JPH09169904A - Highly adhesive heat-resistant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of also improving its adhesiveness to epoxy-based sealing material while retaining its adhesiveness to silicone boards, etc., thus useful for highly reliable semiconductor elements and multilayer wiring boards, etc., essentially comprising each specific polyamic acid ester and organosilicon compound. SOLUTION: This resin composition essentially comprises (A) 100 pts.wt. of a polyamic acid ester of formula I (R1 is a tetravalent organic residue such as benzene-1,2,4,5-tetrayl, biphenyl-3,4,4',5'-tetrayl or diphenylketone-3,3',4,4'- tetrayl; R2 is a divalent organic diamine residue such as 1,4-phenylene, 2- methyl-1,4-phenylene, 2,5 or 2,6-dimethyl-1,4-phenylene or phenyl ether-4,4'-diyl; (n) is 10-500) and (B) e.g. 0.01-10 pts.wt. of a compound of formula II (R3 is a tetravalent aromatic residue; R4 is a divalent organic group; R5 and R6 are each a monovalent organic group; (1) is 0-2) of formula III (R7 is a divalent armoatic residue or vinylene).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyamic acid composition used for semiconductor devices, multilayer wiring boards, microelectronic devices, etc.
Not only does it provide high adhesion to silicon-containing films such as N and SiON, but it also provides adhesion to epoxy-based encapsulating materials used in plastic packages, even after plasma treatment and moisture absorption treatment. It is characterized by not decreasing.

[0002]

2. Description of the Related Art As semiconductor chips become finer and larger,
Polyimide resin coating is an essential technology for ensuring reliability. When polyimide resin is used for the surface protection film or interlayer insulating film of semiconductor elements, Si, SiO ₂ ,
A structure having a siloxane bond is introduced into the polyimide skeleton for the purpose of improving the adhesiveness to an inorganic underlayer film such as Si ₃ N ₄ or a metal for forming a circuit such as Al or Cu (Japanese Patent Laid-Open No. Sho 6-96).
No. 1-64730), a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, etc. have been usually added (Japanese Patent Laid-Open No. Sho 5).
9-160140, 63-15847).
However, if the polyimide resin film is exposed to the dry etching process of forming a hole in the inorganic passivation film during the semiconductor manufacturing process, the adhesion between the polyimide surface and various metals or the sealing resin is extremely reduced, and the There has been a problem that the reliability of the device is greatly reduced. Further, when a structure having a siloxane bond is introduced into the polyimide skeleton, the linear expansion coefficient of the cured film becomes large, and the substrate is warped.

[0003]

DISCLOSURE OF THE INVENTION According to the present invention, a polyamic acid and an organosilicon compound are blended in a specific amount to improve the adhesiveness to an epoxy type encapsulating material while maintaining the adhesiveness to a substrate such as Si. A high adhesion polyimide resin composition is also provided.

[0004]

According to the present invention, (A) a polyamic acid represented by the following general formula (1) and (B) an organosilicon compound represented by the following general formula (2) are essential components. A highly adherent heat resistant resin composition, wherein R ₁ in the polyamic acid represented by formula (1) is a heat resistant resin composition containing at least one selected from the following formula (3): R ₂ in the polyamic acid represented by the formula (1) is a heat-resistant resin composition containing at least one selected from the following formula (4), and preferably the organosilicon compound is based on 100 parts by weight of the polyamic acid. The heat-resistant resin composition contains 0.01 to 10 parts by weight.

[0005]

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[0006]

[Chemical 6]

[0007]

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[0008]

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[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamic acid used in the present invention is obtained by reacting a tetracarboxylic dianhydride with a diamine. The acid dianhydride used in the present invention is pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 3,3'4,4'-biphenyltetracarboxylic dianhydride. , Benzene-1,2,3
4-tetracarboxylic dianhydride, 2,2 ', 3,3'-
Benzophenone tetracarboxylic dianhydride, 2,3
3 ', 4'-benzophenone tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene- 1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4 , 8-dimethyl-1,2,
3,5,6,7-hexahydronaphthalene-1,2,2
5,6, -tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2 , 6
-Dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4
5,8-Tetracarboxylic acid dianhydride, 2,3,6,7-
Tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride,
2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) Ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-
Dicarboxyphenyl) methane dianhydride, bis (3,4
-Dicarboxyphenyl) methane dianhydride, bis (2,
3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-
Tetracarboxylic acid dianhydride, perylene-3,4,9,1
0-tetracarboxylic dianhydride, perylene-4,5,1
0,11-tetracarboxylic dianhydride, perylene-5,
6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride,
Phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-
Tetracarboxylic acid dianhydride, pyrazine-2,3,5,6
-Tetracarboxylic dianhydride, pyridine-2,3,4
5-tetracarboxylic dianhydride, thiophene-2,3
Examples include 4,5-tetracarboxylic dianhydride,
It is not limited to these. In use, one kind or a mixture of two or more kinds may be used.

Preferably, pyromellitic dianhydride,
3,3'4,4'-biphenyltetracarboxylic acid dianhydride and 3,3'4,4'-benzophenonetetracarboxylic acid dianhydride are preferred because they provide good adhesion and film properties. The reaction between the diamine and the tetracarboxylic dianhydride in the present invention is preferably carried out in an equimolar amount as much as possible, and the degree of polymerization also becomes large. Either one is 10
When the amount is more than mol%, the degree of polymerization is remarkably lowered, and a low molecular weight product having poor film-forming property is obtained, which is not preferable. Usually, it is preferable to use 1 to 3 mol% of the diamine component or the acid component in a large amount in order to improve the film characteristics.

The diamines used in the present invention are p-
Phenylenediamine, 2,5-diaminotoluene, 2,
5-diamino-p-xylene, m-phenylenediamine, 3,5-diamino-toluene, 2,6-diamino-
m-xylene, 2,6-diamino-p-xylene, 4,
4'-diaminodiphenyl ether, 1-isopropyl-2,4-phenylene-diamine, 4,4'-diamino-diphenylpropane, 3,3'-diamino-diphenylpropane, 4,4'-diamino-diphenylethane,
3,3'-diamino-diphenylethane, 4,4'-diamino-diphenylmethane, 3,3'-diamino-diphenylmethane, 4,4'-diamino-diphenyl sulfide, 3,3'-diamino-diphenyl sulfide,
4,4'-diamino-diphenylsulfone, 3,3'-
Diamino-diphenyl sulfone, 3,3'-diamino-
Diphenyl ether, benzidine, 3,3'-diamino-biphenyl, 3,3'-dimethyl-4,4'-diamino-biphenyl, 3,3'-dimethoxy-benzidine,
4,4′-diamino-p-terphenyl, 3,3 ″ -diamino-p-terphenyl, bis (p-amino-cyclohexyl) methane, bis (p-β-amino-t-butylphenyl) ether, bis (P-β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl-4-amino-pentyl) benzene, p-bis (1,1-dimethyl-5-amino-pentyl) benzene, 1, 5-diamino-naphthalene, 2,6-diamino-naphthalene, 2,
4-bis (β-amino-t-butyl) toluene, 2,4
-Diamino-toluene, 2,6-diamino-pyridine,
2,5-diamino-pyridine, 2,5-diamino-1,
3,4-oxadiazole, 1,4-diamino-cyclohexane, piperazine, methylene-diamine, ethylene-diamine, propylene-diamine, 2,2-dimethyl-propylene-diamine, tetramethylene-diamine,
Pentamethylene-diamine, hexamethylene-diamine, 2,5-dimethyl-hexamethylene-diamine, 3
-Methoxy-hexamethylene-diamine, heptamethylene-diamine, 2,5-dimethyl-heptamethylene-diamine, 3-methyl-heptamethylene-diamine, 4,
4-dimethyl-heptamethylene-diamine, octamethylene-diamine, nonamethylene-diamine, 5-methyl-nonamethylene-diamine, 2,5-dimethyl-nonamethylene-diamine, decamethylene-diamine, 1,10
-Diamino-1,10-dimethyl-decane, 2,11-
Diamino-dodecane, 1,12-diamino-octadecane, 1,12-diamino-octadecane, 2,17-diamino-icosane, diaminosiloxane, 2,6-diamino-4-carboxylic benzene, 3,3'-diamino- Examples thereof include, but are not limited to, 4,4′-dicarboxylic benzidine and the like. In use, one kind or a mixture of two or more kinds may be used. Among these, p-phenylenediamine, 2,5-
Diaminotoluene, 2,5-diamino-p-xylene,
By using 2,6-diamino-p-xylene or diaminodiphenyl ether, a polyimide resin having high strength and a low linear expansion coefficient is obtained, which is preferable.

The solvent of the reaction system in the present invention is an organic polar solvent having a dipole moment whose functional group does not react with tetracarboxylic dianhydride or diamine. Besides being inert to the system and a solvent to the product, the organic polar solvent must be a solvent for at least one of the reaction components, preferably both. A typical solvent of this type is N
-N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethylsulfoxide, hexamethylphosphoramide, N-methyl-2- There are pyrrolidone, pyridine, dimethyl sulfone, tetramethyl sulfone, dimethyl tetramethylene sulfone and the like, and these solvents may be used alone or as a mixture. In addition to these, as those used in combination as a solvent, benzene, benzonitrile, dioxane, γ-butyrolactone, xylene, toluene,
A non-solvent such as cyclohexanone is used as a dispersion medium of the raw material, a reaction regulator, a volatilization regulator of the solvent from the product, a film smoothing agent, or the like.

The reaction is generally preferably carried out under anhydrous conditions. This is because the tetracarboxylic dianhydride may be ring-opened by water, inactivated, and stop the reaction. Therefore, it is necessary to remove both the water content in the raw material and the water content in the solvent. Further, the reaction is preferably carried out in an inert gas atmosphere. This is to prevent oxidation of the diamine. Dry nitrogen gas is generally used as the inert gas.

The organosilicon compound of the present invention is used for exhibiting good adhesion between the patterned polyimide and the inorganic passivation film, the circuit-forming metal and the semiconductor encapsulating resin. The structure is a compound represented by the general formula (2), but it is usually obtained by reacting a silane coupling agent having an amino group with a carboxylic acid anhydride. Examples of silane coupling agents include γ-aminopropyltrimethoxysilane, γ
-Aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-glycidoxydimethylmethoxysilane, γ-aminopropyldimethylethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropyldiethylmethoxysilane, γ-aminopropyldiethylethoxysilane, N- (β-aminoethyl)- γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, 4-aminobutyldimethylmethoxysilane and the like. Examples of the carboxylic acid anhydride include R which is a constituent component of the above-mentioned polyamic acid.
Tetracarboxylic dianhydride, phthalic anhydride, maleic anhydride or the like containing _one residue can be used. The silane coupling agent and the tetracarboxylic dianhydride may be used alone or in combination of two or more. The reaction is preferably carried out in an organic solvent under anhydrous conditions. The reaction is carried out at a temperature of 0 to 80 ° C for 5 to 16 hours.

In the heat resistant resin composition of the present invention, the organosilicon compound represented by the general formula (2) is preferably used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the polyamic acid ester. If it is less than 0.01 part by weight, the effect of improving adhesion to metal, inorganic, and semiconductor encapsulation resins cannot be obtained, and if it exceeds 10 parts by weight, the heat resistance of the polyimide film subjected to the final curing treatment is lowered, It is not preferable because the strength decreases, the linear expansion coefficient increases, and the adhesiveness itself deteriorates.

When the heat-resistant resin composition produced by the method of the present invention is used, other silane coupling agents, borane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and other chelate-based adhesives are used. In addition to these, a small amount of usual acid curing agent, amine curing agent, polyamide curing agent and curing accelerators such as imidazole and tertiary amine may be used in combination. May be added,
Also, flexibility-imparting agents and viscosity modifiers such as rubber, polysulfide, polyester and low molecular weight epoxy, talc, clay, mica, feldspar powder, quartz powder, fillers such as magnesium oxide, colorants such as carbon black and phthalocyanine blue. A small amount of a flame retardant such as tetrabromophenyl methane and tributyl phosphate, and a flame retardant aid such as antimony trioxide and barium metaborate may be added, and addition of these opens many uses.

[0017]

EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 0.99 mol of 4,4'-diaminodiphenyl ether was added to 3310 g of N-methyl-2-pyrrolidone.
It was dissolved with stirring. Next, 0.53 mol of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 0.50 mol of pyromellitic dianhydride were added, and the mixture was stirred at 80 ° C for 3 minutes.
Allowed to react for hours. Further, 2 mol of γ-aminopropyltrimethoxysilane and 1 mol of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride were stirred in 2000 g of N-methyl-2-pyrrolidone at 25 ° C. for 5 hours. It was made to react. 1 part by weight of the solid content of the obtained organosilicon compound was added to 100 parts by weight of the polyamic acid solid content to obtain a polyamic acid composition. Using a spinner on a silicon wafer with a nitride film (SiN), the cured film thickness is 5 μm.
It was applied so as to have a thickness of m. Further, in a curing furnace, in nitrogen 15
It was cured at 0 ° C./30 minutes and 350 ° C./60 minutes to obtain a polyimide film. The adhesion of this film to a silicon wafer with SiN was measured according to JIS-D-0202, and it was 0/100 (the number of peeling / total number of peeling even after 48 hours of treatment with a pressure cooker at 125 ° C / 2.3 atm). ) Showed hard adhesion.

Next, a polyimide film-coated wafer separately prepared by the same method is divided into two, and one of them is manufactured by Tokyo Ohka Kogyo Co., Ltd.
100 W for 10 minutes (1 Torr, O ₂ flow rate: 100 cs) using a plasma etching apparatus OPM-EM1000
sm) was applied. 175 of Sumitomo Bakelite Co., Ltd.'s epoxy-based semiconductor encapsulation material "Sumicon EME-6300H" on the final cured polyimide film
Transfer mold at 2 ℃ for 2 minutes, vertical 2m
Ten pieces each were obtained with m, width 2 mm, height 2 mm, and with or without plasma treatment. After post-curing at 175 ° C. for 4 hours, five shear peel strength tests were performed on the side of the molded product as shown in FIG. 1 with a Tensilon universal testing machine to test the interface between the molded product and the polyimide interface or the polyimide and silicon wafer interface. When the adhesive strength was measured, the average value without plasma treatment was 4.1 kgf.
/ Mm ² , average value with plasma treatment is 3.9kgf / mm ²
Met. For each of the remaining 5 molded products, 120 ° C,
2.1 atm pressure cooker (PCT) treatment 10
Was subjected to 0 hours, average 1.5 kgf / mm ² without plasma treatment was measured similarly bonding strength, to obtain a mean value 1.4 kgf / mm ² of there plasma treatment.

<< Examples 2 to 6 >> Polyamic acid was obtained by reacting in the same manner as in Example 1 according to the formulation and reaction conditions shown in Table 1 and evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.
Shown in Both the dense SiN substrate after curing and the epoxy-based encapsulating material showed good values. Table 1 shows the evaluation results. << Comparative Examples 1 and 2 >> Polyamic acid was obtained by carrying out a reaction in the same manner as in Example 1 with the reaction recipe shown in Table 1 for the purpose of introducing a siloxane bond into the polyimide skeleton. Table 1 shows the evaluation results. When the same evaluation as in Example 1 was performed,
When the amount of silicone diamine is 0.02 mol, 100/100 is completely peeled off from the SiN substrate, and when it is 0.12 mol, the adhesion to the molding material after the plasma treatment is significantly reduced. Oops. << Comparative Examples 3 and 4 >> The same reaction as in Example 1 was carried out to obtain a polyamic acid ester, the organosilicon compound was replaced with trimethoxylylpropyl methacrylate, and 3 or 15 parts by weight of 100 parts of the polyamic acid solid content was blended. . Table 1 shows the evaluation results. The same evaluation as in Example 1 was performed, and in the case of 3 parts by weight, 100/100% with respect to the SiN substrate.
When the amount was 15 parts by weight, the adhesion to the molding material after the plasma treatment was significantly reduced.

The raw materials used are as follows.・ Pyromellitic dianhydride: PMDA ・ 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride: BPDA ・ 3,3', 4,4'-benzophenone tetracarboxylic dianhydride: BTDA ・4,4'-Diaminodiphenyl ether: DDE * 2,5-diamino-p-xylene: DPX * p-phenylenediamine: PPD * 1,3-bis (3-aminopropyl) -1,1,3,3-tetra Methyldisiloxane: APDS-Organosilicon compound: reaction product of γ-aminopropyltrimethoxysilane and BTDA-Organosilicon compound: reaction product of γ-aminopropyltriethoxysilane and BTDA-Organosilicon compound: γ-aminopropyl Reaction product of triethoxysilane and BPDA-Organosilicon compound: Reaction product of γ-aminopropyltriethoxysilane and maleic anhydride-Trimethoxysilane Rylpropyl methacrylate

Table 1 Example 1 2 3 4 5 6 Polyamide ester compounding (mol%) PMDA 0.50 0.50 0.50 0.50 BPDA 0.50 0.70 1.00 0.50 0.50 0.50 BTDA 0.30 DDE 0.99 1.01 1.00 1.00 DPX 1.01 PPD 1.10・ Organosilicon compound 1 2 8 ・Organosilicon compound 2 Organosilicon compound 5 Organosilicon compound 1 Characteristic ・ SiN adhesiveness 0 0 0 0 0 0 0 Adhesiveness with epoxy-based encapsulant No plasma treatment Normal 4.1 4.2 4.0 4.5 4.4 4.5 PCT treatment 1.5 1.6 1.6 1.9 1.8 2.0 With plasma treatment Normal 3.9 3.8 3.8 3.6 3.7 3.8 PCT treatment 1.4 1.5 1.5 1.4 1.4 1.6 Note: Addition amount of organosilicon compound to 100 parts by weight of polyamic acid (parts by weight)

Table 2 Comparative Example 1 2 3 4 Polyamide ester compound (mol%) PMDA 0.70 0.50 0.50 BPDA 0.90 0.50 0.50 BTDA 0.30 0.10 DDE 0.99 0.99 0.99 0.99 DPX 0.90 APDS 0.03 0.12 Trimethoxysilyl fluoromethacrylate 215 Properties / SiN adhesion 100 0 100 0・ Adhesion with epoxy type encapsulation material No plasma treatment Normal 4.0 4.2 3.9 4.3 PCT treatment 0.5 1.4 0.2 1.2 With plasma treatment Normal 3.8 2.1 3.9 2.4 PCT treatment 0.4 0.3 0.4 0.5 Note: Trimethoxysilylpropyl methacrylate is polyamide Addition amount (part by weight) to 100 parts by weight of acid

[0023]

In the past, there have been many inventions relating to the substrate such as SiN and SiO ₂ and the adhesion between polyimide / polyimide. In these inventions, a method of introducing a siloxane bond into a polyimide or adding a silane coupling agent was used, but unless a considerably large amount of Si is added, there is no effect. Characteristics and the reliability of the semiconductor device was lowered. However, according to the present invention, the adhesion to the substrate is improved by adding a small amount of the organosilicon compound, and the adhesion to the molding material after the plasma treatment is also good, and the addition of the organosilicon compound is sufficient. Therefore, it is possible to obtain a high adhesion heat resistant resin while maintaining the properties of the polyimide without changing the polyimide structure.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing that a shear peel strength test is performed on a side part of a molded product by a Tensilon universal tester.

Claims (4)

[Claims] 1. A high adhesion heat resistant resin comprising (A) a polyamic acid represented by the following general formula (1) and (B) an organosilicon compound represented by the following general formula (2) as essential components. Composition. Embedded image Embedded image 2. R in the polyamic acid represented by the formula (1)
_1, high adhesion heat resistant resin composition according to claim 1 further comprising one or more selected from the following formula (3). Embedded image 3. R in the polyamic acid represented by the formula (1)
_2, according to claim 1 or 2 highly adhesive heat resistant resin composition according comprises at least one selected from the following formula (4). Embedded image 4. An organic silicon compound is polyamic acid 100.
The high adhesion heat resistant resin composition according to claim 1, 2 or 3, which is contained in an amount of 0.01 to 10 parts by weight based on parts by weight.