JP2720686B2 - Polyimide, method for producing the same, and photosensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive polyimide, a method for producing the same, and a photosensitive resin composition. And a polyimide useful as a photosensitive resin component of a photosensitive resin composition capable of forming a coating film having excellent mechanical properties, a method for producing the same, and the composition.

[0002]

2. Description of the Related Art
As a heat-resistant photosensitive material for forming a pattern on a semiconductor element, a material comprising a polyamic acid and a dichromate (Japanese Patent Laid-Open No. 49-17374), a photosensitive group formed by an ester bond to a carboxyl group of the polyamic acid is used. Materials to be introduced (Japanese Unexamined Patent Publication Nos. 49-115541 and 6
0-37550), a material comprising a polyamic acid and an amine compound having a photosensitive group (JP-A-54-145).
794), a material obtained by reacting a polyamic acid with an epoxy having a photosensitive group (JP-A-55-457).
No. 46) has been proposed.

However, since these polyimides are generally insoluble in solvents, they need to be coated on the device in the form of a polyamic acid and post-baked at a high temperature after photo-curing to obtain a polyimide. There is a problem that distortion or stress due to mechanical influence or shrinkage may be given.

Further, it has been proposed to obtain an organic solvent-soluble photosensitive polyimide from a polycondensation product of a specific tetracarboxylic acid component and an aromatic diamine compound (Japanese Patent Application Laid-Open No. Sho 6).
0-72925).

However, when the polyimide thus obtained is used as a material for forming a relief pattern in a solution,
It is insoluble only in polar solvents such as N, N-dimethylformamide and N-methyl-2-pyrrolidone, and is inferior in practicality in forming a relief pattern because the solvent is limited.

The present invention has been made in view of the above circumstances,
Polyimide having photosensitivity and soluble in various solvents and a method for producing the same, and a coating film containing such a polyimide, which does not require a curing step at a high temperature and is excellent in heat resistance, electrical and mechanical properties It is an object of the present invention to provide a photosensitive resin composition capable of forming a polymer.

[0007]

The present inventors have made intensive studies to achieve the above object, and as a result, have found that 3- (dichloroorganosilyl) represented by the following general formula (5).
By co-hydrolyzing propyl methacrylate and chloro (4'-phthalic anhydride) diorganosilane represented by the following general formula (6), phthalic anhydride is bonded to both ends of the siloxane chain, and It has been found that a novel methacryl group-containing bis (4′-phthalic anhydride) siloxane compound represented by the following general formula (2) having a methacryl group introduced into a side chain thereof can be obtained.

[0008]

Embedded image (Wherein, R ¹ , R ² and R ³ are the same or different and each represents a monovalent group selected from an alkyl group, an aryl group and an alkenyl group having 1 to 10 carbon atoms, and k is 1 to 20)
Is an integer. )

Further, if necessary, another tetracarboxylic dianhydride represented by the following general formula (3) is added to the siloxane compound represented by the general formula (2), and a diamine represented by the following general formula (4) is added thereto. By reacting the components, a polyimide comprising a repeating unit represented by the formula (A) or a repeating unit represented by the formula (A) and the formula (B) is obtained. It has been found that it is effective as a photosensitive resin component.

[0010]

Embedded image

[0011]

Embedded image A tetravalent group selected from: Y is an aromatic ring-containing diamine residue having 6 to 30 carbon atoms; It is a divalent group selected from diamine residues of siloxane having 2 to 20 silicon atoms, silalkylene and silarylene. )

[0012]

Embedded image (However, X, Y, R ¹ , R ² , R ³ , and k have the same meaning as described above, and the ratio B / A between the unit A and the unit B indicates a value of 0 to 5.)

Since such polyimide has photosensitivity and excellent heat resistance, it does not require a separate photoresist for image formation unlike conventional non-photosensitive polyimide, and simplifies the step of forming a relief pattern. it can. Moreover, it has higher solubility in organic solvents than polyimides having conventional photosensitive groups, and is soluble in a wide range of solvents such as amides, ethers, cellosolves, ketones, and esters, and is practical in forming a relief pattern. The imidization step required when using the photosensitive polyamic acid can be omitted, and no distortion or stress due to thermal influence or shrinkage is applied to the semiconductor element.

For this reason, a photosensitive resin composition containing the above-mentioned polyimide, particularly a photosensitive resin solution composition obtained by mixing a photopolymerization initiator and an organic solvent with this polyimide, for example, forms a fine pattern directly on a semiconductor element by light. Since it can be formed and gives a coating film with excellent heat resistance, electrical and mechanical properties, it is useful as a coating application for various semiconductor devices, liquid crystal display device alignment films, multilayer printing plate insulation films, etc. Thus, the present invention has been accomplished.

Accordingly, the present invention provides a polyimide comprising the above repeating unit A or the above repeating units A and B, a compound of the formula (2), if necessary, a compound of the formula (3),
It is intended to provide a method for producing the above polyimide by reacting this with a compound of the formula (4), and a photosensitive resin composition containing the above polyimide as a photosensitive resin.

Hereinafter, the present invention will be described in more detail. The polyimide of the present invention comprises the following repeating unit A or repeating units A and B.

[0017]

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Wherein R ¹ , R ² and R ³ are each a monovalent group selected from the same or different alkyl, aryl and alkenyl groups having 1 to 10 carbon atoms;
For example, typical examples include a lower alkyl group such as a methyl group, an ethyl group and a propyl group; a lower alkenyl group such as a vinyl group and an allyl group; and an aryl group such as a phenyl group and a tolyl group. K is an integer of 1 to 20, preferably 1 to 10. Further, X is a tetravalent organic group and Y is a divalent organic group, and specific examples thereof will be described later. The ratio B / A between the unit A and the unit B is 0 to 5, but when the polyimide is used as a photosensitive resin, B / A ≧ 3 is preferable in terms of sensitivity.

The molecular weight of the formula (1) is usually 1,500
~ 500,000.

This polyimide is, as described above, a siloxane compound represented by the following formula (2), another tetracarboxylic dianhydride represented by the following formula (3), and a polyimide represented by the following formula (4). It can be synthesized from a diamine component.

[0021]

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Here, the siloxane compound represented by the formula (2) is a novel compound, and this siloxane compound is, as described above, 3- (dichloroorganosilyl) propyl methacrylate represented by the following general formula (5) and It can be obtained by co-hydrolyzing chloro (4′-phthalic anhydride) diorganosilane represented by the formula (6).

[0023]

Embedded image (However, R ¹ , R ² and R ³ in the formula have the same meaning as described above.)

In this case, chloro (4'-phthalic anhydride) diorganosilane represented by the formula (6) is added to 0.1 mol of 3- (dichloroorganosilyl) propyl methacrylate represented by the formula (5) in an amount of 0.1 mol. It is used in the range of from 01 to 5 mol, preferably from 0.1 to 2 mol, and can preferably be co-hydrolyzed using a solvent. Examples of the solvent for the reaction include tetrahydrofuran, acetone, diethyl ether, isopropyl ether, dichloromethane, chloroform, toluene, xylene and the like, and these can be used alone or as a mixture of two or more. Among these solvents, tetrahydrofuran and acetone are preferred. The reaction temperature at this time is from 0 ° C to the boiling point of the solvent, preferably from 0 ° C to room temperature. The reaction time is usually 1 to 48 hours,
Typically, it is 6 to 24 hours.

The amount of water used for the hydrolysis is used in a large excess with respect to the compounds of the formulas (2) and (3), and specifically, the compounds of the formulas (2) and (3) Is preferably in the range of 500 to 3,000 parts by weight with respect to 100 parts by weight in total. In the hydrolysis, first, a mixture of water and a solvent is added to 3- (dichloroorganosilyl) represented by the formula (2).
It is preferable to slowly drop propyl methacrylate and then slowly drop chloro (4'-phthalic anhydride) diorganosilane represented by the formula (3).

After completion of the reaction, a solvent such as toluene, diethyl ether or isopropyl ether is added, the reaction product is transferred to this solvent layer, and the solvent layer is collected, washed with water, and hydrochloric acid is removed. By leaving, a crude product of the siloxane compound represented by the formula (2) can be obtained.

Acetic anhydride was added to the crude product of the cohydrolysis in an amount of 1 to 1 mol per 1 mol of the compound of the formula (6).
Addition of 2 moles, further addition of a polymerization inhibitor, for example, hydroquinone monomethyl ether, and heat dehydration reaction using a solvent such as toluene and xylene to convert a by-product into a target siloxane compound of the formula (2). preferable.
The reaction temperature in this case is from 50 ° C to the boiling point of the solvent, preferably from 50 to 90 ° C. The reaction time is usually 10 minutes to 3 hours,
Typically, it is 30 minutes to 1 hour. After the reaction, reprecipitation is performed using hexane or the like to obtain a siloxane compound represented by the formula (2).

This formula (2) is used for the production of the polyimide of the present invention.
The tetracarboxylic dianhydride which can be used together with the siloxane compound of the formula (1) is represented by the following formula (3).

[0029]

Embedded image In the formula, X is a tetravalent organic group, and specific examples of X and tetracarboxylic dianhydride are as follows.

[0030]

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The tetracarboxylic dianhydride can be used alone or in combination of two or more. Therefore, X in the unit B may be one type or a combination of two or more types.

On the other hand, the diamine used as a raw material of the photosensitive polyimide of the present invention is represented by the following formula (4).

[0033]

Embedded image H ₂ N—Y—NH ₂ (4)

In this formula, Y is a diamine residue, and among the diamines having such a diamine residue, C 6-30
Specific examples of the aromatic ring-containing diamine are p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, and 2,2′-bis (4-aminophenyl ) Propane, 4,4′-diaminodiphenylsulfone, 4,
4'-diaminodiphenyl sulfide, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4
-Aminophenoxy) benzene, 1,4-bis (m-aminophenylsulfonyl) benzene, 1,4-bis (p
-Aminophenylsulfonyl) benzene, 1,4-bis (m-aminophenylthioether) benzene, 1,4
-Bis (p-aminophenylthioether) benzene,
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, 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, 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, bis [4- (4-aminophenoxy) phenyl] sulfone,
C6-C30 selected from 2,2-bis [4- (4-aminophenoxy) phenyl] perfluoropropane
Is an aromatic ring-containing diamine. Further, Y may be a diamine having a core substituent of an amino group or an amide group represented by the following formula.

[0035]

Embedded image

Further, diamines having diamine residues of siloxane, silalkylene and silarylene having 2 to 20 silicon atoms are as follows.

[0037]

Embedded image

[0038]

Embedded image

These diamines may be used alone or in combination of two or more. Y in the photosensitive polyimide of the present invention is the above-mentioned diamine residue, and therefore, Y may be one type or a combination of two or more types.

The photosensitive polyimide of the present invention can be generally obtained by the following procedure.

That is, first, a siloxane compound represented by the formula (2), a tetracarboxylic acid component composed of a tetracarboxylic dianhydride represented by the formula (3), and a diamine component composed of a diamine represented by the formula (4) Are polymerized in an organic solvent in a proportion of about equimolar to obtain a polyamic acid solution. The reaction temperature at this time is 0 to 100 ° C., particularly 80
It is preferable to carry out the reaction at a temperature of not more than ° C for 1 to 48 hours.

An imidizing agent such as acetic anhydride, pyridine and tertiary amine is further added to the obtained polyamic acid solution,
An imidization reaction is performed. The reaction temperature at this time is 0 to 100
The reaction is preferably carried out at a temperature of at most 80 ° C, particularly at most 80 ° C for 30 minutes to 5 hours.

Solvents that can be used in these polymerization and imidation reactions include, for example, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, N, N-dimethylsulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, N- Methyl-2-pyrrolidone, hexamethylenephosphamide,
Cyclohexanone, cyclopentanone, γ-butyrolactone, butyl acetate, ethyl acetate and the like can be used.

By this reaction, the photosensitive polyimide of the present invention is obtained.

The polyimide of the present invention can be used as a photosensitive resin to form a photosensitive resin composition. In this case, a photopolymerization initiator is preferably added to the composition, and an organic solvent is preferably added to dissolve the polyimide and make the composition into a solution.

The following can be mentioned as the photopolymerization initiator. For example, Michler's ketone,
Benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2
-T-butylanthraquinone, 1,2-benzo-9,1
0-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-
Phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl- [4- (methylthio)
Phenyl] -2-morpholino-1-propanone, diacetyl, benzyl, benzyldimethylketal, benzyldiethylketal, diphenyldisulfide, anthracene, 2-nitrofluorene, dibenzalacetone,
1-nitropyrene, 1,8-dinitropyrene, 1,2-
Naphthoquinone, 1,4-naphthoquinone, 1,2-benzanthraquinone, 3,3′-carbonylbis (7-diethylaminocoumarin), N-phenylglycine, 2,6
-Di (p-azidobenzal) -4-methylcyclohexanone, 2,6-di (p-azidobenzal) cyclohexanone, 4,4'-diazidochalcone, 4,4'-diazidobenzalacetone, 4,4'- Diazide stilbene,
4,4'-diazidobenzophenone, 4,4'-diazidodiphenylmethane, 4,4'-diazidodiphenylamine and the like.

These photopolymerization initiators may be used alone or in combination of two or more.
It is preferable to use it in the range of 1 to 20% by weight, particularly 0.1 to 10% by weight.

Further, as the organic solvent, it is preferable to select an organic solvent that dissolves both the polyimide of the present invention and the photopolymerization initiator. Specifically, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide,
Amides such as N, N-dimethylformamide; ethers such as tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve; acetone, methyl ethyl ketone, methyl isobutyl ketone; Ketones such as cyclopentanone and cyclohexanone; γ-
A wide range of organic solvents such as esters such as butyrolactone, butyl cellosolve acetate, butyl acetate and ethyl acetate can be used. Therefore, a photosensitive resin solution composition in which polyimide is dissolved using such an organic solvent is practical for forming a relief pattern.

These organic solvents can be used alone or as a mixture of two or more. Also,
The amount used is 30 to 98% by weight of the entire photosensitive resin composition,
Particularly, a range of 40 to 95% by weight is preferable.

In addition to the above-mentioned organic solvents, organic solvents such as toluene and xylene can be added to improve the coating properties to such an extent that the solubility of the polyimide of the present invention and the photopolymerization initiator is not impaired.

Further, a compound having a photopolymerizable functional group may be added to the photosensitive resin composition of the present invention for the purpose of improving the photosensitivity. Such compounds include:
For example, butyl acrylate, cyclohexyl acrylate, dimethylaminoethyl methacrylate, benzyl acrylate, carbitol acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxy Ethyl methacrylate, 2
-Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, N
-Methylolacrylamide, N-diacetoneacrylamide, N, N'-methylenebisacrylamide, N-
Vinylpyrrolidone, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, butylene glycol diacrylate, butylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1: 4 -Butanediol diacrylate, 1: 6-hexanediol diacrylate, 1: 6-hexanediol dimethacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolpropane triacrylate Methacrylate and the like can be mentioned.

According to the photosensitive resin composition of the present invention, for example, a patterned polyimide film having excellent heat resistance, electrical and mechanical properties can be obtained on the surface of a semiconductor element.

In forming this patterned polyimide film, the following method can be generally employed. First, the photosensitive resin composition of the present invention is spin-coated,
By a known method such as immersion or printing, silicon wafer,
It is applied on a substrate such as a metal plate or a glass plate. Next, the coating film is heated using a heating means such as an electric furnace or a hot plate, and prebaked at a temperature of 30 to 150 ° C. for several minutes to several tens minutes to remove most of the solvent in the coating film. Put a negative mask on this coating, visible light, ultraviolet light or radiation,
Irradiation with ultraviolet rays is preferred. Next, the unexposed portion is dissolved and removed with a developer to obtain a relief pattern. As the developer, the organic solvents exemplified as being usable in the photosensitive resin composition of the present invention can be used. In addition, non-solvents methanol, ethanol, and propanol which do not dissolve the polyimide of the present invention can be used. A mixed solution with a lower alcohol such as the above can also be used. If desired, rinse in the non-solvent, and if necessary, at the temperature of 150 to 200 ° C. for several tens of minutes by the heating means.
The solvent can be volatilized by heating for several hours.

Therefore, according to the photosensitive resin composition of the present invention, a separate photoresist for image formation is not required unlike the conventional non-photosensitive polyimide, and the step of forming a relief pattern can be simplified. . In addition, the polyimide film may be formed by evaporating the solvent, and can omit the imide process at a high temperature required when using a conventional polyamic acid, without giving any distortion or stress due to thermal influence or shrinkage on the element, A highly reliable semiconductor can be obtained.

The photosensitive resin composition of the present invention can be used for a semiconductor element such as a surface protection film for a semiconductor element such as a junction coat film, a passivation film, a buffer coat film, an α-ray shielding film, or an interlayer insulating film for multilayer wiring. It can be suitably used for forming a film such as an insulating film, an alignment film for a liquid crystal display element, and an insulating film for a multilayer printed board.

[0056]

【Example】

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

First, the siloxane compound represented by the formula (2) used in the examples was synthesized as follows.

Synthesis Example 1 (1) Co-hydrolysis 500 ml of pure water and 150 ml of tetrahydrofuran were charged into a 2 liter flask equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel. After cooling, 3- (dichloromethylsilyl) -propyl methacrylate (12.0 g, 5.0 × 10 ⁻²⁾
(Mol) of tetrahydrofuran was added dropwise over 2 hours. After dropping, the reaction solution is stirred at 5 ° C.
For 1 hour.

After completion of the ripening, 4- (chlorodimethylsilyl) -phthalic anhydride (24.0 g,
1.0 × 10 ⁻¹ mol) in tetrahydrofuran solution 22
0 ml was added dropwise over 4 hours. After completion of the dropwise addition, the reaction solution was aged at 25 ° C. for 12 hours while stirring. After completion of the reaction, 200 ml of toluene was added, the organic layer was washed three times with 250 ml of water, and the solvent was distilled off under reduced pressure to obtain 31.8 g of a colorless liquid.

(2) Dehydration by heating The reaction product and acetic anhydride (10.5) were placed in a 500 ml flask equipped with a reflux condenser, a thermometer and a stirrer.
g, 1.0 × 10 ⁻¹ mol), 150 ml of toluene and 0.1 g of hydroquinone monomethyl ether, and the reaction solution was heated at 80 ° C. for 30 minutes while stirring. After completion of the heating, reprecipitation was performed using hexane to obtain 15.7 g of a white solid (yield: 52%).

The obtained compound was identified by ¹ H-NMR and infrared absorption spectrum. as a result,
It was confirmed that the obtained compound had a structure represented by the following formula (2-a).

[0063]

Embedded image

[0064]

Embedded image¹ H-NMR; acetone-d₆  δ (ppm)Infrared absorption spectrum; (cm^-1) 1854,1778 (C = O acid anhydride) 1715 (C = O methacrylic group) 1081 (Si-O) 1257,796 (Si-CH)₃)

[Synthesis Example 2] (1) Co-hydrolysis 400 ml of pure water and 120 ml of tetrahydrofuran were charged into a 2-liter flask equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel. After cooling, a solution of 3- (dichloromethylsilyl) propyl methacrylate (12.0 g, 5.0 × 10 ⁻² mol) in 80 ml of tetrahydrofuran was added dropwise over 2 hours. After completion of the dropwise addition, the reaction solution was aged at 5 ° C. for 1 hour while stirring.

After completion of the ripening, 4- (chlorodimethylsilyl) -phthalic anhydride (8.0 g,
3.3 × 10 ⁻² mol) in tetrahydrofuran solution 15
0 ml was added dropwise over 3 hours. After completion of the dropwise addition, 200 ml of toluene was added, and the organic layer was washed three times with 250 ml of water. Then, the solvent was distilled off to obtain a colorless liquid 16.5.
g was obtained.

(2) Heat Dehydration The reaction product and acetic anhydride (3.4) were placed in a 500 ml flask equipped with a reflux condenser, a thermometer and a stirrer.
g, 3.3 × 10 ⁻² mol), 100 ml of toluene and 0.1 g of hydroquinone monomethyl ether, and the reaction solution was heated at 80 ° C. for 30 minutes while stirring. After completion of the heating, reprecipitation was performed using hexane to obtain 7.3 g of a white solid (yield: 45%). From proton NMR and IR analysis, the product was represented by the following formula (2-b)
It was confirmed that the compound had the structure represented by

[0068]

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Example 1 A solution obtained by dissolving the siloxane compound represented by the formula (2-a) (8.7 g, 0.014 mol) obtained in Synthesis Example 1 in 30 g of diethylene glycol dimethyl ether in a nitrogen stream was used. Prepared. Next, an amine solution obtained by dissolving 2,2-bis [4- (4-aminophenoxy) phenyl] propane (5.8 g, 0.014 mol) in 30 g of diethylene glycol dimethyl ether was added to the solution at a temperature of 40 ° C. It was dropped so as not to exceed. After the completion of the dropwise addition, the mixture was further stirred for 15 hours to obtain a polyamic acid solution.

Next, acetic anhydride (29 g, 0.28 mol) and pyridine (11 g, 0.08 mol) were added to the polyamic acid solution.
14 mol) and stirred at 50 ° C. for 2 hours. After the reaction, reprecipitation was performed using methanol to obtain 12 g (85%) of a photosensitive polyimide having a repeating unit represented by the following formula (1-A). The weight average molecular weight of this polyimide is 20,000
Met.

[0071]

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5 g of the obtained polyimide was dissolved in 15 g of triethylene glycol dimethyl ether.
-0.1 g of diethylthioxanthone and 2-benzyl-2
-Dimethylamino-1- (4-morpholinophenyl)
0.25 g of -butan-1-one was added to prepare a photosensitive resin solution composition.

This composition was spin-coated on a silicon wafer with a spinner, and then dried at 80 ° C. for 1 hour.
A μm coating was obtained. The coating surface was exposed for 1 minute with a high-pressure mercury lamp (250 W) through a mask. After exposure, the film was developed with diethylene glycol dimethyl ether and rinsed with 2-propanol.
Heat treatment was performed at 00 ° C. for 1 hour to obtain a clear resin pattern.

The heat resistance of the obtained polyimide resin film was 3
The temperature was 50 ° C. or higher, showing good heat resistance, and good adhesion to a silicon wafer.

Example 2 A siloxane compound represented by the formula (2-a) obtained in Synthesis Example 1 in a nitrogen stream (6.
(1 g, 0.01 mol) and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (2.9 g, 0.01 mol) were dissolved in 35 g of diethylene glycol dimethyl ether to prepare a solution. Next, an amine solution obtained by dissolving 2,2-bis [4- (4-aminophenoxy) phenyl] propane (8.2 g, 0.02 mol) in 35 g of diethylene glycol dimethyl ether was added to the solution at a temperature of 40 ° C. It was dropped so as not to exceed. After the completion of the dropwise addition, the mixture was further stirred for 15 hours to obtain a polyamic acid solution.

Next, acetic anhydride (41 g, 0.4 mol) and pyridine (16 g, 0.2 mol) were added to the polyamic acid solution, followed by stirring at 50 ° C. for 2 hours. After the reaction, reprecipitation was performed using methanol, and 14 g of a photosensitive polyimide comprising repeating units m and n represented by the following formula (1-B)
(84%). The weight average molecular weight of this polyimide was 32,000.

[0077]

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5 g of the obtained polyimide was dissolved in 15 g of triethylene glycol dimethyl ether.
-0.1 g of diethylthioxanthone and 2-benzyl-2
-Dimethylamino-1- (4-morpholinophenyl)
0.25 g of -butan-1-one was added, and 0.5 g of a compound having the following structural formula was added thereto.

[0079]

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The photosensitive resin solution composition was spin-coated on a silicon wafer with a spinner, and then dried at 80 ° C. for 1 hour to obtain a coating film having a thickness of 2 mm. The coating surface was exposed for 1 minute with a high-pressure mercury lamp (250 W) through a mask. After exposure, the film was developed with diethylene glycol dimethyl ether and rinsed with 2-propanol.
For 1 hour and further at 200 ° C. for 1 hour to obtain a clear resin pattern. The adhesion of the obtained polyimide resin film to the silicon wafer was good.

Example 3 In a nitrogen stream, the siloxane compound (9.8 g, 0.01 mol) represented by the formula (2-b) obtained in Synthesis Example 2 and 2,2-bis (3 , 4-benzenedicarboxylic acid anhydride) perfluoropropane (4.4 g, 0.0
1 mol) with diethylene glycol dimethyl ether 80
g was prepared. Next, add 4
4′-diaminodiphenyl ether (4.0 g, 0.0
2 mol) and stirred. The mixture was stirred for 20 hours to obtain a polyamic acid solution.

Next, acetic anhydride (41 g, 0.4 mol) and pyridine (16 g, 0.2 mol) were added to the polyamic acid solution, and the mixture was stirred at 50 ° C. for 2 hours. After the reaction, reprecipitation was performed using methanol, and 14 g of a photosensitive polyimide comprising repeating units m and n represented by the following formula (1-C)
(80%). The weight average molecular weight of this polyimide was 36,000.

[0083]

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5 g of the obtained polyimide was dissolved in 15 g of triethylene glycol dimethyl ether.
3'-carbonylbis (7-diethylaminocoumarin)
0.1 g and 0.25 g of N-phenylglycine were added to prepare a photosensitive resin solution composition.

The obtained composition was spin-coated on a silicon wafer with a spinner, and then dried at 80 ° C. for 1 hour to obtain a coating having a thickness of 3 mm. The coating surface was exposed for 1 minute with a high-pressure mercury lamp (250 W) through a mask. After the exposure, the film was developed with diethylene glycol dimethyl ether, rinsed with 2-propanol, and heated at 150 ° C. for 1 hour and further at 200 ° C. for 1 hour to obtain a clear resin pattern. The heat resistance of the obtained polyimide resin film is 350 ° C.
As described above, good heat resistance was exhibited, and adhesion to the silicon wafer was also good.

[0086]

As described above, the polyimide of the present invention has photosensitivity and is soluble in various solvents, and a photosensitive resin composition containing the solvent-soluble photosensitive polyimide is a conventional resin composition. Unlike a non-photosensitive polyimide, it does not require a separate photoresist for image formation, simplifies the relief pattern formation process, and eliminates the need for an imidation process at high temperatures, which has a thermal effect on the device. A fine-patterned film can be directly formed without giving strain or stress due to shrinkage or shrinkage.This film has excellent heat resistance, electrical and mechanical properties, It can be suitably used for an insulating film for a semiconductor element and the like. Further, according to the production method of the present invention, such a polyimide can be easily produced.

Claims (6)

(57) [Claims] 1. A polyimide comprising the following repeating units A and B: Embedded image Embedded image A tetravalent group selected from: Y is an aromatic ring-containing diamine residue having 6 to 30 carbon atoms; Siloxane having 2 to 20 silicon atoms, divalent group selected from diamine residues of silalkylene and silarylene, R ¹ , R ² and R ³ are the same or different alkyl groups having 1 to 10 carbon atoms, A monovalent group selected from an aryl group and an alkenyl group, k represents an integer of 1 to 20,
The ratio B / A of the unit A and the unit B is 0 <B / A ≦ 5. ) 2. A polyimide comprising the following repeating unit A. Embedded image (Where Y is an aromatic ring-containing diamine residue having 6 to 30 carbon atoms, Siloxane having 2 to 20 silicon atoms, divalent group selected from diamine residues of silalkylene and silarylene, R ¹ , R ² and R ³ are the same or different alkyl groups having 1 to 10 carbon atoms, K is a monovalent group selected from an aryl group and an alkenyl group, and k represents an integer of 1 to 20. ) 3. A tetracarboxylic dianhydride represented by the following general formula (3) is added to a siloxane compound represented by the following general formula (2), and this is reacted with a diamine represented by the following general formula (4). The method for producing a polyimide according to claim 1, wherein: Embedded image Embedded image A tetravalent group selected from: Y is an aromatic ring-containing diamine residue having 6 to 30 carbon atoms; Siloxane having 2 to 20 silicon atoms, divalent group selected from diamine residues of silalkylene and silarylene, R ¹ , R ² and R ³ are the same or different alkyl groups having 1 to 10 carbon atoms, K is a monovalent group selected from an aryl group and an alkenyl group, and k represents an integer of 1 to 20. ) 4. The method according to claim 2, wherein the siloxane compound represented by the following general formula (2) is reacted with a diamine represented by the following general formula (4). Embedded image (Where Y is an aromatic ring-containing diamine residue having 6 to 30 carbon atoms, Siloxane having 2 to 20 silicon atoms, divalent group selected from diamine residues of silalkylene and silarylene, R ¹ , R ² and R ³ are the same or different alkyl groups having 1 to 10 carbon atoms, K is a monovalent group selected from an aryl group and an alkenyl group, and k represents an integer of 1 to 20. ) 5. A photosensitive resin composition comprising the polyimide according to claim 1 as a photosensitive resin. 6. The composition according to claim 5, which contains a photopolymerization initiator and an organic solvent and is prepared in the form of a solution.