JPH1129637A - Production of polyamideimide resin and polyamideimide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin having low elastic modulus and warpage and excellent in flexibility by reacting the mixture of a carboxylic acid derivative and a dicarboxylic acid with an aromatic polyisocyanate in a specific solvent. SOLUTION: This resin is obtained by reacting the mixture of (A) the derivative of a tribasic carboxylic acid having an acid anhydride group, (B) a dicarboxylic acid of formula I (a)-(c) are each 0-80; (a)/(b)=1/0 to 0/1; [(a)+(b)]/(c)=1/0 to 0/1; (a)+(b)+(c)=1 to 80; R1 is H, methyl; R2 is cyano, carboxyl, amino, etc.}, or a dicarboxylic acid of formula II ((d)-(f) is each 0-80; (d)/(e)=1/0 to 0/1; [(d)+(e)]/(f)=1/0 to 0/1; (d)+(e)+(f)=1 to 80}, and a dicarboxylic acid of formula III [(n) is 1-100; R3 is a divalent aliphatic group; R4 is a monovalent aliphatic or aromatic group] with (D) an aromatic polyisocyanate in a nitrogen-free polar solvent (preferably a mixture solvent of γ-butyrolactone with triethylene glycol dimethyl ether).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyamideimide resin, a polyamideimide resin, a polyamideimide resin composition, and a film-forming material containing the polyamideimide resin.

[0002]

2. Description of the Related Art In recent years, in the field of electronic components, polyimide resins have been used in place of epoxy resins as heat-resistant resins having excellent heat resistance, electrical properties, adhesion, moisture resistance and workability.
Polyamide imide resin and polyamide resin are used. These resins have a rigid resin structure and, when used as a thin film substrate, have a problem that the substrate after curing is greatly warped, and the cured film lacks flexibility and is inferior in flexibility.

Therefore, in order to improve low warpage and flexibility, a polyamideimide resin in which the resin is made flexible and has a low elastic modulus (Japanese Patent Application No. 60-244066, Japanese Patent Application Laid-Open No.
No. 12763, JP-A-7-196798) have been proposed. However, N-methyl-2- as a solvent
Since a high-boiling nitrogen-containing polar solvent such as pyrrolidone is used, a high-temperature curing of 200 ° C. or more is required at the time of curing, and there is a problem that thermal deterioration of an electronic member occurs. In addition, when the varnish is applied to the base material and then left for a long time, there is a problem in that whitening and voids occur in the coating film due to moisture absorption, which complicates working conditions.

On the other hand, it is soluble in non-nitrogen-containing polar solvents,
Resins having low warpage and flexibility are described in, for example,
No. 34950 and JP-A-8-333455. The polyimide siloxane described here is inferior in economical efficiency because it uses a very expensive diamine having a dimethylsiloxane bond as a starting material for lowering the elastic modulus. In addition, solvent resistance, chemical resistance (tin plating liquid resistance, solder flux resistance), and adhesion decrease with an increase in the amount of siloxane modification.

[0005]

DISCLOSURE OF THE INVENTION The present invention can be synthesized in a non-nitrogen-containing polar solvent, has a low elasticity, is excellent in low warpage and flexibility, has low-temperature curability, heat resistance, electrical properties, An object of the present invention is to provide a polyamide-imide resin excellent in adhesion, moisture resistance, flexibility, workability, economy and the like, and a method for producing the same.

The present invention also provides a solvent which is soluble in a non-nitrogen-containing polar solvent, has low-temperature curability, has a low elasticity, low warpage and excellent flexibility, and has solvent resistance, chemical resistance and storage stability. An object of the present invention is to provide a polyamide-imide resin composition having excellent properties, adhesiveness with a sealing material, heat resistance, electrical properties, moisture resistance, workability, economy, and the like, and a film-forming material containing the same.

[0007]

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

[0008]

Embedded image Wherein a, b and c are integers from 0 to 80, and a / b
Is 1/0 to 0/1, and the ratio of (a + b) / c is 1
/ 0 to 0/1, a + b + c is 1 to 80, and R
₁ represents hydrogen or a methyl group, R ₂ is cyano acid, carboxyl group, an amino group, a hydroxyl group, an organic group selected from among epoxy group and a phenyl group, R ₁ and R
₂ each may include two or more in one molecule. A dicarboxylic acid represented by the formula:

[0009]

Embedded image [Wherein, d, e and f are integers from 0 to 80, and d / e
Is 1/0 to 0/1, and the ratio of (d + e) / f is 1
/ 0 to 0/1, d + e + f is 1 to 80, and R
₁ and R ₂ have the same meaning as above. (C) General Formula (III)

[0010]

Embedded image [In the formula, n is an integer of 1 to 100, R ₃ is a divalent aliphatic group, and R ₄ is a monovalent aliphatic or aromatic group. A mixture of the dicarboxylic acid represented by the formula (I) and an aromatic polyisocyanate (d) in a non-nitrogen-containing polar solvent.

[0011] The present invention also provides a polyamide-imide resin produced by the above-mentioned production method.

The present invention also relates to (A) 100 parts by weight of the polyamideimide resin and (B) epoxy resins 1 to 5
It is intended to provide a polyamideimide resin composition containing 0 parts by weight.

The present invention also provides a film-forming material containing the above-mentioned polyamideimide resin or polyamideimide resin composition.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION As the (a) trivalent carboxylic acid derivative having an acid anhydride group used in the production of the polyamideimide resin of the present invention, for example, compounds represented by formulas (IV) and (V) Can be used as long as it is a derivative of a trivalent carboxylic acid having an acid anhydride group that reacts with an isocyanate group or an amino group, and is not particularly limited.
In consideration of heat resistance, cost, and the like, trimellitic anhydride is particularly preferable.

[0015]

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—) 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 acids (succinic acid, glutaric acid, adipic acid, azelaic acid,
Suberic acid, sebacic acid, decandioic acid, dodecandioic acid,
Dimer acid), aromatic dicarboxylic acids (isophthalic acid, terephthalic acid, phthalic acid, naphthalenedicarboxylic acid, oxydibenzoic acid) and the like can be used.

In the present invention, (b) the dicarboxylic acid represented by the general formula (I) includes, for example, Nippon Soda Co., Ltd.
Nisso-PB series, Ube Industries, Ltd. H
ycar-RLP series, Thiokol HC
-Polymer series, General Tire
Telagen Series, PhillipsPe
Butaretz series manufactured by troleum and the like.

In the general formula (I), a + b + c is from 1 to 80, preferably from 5 to 70, more preferably from 10 to 60. If a + b + c is less than 1, warpage tends to decrease, and if a + b + c exceeds 80, heat resistance and reactivity tend to decrease. In the formula, a / b is 1/0 to 0 /
1, preferably 1/0 to 0.2 / 0.8, more preferably 1/0 to 0.4 / 0.6, and 0.9 / 0.1 to 0.4. /0.6 is particularly preferred. When a / b is 1/0, the solubility tends to decrease, and when a / b becomes 0/1, the heat resistance tends to decrease. In the formula, (a + b) / c is from 1/0 to 0/1,
It is preferably 0.95 / 0.05 to 0.2 / 0.8, and more preferably 0.9 / 0.1 to 0.4 / 0.6. When (a + b) / c is 0/1, heat resistance,
The electrical properties tend to decrease, and when it is 1/0, the solubility and adhesion tend to decrease. In the general formula (II),
d + e + f is 1 to 80, preferably 5 to 70, and more preferably 10 to 60. d + e
If + f is less than 1, the warpage tends to decrease, and
If it exceeds 300, heat resistance and reactivity tend to decrease. In the formula, d / e is 1/0 to 0/1, and 1/0 to 0.2 /
0.8, preferably 1/0 to 0.4 / 0.6
More preferably, 0.9 / 0.1 to 0.4 /
It is particularly preferred to be 0.6. When d / e is 1/0, the solubility tends to decrease, and when it is 0/1, the heat resistance tends to decrease. Where (d + e) / f is 1 /
0 to 0/1, and 0.95 / 0.05 to 0.2 / 0.
8, preferably 0.9 / 0.1 to 0.4 /
More preferably, it is 0.6. (D + e) / f is 0
/ 1, heat resistance and electrical properties tend to decrease,
If the ratio is 1/0, the solubility and adhesion tend to decrease.
In the general formulas (I) and (II), R ₁ and R ₂ represent adhesion,
Considering the balance of solubility, workability and cost,
It is particularly preferred that R ₁ is hydrogen and R ₂ is a cyano group or a carboxyl group.

In the present invention, (c) the dicarboxylic acid represented by the general formula (III) includes F
Examples include the M series, the X22 series manufactured by Shin-Etsu Chemical Co., Ltd., and the BY series manufactured by Dow Corning Toray Silicone Co., Ltd. In the formula, n is an integer of 1 to 100, preferably 3 to 90, and more preferably 5 to 80. If n is less than 1, warpage tends to decrease, and if n exceeds 100, reactivity and adhesion tend to decrease. Examples of R ₃ include an alkylene group having 1 to 20 carbon atoms, for example, methylene, ethylene, propylene, and butylene, and propylene is preferable. R ₄
As, for example, an alkyl group having 1 to 20 carbon atoms such as methyl, ethyl, propyl, butyl, and 6 to 12 carbon atoms
Aryl groups such as phenyl, naphthyl and biphenyl, and methyl and phenyl are preferred.

As the aromatic polyisocyanate (d) in the present invention, for example, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4 '-[2, 2-bis (4-phenoxyphenyl) propane] diisocyanate, biphenyl-4,4'-diisocyanate, biphenyl-
3,3'-diisocyanate, biphenyl-3,4'-
Diisocyanate, 3,3'-dimethylbiphenyl-
4,4'-diisocyanate, 2,2'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'-diethylbiphenyl-4,4'-diisocyanate, 2,
2'-diethylbiphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 2,2'-dimethoxybiphenyl-4,
4'-diisocyanate, naphthalene-1,5-diisocyanate, naphthalene-2,6-diisocyanate and the like can be used. These can be used alone or in combination. If necessary, a part of this may be substituted with hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, transcyclohexane-1,4-
Aliphatic or alicyclic isocyanates such as diisocyanate, hydrogenated m-xylylene diisocyanate, lysine diisocyanate and the like and tri- or higher functional polyisocyanates may be used, and those stabilized with a blocking agent necessary to avoid aging are used. May be used.

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

In the present invention, the compounding ratio of (a) a derivative of a trivalent carboxylic acid having an acid anhydride group, (b) a dicarboxylic acid of the general formula (I) and (c) a dicarboxylic acid of the general formula (II) (A) / [(b) + (c)]} is an equivalent ratio,
The ratio is preferably 0.1 / 0.9 to 0.9 / 0.1, more preferably 0.2 / 0.8 to 0.8 / 0.2, and 0.3 / 0.7. It is particularly preferable to set the ratio to 0.7 / 0.3. If it is less than 0.1 / 0.9, the film properties such as heat resistance tend to decrease, and if it exceeds 0.9 / 0.1, the elasticity cannot be reduced and the warpage and adhesion tend to decrease. is there.

In the present invention, the compounding ratio [(b) / (c)] of (b) the dicarboxylic acid of the general formula (I) and (c) the dicarboxylic acid of the general formula (II) is 0.9 / 0 in equivalent ratio. .1 to
0.1 / 0.9, preferably 0.2 / 0.8
０．８0.8 / 0.2, more preferably 0.3 / 0.2.
It is particularly preferred to be 0.7 to 0.7 / 0.3.
If it is less than 0.1 / 0.9, the adhesiveness, solvent resistance and economy tend to decrease, and if it exceeds 0.9 / 0.1, the heat resistance and electrical properties tend to decrease.

(D) The mixing ratio of the aromatic polyisocyanate is such that the ratio of the total number of isocyanate groups of (d) to the total number of carboxyl groups and acid anhydride groups of (a), (b) and (c) is 0. It is preferably set to 6 to 1.4, more preferably set to 0.7 to 1.3, and particularly preferably set to 0.8 to 1.2. If it is less than 0.6 or more than 1.4, it tends to be difficult to increase the molecular weight of the resin.

The reaction in the method for producing a polyamide-imide resin of the present invention is carried out by heating and condensing in the presence of a non-nitrogen-containing polar solvent while removing the carbon dioxide gas liberated from the reaction system.

The reaction temperature is preferably from 80 to 210 ° C., more preferably from 100 to 190 ° C., particularly preferably from 120 to 180 ° C. 80
If the temperature is lower than ℃, the reaction time becomes too long. If the temperature is higher than 210 ° C, a three-dimensional reaction occurs during the reaction and gelation is liable to occur. The reaction time can be appropriately selected depending on the scale of the batch and the reaction conditions employed. If necessary, the reaction may be carried out in the presence of a catalyst such as a tertiary amine, an alkali metal, an alkaline earth metal, a metal such as tin, zinc, titanium and cobalt, or a metalloid compound.

The polyamideimide resin of the present invention can be obtained by the following production method. (1) A method in which an acid component (a), (b) or (c) and an isocyanate component (d) are used at once and reacted to obtain a polyamideimide resin. (2) After reacting the acid components (b) and (c) with an excess amount of the isocyanate component (d) to synthesize an amide imide oligomer having an isocyanate group at the terminal, the acid component (a) is added and reacted. To obtain a polyamide-imide resin. (3) After reacting an excess amount of the acid component (a) with the isocyanate component (d) to synthesize an amide imide oligomer having an acid or acid anhydride group at a terminal, the acid components (b) and (c) and the isocyanate A method of adding a component (d) and reacting to obtain a polyamideimide resin.

As the non-nitrogen-containing polar solvent used in the reaction, ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, sulfur-containing solvents,
For example, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, sulfolane, ester solvents,
For example, γ-butyrolactone, cellosolve acetate, ketone solvents, for example, cyclohexanone, methyl ethyl ketone, aromatic hydrocarbon solvents, for example, toluene, xylene, etc., can be used alone or in combination of two or more. It is preferable to select and use a solvent that dissolves the produced resin. A mixed solvent system of [gamma] -butyrolactone and triethylene glycol dimethyl ether is most preferred in order to impart high volatility, impart low-temperature curability, and efficiently carry out the reaction in a homogeneous system. The weight ratio is preferably from 9/1 to 1/9, and from 8/2 to 2/9.
/ 8 is more preferable, and 3/7 to 7/3 is particularly preferable. When the ratio is less than 9/1, the solubility of the resin in the solvent is reduced, so that the workability tends to decrease. When the ratio is more than 1/9, the amide imide formation reaction is inhibited, and it is difficult to increase the molecular weight of the resin, and the heat resistance is lowered. Tends to decrease.

The amount of the non-nitrogen-containing polar solvent used is preferably 0.8 to 5.0 times (weight ratio) the polyamideimide resin to be produced. If it is less than 0.8 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 thus obtained polyamideimide resin of the present invention has a number average molecular weight (measured by GPC method and calculated using a calibration curve based on standard polystyrene) of 4,000.
Preferably from 0 to 30,000, from 5,000 to
More preferably, 28,000, 6,000 ~
Particularly preferred is 26,000. If the number average molecular weight is less than 4,000, the film properties such as heat resistance tend to decrease, and if it exceeds 30,000, it is difficult to dissolve in a non-nitrogen-containing polar solvent and easily insoluble during synthesis. Also,
Workability tends to be poor.

The acid value (K) of the polyamideimide resin of the present invention
OH mg / g) is preferably 1 to 80, and 3
It is more preferably from 70 to 70, and particularly preferably from 5 to 60. If the acid value is less than 1, the curability and adhesion tend to decrease, and if it exceeds 80, the film properties such as viscosity stability (storage stability) and heat resistance tend to decrease.

After the completion of the synthesis, the isocyanate group at the terminal of the resin can be blocked with a blocking agent such as an alcohol group, lactams or oximes.

The polyamide-imide resin composition of the present invention comprises:
It contains (A) 100 parts by weight of the polyamideimide resin of the present invention and (B) 1 to 50 parts by weight of an epoxy resin. Epoxy resin is used for tin plating resistance,
It is preferable for improving solder flux resistance.

The epoxy resin (B) used in the present invention is, for example, Epicoat 815, 825, 827, 828, 834, 100 manufactured by Yuka Shell Epoxy Co., Ltd.
1,1004, 1007, 1009, etc., bisphenol II type epoxy resin, Epicoat 152, 154, Nippon Kayaku Co., Ltd. EPPN-201, Dow Chemical Co. DE
A phenol novolak type epoxy resin such as N-438,
Nippon Kayaku Co., Ltd. EOCN-125S, 103S, 10
O-cresol novolak type epoxy resin such as 4S, Epon 1031S manufactured by Yuka Shell Epoxy, Araldite 0163 manufactured by Ciba Geigy, Denacol EX-611, EX-614, E manufactured by Nagase Kasei Co., Ltd.
X-614B, EX-622, EX-512, EX-5
Polyfunctional epoxy resins such as 21, EX-421, EX-411, EX-321, Epicoat 604 manufactured by Yuka Shell Epoxy Co., Ltd., YH-434 manufactured by Toto Kasei Co., Ltd., and TETRAD- manufactured by Mitsubishi Gas Chemical Co., Ltd. X, TETRAD-
C, GΑN manufactured by Nippon Kayaku Co., Ltd., EL manufactured by Sumitomo Chemical Co., Ltd.
Amine-type epoxy resins such as M-120, heterocyclic-containing epoxy resins such as Araldite PT810 manufactured by Ciba-Geigy, ERL4234, 4299, 4221 manufactured by UCC;
An alicyclic epoxy resin such as 4206 can be used, and one or more of these can also be used.

Among them, Denacol EX-611, which is an aliphatic epoxy resin having two or more epoxy groups,
EX-612, EX-614, EX-614B, EX-
622, EX-651, EX-651Α, EX-51
2, EX-521, EX-421, EX-411, EX
-301, EX-313, EX-314, EX-32
1, EX-211, EX-212, EX-800 series, E
X-900 series and the like are preferable, and Denacol EX-611,
EX-612, EX-614, EX-614B, EX-
622, EX-651, EX-651Α, EX-51
2, EX-521, EX-421, EX-411, EX
−301, EX-313, EX-314, EX-321
Is more preferred.

From the viewpoint of adhesion to the sealing material, bisphenol Α epoxy resins and aliphatic epoxy resins are preferred. Further, an aliphatic epoxy resin is most preferable from the viewpoint of excellent solvent resistance (acetone), tin plating liquid resistance, and solder flux resistance.

The amount of the epoxy resin used in the present invention is:
1 to 50 parts by weight, preferably 2 to 40 parts by weight, more preferably 3 to 100 parts by weight, based on 100 parts by weight of the polyamideimide resin.
30 parts by weight. If the compounding amount of the epoxy resin is less than 1 part by weight, the solvent resistance and chemical resistance (tin plating liquid resistance, solder flux resistance) tend to decrease, and if it exceeds 50 parts by weight, storage stability, sealing material Adhesion and heat resistance tend to decrease.

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

The polyamide-imide resin and the polyamide-imide resin composition of the present invention are each suitably used as a film-forming material. In order to improve the workability during coating and the film properties before and after the formation of the coating, the polyamideimide resin or the polyamideimide resin composition includes surfactants such as organic or inorganic fillers, defoamers, and leveling agents. , A colorant such as a dye or a pigment, a heat stabilizer, an antioxidant, a flame retardant, and a lubricant can also be added.

An amine compound may be added to the polyamide-imide resin and the polyamide-imide resin composition of the present invention in order to improve the curability.

As the amine compound, for example, 4,
Primary amines such as 4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 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, trimethylamino Ethyl piperazine, 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- (dimethyl Aminomethyl)
Phenol, 2,4,6-tris (dimethylaminomethyl) phenol, N, N'-dimethylpiperazine, pyridine, picoline, 1,2,2,6,6-pentamethyl-
Tertiary amines such as 4-piperidinol and triethylamine, dicyandiamide and the like can be used. The addition amount is 0.1 parts by weight based on 100 parts by weight of the polyamideimide resin.
It is preferably from 10 to 10 parts by weight.

To the polyamide-imide resin and the polyamide-imide resin composition according to the present invention, an organic aluminum compound, an organic silane compound, an organic titanium compound, an organic zirconia compound or the like is added as necessary to improve the adhesion. You can also. The addition amount is preferably 0.05 to 50 parts by weight based on 100 parts by weight of the polyamideimide resin.

The organoaluminum compound is not particularly restricted but includes, for example, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, aluminum monoacetylacetonate bis (ethyl acetoacetate) ), Aluminum tris (acetylacetonate), aluminum =
Aluminum chelate compounds such as monoisopropoxy monooleoxyethyl acetoacetate, aluminum-di-n-butoxide-mono-ethylacetoacetate, aluminum-di-iso-propoxide-mono-ethylacetoacetate, aluminum isopropylate, mono- Aluminum alcoholates such as sec-butoxyaluminum diisopropylate, aluminum-sec-butyrate and aluminum ethylate can be used, and one or more of these can be used.

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-aminopropylmethyldimethoxysilane, 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-methyldimethoxysilane, 3-cyanopropyl-triethoxysilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, methyltrimethoxysilane, methyltriethoxysilane Ethyltrichlorosilane, n- propyltrimethoxysilane, isobutyltrimethoxysilane, amyl trichlorosilane, octyl triethoxysilane, phenyl trimethoxysilane, phenyl triethoxysilane, methyl tri (methacryloyloxy Oki ethoxy) silane, methyltri (glycidyloxy) silane,
N-β (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldichlorosilane, γ-chloropropylmethyldimethoxysilane , Γ-
Chloropropylmethyldiethoxysilane, trimethylsilyl isocyanate, dimethyl isocyanate, methylsilyl triisocyanate, vinylsilyl triisocyanate, phenylsilyl triisocyanate, tetraisocyanate silane, ethoxy silane isocyanate and the like can be used. The above can also be used.

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 (ditridecylphosphite) 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 triethanol 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 (I
V), diisopropyl-bis-triethanolamino-
Titanate, octylene glycol titanate HV, tetra-n-butoxytitanium polymer, tri-n-butoxytitanium monostearate polymer, tri-n-butoxytitanium monostearate, and the like can be used.
One or more of these may be used.

The organic zirconia compound is not particularly limited. For example, tetrapropyl zircoaluminate,
Tetrabutyl zirconate, tetra (triethanolamine) zirconate, tetaraisopropyl zirconate, zirconium acetylacetonate, acetylacetone zirconium butyrate, zirconium lactate, zirconium butyrate stearate, @ PG-X
(CAVEDON CHEMICAL CO., IN
C. Product name) can be used.
Species or two or more species can also be used.

The polyamide-imide resin and the polyamide-imide resin composition of the present invention are, for example, overcoat materials for electronic parts, liquid sealing materials, varnishes for enameled wires, impregnated varnishes for electrical insulation, cast varnishes, and mica, respectively. Varnish for sheets in combination with glass cloth and other substrates, MC
It can be used for varnish for L laminated board, varnish for friction material, interlayer insulating film, surface protection film, solder resist layer, adhesive layer, etc. in the field of printed circuit board, and electronic parts such as semiconductor elements, and is suitable as a film forming material. Used.

[0047]

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 One liter equipped with a stirrer, a cooling pipe, a nitrogen introduction pipe and a thermometer
CTBN13 as a component (b) in a four-necked torr flask
00X9 [trade name of Ube Industries, Ltd., a of general formula (I)
+ B + c = 63, a / b = 1/0, (a + b) / c =
0.83 / 0.17, R₁= H, R_Two= -CN (slightly
-COOH is bound)] 105.0 g (0.03
Mol), BY16-750 as component (c) [Toray
Dow Corning Silicone Co., Ltd. product name, general formula
N = 16 of (II), R_Three= (CH_Two) _Three, R_Four= CH_Three]
168.0 g (0.12 mol), as component (d)
4,4'-diphenylmethane diisocyanate 75.0
g (0.3 mol), 208.8 g of γ-butyrolactone
And triethylene glycol dimethyl ether 139.2
g, the temperature is raised to 180 ° C., and the reaction is carried out for 2 hours.
Further, anhydrous trimellit as component (a) was added to the reaction solution.
28.8 g (0.15 mol) of tonic acid and triethylene glyco
Of dimethyl ether at 160 ° C.
Reaction for 2 hours to obtain resin with acid value 20KOHmg / g
Was. Triethylene glycol dimethyl ether
Diluent, polyamide imid with a nonvolatile content of 40% by weight
A resin varnish was obtained.

Example 2 In the same flask as in Example 1, CTB was used as the component (b).
N1300X9, 175.0 g (0.05 mol),
(16) BY-750 as a component (c), 150.0 g
(0.075 mol), 62.5 g (0.25 g) of 4,4'-diphenylmethane diisocyanate as the component (d)
Mol), 239.8 g of γ-butyrolactone and 102.7 g of triethylene glycol dimethyl ether, and the mixture is heated to 180 ° C. and reacted for 2 hours. Further, trimellitic anhydride 2 as component (a) is added to the reaction mixture.
4.0 g (0.125 mol) and 105.4 g of triethylene glycol dimethyl ether were charged and reacted at 160 ° C. for 2 hours to obtain a resin having an acid value of 20 KOH mg / g. The obtained resin was diluted with triethylene glycol dimethyl ether to obtain a polyamideimide resin varnish having a nonvolatile content of 40% by weight.

Comparative Example 1 In the same flask as in Example 1, 76.8 g (0.4 mol) of trimellitic anhydride as component (a) and 4,4'-diphenylmethane diisocyanate 1 as component (b)
02.0 g (0.408 mol) and 375.48 g of N-methyl-2-pyrrolidone were charged, heated to 130 ° C., and reacted for 4 hours to obtain a resin having an acid value of 25 KOH mg / g. The obtained resin was diluted with N, N'-dimethylformamide to obtain a polyamideimide resin varnish having a nonvolatile content of 30% by weight.

Comparative Example 2 In the same flask as in Example 1, CTB was used as the component (b).
N1300X9, 262.5 g (0.075 mol),
62.5 g (0.25 mol) of 4,4'-diphenylmethane diisocyanate as the component (d) and 325.0 g of γ-butyrolactone were charged, and the temperature was raised to 180 ° C.
Incubate for 1.5 hours. Further, 33.6 g (0.175 mol) of trimellitic anhydride and 113.3 g of γ-butyrolactone as the component (a) were charged into the reaction mixture, and
The reaction was carried out at 1.5 ° C. for 1.5 hours to obtain a resin having an acid value of 20 KOH mg / g. The obtained resin was diluted with γ-butyrolactone to obtain a polyamideimide resin varnish having a nonvolatile content of 40% by weight.

Comparative Example 3 In the same flask as in Example 1, BY as the component (c) was added.
16-750, 210.0 g (0.15 mol), (d)
75.0 g (0.3 mol) of 4,4'-diphenylmethane diisocyanate as a component, γ-butyrolactone 1
42.5 g and triethylene glycol dimethyl ether 142.5 g were charged, and the temperature was increased to 180 ° C.
Let react for hours. Further, 28.8 g (0.15 mol) of trimellitic anhydride as the component (a) and 98.5 g of triethylene glycol dimethyl ether were charged into the reaction mixture and reacted at 160 ° C. for 2 hours to obtain an acid value of 20 KOH mg / kg.
g of resin were obtained. The obtained resin was diluted with triethylene glycol dimethyl ether to obtain a polyamideimide resin varnish having a nonvolatile content of 40% by weight.

The properties of the polyamide-imide resins obtained in the above Examples and Comparative Examples were measured by the following methods.
It was shown to.

(1) Adhesion The obtained polyamideimide resin varnish was applied on a rough surface of an electrolytic copper foil having a thickness of 35 μm or on a polyimide film having a thickness of 50 μm. After drying at 90 ° C for 15 minutes, the coating film obtained by heating at 160 ° C for 60 minutes in an air atmosphere (thickness: 20
Pressure cooker test (P
CT, conditions: 121 ° C., 2.0265 × 10 ⁵ Pa, 3
(00 hours).

The cross-cut test was conducted according to JIS K540.
The number of remaining eyes was described for 100 squares according to 0.

(2) Adhesion to Sealing Material The obtained polyamideimide resin varnish was applied on a rough surface of an electrolytic copper foil having a thickness of 35 μm or on a polyimide film having a thickness of 50 μm. After drying at 90 ° C for 15 minutes, the coating film obtained by heating at 160 ° C for 60 minutes in an air atmosphere (thickness: 20
0.06 g of an epoxy-based encapsulant [separately using trade names 8103 and 8107 manufactured by Namics Corp. and trade name CEL-C-5020 manufactured by Hitachi Chemical Co., Ltd.] on the epoxy resin, and 120 ° C. At 150 ° C. for 120 minutes. The obtained coating film was bent so that the sealing material side was outside, and the mode of peeling was evaluated. ○: Interfacial peeling of substrate / coating, △: Interfacial peeling of coating / sealing material, ×: No adhesion (3) Solder heat resistance Obtained on a rough surface of electrolytic copper foil with a thickness of 35 μm The resulting polyamide-imide resin varnish was applied. After drying at 90 ° C. for 15 minutes, the coating film (thickness: 20 to 30 μm) obtained by heating at 160 ° C. for 60 minutes in an air atmosphere was brought into contact with a solder bath at 260 ° C. for 10 seconds, The change in the appearance of the coating film was evaluated. ：: No change in appearance, Δ: Partial change in appearance, ×: Change in overall appearance (4) Warpage The obtained polyamideimide resin was applied on a polyimide film having a thickness of 50 μm, a length of 35 mm and a width of 20 mm. After drying at 90 ° C. for 15 minutes, 160
The coated film (thickness: 20 μm) obtained by heating at 60 ° C. for 60 minutes is placed on a surface plate with the coated surface facing down, and the warpage height is evaluated.

(5) Modulus of Elasticity The obtained polyamide-imide resin was applied on a glass plate. After drying at 90 ° C. for 15 minutes, 160
Coating film (thickness: 30 μm) obtained by heating at 60 ° C. for 60 minutes, a universal testing machine (Tensilon UC manufactured by Orientec Co., Ltd.)
(T-5T type), a tensile test was performed under the following conditions, and a tensile elastic modulus was measured. (Measurement temperature: 23 ° C., tensile speed: 5 mm / min) (6) Flexibility The obtained polyamideimide resin was applied on a rough surface of an electrolytic copper foil having a thickness of 35 μm. After drying at 90 ° C for 15 minutes,
For a coating film (thickness: 20 to 30 μm) obtained by heating at 160 ° C. for 60 minutes in an air atmosphere, R: 0.3, 180 ° C.
The coating was bent so that the coating surface was on the outside under the above conditions, and the presence or absence of cracks in the bent portion was evaluated. ○: no crack, ×: crack

[0058]

[Table 1] Example 3 Example 1 Resin content of polyamideimide resin obtained 100
5 parts by weight of Denacol EX-411 (trade name of Nagase Kasei Co., Ltd., 4-functional aliphatic epoxy resin, epoxy equivalent: 231) was added to the parts by weight, and the mixture was diluted with triethylene glycol dimethyl ether to give a nonvolatile content of 40% by weight. A resin composition was obtained.

Example 4 A resin composition having a nonvolatile content of 40% by weight was obtained in exactly the same manner as in Example 3, except that Denacol EX-411 and 5 parts by weight were changed to 10 parts by weight. .

Example 5 In Example 3, 5 parts by weight of Denacol EX-611 (trade name of Nagase Kasei Co., Ltd., 4-functional aliphatic epoxy resin, epoxy equivalent 170) instead of 5 parts by weight of Denacol EX-411 The same operation as in Example 3 was performed except that the resin composition was used as a part to obtain a resin composition having a nonvolatile content of 40% by weight.

Example 6 A resin composition having a non-volatile content of 40% by weight was obtained in the same manner as in Example 5, except that Denacol EX-611 was replaced by 5 parts by weight and 10 parts by weight. .

Example 7 In Example 3, 5 parts by weight of Denacol EX-321 (trade name of Nagase Kasei Co., Ltd., trifunctional aliphatic epoxy resin, epoxy equivalent: 145) was used instead of 5 parts by weight of Denacol EX-411. The same operation as in Example 3 was performed except that the resin composition was used as a part to obtain a resin composition having a nonvolatile content of 40% by weight.

Example 8 A resin composition having a non-volatile content of 40% by weight was obtained in exactly the same manner as in Example 7, except that 10 parts by weight of Denacol EX-321 and 5 parts by weight were used. .

Example 9 The resin content of the polyamideimide resin obtained in Example 2 was 10%.
5 parts by weight of Denacol EX-411 (trade name of Nagase Kasei Co., Ltd., 4-functional aliphatic epoxy resin, epoxy equivalent: 231) was added to 0 parts by weight, and diluted with triethylene glycol dimethyl ether to obtain a nonvolatile content of 40% by weight. Was obtained.

Example 10 A resin composition having a nonvolatile content of 40% by weight was obtained in the same manner as in Example 9 except that Denacol EX-411 and 5 parts by weight were changed to 10 parts by weight. .

Example 11 In Example 9, 5 parts by weight of Denacol EX-611 (trade name of Nagase Kasei Co., Ltd., 4-functional aliphatic epoxy resin, epoxy equivalent 170) was used instead of 5 parts by weight of Denacol EX-411. The same operation as in Example 9 was carried out, except that the resin component was used as a part, to obtain a resin composition having a nonvolatile content of 40% by weight.

Example 12 The same operation as in Example 11 was carried out except that Denacol EX-611 and 5 parts by weight were changed to 10 parts by weight, to obtain a resin composition having a nonvolatile content of 40% by weight. .

Example 13 In Example 9, 5 parts by weight of Denacol EX-321 (trade name of Nagase Kasei Co., Ltd., trifunctional aliphatic epoxy resin, epoxy equivalent: 145) was used instead of 5 parts by weight of Denacol EX-411. The same operation as in Example 9 was carried out, except that the resin component was used as a part, to obtain a resin composition having a nonvolatile content of 40% by weight.

Example 14 A resin composition having a nonvolatile content of 40% by weight was obtained in the same manner as in Example 13, except that Denacol EX-321 was replaced by 5 parts by weight and 10 parts by weight. .

Reference Example 1 A resin composition having a nonvolatile content of 40% by weight was obtained in the same manner as in Example 3, except that Denacol EX-411 and 5 parts by weight were changed to 0 parts by weight. .

The properties of the polyamide-imide resin compositions obtained in the above Examples and Reference Examples were measured by the methods described above and below, and the results are shown in Table 2.

(7) Solvent Resistance The obtained polyamideimide resin composition was applied on the roughened surface of an electrolytic copper foil having a thickness of 35 μm. After drying at 90 ° C. for 15 minutes, the coating film (thickness: 20 to 30 μm) obtained by heating at 160 ° C. for 60 minutes in an air atmosphere is immersed in acetone for 1 hour at room temperature to form a coating film. The change in appearance was evaluated. ○: No change in appearance, Δ: Partial change in appearance, ×: Change in overall appearance (8) Tin plating solution resistance The obtained polyamideimide resin composition was applied on the rough surface of an electrolytic copper foil having a thickness of 35 μm. did. After drying at 90 ° C. for 15 minutes, the coating film (thickness: 20 to 30 μm) obtained by heating at 160 ° C. for 60 minutes in an air atmosphere, tin plating solution heated to 70 ° C. (Shipley Far East Co., Ltd.) Made
The coated film is immersed in TEINposit LT34) for 4 minutes, taken out, washed with 60 ° C warm water for 5 minutes,
The coated film was dried by heating for minutes, and the change in the appearance of the coating film was evaluated. ○: No change in appearance, Δ: Partial change in appearance, ×: Change in overall appearance (9) Solder flux resistance The obtained polyamideimide resin composition was applied on the rough surface of an electrolytic copper foil having a thickness of 35 μm. did. After drying at 90 ° C. for 15 minutes, the coating film (thickness: 20 to 30 μm) obtained by heating at 160 ° C. for 60 minutes in an air atmosphere was fluxed at room temperature (ULF-500VS manufactured by Tamura Kaken Corp.). 5 in
The coating film was immersed for another minute, and the coating surface was further contacted with a solder bath at 260 ° C. for 10 seconds to evaluate the change in the appearance of the coating film. ：: No change in appearance, Δ: Partial change in appearance, ×: Change in overall appearance (10) Storage stability Evaluated by the rate of increase in viscosity after standing at 25 ° C. for one month (measured with an E-type viscometer).

[0073]

[Table 2]

[0074]

The polyamideimide resin of the present invention has low elasticity and low warpage, and is excellent in heat resistance, electrical properties and economy.

The polyamide resin composition of the present invention is soluble in a non-nitrogen-containing polar solvent, has low curability, has a low elastic modulus, has excellent warpage and flexibility, and has solvent resistance and chemical resistance. It has good storage stability, good adhesion to sealing materials, and is excellent in heat resistance, electrical properties, moisture resistance, workability, economy, and the like.

The coating-forming material of the present invention has the above-mentioned excellent properties, and includes an overcoat material for electronic parts, a liquid sealing material,
Varnish for enameled wire, impregnated varnish for electrical insulation, cast varnish, mica, varnish for sheet combined with substrate such as glass cloth, varnish for MCL laminate, varnish for friction material, interlayer insulating film in printed circuit board field, etc. It is suitably used for electronic components such as a surface protective film, a solder resist layer, an adhesive layer, and a semiconductor element.

Claims (9)

[Claims] 1. A derivative of a trivalent carboxylic acid having an acid anhydride group, (b) a general formula (I) or (II) Wherein a, b and c are integers from 0 to 80, and a / b
Is 1/0 to 0/1, and the ratio of (a + b) / c is 1
/ 0 to 0/1, a + b + c is 1 to 80, and R
₁ represents hydrogen or a methyl group, R ₂ is a cyano group, a carboxyl group, an amino group, a hydroxyl group, an organic group selected from among epoxy group and a phenyl group, R ₁ and R
₂ each may include two or more in one molecule. A dicarboxylic acid represented by the formula: [Wherein, d, e and f are integers from 0 to 80, and d / e
Is 1/0 to 0/1, and the ratio of (d + e) / f is 1
/ 0 to 0/1, d + e + f is 1 to 80, and R
₁ and R ₂ have the same meaning as above. (C) General Formula (III) [In the formula, n is an integer of 1 to 100, R ₃ is a divalent aliphatic group, and R ₄ is a monovalent aliphatic or aromatic group. A method of producing a polyamideimide resin, comprising reacting a mixture of the dicarboxylic acid represented by the formula (1) and (d) an aromatic polyisocyanate in a non-nitrogen-containing polar solvent. 2. The mixing ratio of (a), (b) and (c) {(a) / [(b) + (c)]} is 0.1 / equivalent.
0.9 to 0.9 / 0.1, and the mixing ratio of (b) and (c) [(b) / (c)] is 0.9 / 0.1 to 0.9 / 0.1 in equivalent ratio.
0.1 / 0.9, and the ratio of the total number of isocyanate groups of (d) to the total number of carboxyl groups and acid anhydride groups of (a), (b) and (c) is 0.6 to 1.4. And
(B) The method for producing a polyamide-imide resin according to claim 1, wherein R ₁ is H and R ₂ is a cyano group and a carboxyl group in the formula (I). 3. The non-nitrogen-containing polar solvent is γ-butyrolactone and triethylene glycol dimethyl ether,
The method for producing a polyamide-imide resin according to claim 1 or 2, wherein the weight ratio is from 9/1 to 1/9. 4. A polyamide-imide resin produced by the method for producing a polyamide-imide resin according to claim 1, 2 or 3. 5. The polyamideimide resin having an acid value of 1 to 80.
The polyamide-imide resin according to claim 4, wherein KOH is mg / g. 6. (A) 100 parts by weight of the polyamideimide resin according to claim 4 or 5, and (B) epoxy resins 1 to 5.
A polyamideimide resin composition containing 0 parts by weight. 7. The polyamide-imide resin composition according to claim 6, wherein the epoxy resin is an aliphatic epoxy resin having two or more epoxy groups. 8. A film-forming material comprising the polyamide-imide resin according to claim 4. 9. A film-forming material comprising the polyamide-imide resin composition according to claim 6.