JPH06308728A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive resin composition having practicably sufficient sensitivity and capable of forming a good positive type relief pattern ands reduced in fluctuation of film thickness with the lapse of time for the purpose of enhancing storage stability. CONSTITUTION:The photosensitive resin composition is characterized by containing 100 pts.wt. of a polyimide precursor comprising 20-80mol pts. of structural units represented by formula I and 80-20mol pts. of those represented by formula II and having a logarithmic viscosity of 0.1-5.0dl/g at 30 deg.C in an N-methylpyrrolidone solvent, and 0.5-50 pts.wt. of an o-quinonediazido compound. In formulae I and II, R<2> is, independently, a divalent organic group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel photosensitive heat resistant polymer and a method for producing the same. More specifically, it relates to a novel polyimide precursor having excellent storage stability and high sensitivity, and a photosensitive resin composition containing the same.

[0002]

2. Description of the Related Art Photosensitive polyimide is widely used as a heat-resistant photosensitive material for semiconductor insulating films and passivation films, but it has various problems. For example, JP-A-5
Japanese Patent Publication No. 4-145794 discloses a method of mixing a compound containing a double bond and an amino group or a quaternized salt thereof with a polyamic acid. However, a large amount of the amino group or its quaternary compound is added to an unstable polyamic acid solution. Since a compound containing a cation salt is added, there is a drawback that the viscosity of the solution changes greatly with time. JP-A-55-45746 and JP-A-60-1001.
Japanese Patent Laid-Open No. 43-43 discloses a method of reacting a carboxyl group of various polyamic acids with an unsaturated epoxy compound or an isocyanate compound having a double bond, but reacting a carboxyl group of a polyamic acid with a photosensitive unsaturated group-containing compound. At this time, there is a drawback that the viscosity of the solution changes due to decomposition of a part of the polyamic acid. Japanese Examined Japanese Patent Publication 55-41
Japanese Patent No. 422 discloses a polymer in which an active functional group such as a double bond is introduced into an ester side chain of a polyamic acid, but removal of an impurity chloride remaining when an acid chloride is reacted with a diamine is a problem. Become. In addition, JP-A-60-67
No. 29 discloses a method of synthesizing a diamine having a double bond in advance and synthesizing a polyimide using these, but the process is complicated because a photosensitive functional group is introduced and the cost is high. Requires. On the other hand, U.S. Pat. No. 4,093,461 discloses a positive type heat-resistant resist in which a quinonediazide compound is added to a polyamic acid, but the polyamic acid has too high solubility in an alkali, resulting in large film loss during development and poor resolution. There is a drawback that. Further, JP-A-4-204738 reports a positive type heat-resistant resist in which a quinonediazide compound is added to a polyamic acid derivative in which a carboxyl group of a polyamic acid is partially esterified, but has a drawback of low sensitivity. . As described above, the conventional techniques have various problems, and development of a photosensitive material that solves these problems has been desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned various problems of the prior art, and particularly to solve the problems of a positive heat-resistant resist obtained by adding quinonediazide to polyamic acid or the like. It is to be. That is, it is to provide a photosensitive resin composition having excellent storage stability, low impurity content, and good sensitivity.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have obtained a highly sensitive positive heat-resistant resist using an orthoquinonediazide compound and a polyimide precursor. Furthermore, the inventors have found that a polyimide precursor obtained by imidizing a part of the amide group of polyamic acid is more effective, and completed the present invention.

The photosensitive resin composition of the present invention has the following general formula (I):

[Chemical 5] The structural unit represented by
I)

[Chemical 6] The structural viscosity of the structural unit represented by the formula is 80 to 20 parts by mole and the logarithmic viscosity number is 0.1 to 5.0 dl / g (30 ° C., N-methyl-2
-Pyrrolidone solvent), and 100 to 50 parts by weight of a polyimide precursor and 0.5 to 50 parts by weight of an orthoquinonediazide compound (provided that in the formulas (I) and (II), R ² is independently It is a divalent organic group).

Preferably, in the general formulas (I) and (II), R ² is a general formula (III)

[Chemical 7] And general formula (IV)

[Chemical 8] Having at least one group selected from the group consisting of

R ² in the general formulas (I) and (II) used in the composition of the present invention is a divalent organic group. For more details,

When R ² is a carbocyclic aromatic group, preferred examples thereof include a monocyclic aromatic group, a fused polycyclic aromatic group, or a non-fused bicyclic aromatic group. .
In the case of this non-fused bicyclic group, the aromatic rings are linked to each other through a bridging group. In this case, the following groups are suitable as possible bridging groups:

[0009]

[Chemical 9]

[Chemical 10]

[Chemical 11]

In the above formula, Q ¹ is an alkyl group or alkylene group having 1 to 6 carbon atoms (preferably 1 to 4) optionally substituted by one or more halogen atoms (preferably fluorine atoms). Represents, or represents a cyclohexyl group, an aryl group or an arylene group, Q ² represents a hydrogen atom, a cycloalkyl group or an aryl group, and optionally a carbon atom substituted with one or more halogen atoms. It represents an alkyl group having 1 to 4 atoms. Further, Q ¹ and Q ² may be groups in which the above groups are bonded to each other through two bridging groups, for example, two —SO ₂ — groups.

When R ² is heterocyclic, particular examples thereof are 5- or 6-membered heterocyclic aromatic radicals containing oxygen, nitrogen and / or sulfur. Further, when R ² is an aliphatic group, an alkylene group having a hetero atom, for example, an oxygen, sulfur or nitrogen atom interposed in an alkylene chain having 2 to 12 carbon atoms is mentioned as an example thereof. Examples of the case where R ² is an alicyclic group include a cyclohexyl group and a dicyclohexylmethane group, while examples of the case where the R ² is an araliphatic group particularly include:
Examples include 1,3-, 1,4- or 2,4-bis-alkylenebenzene groups and 4,4′-bis-alkylene-diphenyl ether groups.

As for R ² , each R ² is independent of each other, and in some cases, a halogen atom or a carbon atom of 1 is present.
To 4 are monocyclic aromatic groups or non-fused bicyclic aromatic groups having one or more alkyl groups or alkoxy groups as substituents, or unsubstituted monocyclic araliphatic groups or the number of carbon atoms It is preferably from 2 to 10 unsubstituted aliphatic groups.

When R ² is a polysiloxane group, the following general formula (VII)

[Chemical 12] It is represented by. Here, R ³ is independently the following formula (VIII), (I
X), (X) or (XI).

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16] (However, R ⁴ independently represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an alkyl-substituted phenyl group having 7 to 12 carbon atoms, 1 ≦ p ≦ 100, and s is an integer of 1 to 4. .)

The photosensitive resin composition of the present invention comprises a polyimide precursor having the structural units represented by the general formulas (I) and (II), at least one orthoquinonediazide compound and a solvent. The polyimide precursor used in the composition of the present invention comprises 20 to 80 parts by mol of the structural unit represented by the general formula (I) and 80 to 20 parts by mol of the structural unit represented by the general formula (II). That is, when the structural unit (I) is defined as mmol and the structural unit (II) is defined as nmol, the following formula

[Equation 1] It is represented by. When this m / (m + n) is less than 0.2, the solubility at the time of development becomes too high, and the film loss in the unexposed area becomes large, which is not preferable. On the other hand, if it exceeds 0.8, the solubility at the time of development becomes too low and the sensitivity is lowered.
It is not preferable because the exposed area does not dissolve.

The photosensitive resin composition of the present invention can be obtained by dissolving the polyimide precursor and the orthoquinonediazide compound as a photosensitizer in a solvent at the above mixing ratio. Furthermore, the logarithmic viscosity number of the polyimide precursor of the present invention is
The range of 0.1 to 5 dl / g is preferable from the viewpoint of film formability.
Here, the logarithmic viscosity number is η _inh expressed by the following equation.

[Equation 2] (Here, the measurement is carried out using a Ubbelohde viscometer at a temperature of 30 ± 0.01 ° C., C is a solution concentration of 0.5 g / dl, η is a measurement value at a solution concentration of 0.5 g / dl, and ηo is a solvent measurement. It is a value.)

The orthoquinonediazide compound used in the composition of the present invention is used as a photosensitizer and is not particularly limited. For example, an orthobenzoquinonediazide compound, an orthonaphthoquinonediazide compound, or an ester thereof with a compound having a free hydroxyl group is used. However, an orthonaphthoquinonediazide compound and an ester of an orthonaphthoquinonediazide compound and a compound having a free hydroxyl group are preferable. Specific examples of preferable ones include hydroxybenzophenone or its derivative, gallic acid or its derivative, 4,4′-isopropylidenediphenol, 4,4′-bis (4-hydroxyphenyl) sulfone and 2,2-bis- ( Examples thereof include esters of bisphenol derivatives such as 4-hydroxyphenyl) hexafluoropropane and orthonaphthoquinonediazidesulfonyl chloride, and compounds of the following formula (Z).

[0017]

[Chemical 17]

The content ratio of the polyimide precursor and the orthoquinonediazide compound in the photosensitive resin composition of the present invention is 0.5 to 50 parts by weight of the orthoquinonediazide compound based on 100 parts by weight of the polyimide precursor. Parts, and preferably 10 to 30 parts by weight. When the content ratio of the orthoquinonediazide compound to 100 parts by weight of the polyimide precursor is less than 0.5 parts by weight, the difference in solubility in the developing solution between the exposed part and the unexposed part is insufficient and the contrast is excellent. I can't get the pattern. On the other hand, when it exceeds 50 parts by weight, the film-forming property is deteriorated to make the film brittle, and the film may be easily peeled off from the substrate.

As the solvent, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoramide, methylformamide, N-acetyl-2-pyrrolidone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, cresol, γ-butyrolactone, N, N-diethylacetamide, N, N-diethylformamide, N, N-dimethylmethoxyacetamide, tetrahydrofuran, N-acetyl-2-pyrrolidone N- methyl -ε- caprolactam, tetrahydrothiophene dioxide [sulfolane (sulpholane)], etc., or can be given these two or more mixed solvents.

The method for producing the polyimide precursor used in the composition of the present invention includes (a) a method of heating a polyamic acid, (b) a method of synthesizing by adding a dehydrating agent and a tertiary amine, or ( c) There is a method in which the polyamic acid is partly imidized in a solvent and then the part of the isoimide is converted to an imide, which will be described in detail below.

(A) The method of heating the polyamic acid is carried out by heating the polyamic acid at a temperature of 80 to 300 ° C. or a solution of the polyamic acid in an organic solvent at a temperature of 50 to 150 ° C. A polyimide precursor used for the product is obtained. (B) The method of obtaining by adding a dehydrating agent and a tertiary amine is, for example, adding a dehydrating agent such as acetic anhydride and a tertiary amine such as pyridine or isoquinoline to a polyamic acid solution, and adding the dehydrating agent to a polyamic acid solution at room temperature near 10 to 50 ° C. The polyimide precursor used in the present invention can be obtained by a known method in which the reaction is carried out at a temperature. (C) The method of converting the above-mentioned isoimide moiety into an imide is carried out by reacting the polyamic acid obtained by reacting the compounds (V) and (VI) described below with Proceedings of Secon.
d International Conference
e onPolyimides (1985) p631, for example, N, N'-dicyclohexylcarbodiimide, N-ethoxycarbonyl-
Converted to isoimide in the presence of dehydrating agents such as 2-ethoxy-1,2-dihydroquinoline and trifluoroacetic anhydride
Then, an imide group is formed by reacting at 0 to 100 ° C. For example, when N, N'-dicyclohexylcarbodiimide is used as the dehydrating agent, the polyamic acid can be partially polyisosimidated by using 0.2 to 1.9 times the molar amount of the compound of the formula (V). Reaction temperature is 0-6
The temperature is 0 ° C, preferably about 10 to 30 ° C. The reaction time is preferably 0.2 to 24 hours, more preferably 1 to 1
It's about two hours. Then, by further heating, the portion of the isoimide is imidized to obtain a polyimide precursor. The reaction temperature is 30 to 100 ° C, preferably 4
It is about 0 to 60 ° C. The reaction time is preferably 1 to 48 hours, more preferably 2 to 24 hours.

The polyamic acid has the general formula (V)

[Chemical 18] And a tetracarboxylic dianhydride represented by the general formula (VI)

[Chemical 19] (Wherein R ² has the same meaning as described above) and is obtained by a reaction with a diamine.

This reaction can be carried out in the above-mentioned organic solvent. In addition, the above organic solvent may be replaced with another aprotic (neutral) organic solvent such as aromatic, alicyclic or aliphatic hydrocarbon or a chlorinated derivative thereof (eg, benzene, toluene, xylenes, cyclohexane, pentane). , Hexane, petroleum ether, methylene chloride, etc.) or those diluted with dioxane can also be used.
For the purpose of controlling the molecular weight of the polyamic acid, the reaction can be carried out by adding a monofunctional acid anhydride such as phthalic anhydride or myric anhydride or an amine such as aniline or monoallylaniline.

The compound name of the tetracarboxylic dianhydride represented by the general formula (V) is 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane.

Known compounds are used as the diamines represented by the general formula (VI). Examples of the carbocyclic aromatic diamine include the following compounds.
o-, m-, and p-phenylenediamine, diaminotoluenes (eg 2,4-diaminotoluene), 1,
4-diamino-2-methoxybenzene, 2,5-diaminoxylenes, 1,3-diamino-4-chlorobenzene, 1,4-diamino-2,5-dichlorobenzene,
1,4-diamino-2-bromobenzene, 1,3-diamino-4-isopropylbenzene, N, N'-diphenyl-1,4-phenylenediamine, 4,4'-diaminodiphenyl-2,2-propane- 4,4 'diaminophenylmethane, 2,2'-diaminostilbene, 4,4'
-Diaminodiphenyl ether, 4,4'-diaminodiphenyl-thioether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone,
4,4'-diaminobenzoic acid phenyl ester, 2,
2'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diaminobenzyl, 4-
(4'-aminophenylcarbamoyl) -aniline, bis (4-aminophenyl) -phosphine oxide, bis (4-aminophenyl) -methyl-phosphine oxide, bis (3-aminophenyl) -methylsulfine oxide, bis (4 -Aminophenyl) -cyclohexylphosphine oxide, N, N-bis (4-aminophenyl) -N-phenylamine, N, N-bis (4-aminophenyl) -N-methylamine, 4,4'-diaminodiphenyl Urea, 1,8-diaminonaphthalene, 1,5-
Diaminoanthraquinone, diaminofluoranthene, bis (4-aminophenyl) -diethylsilane, bis (4
-Aminophenyl) -dimethylsilane, bis (4-aminophenyl) -tetramethyldisiloxane, 3,4'-
Diaminodiphenyl ether, benzidine, 2,2'-
Dimethylbenzidine, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] sulfone, 4,4'-bis (4-aminophenoxy) biphenyl, 2 , 2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 1,4-bis (4-aminophenoxy)
Benzene, 1,3-bis (4-aminophenoxy) benzene, etc. Particularly preferred diamines are 4,4'-bis (4-aminophenoxy) biphenyl and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane.

The heterocyclic diamines are, for example, the following compounds. 2,6-diaminopyridine, 2,4-diaminopyrimidine, 2,4-diamino-s-triazine, 2,
7-diamino-dibenzofuran, 2,7-diaminocarbazole, 3,7-diaminophenothiazine, 2,5-
Diamino-1,3,4-thiadiazole, 2,4-diamino-6-phenyl-s-triazine and the like.

Further, examples of the aliphatic diamine are the following compounds. Dimethyldiamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,2-dimethylpropylenediamine, 2,5-
Dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 3-
Methoxyheptamethylenediamine, 5-methylnonamethylenediamine, 2,11-diaminododecane, 1,12
-Diaminooctadecane, 1,2-bis (3-aminopropoxy) -ethane, N, N'-dimethyl-ethylenediamine, N, N'-dimethyl-1,6-diaminohexane, formula: H ₂ N (CH ₂ ) ₃ O (CH ₂ ) ₂ O (CH ₂ ) ₃ NH ₂ and the like diamines.

Further suitable compounds as alicyclic diamines are 1,4-diaminodicyclohexane and 4,4 '.
-Diamino-dicyclohexylmethane, etc., and as the araliphatic diamine, 1,4-bis (2-methyl-
4-aminopentyl) benzene, 1,4-bis (1,1
-Dimethyl-5-aminopentyl) -benzene, 1,3
-Bisaminomethyl) -benzene and 1,4-bis (aminomethyl) -benzene are suitable.

Further, the following compounds can be listed as the diaminopolysiloxane.

[Chemical 20]

[Chemical 21]

[Chemical formula 22]

[Chemical formula 23]

[Chemical formula 24] (Here, x is 1 to 100.)

A method for forming a patterned polyimide film using the photosensitive resin composition of the present invention will be described. The photosensitive resin composition of the present invention is applied onto a substrate such as a silicon wafer, a metal plate, a plastic plate or a glass plate by a known method such as spin coating, dipping or spray printing.
The obtained coating film is prebaked at a temperature of 30 to 150 ° C. for several minutes to several tens of minutes using a heating means such as an electric furnace and a hot plate to remove most of the solvent in the coating film. A negative mask is placed on the coating film from which the solvent has been removed, and actinic radiation is applied. Then, the exposed portion is dissolved and removed with a developing solution containing an alkaline aqueous solution to obtain a positive relief pattern.

If necessary, it is rinsed in water or a monohydric or polyhydric alcohol solvent and dried at a temperature of 150 ° C. or lower to stabilize the relief pattern. Also,
The film can be peeled off from the substrate at any time after the prebaking and used as a single film.

Since the polymer of the relief pattern formed by development is in the form of a precursor, it is heated at 200 to 500 ° C., preferably 300 to 400 by the above heating means.
A patterned polyimide film is formed by heating at a temperature of ℃ for several tens of minutes to several hours. The chemical reaction in this case is as shown below, and the photosensitizer is volatilized by thermal decomposition to form a polyimide film.

[0033]

[Chemical 25]

Examples of the above-mentioned actinic rays include X-rays, electron beams, ultraviolet rays, far ultraviolet rays and visible rays, and ultraviolet rays or far ultraviolet rays are particularly preferable. Further, as the developing solution, inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia water, primary amines such as ethylamine and n-propylamine, diethylamine, Secondary amines such as di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and quaternary amines such as tetramethylammonium hydroxide and trimellits hydroxyethylammonium hydroxide, either alone or A mixed aqueous solution or a solution obtained by adding a monohydric or polyhydric alcohol and / or a surfactant to the mixed aqueous solution is used.

The photosensitive resin composition of the present invention forms a heat-resistant polyimide film patterned as described above, but is used for electronic materials, particularly various semiconductor protective films, flattening films, passivation films, Buffer coat film, LSI
It can be applied to an α-ray shielding film of a memory, an interlayer insulating film, an interlayer film of a multilayer board of a printed wiring board, a liquid crystal alignment film, or a heat storage material of a thermal head.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. The synthesis examples, examples, and
Various measurements were carried out in the comparative example as follows. Logarithmic Viscosity: Using an Ubbelohde viscometer, N-methyl-
Measured at 30 ± 0.01 ° C. in 2-pyrrolidone solvent. Imidization rate: 1780 cm in infrared absorption spectrum
The area of the absorption spectrum based on the imide group of ^-1 was measured and calculated from the following formula. Rotational viscosity: E-type viscometer (VISCO manufactured by Tokyo Keiki Co., Ltd.
Viscosity measured at 25 ° C. using NIC EMD ™. Stability of compositions over time: The rotational viscosity numbers of the compositions after preparation and after standing for 1 month at room temperature were compared.

Synthesis Example 1 (Synthesis of Polyimide Precursor) A 1 liter flask equipped with a stirrer, a dropping funnel, a thermometer, a condenser and a nitrogen substitution device was fixed in a constant temperature bath. Dehydrated and purified 385.0 g of N in this flask
-Methyl-2-pyrrolidone (hereinafter abbreviated as "NMP") and 51.8 g (0.10 mol) of 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane (hereinafter "HFBAPP"). It abbreviated as "." Was added and stirring was continued. 44.4 g in the obtained solution
(0.10 mol) of 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane (6FDA) was added, and a polyamic acid solution was obtained by reaction at 20 to 30 ° C for 8 hours. 28.9 g (0.14 mol) of N, N'-dicyclohexylcarbodiimide (hereinafter referred to as "D
CC "is abbreviated. ) Is added and at this temperature another 30
The reaction was carried out for a minute to polyisimidize. Then 50
The reaction was carried out at -60 ° C for 12 hours. The white precipitate N, N'-dicyclohexylurea that formed was removed by filtration, the resulting solution was added dropwise to a large amount of ethanol, and the resulting precipitate was filtered and dried under reduced pressure at 50 ° C for one day to produce a polyimide precursor. Got the body This polyimide precursor has an inherent viscosity of 0.80 dl / g and an imidization ratio of 0.65.
Met.

Synthesis Examples 2 to 7 (Synthesis of Polyimide Precursor) Polyimide precursors were synthesized in the same manner as in Synthesis Example 1 under the synthesis conditions shown in Table 1. The results are shown in Table 1.

Synthesis Comparative Example 1 (Synthesis of Polyamic Acid) Using the same apparatus and method as in Synthesis Example 1, 80 g of NMP, 1
2.34 g (0.038 mol) of benzophenone 3,
3'-5,5'-Tetracarboxylic acid dianhydride (BTD
A) and 7.66 g (0.0383 mol) of 4,4'-
A polyamic acid solution having an inherent viscosity of 1.1 dl / g was synthesized from diaminodiphenyl ether (DDE). The results are shown in Table 1.

[0040]

[Table 1]

The abbreviations listed in Table 1 are as follows. (A) Tetracarboxylic dianhydride 6FDA: 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane BTDA: Benzophenone-3,3'-5,5'-tetracarboxylic dianhydride (b ) Amine HFBAPP: 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane DDS: 3,3'-diaminodiphenyl sulfone DDE: 4,4'-diaminodiphenyl ether BAPB: 4,4'-bis (4-Aminophenoxy) biphenyl DDCM: 4,4'-diaminodicyclohexylmethane

Example 1 20.0 obtained in Synthesis Example 1
g of polyimide precursor was dissolved in 60.0 g of NMP, and a triester of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid was added to this solution (hereinafter referred to as “NT-300”). 2.0 g was added to prepare a photosensitive resin composition of the present invention. The rotational viscosity of this composition is 3000 c immediately after preparation.
ps was 3010 cps after standing at room temperature for one month. This composition was spin-coated on a silicon wafer,
Prebaking was performed at 0 ° C. for 30 minutes to form a uniform film having a thickness of 8 μm. Next, it was exposed through a mask with an ultra-high pressure mercury lamp (10 mW / cm ² ) for 15 seconds.
This was developed by immersing it in an alkaline developer composed of 0.40 parts by weight of tetramethylammonium hydroxide and 10 parts by weight of ethanol for 2 minutes, rinsed with water and dried. In this way, the hole of 5 μm
Got the pattern. Do this at 150 ° C for 60 minutes, then 4
As a result of firing in an electric furnace at 00 ° C. for 60 minutes, a relief pattern of polyimide having a film thickness of 5 μm was obtained without breaking the pattern.

(Examples 2 to 5) A photosensitive resin composition was prepared in the same manner as in Example 1 under the conditions shown in Table 2.
An evaluation was performed. The results are shown in Table 2.

Comparative Example 1 Synthesis 10 obtained in Comparative Example 1
2.0 g of NT-300 was mixed with 0 g of a polyamic acid solution to prepare a photosensitive resin composition. In the same manner as in Example 1, the photosensitivity test and the temporal stability of the photopolymer composition were performed.
The results are shown in Table 2.

(Comparative Examples 2 to 3) In the same manner as in Example 1,
The photosensitive resin composition was prepared under the conditions shown in Table 2. The evaluation results are shown in Table 3.

[0046]

[Table 2]

[0047]

EFFECT OF THE INVENTION The photosensitive resin composition of the present invention has a highly sensitive and practical photosensitivity, and has a positive positive relief.
A pattern can be formed. Further, since the storage stability is excellent, there is little variation in film thickness over time.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical display location G03F 7/022 7/039 501 H01L 21/027 21/312 B 7352-4M

Claims (2)

[Claims] 1. A compound represented by the general formula (I): The structural unit represented by the formula (20) is 20 to 80 parts by mole and is represented by the general formula (II): The structural viscosity of the structural unit represented by the formula is 80 to 20 parts by mole and the logarithmic viscosity number is 0.1 to 5.0 dl / g (30 ° C., N-methyl-2
-Pyrrolidone solvent) 100 parts by weight of a polyimide precursor and 0.5 to 50 parts by weight of an orthoquinonediazide compound, wherein a photosensitive resin composition (wherein formulas (I) and (II): R ² is independently a divalent organic group). 2. In the general formulas (I) and (II), R ²
Is represented by the general formula (III): And the general formula (IV): The photosensitive resin composition according to claim 1, which comprises at least one group selected from the group consisting of: