JPH08254831A - Photosensitive polyimide resin composition - Google Patents

Abstract

PURPOSE: To provide a high purity resin compsn. having satisfactory heat resistance as a protective film for electronic parts, developable with an aq. alkali soln. owing to its being a high purity positive photosensitive material, capable of regulating solution velocity, less liable to the reduction of film thickness, adaptable to various starting materials and also having satisfactory sensitivity. CONSTITUTION: This resin compsn. contains a precursor of polyimide resin having repeating units represented by formula I [where X is a tetravalent org. group, Y is a divalent org. group and each of R and R' is a group represented by formula II (where each of R<1> -R<3> is a 1-8C monovalent org. group or H)] and having a wt. average mol.wt. of 20,000-100,000, a dihydropyridine compd. represented by formula III [where R<4> is optionally substd. hydrocarbon, each of R<5> and R<6> is alkyl, R<5> and R<6> may be different from each other and each of T<7> and R<8> is -COOR", -COR" or -CN (R" is alkyl)] and a hexaarylbiimidazole compd. represented by formula IV (where each of R<9> -R<11> is optionally substd. aryl and R<9> -R<11> may be different from one another).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive polyimide resin composition useful as a protective insulating film for semiconductor devices, an alignment film for liquid crystal devices, an insulating film for multilayer printed circuit boards and the like.

[0002]

2. Description of the Related Art Polyimide has excellent heat resistance and mechanical properties and is widely used as a surface protective film for semiconductor elements and an interlayer insulating film. When polyimide is used for these purposes, it is necessary to form a through hole or the like in order to connect the conductive parts of the upper and lower conductor layers and the external lead wire. This step is generally performed by an etching process using a photoresist. Has been done. However, the process includes coating and peeling of the photoresist, which complicates the process. Therefore, in order to simplify the process, studies have been made on polyimide having photosensitivity.

As the positive type photosensitive polyimide, a composition containing a polyamic acid and a naphthoquinonediazide compound (JP-A-52-13315), a polyamic acid ester having an o-nitrobenzyl ester introduced into its side chain (J.
Appl. Polym. Sci., 33,1763 (1987)) or a soluble polyimide having a phenolic hydroxyl group and naphthoquinonediazide introduced (Macromolecules 23,4796 (1990); Ma
cromol. Chem., RapidCommun 10,521 (1989)). The positive-type photosensitive polyimide that can be developed with an aqueous alkaline solution can be used in existing photoresist developing devices, and is characterized in that the film does not swell during development.

[0004]

However, a composition containing a polyamic acid and a naphthoquinonediazide compound has a large film loss in the unexposed area at the time of development, and a composition containing o-nitrobenzyl ester in the side chain is o- Since the absorption band of nitrobenzyl ester overlaps the absorption band of aromatic, there is a problem that sensitivity is not good. Further, in the soluble polyimide having naphthoquinonediazide in the side chain, diamine having a phenolic hydroxyl group is used as a raw material, and naphthoquinonediazide sulfonyl chloride is present in the polyimide obtained by reacting this with tetracarboxylic dianhydride. Although it is synthesized by reacting under the following conditions, there are problems that the type of raw material is limited and the reaction process becomes complicated because it is soluble in an organic solvent.

[0005]

Means for Solving the Problems As a result of studies to solve the above-mentioned problems, the present inventors have found that a polyamic acid silyl ester to which a hexaarylbiimidazole and a dihydropyridine compound are added is a protective material for electronic parts. Excellent properties such as sufficient heat resistance and mechanical properties as a film, few impurities, easy production, adjustable alkali dissolution rate, adaptable to a wide range of raw materials, and good sensitivity. The present invention has been completed and the present invention has been completed.

That is, the present invention provides (a) the following general formula (1):

[0007]

Embedded image [Wherein, X is a tetravalent organic group, Y is a divalent organic group, and R and R ′ are of the formula:

[0008]

[Chemical 6] (Here, R ¹ , R ² and R ³ are 1 having 1 to 8 carbon atoms.
It is a valent organic group or a hydrogen atom. )] And the weight average molecular weight is 20,000 to 10
A polyimide resin precursor which is 000, and (b) the following general formula (2):

[0009]

[Chemical 7] [Wherein R ⁴ is a substituted or unsubstituted hydrocarbon group, and R 4
⁵ and R ⁶ are the same or different alkyl groups, and R ⁷ and R ⁸ are the same or different -COOR ", -COR" or -CN
(However, R ″ is an alkyl group.)], And (c) the following general formula (3):

[0010]

Embedded image [In the formula, R ⁹ , R ¹⁰ and R ¹¹ are the same or different and each is a substituted or unsubstituted aryl group] The present invention relates to a photosensitive polyimide resin composition containing a hexaarylbiimidazole compound.

(A) Polyimide Precursor The polyimide precursor of the general formula (1) can be prepared by a known method (Japanese Patent Publication No.
43-18790), and can be synthesized. Generally, a tetracarboxylic dianhydride of formula (4) and a formula
It can be obtained by reacting (5) N, N-bis (triorganosilyl) diamine with an approximately equal amount in an inert solvent, but is not limited to this method.

[0012]

[Chemical 9] (In the formula, X, Y, R and R ′ are as described above)

The tetravalent organic group X in the general formula (1) is derived from the tetracarboxylic dianhydride represented by the above formula (4). Specific examples of the tetracarboxylic dianhydride are as follows. 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-benzenedicarboxylic acid hydrido) perfluoropropane, bis (3,4-dicarboxyphenyl) dimethylsilane Hydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1,
3,3-Tetramethyldisiloxane anhydride, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane, 3,3'4,4'-benzophenone tetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone and the like. However, the tetracarboxylic dianhydride is not limited to these.

X in the general formula (1) may be one kind or a combination of two or more kinds. In the above production method, when two or more kinds of tetracarboxylic dianhydrides are used as raw materials, a polyimide precursor (a) containing two or more kinds of X is obtained. The tetracarboxylic dianhydride which provides X particularly preferable in the general formula (1) is

[0015]

[Chemical 10] Is.

The N, N-bis (triorganosilyl) diamine of the formula (5) used in the above-mentioned production method is obtained by reacting the diamine of the general formula (6) and the triamine of the general formula (7) as shown in the following reaction formula. It is obtained by condensing with organochlorosilane in the presence of a base. This reaction is usually 25 to 12 in an organic solvent.
It is carried out at 5 ° C. As the organic solvent, those exemplified as the solvent for the composition described later are used.

[Chemical 11]

Y in the general formula (1) is a divalent organic group,
In the above production method, the diamine is derived from the general formula (6). Examples of the diamine are as follows. p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 2,2'-bis (4-aminophenyl) propane, 4,4 '
-Diaminodiphenyl sulfone, 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-amino) Phenoxy) phenyl] methane, bis [4- (4-aminophenoxy)
Phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] perfluoropropane; and the formula shown below:

[0018]

[Chemical 12] Examples thereof include diaminosiloxane and the like, but the invention is not limited thereto. General formula among these
The diamine that provides particularly preferable Y as (1) is

[0019]

[Chemical 13] Is.

In the general formula (1), the divalent organic group Y is 1
The seeds may be used alone or in combination of two or more. According to the above production method, when two or more kinds of diamines of the general formula (6) are used, a polyimide precursor (a) containing two or more kinds of Y
Is obtained.

In the general formula (1), R ¹ , R ² and R ³ are each a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, which may be the same or different. A hydrocarbon group is typical as the monovalent organic group, and more specifically,
Alkyl groups such as methyl group, ethyl group, propyl group, butyl group; alkenyl groups such as vinyl group, allyl group, butenyl group; aryl groups such as phenyl group, tolyl group; hydrogen bonded to carbon atoms of these hydrocarbon groups A halogen atom, a cyano group, a substituted hydrocarbon group in which some or all of the atoms are substituted with an alkoxy group, for example, a chloromethyl group, a chloropropyl group, a 3,3,3-trifluoropropyl group, a 2-cyanoethyl group, Examples thereof include, but are not limited to, a methoxy group and an ethoxyethyl group.

The above R ¹ , R ² and R ³ are derived from the triorganochlorosilane of the general formula (7) according to the above-mentioned production method. The triorganochlorolane may be used alone or in combination of two or more. When two or more kinds are used in combination, a polyimide precursor of the general formula (1) having two or more kinds of triorganosilyl groups can be obtained.

(B) Dihydropyridine Compound In the dihydropyridine compound represented by the general formula (2),
For example, R ⁴ is alkyl having 1 to 11 carbons, alkenyl, aralkyl, aralkenyl, aryl and heteroaryl. Specifically, R ⁴ has 1 to 11 carbons such as methyl group, ethyl group, propyl group and butyl group. 3 to 3 carbon atoms such as alkyl group, vinyl group, allyl group, butenyl group
Bonded to an aryl group having 6 to 10 carbon atoms such as 11 alkenyl groups, phenyl groups and tolyl groups, and a heteroaryl group having 4 to 10 carbon atoms such as pyridyl groups and furyl groups, or carbon atoms of these groups A 2-nitrophenyl group or the like in which a part of the hydrogen atom is substituted with a nitro group or the like, R
⁵ and R ⁶ are the same or different and are alkyl having 1 to 4 carbons, and R ⁷ and R ⁸ are the same or different and are COOR ′,
COR 'or CN (wherein R'is an alkyl group having 1 to 11 carbon atoms).

Examples of the dihydropyridine compound represented by the general formula (2) include, for example, nifedipine, 1,
4-dihydro-2,6-dimethyl-4- (2-nitrophenyl) -3,5-
Pyridine-dicarboxylic acid dimethyl ester), 2,4,6-trimethyl-3,5-bis (carbethoxy) -1,4-dihydropyridine, 2,6-dimethyl-4-ethyl-3,5-bis (carbethoxy) ) -1,4-Dihydropyridine, 2,6-dimethyl-4-
Ethyl-n-propyl-3,5-bis (carbethoxy) -1,4
-Dihydropyridine, 2,6-dimethyl-4-benzyl-3,5-
Examples thereof include bis (carbethoxy) -1,4-dihydropyridine. Of these, nifedipine is preferred.

(C) Hexaarylbiimidazole Compound The hexaarylbiimidazole compound of the general formula (3) used as the component (c) is known from German Patent No. 1300013 and US Pat. No. 3,630,736. General formula
In (3), R ⁹ , R ¹⁰ and R ¹¹ may be the same or different and each is a group having a substituted or unsubstituted aromatic ring derived from a carbocyclic or heterocyclic aromatic compound, particularly a carbon atom. An aryl group of formulas 6 to 10, for example, a phenyl group, a tolyl group and the like, and at least a part of hydrogen atoms of these aryl groups are substituted with a halogen atom such as chlorine, an alkoxy group such as a methoxy group and an ethoxy group There are things. Specific examples thereof include a phenyl group, a chlorophenyl group, a methoxyphenyl group, and the like. Among them, a preferable one is a phenyl group, a chlorophenyl group, a methoxyphenyl group and the like. Particularly preferred as the hexaarylbiimidazole of the general formula (3) are those in which R ⁹ , R ¹⁰ and R ¹¹ are the groups shown in Table 1.

[0026]

[Table 1]

Composition In the composition of the present invention, the polyimide precursor (a) represented by the general formula (1), the dihydropyridine compound (b) represented by the general formula (2) and the general formula (3) are represented. The hexaarylbiimidazole (c) can be mixed and used in an arbitrary ratio. In terms of obtaining good photosensitivity and storage stability,
With respect to 100 parts by weight of the polyimide precursor (a), the dihydropyridine compound (b) 2 to 100 parts by weight, hexaarylbiimidazole (c) preferably 1 to 100 parts by weight, further 100 parts by weight of the polyimide precursor (a) More preferably, 4 to 60 parts by weight of the dihydropyridine compound (b) and 1 to 60 parts by weight of the hexaarylbiimidazole (c) are used per part.

This composition generally comprises the above-mentioned component (a).
, (B) and (c) are dissolved in a suitable organic solvent to be used for application to a substrate in a solution state. As the solvent used here, for example, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether-2-acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclo Hexanone, γ-butyrolactone, butyl cellosolve acetate, butyl acetate, ethyl acetate, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, toluene, xylene, etc. Alternatively, two or more kinds can be used. Among these, preferred are diethylene glycol dimethyl ether, propylene glycol monomethyl ether-2-acetate, cyclohexanone, γ-butyrolactone, N-
Methyl-2-pyrrolidone and N, N-dimethylacetamide.

The composition of the present invention contains, in addition to the above-mentioned essential components and solvent, known additives which are usually added to polyimide resin compositions of this type in some cases, such as sensitizers and stabilizers.
It may contain coating aids, adhesion aids and the like. As the sensitizer, Michler's ketone, dithioxanthone derivative and the like are suitable.

The liquid composition of the present invention is applied onto a substrate such as a silicon wafer, a metal plate, a glass plate or a ceramic substrate by a known method such as spin coating, dipping or printing, and dried. After forming the coating film, exposure,
Through various steps of alkali development and curing, a polyimide-based protective film having excellent heat resistance and the like is formed.

The coating film is formed by drying by, for example, a drier,
It can be carried out by prebaking at a temperature of 30 to 180 ° C. for several minutes to several hours using a heating means such as a hot plate to remove most of the organic solvent in the coating film.

The exposure is carried out by placing a mask on the film formed by the above method and irradiating with light such as visible light or ultraviolet light for several seconds to several minutes.

After the exposure, a relief pattern can be obtained by dissolving and removing the exposed portion with a developing solution. Here, an alkaline aqueous solution is preferably used as the developer, and examples of the alkaline aqueous solution used include an aqueous solution of tetramethylammonium hydroxide.

Further, the resin having a relief pattern formed by development is heated at a temperature of usually 200 to 500 ° C., preferably 300 to 400 ° C. for several tens of minutes to several hours by a heating means such as a dryer or an electric furnace. As a result, a patterned polyimide film can be formed.

[0035]

EXAMPLES The present invention will now be specifically described with reference to examples, but these are for the purpose of explanation and do not limit the present invention in any way. First, as shown in the following reference example, a polyimide silyl ester polymer of the photosensitive resin composition of the present invention was synthesized.

Reference Example 1 2,2-bis as an acid anhydride was placed in a flask equipped with a stirrer, a thermometer and a nitrogen purging device.
(3,4-Benzenedicarboxylic acid hydride) Perfluoropropane 22.2 g (0.05 mol), diethylene glycol dimethyl ether 20 g as solvent, γ-butyrolactone
Charged 100g. In addition to this, N, N 'as silylated diamine
-Bis (t-butyldimethylsilyl) -4,4'-diaminodiphenyl ether 20.54 g (0.048 mol) and 1,3-bis [3- (N-
(Trimethylsilyl) aminopropyl] -1,1,3,3-tetramethyldisiloxane 0.79 g (0.002 mol) dissolved in 55 g of diethylene glycol dimethyl ether, and the solution is stirred so that the reaction temperature of the system does not exceed 40 ° C. While dripping. After dropping, stir for an additional 10 hours and the viscosity becomes 3300.
A solution of a polyimide precursor having a repeating unit of the following formula (8) having cP and a weight average molecular weight of 4.2 × 10 ⁴ was obtained.

[0037]

Embedded image (In the formula, R ¹² is a trimethylsilyl group, R ¹³ is a t-butyldimethylsilyl group, and the ratio of a / b is 96/4.)

Reference Example 2 16.11 g (0.05 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride as an acid anhydride, 100 g of diethylene glycol dimethyl ether and 50 g of N, N-dimethylacetamide as a solvent. , N, N'-bis (trimethylsilyl) -4,4'-diaminodiphenyl ether as silylated diamine 16.51 g (0.048 mol) and 1,3-
Bis [3- (N-trimethylsilyl) aminopropyl] -1,1,3,
A polyimide precursor consisting of repeating units of the following formula (9) having a viscosity of 4800 cP and a weight average molecular weight of 5.4 × 10 ⁴ was prepared in the same manner as in Reference Example 1 except that 0.79 g (0.002 mol) of 3-tetramethyldisiloxane was used. A body solution was obtained.

[0039]

[Chemical 15] [In the formula, R ¹² is a trimethylsilyl group, and a / b = 96.
/ 4. ]

Reference Example 3 As an acid anhydride, 13.24 g (0.045 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride
1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3, -tetramethyldisiloxane anhydride 2.13 g (0.005 mol),
100g of diethylene glycol dimethyl ether as a solvent
Example 1 except that 40 g of N, N-dimethylacetamide and 17.13 g (0.05 mol) of N, N-bis (trimethylsilyl) -4,4'-diaminodiphenylmethane were used as silylated diamine.
Similarly, the viscosity is 7600 cP, the weight average molecular weight is 7.1 ×
A polyimide resin precursor composed of 10 ⁴ of the following repeating units was synthesized.

Embedded image [In the formula, R ¹² is a trimethylsilyl group, and a / b = 9 /
It is 1. ]

Example 1 20 parts by weight of nifedipine as a dihydropyridine compound and 2,2'-bis (o-chlorophenyl) -4,5,4 'as a hexaarylbiimidazole compound were added to 100 parts by weight of the polyimide precursor solution of Reference Example 1. A photosensitive resin composition was prepared by adding 5 parts by weight of 5,5'-tetraphenyl-1,2'-biimidazole and 1 part by weight of 2,4-diethyl-9H-thioxanthen-9-one as a sensitizer. . This composition was applied to a silicon wafer using a spin coater and dried in a dryer at 95 ° C for 30 minutes. A photomask with a pattern for resolution measurement was brought into close contact with the resulting coating film and exposed with a high-pressure mercury lamp (exposure amount 600 m
J / cm ² ). Next, it was developed with a 2.3 wt% tetramethylammonium hydroxide aqueous solution and rinsed with pure water to obtain a polyimide precursor film having a positive pattern. The film thickness of the unexposed portion of the obtained film, the minimum line width of the pattern, and the heat resistance after the film was heated to 350 ° C. in a dryer and cured were examined. The results are shown in Table 2.

Example 2 20 parts by weight of nifedipine as a dihydropyridine compound and 2,2'-bis (o-chlorophenyl) -4,5,4 'as a hexaarylbiimidazole compound were added to 100 parts by weight of the polyimide precursor solution of Reference Example 2. A photosensitive resin composition was prepared by adding 5 parts by weight of 5,5'-tetraphenyl-1,2'-biimidazole and 1 part by weight of 2,4-diethyl-9H-thioxanthen-9-one as a sensitizer. . This photosensitive resin precursor composition was applied to a silicon wafer using a spin coater and dried in a drier.
Dry at 30 ° C. for 30 minutes. A photomask having a pattern for resolution measurement was brought into close contact with the obtained coating film and exposed with a high pressure mercury lamp (exposure amount 600 mJ / cm ² ). Next, it was developed with a 2.3% tetramethylammonium hydroxide aqueous solution and rinsed with pure water to obtain a polyimide precursor film having a positive pattern.
The obtained film was subjected to the same measurement as in Example 1. Table 2 shows the results.

[0043] Example 3 20 parts of nifedipine as the dihydropyridine compounds in the polyimide precursor solution 100 parts of Reference Example 3, 2,2'-bis (o-chlorophenyl) as a hexaarylbiimidazole compound -4,5,4 ', 5 A photosensitive resin composition was prepared by adding 5 parts of'-tetraphenyl-1,2'-biimidazole and 1 part of 2,4-diethyl-9H-thioxanthen-9-one as a sensitizer.
This photosensitive resin precursor composition was applied to a silicon wafer using a spin coater and dried in a dryer at 95 ° C for 30 minutes. A photomask with a pattern for resolution measurement was brought into close contact with the resulting coating film and exposed with a high-pressure mercury lamp (exposure amount 600 m
J / cm ² ). Next, it was developed with a 2.3% tetramethylammonium hydroxide aqueous solution and rinsed with pure water to obtain a polyimide precursor film having a positive pattern. Table 2 shows the physical properties of this film measured in the same manner as in Example 1.

Comparative Example 1 In a flask equipped with a stirrer, a thermometer, a condenser and a nitrogen purging apparatus, 14.71 g (0.05 mol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, o- Nitrobenzyl alcohol
16.69 g (0.12 mol) and 150 g of toluene were charged, 0.2 g of pyridine was added as a catalyst, and the mixture was reacted at 110 ° C. for 10 hours. The precipitate was washed with methanol and dried to obtain 26 g of tetracarboxylic acid diester. This tetracarboxylic acid diester 10
A mixed solution of 100 ml of toluene and 150 ml of thionyl chloride and a few drops of N, N-dimethylformamide were added to g, and the mixture was reacted at 80 ° C for 2 hours. The reaction solution was concentrated and cooled to obtain 8 g of tetracarboxylic acid diester dichloride. 2 g (3.14 mmol) of this tetracarboxylic acid diester dichloride was added to a mixed solution of 0.44 g (2.10 mmol) of 4,4-diaminodiphenyl ether, 22 ml of N, N-dimethylacetamide and 0.5 g (6.3 mmol) of pyridine, and 0 to 5 The reaction was carried out at 4 ° C. for 4 hours and at room temperature for 4 hours. The resulting polymer was reprecipitated with methanol, washed with water and dried. 1 g of this polymer was dissolved in 7 g of N-methyl-2-pyrrolidone to obtain a photosensitive resin precursor composition. This photosensitive resin precursor composition was applied to a silicon wafer using a spin coater and dried in a dryer at 70 ° C. for 15 minutes. A photomask having a pattern for resolution measurement was brought into close contact with the obtained coating film and exposed with a high pressure mercury lamp (exposure amount 600 mJ / cm ² ). Next, it was developed with a 2% aqueous solution of potassium hydroxide and rinsed with pure water, but a pattern could not be obtained due to insufficient exposure.

Comparative Example 2 22.2 g (0.05 mol) of 2,2-bis (3,4-benzenedicarboxylic acid hydride) perfluoropropane as an acid anhydride was placed in a flask equipped with a stirrer, a thermometer and a nitrogen purging device.
l), 160 g of N-methyl-2-pyrrolidone as a solvent,
To this, 18.29 g of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added and reacted at room temperature for 12 hours. To this, 30 g of xylene was added, and azeotropic dehydration was carried out at 150 ° C. for 2 hours for imidization. The produced polyimide was poured into water to be precipitated and dried to obtain a polyimide. 3 g of this polyimide was added to diethylene glycol dimethyl ether.
After dissolving in 27 g, 0.19 g of 5- (chlorosulfonyl) -1,2-naphthoquinonediazide and 0.07 g of triethylamine were added and reacted at room temperature for 12 hours. The produced triethylamine hydrochloride was filtered off, reprecipitated with methanol / water (1: 1), washed with water and dried to obtain 2.8 g of a polyimide having naphthoquinonediazide introduced therein. Dissolve this polyimide in 16 g of diethylene glycol dimethyl ether, apply it to a silicon wafer using a spin coater, and apply 70% in a drier.
It was dried at ℃ for 15 minutes. A photomask having a pattern for resolution measurement was brought into close contact with the obtained coating film and exposed with a high pressure mercury lamp (exposure amount 600 mJ / cm ² ). Next, it was developed with a 0.5% tetramethylammonium hydroxide aqueous solution and rinsed with pure water. The pattern formability measured in the same manner as in Example 1 is shown in Table 2.

[0046]

[Table 2] From the above results, the photosensitive resin of Comparative Example 1 does not have sufficient sensitivity, and the photosensitive resin of Comparative Example 2 has limited raw materials. It can be seen that the photosensitive resin composition is a positive-type photosensitive heat-resistant material with little film loss, good sensitivity, excellent pattern formability, and a wide range of raw materials that can be used.

[0047]

EFFECT OF THE INVENTION The photosensitive polyimide resin composition of the present invention has sufficient heat resistance as a protective film for electronic parts, has high purity, and is a positive type photosensitive material, so that it can be developed with an alkaline aqueous solution. Its dissolution rate can be adjusted, film loss is small, it can be applied to a wide range of raw materials, and its sensitivity is also good.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03F 7/038 504 G03F 7/038 504

Claims (1)

[Claims] 1. (a) The following general formula (1): [Wherein, X is a tetravalent organic group, Y is a divalent organic group, and R and R'are of the formula: (Here, R ¹ , R ² and R ³ are 1 having 1 to 8 carbon atoms.
It is a valent organic group or a hydrogen atom. )], A polyimide resin precursor having a repeating unit represented by the formula: and a weight average molecular weight of 20,000 to 100,000, and (b) the following general formula (2): [Wherein R ⁴ is a substituted or unsubstituted hydrocarbon group, and R 4
⁵ and R ⁶ are the same or different alkyl groups, and R ⁷ and R ⁸ are the same or different -COOR ", -COR" or -CN
(However, R ″ is an alkyl group.)], And (c) the following general formula (3): A photosensitive polyimide resin composition containing a hexaarylbiimidazole compound represented by the formula: wherein R ⁹ , R ¹⁰ and R ¹¹ are the same or different and are substituted or unsubstituted aryl groups.