JPH10330449A - Production of modified polyamideimide resin and modified polyamideimide resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin that has low elasticity, low warpage, high adhesion and is further imparted with excellent heat resistance, economical advantage and cold hardenability by carrying out the reactions in a nitrogen-free polar solvent. SOLUTION: (A) An aromatic polyisocyanate, (B) a tricarboxylic acid bearing acid anhydride group and (C) a dicarboxylic acid of formula I ((a), (b) are each 0-80 where a+b=1-80, a/b ratio =1/0-0/1) or formula II ((c), (d) are each 0-80, c+d=1-80, c/d ratio is 1/0-0/1) are mixed and allowed to react with one another in (D) a nitrogen-free polar solvent (suitably γ-butyrolactone). In a preferred embodiment, a mixture of the component A, the component B, the component C and (E) a dimer acid are allowed to react with one another in the component D at a molar ratio (B/C) of 0.1/0.9-0.9/0.1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a modified polyamideimide resin and a modified polyamideimide resin.

[0002]

2. Description of the Related Art In recent years, in the field of electronic parts, there has been a strong demand for the development of inexpensive heat-resistant resins which are excellent in heat resistance, low warpage to a substrate, adhesion and workability, and are inexpensive as the size and weight are reduced. Have been. In order to achieve low warpage and high adhesion, a method of reducing the elasticity of a polyimide resin or a polyamideimide resin which is a heat-resistant resin is generally used. In consideration of economy, a method of modifying a polyamideimide resin obtained by using an aromatic polyisocyanate and a trivalent polycarboxylic acid having an acid anhydride group as a starting material with a polybutadiene dicarboxylic acid is excellent.

However, when the above-mentioned modified polyamideimide resin is synthesized with a high-boiling nitrogen-containing polar solvent such as N-methyl-2-pyrrolidone which is a conventional synthesis solvent, a cured film is formed from the obtained varnish. Therefore, curing at a high temperature of 200 ° C. or higher is necessary, and there is a problem that electronic members are thermally degraded during curing.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a modified polyamideimide resin having a low modulus of elasticity, low warpage, high adhesion, excellent heat resistance, economical efficiency, and the like. It is intended to provide a method for producing a modified polyamide-imide resin and a modified polyamide-imide resin.

[0005]

That is, the present invention provides:
(A) an aromatic polyisocyanate, (b) a derivative of a trivalent carboxylic acid having an acid anhydride group, and (c) a general formula (I) or (II)

[0006]

Embedded image (Where a and b are each an integer of 0 to 80, and a + b
Is 1 to 80, and the ratio of a / b is 1/0 to 0/1. )

[0007]

Embedded image (Where c and d are each an integer of 0 to 80, and c + d
Is 1 to 80, and the ratio of c / d is 1/0 to 0/1. A) reacting a mixture of dicarboxylic acids represented by the formula (1) in a solvent containing a non-nitrogen-containing polar solvent.

[0008]

DETAILED DESCRIPTION OF THE INVENTION As the aromatic polyisocyanate of the component (a) used in the present invention, for example, 4,4 '
-Diphenylmethane diisocyanate, trisilylene diisocyanate, xylylene diisocyanate, 4,4 '
-Diphenyl ether diisocyanate, 4,4'-
[2,2-bis (4-phenoxyphenyl) propane]
Diisocyanate, biphenyl-4,4'-diisocyanate, biphenyl-3,3'-diisocyanate, biphenyl-3,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 2,
2'-dimethoxybiphenyl-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-2,6
-Diisocyanate and the like. These alone,
Alternatively, they can be used in combination. If necessary, part of this is hexamethylene diisocyanate, 2,
2,4-trimethylhexamethylene diisocyanate,
Used in place of aliphatic, alicyclic isocyanates such as isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-xylene diisocyanate, lysine diisocyanate, and polyisocyanates having three or more functions. Alternatively, those stabilized with an appropriate blocking agent may be used to avoid aging.

Considering the balance among heat resistance, solubility, mechanical properties, cost and the like, 4,4'-diphenylmethane diisocyanate is particularly preferred.

As the trivalent carboxylic acid derivative having an acid anhydride group as the component (b) used in the present invention, for example, a compound represented by the following general formula (III) or (IV) is preferably used. There is no particular limitation as long as it is a trivalent carboxylic acid derivative having an acid anhydride group.
Considering cost and the like, trimellitic anhydride is particularly preferred.

[0011]

Embedded image (Where R represents hydrogen, an alkyl group having 1 to 10 carbon atoms or a phenyl group, and Y represents —CH ₂ —, —CO—,
—SO ₂ — or —O— is shown. In addition to these, if necessary, tetracarboxylic dianhydride (pyromellitic dianhydride, 3,3 ′, 4,4 ′)
-Benzophenonetetracarboxylic dianhydride, 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,
1,1,1,3,3,3-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, butanetetra Carboxylic anhydride, bicyclo- [2,2,2] -oct-7-ene-2: 3: 5:
6-tetracarboxylic dianhydride, aliphatic dicarboxylic acid (succinic acid, glutaric acid, adipic acid, azelaic acid,
Suberic acid, sebacic acid, decandioic acid, dodecandioic acid), aromatic dicarboxylic acids (isophthalic acid, terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid) and the like can be used. The amount of these components is preferably less than 50 mol% based on the total amount of the components (b) and (c).

The dicarboxylic acid represented by the general formula (I) or (II) as the component (c) used in the present invention includes, for example, Nisso PB series manufactured by Nippon Soda Co., Ltd., and Ube Industries, Ltd. Hycar RLP Series, T
HC-polymer series manufactured by hiokol, G
general Tire's Telagen series, Phillips Petroleum's Butt
artet series and the like. The dicarboxylic acid having a number average molecular weight of 1,000 to 7,000 is preferably used. Further, the ratio of a / b and the ratio of c / d are 0.1.
Those having a ratio of 9 / 0.1 to 0.1 / 0.9 are preferably used.
~ 0.1 / 0.9

In the dicarboxylic acid represented by the above general formula (I) or (II), each structural unit of the dicarboxylic main chain may be present at random.

In the present invention, if necessary, a dimer acid (d) can be reacted in addition to the components (a), (b) and (c). As the dimer acid of the component (d), for example, a dimer produced by polymerization of an unsaturated fatty acid represented by the following general formula (V) and a hydride thereof can be used.

[0015]

Embedded image These can be used alone or in combination. Further, dimer acid usually contains a small amount of trimer acid and monomeric acid, but there is no particular problem if it is used as it is as a raw material of the modified polyamideimide resin.

Commercially available dimer acids include, for example, Haridimer series manufactured by Harima Chemicals Co., Ltd. and Empol series manufactured by Hakusui Henkel Co., Ltd.

In the present invention, a trivalent carboxylic acid derivative having an acid anhydride group as the component (b), a dicarboxylic acid represented by the general formula (I) or (II) as the component (c) and (d)
The reaction ratio of the component dimer acid is represented by (b) component / [(c) +
(D)] The component (molar ratio) is 0.1 / 0.9 to 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. 0.1 /
If it is less than 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 adhesion tends to decrease.

In the present invention, when the component (d) is used, the amount of the component (c) and the component (d) used is the ratio of the component (c) /
Component (d) (molar ratio) is 0.1 / 0.9 to 0.9 / 0.
1, preferably 0.2 / 0.8 to 0.8 /
0.2 is more preferable, and 0.3 / 0.7-
It is particularly preferred to be 0.7 / 0.3. 0.1 /
If the ratio is less than 0.9, the solubility of the resin in the solvent is reduced, so that the workability tends to decrease. If the ratio exceeds 0.9 / 0.1, the storage stability tends to decrease.

The components (a) and (b) according to the present invention,
The amount of the components (c) and (d) used is such that the ratio of the isocyanate group to the carboxyl group and the acid anhydride group is set at 0.1.
It is preferably from 7 to 1.5, and more preferably around 1.0. If less than 0.7 or more than 1.5,
It tends to be difficult to increase the molecular weight of the resin.

The reaction in the process for producing the modified polyamideimide resin of the present invention is carried out by heat condensation in a solvent containing a non-nitrogen-containing polar solvent while removing carbon dioxide gas liberated from the reaction system. Will be

As the non-nitrogen-containing polar solvent used in the reaction, for example, dimethyl sulfoxide, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, γ-butyrolactone, sulfolane and the like are preferably used. Γ-butyrolactone, which can impart properties, is most preferred. The non-nitrogen-containing polar solvent is preferably contained in the solvent in an amount of 50% by weight or more.

When γ-butyrolactone and cyclohexane are used in combination such that the weight ratio of γ-butyrolactone / cyclohexanone is preferably 99/1 to 50/50, turbidity and gelation of the varnish during the reaction can be prevented. . The weight ratio is more preferably from 97/3 to 60/40, particularly preferably from 95/5 to 70/30. If the ratio is less than 99/1, as the scale of the synthesis increases, the inside of the synthesis system becomes uneven during the heat synthesis, and the varnish tends to be turbid or partially gelled. 50 /
If it exceeds 50, the amide imide formation reaction is inhibited, and it tends to be difficult to increase the molecular weight of the resin.

The amount of the solvent used is preferably 1.0 to 5.0 times (by weight) the polyamideimide resin to be produced. If it is less than 1.0 times, 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 it exceeds 5.0 times, the reaction rate tends to decrease.

The reaction temperature is preferably from 80 to 200 ° C., more preferably from 100 to 180 ° C., and particularly preferably from 120 to 160 ° C. 8
If the temperature is lower than 0 ° C., the reaction time becomes too long, and if it exceeds 200 ° C., the volatilization of the solvent becomes remarkable. The reaction time can be appropriately selected depending on the scale of the synthesis scale and the reaction conditions employed.

Number average molecular weight of the modified polyamideimide resin of the present invention obtained by the production method of the present invention (measured by GPC method and calculated using a calibration curve with standard polystyrene)
Is preferably 4,000 to 30,000,
More preferably, 5,000 to 28,000,
It is particularly preferred to be 5,000 to 24,000.
When the number average molecular weight is less than 4,000, the film properties such as heat resistance tend to decrease, and when the number average molecular weight exceeds 30,000, it becomes difficult to dissolve in a solvent and easily insoluble during synthesis. Also, the workability tends to be poor.

The acid value (KOH mg / g) of the modified polyamideimide resin of the present invention is preferably 1 to 60, more preferably 3 to 50, and more preferably 5 to 50.
Is particularly preferred. If the acid value is less than 1, the curability tends to decrease, and if it exceeds 60, the viscosity stability tends to deteriorate.

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.

The modified polyamideimide resin of the present invention includes:
In order to improve the curability, a stabilized polyisocyanate compound may be added.

Examples of the stabilized polyisocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, diphenyl sulfone diisocyanate, triphenylmethane diisocyanate, hexamethylene diisocyanate, and 3-isocyanatomethyl-isocyanate.
3,5,5-trimethylcyclohexyl isocyanate, 3-isocyanatoethyl-3,5,5-triethylcyclohexyl isocyanate, diphenylpropane diisocyanate, phenylene diisocyanate, cyclohexylylene isocyanate, 3,3'-diisocyanate dipropyl ether, triphenyl Polyisocyanates such as methane triisocyanate and diphenyl ether-4,4'-diisocyanate or multimers thereof are converted into phenols such as phenol and xylenol, oximes, imides, mercaptans, alcohols, ε-caprolactam, ethyleneimine, α -Blocked with pyrrolidone, diethyl malonate, sodium bisulfite, boric acid, etc., and examples thereof include Sumitomo Bayer Urethane Co., Ltd. SUMODULE BL3175, Α
P stable, $ P-12 stable, CT stable, BL1100, BL1190, BL1265, $ P
-2170 Stable, BL4165, TPLS-27
59, Desmo Cup 11, 12, Cleran UT, U
I, U12, TPKL5-2668, TPLS-272
7, Desmotherm 2170, 2265, WD2502 manufactured by Hitachi Chemical Co., Ltd., or the like, and one or more of these can also be used.

As a method for adding the stabilized polyisocyanate compound, the stabilized polyisocyanate compound to be added may be dissolved in the same solvent as the solvent contained in the modified polyamide-imide resin in advance and then added. You may add to a polyamide imide resin.

The amount of the stabilizing polyisocyanate compound is based on 100 parts by weight of the modified polyamideimide resin.
0.1 to 40 parts by weight, preferably 0.5 to 3 parts by weight.
More preferably, it is 0 parts by weight. When the amount added is 0.
If the amount is less than 1 part by weight, the curability may be insufficiently improved, and if it exceeds 40 parts by weight, the viscosity stability tends to be poor.

The modified polyamideimide resin of the present invention includes:
An epoxy resin can be added to improve the curability.

As the epoxy resin, for example, Epicoat 815, 825, 82 manufactured by Yuka Shell Epoxy Co., Ltd.
7, 828, 834, 1001, 1004, 1007,
Bisphenol II type epoxy resin such as 1009, Epicoat 152, 154, EPPN-2 manufactured by Nippon Kayaku Co., Ltd.
01, phenol novolak type epoxy resin such as DEN-438 manufactured by Dow Chemical Company, EO manufactured by Nippon Kayaku Co., Ltd.
O-Cresol novolak type epoxy resins such as CN-102S, 103S, 104S, etc., Epon 1031S manufactured by Yuka Shell Epoxy Co., Ltd., Araldite 0163 manufactured by Ciba Geigy Co., Ltd., and Denacol EX manufactured by Nagase Kasei Co., Ltd.
-611, EX-614, EX-614B, EX-62
2, EX-512, EX-521, EX-421, EX
-411, EX-321 and other multifunctional epoxy resins, Yuka Shell Epoxy Co., Ltd. Epicoat 604, Toto Kasei Co., Ltd. YH-434, Mitsubishi Gas Chemical Co., Ltd. TE
TRAD-X, TETRAD-C, manufactured by Nippon Kayaku Co., Ltd.
GAN, Sumitomo Chemical Co., Ltd. ELM-120 and other amine-type epoxy resins, Ciba-Geigy Co., Ltd. Araldite PT
Heterocycle-containing epoxy resin such as 810, ER manufactured by UCC
An alicyclic epoxy resin such as L4234, 4299, 4221, or 4206 can be used, and one or more of these can also be used.

As a method of adding the epoxy resin, the epoxy resin to be added may be dissolved in the same solvent as that contained in the modified polyamideimide resin in advance and then added.
Further, it may be directly added to the modified polyamideimide resin.

The amount of the epoxy resin to be added is preferably 1 to 10 parts by weight based on 100 parts by weight of the modified polyamideimide resin. If the amount is less than 1 part by weight, the curability may not be sufficiently improved, and if it exceeds 40 parts by weight, the viscosity stability tends to be poor.

The modified polyamideimide resin of the present invention includes:
An amine compound can be added to improve the curability.

As the amine compound, for example, 4,
Primary amines such as 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether and 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 (dimethylaminomethyl) phenol, N, N'-dimethylpiperazine,
Tertiary amines such as pyridine, picoline, 1,2,2,6,6-pentamethyl-4-piperidinol and triethylamine, dicyandiamide and the like can be used.

The amount of the amine compound is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the modified polyamideimide resin. If the added amount is less than 0.1 part by weight, the curability may be insufficiently improved,
If it exceeds 10 parts by weight, viscosity stability tends to be poor.

The modified polyamideimide resin of the present invention includes:
An organoaluminum compound, an organosilane compound, an organotitanium compound, if necessary to improve its adhesion,
An organic zirconia compound or the like can be added.

The organic aluminum compound is not particularly limited. For example, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum dipropylate, aluminum monoacetylacetonate bis (ethyl acetoacetate) ), Aluminum tris (acetylacetonate), aluminum monoisopropoxy monooleoxyethyl acetoacetate, aluminum di-n-butoxide-mono-ethyl acetoacetate, aluminum di-iso-propoxide-mono-ethyl acetoacetate Aluminum chelate compounds such as, aluminum isopropylate, mono-sec-butoxyaluminum diisopropylate,
Aluminum alcoholate such as aluminum-sec-butylate and aluminum ethylate can be used, and one or more of these can also be used.

The amount of the organic aluminum compound added is 0.05 to 100 parts by weight of the modified polyamideimide resin.
It is preferable to set it to 50 parts by weight. This addition amount
If the amount is less than 0.05 part by weight, the adhesion may be insufficiently improved, and if it exceeds 50 parts by weight, the viscosity stability tends to be poor.

The organic silane compound is not particularly restricted but includes, for example, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ- Methacryloxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldi Ethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, n-
β (aminoethyl) -γ-aminopropylmethylmethoxydimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane , 3-
Aminopropyl-methyl-diethoxysilane, 3-ureidopropyltriethoxysilane, 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, -beta (N-vinylbenzyl aminoethyl)-.gamma.-aminopropyltrimethoxysilane,
Octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldichlorosilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane, trimethylsilyl isocyanate, dimethylsilyl isocyanate, methylsilyl tri Isocyanate,
Vinylsilyl triisocyanate, phenylsilyl triisocyanate, tetraisocyanate silane, ethoxy silane isocyanate and the like can be used, and one or more of these can also be used.

The amount of the organic silane compound is 0.05 to 50 parts by weight based on 100 parts by weight of the modified polyamideimide resin.
It is preferable to use parts by weight. When the amount added is 0.05
If the amount is less than 10 parts by weight, the adhesion may be insufficiently improved. If the amount exceeds 50 parts by weight, the viscosity stability tends to be poor.

The organic titanium compound is not particularly limited. For example, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate Isopropyl tricumylphenyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (n-aminoethyl-aminoethyl) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate,
Tetra (2,2-diallyloxymethyl-1-butyl)
Bis (ditridecyl) phosphite titanate, dicumylphenyloxyacetate titanate, bis (dioctylpyrophosphate) oxyacetate titanate, tetraisopropyl titanate, tetra-n-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 thioethanolamine, polyhydroxytitanium stearate, tetra Methyl orthotitanate,
Tetraethyl orthotitanate, tetrapropyl orthotitanate, tetraisobutyl orthotitanate, stearyl titanate, cresyl titanate monomer, cresyl titanate polymer, di-isopropoxy-bis-
(2,4-pentadionate) -titanium (IV),
Use di-isopropyl-bis-triethanolamino-titanate, octylene glycol titanate HV, tetra-n-butoxytitanium polymer, tri-n-butoxytitanium monostearate polymer, tri-n-butoxytitanium monostearate and the like. And one or more of these can also be used.

The addition amount of the organic titanium compound is 0.05 to 50 parts by weight based on 100 parts by weight of the modified polyamideimide resin.
It is preferable to use parts by weight. When the amount added is 0.05
If the amount is less than 10 parts by weight, the adhesion may be insufficiently improved. If the amount exceeds 50 parts by weight, the viscosity stability tends to be poor.

The organic zirconia compound is not particularly restricted but includes, for example, tetrapropyl zircoaluminate,
Tetrabutyl zirconate, tetra (triethanolamine) zirconate, tetraisopropyl zirconate, zirconium acetylacetonate, acetylacetone zirconium butyrate, zirconium lactate, zirconium butyrate stearate, @ PG-X
(CAVEDON CHEMICAL CO., IN
C. And the like, and one or more of these can be used.

The addition amount of the organic zirconia compound is 0.05 to 100 parts by weight of the modified polyamideimide resin.
Preferably it is 50 parts by weight. If the amount added is 0.
If the amount is less than 05 parts by weight, the adhesion may be insufficiently improved, and if it exceeds 50 parts by weight, the viscosity stability tends to be poor.

The modified polyamideimide resin of the present invention may be, for example, an overcoat material for an electronic component, a liquid sealing material, a varnish for an enameled wire, an impregnated varnish for electrical insulation, a cast varnish,
Varnishes for sheets, varnishes for metal-clad laminates, varnishes for friction materials, interlayer insulating films, surface protection films in the field of printed circuit boards, etc., combined with substrates such as mica and glass cloth.
It can also be used for solder resist layers, adhesive layers, and electronic components such as semiconductor elements.

[0049]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 500 equipped with a stirrer, a cooling pipe, a nitrogen introducing pipe and a thermometer
ml, 4,4'- as the component (a)
15.0 g of diphenylmethane diisocyanate (0.0
6 mol), trimellitic anhydride as component (b) 5.
76 g (0.03 mol), Niss as component (c)
o PB C-1000 (trade name, manufactured by Nippon Soda Co., Ltd., a / b of the general formula (I) = 0.112 / 0.888, number average molecular weight about 1,930) 57.93 g (0.03 mol) And γ-butyrolactone (165.25 g),
After raising the temperature to 0 ° C., the mixture was reacted for 5 hours to obtain a resin having a number average molecular weight of 18,600. The obtained resin was diluted with cyclohexanone to obtain a modified polyamideimide resin having a nonvolatile content of 25% by weight.

Example 2 The same operation as in Example 1 was carried out except that the reaction time was changed from 5 hours to 2 hours, to obtain a number average molecular weight of 9,300.
A modified polyamideimide resin having a nonvolatile content of 25% by weight was obtained.

Example 3 The same flask as in Example 1 was charged with 4, as the component (a).
12.0 g of 4'-diphenylmethane diisocyanate,
(0.048 mol) and tolylene diisocyanate
208 g (0.012 mol), 5.76 g of trimellitic anhydride as the component (b), (0.03 mol), (c)
Nisso PB C-1000 as a component 57.
93 g (0.03 mol) and γ-butyrolactone 16
After charging 3.59 g, the temperature was raised to 160 ° C., and the mixture was reacted for 2 hours to obtain a resin having a number average molecular weight of 10,100. The obtained resin was diluted with cyclohexanone to obtain a modified polyamideimide resin having a nonvolatile content of 25% by weight.

Example 4 In the same flask as in Example 1, 6.25 of 4,4'-diphenylmethane diisocyanate as the component (a) was added.
g (0.025 mol), 2.4 g (0.0125 mol) of trimellitic anhydride as the component (b), HYCAR CTB 2000 × 162 as the component (c) (trade name, manufactured by Ube Industries, Ltd. A / b of the formula (I) = 0.88 /
0.12, number average molecular weight about 5,905) 73.81 g
(0.0125 mol) and γ-butyrolactone.
After charging 17 g and raising the temperature to 160 ° C., the mixture was reacted for 6 hours to obtain a resin having a number average molecular weight of 12,700. The obtained resin was diluted with cyclohexanone to obtain a modified polyamideimide resin having a nonvolatile content of 25% by weight.

Example 5 The same operation as in Example 2 was carried out except that the solvent to be diluted after the completion of the synthesis was changed from cyclohexanone to γ-butyrolactone, and the number average molecular weight was 17,600 and the non-volatile content was 25% by weight. A polyamide imide resin was obtained.

Comparative Example 1 In the same flask as in Example 1, 51.0 g (0.204 mol) of 4,4'-diphenylmethane diisocyanate was added.
38.4 g (0.2 mol) of trimellitic anhydride and N-
187.74 g of methyl-2-pyrrolidone was charged and 13
After the temperature was raised to 0 ° C., the reaction was carried out for 4 hours to obtain a resin having a number average molecular weight of 17,000. The obtained resin was diluted with N, N-dimethylformamide to obtain a modified polyamideimide resin having a nonvolatile content of 25% by weight.

Comparative Example 2 In the same flask as in Example 1, 4 was used as the component (a).
15.0 g of 4'-diphenylmethane diisocyanate
(0.06 mol), 5.7 g (0.03 mol) of trimellitic anhydride as component (b), Ni as component (c)
ssoPB C-1000, 57.93 g (0.03 mol) and N-methyl-2-pyrrolidone 165.25 g were charged, heated to 130 ° C., and reacted for 4 hours.
A resin having a number average molecular weight of 16,500 was obtained. The obtained resin was diluted with N, N-dimethylformamide,
5% by weight of a modified polyamideimide resin was obtained.

Comparative Example 3 In the same flask as in Example 1, 4 was used as the component (a).
55.0 g of 4'-diphenylmethane diisocyanate
(0.22 mol), 42.24 g (0.22 mol) of trimellitic anhydride as the component (b) and 204.20 g of γ-butyrolactone were charged, the temperature was raised to 160 ° C., and the mixture was reacted for 5 hours. A resin having a number average molecular weight of 19,500 was obtained. Dilute the obtained resin with cyclohexanone,
A modified polyamideimide resin having a nonvolatile content of 25% by weight was obtained.

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

(1) Adhesion Copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., MCL E-6)
After the surface of 7) was buffed and scrub mechanically polished, the resulting modified polyamideimide resin or polyamideimide resin was applied. After drying at 90 ° C. for 480 seconds, the coating film obtained by heating at 160 ° C. for 60 minutes in an air atmosphere (film thickness: 30)
μm), the initial and pressure cooker test (PCT, conditions: 121 ° C., 2.0265 × 10 ⁵ P)
a, 500 hours).

The cross cut test was carried out with a cutter knife of 1 m.
Scratch on the grid so that 100 squares can be formed with m, peel it off with cellophane tape according to JIS standard (JIS K5400), and express the number of remaining squares for 100 squares Is the way.

(2) Glass Transition Temperature The obtained modified polyamideimide resin was applied on a glass plate and dried at 90 ° C. for 480 seconds.
The coating film (thickness: 30 μm) obtained by heating at 0 ° C. for 60 minutes was measured by TMA-120 manufactured by Seiko Instruments Inc.

(3) Modulus of elasticity A modified polyamide-imide resin or a polyamide-imide resin is coated on a glass plate and dried at 90 ° C. for 480 seconds.
About the coating film (thickness: 30 μm) obtained by heating at 160 ° C. for 60 minutes in an air atmosphere, the tensile elastic modulus was measured under the following conditions using a universal testing machine (Tensilon UCT-5T manufactured by Orientec). .

Measurement temperature: 23 ° C. Tensile speed: 5 mm / min

[0064]

[Table 1] Example 6 500 equipped with a stirrer, a cooling pipe, a nitrogen introducing pipe and a thermometer
ml, 4,4'- as the component (a)
25.0 g of diphenylmethane diisocyanate (0.1
Mol), 9.6 of trimellitic anhydride as component (b)
g (0.05 mol), Nisso as component (c)
38.62 g (0.02 mol) of PB C-1000,
(D) Empol 1008 as a component (trade name, manufactured by Henkel Hakusui Co., Ltd., dimer acid (dimer of linolenic acid))
17.1 g (0.03 mol) and γ-butyrolactone 1
After charging 89.67 g, the temperature was raised to 160 ° C., and the mixture was reacted for 2 hours to obtain a resin having a number average molecular weight of 15,900. The obtained resin was diluted with cyclohexanone to obtain a modified polyamideimide resin having a nonvolatile content of 25% by weight.

Example 7 The same operation as in Example 6 was carried out except that the reaction time was changed from 2 hours to 3 hours, to obtain a number average molecular weight of 20,000.
0, a modified polyamideimide resin having a nonvolatile content of 25% by weight was obtained.

Example 8 The same operation as in Example 6 was carried out except that the reaction time was changed from 2 hours to 4.5 hours, to obtain a number average molecular weight of 28,0.
Thus, a modified polyamideimide resin having a nonvolatile content of 25% by weight was obtained.

Example 9 In a flask similar to that of Example 6, 25.0 of 4,4'-diphenylmethane diisocyanate as the component (a) was added.
g (0.1 mol), 9.6 g (0.05 mol) of trimellitic anhydride as the component (b), and N as the component (c)
57.93 g of isso PBC-1000 (0.03
Mol), 17.1 g (0.03 mol) of Empol 1008 (trade name, manufactured by Henkel Hakusui Co., Ltd., dimer acid (dimer of linolenic acid)) as component (d) and 218.25 g of γ-butyrolactone were charged. After raising the temperature to 160 ° C., the mixture was reacted for 2 hours to obtain a resin having a number average molecular weight of 10,100. Dilute the obtained resin with cyclohexanone,
A modified polyamideimide resin having a nonvolatile content of 25% by weight was obtained.

Comparative Example 4 In the same flask as in Example 6, 4 was added as the component (a).
30.0 g of 4'-diphenylmethane diisocyanate
(0.12 mol), 11.52 g (0.06 mol) of trimellitic anhydride as the component (b), Empol 1008 (trade name, manufactured by Henkel Hakusui Co., Ltd., dimer acid (linolenic acid) as the component (d) 34.2 g)
(0.06 mol) and γ-butyrolactone 227.16
g, heated to 160 ° C., and reacted for 3 hours to obtain a resin having a number average molecular weight of 20,500. The obtained resin was diluted with cyclohexanone to obtain a modified polyamideimide resin having a nonvolatile content of 25% by weight.

The properties of the modified polyamideimide resin and the polyamideimide resin obtained in the above Examples and Comparative Examples were measured by the above-mentioned methods. The results are shown in Table 2.

[0070]

[Table 2] Example 10 In a 1-liter four-necked flask equipped with a stirrer, a cooling pipe, a nitrogen introducing pipe, and a thermometer, 4,4′-component (a) was added.
75.0 g of diphenylmethane diisocyanate (0.3
Mole), trimellitic anhydride as component (b) 28.
8 g (0.15 mol), Nisso as component (c)
115.86 g (0.06 mol) of PB C-1000, 51.3 g (0.09) of Empol 1008 (trade name, manufactured by Henkel Hakusui Co., Ltd., dimer acid (dimer of linolenic acid)) as component (d) Mol), 452.89 g of γ-butyrolactone and 50.32 g of cyclohexanone
After heating to 160 ° C., the mixture was reacted for 2.5 hours to obtain a resin having a number average molecular weight of 18,500. The obtained resin was diluted with cyclohexanone to obtain a modified polyamideimide resin having a nonvolatile content of 25% by weight.

Example 11 The flask of Example 10 was made up to 3 liters, and 4,4'-diphenylmethane diisocyanate 2 as the component (a) was used.
25.0 g, (0.9 mol), 86.4 g (0.45 mol) of trimellitic anhydride as the component (b), Nisso PB C-1000 347. as the component (c).
58 g (0.18 mol), Empo as component (d)
l 1008 153.9 g (0.27 mol), γ-butyrolactone 1358.67 g and cyclohexanone 1
After charging 50.96 g, the temperature was raised to 160 ° C., and the mixture was reacted for 3 hours to obtain a resin having a number average molecular weight of 18,000.
The obtained resin was diluted with cyclohexanenone to obtain a modified polyamideimide resin having a nonvolatile content of 25% by weight.

Example 12 The flask of Example 10 was made up to 5 liters, and 4,4'-diphenylmethane diisocyanate 3 was used as the component (a).
75.0 g, (1.5 mol), 144.0 g of trimellitic anhydride as the component (b), (0.75 mol),
(C) Nisso PB C-1000 as a component
579.3 g (0.3 mol), Em as the component (d)
pol 1008 256.5 g (0.45 mol), γ
-After charging 264.45 g of butyrolactone and 251.60 g of cyclohexanone and heating to 160 ° C.,
The reaction was carried out for 3.5 hours to obtain a resin having a number average molecular weight of 18,900. Dilute the obtained resin with cyclohexanone,
A modified polyamideimide resin having a nonvolatile content of 25% by weight was obtained.

Example 13 Instead of 452.89 g of γ-butyrolactone and 50.32 g of cyclohexanone of Example 10, 301.93 g of γ-butyrolactone and 201.28 g of cyclohexanone were used.
The same procedure as in Example 10 was repeated except that g was used.
After raising the temperature to ℃, the reaction was carried out for 8.0 hours to obtain a modified polyamideimide resin having a number average molecular weight of 18,200 and a nonvolatile content of 25% by weight.

Example 14 Instead of 1358.6 g of gamma-butyrolactone and 150.96 g of cyclohexanone of Example 11, 905.78 g of gamma-butyrolactone and 603.8 g of cyclohexanone
Charged in the same manner as in Example 11 except that 5 g was used.
After the temperature was raised to 0 ° C., the mixture was reacted for 9.0 hours to obtain a modified polyamideimide resin having a number average molecular weight of 17,800 and a nonvolatile content of 25% by weight.

Example 15 In place of 226.45 g of γ-butyrolactone and 251.60 g of cyclohexanone of Example 12, 1509.63 g of γ-butyrolactone and 100 parts of cyclohexanone were used.
Except for using 6.42 g, the same procedure as in Example 12 was followed, the temperature was raised to 160 ° C., and the mixture was reacted for 10.5 hours to obtain a modified polyamideimide resin having a number average molecular weight of 18,000 and a nonvolatile content of 25% by weight. I got

Example 16 The flask of Example 10 was made up to 500 ml, and 4,4'-diphenylmethane diisocyanate 2 as the component (a) was used.
5.0 g (0.1 mol), 9.6 g (0.05 mol) of trimellitic anhydride as the component (b), 38.62 g of NissoPB C-1000 as the component (c)
(0.02 mol), Empol 1 as component (d)
008 17.1 g (0.03 mol) and 167.74 g of γ-butyrolactone were charged, heated to 160 ° C., and reacted for 2 hours to obtain a resin having a number average molecular weight of 19,100. The obtained resin was diluted with cyclohexanone to obtain a modified polyamideimide resin having a nonvolatile content of 25% by weight.

Comparative Example 5 In the flask of Example 10, 4,4'-
112.5 g of diphenylmethane diisocyanate,
(0.45 mol), 43.2 g of trimellitic anhydride as component (b), (0.225 mol), 128.25 g of Empol 1008 (0.22 mol) as component (d)
54.6 mol), 474.61 g of γ-butyrolactone and 52.73 g of cyclohexanone, heated to 160 ° C., and reacted for 2.5 hours to obtain a number average molecular weight of 17,9.
00 resin was obtained. The obtained resin was diluted with cyclohexanone to obtain a modified polyamideimide resin having a nonvolatile content of 25% by weight.

The properties of the modified polyamideimide resin and the polyamideimide resin obtained in the above Examples and Comparative Examples were measured by the above-mentioned methods, and the results are shown in Table 3.

[0079]

[Table 3] As is clear from the results shown in Table 3, the modified polyamideimide resin according to the present invention (Examples 10 to 15) uses a mixed solvent of γ-butyrolactone and cyclohexanone as a solvent at the time of synthesis, and the ratio of γ-butyrolactone is When it is large, a modified polyamideimide resin having excellent varnish characteristics and cured product characteristics can be obtained regardless of the size of the synthetic scale.

However, when the synthesis solvent is only γ-butyrolactone, a good result is obtained as in Example 16 when the synthesis scale is small, but when the scale-up is performed, varnish becomes turbid and microgels are generated, and the varnish becomes stable. There is a tendency that excellent synthesis results cannot be obtained. When the amount of cyclohexanone increases in the mixed solvent, it tends to be difficult to increase the molecular weight of the resin. In Comparative Example 5 not using the component (c), the solubility of the resin in the solvent is poor,
Lack of storage stability.

[0081]

The modified polyamideimide resin of the present invention is
Low modulus, low warpage, and excellent adhesion.

According to the production method of the present invention, the above-mentioned modified polyamideimide resin can be produced with good workability, economy and productivity.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Taichi Sakata 4-3-1-1, Higashicho, Hitachi City, Ibaraki Prefecture Inside the Ibaraki Research Laboratory, Hitachi Chemical Co., Ltd.

Claims (7)

[Claims] (1) an aromatic polyisocyanate,
(B) a derivative of a trivalent carboxylic acid having an acid anhydride group and (c) a compound of the general formula (I) or (II) (Where a and b are each an integer of 0 to 80, and a + b
Is 1 to 80, and the ratio of a / b is 1/0 to 0/1. ) (Where c and d are each an integer of 0 to 80, and c + d
Is 1 to 80, and the ratio of c / d is 1/0 to 0/1. A method for producing a modified polyamideimide resin, comprising reacting a mixture of dicarboxylic acids represented by the formula (1) in a solvent containing a non-nitrogen-containing polar solvent. 2. (a) an aromatic polyisocyanate,
(B) a derivative of a trivalent carboxylic acid having an acid anhydride group,
(C) Formula (I) or (II) (Where a and b are each an integer of 0 to 80, and a + b
Is 1 to 80, and the ratio of a / b is 1/0 to 0/1. ) (Where c and d are each an integer of 0 to 80, and c + d
Is 1 to 80, and the ratio of c / d is 1/0 to 0/1. A method for producing a modified polyamideimide resin, comprising reacting a mixture of the dicarboxylic acid represented by formula (1) and (d) dimer acid in a solvent containing a non-nitrogen-containing polar solvent. 3. The solvent containing a non-nitrogen-containing polar solvent is γ
The method for producing a modified polyamideimide resin according to claim 2, wherein the resin is -butyrolactone. 4. The solvent containing a non-nitrogen-containing polar solvent is γ
-Butyrolactone and cyclohexanone at 99/1 to 50
The method for producing a modified polyamide-imide resin according to claim 2, wherein the solvent is a solvent mixed at a weight ratio of / 50. 5. A component (b) / (c) component of (b) a trivalent carboxylic acid derivative having an acid anhydride group and (c) a dicarboxylic acid represented by the general formula (I) or (II). (Molar ratio)
Is 0.1 / 0.9 to 0.9 / 0.1, the method for producing a modified polyamideimide resin according to claim 1 or 2. 6. A modified polyamide-imide resin obtained by the method for producing a modified polyamide-imide resin according to claim 1, 2, 3, 4, or 5. 7. The modified polyamideimide resin according to claim 6, wherein the number average molecular weight of the modified polyamideimide resin is 4,000 to 30,000.