JP2954460B2 - Curable polyimide resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable polyimide resin composition capable of forming a polyimide film suitable as a protective film for electronic parts.

[0002]

2. Description of the Related Art Polyimide resins have excellent heat resistance, electrical properties, mechanical properties, and the like, and are used as insulating protective films for electronic parts. However, since a polyimide resin is insoluble in an organic solvent, it is difficult to form a solution containing a polyimide resin and apply it to a substrate when forming a film. Therefore, conventionally, in order to form a film made of a polyimide resin, a solution containing a polyamic acid, which is a precursor of the polyimide resin, is applied to a substrate and cured by heating to form a polyimide resin film. However, the solution containing the polyamic acid has a very high viscosity and is inferior in workability, and the adhesion of a polyimide resin film obtained to a semiconductor element material such as nickel, aluminum, silicon, or silicon oxide film is low. There are disadvantages.

Therefore, it has been proposed to use a polyamic acid containing a siloxane bond synthesized by replacing a part of the diamine component with a diamine having a siloxane bond (JP-B-43-27439, JP-B-59-72).
No. 13). However, the adhesion of the polyimide resin film thus obtained to the substrate is improved, and the viscosity of the solution containing the siloxane bond-containing polyamic acid is also relatively reduced, but is not satisfactory, and the workability is still insufficient. Not.

On the other hand, it has been proposed to use a low molecular weight polyamic acid obtained by reacting an aromatic tetracarboxylic acid ester with a mixture of an aromatic diamine and a siloxane diamine (JP-A-61-83229). However, in this case, the viscosity of the polyamic acid solution is relatively low, and the workability is improved. However, when the siloxane diamine used has a low molecular weight, the siloxane diamine having a low molecular weight is volatile, so that the heating is difficult. It volatilizes during curing to change the acid / amine ratio in the composition, so that a desired cured film cannot be obtained. When the siloxane diamine has a high molecular weight, the siloxane diamine has a low compatibility with an organic solvent and therefore has a low uniformity. Since a liquid of the composition cannot be obtained, a uniform and good film cannot be obtained.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a polyimide resin film having excellent heat resistance, mechanical properties, electrical properties, solvent resistance, adhesiveness, etc. An object of the present invention is to provide a good curable polyimide resin composition.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention provides (A) the following general formula (1):

Embedded image (Wherein R ¹ may be the same or different, and has 1 carbon atom
And R ² may be the same or different and is a monovalent organic group having 1 to 8 carbon atoms;
Is

Embedded image ,

Embedded image as well as

Embedded image Is a tetravalent aromatic group selected from the group consisting of
A polyamic acid represented by the following general formula (2):

Embedded image (Wherein R ³ may be the same or different and is an alkyl group, X is as defined above), (C) an aromatic diamine, and (D) an organic diamine. Provided is a curable polyimide resin composition containing a solvent.

Hereinafter, the present invention will be described in detail. (A) Polyamic Acid In the composition of the present invention, the polyamic acid of the component (A) is a polyimide precursor, and the acid undergoes dehydration ring closure or the aromatic tetracarboxylic acid diester of the component (B) and (C) And dehydration condensation with the aromatic diamine of the component to form a polyimide resin having excellent heat resistance.

In the above general formula (1) representing the polyamic acid, examples of the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R ¹ include a methylene group, an ethylene group, a propylene group, Alkylene groups such as propylene, butylene, isobutylene, hexylene, and octylene; p-phenylene, m-phenylene,
An arylene group such as a tolylene group;

Embedded image And a substituted hydrocarbon group in which part or all of the hydrogen atoms of these hydrocarbon groups are substituted with chlorine, fluorine, or the like. Preferably, a propylene group, a butylene group, p
-Phenylene group, m-phenylene group and

Embedded image It is. 2 or more of R ¹ contained in the molecule may be either of the same kind of different. From the availability of raw materials, R
¹ is typically a propylene, butylene, p-phenylene or m-phenylene group.

The monovalent hydrocarbon group having 1 to 8 carbon atoms represented by R ² includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
Alkyl groups such as pentyl group, hexyl group, heptyl group, octyl group and decyl group; aryl groups such as phenyl group and tolyl group; and hydrogen atoms such as chloromethyl group, 3,3,3-trifluoropropyl group being chlorine, Examples thereof include an alkyl group substituted with fluorine and the like. Preferably, they are a methyl group and a phenyl group. Two or more R ¹ in the molecule may be the same or different. Due to the availability of raw materials, R ²
Is typically a methyl group, an isopropyl group and a phenyl group.

M, which represents the length of the siloxane chain in the molecule, is 1
It is an integer of 1 to 40, preferably an integer of 1 to 20. If m exceeds 40, the adhesiveness to the substrate will decrease. N, which indicates the degree of polymerization of the polyamic acid, is an integer of 2 or more, and is preferably 10 or more from the viewpoint that properties of the obtained cured film, for example, tensile strength are particularly good,
Generally, 10 to 1000 is preferable.

The polyamic acid has a general formula (3):

Embedded image (Wherein X is as defined above) and an aromatic tetracarboxylic dianhydride represented by the general formula (4):

Embedded image (Wherein R ¹ , R ² and m are as defined above) in an organic solvent by a known method. Specifically, it is obtained by a method of dropping siloxane diamine into a solution of aromatic tetracarboxylic dianhydride dissolved in an organic solvent.

The aromatic tetracarboxylic dianhydride represented by the general formula (3) includes pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride and 3,3 ', 4,
4'-biphenyltetracarboxylic dianhydride is exemplified. These may be used alone or in combination of two or more.

As the siloxydiamine represented by the general formula (4), for example,

Embedded image And the like. These may be used alone or in combination of two or more.

(B) Aromatic Tetracarboxylic Diester In the general formula (2) representing the aromatic tetracarboxylic diester used as the component (B), X is an aromatic group as described above. Examples of the alkyl group represented by R ³ include those having 1 to 4 carbon atoms, such as methyl, ethyl, propyl and butyl.

Specific examples of the aromatic tetracarboxylic diester include pyromellitic dialkyl ester, benzophenone tetracarboxylic dialkyl ester and 3,3 ', 4,4'-biphenyltetracarboxylic dialkyl ester. These may be used alone or in combination of two or more.

The aromatic tetracarboxylic diester is, for example, an aromatic tetracarboxylic dianhydride represented by the general formula (4) and a general formula (5): R ³ OH (5) R ³ is as described above), and is reacted with a known method. Specifically, a method in which a necessary amount of an aromatic tetracarboxylic dianhydride and an alcohol are charged in an appropriate solvent and left as it is or heated at about 30 to 70 ° C. as necessary is used. At this time, an amine catalyst or the like may be used. As the alcohol of the general formula (5), for example,
Examples include methanol, ethanol, propanol, isopropanol and butanol.

(C) Aromatic Diamine The aromatic diamine of the component (C) is represented by a general formula: H ₂ N—Y—NH ₂ [wherein, Y represents a divalent aromatic group]. Examples of the aromatic diamine include phenylenediamines such as p-phenylenediamine and m-phenylenediamine;
Diaminodiphenylmethane such as 4,4'-diaminodiphenylmethane; diaminodiphenylether such as 4,4'-diaminodiphenylether and 3-carbamoyl-4-aminophenyl (4'-aminophenyl) ether; 4,4'-diaminobiphenyl, Diaminobiphenyl such as carbamoyl-4,4'-diaminobiphenyl; bis (aminophenyl) propane such as 2,2'-bis (4-aminophenyl) propane; diaminodiphenylsulfone such as 4,4'-diaminodiphenylsulfone Diaminodiphenyl sulfides such as 4,4'-diaminodiphenyl sulfide; bis (aminophenoxy) benzenes such as 1,4-bis (3-aminophenoxy) benzene and 1,4-bis (4-aminophenoxy) benzene; , 4-bis (p-aminoph Bis (aminophenylsulfonyl) benzene such as 1,4-bis (m-aminophenylsulfonyl) benzene, 1,4-bis (p-aminophenylthioether) benzene, 1,4-bis (m- Bis (aminophenylthioether) benzene such as aminophenylthioether) benzene; 2,2-bis [4- (p-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (p-aminophenoxy) ) Phenyl] propane, bis [4- (p-aminophenoxy) phenyl] propane such as 2,2-bis [3-chloro-4- (p-aminophenoxy) phenyl] propane; 1,1-bis [4
-(P-aminophenoxy) phenyl] ethane, 1,1
-Bis [3-methyl-4- (p-aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (p
Bis [4- (p-aminophenoxy) phenyl] ethane such as -aminophenoxy) phenyl] ethane and 1,1-bis [3,5-dimethyl-4- (p-aminophenoxy) phenyl] ethane; bis [4 -(P-aminophenoxy) phenyl] methane, bis [3-methyl-4- (p
Bis [4-aminophenoxy) phenyl] methane, bis [3-chloro-4- (p-aminophenoxy) phenyl] methane, bis [4,5-dimethyl-4- (p-aminophenoxy) phenyl] methane -(P-aminophenoxy) phenyl] methane; bis [4- (p-aminophenoxy) phenyl] sulfone; 2,2-bis [4-
Bis [4- (p-aminophenoxy) phenyl] perfluoropropane such as (p-aminophenoxy) phenyl] perfluoropropane. Among these, preferred are 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, bis (aminophenyl) propane, bis (aminophenyl) sulfone, bis (aminophenyl) perfluoropropane,
And bis (aminophenoxy) benzene.

(D) Organic Solvent The organic solvent of the component (D) is not particularly limited, but a polar organic solvent is preferred. As the organic solvent, for example, N-
Cyclic amines such as methyl-2-pyrrolidone; amides such as dimethylacetamide, dimethylformamide and hexamethylphosphoramide; methylcellosolve, butylcellosolve, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetrahydrofuran, 1,4-
Ethers such as dioxane; ketones such as cyclohexanone; esters such as γ-butyrolactone and butyl cellosolve acetate; aromatic compounds such as toluene and xylene.

Composition The range of the aromatic tetracarboxylic diester (B) and the aromatic diamine (C) in the composition of the present invention is based on 100 parts by weight of the polyamic acid (A) and the aromatic tetracarboxylic diester (B). ) And the aromatic diamine (C) are preferably 20 to 2,000 parts by weight, more preferably 80 to 2,000 parts by weight. At this time, aromatic tetracarboxylic acid diester (B) / aromatic diamine (C)
The ratio is preferably in the range of 0.9 to 1.1 in terms of molar ratio, and more preferably in the range of 0.95 to 1.05.

The amount of the organic solvent (D) is [(A) + (B)
+ (C)] It is preferably in the range of 100 to 1,000 parts by weight per 100 parts by weight. In addition to the components (A) to (D), aminopropyltriethoxysilane and the like can be added to the composition of the present invention, if necessary. These are added in a range that does not impair the properties of the obtained cured film. The composition of the present invention comprises the above (A) to (D)
And any other optional components added as needed are obtained by blending in appropriate amounts. The composition liquid thus obtained may contain a solid content of 30% by weight or more, but has low viscosity and good workability.

Formation of Polyimide Film In order to form a polyimide resin film using the composition of the present invention, the composition is applied to a substrate by a known method such as potting, spin coating, dipping, or printing.
150 to 500 ° C, more preferably 200 to 400 ° C
It may be cured by heating at a temperature of several ten minutes to several hours. Various heating means can be used, and examples thereof include a dryer and an electric furnace.

Applications The polyimide resin film obtained by curing the composition of the present invention may be, for example, a diode, a transistor,
It is useful as a protective film for electronic parts such as C and LSI. Specifically, for example, diode, transistor, IC, LS
Junction coat film, passivation film and buffer coat film on the surface of semiconductor device such as I; α-ray shielding film such as LSI; interlayer insulating film of multilayer wiring; conformal coat of printed circuit board; alignment film of liquid crystal display device;
An ion implantation mask or the like can be used.

[0023]

Next, examples of the present invention will be described. The present invention is not limited at all by the following Examples. In the following description, the viscosity indicates a value measured at 25 ° C. Preparation Example 1 ( Preparation of polyamic acid) In a flask equipped with a thermometer, a stirrer and a nitrogen purging apparatus, 128.89 g (0.4 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and N 500 g of -methyl-2-pyrrolidone were charged. Then, 1,
A solution prepared by dissolving 99.41 g (0.4 mol) of 3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane in 185 g of N-methyl-2-pyrrolidone was heated to a temperature of the reaction system. The solution was dropped so as not to exceed 40 ° C. After completion of the dropwise addition, the mixture was stirred for 10 hours so as not to exceed 40 ° C., and then heated and stirred at 70 ° C. for 4 hours. Thus, a solution of polyamic acid [I] having a viscosity of 95 cP was obtained.

Preparation Example 2 ( Preparation of polyamic acid) As an aromatic tetracarboxylic dianhydride, 3,3 ', 4,4
Instead of 4'-benzophenone tetracarboxylic dianhydride, 21.81 g (0.1 mol) of pyromellitic dianhydride and 132.22 g of 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride ( 0.1 mol)
355 g of N-methyl-2-pyrrolidone was used as the solvent. Further, instead of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane as a siloxane diamine, a formula:

Embedded image Was dissolved in 300 g of diethylene glycol dimethyl ether and used. A solution of polyamic acid [II] having a viscosity of 80 cP was obtained in the same manner as in Preparation Example 1 except for the above change.

Comparative Preparation Example 1 (Polyamic acid) As an aromatic tetracarboxylic dianhydride, 3,3 ', 4,4
Instead of 4'-benzophenonetetracarboxylic dianhydride, 64.45 g (0.2 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 3,3
14.71 g (0.05 mol) of 3 ', 4,4'-biphenyltetracarboxylic dianhydride was used, and 340 g of N-methyl-2-pyrrolidone was used as the solvent. Also,
1,3-bis (3-aminopropyl)-as diamine
1,1,3,3-tetramethyldisiloxane 99.41
Instead of g, 1,3-bis (3-aminopropyl)-
49.7 g of 1,1,3,3-tetramethyldisiloxane
(0.2 mol) and 10.01 g (0.05 mol) of 4,4'-diaminodiphenyl ether were used by dissolving N-methyl-2-pyrrolidone in 340 g of N-methyl-2-pyrrolidone. Except having been changed as described above, a polyamic acid [III] having a viscosity of 2800 cP was prepared in the same manner as in Preparation Example 1.
Was obtained.

Example 1 Solution 320 of polyamic acid [I] obtained in Preparation Example 1
In parts by weight, the following formula:

Embedded image 444 parts by weight of pyromellitic diester represented by
315 parts by weight of 4,4'-diaminodiphenyl ether and 1070 parts by weight of N-methyl-2-pyrrolidone were added and mixed to obtain a composition solution I.

Example 2 Solution 320 of polyamic acid [I] obtained in Preparation Example 1
In parts by weight, the following formula:

Embedded image 16,3 parts by weight of dimethyl 3,3 ', 4,4'-biphenyltetracarboxylate, 9 parts by weight of 4,4'-diaminodiphenyl ether and 86 parts by weight of N-methyl-2-pyrrolidone were added and mixed. A composition solution II was obtained.

Example 3 A solution 400 of the polyamic acid [II] obtained in Preparation Example 2
In parts by weight, the following formula:

Embedded image 342 parts by weight of an aromatic tetracarboxylic diester represented by the formula: 2,2′-bis [4- (4-aminophenoxy)
Phenyl] propane 339 parts by weight and N-methyl-2-
1223 parts by weight of pyrrolidone were added and mixed to obtain a curable composition solution III. The solid content, viscosity and film properties (strength and adhesiveness) of the obtained curable composition solution III were determined by the following methods. Table 1 shows the results.

Comparative Example 1 The solution of polyamic acid [III] obtained in Comparative Preparation Example 1 was used as it was.

The solid contents and the viscosities of the composition solutions of Examples 1 to 3 and Comparative Examples obtained as described above were measured.
The viscosity was measured immediately after preparation and after storage at 5 ° C. for 3 months. Further, each composition was spin-coated on a silicon wafer, heated at 150 ° C. for 1 hour using a drier, and further heated at 350 ° C. for 0.5 hour to cure, thereby forming a polyimide film. The strength and adhesiveness of the obtained film were measured by the following methods.

Film strength: A film having a thickness of 50 μm and a width of 1 cm was prepared and measured with a tensile tester.

Adhesion: Measured by a grid test. In other words, the coating on the wafer is cross-cut (dimensions per square: 1 mm x
1mm), and the adhesive surface of the cellophane tape was sufficiently adhered. The tape was then peeled off in a manner perpendicular to the wafer. The mass of the polyimide film peeled off together with the tape was counted, and the number of peeled masses per 100 squares was determined.

Table 1 shows the above results.

[Table 1]

[0034]

According to the curable polyimide resin composition of the present invention, a cured polyimide film having excellent heat resistance, mechanical properties, electrical properties, solvent resistance, adhesiveness, etc. can be formed, and a conventional polyimide film can be formed. It has remarkably low viscosity compared to the polyamic acid-containing solution that has been used for, and is excellent in workability when forming a polyimide film on a base material such as a silicon wafer, a metal plate, a glass plate, and a ceramic substrate. I have. Further, the viscosity of the composition is excellent in stability over time, so that it has high industrial practicality.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-62-227979 (JP, A) JP-A-61-242573 (JP, A) JP-A-53-82898 (JP, A) JP-A-60-1985 108464 (JP, A) JP43-27439 (JP, B1)

Claims (1)

(57) [Claims] (A) The following general formula (1): (Where R¹May be the same or different and have 1 carbon atom
A divalent organic group of 10 to 10,^TwoAre the same but different
And a monovalent organic group having 1 to 8 carbon atoms;
IsEmbedded imageAndIs a tetravalent aromatic group selected from the group consisting of
Is an integer of from 40 to 40, and n is an integer of 2 or more.
Polyamic acid, (B) the following general formula (2):(Where R^ThreeMay be the same or different.
And X is as defined above)
Lacarboxylic diester, (C) aromatic diamine, and
(D) Curable polyimide resin containing an organic solvent
Composition.