JPH06340847A - Adhesive and heat-resistant coating film - Google Patents

Abstract

PURPOSE:To provide a heat-resistant or both heat-resistant and solvent-resistant coating film excellent in adhesion to a variety of semiconductors such as coated silicon wafers by using a polyimide film excellent in solubility in a low-boiling solvent. CONSTITUTION:The coating film comprises a polyimide comprising repeating units of formula I (wherein X is a tetravalent organic group containing a structure of formula II; Y is a bivalent organic group; and Z is a hydrogen atom, an alkyl group or a substituted alkyl group) and having an intrinsic viscosity of 0.1dl/g or above. A solvent-resistant, adhesive and heat-resistant coating film prepared by heat-treating a film made of said polyimide is also provided. A polyimide-film-coated semiconductor prepared by coating a semiconductor with any one of the above coating films is also provided.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is for passivation,
The present invention relates to an adhesive, heat-resistant coating film obtained by coating polyimide on a semiconductor such as a silicon-based wafer and a polyimide-coated semiconductor, which is used for insulation, protection, or α-ray shielding.

[0002]

2. Description of the Related Art Polyimide is excellent in heat resistance and is therefore used as a heat resistant coating film for passivation, insulation, protection or α-ray shielding.
However, conventional polyimide is insoluble in other than some high-boiling solvent, not only apply a polar solvent solution of a polyamic acid that is a precursor polymer of the polyimide to the substrate, and not only dry the solvent, It was necessary to perform heat treatment at a high temperature of 300 ° C. or higher for a long time to imidize.

[0003]

However, in the case of this method, the boiling point of a polar solvent such as N-methyl-2-pyrrolidone is high, and therefore a high temperature and long time heat treatment condition is required for complete removal of the solvent. And, there was a problem in its workability.

Further, in this method, the corrosiveness due to polyamic acid also poses a problem (Journal of the Institute of Electronics, Information and Communication Engineers, C, Vo.
l. J71-C, No. 11. pp1510 (1988)
), IEICE Transactions C, Vol. J71-
C, No. 11. pp1516 (1988)), and the adhesiveness is also reduced by stress generated during imidization accompanied by structural change due to heat treatment.

The present invention is intended to solve such problems, and is composed of a polyimide film having excellent solubility in a solvent having a low boiling point, and has excellent heat resistance with excellent adhesion to various semiconductors such as silicon wafers after coating. An object of the present invention is to provide a coating film, a coating film having solvent resistance in addition to adhesiveness and heat resistance, and a polyimide-coated semiconductor obtained by coating the semiconductor film with the coating film.

[0006]

In order to solve the above-mentioned problems, the present inventors provide the polyimide used as a heat-resistant coating film with adhesiveness to various semiconductors and workability during coating. As a result of earnestly studying the above, the present invention has been completed.

That is, the present invention comprises repeating units represented by the following general formula (I) and has an intrinsic viscosity of 0.1 dl /
It is an adhesive and heat resistant coating film made of polyimide having a weight of at least g.

[0008]

[Chemical 5]

(In the formula, X represents a tetravalent organic group containing a structure represented by the following formula (II), and Y represents a divalent organic group. Z
Represents a hydrogen atom, an alkyl group or a substituted alkyl group. )

[0010]

[Chemical 6]

The present invention is also a polyimide-coated semiconductor obtained by coating the semiconductor with an adhesive and heat-resistant coating film made of the above polyimide.

Further, the present invention comprises a repeating unit represented by the following general formula (I) and has an intrinsic viscosity of 0.1 dl.
It is a solvent-resistant, adhesive, and heat-resistant coating film obtained by heat-treating a polyimide coating having a weight ratio of at least 1 g / g.

[0013]

[Chemical 7]

(In the formula, X represents a tetravalent organic group containing a structure represented by the following formula (II), and Y represents a divalent organic group. Z
Represents a hydrogen atom, an alkyl group or a substituted alkyl group. )

[0015]

[Chemical 8]

The present invention is also a polyimide-coated semiconductor obtained by coating the above solvent-resistant, adhesive, and heat-resistant coating film on a semiconductor.

The present invention will be described in more detail below. The polyimide used in the present invention has a structure composed of repeating units represented by the following general formula (I).

[0018]

[Chemical 9]

The repeating unit represented by the general formula (I) of the present invention has X in the formula, and this X is a tetravalent organic group containing a partial structure represented by the following formula (II). is there.

[0020]

[Chemical 10]

In the above formula (II), Z represents a hydrogen atom, an alkyl group or a substituted alkyl group. The alkyl group is a methyl group, an ethyl group or the like, and the substituted alkyl group is a halogenated methyl group or an ethyl halide. Groups and the like.

Examples of the monomer as a group containing the partial structure represented by the above formula (II) include bis- [4- (1,2,3,6-tetrahydroanhydrophthalic anhydride) represented by the following formula (III). Acid)] silane or a bis-formula such as formula (IV)
[4- (1,2,3,6-tetrahydrophthalic anhydride)] methylsilane, and bis [4- (1,2,3,4)
6-Tetrahydrophthalic anhydride)] ethylsilane, bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] (chloromethyl) silane, bis [4- (1,2,2)
3,6-Tetrahydrophthalic anhydride)] (fluoromethyl) silane, bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] (bromomethyl) silane, bis [4
-(1,2,3,6-Tetrahydrophthalic anhydride)]
(Dichloromethyl) silane, bis [4- (1,2,3,3
6-Tetrahydrophthalic anhydride)] (difluoromethyl) silane, bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] (dibromomethyl) silane, bis [4- (1,2,3,3) 6-tetrahydrophthalic anhydride)] (trichloromethyl) silane, bis [4- (1,
2,3,6-Tetrahydrophthalic anhydride)] (trifluoromethyl) silane, bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] (tribromomethyl) silane, bis [4- ( 1,2,3,6-tetrahydrophthalic anhydride)] (chloroethyl) silane, bis [4- (1,
2,3,6-Tetrahydrophthalic anhydride)] (bromoethyl) silane, bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] (fluoroethyl) silane, bis [4- (1,2) , 3,6-Tetrahydrophthalic anhydride)] (dichloroethyl) silane, bis [4- (1,
2,3,6-tetrahydrophthalic anhydride)] (dibromoethyl) silane, bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] (difluoroethyl) silane,
Bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] (Perchlorethyl) silane, bis [4- (1,
Examples include 2,3,6-tetrahydrophthalic anhydride)] (perbromoethyl) silane and bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] (perfluoroethyl) silane.

[0023]

[Chemical 11]

[0024]

[Chemical 12]

In the general formula (I) of the present invention, Y
Is at least one kind of divalent organic group, and examples of the monomer that is the base include reactive derivatives of diamine such as diamine and diisocyanic acid.

Suitable Y-source monomers for use in the present invention include, but are not limited to:

M-phenylenediamine, p-phenylenediamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6
-Diaminonaphthalene, 2,7-diaminonaphthalene,
2,6-diaminoanthracene, 2,7-diaminoanthracene, 1,8-diaminoanthracene, 2,4-diaminotoluene, 2,5-diamino (m-xylene),
2,5-diaminopyridine, 2,6-diaminopyridine, 3,5-diaminopyridine, 2,4-diaminotoluenebenzidine, 3,3'-diaminobiphenyl, 3,
3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine, 2,2'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenyl ether, 4,
4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylsulfone, 4,
4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl thioether, 4,4'-diamino-3,3 ', 5,5' -Tetramethyldiphenyl ether, 4,4'-diamino-
3,3 ', 5,5'-tetraethyldiphenyl ether, 4,4'-diamino-3,3', 5,5'-tetramethyldiphenylmethane, 1,3-bis (3-aminophenoxy) benzene, 1,3 -Bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy)
Benzene, 2,6-bis (3-aminophenoxy) pyridine, 1,4-bis (3-aminophenylsulfonyl)
Benzene, 1,4-bis (4-aminophenylsulfonyl) benzene, 1,4-bis (3-aminophenylthioether) benzene, 1,4-bis (4-aminophenylthioether) benzene, 4,4'-bis (3-Aminophenoxy) diphenylsulfone, 4,4'-bis (4-aminophenoxy) diphenylsulfone, bis (4-aminophenyl) amine, bis (4-aminophenyl) -N-methylamine, bis (4- Aminophenyl) -N-phenylamine, bis (4-aminophenyl) phosphine oxide, bis (4-aminophenyl)
Dimethylsilane, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) methylphenylsilane, bis (4-aminophenyl) diphenylsilane,
1,1-bis (3-aminophenyl) ethane, 1,1-
Bis (4-aminophenyl) ethane, 2,2-bis (3
-Aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-amino-
3,5-Dimethylphenyl) propane, 4,4′-bis (4-aminophenoxy) biphenyl, bis [4- (3
-Aminophenoxy) phenyl] sulfone, bis [4-
(4-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether,
Bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl-4- (4-aminophenoxy)
Phenyl] methane, bis [3-chloro-4- (4-aminophenoxy) phenyl] methane, bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4-Aminophenoxy) phenyl] ethane, 1,1-bis [3-methyl-4- (4-
Aminophenoxy) phenyl] ethane, 1,1-bis [3-chloro-4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [3,5-dimethyl-4-
(4-Aminophenoxy) phenyl] ethane, 2,2-
Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-chloro-4- (4 -Aminophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4
-(4-aminophenoxy) phenyl] butane, 2,2
-Bis [3-methyl-4- (4-aminophenoxy) phenyl] butane, 2,2-bis [3,5-dimethyl-4
-(4-aminophenoxy) phenyl] butane, 2,2
-Bis [3,5-dibromo-4- (4-aminophenoxy) phenyl] butane, 1,1,1,3,3,3-hexafluoro-2,2-bis (4-aminophenyl) propane, 1 , 1,1,3,3,3-hexafluoro-2,
2-bis [3-methyl-4- (4-aminophenoxy)
Phenyl] propane, bis (3-aminophenyl)-
1,1,3,3-tetramethyldisiloxane, bis (4
-Aminophenyl) -1,1,3,3-tetramethyldisiloxane, bis (3-aminophenoxy) -1,1,
3,3-tetramethyldisiloxane, bis (4-aminophenoxy) -1,1,3,3-tetramethyldisiloxane, bis (3-aminophenyl) tetramethyldisilane, bis (4-aminophenyl) tetramethyl Disilane, bis (3-methyl-4-aminophenyl) tetramethyldisilane, bis (3-aminophenoxy) tetramethyldisilane, bis (4-aminophenoxy) tetramethyldisilane, p-phenylene diisocyanate, 4,4
-Diisocyanic acid diphenyl ether.

Preferred examples of the polyimide comprising the repeating unit represented by the general formula (I) in the present invention are:
The polyimide represented by the following general formula (V) may be mentioned.

[0029]

[Chemical 13]

Generally, the specific viscosity of a solution is measured at two or more points,
The value obtained by dividing them by the concentration is called the intrinsic viscosity. And
A value obtained by extrapolating this intrinsic viscosity to a concentration of 0.0 g / dl is called intrinsic viscosity. This intrinsic viscosity means the apparent effective volume occupied by one molecule in a solution, and is a value that depends on the type of polymer, the molecular weight, the type of solvent, and the temperature. It is possible to define the magnitude relationship of molecular weights under a constant condition.

On the other hand, in the solution, the effective volume occupied by one molecule of the polymer changes greatly depending on the affinity with the solvent. That is, in a solvent having a good affinity with itself, the effective volume becomes large, which makes it easy to compare the molecular weights.

Therefore, in the present invention, the molecular weight of the polyimide is pyridine, tetrahydrofuran, dichloromethane, N, N-dimethylformamide, N-methyl-2-.
In a solvent of at least one of pyrrolidone and concentrated sulfuric acid, an intrinsic viscosity at 30 ° C. is at least 0.1 dl /
It is desirable that it is g or more, preferably 0.5 dl / g or more, and more preferably 1.0 dl / g or more. If the intrinsic viscosity is less than 0.1 dl / g, a polyimide having sufficient strength cannot be obtained.

In the present invention, polyimide is excellent in solvent solubility in a low boiling point solvent, but the low boiling point solvent is a solvent having a lower boiling point than N, N-dimethylformamide (boiling point 153 ° C.).

The term "soluble in a low boiling point solvent" as used in the present invention means that at least one low boiling point solvent is 10 g at room temperature.
/ It means that it dissolves by 1 or more.

The solvent for dissolving the polyimide is as follows, but the solvent is not limited thereto. Further, these solvents can be used as they are or as a mixture.
Chloroform, dichloromethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,
Organic halides such as 1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, trichloroethylene and tetrachloroethylene. Pyridine, 2-picoline, 3-picoline, 4-picoline, 2,3-lutidine,
Heteroaromatic compounds such as 2,4-lutidine, 2,5-lutidine, 2,6-lutidine, 3,4-lutidine, 3,5-lutidine, and 2,6-lutidine. N, N-dimethylformamide (DMF), N, N-dimethylacetamide,
An aprotic polar solvent such as N-methyl-2-pyrrolidone. Cyclic ethers such as tetrahydrofuran and dioxane. Lactones such as γ-butyrolactone. Methanol-
A mixed solvent of an alcohol and a cyclic ether such as a tetrahydrofuran mixed solvent or an ethanol-tetrahydrofuran mixed solvent.

Since the polyimide of the present invention has excellent adhesiveness to an inorganic material such as a semiconductor, an adhesive and heat resistant coating film can be formed. In addition, a polyimide-coated semiconductor can be obtained by coating the semiconductor with the adhesive and heat-resistant coating film made of the polyimide.

As the semiconductor, silicon, silicon oxide,
Silicon-based wafers such as silicon nitride, germanium,
Examples thereof include gallium arsenide.

In the method for forming a polyimide film according to the present invention, the film can be formed by applying a solution of polyimide dissolved in a solvent in which the polyimide is dissolved to a semiconductor and evaporating the solvent.

Next, a coating film made of polyimide composed of the repeating unit represented by the general formula (I) in the present invention is heat-treated to obtain a coating film excellent in solvent resistance as well as adhesiveness and heat resistance. Can be formed.
Further, the polyimide-coated semiconductor can be obtained by coating the semiconductor with the solvent resistant, adhesive and heat resistant coating film made of the polyimide.

In the present invention, the heat treatment condition for the polyimide coating is 150 to 400 ° C., preferably 18
It is desirable that the temperature is 0 to 350 ° C, more preferably 200 to 300 ° C, and most preferably 220 to 280 ° C.

The solvent resistance of the coating film, which is excellent in solvent resistance in addition to the adhesiveness and heat resistance obtained by heat treatment of the polyimide coating, is N, N-dimethylformamide (DMF), dichloromethane, tetrahydrofuran or pyridine. It means that neither of them dissolves at 10 g / ml or more at room temperature and does not swell.

The coating film obtained by coating the polyimide of the present invention on a semiconductor can be used for passivation, insulation, protection, or α-ray shielding.

[0043]

EXAMPLES The present invention will be described in detail below with reference to synthesis examples and examples.

Synthesis Example 1 Synthesis of bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] silane In a 1000 ml separable flask equipped with a reflux condenser, thermometer, stirrer and dropping funnel, bis was added. [2- (1,3-Butadienyl)] silane 14.3 g
Tetrahydrofuran containing (0.105 mol) (hereinafter,
425 g of a solution (referred to as THF) was charged, the internal temperature was raised to 60 ° C. under a nitrogen gas atmosphere, and stirring was started. From a suitable funnel, 40 g of a THF solution containing 23.3 g (0.238 mol) of maleic anhydride was added over 40 minutes. Furthermore, the reaction was continued at 60 ° C. for 3 hours. 1000 cc of hexane was added to this reaction solution at room temperature, and the precipitate was collected by suction filtration under a nitrogen atmosphere, further dissolved in acetone, reprecipitated with hexane, and dried under heating and vacuum to obtain 21.5 g of a white powder. Recovered. (Yield 72%)

This compound was analyzed by NMR, mass spectrum and infrared absorption spectrum. The results are shown below. From the results, this white powder was confirmed to be bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] silane.

¹ HNMR; acetone-d ₆ (27
C) δ (ppm) 6.55 to 6.65 (m, 2H, HC = C) 4.14 (S, 2H, SiH ₂ ) 3.57 to 3.68 (m, 4H, CH) 2.20 _{~2.71 (m, 8H, CH 2} )

Infrared absorption spectrum (cm ^-1 ) 2120 (Si-H) 1600 (C = C) 1840, 1770, 1240, 1050, 940
(O = C-O-C = O) 2950, 1440 (C-H)

Mass spectrum 332 (M ⁺ )

[0049]

[Chemical 14]

Synthesis Example 2 Synthesis of bis [4- (1,2,3,6-tetrahydrophthalic anhydride)] methylsilane Using the same apparatus as in Synthesis Example 1, bis [2- (1,3-butadienyl)] 425 g of a THF solution containing 15.8 g (0.105 mol) of methylsilane was charged, the internal temperature was raised to 60 ° C. under a nitrogen gas atmosphere, and stirring was started. From the lower funnel, maleic anhydride 23.3 g (0.238 mol)
40 g of a THF solution containing was added over 40 minutes. Further, the reaction was continued at 60 ° C. for 3 hours. Then, 1000 cc of hexane was added at room temperature, and the precipitate was collected by suction filtration under a nitrogen atmosphere. Furthermore, this precipitate was heated and vacuum dried to collect 23 g of a white powder. (70% yield)

This compound was analyzed by NMR, mass spectrum and infrared absorption spectrum. The results are shown below. The white powder was bis [4- (1,
2,3,6-tetrahydrophthalic anhydride)] methylsilane.

¹ HNMR; acetone-d ₆ (30
C) δ (ppm) 6.41 to 6.55 (m, 2H, HC = C) 4.06 to 4.15 (m, 1H, SiH) 3.55 to 3.68 (m, 4H, CH) _{2.25~2.71 (m, 8H, CH 2} ) 0.18~0.30 (m, 3H, CH 3)

Infrared absorption spectrum (cm-1) 2120 (Si-H) 1600 (C = C) 1840, 1770, 1240, 1050, 940
(O = C-O-C = O) 2950, 1440 (C-H)

Mass spectrum 346 (M ⁺ ) 331 (M-CH ₃ ) ⁺

[0055]

[Chemical 15]

Example 1 2.14 g of 4,4'-diaminodiphenyl ether (1
0.7 mmol) to N, N-dimethylformamide 4
It was dissolved in 1.7 g. Bis- [4- (1,
2,3,6, -Tetrahydrophthalic anhydride)] silane 3.55 g (10.7 mmol) was added to obtain a polyamic acid N, N-dimethylformamide solution.

The polymerization solution was formed into a film by the casting method, and the film was dipped (acetic anhydride-pyridine (1:
1) Mixed solvent, 5 hours) to obtain a polyimide film. Further, the intrinsic viscosity is 0. 0 as a value measured at 30 ° C. using an Ubbelohde viscometer using dichloromethane as a solvent.
It was 66 dl / g.

Furthermore, the obtained polyimide film 1.
0 g was dissolved in 7.5 ml of γ-butyrolactone, and this was applied to a silicon-based wafer such as silicon, silicon oxide, or silicon nitride, and γ-butyrolactone was evaporated to form a polymer layer. For these, heat treatment (1
mmHg, 200 ° C., 1 hour) (film thickness: 6 to
8 μm), the adhesiveness is cross-cut tape method JIS-K5400
The evaluation was performed at an interval of 1 mm and a number of squares of 100. As a result, all of 100 pieces remained without peeling.

Further, after pressure cooker treatment (125 ° C., 5 hours) was performed on these samples, the adhesiveness was evaluated again by the cross-cut tape method JIS-K5400 (interval 1 mm, square 100). went. The evaluation results are shown in Table 1.

Example 2 A sample (having a polymer layer formed on a silicon-based wafer) which was not peeled off in the evaluation of adhesiveness by the cross-cut tape method performed in Example 1 was heat-treated in an electric furnace ( 1 mmHg, 250 ° C., 5 hours). And
The polymer layer was scraped off and immersed in 1 ml each of N, N-dimethylformamide (DMF), dichloromethane, tetrahydrofuran or pyridine (1 ml) for 24 hours. As a result, it was not dissolved in any case.

Example 3 1.48 g of 4,4'-diaminodiphenyl ether
(7.39 mmol) was dissolved in 29.65 g of N, N-dimethylformamide. Bis- [4-
2.56 g (7.39 mmol) of (1,2,3,6-tetrahydrophthalic anhydride)] methylsilane was added to obtain a polyamic acid N, N-dimethylformamide solution.

The polymerization solution was formed into a film by the casting method, and the film was dipped (acetic anhydride-pyridine (1:
1) Mixed solvent, 5 hours) to obtain a polyimide film. Further, the intrinsic viscosity is 0. 0 as a value measured at 30 ° C. using an Ubbelohde viscometer using dichloromethane as a solvent.
It was 37 dl / g.

Further, the obtained polyimide film 1.
0 g was dissolved in 7.5 ml of γ-butyrolactone, and this was applied to a silicon-based wafer such as silicon, silicon oxide, or silicon nitride, and γ-butyrolactone was evaporated to form a polymer layer. For these, heat treatment (1
mmHg, 200 ° C., 1 hour) (film thickness: 6 to
9 μm), the adhesiveness is cross-cut tape method JIS-K5400
The evaluation was performed at an interval of 1 mm and a number of squares of 100. As a result, all of 100 pieces remained without peeling.

Further, after pressure cooker treatment (125 ° C., 5 hours) was performed on these samples, the adhesiveness was evaluated again by the cross-cut tape method JIS-K5400 (interval 1 mm, interval 100). went. The evaluation results are shown in Table 1.

Example 4 A sample (having a polymer layer formed on a silicon-based wafer) that was not peeled off in the evaluation of adhesiveness by the cross-cut tape method performed in Example 3 was heat-treated in an electric furnace ( 1 mmHg, 250 ° C., 5 hours). And
The polymer layer was scraped off and immersed in 1 ml each of N, N-dimethylformamide (DMF), dichloromethane, tetrahydrofuran or pyridine (1 ml) for 24 hours. As a result, it was not dissolved in any case.

Comparative Example 1 4,4'-diaminodiphenyl ether 2.02 g (1
0.09 mmol) to N, N-dimethylformamide 4
It was dissolved in 1.47 g. Bis- [4-
(1,2,3,6-Tetrahydrophthalic anhydride)] dimethylsilane (3.64 g, 10.10 mmol) was added to obtain a polyamic acid N, N-dimethylformamide solution.

The polymerization solution was formed into a film by the casting method, which was then subjected to a dipping treatment (acetic anhydride-pyridine (1:
1) Mixed solvent, 5 hours) to obtain a polyimide film. Further, the intrinsic viscosity is 0. 0 as a value measured at 30 ° C. using an Ubbelohde viscometer using dichloromethane as a solvent.
It was 53 dl / g.

Further, 1.0 g of the obtained polyimide was γ
-Butyrolactone was dissolved in 7.5 ml, and this was applied to a silicon-based wafer such as silicon, silicon oxide, and silicon nitride, and γ-butyrolactone was evaporated to form a polymer layer. Heat treatment for these with an electric furnace (1 mmH
g, 200 ° C., 1 hour) (film thickness: 5 to 9 μ)
m), and the adhesiveness was evaluated by a cross-cut tape method JIS-K5400 (interval 1 mm, number of squares 100). As a result, all of 100 pieces remained without peeling.

Furthermore, after pressure cooker treatment (125 ° C., 5 hours) was performed on these samples, the adhesiveness was evaluated again by the cross-cut tape method JIS-K5400 (interval 1 mm, square 100). went. The evaluation results are shown in Table 1.

Comparative Example 2 A sample (having a polymer layer formed on a silicon-based wafer) that was not peeled off in the evaluation of the adhesiveness by the cross-cut tape method performed in Comparative Example 1 was heat-treated in an electric furnace ( 1 mmHg, 250 ° C., 5 hours). And
The polymer layer was scraped off and immersed in 1 ml each of N, N-dimethylformamide (DMF), dichloromethane, tetrahydrofuran or pyridine (1 ml) for 24 hours. As a result, swelling occurred in all cases.

[0071]

[Table 1]

(Note) (1) The structural formula (VI) of polyimide is shown below.

[0073]

[Chemical 16]

(2) Pressure cooker processing (125
The adhesiveness after conducting the test for 5 hours (° C, 5 hours)
The result of having evaluated by S-K5400 (spacing 1 mm, number 100 of squares) is shown. (3) The data of Examples and Comparative Examples in Table 1 show the values obtained from three samples.

Accelerated over-humidity test for adhesion between pressure cooker treated inorganic material and coating film coated on it. Water and the sample were put in a pressure vessel so as not to be immersed in water and sealed, and the temperature was raised to 125 ° C. to make the humidity 100% with saturated steam, and then kept at 125 ° C. for 5 hours.

From the results shown in Table 1, when the pressure cooker treatment was performed as a harsh test, the Si-H group was introduced into the polyimide in the silicon-based wafer that was subjected to the nitride film and oxide film treatment and the untreated silicon-based wafer. It was confirmed that the effect of

Example 5 The same results as in Example 1 were obtained when N, N-dimethylformamide (DMF) was used as the solvent instead of γ-butyrolactone as the solvent in Example 1.

Example 6 The same results as in Example 3 were obtained when N, N-dimethylformamide (DMF) was used as the solvent instead of γ-butyrolactone as the solvent in Example 3.

[0079]

As described above, the adhesive and heat-resistant coating film made of the polyimide according to the present invention has excellent solubility in a solvent having a low boiling point, excellent workability during coating, and various semiconductors such as silicon wafers. It has an excellent effect on adhesiveness.

By heating the polyimide film according to the present invention, a coating film having solvent resistance as well as adhesiveness and heat resistance can be obtained. further,
By coating such a coating film on a semiconductor, a polyimide-coated semiconductor having adhesiveness, heat resistance and solvent resistance can be obtained.

Claims (6)

[Claims] 1. An adhesive and heat-resistant coating film comprising a repeating unit represented by the following general formula (I) and comprising a polyimide having an intrinsic viscosity of 0.1 dl / g or more. [Chemical 1] (In the formula, X includes a structure represented by the following formula (II) 4
A valent organic group, and Y represents a divalent organic group. Z is a hydrogen atom,
An alkyl group or a substituted alkyl group is shown. ) [Chemical 2] 2. A polyimide-coated semiconductor obtained by coating the adhesive and heat-resistant coating film of the polyimide according to claim 1 on a semiconductor. 3. The polyimide-coated semiconductor according to claim 2, wherein the semiconductor is a silicon-based wafer. 4. A solvent resistance, an adhesive property, and a heat resistance obtained by heat-treating a coating film composed of a repeating unit represented by the following general formula (I) and having an intrinsic viscosity of 0.1 dl / g or more. Coating film. [Chemical 3] (In the formula, X includes a structure represented by the following formula (II) 4
A valent organic group, and Y represents a divalent organic group. Z is a hydrogen atom,
An alkyl group or a substituted alkyl group is shown. ) [Chemical 4] 5. A polyimide-coated semiconductor obtained by coating the solvent-resistant, adhesive, and heat-resistant coating film according to claim 4 on a semiconductor. 6. The polyimide-coated semiconductor according to claim 5, wherein the semiconductor is a silicon-based wafer.