JP2003335943A - Polyamideimide resin paste and coating film-forming material containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamideimide resin paste which is soluble in nitrogen- containing polar solvents, has low temperature curability, excellent workability and excellent shape retainability in addition to the original heat resistance and the like of the polyamideimide resin, and to provide a coating film-forming material containing the same. <P>SOLUTION: This polyamideimide resin paste is characterized by comprising (A) 100 pts.wt. of a polyamideimide resin obtained by reacting a diisocyanate component containing an aromatic diisocyanate compound represented by the general formula (I) (R<SP>1</SP>and R<SP>2</SP>are each identically or differentially H, a 1 to 6C alkyl or a 1 to 6C alkoxy) in an amount of 10 to 90 mol.% in the diisocyanate component with a polycarboxylic acid having acid anhydride groups or its derivative in an organic solvent, (B) 1 to 50 pts.wt. of an epoxy resin, and (C) 1 to 90 pts.wt. of inorganic and/or organic fine particles, and having a thixotropic property, and the coating film-forming material containing the same. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

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

[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. However, since a high boiling point nitrogen-containing polar solvent such as N-methyl-2-pyrrolidone has been conventionally used as a solvent for varnishing, it is 250 ° C. at the time of curing.
The above high temperature curing is required, and there is a problem that the electronic member is thermally deteriorated. Also, after applying varnish to the electronic member,
When left for a long time, there is a problem that whitening of the coating film and voids occur due to moisture absorption, and working conditions become complicated. Further, in order to improve the productivity and reduce the dimensional variation of the electronic member that occurs during curing, it is desired to lower the curing temperature.

[0003]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and in addition to the heat resistance and the like inherent in polyamideimide resin, it is soluble in a non-nitrogen-containing polar solvent and is low-temperature curable. The present invention provides a polyamide-imide resin paste having excellent workability and shape retention property, and a film forming material using the same, which has excellent properties described above.

[0004]

The present invention provides (A) general formula (I)

[0005]

[Chemical 2]

(In the formula, R ¹ and R ² may be the same or different and each represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms). The ratio of the aromatic diisocyanate compound in the diisocyanate component in the range of 10 to 90 mol% was obtained by reacting a mixture of the diisocyanate component and a polycarboxylic acid having an acid anhydride group or a derivative thereof in an organic solvent. A polyamideimide resin paste containing 100 parts by weight of a polyamideimide resin, 1 to 50 parts by weight of (B) an epoxy resin, and 1 to 90 parts by weight of (C) inorganic and / or organic fine particles, and having thixotropic properties. It is provided. The present invention also provides a film forming material containing the polyamide-imide resin paste.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamide-imide resin paste of the present invention comprises 100 parts by weight of the above-mentioned (A) polyamide-imide resin, 1 to 50 parts by weight of (B) epoxy resin,
(C) Contains 1 to 90 parts by weight of inorganic and / or organic fine particles as an essential component.

Examples of the aromatic diisocyanate compound represented by the general formula (I) used in the production of the polyamideimide resin (A) in the present invention include diphenylmethane-2,4'-diisocyanate and 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, Two
'-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 and the like,
These may be used alone or in combination of two or more.

Among the above-mentioned aromatic isocyanate compounds, diphenylmethane-2,4'-diisocyanate represented by the following formula (II) is most preferable in terms of heat resistance, availability and cost.

[0010]

[Chemical 3]

Examples of the diisocyanate component used in combination with the aromatic diisocyanate compound represented by the general formula (I) include diphenylmethane-4,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate and diphenylmethane-.
3,4'-diisocyanate, diphenyl ether-
4,4'-diisocyanate, benzophenone-4,4
'-Diisocyanate, diphenylsulfone-4,4
'-Diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, m-xylylenediisocyanate, p-xylylenediisocyanate, naphthalene-2,6-diisocyanate, 4,
4 ′-[2,2-bis (4-phenoxyphenyl) propane] diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, 2,2,4-trimethylmexamethylenediisocyanate, isophorone Diisocyanate, 4,4'-
Examples thereof include dicyclohexylmethane diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, and lysine diisocyanate, and these can be used alone or in combination of two or more kinds. Pre-synthesized polyisocyanate may be used, or a polyisocyanate stabilized with an appropriate blocking agent may be used in order to avoid aging.
The blocking agent includes alcohol, phenol, oxime, etc., but is not particularly limited.

Of the diisocyanate component as a raw material for the (A) component polyamideimide resin used in the present invention, the proportion of the aromatic diisocyanate compound represented by the general formula (I) in the diisocyanate component is 10 to 9.
The content is 0 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%. The proportion of the aromatic diisocyanate compound represented by the general formula (I) is 10 mol%.
When it is less than 90%, the effect of improving the solubility in the non-nitrogen-containing polar solvent decreases, and when it exceeds 90 mol%, the mechanical strength and the adhesiveness decrease.

The polyamide-imide resin as the component (A) used in the present invention is obtained by reacting a diisocyanate component with a polycarboxylic acid having an acid anhydride group or a derivative thereof. The polycarboxylic acid having an acid anhydride group or a derivative thereof to be reacted with the diisocyanate component may be a trivalent or higher polycarboxylic acid having an acid anhydride group reactive with an isocyanate group or an amino group or a derivative thereof, Although not particularly limited, for example, general formulas (III) and (IV)

[0014]

[Chemical 4] (However, in both formulas, R represents hydrogen, an alkyl group having 1 to 6 carbon atoms or a phenyl group, and Y represents —CH ₂ —, —CO—,
A compound represented by —SO ₂ — or —O—) can be used. Considering heat resistance and cost,
Trimellitic acid is particularly preferred.

If necessary, a part of a tricarboxylic or higher polycarboxylic acid having an acid anhydride group or a derivative thereof is used, if necessary, pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride, 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 acid dianhydride, 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride, bis {exobicyclo [2,2,1} heptane-2,3-dicarboxylic acid anhydride] sulfone, bicyclo- Tetracarboxylic acids such as (2,2,2) -oct (7) -ene-2,3,5,6-tetracarboxylic acid dianhydride and tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride It may be replaced with an acid dianhydride, an aliphatic or aromatic dibasic acid, or the like.

The amount of the above polycarboxylic acid or its derivative diisocyanate component used is such that the ratio of the isocyanate group to the carboxyl group or its derivative group and the acid anhydride group is
It is preferable to select it to be 0.7 to 1.5,
In order to obtain a high molecular weight resin, it is more preferable to set the ratio of the isocyanate group to the carboxyl group or its derivative group and the acid anhydride group to around 1.0. If it is less than 0.7 or more than 1.5, the film formability tends to decrease.

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 in the presence of an organic solvent, preferably a non-nitrogen-containing polar solvent, from which carbon dioxide gas liberated from the reaction system is generated. It can be carried out by heat condensation while removing.

Examples of the non-nitrogen-containing polar solvent include ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, and sulfur-containing solvents such as
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 resin containing the imide bond formed. 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, more preferably 100 to 190 ° C, and particularly preferably 120 to 180 ° C. 80
If it is less than 0 ° 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 polyamideimide resin thus obtained is preferably 4,000-40,000, more preferably 5,000-35,000, and more preferably 6,000-. Particularly preferably, it is 30,000. 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.

After the synthesis is completed, the isocyanate group at the terminal of the resin can be blocked with a blocking agent such as alcohols, lactams and oximes.

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 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, YDF-817C and YD are preferable in terms of mechanical properties, adhesion and bending resistance.
F-170, YDF-175S, YDF-2001, Y
A bisphenol F type epoxy resin such as DF-2004 is more preferable, and YDF- having an epoxy equivalent of 155 to 500 is used.
817C, YDF-170, YDF-175S, YDF
A bisphenol F type epoxy resin represented by -2001 is particularly preferable.

The amount of the (B) epoxy resin used in the present invention is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, relative to 100 parts by weight of the (A) polyamideimide resin.
By weight, more preferably 3 to 30 parts by weight. When the compounding amount of the epoxy resin is less than 1 part by weight, curability, mechanical properties, adhesion and flex resistance tend to be lowered, and 5
If it exceeds 0 parts by weight, heat resistance and viscosity stability tend to be lowered.

As the method for 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 added directly.

The inorganic and / or organic fine particles used as the component (C) in the present invention are prepared by adding the polyamideimide resin or polyamideimide resin solution as the component (A) and the epoxy resin or epoxy resin solution as the component (B). There is no particular limitation as long as it is dispersed to form a paste. Examples of such inorganic fine particles include silica (SiO2), alumina (Al2O3), titania (T
iO2), tantalum oxide (Ta2O5), zirconia (ZrO2), silicon nitride (Si3N4), barium titanate (BaO.TiO2), barium carbonate (BaCO)
3), lead titanate (PbO.TiO2), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga2O3), spinel (MgO.Al2O3), mullite (3Al2O3.2).
SiO2), cordierite (2MgO.2Al2O)
3 / 5SiO2), talc (3MgO.4SiO2.H)
2O), aluminum titanate (TiO2-Al2O)
3), yttria-containing zirconia (Y2O3-ZrO
2), barium silicate (BaO.8SiO2), boron nitride (BN), calcium carbonate (CaCO3), calcium sulfate (CaSO4), zinc oxide (ZnO), magnesium titanate (MgO.TiO2), barium sulfate (B)
aSO4). Organic bentonite, carbon (C) and the like can be used, and one or more of these can also be used.

The organic fine particles used in the present invention are dispersed in the above-mentioned component (A) polyamideimide resin or polyamideimide resin solution and component (B) epoxy resin or epoxy resin solution to form a paste. If it does, there is no particular limitation. 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. From the viewpoints of heat resistance and mechanical properties, polyimide resin or its precursor, polyamideimide resin or its precursor, or fine particles of polyamide resin are preferably used as the heat resistant resin.

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 in an amount of more than 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,
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-cyclobutanetetracarboxylic 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 may 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 that the aromatic tetracarboxylic dianhydride and the aromatic diamine compound are reacted in substantially equimolar amounts.

The reaction between the aromatic tetracarboxylic dianhydride and the aromatic diamine compound is carried out 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, lactones such as ε-caprolactone, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, triethylene glycol (or diethyl, dipropyl, dibutyl) ether,
Ethers such as tetraethylene glycol dimethyl (or diethyl, dipropyl, dibutyl) ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone ketones, butanol, octyl alcohol, ethylene glycol, glycerin, diethylene glycol monomethyl (or monoethyl) ether, triethylene Alcohols such as glycol monomethyl (or monoethyl) ether and tetraethylene glycol monomethyl (or monoethyl) ether, phenols such as phenol, cresol and xylenol, ethyl acetate, butyl acetate, ethyl cellosolve acetate,
Esters such as butyl cellosolve acetate, hydrocarbons such as toluene, xylene, diethylbenzene and cyclohexane, trichloroethane, tetotachloroethane,
Halogenated hydrocarbons such as 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 0-5.
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 anhydride, or a carbodiimide compound such as dicyclohexylcarbodiimide as a 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 polyimide resin or its precursor, instead of the aromatic tetracarboxylic dianhydride, a trivalent tricarboxylic acid such as trimellitic anhydride or a trimellitic anhydride derivative such as chloride of trimellitic anhydride. It can be produced by using an acid anhydride or a derivative thereof. 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 obtained 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 above aromatic diamine compound or other diamine compound. Can be manufactured by.

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 polyamide-imide 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. 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 of forming fine particles, for example, a non-aqueous dispersion polymerization method (Japanese Patent Publication No. 60-48531, JP-A-59).
No. 230018, precipitation polymerization method (JP-A-59-10)
8030 gazette, JP-A-60-221425),
A method of mechanically pulverizing a powder modified from a resin solution, a method of forming fine particles under high shear while adding a resin solution to a poor catalyst, a method of drying a spray solution of a resin solution to obtain fine particles,
There is a method of precipitating fine particles of a resin having temperature dependency of solubility in a solvent in a detergent or a resin solution.

In the polyamide-imide 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 the polyamide-imide resin and the organic solvent before heat drying is used. On the other hand, organic fine particles are present as a non-uniform layer, and a mixture is preferably used so that a uniform layer containing a thermosetting resin and organic fine particles as essential components is formed after heating and drying.

As the organic solvent, one that dissolves the above-mentioned thermosetting resin is used. When using organic particles,
It is also preferable to use both the thermosetting resin and the organic fine particles which have the property of dissolving in the organic solvent at the temperature when the resin paste is heated and dried.

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.
When the average particle size exceeds 50 μm, it becomes difficult to obtain a paste having a thixotropy coefficient of 1.1 or more, which will be described later, and when the maximum particle size exceeds 100 μm, the appearance and adhesion of the coating film tend to be insufficient.

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 any method may be used as long as sufficient dispersion is performed.

The polyamide-imide resin paste of the present invention has a viscosity of 0.5 Pa at 25 ° C. measured by a rotary viscometer.
It is preferable that the s-500 Pa · s and the thixotropic coefficient are 1.1 or more. If the viscosity is less than 0.5 Pa · s, the flow of the paste after printing becomes large and the film thickness tends to be thin. If the viscosity exceeds 500 Pa · s, the transferability of the paste to the base material tends to decrease, and voids and pinholes in the printed film tend to increase. When the thixotropy coefficient is less than 1.1, the stringiness of the paste increases, the flow-out of the paste after printing becomes large, and the film thickness tends to be thin.

Here, the viscosity of the paste was measured using an E-type viscometer (RE80U type, manufactured by Toki Sangyo Co., Ltd.), and the sample amount was 0.
It is expressed as the viscosity at a rotation speed of 10 rpm measured in 2 ml or 0.5 ml. The thixotropy coefficient (TI value) of the paste is an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE80U).
It is expressed as a ratio η1 / η10 of η1 and η10, which is the apparent viscosity of paste at a rotation speed of 1 rpm and 10 rpm measured with a sample amount of 0.2 ml or 0.5 ml.

In the polyamide-imide resin paste of the present invention, the amount of the inorganic and / or organic fine particles used as the component (C) is preferably in the range of 1 to 90 parts by weight with respect to 100 parts by weight of the polyamide-imide resin. . When the amount is less than this, the viscosity and thixotropy coefficient of the paste become low, the stringiness of the paste increases, the flow-out of the paste after printing becomes large, and the film thickness tends to be thin. On the other hand, if it is more than the above range, the viscosity and thixotropy coefficient of the paste become high, the transferability of the paste to the substrate decreases, and voids and pinholes in the printed film tend to increase.

The polyamide-imide resin paste of the present invention is colored with a surface active agent such as an antifoaming agent or a leveling agent, a dye or a pigment in order to improve workability during coating and film properties before and after film formation. Agents, curing accelerators, heat stabilizers, antioxidants, flame retardants and lubricants can also be added.

[0055]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. Example 1 227.5 g of diphenylmethane-2,4′-diisocyanate was added to a 2-liter four-necked flask equipped with a stirrer, a condenser tube with an oil / water separator, a nitrogen introduction tube and a thermometer.
909 mol), diphenylmethane-4,4'-diisocyanate 227.5 g (0.909 mol), trimellitic anhydride 345.8 g (1.8 mol) and γ-butyrolactone 981.3 g were charged, and the temperature was raised to 170 ° C. After that, the mixture was reacted for 6 hours to obtain a resin having a number average molecular weight of 18,000. The obtained resin was diluted with γ-butyrolactone, 22.8 g of 2-butanone oxime was further added, and the mixture was heated at 90 ° C. for 3 hours to obtain a polyamideimide resin solution having a nonvolatile content of 40% by weight. YDF-17 was added to 100 parts by weight of the resin content of the obtained polyamide-imide resin solution.
5 parts by weight of 0 (trade name of bisphenol F type epoxy resin manufactured by Tohto Kasei Co., Ltd., epoxy equivalent of about 160 to 180) was added and diluted with γ-butyrolactone to obtain a polyamideimide resin composition having a nonvolatile content of 40% by weight. It was

Polyamideimide resin composition 10 thus obtained
Aerosil 380 (trade name, manufactured by Nippon Aerosil Co., Ltd., average particle diameter 0.2 μm or less, silica fine particles) 4 in 50 g
0.0 g was added, and the mixture was first roughly kneaded and then repeatedly kneaded three times using a high-speed three-roll to perform main kneading to obtain a polyamideimide resin paste in which silica fine particles were uniformly dispersed. This paste had a viscosity of 40.5 Pa · s and a TI value of 2.1.

Example 2 In Example 2, instead of 5 parts by weight of YDF-170, 5 parts by weight of Epicoat 828 (trade name of bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., epoxy equivalent of about 189) was used. The same operation as in Example 1 was carried out except that was used, and the viscosity was 41.0 Pa · s and the TI value was 2.1.
A polyamide-imide resin paste of was obtained.

Comparative Example 1 Example 1 except that Aerosil 380 was not used.
Completely the same operation as above, viscosity 28.0 Pa · s, TI
A polyamideimide resin composition having a value of 1.0 was obtained.

Comparative Example 2 The same operation as in Example 1 was carried out except that YDF-170 was not used, to obtain a polyamideimide resin paste having a viscosity of 47.0 Pa · s and a TI value of 2.1.

Comparative Example 3 A flask similar to that used in Example 1 was charged with diphenylmethane-4,
382.9 g (1.53 mol) of 4'-diisocyanate, 288.2 g (1.50 mol) of trimellitic anhydride and 1006.7 g of N-methyl-2-pyrrolidone were charged, and the temperature was raised to 130 [deg.] C., then 5. Let it react for hours
A resin having a number average molecular weight of 19,000 was obtained. The obtained resin was diluted with xylene to obtain a polyamideimide resin solution having a viscosity of 18.0 Pa · s and a nonvolatile content of 37% by weight. YDF-170 (trade name of bisphenol F type epoxy resin manufactured by Tohto Kasei Co., Ltd., epoxy equivalent of about 160) based on 100 parts by weight of the resin content of the obtained polyamideimide resin solution.
~ 180) 5 parts by weight and diluted with N-methyl-2-pyrrolidone to obtain a polyamide-imide resin composition having a nonvolatile content of 37% by weight.

Polyamideimide resin composition 10 thus obtained
Aerosil 380 (trade name, manufactured by Nippon Aerosil Co., Ltd., average particle diameter 0.2 μm or less, silica fine particles) 3 in 50 g
7.0 g was added, and the mixture was first roughly kneaded and then repeatedly kneaded three times using a high-speed three-roll to perform main kneading to obtain a polyamideimide resin paste in which silica fine particles were uniformly dispersed. This paste had a viscosity of 35.0 Pa · s and a TI value of 3.0. The properties of the polyamideimide resin paste 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.

[0062]

[Table 1]

(1) A shape-retaining polyamide-imide resin paste or composition is prepared according to JIS H
Aluminum plate A1050P specified in -4000
After coating on (dimensions 1 mm × 50 mm × 150 mm), it is heated and cured at 190 ° C. for 60 minutes to form a coating film having a film thickness of about 20 μm. The shape change rate of the obtained coating film before and after curing was evaluated using a universal projector (manufactured by Nikon Corporation, magnification 50 times). O: Shape change rate of coating film 0 to less than 5% B: Shape change rate of coating film 5 to less than 10% X: Shape change rate of coating film 10% or more

(2) Coating film whitening time The polyamideimide resin paste or composition was applied to an aluminum substrate in an atmosphere of a temperature of 23 ° C. and a humidity of 56% RH, and the time until the coating solution was whitened was evaluated. ○: 4 hours or more △: 4 hours or less ×: 10 minutes or less

(3) Adhesion (cross-cut test) A polyamideimide resin paste or composition was measured according to JIS H
Aluminum plate A1050P specified in -4000
After coating on (dimensions 1 mm × 50 mm × 150 mm), it is heated and cured at 190 ° C. for 60 minutes to form a coating film having a film thickness of about 20 μm. JIS D0 using the obtained coated plate
Tested according to 202. ◯: Number of grids not peeled = 100/100 △: Number of grids not peeled = 50/100 or more ×: Number of grids not peeled = 50/100 or less

(4) A flexible polyamide-imide resin paste or composition is prepared according to JIS H
Aluminum plate A1050P specified in -4000
After coating on (dimensions 1 mm × 50 mm × 150 mm), it is heated and cured at 190 ° C. for 60 minutes to form a coating film having a film thickness of about 20 μm. The obtained coated plate was bent 180 ° at 1.0R so that the coated surface was on the outside, and the presence or absence of cracks in the bent portion was evaluated. ○: No crack ×: Crack

(5) Mechanical Properties The polyamide-imide resin paste or composition is heated and cured at 190 ° C. for 60 minutes to form a coating film having a film thickness of about 30 μm, a width of 10 mm and a length of 60 mm. Using the obtained coating film, a tensile test was carried out under the conditions of a chuck length of 20 mm and a tensile speed of 5 mm / min to determine the elastic modulus and the elongation.

(6) 5% weight loss temperature The polyamideimide resin paste or composition is heated and cured at 190 ° C. for 60 minutes to form a coating film. Using the obtained coating film, the 5% weight loss temperature was measured by the TG-DTA method.

[0069]

The polyamide-imide resin paste of the present invention is a polyamide-imide resin paste which is soluble in a non-nitrogen-containing polar solvent and is curable at low temperature, and has shape retention, hygroscopicity,
It has excellent adhesion, flexibility, mechanical properties and heat resistance. Further, the film-forming material of the present invention can form a film having the above-mentioned excellent properties, an overcoat material for semiconductor elements and various electronic components, an interlayer insulating film in the field of rigid or flexible substrates, a surface protective film, Sheet resist varnish combined with solder resist layer, adhesive layer, etc., liquid encapsulant, varnish for enameled wire, impregnated varnish for electrical insulation, cast varnish, mica, glass cloth, etc., MC
It is preferably used as a varnish for L laminates and a varnish for friction materials.

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Claims (4)

[Claims] 1. (A) General formula (I): (In formula, R < ¹ > and R < ² > may be the same or different and are a hydrogen atom, a C1-C6 alkyl group, or a C1-C1.
Of the aromatic diisocyanate compound represented by the formula (1) to (6) is contained in the diisocyanate component in the range of 10 to 90 mol% and the polycarboxylic acid having an acid anhydride group or a derivative thereof. 100 parts by weight of polyamide-imide resin obtained by reacting the mixture in an organic solvent and (B) epoxy resin 1
To 50 parts by weight and (C) inorganic and / or organic fine particles 1
A polyamide-imide resin paste containing 90 to 90 parts by weight and having thixotropy. 2. The epoxy resin has an epoxy equivalent of 155-5.
A bisphenol F type epoxy resin of No. 00.
The polyamide-imide resin paste described. 3. The polyamideimide resin paste according to claim 1, which contains a non-nitrogen-containing polar solvent as the organic solvent. 4. A film forming material containing the polyamide-imide resin paste according to claim 1, 2 or 3.