JPH0741671A - Curable polyimide-based resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject low-viscosity resin composition suitable for protecting electronic parts, etc., excellent in heat resistance, mechanical characteristics, electrical characteristics, solvent resistance and adhesiveness, comprising a specific polyamic acid, a prescribed aromatic tetracarboxylic acid diester, an aromatic diamine and an organic solvent. CONSTITUTION:This composition comprises (A) a polyamic acid of formula I (R<1> is 1-10C bifunctional organic group; R<2> is 1-8C monofunctional organic group; X is group of formula II, etc.; m is 1-40; n is >=2), (B) an aromatic tetracarboxylic acid diester of formula III (R<1> is alkyl), (C) an aromatic diamine such as p-phenylenediamine and (D) an organic solvent such as N-methyl-2- pyrrolidone. The blending ratio of the component A to the component D is 80-2,000 pts.wt. of the total of the components B and C (based on 100 pts.wt. of the component A), preferably 0.95-1.05 molecular ratio of the component B/C and 100-1,000 pts.wt. of the component D based on 100 pts.wt. of the total of the component A to the component C. The composition is cured to give a cured material.

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 are excellent in heat resistance, electrical characteristics, mechanical characteristics, etc. and are used as insulating protective films for electronic parts. However, since the polyimide resin is insoluble in an organic solvent, it is difficult to form a solution containing a composition containing the 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 that is a precursor of the polyimide resin is applied to a base material and heat-cured to form a polyimide resin film. However, since the solution containing this polyamic acid has a very high viscosity, it is inferior in workability, and the adhesiveness of the obtained polyimide resin film to semiconductor element materials such as nickel, aluminum, silicon, and silicon oxide film is low. There is a drawback of.

Therefore, it has been proposed to use a siloxane bond-containing polyamic acid synthesized by replacing a part of the diamine component with a diamine having a siloxane bond (Japanese Patent Publication No. 43-27439 and Japanese Patent Publication No. 59-72).
13 publication). However, although 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 lowered, it is not satisfactory and workability is still sufficient. Not.

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

[0005]

Therefore, an object of the present invention is to form 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 inventors of the present invention have made extensive studies in order to solve the above-mentioned problems, and as a result, arrived at the present invention. That is, the present invention provides (A) the following general formula (1):

[Chemical 6] (In the formula, R ¹ may be the same or different and has 1 carbon atom.
10 to 10 divalent organic groups, R ^{2 s} may be the same or different, are monovalent organic groups having 1 to 8 carbon atoms, and X 2
Is

[Chemical 7] ,

[Chemical 8] as well as

[Chemical 9] Is a tetravalent aromatic group selected from the group consisting of
A polyamic acid represented by the following general formula (2):

[Chemical 10] (In the formula, R ³ may be the same or different, is an alkyl group, and X is as described above), an aromatic tetracarboxylic acid diester, (C) an aromatic diamine, and (D) an organic compound. Provided is a curable polyimide resin composition containing a solvent.

The present invention will be described in detail below. (A) Polyamic acid In the composition of the present invention, the polyamic acid as the component (A) is a polyimide precursor, and the acid is dehydrated and ring-closed, or the aromatic tetracarboxylic acid diester and the component (C) as the component (B) are used. ) Component Aromatic diamine is dehydrated and condensed to form a polyimide resin having excellent heat resistance.

In the general formula (1) representing the polyamic acid, the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R ¹ is, for example, a methylene group, an ethylene group, a propylene group or an isocyclic group. Alkylene groups such as propylene group, butylene group, isobutylene group, hexylene group, octylene group; p-phenylene group, m-phenylene group,
An arylene group such as a tolylene group;

[Chemical 11] Etc., and substituted hydrocarbon groups in which some or all of the hydrogen atoms of these hydrocarbon groups are substituted with chlorine, fluorine, etc. Preferably, propylene group, butylene group, p
-Phenylene group, m-phenylene group and

[Chemical 12] Is. Two or more R ¹ 's contained in the molecule may be the same or different. From the ease of obtaining the raw materials, R
¹ is typically a propylene group, a butylene group, a p-phenylene group and an m-phenylene group.

Examples of the monovalent hydrocarbon group having 1 to 8 carbon atoms represented by R ² include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group,
An alkyl group such as a pentyl group, a hexyl group, a heptyl group, an octyl group and a decyl group; an aryl group such as a phenyl group and a tolyl group; a hydrogen atom such as a chloromethyl group and a 3,3,3-trifluoropropyl group; Examples thereof include an alkyl group substituted with fluorine and the like. Of these, a methyl group and a phenyl group are preferred. Two or more R ^{1 s} in the molecule may be the same or different. Because of the ease of availability of raw materials, R ²
Is typically a methyl group, an isopropyl group and a phenyl group.

The length m of the siloxane chain in the molecule is 1
It is an integer of -40, Preferably it is an integer of 1-20. When m exceeds 40, the adhesiveness to the base material will be reduced. N indicating 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 the properties of the obtained cured film, for example, tensile strength is particularly good.
Generally, 10 to 1000 is preferable.

The polyamic acid has the general formula (3):

[Chemical 13] (Wherein X is as described above), and an aromatic tetracarboxylic dianhydride represented by the general formula (4):

[Chemical 14] It is obtained by reacting a siloxane diamine represented by the formula (wherein R ¹ , R ² and m are as described above) in an organic solvent by a known method. Specifically, it can be 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, benzophenonetetracarboxylic dianhydride and 3,3 ', 4,
An example is 4'-biphenyltetracarboxylic dianhydride. These may be used alone or in combination of two or more.

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

[Chemical 15] Etc. These may be used alone or in combination of two or more.

In the general formula (2) representing the aromatic tetracarboxylic acid diester used as the component (B) aromatic tetracarboxylic acid diester (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 acid diester include pyromellitic acid dialkyl ester, benzophenone tetracarboxylic acid dialkyl ester and 3,3 ', 4,4'-biphenyltetracarboxylic acid dialkyl ester. These may be used alone or in combination of two or more.

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

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

(D) Organic solvent The organic solvent of the component (D) is not particularly limited, but a polar organic solvent is preferable. As the organic solvent, for example, N-
Cyclic amines such as methyl-2-pyrrolidone; amides such as dimethylacetamide, dimethylformamide, hexamethylphosphoramide; methyl cellosolve, butyl cellosolve, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, tetrahydrofuran, 1,4-
Examples include 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 aromatic tetracarboxylic acid diester (B) and aromatic diamine (C) in the composition of the present invention is such that aromatic tetracarboxylic acid diester (B) is added to 100 parts by weight of polyamic acid (A). ) And the aromatic diamine (C) are preferably 20 to 2000 parts by weight, more preferably 80 to 2000 parts by weight. At this time, aromatic tetracarboxylic acid diester (B) / aromatic diamine (C)
The molar ratio is preferably in the range of 0.9 to 1.1, more preferably 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 1000 parts by weight per 100 parts by weight. In addition to the above-mentioned components (A) to (D), aminopropyltriethoxysilane and the like can be added to the composition of the present invention, if necessary. These are added within a range that does not impair the properties of the obtained cured film. The composition of the present invention has the above (A) to (D).
It can be obtained by blending a proper amount of the above components and other optional components added as necessary. The composition liquid thus obtained may contain a solid content of 30% by weight or more, but its viscosity is low and good workability is exhibited.

Formation of Polyimide Film 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.
150-500 ° C, more preferably 200-400 ° C
It may be cured by heating at the temperature of several tens of minutes to several hours. Various heating means can be used, and examples thereof include a dryer and an electric furnace.

Uses Polyimide resin coatings obtained by curing the composition of the present invention include, for example, diodes, transistors, I
It is useful as a protective film for electronic components 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]

EXAMPLES Next, examples of the present invention will be shown. The present invention is not limited to the following examples. In the following description, the viscosity indicates the 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 device, 128.89 g (0.4 mol) of 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and N were added. -Methyl-2-pyrrolidone 500 g was 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 used at a temperature of the reaction system. It was added dropwise so as not to exceed 40 ° C. After completion of the dropping, the mixture was stirred for 10 hours so that the temperature did not 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) 3,3 ′, 4, as an aromatic tetracarboxylic dianhydride
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),
As the solvent, 355 g of N-methyl-2-pyrrolidone was used. Further, instead of 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane as the siloxane diamine, the formula:

[Chemical 16] 164.0 g (0.2 g) represented by the above formula 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 changes.

Comparative Preparation Example 1 (Polyamic Acid) 3,3 ′, 4 as an aromatic tetracarboxylic dianhydride
64.45 g (0.2 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride instead of 4′-benzophenonetetracarboxylic dianhydride and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride
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
1,3-bis (3-aminopropyl) -instead of g
4,9.7 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. A polyamic acid [III] having a viscosity of 2800 cP was prepared in the same manner as in Preparation Example 1 except that the above modification was made.
A solution of

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

[Chemical 17] 444 parts by weight of pyromellitic acid 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:

[Chemical 18] 16 parts by weight of dimethyl 3,3 ′, 4,4′-biphenyltetracarboxylic acid represented by, 9 parts by weight of 4,4′-diaminodiphenyl ether and 86 parts by weight of N-methyl-2-pyrrolidone are added and mixed, A composition solution II was obtained.

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

[Chemical 19] 342 parts by weight of an aromatic tetracarboxylic acid 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 was added and mixed to obtain a curable composition solution III. The solid content, viscosity and film characteristics (strength and adhesiveness) of the obtained curable composition solution III were determined by the following methods. The results are shown in Table 1.

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

The solid content and viscosity of the composition solutions of Examples 1 to 3 and Comparative Example 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, then heated at 150 ° C. for 1 hour using a drier and further heated at 350 ° C. for 0.5 hour to be cured to form a polyimide film. The strength and adhesiveness of the obtained film were measured by the following methods.

Strength of film: A film having a film thickness of 50 μm and a width of 1 cm was prepared and measured by a tensile tester.

Adhesion: Measured by a cross-cut test. That is, the film on the wafer has a grid pattern (1 square size: 1 mm x
After making a cut into 1 mm), the adhesive surface of the cellophane tape was sufficiently attached. The tape was then peeled off in a vertical manner 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 masses was obtained.

The above results are shown in Table 1.

[Table 1]

[0034]

The curable polyimide resin composition of the present invention can form a cured polyimide film having excellent heat resistance, mechanical properties, electrical properties, solvent resistance, adhesiveness, etc. Since it has a remarkably low viscosity compared to the polyamic acid-containing solution that has been used for, it has excellent workability when forming a polyimide film on a substrate such as a silicon wafer, a metal plate, a glass plate, or a ceramics substrate. There is. Moreover, since the viscosity of the composition is excellent in stability over time, it has high industrial practicality.

Claims (2)

[Claims] 1. (A) The following general formula (1): (In the formula, R ¹ may be the same or different and has 1 carbon atom.
10 to 10 divalent organic groups, R ^{2 s} may be the same or different, are monovalent organic groups having 1 to 8 carbon atoms, and X 2
Is , And Is a tetravalent aromatic group selected from the group consisting of
Is an integer of ˜40, and n is an integer of 2 or more), (B) the following general formula (2): (In the formula, R ³ may be the same or different, is an alkyl group, and X is as described above), an aromatic tetracarboxylic acid diester, (C) an aromatic diamine, and (D) an organic compound. A curable polyimide resin composition containing a solvent. 2. A cured product obtained by curing the curable polyimide resin composition according to claim 1.