalent or higher polycarboxylic acid having an acid anhydride group or a derivative thereof used as the component (a) in the production of the polyamideimide resin of the component (A) is not particularly limited. , General formulas (II) and (III)

Embedded image [Wherein, R represents hydrogen, an alkyl group or phenyl group having 1 to 10 carbon atoms, Y is _{-CH 2 -, - CO -,} - SO 2 -
Or -O-]] as long as it has an acid anhydride group capable of reacting with an isocyanate group. Considering heat resistance, cost, and the like, trimellitic anhydride is particularly preferred.

In addition to the above-mentioned polycarboxylic acids and 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-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 1,1,1
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 dicarboxylic acid represented by the general formula (I) used as the component (b) in the present invention is represented by the general formula (IV)

Embedded image [Wherein, a plurality of Rs each independently have 1 to 12 carbon atoms.
Wherein m is an integer of 1 to 20], and a carbonate diol represented by the general formula (V):

Embedded image [Wherein, X represents an alkylene group having 1 to 12 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 is obtained by reacting a dicarboxylic acid with no solvent or in an organic solvent.

Examples of the carbonate diols represented by the above general formula (IV) include, for example, PLACCEL, CD-205, 210, 220 (trade name) manufactured by Daicel Chemical Industries, Ltd.
And these are used alone or in combination of two or more. The dicarboxylic acids represented by the general formula (V) include, for example, aliphatic dicarboxylic acids (succinic acid, glutaric acid, adipic acid, azelaic acid, suberic acid, sebacic acid, decandioic acid, dodecandioic acid, Dimer acid), aromatic dicarboxylic acids (isophthalic acid, terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid, etc.), and the like, and these are used alone or in combination of two or more. The amounts of the carbonate diols represented by the general formula (IV) and the dicarboxylic acids represented by the general formula (V) are such that the ratio of the number of hydroxyl groups to the number of carboxyl groups is such that the ratio of carboxyl groups / hydroxyl groups is 1.01 or more. Preferably.

The reaction can be carried out without a solvent or in the presence of an organic solvent. From the viewpoint of cost and the like, it is preferable to use no solvent. The reaction temperature is preferably from 80 to 250 ° C., and the reaction time can be appropriately selected according to the scale of the batch, the reaction conditions employed, and the like. Examples of usable organic solvents include ketone solvents (eg, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester solvents (eg, ethyl acetate, butyl acetate, γ-butyrolactone), and ether solvents (eg, diethylene glycol dimethyl ether, triethylene glycol). Dimethyl ether, etc.), cellosolve solvents (butyl cellosolve acetate, ethyl cellosolve acetate,
Methylcellosolve acetate, etc.), aromatic hydrocarbon solvents (toluene, xylene, p-cymene, etc.), tetrahydrofuran, dioxane, N-methyl-2-pyrrolidone,
N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and the like can be mentioned.

The number average molecular weight of the dicarboxylic acid (b) thus obtained is preferably from 1,000 to 10,000, more preferably from 1500 to 9,500, and particularly preferably from 2,000 to 8,000. . When the number average molecular weight is less than 1,000, the low warpage tends to deteriorate, and when it exceeds 10,000, the reactivity of the dicarboxylic acid decreases, and it tends to be difficult to form a polyamideimide resin. In the present specification, the number average molecular weight is a value measured by gel permeation chromatography and converted using a calibration curve of standard polystyrene.

The polyisocyanate compound of the component (c) in the present invention is not particularly limited.
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'-dimethylbiphenyl-4,4'-diisocyanate, 2,2'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'-diethylbiphenyl-4,4 '
-Diisocyanate, 2,2'-diethylbiphenyl-
4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2'-dimethoxybiphenyl-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, naphthalene-
It is preferred to use aromatic polyisocyanates such as 2,6-diisocyanate. These can be used alone or in combination of two or more. Also, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, transcyclohexane-1,4-
Aliphatic or alicyclic isocyanates such as diisocyanate, hydrogenated m-xylylene diisocyanate, lysine diisocyanate, etc. and tri- or higher functional polyisocyanates may be used, and those stabilized with a blocking agent necessary to avoid aging are used. May be used. Examples of the blocking agent include alcohol, phenol and oxime, but there is no particular limitation.

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

In the present invention, the blending ratio of the tricarboxylic acid or higher polycarboxylic acid having an acid anhydride group of the component (a) and the dicarboxylic acid represented by the general formula (I) of the component (b) is as follows: / (B) 0.1 / 0.9-0.9 /
0.1, preferably 0.2 / 0.8 to 0.8
/0.2, more preferably from 0.3 / 0.7 to
It is particularly preferred to be 0.7 / 0.3. If the equivalent ratio is less than 0.1 / 0.9, the film properties such as heat resistance tend to decrease, and if it exceeds 0.9 / 0.1, the elastic modulus cannot be reduced, and the warpage and the adhesion are not achieved. Tends to decrease.

The mixing ratio of the polyisocyanate compound of component (c) is determined by the ratio of the total number of isocyanate groups of component (c) to the total number of carboxyl groups and acid anhydride groups in components (a) and (b). Is preferably from 0.6 to 1.4, more preferably from 0.7 to 1.3, and particularly preferably from 0.8 to 1.2. . If this ratio is less than 0.6 or 1.4
When it exceeds, it tends to be difficult to increase the molecular weight of the polyamideimide resin.

The polyamideimide resin used in the present invention can be produced, for example, by the following method. A method in which the components (a) and (b), which are acid components, and the component (c), which is an isocyanate component, are used at once and reacted. After reacting the component (b) of the acid component with an excess amount of the component (c), which is an isocyanate component, to synthesize an amide imide oligomer having an isocyanate group at a terminal,
A method in which the component (a) of the acid component is added and reacted. After reacting an excess amount of the component (a) as an acid component with the component (c) as an isocyanate component to synthesize an amide imide oligomer having an acid or anhydride group at a terminal, the component (b) as an acid component And adding the remaining isocyanate component (c) to react.

The above reaction can be carried out by heating and condensing in the presence of an organic solvent, preferably a non-nitrogen-containing polar solvent, while removing the liberated carbon dioxide from the reaction system. As the non-nitrogen-containing polar solvent, ether solvents, for example, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, sulfur-containing solvents, for example,
Dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane, ester solvents such as γ
-Butyrolactone, cellosolve acetate, ketone solvents, for example, cyclohexanone, methyl ethyl ketone, aromatic hydrocarbon solvents, for example, toluene, xylene and the like, which 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 (weight ratio) 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., more preferably from 100 to 190 ° C., and particularly preferably from 120 to 180 ° C. 80
If the temperature is lower than ℃, the reaction time becomes too long. If the temperature is higher than 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 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 polyamideimide resin thus obtained preferably has a number average molecular weight of 4,000 to 30,000, more preferably 5,000 to 28,000, particularly preferably 6,000 to 26,000. If the number average molecular weight is less than 4,000, the film properties such as heat resistance tend to decrease, and if it exceeds 30,000, it becomes difficult to dissolve in a non-nitrogen-containing polar solvent and easily insoluble 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.

As the epoxy resin (B) used in the present invention, a compound having two or more epoxy groups in one molecule is used. For example, Epicoat 828 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd. Bisphenol A type epoxy resin, bisphenol F type epoxy resin such as YDF-170 manufactured by Toto Kasei Co., Ltd.
Epikote 152, 154 manufactured by Nippon Kayaku
Phenol novolak-type epoxy resins such as EPPN-201 (trade name, manufactured by Dow Chemical Company) and DEN-438 (trade name, manufactured by Dow Chemical Company); EOCN-125 (trade name, manufactured by Nippon Kayaku Co., Ltd.)
O-cresol novolak type epoxy resin such as S, 103S, 104S, etc., trade name E manufactured by Yuka Shell Epoxy Co., Ltd.
pon1031S, trade name Araldite 0163 manufactured by Ciba-Geigy Co., Ltd., trade name Denacol E manufactured by Nagase Kasei Co., Ltd.
X-611, EX-614, EX-614B, EX-6
22, EX-512, EX-521, EX-421, E
Polyfunctional epoxy resins such as X-411 and EX-321, trade name Epicoat 604 manufactured by Yuka Shell Epoxy Co., Ltd., trade name YH-434 manufactured by Toto Kasei Co., Ltd., trade name manufactured by Mitsubishi Gas Chemical Co., Ltd. TETRAD-X, TETRAD-C, trade name GAN manufactured by Nippon Kayaku Co., Ltd., trade name EL manufactured by Sumitomo Chemical Co., Ltd.
Amine-type epoxy resins such as M-120, heterocyclic-containing epoxy resins such as Araldite PT810 (trade name, manufactured by Ciba-Geigy), ERL4234, 4299, 4 manufactured by UCC
And alicyclic epoxy resins such as 221 and 4206. 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 paste 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 polyamideimide resin. Examples of such epoxy compounds include n-butyl glycidyl ether, phenyl glycidyl ether, dibromophenyl glycidyl ether, dibromocresyl glycidyl ether, and the like. 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 epoxy resin used as the component (B) is determined based on the amount of the polyamideimide resin 100 as the component (A).
The amount is 1 to 50 parts by weight, preferably 2 to 45 parts by weight, more preferably 3 to 40 parts by weight based on parts by weight. If the amount of the epoxy resin is less than 1 part by weight, the solvent resistance, chemical resistance and moisture resistance will be reduced, and if it exceeds 50 parts by weight, the heat resistance and the viscosity stability will be reduced. 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 inorganic fine particles or organic fine particles of the component (C) used in the present invention may be any as long as they can be dispersed in the above-mentioned polyamideimide resin solution to form a paste and give the paste a thixotropic property. There is no particular limitation. Examples of such inorganic fine particles include silica (SiO ₂ ), alumina (Al ₂ O ₃ ), titania (TiO ₂ ), tantalum oxide (Ta ₂ O ₅ ), zirconia (ZrO ₂ ), and silicon nitride (Si ₃ N ₄ ), barium titanate (BaO.TiO ₂ ), barium carbonate (BaC)
O _3), lead titanate (PbO · TiO _2), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga ₂ O _3), spinel (MgO · Al ₂ O ₃ ), mullite (3Al ₂ O ₃ · 2Si
O ₂ ), cordierite (2MgO.2Al ₂ O ₃ .5)
SiO ₂ ), talc (3MgO.4SiO ₂ .H ₂ O),
Aluminum titanate _{(TiO 2 -Al 2 O 3)} , yttria-containing zirconia _{(Y 2 O 3 -ZrO 2)} , barium silicate (BaO · 8SiO _2), boron nitride (BN), calcium carbonate (CaCO _3), calcium sulfate (CaS
O ₄ ), zinc oxide (ZnO), magnesium titanate (MgO.TiO ₂ ), barium sulfate (BaSO ₄ ), organic bentonite, carbon (C), and the like. These may be used alone or in combination of two or more. can do.

The organic fine particles are not particularly limited as long as they can be dispersed in the above-mentioned polyamideimide resin solution to form a paste and give the paste a thixotropic property. 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 preferred. As such a heat-resistant resin, from the viewpoint of heat resistance and mechanical properties, preferably, a polyimide resin or a precursor thereof, a polyamideimide resin or a precursor thereof, or a polyamide resin is used.

The polyimide resin can be obtained by reacting an aromatic tetracarboxylic dianhydride with an aromatic diamine compound. As the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, 3,3 ′, 4,
4'-biphenyltetracarboxylic dianhydride, 2,
2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,2-bis (2,3- or 3,4-di (Carboxyphenyl) propane dianhydride, 1,1-bis (2,3- or 3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3- or 3,4-dicarboxyphenyl) methane dianhydride Product, 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'-benzophenonetetracarboxylic dianhydride, 2,3,2', 3'-benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic dianhydride, 1, 4,5,8-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5 , 8-Tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic 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 anhydride, 1,4- Bis (3,4-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3
4-dicarboxyphenyl) -1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic acid monoester anhydride), 2,2-bis (3,4-dicarboxy) Phenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxy) Phenoxy) phenyl] propane dianhydride, 4,4-bis [4- (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitate anhydrous) Product), 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 (trimellitate) Anhydride), 1,6- (hexamethylene) bis (trimellitate anhydride), 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- (hexadeca Methylene) bis (trimellitate anhydride), 1,18- (octadecamethylene) bis (trimellitate anhydride) and the like can be used alone or in combination of two or more.

The aromatic tetracarboxylic dianhydride may contain a tetracarboxylic dianhydride other than the aromatic tetracarboxylic dianhydride in an amount exceeding 50 mol% of the aromatic tetracarboxylic dianhydride depending on the purpose. It can be used in a range that does not exist. As such a tetracarboxylic dianhydride,
For example, ethylene tetracarboxylic dianhydride, 1,2,2
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 dianhydride, pyrrolidine-2,3,4
5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [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)
-3-Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride and the like.

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'-diaminodiphenylsulfide, 3,
4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone, 3,4'-diaminodiphenyl ketone,
4,4'-diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2- (3,4 '
-Diaminodiphenyl) propane, 2,2-bis (4-
Aminophenyl) propane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3
4'-diaminodiphenyl) hexafluoropropane,
2,2-bis (4-aminophenyl) hexafluoropropane, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene,
3,3 '-[1,4-phenylenebis (1-methylethylidene)] bisalinine, 3,4'-[1,4-phenylenebis (1-methylethylidene)] bisalinine,
4,4 '-[1,4-phenylenebis (1-methylethylidene)] bisalinine, 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) phenyl] sulfide, bis [4- (3-aminophenoxy)
Phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, and the like, and these can be used alone or in combination of two or more.

As the aromatic diamine compound, a diamine compound other than the aromatic diamine compound may be used in an amount 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, and 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) tetramethylpolysiloxane and the like.

The aromatic tetracarboxylic dianhydride and the aromatic diamine compound are preferably reacted with each other in an organic solvent at almost equimolar from the viewpoint of film properties.

Examples of the organic solvent include N-methylpyrrolidone, dimethylacetamide, dimethylformamide, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1,3-dimethyl- 2-
Nitrogen-containing compounds such as imidazolidinone, sulfolane, sulfur compounds such as 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 dimethyl (or diethyl, dipropyl, dibutyl) ether, tetraethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, methyl ethyl ketone, Ketones such as methyl isobutyl ketone, cyclohexanone, acetophenone, butanol, octyl alcohol, ethylene glycol, glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene glycol monomethyl (or monoethyl) ether, tetraethylene glycol monomethyl (or monoethyl) ether, etc. Phenols such as alcohols, phenol, cresol, xylenol Esters, esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, and butyl cellosolve acetate; hydrocarbons such as toluene, xylene, diethylbenzene, and cyclohexane; and halogenated hydrocarbons such as trichloroethane, tetrachloroethane, and monochlorobenzene. These can be used alone or in combination of two or more. Solubility,
Considering low moisture absorption, low temperature curing, environmental safety, etc.,
It is preferable to use lactones, ethers, ketones and the like.

The reaction temperature is 80 ° C. or less, preferably 0 to
50 ° C. As the reaction proceeds, the reaction liquid gradually increases in viscosity. In this case, a polyamic acid which is a precursor of the polyimide resin is generated. This polyamic acid may be partially imidized, which is also included in the precursor of the polyimide resin.

The polyimide resin is obtained by dehydrating and ring-closing the above reaction product (polyamic acid). Dehydration ring closure is 120 ~
It can be performed by a method of performing 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 performing heat treatment at 20 to 250 ° C., it is preferable to perform the method while removing water generated by the dehydration reaction outside the system. At this time, water may be azeotropically removed using benzene, toluene, xylene, or the like.

In the case of performing ring closure by dehydration using a dehydrating agent, it is preferable to use acid anhydrides such as acetic anhydride, propionic anhydride and benzoic anhydride, and carbodiimide compounds such as dicyclohexylcarbodiimide as the dehydrating agent. At this time, if necessary, a dehydration catalyst such as pyridine, isoquinoline, trimethylamine, aminopyridine, imidazole and the like may be used. The dehydrating agent or the dehydrating catalyst is preferably used in an amount of 1 to 8 mol per 1 mol of the aromatic tetracarboxylic dianhydride.

The polyamideimide resin or its precursor used as the organic fine particles may be a trimellitic anhydride or trimellitic anhydride in place of the aromatic tetracarboxylic dianhydride in the production of the polyimide or the precursor thereof. It can be produced by using a trivalent tricarboxylic anhydride such as a trimellitic anhydride derivative such as chloride of the product or a derivative thereof. Also, instead of the aromatic diamine compound or other diamine compound,
It can be produced using a diisocyanate compound in which a residue other than an amino group corresponds to the diamine compound. The diisocyanate compound that can be used is one obtained by reacting the aromatic diamine compound or another diamine compound with phosgene or thionyl chloride.

The polyamide resin is obtained by reacting an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid or phthalic acid, or a derivative thereof such as dichloride or acid anhydride with the above aromatic diamine compound or another diamine compound. Can be manufactured.

Examples of the heat-resistant resin having an ester bond include a polyester resin. Examples of the polyester resin include the above-mentioned terephthalic acid, isophthalic acid,
Aromatic dicarboxylic acids such as phthalic acid, derivatives thereof such as dichlorides and acid anhydrides, and 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 with an aromatic diamine compound containing isophthalic dihydrazide as an essential component is preferably used. As the aromatic tetracarboxylic dianhydride and the aromatic diamine compound, those described above are used.
The molar ratio of isophthalic dihydrazide in the aromatic diamine compound is preferably from 1 to 100 mol%, and preferably 1 to 100 mol%.
It is more preferably 0 to 80 mol%, and 20 to 70 mol%
It is particularly preferable to set it as mol%. When the amount is less than 1 mol%, the solubility resistance to the modified polyamideimide resin tends to decrease, and when the content of isophthalic acid dihydrazide is large, the moisture resistance of the layer formed by the paste of the present invention tends to decrease. is there. This polyamide-imide resin can be obtained in the same manner as in the synthesis of the polyimide resin, such as the mixing ratio of the aromatic tetracarboxylic dianhydride and the aromatic diamine compound, the organic solvent used, and the synthesis method.

A polyamideimide resin obtained by reacting trimellitic anhydride and, if necessary, a dicarboxylic acid with a polyisocyanate is likely to become insoluble in an organic solvent by heating. Can also be used. This polyamide-imide resin can also be manufactured in the same manner as the above-described method for manufacturing a polyamide-imide resin.

Examples of a method for forming fine particles include a non-aqueous dispersion polymerization method (Japanese Patent Publication No. 60-48531, Japanese Patent Application Laid-Open No. 59-1984).
-230018), a precipitation polymerization method (Japanese Patent Laid-Open No.
No. 08030 and No. 60-221425), a method of mechanically pulverizing a powder recovered from a resin solution, a method of pulverization under high shear while adding a resin solution to a poor catalyst, and a method of drying a spray solution of a resin solution to obtain fine particles. And a method in which a resin having a temperature dependency of solubility in a solvent in a detergent or a resin solution is formed into fine particles by precipitation.

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

As the organic solvent, one that dissolves the above-mentioned polyamideimide resin is used. In the case of using organic fine particles, it is preferable to use one in which both the polyamideimide resin and the organic fine particles dissolve in the organic solvent at the temperature at which the resin paste is heated and dried.

As the inorganic fine particles and / or organic fine particles used in the present invention, those having an average particle diameter of 50 μm or less and a maximum particle diameter of 100 μm or less are preferable. When the average particle size exceeds 50 μm, it is difficult to obtain a paste having a thixotropy coefficient of 1.3 or more as described later, and when 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 fine particles and / or the organic fine particles is preferably in the range of 1 to 90 parts by weight based on 100 parts by weight of the polyamide-imide resin (A).
Particularly preferred is 50 parts by weight. This usage is 1
If the amount is less than part by weight, it is difficult to obtain a paste having a thixotropy coefficient of 1.3 or more, and if it exceeds 90 parts by weight, the fluidity of the paste tends to be impaired. As a method of dispersing the inorganic fine particles and / or organic fine particles in the solution of the polyamideimide resin, roll kneading usually performed in the field of coating, mixing with a mixer, or the like is applied, provided that sufficient dispersion is performed. There is no particular limitation. Multiple kneading with three rolls is most preferred.

The polyamide-imide resin paste of the present invention preferably has a thixotropic coefficient of 1.3 or more. For example, when a printing machine forms a pattern by a coating method using a dispenser, if the thixotropy coefficient is less than 1.3, the shape retention after coating is insufficient, so that dripping and run-off occur, which is practically necessary. There is a tendency that the pattern accuracy cannot be satisfied. In this specification,
The thixotropy coefficient (TI value) of the paste was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE80U type) at a rotational speed of 1 rpm and 1 rpm at a sample volume of 0.5 ml and a measurement temperature of 25 ° C.
When the apparent viscosity of the paste at 0 rpm is η ₁ and η ₁₀ , respectively, the ratio is expressed as η ₁ / η ₁₀ .

The polyamide-imide resin paste of the present invention has a viscosity of 1 to 1000 Pa · s and a thixotropy coefficient (T
(I value) in the range of 1.3 to 10 is preferred, and those having a viscosity of 2 to 700 Pa · s and a TI value of 1.5 to 8.0 are particularly preferred. As the organic solvent contained in the polyamideimide resin paste of the present invention, it is preferable to use the above-mentioned non-nitrogen-containing polar solvent. The amount used is determined in consideration of the thixotropy coefficient and viscosity described above.

The polyamideimide resin paste of the present invention is optionally provided with a curing accelerator, an adhesion promoter, an antifoaming agent, a leveling agent, in order to improve the workability during coating and the film properties before and after film formation. And the like, a colorant such as a dye or a pigment, a heat stabilizer, an antioxidant, a flame retardant, a lubricant, and the like.

The polyamide-imide resin paste of the present invention can be used, for example, with a base material such as an overcoat agent for electronic parts, a liquid sealant, a varnish for enameled wire, an impregnated varnish for electrical insulation, a cast varnish, mica, and glass cloth. Combined sheet varnish, MCL laminate 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 suitably used as a film forming material. The intended effect of the polyamide-imide resin paste of the present invention can be obtained by using the polyamide-imide resin obtained by using the dicarboxylic acid as the component (b) and further by using an epoxy resin.

[0051]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 PLACCE was placed in a three-liter four-necked flask equipped with a stirrer, a condenser with an oil-water separator, a nitrogen inlet, and a thermometer.
L CD-220 (trade name of 1,6-hexanediol-based polycarbonate diol manufactured by Daicel Chemical Industries, Ltd.) 20
00.0 g (1.00 mol), adipic acid 292.0 g
(2.00 mol) and 114.6 g of xylene,
On the way, the temperature was raised to 200 ° C. while distilling off by-product condensed water. The reaction was carried out at 200 ° C. for 2 hours, and the acid value was 49.7.
A dicarboxylic acid of KOH mg / g [a dicarboxylic acid of the general formula (I) in which R represents all hexamethylene groups, Z represents a butylene group, and m = 13 and n = 1] was obtained.

Example 1 In a 2 liter four-necked flask equipped with a stirrer, a cooling tube, a nitrogen inlet tube and a thermometer, 4,4'-component (c) was added.
150.00 g of diphenylmethane diisocyanate
(0.60 mol), 69.12 g (0.36 mol) of trimellitic anhydride as the component (a), and 541.44 g (0.26 g) of the dicarboxylic acid obtained in Synthesis Example 1 as the component (b).
4 mol) and 760.56 g of γ-butyrolactone, heated to 160 ° C., and reacted for 3 hours to obtain a resin having a number average molecular weight of 12,000. The obtained resin is γ
-Diluted with butyrolactone to obtain a polyamideimide resin solution having a nonvolatile content of 40% by weight. The component (a) /
The molar ratio of the component (b) is 0.6 / 0.4.

YH-434 (trade name of an amine type epoxy resin manufactured by Toto Kasei Co., Ltd., epoxy equivalent: about 12 parts by weight) relative to 100 parts by weight of the resin component of the obtained polyamideimide resin solution.
(0, 4 epoxy groups / molecule) 10 parts by weight, and diluted with triethylene glycol dimethyl ether to obtain a polyamideimide resin composition having a nonvolatile content of 40% by weight. 1200 g of this composition is mixed with Aerosil 380 (Nippon Aerosil)
34.0 g of silica fine particles (trade name, manufactured by Co., Ltd., average particle size: 0.2 μm or less) was added, coarse kneading was performed first, and kneading was repeated three times using a high-speed three-roll mill to perform main kneading. A polyamide-imide resin paste in which silica fine particles were dispersed was obtained. After allowing the paste to stand for 12 hours, the viscosity at 25 ° C. was measured with an E-type viscometer (RE80U type, manufactured by Toki Sangyo Co., Ltd.). At this time, the viscosity was 90 Pa · s, and the TI value was 2.1.

Example 2 In Example 1, instead of YH434 and 10 parts by weight, Epicoat 828 (trade name of bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: about 189, 2 epoxy groups / (Molecule) Except for using 10 parts by weight, the same operation as in Example 1 was performed, and the viscosity was 89 Pa ·
A paste having a s and a TI value of 2.1 was obtained.

Comparative Example 1 Example 1 was repeated except that Aerosil 380 was not used.
The same operation as above was carried out to obtain 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 performed except that YH434 was not used, to obtain a paste having a viscosity of 98 Pa · s and a TI value of 2.0.

Comparative Example 3 In the same flask as in Example 1, 4 was added as the component (c).
4'-diphenylmethane diisocyanate 150.00
g (0.60 mol), 69.12 g (0.36 mol) of trimellitic anhydride as the component (a), and silicon dicarboxylic acid BY16-750 [a dimethylpolysiloxane-based dicarboxylic acid manufactured by Dow Corning Toray Silicone Co., Ltd.] 335.04 g (0.24 mol), 277.08 g of γ-butyrolactone and 277.08 g of N-methyl-2-pyrrolidone were added, and the temperature was raised to 160 ° C.
The reaction was carried out for a time to obtain a resin having a number average molecular weight of 12,600. The obtained resin was diluted with γ-butyrolactone to obtain a polyamideimide resin solution having a nonvolatile content of 40% by weight.

1200 g of the obtained polyamide-imide resin
34.0 g of Aerosil 380 (trade name of silica fine particles manufactured by Nippon Aerosil Co., Ltd., average particle diameter 0.2 μm or less) was added to the mixture, and the mixture was first roughly kneaded, and then mixed with a high-speed three-roll mill.
The main kneading was performed by repeating the kneading twice to obtain a polyamide-imide 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.)
, RE80U type) at 25 ° C. At this time, the viscosity was 30 Pa · s, and the TI value was 2.9.

The 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. Shape-holding property The obtained polyamide-imide resin paste was applied on a polyimide film, dried at 90 ° C for 15 minutes, and then heated at 160 ° C for 60 minutes in an air atmosphere to obtain an obtained coating film (thickness: 20 to 20). With respect to 30 μm, 5 mm square, the shape change rate of the coating film before and after curing was evaluated using a universal projector (manufactured by Nikon Corporation, magnification: 50 ×) according to the following criteria. ：: Change in coating film shape 0 to less than 5% △: Change in coating film shape 5 to less than 10% ×: Change in coating film shape 10% or more

The obtained polyamide-imide resin paste is applied on a polyimide film having a thickness of 50 μm, a length of 35 mm and a width of 20 mm, and dried at 90 ° C. for 15 minutes.
After heating at 60 ° C. for 60 minutes, the obtained coating film (thickness: 20 μm) was placed on a platen with the coating surface facing down, and the warpage height was evaluated.

Solvent Resistance The obtained polyamideimide resin paste is applied on a rough surface of an electrolytic copper foil having a thickness of 35 μm, dried at 90 ° C. for 15 minutes, and then heated at 160 ° C. for 60 minutes in an air atmosphere. The obtained coating film (thickness: 20 to 30 μm) was immersed in acetone at room temperature for 1 hour, and 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

Chemical resistance (tin plating liquid resistance) The obtained polyamideimide resin paste 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 under air atmosphere. The coating film (thickness: 20 to 30 μm) was heated at 60 ° C. for 60 minutes, and the coating film was immersed in a tin plating solution (Tyneposit LT34, manufactured by Shipley First Co., Ltd.) heated to 70 ° C. for 4 minutes. The film was taken out, washed with warm water of 60 ° C. for 5 minutes, heated at 100 ° C. for 10 minutes and dried, and the change of the coating film appearance was evaluated according to the following criteria. ○: no change in appearance △: some change in appearance ×: change in overall appearance

Adhesion to Sealant The obtained polyamide-imide resin paste is 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. It was heated at 160 ° C. for 60 minutes in an atmosphere to obtain a coating film (thickness 2).
0-30 μm), an epoxy-based sealant (Hitachi Chemical Industries, Ltd.)
Potting 0.06 g of CEL-C-5020 (trade name, manufactured by Co., Ltd.), 120 minutes at 120 ° C., and 1 minute at 150 ° C.
Heat for 20 minutes. The obtained coating film was bent so that the sealant side was on the outside, and the peeling mode was evaluated according to the following criteria. ：: Interfacial peeling of substrate / coating film △: Interfacial peeling of coating film / sealant ×: No adhesion

Moisture Resistance (Pressure Cooker Test) The obtained polyamideimide resin paste 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. It was heated at 160 ° C. for 60 minutes in an air atmosphere to obtain a coating film (thickness 2).
Pressure cooker test (abbreviated as PCT, condition: 121 ° C., 2.0265 × 10 ⁵ P)
a, 100 hours) was evaluated according to the following criteria. ○: no change in appearance △: some change in appearance ×: change in overall appearance

[0066]

[Table 1]

[0067]

The polyamide-imide resin paste of the present invention is excellent in low warpage, flexibility, adhesion to a sealing agent, solvent resistance and chemical resistance, and is soluble in a non-nitrogen-containing polar solvent. It has low-temperature curability, and is excellent in heat resistance, electrical properties, workability, shape retention, and economy. In addition, the film-forming material of the present invention can form a film having the above-described excellent properties, and can be used as an overcoat agent for electronic parts, a liquid sealant, a varnish for enameled wire, an impregnated varnish for electrical insulation, and casting. Varnishes, varnishes for sheets combined with substrates such as mica, glass cloth, varnishes for MCL laminates, varnishes for friction materials, interlayer insulating films in the field of printed circuit boards, surface protective films, solder resist layers, adhesive layers, etc. It is suitably used for electronic components such as semiconductor elements.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court II (Reference) (C08L 79/08 63:00) (72) Inventor Katsuhiro Onose 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Plant F-term (reference) 4J002 CD023 CD053 CD063 CD073 CD133 CL002 CM041 CM042 DA016 DE096 DE136 DE146 DE186 DE236 DG056 DJ006 DJ016 DJ046 DK006 FD012 GQ00 4J036 AD08 AF06 AJ09 FA03 FA05 FA11 FB38 DB02 DJ051 HA026 HA216 HA246 HA376 HA446 HA456 HA536 HA556 KA20 MA07 MA14 MA15 NA04 NA14 NA21 NA23 PB09

Claims (6)

[Claims] (A) (A) (a) a tri- or higher valent polycarboxylic acid having an acid anhydride group or a derivative thereof, (b) a general formula (I) [Wherein, a plurality of Rs each independently have 1 to 12 carbon atoms.
A plurality of X each independently represents an alkylene group having 1 to 12 carbon atoms or an arylene group,
m and n each independently represent an integer of 1 to 20], and 100 parts by weight of a polyamideimide resin obtained by reacting a dicarboxylic acid having a number average molecular weight of 1,000 to 10,000 and (c) a polyisocyanate compound. ,
A polyamide-imide resin paste containing (B) 1 to 50 parts by weight of an epoxy resin and (C) 1 to 90 parts by weight of inorganic fine particles and / or organic fine particles. 2. The polyamide-imide resin paste according to claim 1, further comprising a non-nitrogen-containing polar solvent as an organic solvent. 3. The compounding ratio of component (a) and component (b) constituting the polyamide-imide resin of component (A) is 0.1 / 0.9 to equivalent ratio of component (a) / component (b). 0.9 /
The ratio of the total number of isocyanate groups of the component (c) to the total number of carboxyl groups and acid anhydride groups in the components (a) and (b) is 0.6 to 1.4. The polyamideimide resin paste as described in the above. 4. The polyamide-imide resin paste according to claim 1, wherein the epoxy resin is an amine type epoxy resin having three or more epoxy groups. 5. A viscosity at 25 ° C. of 1 to 1000 Pa · s.
The polyamide-imide resin paste according to any one of claims 1 to 4, wherein a thixotropic coefficient is in a range of 1.3 to 10. 6. A film-forming material comprising the polyamideimide resin paste according to claim 1, 2, 3, 4, or 5.