JPH0912879A - Polyamide-imide resin composition - Google Patents

Abstract

PURPOSE: To obtain a polyimide-imide compsn. excellent in adhesion, low-temp. curability and shelf stability by blending a specific component with a modified polyamide-imide resin obtd. through a reaction with a specific compd. CONSTITUTION: This polyamide-imide resin compsn. comprises 100 pts.wt. modified polyamide-imide resin obtd. by reacting a polyamide-imide resin with a bisoxazoline compd. of the formula (R1 , R2 , R4 and R5 are each H, a lower alkyl, phenyl, or hydroxymethyl; R3 and R6 are each H, methyl, or phenyl; X is a 1-8C alkylene or phenylene; and m is 0 to 1); and 0.05-50 pts.wt. coupling agent blended therewith. Pref. examples of the coupling agent include organosilane compds., organotitanium compds., and organozirconium compds. This compsn. may comprise an epoxy resin. The compsn. is pref. used after the resin component is dissolved in an org. solvent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamideimide resin composition, and more particularly to a low temperature curable polyamideimide resin composition.

[0002]

2. Description of the Related Art Polyamide-imide resins have excellent heat resistance, chemical resistance, solvent resistance, abrasion resistance, etc. and are therefore widely used as varnishes for enameled wires and heat-resistant paints as coating agents for various base materials. ing. However, when a polyamide-imide resin is used for heat-resistant coating, for example, in the coating film formation process, the coating film shrinks due to solvent volatilization or curing reaction and subsequent cooling, causing internal stress, and peeling from the substrate. Therefore, it is desired to improve the adhesiveness.
Although addition of an organic silane compound or the like has been studied in order to improve the adhesion of the polyamide-imide resin, there is a problem that the storage stability becomes poor and the range of use is limited.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a polyamide-imide resin composition having excellent adhesion, low-temperature curability and storage stability.

[0004]

The present invention provides a polyamideimide resin having the general formula (I)

[0005]

Embedded image [In the formula, R ₁ , R ₂ , R ₄ and R ₅ are each independently hydrogen,
Selected from the group consisting of a lower alkyl group, a phenyl group and a hydroxymethyl group, R ₃ and R ₆ are each independently selected from the group consisting of hydrogen, a methyl group and a phenyl group,
X is selected from the group consisting of an alkylene group having 1 to 8 carbon atoms and a phenylene group, and m is an integer of 0 or 1] to 100 parts by weight of a modified polyamideimide resin obtained by reacting a bisoxazoline compound represented by On the other hand, the present invention relates to a polyamide-imide resin composition containing 0.05 to 50 parts by weight of a coupling agent.

Polyamideimide resin is disclosed in Japanese Examined Patent Publication No. 44-1.
Manufactured by a known production method shown in Japanese Patent Publication No. 9274, etc., for example, a trivalent polycarboxylic acid having an acid anhydride group or a derivative thereof and an aromatic isocyanate or an aromatic diamine are reacted in an organic polar solvent. Can be obtained.

The trivalent polycarboxylic acid having an acid anhydride group or its derivative may be a tricarboxylic acid anhydride having an acid anhydride group and a carboxyl group which react with an isocyanate group or an amino group or a derivative thereof, Although not particularly limited, for example, the general formula (II) or (III)

Embedded image Wherein R represents hydrogen, an alkyl group or a phenyl group;
Y is _{-CH 2 -, - CO -,} - SO 2 - or -O- shown is able to use the compound in the shown], for example,
Examples include trimellitic acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, and 3,4,4'-benzophenonetricarboxylic acid-3,4-anhydride. Heat-resistant,
Considering cost and the like, trimellitic anhydride is particularly preferred.

If necessary, a part of this may be pyromellitic dianhydride, benzophenonetetracarboxylic dianhydride,
Butanetetracarboxylic dianhydride, bicyclo- [2,
2,2] -Oct-7-ene-2: 3: 5: 6-tetracarboxylic dianhydride such as tetracarboxylic dianhydride, or an aliphatic or aromatic dibasic acid may be substituted.

Examples of aromatic diisocyanates include 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate,
4,4 '-[2,2-bis (4-phenoxyphenyl)
Propane] diisocyanate and the like can be used alone or in combination of two or more kinds. Moreover, you may use the dimer of these diisocyanates, a trimer, etc.,
You may use what was stabilized with the suitable blocking agent in order to avoid a secular change.

As the aromatic diamine, for example, 4,
4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, m-xylenediamine, toluylenediamine, p-phenylenediamine, 2,2-bis [4- (4-aminophenoxy) phenyl] propane and the like, These may be used alone or in combination of two or more.

The amount of the above-mentioned polycarboxylic acid or derivative thereof and the aromatic diisocyanate or aromatic diamine used is
A carboxyl group or a derivative group thereof (these are represented by the general formula (I
I) or (III) is represented by COOR) and the ratio of the isocyanate group or the amino group to the total of the acid anhydride groups is preferably selected to be 1.5 to 0.7. In order to obtain the above, it is particularly preferable that the ratio of the isocyanate group or the amino group to the total of the carboxyl group or the derivative group thereof and the acid anhydride group is around 1.0. In order to obtain a carboxyl group-terminated polyamideimide resin, the ratio is preferably set to 0.7 to less than 1.0.

The reaction is carried out in the temperature range of 80 to 150 ° C. in the presence of an organic polar solvent by heat condensation while removing carbon dioxide gas which is liberated when an aromatic diisocyanate is used, from the reaction system. The reaction time is appropriately selected depending on the scale of the batch and the reaction conditions adopted.

Examples of the organic polar solvent include N-methyl-2-pyrrolidone, N, N-dimethylformamide,
N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and the like can be used alone or in combination of two or more thereof, and the amount thereof is 1. 0 to 5.0 times (weight) is preferable. When an aromatic diisocyanate is used after the synthesis of the polyamide-imide resin, the isocyanate group at the resin end can be blocked with a blocking agent such as alcohols, lactams, and oximes.

The number average molecular weight of the polyamide-imide resin is preferably 1,000 to 100,000, more preferably 5,000 to 80,000, and even more preferably 7,000 to 50,000. Is particularly preferred. If the molecular weight is too small, the viscosity stability when dissolved in a solvent will be poor, and if the molecular weight is too large, the viscosity will be high when dissolved in a solvent, resulting in poor workability.
The number average molecular weight is measured by gel permeation chromatography (GPC) using a standard polystyrene calibration curve. The polyamide-imide resin used in the present invention has an acid value of 5 to 100 KOHmg / g.
Those having 10 to 60 KOHmg / g are more preferable, and those having 15 to 50 KOHmg / g are particularly preferable. When the acid value is less than 5 KOHmg / g, the low temperature curability tends to decrease, and when it exceeds 100 KOHmg / g, various properties such as heat resistance tend to decrease when the coating film is formed.

In the present invention, the polyamide-imide resin as described above is modified with the bisoxazoline compound represented by the general formula (I) before use. Here, the general formula (I)
As the bisoxazoline compound represented by, for example,
2,2'-bis (2-oxazoline), 5,5'-dimethyl-2,2'-bisoxazoline, 4,4,4 ',
4'-tetramethyl-2,2'-bisoxazoline,
4,4'-diethyl-2,2'-bisoxazoline,
2,2'-methylenebis (2-oxazoline), 2,
2'-ethylenebis (2-oxazoline), 2,2'-
Ethylene bis (4,4-dimethyl-2-oxazoline), 2,2'-trimethylene bis (4,4-dimethyl-2-oxazoline), 2,2'-tetramethylene bis (4,4-dimethyl-2) -Oxazoline), 2,2'-
Pentamethylenebis (4,4-dimethyl-2-oxazoline), 2,2'-hexamethylenebis (4,4-dimethyl-2-oxazoline), 2,2'-heptamethylenebis (4,4-dimethyl-) 2-oxazoline), 2,
2'-octamethylenebis (4,4-dimethyl-2-oxazoline), 2,2'-ethylenebis (4-methyl-
2-oxazoline), 2,2'-trimethylenebis (4
-Methyl-2-oxazoline), 2,2'-tetramethylenebis (4-methyl-2-oxazoline), 2,2 '
-Pentamethylenebis (4-methyl-2-oxazoline), 2,2'-hexamethylenebis (4-methyl-2)
-Oxazoline), 2,2'-heptamethylenebis (4
-Methyl-2-oxazoline), 2,2'-tetramethylenebis (5-methyl-2-oxazoline), 2,2 '
-Tetramethylenebis (4,4-diphenyl-2-oxazoline), 2,2'-tetramethylenebis-2-oxazoline-4-methanol, 2,2'-tetramethylenebis-2-oxazoline-4,4 ' -Dimethanol,
2,2'-tetramethylenebis-2-oxazoline,
2,2'-octamethylenebis-2-oxazoline,
2,2'-tetramethylenebis [4- (hydroxymethyl) -4-methyloxazoline], 2,2'-heptamethylenebis [4- (hydroxymethyl) -4-methyloxazoline], 2,2 '-( 1,3-phenylene) bis (2-oxazoline), 2,2′-p-phenylenebis-2-oxazoline, 2,2′-p-phenylenebis (4,4-dimethyl-2-oxazoline), 2, 2'-
p-phenylene bis (5-phenyl-2-oxazoline) and the like can be mentioned.

The amount of the bisoxazoline compound represented by the general formula (I) used is preferably an equivalent to 10 times the equivalent of the terminal carboxyl group of the polyamideimide resin. If the amount of the bisoxazoline compound used is less than this, the storage stability of the polyamide-imide resin composition tends to decrease, and conversely, if the amount of the bisoxazoline compound used is too large, unreacted bisoxazoline compound or The reaction product with water increases, which causes deterioration of coating film characteristics (especially abrasion resistance).

The reaction between the polyamideimide resin and the bisoxazoline compound, that is, the reaction between the carboxyl group and the oxazoline, is described in US Pat. No. 3,476,712.
As described in JP-A-2-120325 and the like, it can be carried out in the presence of a polar solvent in the temperature range of 50 to 200 ° C. The reaction time is appropriately selected depending on the scale of the batch and the reaction conditions adopted. As a polar solvent,
Chemically inert organic solvents such as N-methyl-2-
Pyrrolidone, N, N-dimethylformamide, N, N-
Dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and the like can be used alone or in combination of two or more,
The polar solvent used for the synthesis of the above-mentioned polyamide-imide resin may be used as it is. The amount of the polar solvent used is preferably 1.0 to 5.0 times (weight) the modified polyamideimide resin produced.

The modified polyamideimide resin in the present invention preferably has an acid value (KOHmg / g) of less than 5, and particularly preferably 2 or less. The polyamideimide resin before modification and the bisoxazoline compound are reacted by appropriately adjusting the compounding amount so that the acid value is less than 5, preferably 2 or less. When the acid value is 5 or more, the storage stability tends to deteriorate.

As the coupling agent in the present invention,
It is preferable to use at least one organometallic compound selected from the group consisting of organosilane compounds, organotitanium compounds and organozirconium compounds.

The organosilane compound used in the present invention is not particularly limited, and examples thereof include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane,
Vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ
-Aminopropyltrimethoxysilane, n-β (aminoethyl) γ-aminopropylmethyldimethoxysilane,
γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, 3-aminopropyl-methyl-diethoxysilane, 3-ureido Propyltriethoxysilane, 3-ureidopropyltrimethoxysilane,
3-aminopropyltrimethoxysilane, 3-aminopropyl-tris (2-methoxy-ethoxy-ethoxy)
Silane, N-methyl-3-aminopropyltrimethoxysilane, triaminopropyl-trimethoxysilane, 3
-4,5-dihydroimidazolepropyltrimethoxysilane, 3-methacryloxypropyl-trimethoxysilane, 3-mercaptopropyl-methyldimethoxysilane, 3-chloropropyl-methyl-dimethoxysilane,
3-cyanopropyl-triethoxysilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, methyltrimethoxysilane, methyltriethoxysilane, ethyltrichlorosilane, n-propyltrimethoxysilane, isobutyltrimethoxysilane, Amyltrichlorosilane, octyltriethoxysilane,
Phenyltrimethoxysilane, phenyltriethoxysilane, methyltri (methacryloyloxyethoxy) silane, methyltri (glycidyloxy) silane, N-β
(N-Vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, octadecyldimethyl [3-
(Trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldichlorosilane, γ-
Examples include chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, trimethylsilylisocyanate, dimethylsilylisocyanate, methylsilyltriisocyanate, vinylsilyltriisocyanate, phenylsilyltriisocyanate, tetraisocyanatesilane, and ethoxysilaneisocyanate. These can be used alone or in combination of two or more.

The organotitanium compound used in the present invention is not particularly limited and includes, for example, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl. Tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (n-aminoethyl-aminoethyl) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditri) Decylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bi (Ditridecyl) phosphite titanate, dicumylphenyloxyacetate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, tetraisopropyl titanate, tetranormal butyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, titanium acetylacetonate, Polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate ammonium salt, titanium lactate, titanium lactate ethyl ester, titanium chiliethanol aminate,
Polyhydroxytitanium stearate, tetramethyl orthotitanate, tetraethyl orthotitanate, tetrapropyl orthotitanate, tetraisobutyl orthotitanate, stearyl titanate, cresyl titanate monomer, cresyl titanate polymer, di-isopropoxy-bis- (2,4- Pentadionate) -titanium (IV), di-isopropyl-bis-triethanolamino-titanate, octylene glycol titanate HV, tetra-n-butoxy titanium polymer, tri-n
-Butoxy titanium monostearate polymer, tri-n
-Butoxy titanium monostearate and the like can be mentioned, and these can be used alone or in combination of two or more kinds.

The organozirconium compound used in the present invention is not particularly limited, and examples thereof include tetrapropyl zircoaluminate, tetrabutyl zirconate, tetra (triethanolamine) zirconate, tetaraisopropyl zirconate and zirconium acetylacetonate. , Acetylacetone zirconium butyrate, zirconium lactate, zirconium butyrate stearate, APG-X (trade name of CAVEDON CHMICAL CO., INC.) And the like, and these may be used alone or in combination of two or more kinds. be able to.

In the present invention, the amount of the coupling agent used is 0.05 to 50 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the modified polyamideimide resin. If the amount of these organometallic compounds used is less than 0.05 parts by weight, the adhesion tends to be insufficiently improved, and if it is more than 50 parts by weight, the storage stability tends to decrease. As a method for adding the above-mentioned organometallic compound, the organometallic compound to be added may be added after being dissolved in the same solvent as the organic solvent contained in the modified polyamideimide resin in advance, or directly to the modified polyamideimide resin. You may add.

The polyamide-imide resin composition of the present invention may contain an epoxy resin in order to improve the curability. The epoxy resin that can be used is not particularly limited, and for example, Epicoat 815, 825, 827, 828, 834, 1001, manufactured by Yuka Shell Epoxy Co., Ltd.,
Bisphenol A type epoxy resin such as 1004, 1007, 1009 (trade name), Epicoat 152, 154,
EPNO-201 (trade name) manufactured by Nippon Kayaku Co., Ltd., DEN-438 (trade name) manufactured by Dow Chemical Co., etc., phenol novolac type epoxy resin, EOCN-10 manufactured by Nippon Kayaku Co., Ltd.
2S, 103S, 104S (trade name) o-cresol novolac type epoxy resin, Yuka Shell Epoxy Co., Ltd.
Epon 1031S (trade name), Ciba Geigy Araldite 0163 (trade name), Denasel EX-611, EX-614, EX-614 manufactured by Nagase Kasei Co., Ltd.
B, EX-622, EX-512, EX-521, EX
-421, EX-411, EX-321 (trade name) and other multifunctional epoxy resins, Yuka Shell Epoxy Co., Ltd. Epicoat 604 (trade name), Tohto Kasei Co., Ltd. YH-434
(Trade name), Mitsubishi Gas Chemical Co., Ltd. TETRAD-X, T
Amine type epoxy resin such as ETRAD-C (trade name), Nippon Kayaku Co., Ltd. GAN (trade name), Sumitomo Chemical Co., Ltd. ELM-120 (trade name), Ciba Geigy Araldite P
Heterocyclic ring-containing epoxy resin such as T810 (trade name), UC
ERL4234, 4299, 4221, 4206 manufactured by C company
Alicyclic epoxy resins such as (trade name) may be mentioned, and these may be used alone or in combination of two or more kinds.

As a 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 modified polyamideimide resin in advance and then added.
Alternatively, it may be directly added to the polyamide-imide resin. The amount of the epoxy resin used is the modified polyamide-imide resin 10
It is preferably used in an amount of 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, based on 0 parts by weight. If the amount of the epoxy resin used is too small, the effect of improving the curability is small, and if the amount of the epoxy resin used is too large, the adhesion tends to decrease.

An amine-based additive may be added to the polyamide-imide resin composition of the present invention in order to improve its curability. Particularly, it is preferable to use the epoxy resin and the epoxy resin at the same time. Examples of the amine-based additive include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, primary amines such as p-phenylenediamine, secondary amines such as piperidine and pyrrolidine, N, N, N ', N'-tetramethylhexamethylenediamine, N, N, N', N'-tetramethylpropylenediamine, N, N, N ', N ",
N ″ -pentamethyldiethylenetriamine, trimethylaminoethylpiperazine, N, N′-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N ′, N ″ -tris (3-dimethylaminopropyl) hexahydro-s -Triazine, N, N-dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, N-trioxyethylene-N, N-dimethylamine, triethylenediamine, 1,8-diazabicyclo (5.4.0) undecene -7, N, N, N-tris (3-dimethylaminopropyl) amine, N-methyldicyclohexylamine, N-methyl-N, N-bis (3-dimethylaminopropyl) amine, 2- (dimethylaminomethyl) Phenol, 2,4,6-tris (dimethylaminomethyi) ) Phenol, N, N'-dimethylpiperazine, pyridine, picoline, 1,2,2,6,6
-Pentamethyl-4-piperidinol, tertiary amines such as triethylamine, dicyandiamide and the like can be mentioned, and these can be used alone or in combination of two or more kinds. These are preferably used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the modified polyamideimide resin. If the amount of the amine-based additive is too small, the effect of improving the curability due to the addition is small, and if the amount of the amine-based additive is too large, the viscosity stability is lowered.

The polyamide-imide resin composition of the present invention is preferably used by dissolving the resin component in an organic solvent. In this case, it is preferable to adjust the resin content to 10 to 40% by weight. As the organic solvent, N-methyl-2-pyrrolidone, N, N-dimethylformamide,
There are polar organic solvents such as N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether. In this case, xylene and NISSEKI are used as cosolvents in consideration of the resin content concentration and viscosity.
HISOL-100, 150, butyl acetate,
Cellosolve acetate, butyl cellosolve acetate,
You may use methyl ethyl ketone, ethylbenzene, p-cymene, etc. together.

The polyamide-imide resin composition of the present invention is used in a heat resistant coating containing the above-mentioned organic solvent. The polyamide-imide resin composition according to the present invention is mainly used for heat-resistant paints, and specific applications include, for example, varnish for enameled wire, impregnated varnish for electrical insulation, cast varnish, mica, glass cloth, etc. It can be used as a varnish for a sheet, a varnish for a MCL laminate, a varnish for a friction material, etc. in combination with the above base material.

[0029]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Comparative Example 1 N-methyl-2-pyrrolidone 74 was placed in a 2-liter four-necked flask equipped with a stirrer, a cooling tube, a nitrogen introducing tube and a thermometer.
7 g, 4,4'-diphenylmethane diisocyanate 2
98 g (1.19 mol) and trimellitic anhydride 227
Charge g (1.18 mol) and raise the temperature to 130 ° C.
When reacted for about 4 hours, the number average molecular weight was 17,000.
A resin having an acid value of 0 and an acid value of 32 KOHmg / g was obtained. This resin is N
It was diluted with -methyl-2-pyrrolidone and N, N-dimethylformamide to obtain a polyamide-imide resin composition having a nonvolatile content of 30% by weight.

Comparative Example 2 23.1 parts by weight of 2,2 '-(1,3-phenylene) bis (2-oxazoline) based on 100 parts by weight of the resin component of the polyamideimide resin composition obtained in Comparative Example 1. (4 times equivalent to the terminal carboxyl group of the polyamide-imide resin) was added, and the temperature was raised to 100 ° C. After reacting for about 3 hours, the number average molecular weight was 22,000 and the acid value was 1.3 KO.
A modified polyamideimide resin of Hmg / g was obtained. After cooling to room temperature, the mixture was diluted with a mixed solvent of 70 parts by weight of N-methyl-2-pyrrolidone and 30 parts by weight of N, N-dimethylformamide to obtain a modified polyamideimide resin composition having a nonvolatile content of 30% by weight.

Comparative Example 3 In Comparative Example 2, 2,2 '-(1,3-phenylene)
Except that the amount of bis (2-oxazoline) used was changed to 34.7 parts by weight (6 times equivalent to the terminal carboxyl group of the polyamideimide resin), the same operation as in Comparative Example 2 was repeated to obtain a number average molecular weight of 22. 1,000, acid value 0.9KOHmg / g
A modified polyamideimide resin of was obtained. After this, Comparative Example 2
A modified polyamideimide resin composition was obtained in the same manner as in.

Example 1 1 part by weight of γ-aminopropyltriethoxysilane was added to 70 parts by weight of N-methyl-2-pyrrolidone, based on 100 parts by weight of the resin content of the modified polyamideimide resin composition obtained in Comparative Example 2. And a solution in which the nonvolatile content was 30% by weight was diluted with a mixed solvent of 30 parts by weight of N, N-dimethylformamide to obtain a modified polyamideimide resin composition having a nonvolatile content of 30% by weight.

Example 2 The same operation as in Example 1 was carried out except that 1 part by weight of γ-ureidopropyltriethoxysilane was used in place of 1 part by weight of γ-aminopropyltriethoxysilane. Then, a modified polyamideimide resin composition having a nonvolatile content of 30% by weight was obtained.

Examples 3 and 4 The procedure of Example 2 was repeated except that the amounts of .gamma.-ureidopropyltriethoxysilane added were 10 parts by weight and 30 parts by weight, respectively. To obtain 30% by weight of a modified polyamideimide resin composition.

Example 5 1 part by weight of γ-aminopropyltriethoxysilane was added to 70 parts by weight of N-methyl-2-pyrrolidone, based on 100 parts by weight of the resin content of the modified polyamideimide resin composition obtained in Comparative Example 2. And a solution obtained by diluting with a mixed solvent of 30 parts by weight of N, N-dimethylformamide to a nonvolatile content of 30% by weight, and Denacol EX-321 (Nagase Chemical Industry Co., Ltd.).
Product name, trimethylolpropane polyglycidyl ether, trifunctional epoxy resin as main component, epoxy equivalent 14
5) 10 parts by weight was diluted with a mixed solvent of 70 parts by weight of N-methyl-2-pyrrolidone and 30 parts by weight of N, N-dimethylformamide to make the nonvolatile content 30% by weight, and the nonvolatile content was 30%. A modified polyamide imide resin composition of weight% was obtained.

Example 6 In Example 5, instead of Denacol EX-321 (10 parts by weight), Denacol EX-411 (trade name, pentaerythritol polyglycidyl ether manufactured by Nagase Kasei Co., Ltd.) was mainly used. Except for using 10 parts by weight of the component, epoxy equivalent 231), the same operation as in Example 5 was performed to obtain a modified polyamideimide resin composition having a nonvolatile content of 30% by weight.

Example 7 In Example 5, TETRAD-X (trade name, N, N, N ', N'-tetraglycidyl-manufactured by Mitsubishi Gas Chemical Co., Inc.) was used in place of Denacol EX-321 (10 parts by weight). m-
Except for using 10 parts by weight of xylenediamine and epoxy equivalent of 100), the same operation as in Example 5 was performed to obtain a modified polyamideimide resin composition having a nonvolatile content of 30% by weight.

Example 8 To 100 parts by weight of the resin component of the modified polyamideimide resin composition obtained in Comparative Example 2, 0.1 parts by weight of γ-aminopropyltriethoxysilane was added to 70 parts of N-methyl-2-pyrrolidone. Parts by weight and N, N-dimethylformamide 30
A solution obtained by diluting with 30 parts by weight of a non-volatile component by diluting with a mixed solvent of parts by weight, and YH-434 (trade name of Tohto Kasei Co., Ltd., amine type epoxy resin, main components are N, N, N ', N'). -Tetraglycidyldiaminodiphenylmethane, epoxy equivalent 121) 10 parts by weight of N-methyl-2-pyrrolidone 7
A solution having a nonvolatile content of 30% by weight diluted with a mixed solvent of 0 parts by weight and 30% by weight of N, N-dimethylformamide was added to obtain a modified polyamideimide resin composition having a nonvolatile content of 30% by weight.

Examples 9 to 12 In Example 8, the amounts of γ-aminopropyltriethoxysilane used were 0.3 parts by weight and 0.5 parts by weight, respectively.
Except for 1 part by weight and 2 parts by weight, the same operation as in Example 8 was performed to obtain a modified polyamideimide resin composition having a nonvolatile content of 30% by weight.

Example 13 1 part by weight of γ-aminopropyltriethoxysilane was added to 70 parts by weight of N-methyl-2-pyrrolidone based on 100 parts by weight of the resin component of the modified polyamideimide resin composition obtained in Comparative Example 3. And a solution containing 30 wt% of N, N-dimethylformamide diluted to a nonvolatile content of 30 wt%, and YH-434 (trade name of Toto Kasei Co., Ltd., amine type epoxy resin, epoxy equivalent 121). 10 parts by weight N
-Methyl-2-pyrrolidone 70 parts by weight and a solution containing 30 parts by weight of non-volatile components diluted with a mixed solvent of 30 parts by weight of N, N-dimethylformamide was added.
A modified polyamide imide resin composition of weight% was obtained.

Example 14 1 part by weight of γ-aminopropyltriethoxysilane was added to 70 parts by weight of N-methyl-2-pyrrolidone, based on 100 parts by weight of the resin content of the modified polyamideimide resin composition obtained in Comparative Example 2. And a solution containing 30 parts by weight of N, N-dimethylformamide diluted to a nonvolatile content of 30% by weight, and 1 part by weight of YH-434 70 parts by weight of N-methyl-2-pyrrolidone and N, N-. Diluted with a mixed solvent of 30 parts by weight of dimethylformamide to obtain a nonvolatile content of 30 wt%
Was added to obtain a modified polyamideimide resin composition having a nonvolatile content of 30% by weight.

Examples 15 and 16 The same operations as in Example 14 were carried out except that the amounts of YH-434 used were 3 parts by weight and 5 parts by weight, respectively, and the nonvolatile content was 30% by weight. A modified polyamideimide resin composition was obtained.

Example 17 N-β (aminoethyl) was added to 100 parts by weight of the resin content of the modified polyamideimide resin composition obtained in Comparative Example 2.
1 part by weight of γ-aminopropyltrimethoxysilane was added to N-
A solution obtained by diluting 70 parts by weight of methyl-2-pyrrolidone and 30 parts by weight of N, N-dimethylformamide to a nonvolatile content of 30% by weight, and 10 parts by weight of YH-434 as N-methyl-2-pyrrolidone. 70 parts by weight and N,
A solution having a nonvolatile content of 30% by weight diluted with a mixed solvent of 30 parts by weight of N-dimethylformamide was added to obtain a modified polyamideimide resin composition having a nonvolatile content of 30% by weight.

Example 18 In Example 17, γ- was used instead of 1 part by weight of N-β (aminoethyl) γ-aminopropyltrimethoxysilane.
Except that 1 part by weight of ureidopropyltriethoxysilane was used, the same operation as in Example 17 was performed to obtain a modified polyamideimide resin composition having a nonvolatile content of 30% by weight.

Example 19 In Example 17, γ-instead of 1 part by weight of N-β (aminoethyl) γ-aminopropyltrimethoxysilane was used.
Except for using 1 part by weight of glycidoxypropylmethyldimethoxysilane, the same operation as in Example 17 was carried out,
A modified polyamideimide resin composition having a nonvolatile content of 30% by weight was obtained.

Example 20 In Example 17, γ-instead of 1 part by weight of N-β (aminoethyl) γ-aminopropyltrimethoxysilane was used.
Except for using 1 part by weight of glycidoxypropyltrimethoxysilane, the same operation as in Example 17 was performed to obtain a modified polyamideimide resin composition having a nonvolatile content of 30% by weight.

Example 21 In Example 17, except that 1 part by weight of methylsilyltriisocyanate was used instead of 1 part by weight of N-β (aminoethyl) γ-aminopropyltrimethoxysilane.
The same operation as in Example 17 was performed to obtain a modified polyamideimide resin composition having a nonvolatile content of 30% by weight.

Example 22 The same procedure as in Example 21 was carried out except that the amount of methylsilyltriisocyanate used was 0.3 part by weight, and the modified polyamideimide having a nonvolatile content of 30% by weight was used. A resin composition was obtained.

Example 23 In the same manner as in Example 21, except that the amount of YH-434 used was 3 parts by weight, the same procedure as in Example 21 was carried out to obtain a modified polyamideimide resin composition having a nonvolatile content of 30% by weight. Obtained.

Example 24 In Example 17, AP was replaced with 1 part by weight of N-β (aminoethyl) γ-aminopropyltrimethoxysilane.
Except for using 1 part by weight of G-X (Kusumoto Kasei Co., Ltd. trade name, zircoaluminate-based coupling agent), the same operation as in Example 17 was performed, and the modified polyamideimide having a nonvolatile content of 30% by weight A resin composition was obtained.

Example 25 The same as Example 17 except that 1 part by weight of tetraisopropyl titanate was used in place of 1 part by weight of N-β (aminoethyl) γ-aminopropyltrimethoxysilane. The operation was performed to obtain a modified polyamideimide resin composition having a nonvolatile content of 30% by weight.

Example 26 Exactly the same as Example 17 except that 1 part by weight of titanium acetylacetonate was used in place of 1 part by weight of N-β (aminoethyl) γ-aminopropyltrimethoxysilane. And the nonvolatile content is 30% by weight.
A modified polyamideimide resin composition of was obtained.

Comparative Example 4 10 parts by weight of YH-434 was added to 70 parts by weight of N-methyl-2-pyrrolidone and N, N based on 100 parts by weight of the resin content of the modified polyamideimide resin composition obtained in Comparative Example 2.
-A solution containing 30 parts by weight of non-volatile components was added by diluting it with a mixed solvent of 30 parts by weight of dimethylformamide to obtain a polyamide-imide resin composition having a non-volatile content of 30% by weight.

Comparative Example 5 Comparative Example 4 except that 10 parts by weight of N, N, N ', N'-tetraglycidyl-m-xylenediamine was used in place of 10 parts by weight of YH-434 in Comparative Example 4. The same operation was performed to obtain a modified polyamideimide resin composition having a nonvolatile content of 30% by weight.

Comparative Example 6 The procedure of Comparative Example 4 was repeated, except that 10 parts by weight of Denacol EX-411 was used instead of 10 parts by weight of YH-434, and the nonvolatile content was 30%.
A modified polyamide imide resin composition of weight% was obtained.

Comparative Example 7 1 part by weight of γ-aminopropyltriethoxysilane was added to 70 parts by weight of N-methyl-2-pyrrolidone based on 100 parts by weight of the resin component of the polyamide-imide resin composition obtained in Comparative Example 1.
A solution having a nonvolatile content of 30% by weight diluted with a mixed solvent of 30 parts by weight of N and N-dimethylformamide was added to obtain a polyamide-imide resin composition having a nonvolatile content of 30% by weight.

Comparative Example 8 The same operation as in Comparative Example 7 was performed except that 1 part by weight of γ-ureidopropyltriethoxysilane was used in place of 1 part by weight of γ-aminopropyltriethoxysilane in Comparative Example 7. A polyamideimide resin composition having a nonvolatile content of 30% by weight was obtained.

Comparative Example 9 Polyamideimide having a nonvolatile content of 30% by weight was carried out in the same manner as in Comparative Example 8 except that the amount of γ-ureidopropyltriethoxysilane used was 5 parts by weight. A resin composition was obtained.

Comparative Example 10 N-methyl-2-pyrrolidone 70 parts by weight of 1 part by weight of γ-aminopropyltriethoxysilane was added to 100 parts by weight of the resin component of the polyamide-imide resin composition obtained in Comparative Example 1.
Parts by weight and a solution containing 30 parts by weight of N, N-dimethylformamide diluted to a nonvolatile content of 30% by weight, and 10 parts by weight of YH-434 70 parts by weight of N-methyl-2-pyrrolidone and N, N-dimethylformamide 3
A solution having a nonvolatile content of 30% by weight diluted with 0 part by weight of a mixed solvent was added to obtain a polyamide-imide resin composition having a nonvolatile content of 30% by weight.

Comparative Example 11 0.01 part by weight of γ-ureidopropyltriethoxysilane was added to 70 parts by weight of N-methyl-2-pyrrolidone based on 100 parts by weight of the resin content of the modified polyamideimide resin composition obtained in Comparative Example 3. 30 parts by weight of non-volatile components by diluting with a mixed solvent of 30 parts by weight of N, N-dimethylformamide and 30 parts by weight of N, N-dimethylformamide.
And a solution of 10 parts by weight of YH-434 diluted with a mixed solvent of 70 parts by weight of N-methyl-2-pyrrolidone and 30 parts by weight of N, N-dimethylformamide to a nonvolatile content of 30% by weight. The nonvolatile content is 30% by weight
A modified polyamideimide resin composition of was obtained.

Comparative Example 12 Comparative Example 8 except that the amount of γ-ureidopropyltriethoxysilane used was 60 parts by weight.
The same procedure as above was performed to obtain a modified polyamideimide resin composition having a nonvolatile content of 30% by weight.

The properties of the polyamide-imide resin compositions obtained in the above Comparative Examples and Examples were measured by the following methods, and the results are shown in Tables 1, 2, 3, 4 and 5. (1) Curable After coating the polyamide-imide resin composition on a glass plate of 20 × 50 mm to a film thickness of 20 μm, 180 ° C.
It was cured by heating for 60 minutes. This is 40 degreeC N-methyl-2
-It was evaluated by the extraction ratio obtained by the following formula 1 when immersed in pyrrolidone for 2 hours.

[0063]

(Equation 1)

(2) Storage stability The viscosity was evaluated by the rate of increase in viscosity after standing at 40 ° C. for 1 month (measured with a B-type viscometer). (3) Adhesion Cross-cut test A polyamide-imide resin composition was used as an aluminum plate A1050P (dimensions: 1 mm x 50 mm x) specified in JIS H4000.
150 mm) and then heat-cured at 180 ° C. for 60 minutes to form a coating film having a thickness of about 20 μm. Using the obtained coated plate, a test was performed according to JIS D0202. That is, after immersing the coated plate in a 1% sodium hydroxide aqueous solution,
A 1 mm grid 10 that reaches the aluminum plate base with a single-edged razor
0 pieces (10 pieces × 10 pieces) were made, a peeling test was performed 5 times with cellophane tape, and the ratio of cross-cuts (cross-cut residual rate;%) that was not peeled off was examined. Ring-on-disc test Orientec friction and wear tester (EF)
(M-III-F type) was used in accordance with JIS-K7218 (evaluation based on the time until peeling). Curing conditions: 170 ° C x 60 minutes Film thickness: 20 μm Base material: Aluminum Measuring conditions Surface pressure: 40 kg / cm ² Speed: 1.0 m / sec Atmosphere: Oil Temperature: Room temperature

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

[Table 3]

[0068]

[Table 4]

[0069]

[Table 5]

As is clear from the results shown in Table 1, Table 2, Table 3, Table 4 and Table 5, the polyamide-imide resin composition of the present invention shows curability, storage stability and adhesion of the cured product. Although excellent in all of them, Comparative Examples 1 to 3 lacked in curability and adhesion, and Comparative Examples 4 to 6 were insufficient in the ring-on-disk test, and Comparative Examples 7 and 9 Nos. 10 and 12 lacked storage stability, Comparative Example 8 had insufficient curability, and Comparative Example 11 lacked adhesion.

[0071]

EFFECTS OF THE INVENTION The polyamide-imide resin composition according to claim 1 or 2 has a cured product excellent in adhesion to a substrate and also in low-temperature curability and storage stability.
The polyamide-imide resin composition according to claim 3 is particularly excellent in low-temperature curability and storage stability. The polyamide-imide resin composition according to claim 4 is useful as a one-component heat-resistant paint.

Claims (4)

[Claims] 1. A polyamideimide resin having the general formula (I): [In the formula, R ₁ , R ₂ , R ₄ and R ₅ are each independently hydrogen,
Selected from the group consisting of a lower alkyl group, a phenyl group and a hydroxymethyl group, R ₃ and R ₆ are each independently selected from the group consisting of hydrogen, a methyl group and a phenyl group,
X is selected from the group consisting of an alkylene group having 1 to 8 carbon atoms and a phenylene group, and m is an integer of 0 or 1] to 100 parts by weight of a modified polyamideimide resin obtained by reacting a bisoxazoline compound represented by A polyamide-imide resin composition containing 0.05 to 50 parts by weight of a coupling agent. 2. The polyamideimide resin composition according to claim 1, wherein the coupling agent is at least one organometallic compound selected from the group consisting of organosilane compounds, organotitanium compounds and organozirconium compounds. 3. The polyamideimide resin composition according to claim 1, which further comprises an epoxy resin. 4. The polyamide-imide resin composition according to claim 1, which is diluted with an organic solvent to a resin content of 10 to 40% by weight.