JP3486093B2 - Polyimide siloxane resin solution composition and semiconductor device using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide resin composition, and more particularly, it relates to a polyimide resin composition capable of obtaining an excellent cured polyimide resin product by heat treatment at a low temperature for a short time.

[0002]

2. Description of the Related Art Generally, a polyimide resin having excellent heat resistance is insoluble in a solvent. Therefore, when this resin is used as a coating material for electronic parts, etc., its precursor polyamic acid is used as an organic material. A method of forming a polyimide resin film by dissolving it in a solvent, applying the obtained solution to a substrate, thinning it into a film, and then heating it at a high temperature for a long time to cure the polyimide resin film is used. Specifically, for example, tetracarboxylic acid dianhydride is subjected to an addition reaction with an aromatic diamine in an organic polar solvent to produce a polyamic acid,
After applying this to a substrate (electronic parts, etc.) to make a thin film,
By heat treatment at a high temperature of 0 ° C or higher for a long time, dehydration and polyimidization are performed.

However, this method is disadvantageous from the viewpoint of energy saving because it requires heating at a high temperature for a long time.
Further, when the heating is insufficient, the polyamic acid remains in the structure of the obtained resin, and the polyamic acid causes a decrease in the moisture resistance and corrosion resistance of the polyimide resin. In particular, when a polyimide coating is formed as an insulating protective film for electronic parts, such deterioration of resin performance leads to deterioration of electronic parts and shortening of life.

On the other hand, a method of applying a solution of a polyimide resin soluble in an organic solvent to a substrate instead of a polyamic acid solution and forming a polyimide resin coating film by volatilization of the solvent by heat treatment has been studied. Polyimide resin has been proposed. That is, a polyimide resin soluble in a phenol solvent, which is obtained by reacting a tetracarboxylic dianhydride and an aromatic diamine under heating in a phenol solvent such as phenol or halogenated phenol (Japanese Patent Publication No. 47- No. 26878, Japanese Patent Publication No. 55-65227, Japanese Patent Publication No. 58-187430.
Japanese Patent Publication No. 60-35026, Japanese Patent Publication No. 60-35026
197731), a polyimide resin soluble in a polar solvent such as N-methyl-2-pyrrolidone obtained by reacting a specific tetracarboxylic dianhydride and a specific diamine (Japanese Patent Publication No. 52-30319). , Japanese Patent Publication No. 61-83228 and Japanese Patent Publication No. 62-18426).

However, the former polyimide solvent-soluble polyimide resin gives off a strong odor of the phenol solvent at the stage of volatilizing the solvent after applying the solution to the substrate, and the phenol solvent adhered to the skin of the worker. In some cases, there are drawbacks in terms of handleability and health and safety, such as causing chemical injury. In addition, since the polar solvent such as N-methyl-2-pyrrolidone used as a solvent for the latter polyimide resin has a high hygroscopic property, the polyimide resin film obtained as a result of moisture absorption when the resin solution is applied to the substrate has cloudiness. It has the drawback that it occurs and the strength of the resulting coating is low.
In addition, since a polar organic solvent such as N-methyl-2-pyrrolidone has a high boiling point, there is a disadvantage that a heat treatment at a high temperature for a long time is required to completely remove the solvent.

As another solvent for the polyimide resin,
Tetrahydrofuran, 1,4-dioxane, diglyme, triglyme, etc., cyclohexanone,
Examples include ketones such as γ-butyrolactone. But,
Tetrahydrofuran, 1,4-dioxane, cyclohexanone, and the like have low boiling points, and therefore foam during heat treatment, and γ-butyrolactone becomes cloudy due to moisture absorption, and a good polyimide coating cannot be obtained in any case. Further, diglyme and triglyme have been pointed out to have an adverse effect on the human body and are not suitable for use as a solvent.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned drawbacks of the prior art. The object is to provide a polyimide resin film having excellent properties by heat treatment at a relatively low temperature for a short time. It is to provide the obtained polyimide resin composition.

[0008]

Means for Solving the Problems In order to solve such problems, the present invention provides (A) (A-1) general formula (1):

[0009]

[Chemical 9] [Where X is an oxygen atom or formula (1-1), (1-2) or (1-3):

[0010]

[Chemical 10] (Wherein, R ¹ and R ² are independently a monovalent hydrocarbon group having 1 to 8 carbon atoms), and the tetracarboxylic dianhydride is represented by 80 A tetracarboxylic dianhydride component contained in an amount of at least mol%, (A-2) general formula (2):

[0011]

Embedded image H ₂ N—Y—NH ₂ [wherein Y is the formula:

[0012]

[Chemical 12] (Wherein R ³ and R ⁴ are independently a hydrogen atom or a methyl group) is a divalent organic group] 50 to 94.5 mol% of the diamine represented by the general formula (3):

[0013]

[Chemical 13] [Here, R is a divalent organic group having 3 to 9 carbon atoms, R ⁵ and R ⁶ are independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, and n Is an integer of 38 to 100] 0.5 to 10 mol% of an organosilicon diamine represented by the general formula (4):

[0014]

[Chemical 14] [Wherein R, R ⁵ and R ⁶ are as described above], a polyimide siloxane resin obtained by polymerizing and imidizing a diamine component containing 5 to 40 mol% of an organosilicon diamine, and ( B) General formula (5):

[0015]

[Chemical 15] [Wherein R ⁷ is a monovalent hydrocarbon group having 1 to 4 carbon atoms] 30 to 70% by weight, and cyclopentanone, cyclohexanone or the formula (6):

[0016]

[Chemical 16] [Wherein, R ⁸ and R ⁹ are independently a monovalent hydrocarbon group having 1 to 4 carbon atoms] or a ketone solvent consisting of a combination of two or more thereof 70 to 30% by weight % Of the mixed solvent, and a polyimide siloxane resin composition containing the mixed solvent.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION (A) Polyimide siloxane resin (A-1) Tetracarboxylic acid dianhydride component The tetracarboxylic acid dianhydride component (A) is a tetracarboxylic acid represented by the general formula (1). 80 mol% dianhydride
Or more, preferably 90 mol% or more, most preferably 10
It consists of 0 mol% of tetracarboxylic dianhydride.
R ¹ and R ² in the general formula (1-2) have 1 to 8 carbon atoms.
A monovalent hydrocarbon group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, cyclohexyl, 2-ethylhexyl,
Alkyl groups such as octyl, alkenyl groups such as vinyl, allyl, propenyl, isopropenyl and butenyl, aryl groups such as phenyl, tolyl and xylyl, aralkyl groups such as benzyl and phenylethyl, and the like, preferably methyl group and ethyl. Group, propyl group and phenyl group.

Specific examples of the tetracarboxylic dianhydride of the general formula (1) include 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride and 3,3', 4,4'-biphenyl. Tetracarboxylic acid dianhydride, 2,2-bis [4-
(3,4-Dicarboxyphenoxy) phenyl] -propane, 2,2-bis (3,4-dicarboxyphenyl)
Hexafluoropropane dianhydride, 1,3-bis (3,3
4-dicarboxyphenyl) -1,1,3,3, -tetramethyldisiloxane anhydride, bis [4- (3,3
4-dicarboxyphenoxy) phenyl] methane, bis (3,4-dicarboxyphenyl) ether dianhydride and the like. These can be used alone or in combination of two or more.

The tetracarboxylic dianhydride component (A-1) contains the general formula (1) within the range of less than 20 mol% and within the range of not impairing the solubility of the obtained polyimidesiloxane resin.
You may use together tetracarboxylic dianhydride other than what is represented by. Examples of such tetracarboxylic acid dianhydrides include 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride and pyromellitic dianhydride. These may be used alone or in combination of two or more.

(A-2) Diamine Component The diamine component (A-2) contains 50 to 94.5 mol%, preferably 60 to 94.5 mol% of the diamine represented by the general formula (2).
And 0.5 to 10 mol% of the diamine represented by the general formula (3),
It is preferably composed of 0.5 to 7 mol% and 5 to 40 mol% of the diamine represented by the general formula (4).

Examples of the diamine compound of the formula (2) include 4,4'-diaminodiphenyl ether; 3,4 '
-Diaminodiphenyl ether; 2,2-bis [4-
(4-Aminophenoxy) phenyl] propane; 1,1
-Bis [4- (4-aminophenoxy) phenyl] ethane; bis [4- (4-aminophenoxy) phenyl] methane; tolylene-2,4-diamine; tolylene-3,4
-Diamines. Preferred is 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane. They are,
They can be used alone or in combination of two or more.

In the polysiloxane diamine represented by the general formula (3), examples of the divalent organic group represented by R and having 3 to 9 carbon atoms include, for example,-(CH ₂ ) ₃ -,-(CH _{2) 4} -, -CH ₂ C
_{H (CH 3) -, -} (CH 2) 6 -, - (CH 2) 8 -
Alkylene groups such as

[0023]

[Chemical 17] And the like, alkylene / arylene groups in which these are combined, oxyalkylene groups such as — (CH ₂ ) ₃ —O—, and — (CH ₂ ) ₄ —O—,

[0024]

[Chemical 18] Oxyarylene groups such as and combinations of these,

[0025]

[Chemical 19] And divalent hydrocarbon groups which may contain an ether oxygen atom, such as oxyalkylene / arylene groups.

Examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms represented by R ⁵ and R ⁶ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, Hexyl, cyclohexyl, 2-
Alkyl groups such as ethylhexyl and octyl, alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl and hexenyl, aryl groups such as phenyl, tolyl and xylyl, aralkyl groups such as benzyl and phenylethyl, and these groups. A group in which some or all of the hydrogen atoms bonded to carbon atoms are substituted with halogen atoms such as fluorine, bromine, chlorine, etc., for example, halogen such as chloromethyl group, bromoethyl group, 3,3,3-trifluoropropyl group. Examples thereof include a substituted alkyl group, and among them, a methyl group and a phenyl group are preferable.

Examples of the polysiloxane diamine represented by the general formula (3) include those represented by the following formula.

[0028]

[Chemical 20] Among these, the preferred one is

[0029]

[Chemical 21] Is. These can be used alone or in combination of two or more. As the disiloxane diamine represented by the general formula (4), for example,

[0030]

[Chemical formula 22] And the like, and preferably

[0031]

[Chemical formula 23] Is. These disiloxane diamines can be used alone or in combination of two or more.

Synthesis The polyimidesiloxane resin (A) is synthesized from the above-mentioned carboxylic acid dianhydride component (A-1) and diamine component (A-2) by a conventionally known method. Specifically, a tetracarboxylic dianhydride component (A-1) and a diamine component (A-
2) and are reacted and polymerized under the same conditions as in the known polyamic acid synthesis to synthesize a precursor boriamic acid, and then the polyamic acid is dehydrated and ring-closed to obtain an imidized compound.

More specifically, the component (A-1) and the component (A-
The reaction with 2) is carried out by dissolving as much as possible in a non-reactive solvent in an inert gas atmosphere such as dry nitrogen and reacting at a temperature of 80 ° C. or lower, preferably around room temperature or lower with stirring. Boriamic acid is synthesized. At this time, the ratio of the component (A-1) to the component (A-2) is (r + 1) mol of the carboxylic dianhydride component (A-1), where r is the desired degree of polymerization. It may be reacted with r moles of the diamine component (A-2). The degree of polymerization r is an integer of 1 or more, but r is preferably 10 to 300 in view of physical properties and workability of a cured film obtained by curing the composition of the present invention. Further, the non-reactive solvent used in the reaction does not need to dissolve all of the above-mentioned monomer compounds, but it is preferable to dissolve the generated polyamic acid. Examples of such a solvent include tetrahydrofuran, 1,4-dioxane, cyclopentanone, cyclohexanone, γ-butyrolactone, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and dimethyl. An aprotic polar solvent such as sulfoxide may be used, and these solvents may be used alone or as a mixture of two or more.

The dehydration ring closure of polyamic acid proceeds by heating the polyamic acid solution at 100 to 200 ° C. At this time, the presence of an azeotropic dehydrating agent such as toluene or xylene promotes dehydration ring closure. The number average molecular weight (in terms of polystyrene) of the thus obtained polyimide siloxane resin (A) measured by gel permeation chromatography (GPC) is usually in the range of 2,000 to 150,000, preferably 10,000 to 100,000.

The polyimide siloxane resin (A) described above is well dissolved in the solvent described below. (B) Solvent The solvent used in the composition of the present invention is represented by the general formula (5).
30 to 70% by weight of an ester compound (B-1) represented by Cyclopentanone, Cyclohexanone or the general formula (6)
It is a mixed solvent consisting of 70 to 30% by weight of a ketone compound (B-2) consisting of a compound represented by or a combination of two or more thereof. Here, R ⁷ , R ⁸ , and R ⁹ are monovalent hydrocarbon groups having 1 to 4 carbon atoms, and each independently represent methyl, ethyl, propyl, isopropyl, butyl, isobutyl, te.
Examples thereof include an alkyl group such as rt-butyl, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, an alkenyl group such as a butenyl group and an isobutenyl group, and the like, and a methyl group and an ethyl group are preferable.

Typical compounds represented by the above general formula (5) include, for example, propylene glycol-1.
-Methyl ether-2-acetate, propylene glycol-1-ethyl ether-2-acetate and the like. These can be used alone or in combination of two or more. Representative examples of the ketone compound of the formula (6) include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone (that is, methyl propyl ketone), 3-pentanone (that is, diethyl ketone),
Examples include diisobutyl ketone.

The ester compound (B-1) of the general formula (5) is
Alone, the solubility in the polyimidesiloxane resin (A) is not sufficient, and it is difficult to use it as a solvent.
When the ketone solvent (B-2) is used alone, the polyimide siloxane resin solution or its cured film may become cloudy, or wrinkles may occur on the surface of the film obtained during curing, resulting in a high-quality polyimide film. Is difficult to form.
If the mixed solvent (B) used in the present invention is used, such a problem can be avoided. Further, there is a problem that the cellosolve-based solvent is not preferable in terms of safety and hygiene, but such a problem can be avoided by using the solvent used in the present invention.

The amount of the solvent (B) contained in the composition of the present invention is usually adjusted so that the concentration of the polyimidesiloxane resin (A) is 5 to 35% by weight. The composition may be prepared and stored at a relatively high concentration for storage, and may be diluted to an appropriate concentration required for use. The viscosity of the liquid composition at the time of use is preferably 5 to 3,000 cSt at 25 ° C. in terms of workability and coating properties.

Uses The composition is applied to a substrate or a substrate by various known coating methods and heat-treated to obtain a polyimide film. The heat treatment at this time is usually performed at 150 to 250 ° C., and the time may be about 0.5 to 4 hours. The thickness of the formed polyimide resin coating is usually 1 to 50 μm.

Thus, the polyimide resin coating formed from the composition of the present invention exhibits good adhesion to various base materials or substrates. Examples of the material of the base or the base material include glass, silicon-containing materials such as silicon wafers, metals such as nickel and copper, and the like. Therefore, the composition is, for example, a semiconductor device, specifically, a passivation film on the surface of a semiconductor element, a protective film, a junction protective film at a junction portion of a diode, a thyristor, a transistor, or the like,
Widely used to form α-ray shield film of VLSI, interlayer insulating film, ion implantation mask, conformal coat of printed circuit board, alignment film of liquid crystal element, glass fiber protective film, solar cell surface protective film, etc. You can In particular, the present invention also relates to a resin-encapsulated semiconductor device using the polyimidesiloxane resin composition.

That is, the present invention is directed to a semiconductor element formed on a semiconductor substrate, a polyimide siloxane resin coating obtained by curing the above-mentioned composition of the present invention so as to cover the semiconductor element, and the coating thus formed. The present invention also provides a resin-encapsulated semiconductor device including a resin that encapsulates the entire semiconductor substrate.

As the resin used in the resin-encapsulated semiconductor device, for example, an epoxy-based encapsulating resin generally used as an encapsulating resin can be used, which can be molded by transfer molding or potting. You can

[0043]

The present invention will be described in detail below with reference to examples, but the invention is not limited to these examples. In addition,
The viscosity shows a measured value at 25 ° C., the average molecular weight of polysiloxane diamine is a value obtained from the measurement of amine equivalent, and the average molecular weight of polyimidesiloxane is the number average molecular weight measured by gel permeation chromatography (polystyrene conversion value). ) Is shown.

The starting compounds used in the following examples are shown by the following abbreviations. 6FDA: 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride BPADA: 2,2-bis [4 -(3,4-Dicarboxyphenoxy) phenyl] propane dianhydride BAPP: 2,2-bis (4- (4-aminophenoxy) phenyl) propane APM: 1,3-bis (3-aminopropyl) -1 ，
1,3,31-Tetramethyldisiloxane APDMS: α, ω-bis (3-aminopropyl) polydimethylsiloxane (Polysiloxane moiety polymerization degree: (n = 78 in general formula (3)) PGMEA: Propylene glycol- 1-monomethyl ether-2-acetate

(Synthesis example 1) BPADA 20.82 g (0.04 mol), A
PDMS 6.0g (average molecular weight 6,000, 0.001mol), APM2.98g
(0.012 mol) and 11.08 g (0.027 mol) of BAPP were reacted in 163 g of N-methyl-2-pyrrolidone for 12 hours at room temperature to obtain a polyamic acid. To this, 30 g of toluene was added, reacted at 200 ° C. for 3 hours, and reprecipitated with methanol to synthesize 35 g of polyimidesiloxane resin. The number average molecular weight of this resin is
It was 27,000. (Synthesis example 2) 6.FDA 5.88g (0.02mol), BPDA 8.88g
(0.02mol), APDMS 6.0g (average molecular weight 6,000, 0.001mo
l), APM 2.98g (0.012mol), and BAPP 11.08g (0.0
27 mol) was reacted in 163 g of N-methyl-2-pyrrolidone for 12 hours at room temperature to obtain a polyamic acid. Toluene
30 g was added and reacted at 200 ° C. for 3 hours and reprecipitated with methanol to synthesize 35 g of polyimidesiloxane resin. The number average molecular weight of this resin was 41,000.

Example 1 10 g of the polyimidesiloxane resin of Synthesis Example 1 was dissolved in a mixed solvent of 45 g of cyclohexanone and 45 g of PGMEA to obtain a polyimidesiloxane resin solution having a viscosity of 110 cSt. (Example 2) Polyimide siloxane resin of Synthesis example 2 10 g
Was dissolved in a mixed solvent of 45 g of cyclohexanone and 45 g of PGMEA to obtain a polyimidesiloxane resin solution having a viscosity of 170 cSt. (Comparative Example 1) Polyimide siloxane resin of Synthesis Example 1 10 g
Dissolved in 90 g of N-methyl-2-pyrrolidone to give a viscosity of 120 cS
A polyimide polyimidesiloxane resin solution of t was obtained. (Comparative Example 2) Polyimide siloxane resin of Synthesis Example 2 10 g
Was dissolved in 90 g of γ-ptyrolactone to obtain a polyimidesiloxane resin solution having a viscosity of 180 cSt. (Comparative Example 3) Polyimide siloxane resin of Synthesis Example 1 10 g
Was dissolved in 90 g of cyclohexanone to obtain a polyimidesiloxane resin solution having a viscosity of 120 cSt. (Comparative Example 4) Polyimide siloxane resin of Synthesis Example 2 10 g
Was dissolved in 90 g of cyclohexanone to obtain a polyimidesiloxane resin solution having a viscosity of 180 cSt. (Comparative Example 5) BPADA 20.82g (0.04mol), APDMS 6.0g
(Average molecular weight 6,000, 0.001mol), and BAPP 16.01g
(0.039 mol) was reacted in 171 g of N-methyl-2-pyrrolidone for 12 hours at room temperature to obtain a polyamic acid. To this, 30 g of toluene was added, reacted at 200 ° C. for 3 hours, and reprecipitated with methanol to synthesize 35 g of polyimidesiloxane resin. 10 g of this resin was dissolved in a mixed solvent of 45 g of cyclohexanone and 45 g of PGMEA to obtain a polyimide siloxane resin solution having a viscosity of 110 cSt. The number average molecular weight of this resin was 31,000.

(Comparative Example 6) 6.FDA 5.88 g (0.02 mol), B
PDA 8.88g (0.02mol), APDMS 6.0g (average molecular weight 6,00
0, 0.001 mol), and 16.01 g (0.039 mol) of BAPP with N-
A polyamic acid was obtained by reacting in 147 g of methyl-2-pyrrolidone for 12 hours at room temperature. To this, add 30 g of toluene and add 200
The mixture was reacted at ℃ for 3 hours and reprecipitated with methanol to synthesize 35 g of polyimide siloxane resin. 10 g of this resin was dissolved in a mixed solvent of 45 g of cyclohexanone and 45 g of PGMEA to obtain a polyimidesiloxane resin solution having a viscosity of 170 cSt. The average molecular weight of this resin was 41,000. (Comparative Example 7) BPADA 20.82 g (0.04 mol), APM 2.98 g
(0.012mol), and BAPP 11.50g (0.028mol) N-
A polyamic acid was obtained by reacting in 141 g of methyl-2-virolidone for 12 hours at room temperature. To this, add 30 g of toluene and add 200
The mixture was reacted at ℃ for 3 hours and reprecipitated with methanol to synthesize 35 g of polyimide siloxane resin. 10 g of this resin was dissolved in a mixed solvent of 45 g of cyclohexanone and 45 g of PGMEA to obtain a polyimide siloxane resin solution having a viscosity of 110 cSt. The number average molecular weight of this resin was 28,000. (Comparative Example 8) 6.FDA 5.88 g (0.02 mol), BPDA 8.88 g
(0.02mol), APM 2.98g (0.012mol), and BAPP 1
1.50 g (0.028 mol) of N-methyl-2-pyrrolidone 117
A polyamic acid was obtained by reacting in g for 12 hours at room temperature. To this, 30 g of toluene was added, reacted at 200 ° C. for 3 hours, and reprecipitated with methanol to synthesize 25 g of a polyimidesiloxane resin. 10g of this resin was added to 45g of cyclohexanone, PGMEA 4
It was dissolved in 5 g of a mixed solvent to obtain a polyimide siloxane resin solution having a viscosity of 170 cSt. The number average molecular weight of this resin is 40,000
Met. With respect to the polyimidesiloxane resin solution of each example prepared as described above, the appearance of the solution and the cured film was visually evaluated as follows. The results are shown in Table 1.

Appearance It was visually inspected. The appearance of the cured coating is 80 ° C after dropping the polyimidesiloxane resin solution on the silicon wafer.
At 0.5 ° C for 0.5 hr, then at 200 ° C for 1 hr to cure,
The surface condition of the obtained coating film was visually inspected.

Criteria for evaluating the appearance of the solution: ○: uniform and transparent △: translucent, cloudy □: The solution after dropping is clouded in 30 minutes after being left in the room temperature atmosphere. -Evaluation criteria for appearance of cured film: ○: Smooth and transparent Δ: Uneven surface (wrinkling)

[0050]

[Table 1]

As is clear from the above table, the polyimide silicone resin composition of the present invention is uniformly transparent and has no cloudiness in a solution state, and the obtained cured film has excellent surface smoothness and transparency.

[0052]

The polyimidesiloxane resin composition according to the present invention comprises a specific low-boiling point organic solvent and a polyimidesiloxane resin exhibiting good solubility in the low-boiling point solvent, and therefore has a high volatility of the low-boiling point solvent, so that it can be used at a low temperature for a short time. The polyimide resin film can be formed by the heat treatment. Therefore, there is an advantage that workability can be greatly improved, and energy saving and cost reduction can be achieved. Moreover, the characteristics of the obtained polyimide resin coating are good.

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Claims (2)

(57) [Claims] 1. (A) (A-1) General formula (1): [Where X is a single bond, an oxygen atom or formula (1-1), (1-
2) or (1-3): [Chemical formula 2] (Wherein, R ¹ and R ² are independently a monovalent hydrocarbon group having 1 to 8 carbon atoms), and the tetracarboxylic dianhydride is represented by 80 A tetracarboxylic dianhydride component contained in an amount of not less than mol%, (A-2) general formula (2): embedded image H ₂ N—Y—NH ₂ [wherein Y represents the formula: (Wherein R ³ and R ⁴ are independently a hydrogen atom or a methyl group) is a divalent organic group] 50 to 94.5 mol% of a diamine represented by the general formula (3): ] [Here, R is a divalent organic group having 3 to 9 carbon atoms, R ⁵ and R ⁶ are independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms, n is an integer of 38 to 100] 0.5 to 10 mol% of the organosilicon diamine,
General formula (4): [Wherein R, R ⁵ and R ⁶ are as described above], a polyimide siloxane resin obtained by polymerizing and imidizing a diamine component containing 5 to 40 mol% of an organosilicon diamine, and ( B) General formula (5): [Wherein R ⁷ is a monovalent hydrocarbon group having 1 to 4 carbon atoms] in an amount of 30 to 70% by weight, and cyclopentanone, cyclohexanone or the formula (6): [Wherein, R ⁸ and R ⁹ are independently a monovalent hydrocarbon group having 1 to 4 carbon atoms] or a ketone solvent consisting of a combination of two or more thereof 70 to 30% by weight % Of a mixed solvent, and a polyimide siloxane resin composition containing the mixed solvent. 2. A semiconductor element formed on a semiconductor substrate,
A resin-encapsulated semiconductor comprising a polyimide siloxane resin film obtained by curing the composition according to claim 1 so as to cover the semiconductor element, and a resin encapsulating the entire semiconductor substrate thus covered. apparatus.