JPH073018A - Polyimide resin - Google Patents

Abstract

PURPOSE:To provide a polyimide resin which is composed of specific repeating units and suitably used as a material to form insulating protecting film for electronic parts because of its excellent heat resistance, insulation, coating film flatness, chemical resistance, adhesion and flexibility. CONSTITUTION:The resin is composed of the recurring units of formula I [R<1> represents tetrafunctional organic residue where more than 50 mole % of the whole acid components constituting R<1> are (biphenyl ether)tetracarboxylic acid; 50 to 99 mole % of the whole diamine constituting R<2> are p-phenylenediamine and 50 to 1 mole % is a diaminosiloxane of formula III (R<3>, R<4> are difunctional organic group; R<5> to R<8> are 1-6C hydrocarbon; n is 0-12)].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to chemical resistance, which is used as a material for forming an insulating protective film for electronic parts such as semiconductor chips.
The present invention relates to a polyimide resin having excellent adhesion and heat resistance.

[0002]

2. Description of the Related Art Since polyimide resin has excellent heat resistance, insulation and flatness of coating film, it is used as an insulating protective film for semiconductor chips, an interlayer insulating film for multilayer wiring, an α-ray shield film for memory, and a flexible circuit board. Widely used as etc. However, ordinary polyimide resins are resistant to various processing chemicals that accompany the recent diversification of semiconductor chip manufacturing processes, such as strong hydrofluoric acid used for etching silicon, silicon oxide films, and other silicon-based inorganic films. ,
It has a drawback that it does not have sufficient chemical resistance.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned drawbacks, and has chemical resistance, adhesion,
It is an object of the present invention to provide a polyimide resin which is excellent in flexibility and which also has the heat resistance, insulating property and flatness of a coating film which conventional polyimide resins have.

[0004]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that the above object can be achieved by using a polyimide resin described later, and It has been completed.

That is, the present invention is a polyimide resin represented by the following general formula:

[0006]

[Chemical 4] (A) In the general formula of the polyimide resin, R ¹ is 4
Showing a divalent organic acid residue, 50 mol% or more of all the acid components constituting R ¹ is a biphenyl ether tetracarboxylic acid represented by the following general formula,

[0007]

[Chemical 5] (B) R ² in the general formula of the above polyimide resin is 2
(B-1) R ² is a para-phenylenediamine compound, and 50 to 99 mol% of all diamine components constituting (b-1) R ² are para-phenylenediamine compounds, and all diamines constituting (b-2) R ² 50 to 1 mol% of the components are diaminosiloxanes represented by the following general formula

[0008]

[Chemical 6] (However, in the formula, R ³ and R ⁴ are divalent organic groups, R ^{5 to} R 4
⁸ represents a hydrocarbon having 1 to 6 carbon atoms, and n represents 0 or a positive integer of 12 or less).

The present invention will be described in detail below.

The polyimide resin of the present invention has the above-mentioned general formula 4, and is obtained by reacting an acid component (A) with a diamine component (B).

As the acid component (A) used in the present invention, the biphenyl ether tetracarboxylic acid component represented by the above general formula 5 can be used. Specific compounds of the biphenyl ether tetracarboxylic acid component include 3,
4,3 ', 4'-biphenyl ether tetracarboxylic acid, 2,
Examples thereof include 3,3 ′, 4′-biphenyl ether tetracarboxylic acid, their acid anhydrides or lower alkyl esters, and these can be used alone or in combination. It is desirable to use the biphenyl ether tetracarboxylic acid component in an amount of 50 mol% or more of the total acid component. 50 m
If it is less than ol%, the acid resistance is poor and it is not preferable.

Acid components other than biphenyl ether tetracarboxylic acid include, for example, pyromellitic acid, 3,4,
3 ', 4'-biphenyltetracarboxylic acid, 2,3,3', 4 '
-Biphenyl tetracarboxylic acid, 3,3 ', 4,4'-benzophenone tetracarboxylic acid, 2,3,3', 4'-benzophenone tetracarboxylic acid, 1,4,5,8-naphthalene tetracarboxylic acid, 2 , 3,6,7-naphthalene tetracarboxylic acid, 1,2,5,
6-naphthalene tetracarboxylic acid, 3,4,9,10-tetracarboxyphenylene, 3,3 ', 4,4'-diphenylmethanetetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (3,4-dicarboxyphenyl)
Hexafluoropropane, 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid, 2,2-bis ([4- (3,4-dicarboxyphenoxy) phenyl] hexafluoropropane, etc. and their anhydrides Alternatively, lower alkyl esters and the like can be mentioned, and these can be used alone or in combination with the above-mentioned biphenyl ether tetracarboxylic acid.

The (B) diamine component used in the present invention includes (b-1) paraphenylenediamine compound and (b-2)
Used together with diaminosiloxane in a fixed ratio.

Specific examples of the (b-1) para-phenylenediamine compound include para-phenylenediamine, ortho-, meta-, and para-alkyl-substituted para-phenylenediamine. These may be used alone or in combination. be able to. This para-phenylenediamine compound is used together with the below-mentioned diaminosiloxane in a fixed ratio.

As the (b-2) diaminosiloxane, one having the following general formula is used.

[0016]

[Chemical 7] (However, in the formula, R ³ and R ⁴ are two organic groups, R ^{5 to} R 4
⁸ represents a hydrocarbon having 1 to 6 carbon atoms, and n represents 0 or a positive integer of 12 or less.) Specific compounds include bis (γ-aminopropyl) tetramethyldisiloxane and bis (4- Aminobutyl) tetramethyldisiloxane, bis (γ-aminopropyl) tetraphenyldisiloxane, 1,4-bis (γ-aminopropyldimethylsilyl) benzene and the like,
These can be used alone or in combination.

It is important to use the above-mentioned (b-1) paraphenylenediamine compound and (b-2) diaminosiloxane together in a fixed ratio. The blending ratio of these is such that (b-1) diamine compound is 50 to 9 with respect to all diamine components.
9 mol%, (b-2) diaminosiloxane 50 to 1 mol
It is desirable to mix them so that the ratio becomes%. (B-1
) If the diamine compound content is less than 50 mol%, the acid resistance will decrease, and if the (b-2) diaminosiloxane content is less than 1 mol%, the adhesion to the inorganic film (silicon dioxide film or silicon nitride film) on the surface of semiconductor chips will be poor. It is not preferable because it decreases.

The polyimide resin obtained by reacting the above-mentioned acid component and diamine component may contain the acid component and diamine component in a block or random manner.

The polyimide resin of the present invention has a logarithmic viscosity at 30 ° C. as a concentration solution of 0.5 g of polyamic acid resin / 10 ml of N-methyl-2-pyrrolidone which is its precursor.
The range is preferably 0.2 to 4.0, and more preferably 0.3 to 2.0. Polyamic acid resin is a mixture of almost equimolar acid and diamine components in an organic solvent at 30 ° C.
The following, preferably at a reaction temperature of 20 ℃ or less 3-12 hours,
It is obtained by an addition polymerization reaction. Examples of the organic solvent in this polymerization reaction include N, N'-dimethyl sulfoxide, N, N'-dimethylformamide, N, N'-diethylformamide, N, N'-dimethylacetamide, N, N'-diethylacetamide. , N-methyl-2-
Pyrrolidone, hexamethylene phosphoamide, etc. are mentioned, and these can be used individually or in mixture. This polyamic acid resin is applied and dried to give 150
A cured product of a tough polyimide resin having excellent heat resistance can be obtained by heat-curing at 400 to 400 ° C., preferably 180 to 350 ° C.

The polyimide resin of the present invention may contain fillers such as silica, calcium carbonate, aluminum hydroxide and the like, pigments, defoaming agents, etc., in addition to the above-mentioned components, as long as the object of the present invention is not impaired. It can be added and compounded.

The polyimide resin thus obtained can be used as a protective film for semiconductor chips, an insulating film such as an interlayer insulating film for multilayer wiring, or an insulating material for a flexible circuit board.
In particular, it is suitable for fields that require heat resistance and electrical characteristics. Further, the chemical resistance associated with the diversification of semiconductor chip manufacturing processes, for example, the acid resistance against hydrofluoric acid, which is an etching solution for silicon and a silicon oxide film, is excellent.

[0022]

The polyimide resin of the present invention, by using a specific acid component and a specific diamine component, imparts chemical resistance to hydrofluoric acid and the like, as well as adhesiveness and flexibility. is there. It also retains the excellent heat resistance, electrical insulation, and coating flatness of the conventional polyimide resin.

[0023]

EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 A flask equipped with a stirrer, a condenser and a nitrogen inlet tube was charged with
71.06 g of paraphenylenediamine, 10.44 g of bis (γ-aminopropyl) tetraphenyldisiloxane, and N-
Methyl-2-pyrrolidone (1750 ml) was added and dissolved. After the dissolution, 205.8 g of 3,3 ′, 4,4′-biphenyl ether tetracarboxylic acid dianhydride was added with stirring. Stirring was continued while suppressing the heat generated by the reaction in ice water, and stirring was continued for 12 hours to produce a polyamic acid resin solution. After the reaction, the reaction solution was poured into a mixed solution of methanol and water to precipitate a polyamic acid resin, which was dried to obtain 286 g of a white polyamic acid resin powder (logarithmic viscosity 0.5 dl / g).

Example 2 A flask equipped with a stirrer, a condenser and a nitrogen inlet tube was charged with
63.5 g of paraphenylenediamine, 10.44 g of bis (γ-aminopropyl) tetraphenyldisiloxane and 4,4 ′
14.0 g of diaminodiphenyl ether was added, and 1100 ml of N-methyl-2-pyrrolidone was added and dissolved. After dissolution, 102.9 g of 3,3 ', 4,4'-biphenyl ether tetracarboxylic dianhydride and 76.3 g of pyromellitic dianhydride were added with stirring. Stirring was continued while suppressing the heat generated by the reaction in ice water, and stirring was continued for 12 hours to produce a polyamic acid resin solution. After the reaction, the reaction solution was poured into a mixed solution of methanol and water to precipitate a polyamic acid resin, which was dried to give a white polyamic acid resin powder (logarithmic viscosity 0.5 dl
/ G) 266 g was obtained.

Example 3 In a flask equipped with a stirrer, a cooler and a nitrogen introducing tube,
45.36 g of paraphenylenediamine, 7.46 g of bis (γ-aminopropyl) tetraphenyldisiloxane and 4,4 ′
10.0 g of diaminodiphenyl ether was added, and 900 ml of N-methyl-2-pyrrolidone was added and dissolved. After dissolution, 73.5 g of 3,3 ', 4,4'-biphenyl ether tetracarboxylic acid dianhydride and 80.5 g of benzophenone tetracarboxylic acid anhydride were added with stirring. Stirring was continued while suppressing the heat generated by the reaction in ice water, and stirring was continued for 12 hours to produce a polyamic acid resin solution. After the reaction, the reaction solution was poured into a mixed solution of methanol and water to precipitate a polyamic acid resin, which was dried to obtain 216 g of a white polyamic acid resin powder (logarithmic viscosity 0.5 dl / g).

Comparative Example A flask provided with a stirrer, a cooler and a nitrogen inlet tube,
Add 100 g of diaminodiphenyl ether, N-methyl-
2-Pyrrolidone (1020 ml) was added and dissolved. After dissolution, the mixture was cooled to 0 ° C., and 155.1 g of 3,3 ′, 4,4′-biphenyl ether tetracarboxylic acid dianhydride was added with stirring. Stirring was continued while suppressing the heat generated by the reaction in ice water, and stirring was continued for 12 hours to produce a polyamic acid resin solution. After the reaction, the reaction solution was poured into a mixed solution of methanol and water to precipitate a polyamic acid resin, which was dried to dissolve white polyamic acid resin powder with N-methyl-2-pyrrolidone.
When the logarithmic viscosity was measured at 30 ° C. with a concentration of 0.5 g / 100 ml, it was 0.8 dl / g.

The polyamic acid resin N-methyl-2-pyrrolidone solutions obtained in Examples 1 to 3 and Comparative Example were applied to a glass plate and heat-treated at 100 ° C. for 30 minutes and 200 ° C. for 30 minutes to form a resin film. Obtained. The resin film was placed in a nitrogen atmosphere at 250 ° C for 30
Heat treatment was performed for 30 minutes at 300 ° C. to obtain a cured polyimide resin. The cured product was tested for thermogravimetric reduction temperature, water absorption rate, volume resistivity, and acid resistance. The results are shown in Table 1. Both have excellent characteristics of the present invention,
The effect of the present invention could be confirmed.

[0029]

[Table 1] * 1: The cured product was heated in a nitrogen atmosphere at a rate of 10 ° C. for 1 minute, and the temperature when the weight was reduced by 5% was measured. * 2: The change in weight when the cured product was boiled for 30 minutes was measured. * 3: A few drops of 2.5% hydrofluoric acid aqueous solution was dropped onto a cured polyimide resin product obtained by applying a polyamic acid resin solution onto a glass plate and heating and curing, then leaving it at different times for washing and rinsing with water to cure the polyimide resin by tape peeling. The time for leaving the object to start peeling was measured.

[0030]

As is clear from the above description and Table 1, the polyimide resin of the present invention is excellent in chemical resistance, adhesion and flexibility, and is particularly suitable for strong hydrofluoric acid used in semiconductor manufacturing processes. It is durable and retains the heat resistance, insulating property, and coating flatness of the conventional polyimide resin, and is suitable as a material for forming a semiconductor element protective film and the like.

Claims (1)

[Claims] 1. A polyimide resin represented by the following general formula, wherein: (A) In the general formula of the polyimide resin, R ¹ is 4
A divalent organic acid residue is shown, and 50 mol% or more of all the acid components constituting R ¹ is a biphenyl ether tetracarboxylic acid represented by the following general formula: (B) R ² in the general formula of the above polyimide resin is 2
(B-1) R ² is a para-phenylenediamine compound, and 50 to 99 mol% of all diamine components constituting (b-1) R ² are para-phenylenediamine compounds, and all diamines constituting (b-2) R ² 50 to 1 mol% of the components are diaminosiloxanes represented by the following general formula: (However, in the formula, R ³ and R ⁴ are divalent organic groups, R ^{5 to} R 4
⁸ represents a hydrocarbon having 1 to 6 carbon atoms, and n represents 0 or a positive integer of 12 or less).