JP3425343B2 - Positive photosensitive polymer resin composition, pattern forming method using the same, and electronic component - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photosensitive polymer resin composition which is preferably used for pattern formation of insulating films, protective films, α-ray blocking films, optical waveguides, etc. of various electronic parts. The present invention relates to a pattern forming method and an electronic component having a polymer resin film obtained by pattern formation as an insulating member, a protective film member, or the like.

[0002]

2. Description of the Related Art In a semiconductor device, a protective film called a passivation film is provided on the surface of a semiconductor substrate on which an element is formed for the purpose of protecting the element from the influence of the external environment and enhancing its reliability. . In general, as a material for such a protective film, a polyimide resin excellent in electrical properties such as insulation, radiation resistance, environmental stability and heat resistance is widely used. In addition, the α-ray blocking film of the semiconductor device,
A polyimide resin having excellent characteristics as described above is also widely used as an interlayer insulating film in a multilayer wiring structure element or a multilayer laminated structure element (multichip module).

Such a polyimide resin can be easily formed into a film form from its precursor polyamic acid. That is, first, a polyamic acid varnish is applied to the surface of a predetermined substrate or the like and heated at a low temperature to form a polyamic acid film. Further, this film is heat-treated at a high temperature to cure the precursor polyamic acid by a dehydration cyclization reaction to form a polyimide film. By using this method, it is possible to easily form a polyimide resin film which is insoluble or hardly soluble in various organic solvents and which is difficult to process due to its high softening point. Therefore, the above-mentioned method is widely used for forming the polyimide film.

On the other hand, semiconductor devices require through holes in a multilayer wiring structure and pad processing for conducting with external leads. To this end, the polyimide film formed as a protective film or an interlayer insulating film as described above must be patterned to form holes or grooves having a predetermined pattern structure. Generally, the patterning of the polyimide film is performed by using PEP (photo-engraving p-type) using a photoresist.
process). That is, after the polyimide film is formed on the surface of the semiconductor substrate on which the element is formed by the method described above, a photoresist film is further formed on the surface, and the photoresist film is exposed.
Development processing is performed to obtain a resist pattern. Then, using this resist pattern as an etching resistant mask, by selectively etching the underlying polyimide film,
A polyimide protective film or an interlayer insulating film having a desired pattern is formed.

However, when the polyimide film pattern is formed by the above-described method, two independent steps, that is, the step of forming the polyimide film and the PEP step for forming the pattern are required, which complicates the work. Is inevitable.

Therefore, in order to eliminate such drawbacks in the process, it is required to pattern a polyimide film without using PEP, and a resin composition containing a polyimide precursor has hitherto been available. It is disclosed.

For example, in JP-A-49-115541, a photopolymerizable group is replaced with an ester bond instead of a tetracarboxylic dianhydride which is usually used in the synthesis process of a polyamic acid as a polyimide precursor. There is disclosed a polyamic acid ester obtained by reacting a tetracarboxylic acid diester dichloride introduced by (1) with a diamino compound. The polyamic acid ester itself has a negative type photosensitivity in which the exposed portion becomes insoluble in the developing solution by light irradiation. For this reason,
Patterning can be performed during the formation of the polyimide film, and a patterned polyimide film can be obtained without using conventional PEP.

However, the process for synthesizing the tetracarboxylic acid diester dichloride having a photopolymerizable group, which is a raw material for the polyamic acid ester, and the process for synthesizing the polyamic acid ester are very complicated. In addition, chlorine ions are included as impurities in the final resin. Furthermore, when a film made of a polyamic acid ester is developed, an organic solvent is used as a developing solution, so a large amount of organic solvent is required in the production line, which is not preferable in terms of safety, hygiene and environment. Moreover, there is also a problem that the polyimide film pattern obtained by developing with an organic solvent swells and the resolution is lowered.

Further, in Japanese Patent Publication No. 59-52822, a negative photosensitive resin composition similar to that described above has a carbon-carbon double bond dimerizable or polymerizable by actinic radiation and an amino group. A heat-resistant photosensitive material containing a compound is disclosed.

When this photosensitive material is used as a protective film in a resin-sealed semiconductor device or the like, the adhesiveness to the semiconductor substrate, the protective film made of an inorganic material on the substrate surface, or the sealing resin is not sufficient. Therefore, there arises a problem that the reliability of the obtained semiconductor device is impaired. in addition,
Such a light-sensitive material, like the above-mentioned polyamic acid ester, must use an organic solvent as a developer,
It is not preferable in terms of safety.

Further, Japanese Patent Publication No. 60-6365 discloses that
A photosensitive resin composition in which a methacrylic acid (N, N-dialkylamino) alkyl ester is added as a salt to the carboxy group of a polyamic acid is disclosed, but this photosensitive resin composition is used as a solvent. On the other hand, it has the drawback of poor solubility.

On the other hand, Japanese Patent Application Laid-Open No. 62-145240 discloses a polymer having an isoimide structure.
Contrary to the above-mentioned composition, this polymer has a positive-type photosensitivity in that the exposed portion exposed to light is solubilized in the developing solution. Since this polymer has positive photosensitivity, it can be developed with an alkaline developer, but it has the drawbacks of poor heat resistance and poor exposure sensitivity, and is used as a protective film in semiconductor devices. To have a problem.

As the photosensitive resin composition having the same positive-type photosensitivity as described above, a solvent-soluble polyimide synthesized from a diamine compound having a hydroxyl group in an aromatic ring and an acid anhydride is used as an o-sensitizer. A composition containing a quinonediazide compound has been disclosed (JP-A-64-6).
0630). Further, as a similar photosensitive resin composition, a composition containing quinonediazide as a photosensitizer (Japanese Patent Laid-Open No. 52-13315 and Japanese Patent Laid-Open No. 62-135).
No. 824) and a composition having an o-nitrobenzyl ester group as a photosensitizer (JP-A-60-37550).

Since these photosensitive resin compositions can be developed with an alkali developing solution, the problems associated with the use of an organic solvent such as the above-mentioned negative photosensitive resin compositions are solved. However, in the development step, the difference in solubility in the alkali developing solution between the exposed portion and the unexposed portion is not sufficient, so that the resolution is low and it is difficult to form a fine pattern. In addition, since the polymer, which is the main component of the resin, is structurally limited, there is the drawback that the adhesiveness with silicon wafers, glass substrates, ceramic substrates, sealing resins, metals, etc. used in various semiconductor devices is poor. Have

[0015]

As described above, the polyimide resin excellent in electrical characteristics, radiation resistance, heat resistance, etc. is a preferable material as a protective film or an interlayer insulating film of a semiconductor device, but it is safe and simple. A photosensitive resin composition capable of obtaining a fine polyimide film pattern excellent in adhesiveness to a substrate or the like in various steps has not yet been obtained.

The present invention has been made in view of the above problems, and its object is to solve the above-mentioned conventional drawbacks and form a polyimide film pattern without separately using a photoresist. It is intended to provide a positive photosensitive polymer resin composition to be obtained, a pattern forming method using the same, and an electronic component having a polymer resin film obtained by forming a pattern.

[0017]

In order to solve the above problems, the present invention provides a repeating unit represented by the following general formula (1).
Contains a thermosetting polymer resin precursor that is dehydrated and cyclized by heating, comprising a polyimide precursor having units, and a photosensitive thermosetting accelerator that deactivates the thermosetting acceleration ability by light irradiation.
However, the photosensitive heat that deactivates the thermosetting acceleration ability by the light irradiation.
The curing accelerator is an azomethyene represented by the following general formula (2).
Compound; nitrogen-containing heterocycle represented by the following general formula (3)
Compounds; fused or non-fused pyridinequinonediazides
A compound or a quinoline quinonediazide compound;
Ringed or non-fused, substituted or unsubstituted 2-hydroxy
Removal of hydroxy group of cypyridine compound by light irradiation
Consisting of a nitrogen-containing heterocyclic compound substituted with a protective substituent
There is provided a positive photosensitive polymer resin composition, which is at least one selected from the group .

[Chemical 5] (In the general formula (1), φ is a tetravalent organic group, and Ψ is a divalent organic group.
Indicates an organic group. )

[Chemical 6] (In the general formula (2), Ar ¹¹ is a pyridine-type nuclear nitrogen source.
Nucleus having a child (-N =) and being adjacent to the nuclear nitrogen atom
Substituted or unsubstituted nitrogen-containing having a bond at a carbon atom
It is an aromatic heterocyclic group, and R ¹¹ is a substituted or unsubstituted aromatic group.
Aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, alicyclic group
It is a hydrocarbon group, an acyl group or a hydrogen atom, and R ¹² is
-OH group, -NH-R ¹³ group (R ¹³ is a substituted or unsubstituted
Aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, fat
Cyclic hydrocarbon group, an acyl group, thiophosphite sill group or carba
It is a moyl group. ), Or a —COOH group. )

[Chemical 7] (In the general formula (3), Ar ²¹ is a pyridine-type nuclear nitrogen source.
Substituted or unsubstituted nitrogen-containing aroma having a child (-N =)
Is a group heterocyclic group, and R ²⁰ is selected from the group shown below.
It is an organic group. )

[Chemical 8] (In the above general formula, R ²¹ and R ²² are substituted or unsubstituted.
Aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, fat
Cyclic hydrocarbon group, alkoxy group, hydroxyl group or
It is a hydrogen atom, and R ²¹ and R ²² are bonded to each other to form an alicyclic group.
It may form a hydrocarbon group. R ²³ , R ²⁴ , R ²⁵ ,
R ³⁰ and R ^31, substituted or unsubstituted Kaoru aromatic hydrocarbons
Group, heterocyclic group, aliphatic hydrocarbon group, alicyclic hydrocarbon group
Or a hydrogen atom; R ²⁶ , R ²⁷ and R ²⁸ are substituted or non-substituted.
Substituted aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group
Or an alicyclic hydrocarbon group; R ²⁹ is a substituted or unsubstituted aromatic group
Aromatic hydrocarbon group or aromatic heterocyclic group; X is a halogen group
And Z is a cyclic amino group. )

The present invention also includes a step of applying the above-mentioned positive-working photosensitive polymer resin composition to the surface of a substrate and heating and drying at a temperature of 180 ° C. or lower to form a resin layer, and a predetermined region of the resin layer. To expose the resin layer to light for exposure, to heat-treat the resin layer after the exposure at a temperature of 50 to 200 ° C., and to remove the exposed portion of the resin layer after the heat treatment with a developing solution to perform development processing. And a pattern forming method comprising:

Further, according to the present invention, a polymer resin film obtained by patterning a layer containing the above-mentioned positive type photosensitive polymer resin composition is provided as an insulating member, a protective member, an optical member or a liquid crystal alignment film. A characteristic electronic component is provided.

The present invention will be described in detail below.

In the positive-type photosensitive polymer resin composition of the present invention, the thermosetting polymer resin precursor which is dehydrated and cyclized by heating to cure is a polyimide precursor, a polybenzoxazole precursor, a polybenzothiazole precursor, Examples include polybenzimidazole precursors, polybenzoquinazolinedione precursors, polybenzoxadiazole precursors, and the like. Particularly preferred is a polyimide precursor (polyamic acid) having a repeating unit represented by the following general formula (1).

[0022]

[Chemical 5]

(In the above general formula (1), φ represents a tetravalent organic group and Ψ represents a divalent organic group.) The polyamic acid represented by the above general formula (1) is represented by the following general formula: It can be synthesized by reacting a tetracarboxylic dianhydride represented by (4) with a diamine compound component represented by the following general formula (5) in an organic solvent.

[0024]

[Chemical 6]

(In the above general formula (4), φ represents a tetravalent organic group.)

[Chemical 7]

(In the above general formula (5), Ψ represents a divalent organic group.) In the tetracarboxylic dianhydride represented by the above general formula (4), the tetravalent organic group φ has a carbon number. 1 to 30 aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group, and aliphatic hydrocarbon group, alicyclic hydrocarbon group, aromatic hydrocarbon group or heterocyclic group Is selected from the group consisting of polycyclic compound groups, either directly or linked to each other by a bridging group.

Specific examples of the tetracarboxylic dianhydride represented by the general formula (4) include, for example, pyromellitic dianhydride, 3-fluoropyromellitic dianhydride, and 3,6-difluoropyromellitic dianhydride. , 3- (trifluoromethyl) pyromellitic dianhydride, 3,6-bis (trifluoromethyl) pyromellitic dianhydride, 1,2,3,4-
Benzenetetracarboxylic dianhydride, 3,3 ', 4
4'-benzophenone tetracarboxylic dianhydride, 2,
2 ', 3,3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3 ", 4,4" -terphenyltetracarboxylic dianhydride Anhydride, 3,3 "', 4,4"'-quaterphenyltetracarboxylic dianhydride, 3,3 "",
4,4 ""-Kinkphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride,
1,1-ethylidene-4,4′-diphthalic acid dianhydride,
2,2-Propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 1,1,1,3,3,3-hexa Fluoro-2,2-propylidene-4,4'-diphthalic dianhydride, difluoromethylene-4,4'-diphthalic dianhydride, 1,1,2,2-tetrafluoro-1,2-ethylene- 4,4'-diphthalic dianhydride, 1,1,2,
2,3,3-hexafluoro-1,3-trimethylene-
4,4'-diphthalic dianhydride, 1,1,2,2,3,
3,4,4-octafluoro-1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,1,2,2
3,3,4,4,5,5-decafluoro-1,5-pentamethylene-4,4'-diphthalic acid dianhydride, oxy-
4,4'-diphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis (3,4-dicarboxyphenyl) ) Benzene dianhydride, 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride, 1,3-bis [ 2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, 1,4-bis [2- (3,4-dicarboxyphenyl) -2-propyl] benzene dianhydride, bis [ 3- (3,4-dicarboxyphenoxy) phenyl] methane dianhydride, bis [4
-(3,4-Dicarboxyphenoxy) phenyl] methane dianhydride, 2,2-bis [3- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-
Bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis [3- (3,4-
Dicarboxyphenoxy) phenyl] -1,1,1,
3,3,3-hexafluoropropane dianhydride, 2,2
-Bis [4- (3,4-dicarboxyphenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane dianhydride, bis (3,4-dicarboxyphenoxy) dimethylsilane dianhydride Thing, 1,3-bis (3,4-
Dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride Anhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride , 1, 2, 7, 8
-Phenanthrenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclo Pentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-
Tetracarboxylic dianhydride, cyclohexane-1,2,
4,5-tetracarboxylic dianhydride, 3,3 ′, 4
4'-bicyclohexyl tetracarboxylic acid dianhydride, carbonyl-4,4'-bis (cyclohexane-1,2-
Dicarboxylic acid) dianhydride, methylene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride,
1,2-ethylene-4,4'-bis (cyclohexane-
1,2-dicarboxylic acid) dianhydride, 1,1-ethylidene-4,4'-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylidene-4,4'-bis ( Cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1,1,3,3,3-hexafluoro-2,2
-Propylidene-4,4'-bis (cyclohexane-
1,2-dicarboxylic acid) dianhydride, oxy-4,4'-
Bis (cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis (cyclohexane-1,2-
Dicarboxylic acid) dianhydride, sulfonyl-4,4′-bis (cyclohexane-1,2-dicarboxylic acid) dianhydride,
2,2'-difluoro-3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 5,5'-difluoro-
3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 6,6'-difluoro-3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 5
5 ', 6,6'-hexafluoro-3,3', 4,4 '
-Biphenyltetracarboxylic dianhydride, 2,2'-bis (trifluoromethyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 5,5'-bis (trifluoromethyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 6,6'-bis (trifluoromethyl) -3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2 , 2 ', 5,5'-Tetrakis (trifluoromethyl) -3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 6,6'-
Tetrakis (trifluoromethyl) -3,3 ', 4
4'-biphenyltetracarboxylic dianhydride, 5,
5 ', 6,6'-tetrakis (trifluoromethyl)-
3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 5,5 ', 6,6'-hexakis (trifluoromethyl) -3,3', 4,4'- Biphenyltetracarboxylic dianhydride, oxy-4,4'-bis (3-fluorophthalic acid) dianhydride, oxy-4,4 '
-Bis (5-fluorophthalic acid) dianhydride, oxy-
4,4'-bis (6-fluorophthalic acid) dianhydride, oxy-4,4'-bis (3,5,6-trifluorophthalic acid) dianhydride, oxy-4,4'-bis [ 3- (trifluoromethyl) phthalic acid] dianhydride, oxy-4,
4'-bis [5- (trifluoromethyl) phthalic acid] dianhydride, oxy-4,4'-bis [6- (trifluoromethyl) phthalic acid] dianhydride, oxy-4,4'-bis [3,5-Bis (trifluoromethyl) phthalic acid] dianhydride, oxy-4,4'-bis [3,6-bis (trifluoromethyl) phthalic acid] dianhydride, oxy-4,4 '
-Bis [5,6-bis (trifluoromethyl) phthalic acid] dianhydride, oxy-4,4'-bis [3,5,6-
Tris (trifluoromethyl) phthalic acid] dianhydride, sulfonyl-4,4′-bis (3-fluorophthalic acid) dianhydride, sulfonyl-4,4′-bis (5-fluorophthalic acid) dianhydride , Sulfonyl-4,4'-bis (6-
Fluorophthalic acid) dianhydride, sulfonyl-4,4'-
Bis (3,5,6-trifluorophthalic acid) dianhydride,
Sulfonyl-4,4'-bis [3- (trifluoromethyl) phthalic acid] dianhydride, sulfonyl-4,4'-bis [5- (trifluoromethyl) phthalic acid] dianhydride, sulfonyl-4, 4'-bis [6- (trifluoromethyl) phthalic acid] dianhydride, sulfonyl-4,4'-bis [3,5-bis (trifluoromethyl) phthalic acid] dianhydride, sulfonyl-4,4 '-Bis [3,6-bis (trifluoromethyl) phthalic acid] dianhydride, sulfonyl-
4,4'-bis [5,6-bis (trifluoromethyl)
Phthalic acid] dianhydride, sulfonyl-4,4'-bis [3,5,6-tris (trifluoromethyl) phthalic acid] dianhydride, 1,1,1,3,3,3-hexafluoro- 2,2-Propylidene-4,4'-bis (3-fluorophthalic acid) dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-bis (5-fluorophthalic acid) dianhydride, 1,1,1,3
3,3-hexafluoro-2,2-propylidene-4,
4'-bis (6-fluorophthalic acid) dianhydride, 1,
1,1,3,3,3-hexafluoro-2,2-propylidene-4,4'-bis (3,5,6-trifluorophthalic acid) dianhydride, 1,1,1,3,3 , 3-Hexafluoro-2,2-propylidene-4,4'-bis [3-
(Trifluoromethyl) phthalic acid] dianhydride, 1,1,
1,3,3,3-hexafluoro-2,2-propylidene-4,4'-bis [5- (trifluoromethyl) phthalic acid] dianhydride, 1,1,1,3,3,3- Hexafluoro-2,2-propylidene-4,4'-bis [6-
(Trifluoromethyl) phthalic acid] dianhydride, 1,1,
1,3,3,3-hexafluoro-2,2-propylidene-4,4'-bis [3,5-bis (trifluoromethyl) phthalic acid] dianhydride, 1,1,1,3,3 , 3-Hexafluoro-2,2-propylidene-4,4'-bis [3,6-bis (trifluoromethyl) phthalic acid] dianhydride, 1,1,1,3,3,3-hexafluoro -2
2-Propylidene-4,4'-bis [5,6-bis (trifluoromethyl) phthalic acid] dianhydride, 1,1,1,
3,3,3-hexafluoro-2,2-propylidene-
4,4'-Bis [3,5,6-tris (trifluoromethyl) phthalic acid] dianhydride, 9-phenyl-9- (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic acid Dianhydride, 9,9-bis (trifluoromethyl) xanthene-2,3,6,7-tetracarboxylic dianhydride and bicyclo [2,2,2] oct-7-ene-2,3,5 , 6-tetracarboxylic dianhydride and the like.

These tetracarboxylic dianhydrides may be used alone or in combination of two or more. Tetracarboxylic acid dianhydride is a compound of the total acid anhydride component of 0.
It is used in an amount of 8 molar equivalents or more, preferably 0.9 molar equivalents or more. The reason for this is that if the blending amount of tetracarboxylic dianhydride is too small, the heat resistance of the obtained polyimide will be reduced.

In the diamine compound represented by the general formula (5), the divalent organic group Ψ is an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic group. It is selected from the group consisting of a cyclic group, and a polycyclic compound group in which an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group is connected to each other directly or by a bridging group.

Specific examples of the diamine compound represented by the general formula (5) include 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 3,3'-diaminobiphenyl and 3 , 4'-
Diaminobiphenyl, 4,4'-diaminobiphenyl,
3,3 "-diaminoterphenyl, 4,4" -diaminoterphenyl, 3,3 "'-diaminoquaterphenyl, 4,4"'-diaminoquaterphenyl, 3,
3 ""-diaminoquincphenyl, 4,4 ""-diaminoquincphenyl, oxy-3,3'-dianiline, oxy-4,4'-dianiline, thio-3,3'-dianiline, thio-4,4 '-Dianiline, sulfonyl-3,
3'-dianiline, sulfonyl-4,4'-dianiline, methylene-3,3'-dianiline, methylene-4,
4'-dianiline, 1,2-ethylene-3,3'-dianiline, 1,1-ethylidene-3,3'-dianiline,
1,1-ethylidene-4,4'-dianiline, 1,3-
Propylene-3,3'-dianiline, 1,3-propylene-4,4'-dianiline, 1,2-ethylene-4,
4'-dianiline, 2,2-propylidene-3,3'-
Dianiline, 2,2-propylidene-4,4'-dianiline, 1,1,1,3,3,3-hexafluoro-2,
2-propylidene-3,3'-dianiline, 1,1,
1,3,3,3-hexafluoro-2,2-propylidene-4,4'-dianiline, 1,1,2,2,3,3-
Hexafluoro-1,3-propylene-3,3'-dianiline, 1,1,2,2,3,3-hexafluoro-
1,3-propylene-4,4'-dianiline, 1,3-
Bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3
-Aminophenylthio) benzene, 1,3-bis (4-
Aminophenylthio) benzene, 1,3-bis (3-aminophenylsulfonyl) benzene, 1,3-bis (4
-Aminophenylsulfonyl) benzene, 1,3-bis [2- (3-aminophenyl) -2-propyl] benzene, 1,3-bis [2- (4-aminophenyl) -2-
Propyl] benzene, 1,3-bis [2- (3-aminophenyl) -1,1,1,3,3,3-hexafluoro-2-propyl] benzene, 1,3-bis [2- (4 −
Aminophenyl) -1,1,1,3,3,3-hexafluoro-2-propyl] benzene, 1,4-bis (3-
Aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenylthio) benzene, 1,4-bis (4-aminophenylthio) benzene, 1,4- Bis (3-aminophenylsulfonyl) benzene, 1,4-bis (4-aminophenylsulfonyl) benzene, 1,4-bis [2- (3
-Aminophenyl) -2-propyl] benzene, 4,
4'-bis (3-aminophenoxy) biphenyl, 4,
4'-bis (4-aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ether,
Bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-Aminophenoxy) phenyl] propane, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,4-bis [2- (3-aminophenyl) -1,
1,1,3,3,3-hexafluoro-2-propyl]
Benzene, 1,4-bis [2- (4-aminophenyl)
-1,1,1,1,3,3,3-hexafluoro-2-propyl] benzene, 2,2-bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3 -Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 5-fluoro-1,3-phenylenediamine, 2 -Fluoro-1,4-phenylenediamine, 2,5-difluoro-1,4-phenylenediamine, 2,4,5,6-hexafluoro-1,3-phenylenediamine, 2,3,5,6-hexa Fluoro-1,
4-phenylenediamine, 3,3'-diamino-5,
5'-difluorobiphenyl, 4,4'-diamino-
2,2'-difluorobiphenyl, 4,4'-diamino-3,3'-difluorobiphenyl, 3,3'-diamino-2,2 ', 4,4', 5,5 ', 6,6'- Octafluorobiphenyl, 4,4'-diamino-2,2 ',
3,3 ′, 5,5 ′, 6,6′-octafluorobiphenyl, oxy-5,5′-bis (3-fluoroaniline), oxy-4,4′-bis (2-fluoroaniline), oxy -4,4'-bis (3-fluoroaniline), sulfonyl-5,5'-bis (3-fluoroaniline), sulfonyl-4,4'-bis (2-fluoroaniline), sulfonyl-4,4 ' -Bis (3-fluoroaniline), 1,3-bis (3-aminophenoxy)-
5-fluorobenzene, 1,3-bis (3-amino-5)
-Fluorophenoxy) benzene, 1,3-bis (3-
Amino-5-fluorophenoxy) -5-fluorobenzene, 5- (trifluoromethyl) -1,3-phenylenediamine, 2- (trifluoromethyl) -1,4-phenylenediamine, 2,5-bis (tri) Fluoromethyl) -1,4-phenylenediamine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 3,3'-bis (trifluoromethyl) -4,4 '
-Diaminobiphenyl, oxy-5,5'-bis [3-
(Trifluoromethyl) aniline], oxy-4,4 ′
-Bis [2- (trifluoromethyl) aniline], oxy-4,4'-bis [3- (trifluoromethyl) aniline], sulfonyl-5,5'-bis [3- (trifluoromethyl) aniline] , Sulfonyl-4,4'-bis [2- (trifluoromethyl) aniline], sulfonyl-4,4'-bis [3- (trifluoromethyl) aniline], 1,3-bis (3-aminophenoxy) -5
(Trifluoromethyl) benzene, 1,3-bis [3-
Amino-5- (trifluoromethyl) phenoxy] benzene, 1,3-bis [3-amino-5- (trifluoromethyl) phenoxy] -5- (trifluoromethyl) benzene, 3,3′-bis (tri Fluoromethyl) -5,
5'-diaminobiphenyl, bis (3-aminophenoxy) dimethylsilane, bis (4-aminophenoxy) dimethylsilane, 1,3-bis (3-aminophenyl)-
1,1,3,3-tetramethyldisiloxane, 1,3-
Bis (4-aminophenyl) -1,1,3,3-tetramethyldisiloxane, methylenediamine, 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentane Diamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-
Decanediamine, 1,2-bis (3-aminopropoxy) ethane, 1,3-diaminocyclohexane, 1,4
-Diaminocyclohexane, bis (3-aminocyclohexyl) methane, bis (4-aminocyclohexyl) methane, 1,2-bis (3-aminocyclohexyl) ethane, 1,2-bis (4-aminocyclohexyl) ethane, 2, 2-bis (3-aminocyclohexyl) propane, 2,2-bis (4-aminocyclohexyl) propane, bis (3-aminocyclohexyl) ether, bis (4-aminocyclohexyl) ether, bis (3-aminocyclohexyl) sulfone , Bis (4-aminocyclohexyl) sulfone, 2,2-bis (3-aminocyclohexyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminocyclohexyl)- 1,1,1,3,3,3-hexafluoropropane, 1,3-xylile Diamine, 1,4-xylylenediamine, 1,8-diaminonaphthalene, 2,7-diaminonaphthalene, 2,6-diaminonaphthalene, 2,5
-Diaminopyridine, 2,6-diaminopyridine, 2,
5-diaminopyrazine, 2,4-diamino-s-triazine, 1,3-bis (aminomethyl) cyclohexane,
1,4-bis (aminomethyl) cyclohexane, 1,4
-Bis (aminopropyldimethylsilyl) benzene and 1,3-bis (3-aminopropyl) -1,1,3
3-tetraphenyldisiloxane may be mentioned.

These diamine compounds may be used alone or in combination of two or more. The diamine compound is 0.8 molar equivalent or more of all the amine compound components,
It is preferably used in an amount of 0.9 molar equivalent or more. The reason for this is that the heat resistance of the polyimide obtained is reduced when the amount of the diamine compound is too small.

Further, in the photosensitive polymer composition of the present invention, a diamine compound represented by the following general formula (6), that is, a bis (aminoalkyl) peroxide, together with the diamine compound represented by the above general formula (5), is used. You may mix | blend an alkyl polysiloxane compound.

[0033]

[Chemical 8]

(In the general formula (6), R ^{1 s} may be the same or different and each represents an alkyl group having 1 to 5 carbon atoms;
q and r are integers of 1 to 10, and p is a positive integer. ) Bis (aminoalkyl) represented by the general formula (6)
Examples of the peralkylpolysiloxane compound include:
1,3-bis (aminomethyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (2-aminoethyl) -1,1,3,3-tetramethyldisiloxane,
1,3-bis (3-aminopropyl) -1,1,3,3
-Tetramethyldisiloxane, 1,3-bis (4-aminobutyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (5-aminopentyl) -1,1,
3,3-tetramethyldisiloxane, 1,3-bis (6
-Aminohexyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (7-aminoheptyl)-
1,1,3,3-tetramethyldisiloxane, 1,3-
Bis (8-aminooctyl) -1,1,3,3-tetramethyldisiloxane, 1,3-bis (10-aminodecyl) -1,1,3,3-tetramethyldisiloxane,
1,5-bis (3-aminopropyl) -1,1,3
3,5,5-hexamethyltrisiloxane, 1,7-bis (3-aminopropyl) -1,1,3,3,5,5,5
7,7-Octamethyltetrasiloxane, 1,11-bis (3-aminopropyl) -1,1,3,3,5,5
7,7,9,9,11,11-dodecamethylhexasiloxane, 1,15-bis (3-aminopropyl) -1,
1,3,3,5,5,7,7,9,9,11,11,1
3,13,15,15-Hexadecamethyloctasiloxane, and 1,19-bis (3-aminopropyl)-
1,1,3,3,5,5,7,7,9,9,11,1
1, 13, 13, 15, 15, 17, 17, 17, 19, 19
-Eicosamethyl decasiloxane and the like.

By blending the bis (aminoalkyl) peralkylpolysiloxane compound represented by the general formula (6), the adhesion and adhesion between the polyimide resin and a semiconductor substrate such as a glass substrate or a silicon substrate can be obtained. It is possible to improve the sex. However, if this compound is excessively blended, the heat resistance of the polyimide resin may decrease, so the blending amount thereof is preferably 0.02 to 0.2 molar equivalent, and more preferably, the whole diamine component. It is 0.05 to 0.15 molar equivalent.

The photosensitive polymer resin composition of the present invention comprises
In addition to the above-mentioned components, a dicarboxylic acid anhydride or a monoamine compound may be added as a terminal treatment agent in order to control the degree of polymerization of the polyamic acid.

Examples of the dicarboxylic acid anhydrides include maleic anhydride, citraconic anhydride, dimethyl maleic anhydride, ethyl maleic anhydride, diethyl maleic anhydride, propyl maleic anhydride, butyl maleic anhydride. Substance, chloromaleic anhydride, dichloromaleic anhydride, bromomaleic anhydride, dibromomaleic anhydride, fluoromaleic anhydride, difluoromaleic anhydride, (trifluoromethyl) maleic anhydride, bis ( Trifluoromethyl) maleic anhydride,
Cyclobutanedicarboxylic acid anhydride, cyclopentanedicarboxylic acid anhydride, cyclohexanedicarboxylic acid anhydride,
Tetrahydrophthalic anhydride, Endomethylenetetrahydrophthalic anhydride, Methyltetrahydrophthalic anhydride, Methylendomethylenetetrahydrophthalic anhydride, Phthalic anhydride, Methylphthalic anhydride, Ethylphthalic anhydride, Dimethylphthalic anhydride , Fluorophthalic anhydride, difluorophthalic anhydride, chlorophthalic anhydride, dichlorophthalic anhydride, bromophthalic anhydride, dibromophthalic anhydride, nitrophthalic anhydride, 2,3-benzophenone dicarboxylic anhydride, Three
4-benzophenone dicarboxylic acid anhydride, 3-phenoxyphthalic anhydride, 4-phenoxyphthalic anhydride, 3
-(Phenylsulfonyl) phthalic anhydride, 4- (phenylsulfonyl) phthalic anhydride, 2,3-biphenyldicarboxylic acid anhydride, 3,4-biphenyldicarboxylic acid anhydride, 1,2-naphthalenedicarboxylic acid anhydride , 2,
3-naphthalenedicarboxylic acid anhydride, 1,8-naphthalenedicarboxylic acid anhydride, 1,2-anthracene dicarboxylic acid anhydride, 2,3-anthracene dicarboxylic acid anhydride, 1,9-anthracene dicarboxylic acid anhydride, 2, Three
-Pyridinedicarboxylic acid anhydride, 3,4-pyridinedicarboxylic acid anhydride, succinic acid anhydride, nadic acid anhydride and the like.

Examples of the monoamine compound include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 1- (3-aminopropyl) -1,1,3,3. , 3-pentamethyldisiloxane, vinylamine, allylamine, glycine, alanine, aminobutyric acid, valine, norvaline, isovaline, leucine, norleucine, isoleucine, glutamine, glutamic acid, tryptophan, aminocrotonic acid, aminoacetonitrile, aminopropionitrile, amino Crotononitrile, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine, aminoadamantane, aminobe Zocyclobutane, aminocaprolactam, aniline, chloroaniline, dichloroaniline, bromoaniline, dibromoaniline, fluoroaniline, difluoroaniline, nitroaniline, dinitroaniline, toluidine, xylidine, ethylaniline, anisidine, phenetidine, aminoacetanilide, aminoacetophenone, amino Benzoic acid, aminobenzaldehyde, aminobenzonitrile, aminophthalonitrile, aminobenzotrifluoride, aminostyrene, aminostilbene, aminoazobenzene, aminodiphenyl ether, aminodiphenylsulfone, aminobenzamide, aminobenzenesulfonamide, aminophenylmaleimide, aminophenylphthalimide , Aminobiphenyl, aminoterphenyl, amino Phthalene, aminoanthracene, aminoanthraquinone, aminofluorene, aminofluorenone, aminopyrrolidine, aminopiperazine, aminopiperidine, aminohomopiperidine, aminomorpholine, aminobenzodioxole, aminobenzodioxane, aminopyridine, aminopyridazine, aminopyrimidine, amino Pyrazine, aminoquinoline, aminocinnoline, aminophthalazine,
Aminoquinazoline, aminoquinoxaline, aminopyrrole, aminoimidazole, aminopyrazole, aminotriazole, aminooxazole, aminoisoxazole, aminothiazole, aminoisothiazole, aminoindole, aminobenzimidazole, aminoindazole, aminobenzoxazole, aminobenzothiazole , Benzylamine, phenethylamine, phenylpropyiamine, phenylbutylamine, benzhydrylamine, aminoethyl-1,3-dioxolane, aminoethylpyrrolidine, aminoethylpiperazine, aminoethylpiperidine, aminoethylmorpholine, aminopropylimidazole, and aminopropylcyclohexane. , Aminophenol, 2- (4-aminophenyl)
2- (4-hydroxyphenyl) propane etc. are mentioned.

The compounding amounts of the above-mentioned dicarboxylic acid anhydride and monoamine compound can be appropriately selected depending on the application, viscosity, etc., but are, for example, 0.1% based on the tetracarboxylic acid dianhydride or diamine compound. 02-0.
It is preferably about 4 molar equivalents.

The method of synthesizing the polyamic acid represented by the general formula (1) is not particularly limited, but a method of polymerizing under anhydrous conditions in an organic polar solvent in an inert gas atmosphere is preferable.

Examples of the organic polar solvent used in this reaction include N, N-dimethylformamide, N, N
-Dimethylacetamide, N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl-2
-Pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphortriamide, N-
Methyl-ε-caprolactam, N-acetyl-ε-caprolactam, 1,2-dimethoxyethane, 1,2-diethoxyethane, bis (2-methoxyethyl) ether,
Bis (2-ethoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, 1-acetoxy-
2-methoxyethane, 1-acetoxy-2-ethoxyethane, (2-acetoxyethyl) (2-methoxyethyl) ether, (2-acetoxyethyl) (2-ethoxyethyl) ether, methyl 3-methoxypropionate, tetrahydrofuran , 1,3-dioxane, 1,3
-Dioxolane, 1,4-dioxane, pyrroline, pyridine, picoline, dimethylsulfoxide, sulfolane,
Examples include γ-butyrolactone, propylene carbonate, phenol, cresol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetonyl acetone. These organic solvents may be used alone or in combination of two or more.

The reaction temperature is usually -20 to 100 ° C, preferably -5 to 30 ° C, and the reaction pressure is not particularly limited.
It can be sufficiently carried out at normal pressure. The reaction time varies depending on the type of tetracarboxylic dianhydride and the type of reaction solvent, but 1 to 24 hours is usually sufficient. As described above, the polyamic acid, which is a component of the photosensitive polymer resin composition of the present invention, can be easily synthesized without any process complexity, and impurities are not mixed in the manufacturing process.

The polyamic acid obtained at this time is
The inherent viscosity (logarithmic viscosity number) of a 0.5 wt% N-methyl-2-pyrrolidone solution at 30 ° C. was 0.
It is preferably 3 (dL / g) or more, more preferably 0.3 (dL / g) or more and 3.0 (dL / g) or less. The reason is that the inherent viscosity of polyamic acid is too low,
That is, if the polymerization degree of the polyamic acid is too low, it may not be possible to obtain a polyimide resin having sufficient heat resistance, while the inherent viscosity is too high, that is, if the polymerization degree is too high, its handling Because it becomes difficult.

Next, the photosensitive heat-curing accelerator, which is incorporated into the positive-type photosensitive polymer resin composition of the present invention and which deactivates the heat-curing promoting ability upon irradiation with light, will be described in detail.

The first photosensitive thermosetting accelerator is an azomethine compound represented by the following general formula (2).

[0046]

[Chemical 9]

In the above general formula (2), Ar ¹¹ has a pyridine type nuclear nitrogen atom (-N =), and has a bond to a nuclear carbon atom adjacent to the nuclear nitrogen atom. Is a nitrogen-containing aromatic heterocyclic group, and examples thereof include groups shown below.

[0048]

[Chemical 10]

(In the above formula, -Z ¹ = is = C (R ¹⁴ )-
Or = N- is shown. In addition, Z ¹ adjacent to each other may be condensed.

--X ¹ --is --O--, --S--, --Se--,
-Te-, or -N (R ¹⁵⁾ - shows the.

Here, R ¹⁴ and R ¹⁵ represent a substituted or unsubstituted aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, alicyclic hydrocarbon group, characteristic group or hydrogen atom. ) As the unsubstituted nitrogen-containing aromatic heterocyclic group introduced as Ar ¹¹ , for example, a 2-pyridyl group, a 2-quinolyl group,
1-isoquinolyl group, 3-isoquinolyl group, 6-phenanthridinyl group, 1,10-phenanthroline-2-yl group, 3-pyridazinyl group, 1-phthalazinyl group, 3-
Cinnolinyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 2-quinazolinyl group, 4-quinazolinyl group, 2-
Pyrazinyl group, 2-quinoxalinyl group, 1,3,5-triazin-2-yl group, 1,2,4,5-tetrazin-
3-yl group, 2-imidazolyl group, 4-imidazolyl group, 2-benzimidazolyl group, 2-naphthoimidazolyl group, 3-pyrazolyl group, 3-indazolyl group, 2-oxazolyl group, 4-oxazolyl group, 2-benzooxa Zolyl group, 2-naphthoxazolyl group, 3-isoxazolyl group, 3-benzisoxazolyl group, 2-thiazolyl group, 4-thiazolyl group, 2-benzothiazolyl group,
2-naphthothiazolyl group, 2-selenazolyl group, 2-benzoselenazolyl group, 2-terrazolyl group, 2-benzoterrazolyl group, 1,2,3-triazol-4-yl group, 1,2,4- Triazol-3-yl group, 1,2,
4-triazol-5-yl group, and 1,2,3,5
-Tetrazol-4-yl group and the like.

Examples of the substituent introduced into these nitrogen-containing aromatic heterocyclic groups to constitute the substituted nitrogen-containing aromatic heterocyclic compound include, for example, di-substituted amino groups (dimethylamino group,
Diethylamino group, dibutylamino group, ethylmethylamino group, butylmethylamino group, diamylamino group, dibenzylamino group, diphenethylamino group, diphenylamino group, ditolylamino group, dixylylamino group, methylphenylamino group, benzylmethylamino group Groups), mono-substituted amino groups (methylamino group, ethylamino group, propylamino group, isopropylamino group, ter
t.-Butylamino group, anilino group, anisidino group, phenetidino group, toluidino group, xylidino group, pyridylamino group, thiazolylamino group, benzylamino group, benzylideneamino group, etc., cyclic amino group (pyrrolidino group, piperidino group, piperazino group) , Morpholino group, 1-
A pyrrolyl group, a 1-pyrazolyl group, a 1-imidazolyl group,
1-triazolyl group, etc., acylamino group (formylamino group, acetylamino group, benzoylamino group, cinnamoylamino group, pyridinecarbonylamino group, trifluoroacetylamino group, etc.), sulfonylamino group (mesylamino group, ethylsulfonylamino group) Group, phenylsulfonylamino group, pyridylsulfonylamino group, tosylamino group, taurylamino group, trifluoromethylsulfonylamino group, sulfamoylamino group,
Methylsulfamoylamino group, sulfanylamino group, acetylsulfanylamino group, etc.), amino group,
Hydroxyamino group, ureido group, semicarbazide group,
Carbazide group, disubstituted hydrazino group (dimethylhydrazino group, diphenylhydrazino group, methylphenylhydrazino group, etc.), monosubstituted hydrazino group (methylhydrazino group, phenylhydrazino group, pyridylhydrazino group,
Benzylidene hydrazino group), hydrazino group, amidino group, hydroxy group, oxime group (hydroxyiminomethyl group, methoxyiminomethyl group, ethoxyiminomethyl group, hydroxyiminoethyl group, hydroxyiminopropyl group, etc.), alkoxyalkyl group ( Hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, etc., cyano group, cyanato group, thiocyanato group, nitro group, nitroso group, oxy group (methoxy group, ethoxy group, propoxy group, butoxy group, hydroxyethoxy group, phenoxy group) , Naphthoxy group, pyridyloxy group,
Thiazolyloxy group, acetoxy group, etc.), thio group (methylthio group, ethylthio group, phenylthio group, pyridylthio group, thiazolylthio group, etc.), mercapto group, halogen group (fluoro group, chloro group, bromo group, iodo group), carboxyl group and Salts, oxycarbonyl groups (methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group, etc.), aminocarbonyl groups (carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, pyridylcarbamoyl group, carbazoyl group, allofanoyl group , Oxamoyl group, succiamoyl group, etc.), thiocarboxyl group and its salt, dithiocarboxyl group and its salt, thiocarbonyl group (methoxythiocarbonyl group, methylthiocarbonyl group) Such as methyl thio thiocarbonyl group), an acyl group (formyl group, an acetyl group, a propionyl group, an acryloyl group, a benzoyl group, a cinnamoyl group, a pyridine group, thiazole group,
Trifluoroacetyl group etc.), thioacyl group (thioformyl group, thioacetyl group, thiobenzoyl group, pyridinethiocarbonyl group etc.), sulfinic acid group and its salt, sulfonic acid group and its salt, sulfinyl group (methylsulfinyl group, ethylsulfinyl group) Group, phenylsulfinyl group, etc.), sulfonyl group (mesyl group, ethylsulfonyl group, phenylsulfonyl group, pyridylsulfonyl group, tosyl group, tauryl group, trifluoromethylsulfonyl group, sulfamoyl group, methylsulfamoyl group, sulfanilyl group, Acetylsulfanylyl group), oxysulfonyl group (methoxysulfonyl group, ethoxysulfonyl group, phenoxysulfonyl group, acetaminophenoxysulfonyl group, pyridyloxysulfonyl group, etc.), thio Rufonyl group (methylthiosulfonyl group, ethylthiosulfonyl group, phenylthiosulfonyl group, acetaminophenylthiosulfonyl group, pyridylthiosulfonyl group, etc.), aminosulfonyl group (sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, Ethylsulfamoyl group, diethylsulfamoyl group, phenylsulfamoyl group, acetaminophenylsulfamoyl group, pyridylsulfamoyl group, etc., ammonio group (trimethylammonio group, ethyldimethylammonio group, dimethylsulfamme) Phenylammonio group, pyridinio group, quinolinio group, etc.), azo group (phenylazo group, pyridylazo group, thiazolylazo group, etc.), azoxy group, halogenated alkyl group (chloromethyl group, bromomethyl group, fluorome Group, dichloromethyl group, dibromomethyl group, a difluoromethyl group, a trifluoromethyl group, pentafluoroethyl group, such as heptafluoropropyl group), a hydrocarbon group (an alkyl group,
Aryl groups, alkenyl groups, alkynyl groups, etc.), heterocyclic groups, organosilicon groups (silyl groups, disilanyl groups, trimethylsilyl groups, triphenylsilyl groups, etc.) and the like.

As Ar ¹¹ in the general formula (2), the acid dissociation constant pKa of the chemical species protonated to the pyridine-type nuclear nitrogen atom (-N =) is pH 1 to 10.
Nitrogen-containing aromatic heterocyclic groups between are preferred. More specifically, 2-pyridyl group, 2-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 6-phenanthridinyl group, 3-pyridazinyl group, 1-phthalazinyl group, 3-
Cinnolinyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 2-quinazolinyl group, 4-quinazolinyl group, 2-
Imidazolyl group, 4-imidazolyl group, 2-benzimidazolyl group, 3-pyrazolyl group, 3-indazolyl group,
Examples thereof include nitrogen-containing aromatic heterocyclic groups such as a 2-thiazolyl group, a 4-thiazolyl group, and a 2-benzothiazolyl group. These nitrogen-containing aromatic heterocyclic groups and substituted nitrogen-containing aromatic heterocyclic groups obtained by substituting these nitrogen-containing aromatic heterocyclic groups with various characteristic groups as described above are particularly desirable.

R ¹¹ in the general formula (2) is a substituted or unsubstituted aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, alicyclic hydrocarbon group, acyl group or hydrogen atom.

Examples of the unsubstituted aromatic hydrocarbon group introduced as R ¹¹ include benzene ring group, naphthalene ring group, anthracene ring group, phenanthrene ring group, tetralin ring group, azulene ring group, biphenylene ring group, Acenaphthylene ring group, acenaphthene ring group, fluorene ring group, triphenylene ring group, pyrene ring group, chrysene ring group, picene ring group, perylene ring group, benzopyrene ring group, rubicene ring group,
Coronene ring group, ovalen ring group, indene ring group, pentalene ring group, heptalene ring group, indacene ring group, phenalene ring group, fluoranthene ring group, acephenanthrylene ring group, aceanthrylene ring group, naphthacene ring group, prey Aden ring group, pentaphene ring group, pentacene ring group, tetraphenylene ring group, hexaphene ring group, hexacene ring group,
Examples thereof include a trinaphthylene ring group, a heptaphene ring group, a heptacene ring group and a pyrantrene ring group. These aromatic hydrocarbon groups may be substituted with the above-mentioned various characteristic groups.

The unsubstituted heterocyclic group introduced as R ¹¹ includes, for example, a pyrrole ring group, a pyrroline ring group,
Pyrrolidine ring group, indole ring group, isoindole ring group, indoline ring group, isoindoline ring group, indolizine ring group, carbazole ring group, carboline ring group, furan ring group, oxolane ring group, coumarone ring group, coumaran ring group , Isobenzofuran ring group, phthalane ring group, dibenzofuran ring group, thiophene ring group, thiolane ring group, benzothiophene ring group, dibenzothiophene ring group, pyrazole ring group, pyrazoline ring group, indazole ring group, imidazole ring group, imidazoline ring group Group, imidazolidine ring group, benzimidazole ring group, benzimidazoline ring group, naphthimidazole ring group, oxazole ring group, oxazoline ring group, oxazolidine ring group, benzoxazole ring group, benzoxazoline ring group, naphthoxazole ring group, iso Oxazole ring group, benzoiso Kisazoru ring group, a thiazole ring group, a thiazoline ring group, a thiazolidine ring group, a benzothiazole ring group, a benzothiazoline ring, naphthothiazole ring group, an isothiazole ring group, a benzisothiazole ring group,
Triazole ring group, benzotriazole ring group, oxadiazole ring group, thiadiazole ring group, benzooxadiazole ring group, benzothiadiazole ring group, tetrazole ring group, purine ring group, pyridine ring group, piperidine ring group, quinoline ring group , Isoquinoline ring group, acridine ring group, phenanthridine ring group, benzoquinoline ring group, naphthoquinoline ring group, naphthyridine ring group, phenanthroline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, piperazine ring group, phthalazine ring Group, quinoxaline ring group, quinazoline ring group, cinnoline ring group, phenazine ring group, perimidine ring group, triazine ring group, tetrazine ring group, pteridine ring group, oxazine ring group, benzoxazine ring group, phenoxazine ring group, thiazine ring group Group, benzothiazine ring group, phenothiazine ring group Oxadiazine ring group, thiadiazine ring group, dioxolane ring group, benzodioxole ring group, dioxane ring group, benzodioxane ring group, dithiolane ring group, benzodithiol ring group, dithiane ring group, benzodithiane ring group, pyrane ring group, chromene Ring group, xanthene ring group, oxane ring group, chroman ring group, isochroman ring group,
Trioxane ring group, thiane ring group, trithiane ring group, morpholine ring group, quinuclidine ring group, selenazole ring group, benzoselenazole ring group, naphthoselenazole ring group, tellurazole ring group, and benzotelrazole ring group . These heterocyclic groups may be substituted with the various characteristic groups described above.

Examples of the unsubstituted aliphatic hydrocarbon group introduced as R ¹¹ include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec.
-Butyl group, tert.-butyl group, pentyl group, tert.-pentyl group, isopentyl group, neopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, nonyl group, decyl group, vinyl group, allyl group, iso Aliphatic hydrocarbon groups such as a propenyl group, a propenyl group, a methallyl group, a crotyl group, a butenyl group, a pentenyl group, a butadienyl group, an ethynyl group, a propynyl group, a butynyl group and a pentynyl group can be mentioned. These aliphatic hydrocarbon groups may be substituted with the above-mentioned various characteristic groups.

The unsubstituted alicyclic hydrocarbon group introduced as R ¹¹ is, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclopentenyl group or a cyclopentyl group. Examples thereof include alicyclic hydrocarbon groups such as hexenyl group, cycloheptenyl group, cyclooctenyl group, cyclopentadienyl group and cyclohexadienyl group. These alicyclic hydrocarbon groups may be substituted with the above-mentioned various characteristic groups.

R ¹² in the general formula (2) is —OH.
A group, a —NH—R ¹³ group, or a —COOH group. R ¹³
Is a substituted or unsubstituted aromatic hydrocarbon group, heterocyclic group,
It is an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an acyl group, a thioacyl group or a carbamoyl group.

The above-mentioned azomethine compound has a thermosetting acceleration ability (dehydration cyclization reaction accelerating ability) before irradiation with light, but it has a thermosetting acceleration ability (dehydration cyclization reaction accelerating ability) upon irradiation with light.
Is a compound that inactivates. Specifically, by irradiating such a compound with light, a photogeometric isomerization reaction occurs and an intramolecular hydrogen bond is formed. The intramolecular hydrogen bond thus formed deactivates the heat curing accelerating ability.

By adding these photosensitive thermosetting accelerators to a thermosetting polymer resin precursor solution which is dehydrated and cyclized by heating such as a polyimide precursor (polyamic acid), coating, exposure, PEB ( The post-exposure bake) and development steps give a positive photosensitive polymer resin composition capable of forming a fine pattern.

These photosensitive thermosetting accelerators may be used alone or in admixture of two or more, and are added in an amount of 0.1 molar equivalent or more per 1 molar equivalent of the repeating unit of the photosensitive polymer resin. It is preferable. The blending amount of the photosensitive thermosetting accelerator is more preferably 0.1 to 4.0 molar equivalents, and most preferably 0.1 to 2.0 molar equivalents. The reason for this is that when the amount of the photosensitive thermosetting accelerator is too small, the photosensitivity of the resin layer becomes insufficient and sufficient resolution cannot be obtained, and conversely, the amount of the photosensitive curing accelerator is too large. In this case, there is a possibility that the film loss may increase or it may be difficult to form a clean thin film.

Next, the second photosensitive thermosetting accelerator which can be incorporated into the photosensitive positive type polymer composition of the present invention will be described in detail.

The second photosensitive thermosetting accelerator is a nitrogen-containing heterocyclic compound represented by the following general formula (3).

[0065]

[Chemical 11]

Ar ²¹ in the general formula (3) is a substituted or unsubstituted nitrogen-containing aromatic heterocyclic group having a pyridine type nuclear nitrogen atom (-N =), and specifically, as shown below. Group.

[0067]

[Chemical 12]

In the above formula, ═Z ² — represents a —C (R ²¹ ) — group or a ═N— group. Two Zs adjacent to each other
² may be condensed. Here, R ²¹ represents a substituted or unsubstituted aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, alicyclic hydrocarbon group, characteristic group or hydrogen atom.

[0069] -X ² - is, -O -, - S -, - Se- or an -Te-.

Examples of the unsubstituted nitrogen-containing aromatic heterocyclic group introduced as Ar ²¹ include, for example, pyridyl group, quinolyl group, isoquinolyl group, phenanthridinyl group, phenanthrolinyl group, pyridazinyl group and phthalazinyl group. , Cinnolinyl group, pyrimidinyl group, quinazolinyl group, pyrazinyl group, quinoxalinyl group, 1,3,5-triazinyl group, 1,2,4,5-tetrazinyl group, imidazolyl group, benzimidazolyl group, naphthimidazolyl group, pyrazolyl group, indazolyl group Group, oxazolyl group, benzoxazolyl group, naphthoxazolyl group, isoxazolyl group, benzoisoxazolyl group, thiazolyl group, benzothiazolyl group, naphthothiazolyl group, selenazolyl group, benzoselenazolyl group, tellrazolyl group, benzoterula Zolyl group, 1, , 3-triazolyl group, 1, 2,
Examples thereof include nitrogen-containing aromatic heterocyclic groups such as 4-triazolyl group, 1,2,3,5-tetrazolyl group, and naphthidinyl group.

Examples of the substituent introduced into these nitrogen-containing aromatic heterocyclic groups to constitute the substituted nitrogen-containing aromatic heterocyclic compound include, for example, di-substituted amino groups (dimethylamino group,
Diethylamino group, dibutylamino group, ethylmethylamino group, butylmethylamino group, diamylamino group, dibenzylamino group, diphenethylamino group, diphenylamino group, ditolylamino group, dixylylamino group, methylphenylamino group, benzylmethylamino group Groups), mono-substituted amino groups (methylamino group, ethylamino group, propylamino group, isopropylamino group, ter
t.-Butylamino group, anilino group, anisidino group, phenetidino group, toluidino group, xylidino group, pyridylamino group, thiazolylamino group, benzylamino group, benzylideneamino group, etc., cyclic amino group (pyrrolidino group, piperidino group, piperazino group) , Morpholino group, 1-
A pyrrolyl group, a 1-pyrazolyl group, a 1-imidazolyl group,
1-triazolyl group, etc., acylamino group (formylamino group, acetylamino group, benzoylamino group, cinnamoylamino group, pyridinecarbonylamino group, trifluoroacetylamino group, etc.), sulfonylamino group (mesylamino group, ethylsulfonylamino group) Group, phenylsulfonylamino group, pyridylsulfonylamino group, tosylamino group, taurylamino group, trifluoromethylsulfonylamino group, sulfamoylamino group,
Methylsulfamoylamino group, sulfanylamino group, acetylsulfanylamino group, etc.), amino group,
Hydroxyamino group, ureido group, semicarbazide group,
Carbazide group, disubstituted hydrazino group (dimethylhydrazino group, diphenylhydrazino group, methylphenylhydrazino group, etc.), monosubstituted hydrazino group (methylhydrazino group, phenylhydrazino group, pyridylhydrazino group,
Benzylidene hydrazino group), hydrazino group, amidino group, hydroxy group, oxime group (hydroxyiminomethyl group, methoxyiminomethyl group, ethoxyiminomethyl group, hydroxyiminoethyl group, hydroxyiminopropyl group, etc.), alkoxyalkyl group ( Hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, etc., cyano group, cyanato group, thiocyanato group, nitro group, nitroso group, oxy group (methoxy group, ethoxy group, propoxy group, butoxy group, hydroxyethoxy group, phenoxy group) , Naphthoxy group, pyridyloxy group,
Thiazolyloxy group, acetoxy group, etc.), thio group (methylthio group, ethylthio group, phenylthio group, pyridylthio group, thiazolylthio group, etc.), mercapto group, halogen group (fluoro group, chloro group, bromo group, iodo group), carboxyl group and Salts, oxycarbonyl groups (methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group, etc.), aminocarbonyl groups (carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, pyridylcarbamoyl group, carbazoyl group, allofanoyl group , Oxamoyl group, succiamoyl group, etc.), thiocarboxyl group and its salt, dithiocarboxyl group and its salt, thiocarbonyl group (methoxythiocarbonyl group, methylthiocarbonyl group) Such as methyl thio thiocarbonyl group), an acyl group (formyl group, an acetyl group, a propionyl group, an acryloyl group, a benzoyl group, a cinnamoyl group, a pyridine group, thiazole group,
Trifluoroacetyl group etc.), thioacyl group (thioformyl group, thioacetyl group, thiobenzoyl group, pyridinethiocarbonyl group etc.), sulfinic acid group and its salt, sulfonic acid group and its salt, sulfinyl group (methylsulfinyl group, ethylsulfinyl group) Group, phenylsulfinyl group, etc.), sulfonyl group (mesyl group, ethylsulfonyl group, phenylsulfonyl group, pyridylsulfonyl group, tosyl group, tauryl group, trifluoromethylsulfonyl group, sulfamoyl group, methylsulfamoyl group, sulfanilyl group, Acetylsulfanylyl group), oxysulfonyl group (methoxysulfonyl group, ethoxysulfonyl group, phenoxysulfonyl group, acetaminophenoxysulfonyl group, pyridyloxysulfonyl group, etc.), thio Rufonyl group (methylthiosulfonyl group, ethylthiosulfonyl group, phenylthiosulfonyl group, acetaminophenylthiosulfonyl group, pyridylthiosulfonyl group, etc.), aminosulfonyl group (sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, Ethylsulfamoyl group, diethylsulfamoyl group, phenylsulfamoyl group, acetaminophenylsulfamoyl group, pyridylsulfamoyl group, etc., ammonio group (trimethylammonio group, ethyldimethylammonio group, dimethylsulfamme) Phenylammonio group, pyridinio group, quinolinio group, etc.), azo group (phenylazo group, pyridylazo group, thiazolylazo group, etc.), azoxy group, halogenated alkyl group (chloromethyl group, bromomethyl group, fluorome Group, dichloromethyl group, dibromomethyl group, a difluoromethyl group, a trifluoromethyl group, pentafluoroethyl group, such as heptafluoropropyl group), a hydrocarbon group (an alkyl group,
Aryl groups, alkenyl groups, alkynyl groups, etc.), heterocyclic groups, organosilicon groups (silyl groups, disilanyl groups, trimethylsilyl groups, triphenylsilyl groups, etc.) and the like.

As Ar ²¹ in the general formula (3), the acid dissociation constant pKa of the chemical species protonated to the pyridine-type nuclear nitrogen atom (-N =) is pH 1 to 10.
Nitrogen-containing aromatic heterocyclic groups between are preferred. More specifically, pyridyl group, quinolyl group, isoquinolyl group, phenanthridinyl group, pyridazinyl group, phthalazinyl group, cinnolinyl group, pyrimidinyl group, quinazolinyl group, imidazolyl group, benzimidazolyl group, pyrazolyl group, indazolyl group, thiazolyl group. , Nitrogen-containing aromatic heterocyclic groups such as benzothiazolyl group and naphthyridinyl group. These nitrogen-containing aromatic heterocyclic groups and substituted nitrogen-containing aromatic heterocyclic groups obtained by substituting these nitrogen-containing aromatic heterocyclic groups with various characteristic groups as described above are particularly desirable.

R ²⁰ in the general formula (3) is a group selected from the following (a-1) to (a-8).

[0074]

[Chemical 13]

Here, R ²¹ and R ²² are a substituted or unsubstituted aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, alicyclic hydrocarbon group, alkoxy group, hydroxy group or hydrogen atom. And R ²¹ and R ²² may combine with each other to form an alicyclic hydrocarbon group. R ²³ , R ²⁴ , R
²⁵ , R ³⁰ and R ³¹ are substituted or unsubstituted aromatic hydrocarbon groups, heterocyclic groups, aliphatic hydrocarbon groups, alicyclic hydrocarbon groups or hydrogen atoms, and R ^{26 to} R ²⁸ are substituted or unsubstituted Substituted aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group or alicyclic hydrocarbon group, R ²⁹ is a substituted or unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group, and X is It is a halogen group and Z is a cyclic amino group.

Examples of the unsubstituted aromatic hydrocarbon group introduced into R ^{21 to} R ³¹ include benzene ring group, naphthalene ring group, anthracene ring group, phenanthrene ring group, tetralin ring group, azulene ring group and biphenylene ring group. Group, acenaphthylene ring group, acenaphthene ring group, fluorene ring group, triphenylene ring group, pyrene ring group, chrysene ring group, picene ring group, perylene ring group, benzopyrene ring group, rubicene ring group,
Coronene ring group, ovalen ring group, indene ring group, pentalene ring group, heptalene ring group, indacene ring group, phenalene ring group, fluoranthene ring group, acephenanthrylene ring group, aceanthrylene ring group, naphthacene ring group, prey Aden ring group, pentaphene ring group, pentacene ring group, tetraphenylene ring group, hexaphene ring group, hexacene ring group,
Examples thereof include aromatic hydrocarbon groups such as trinaphthylene ring group, heptaphene ring group, heptacene ring group, and pyrantrene ring group. These aromatic hydrocarbon groups may be substituted with the above-mentioned various characteristic groups.

Examples of the unsubstituted heterocyclic group introduced as R ^{21 to} R ³¹ include a pyrrole ring group, a pyrroline ring group,
Pyrrolidine ring group, indole ring group, isoindole ring group, indoline ring group, isoindoline ring group, indolizine ring group, carbazole ring group, carboline ring group, furan ring group, oxolane ring group, coumarone ring group, coumaran ring group , Isobenzofuran ring group, phthalane ring group, dibenzofuran ring group, thiophene ring group, thiolane ring group, benzothiophene ring group, dibenzothiophene ring group, pyrazole ring group, pyrazoline ring group, indazole ring group, imidazole ring group, imidazoline ring group Group, imidazolidine ring group, benzimidazole ring group, benzimidazoline ring group, naphthimidazole ring group, oxazole ring group, oxazoline ring group, oxazolidine ring group, benzoxazole ring group, benzoxazoline ring group, naphthoxazole ring group, iso Oxazole ring group, benzoiso Kisazoru ring group, a thiazole ring group, a thiazoline ring group, a thiazolidine ring group, a benzothiazole ring group, a benzothiazoline ring, naphthothiazole ring group, an isothiazole ring group, a benzisothiazole ring group,
Triazole ring group, benzotriazole ring group, oxadiazole ring group, thiadiazole ring group, benzooxadiazole ring group, benzothiadiazole ring group, tetrazole ring group, purine ring group, pyridine ring group, piperidine ring group, quinoline ring group , Isoquinoline ring group, acridine ring group, phenanthridine ring group, benzoquinoline ring group, naphthoquinoline ring group, naphthyridine ring group, phenanthroline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, piperazine ring group, phthalazine ring Group, quinoxaline ring group, quinazoline ring group, cinnoline ring group, phenazine ring group, perimidine ring group, triazine ring group, tetrazine ring group, pteridine ring group, oxazine ring group, benzoxazine ring group, phenoxazine ring group, thiazine ring group Group, benzothiazine ring group, phenothiazine ring group Oxadiazine ring group, thiadiazine ring group, dioxolane ring group, benzodioxole ring group, dioxane ring group, benzodioxane ring group, dithiolane ring group, benzodithiol ring group, dithiane ring group, benzodithiane ring group, pyrane ring group, chromene Ring group, xanthene ring group, oxane ring group, chroman ring group, isochroman ring group,
Heterocycles such as trioxane ring group, thiane ring group, trithiane ring group, morpholine ring group, quinuclidine ring group, selenazole ring group, benzoselenazole ring group, naphthoselenazole ring group, tellurazole ring group, and benzotelrazole ring group Groups. These heterocyclic groups may be substituted with the various characteristic groups described above.

The unsubstituted aliphatic hydrocarbon group introduced as R ^{21 to} R ²⁸ , R ³⁰ and R ³¹ is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or an isobutyl group. , Sec.- butyl group, tert.-
Butyl group, pentyl group, tert.-pentyl group, isopentyl group, neopentyl group, hexyl group, isohexyl group,
Heptyl group, octyl group, nonyl group, decyl group, vinyl group, allyl group, isopropenyl group, propenyl group, methallyl group, crotyl group, butenyl group, pentenyl group, butadienyl group, ethynyl group, propynyl group, butynyl group,
And aliphatic hydrocarbon groups such as pentynyl groups. These aliphatic hydrocarbon groups may be substituted with the above-mentioned various characteristic groups.

The unsubstituted alicyclic hydrocarbon group introduced as R ^{21 to} R ²⁸ , R ³⁰ and R ³¹ is, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cycloheptyl group. , A cyclooctyl group, a cyclopentenyl group, a cyclohexenyl group,
Examples thereof include alicyclic hydrocarbon groups such as cycloheptenyl group, cyclooctenyl group, cyclopentadienyl group and cyclohexadienyl group. These alicyclic hydrocarbon groups are
It may be substituted with the various characteristic groups described above.

Examples of the unsubstituted aromatic heterocyclic group introduced as R ²⁹ include pyrrole ring group, indole ring group, isoindole ring group, carbazole ring group, furan ring group, coumarone ring group, isobenzofuran ring group. Group, thiophene ring group, benzothiophene ring group, dibenzothiophene ring group, pyrazole ring group, indazole ring group, imidazole ring group, benzimidazole ring group, naphthimidazole ring group, oxazole ring group, benzoxazole ring group, naphthoxazole ring group Group, isoxazole ring group, benzisoxazole ring group, thiazole ring group, benzothiazole ring group, naphthothiazole ring group, isothiazole ring group,
Benzisothiazole ring group, triazole ring group, benzotriazole ring group, oxadiazole ring group, thiadiazole ring group, benzooxadiazole ring group, benzothiadiazole ring group, tetrazole ring group, purine ring group, pyridine ring group, quinoline Ring group, isoquinoline ring group, acridine ring group, phenanthridine ring group, benzoquinoline ring group, naphthoquinoline ring group, naphthyridine ring group, phenanthroline ring group, pyridazine ring group, pyrimidine ring group, pyrazine ring group, piperazine ring group, Phthalazine ring group, quinoxaline ring group, quinazoline ring group, cinnoline ring group, phenazine ring group, perimidine ring group, triazine ring group, tetrazine ring group, pteridine ring group, oxazine ring group, benzoxazine ring group, phenoxazine ring group, Thiazine ring group, benzothiazine ring group, phenothi Zin ring group, oxadiazine ring group, thiadiazine ring group, benzodioxole ring group, benzodioxane ring group, pyran ring group, chromene ring group, xanthene ring group, chroman ring group, isochroman ring group, selenazole ring group, benzoselena Examples of the heterocyclic group include a azole ring group, a naphthoselenazole ring group, a tellurazole ring group, and a benzotelrazole ring group. These heterocyclic groups may be substituted with the various characteristic groups described above.

Examples of the halogen group introduced as X include a fluoro group, a chloro group, a bromo group and an iodo group.

The substituted amino group introduced as Z is, for example, a pyrrol-1-yl group, a pyrrolin-1-yl group, a pyrrolidin-1-yl group, an indol-1-yl group, an isoindol-2-yl group. Group, indoline-1-yl group, isoindoline-2-yl group, carbazol-9
-Yl group, pyrazol-1-yl group, pyrazoline-1-
Ile group, pyrazolidin-1-yl group, imidazole-1
-Yl group, imidazolin-1-yl group, imidazolidin-1-yl group, piperazin-1-yl group, piperidine-
1-yl group, morpholin-4-yl group, 2-pyrrolidinone-1-yl group, 2-piperidin-1-yl group, piperazin-2,5-dione-1-yl group, pyrrolidine-2,
5-dione-1-yl group, pyrrole-2,5-dione-
1-yl group, isoindole-1,3-dione-2-yl group, benzo [f] isoindole-1,3-dione-
2-yl group, piperidin-2,5-dione-1-yl group, benzo [de] isoquinolin-1,3-dione-2
An yl group and the like.

In the general formula (3), R ²⁰ is a group represented by the above-mentioned (a-1), (a-2), (a-5), (a-7) and (a-8). The nitrogen-containing heterocyclic compound is particularly preferable because it is easy to synthesize, there are few residues, and the resulting photosensitive polymer resin composition has high sensitivity. For example, a nitrogen-containing heterocyclic compound in which R ²⁰ is represented by (a-5) can be synthesized by reacting a heteroarylcarboxylic acid chloride with nitroarylmethanol.

Although the above-mentioned nitrogen-containing heterocyclic compound has a thermosetting acceleration ability (dehydration cyclization reaction accelerating ability) before light irradiation, it has a thermosetting acceleration ability (dehydration cyclization reaction accelerating ability) by light irradiation. )
Is a compound that inactivates. Specifically, by irradiating such a compound with light, a photodecomposition reaction occurs, and a nitrogen-containing heterocyclic compound having a carboxyl group in its side chain is formed. The compound thus formed deactivates the thermosetting ability.

By adding these photosensitive thermosetting accelerators to a thermosetting polymer resin precursor solution which is dehydrated and cyclized by heating such as a polyamide precursor (polyamic acid) to cure, coating, exposure, PEB ( The post-exposure bake) and development steps give a positive photosensitive polymer resin composition capable of forming a fine pattern.

These photosensitive thermosetting accelerators may be used alone or in admixture of two or more, and are added in an amount of 0.1 molar equivalent or more per 1 molar equivalent of the repeating unit of the photosensitive polymer resin. It is preferable. The blending amount of the photosensitive thermosetting accelerator is more preferably 0.1 to 4.0 molar equivalents, and most preferably 0.1 to 2.0 molar equivalents. The reason for this is that when the amount of the photosensitive curing accelerator is too small, the photosensitivity of the resin layer is insufficient and sufficient resolution cannot be obtained, and conversely, when the amount of the photosensitive curing accelerator is too large. This is because there is a possibility that the film loss may increase or it may be difficult to form a clean thin film.

The third photosensitive thermosetting accelerator is a condensed or non-condensed substituted or unsubstituted pyridinequinonediazide compound or quinolinequinonediazide compound.

Examples of the unsubstituted pyridinequinonediazide compound that can be used here include pyridine-3,4-quinone-3-diazide. Further, as the unsubstituted quinolinequinonediazide compound, quinoline-3,4
-Quinone-3-diazide, quinoline-3,4-quinone-
4-diazide, quinoline-5,6-quinone-5-diazide, quinoline-5,6-quinone-6-diazide, quinoline-7,8-quinone-8-diazide, quinoline-7,8
-Quinone-7-diazide, benzo [f] quinoline-3,
4-quinone-3-diazide, benzo [g] quinoline-
3,4-quinone-3-diazide, and benzo [h] quinoline-3,4-quinone-3-diazide.

Examples of the substituent which is introduced into these pyridinequinonediazide compounds or quinolinequinonediazide compounds to form the substituted pyridinequinonediazide compounds or substituted quinolinequinonediazide compounds include disubstituted amino groups (dimethylamino group, diethylamino group,
Dibutylamino group, ethylmethylamino group, butylmethylamino group, diamylamino group, dibenzylamino group,
Diphenethylamino group, diphenylamino group, ditolylamino group, dixylylamino group, methylphenylamino group, benzylmethylamino group, etc.), mono-substituted amino group (methylamino group, ethylamino group, propylamino group, isopropylamino group, tert.-Butylamino group, anilino group, anisidino group, phenetidino group, toluidino group, xylidino group, pyridylamino group, thiazolylamino group, benzylamino group, benzylideneamino group, etc., cyclic amino group (pyrrolidino group, piperidino group, piperazino group) , Morpholino group, 1-pyrrolyl group, 1-pyrazolyl group, 1-imidazolyl group, 1-triazolyl group), acylamino group (formylamino group, acetylamino group, benzoylamino group, cinnamoylamino group,
Pyridine carbonylamino group, trifluoroacetylamino group, etc.), sulfonylamino group (mesylamino group,
Ethylsulfonylamino group, phenylsulfonylamino group, pyridylsulfonylamino group, tosylamino group, taurylamino group, trifluoromethylsulfonylamino group, sulfamoylamino group, methylsulfamoylamino group, sulfanylamino group, acetylsulfanylamino group, etc. ), Amino group, hydroxyamino group, ureido group, semicarbazide group, carbazide group, disubstituted hydrazino group (dimethylhydrazino group, diphenylhydrazino group, methylphenylhydrazino group, etc.), monosubstituted hydrazino group (methylhydrazino group) , Phenylhydrazino group, pyridylhydrazino group, benzylidenehydrazino group, etc.), hydrazino group, amidino group, oxime group (hydroxyiminomethyl group, methoxyiminomethyl group, ethoxyiminomethyl group) , Hydroxyiminoethyl, hydroxyiminopropyl, etc.), hydroxy, oxy (methoxy, ethoxy, propoxy, butoxy, hydroxyethoxy, phenoxy, naphthoxy, pyridyloxy, thiazolyloxy, acetoxy) Etc.), thio group (methylthio group, ethylthio group, phenylthio group, pyridylthio group, thiazolylthio group, etc.), alkoxyalkyl group (hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, etc.), cyano group, cyanato group, thiocyanato group, Nitro group, nitroso group, mercapto group, halogen group (fluoro group, chloro group, bromo group, iodo group), carboxyl group and salts thereof, oxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbo group) Group, pyridyloxycarbonyl group, etc.), aminocarbonyl group (carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, pyridylcarbamoyl group, carbazoyl group, allofanoyl group, oxamoyl group, succinamoyl group, etc.), thiocarboxyl group and salts thereof, Dithiocarboxyl group and salts thereof, thiocarbonyl group (methoxythiocarbonyl group, methylthiocarbonyl group, methylthiothiocarbonyl group, etc.), acyl group (formyl group, acetyl group, propionyl group, acryloyl group, benzoyl group, cinnamoyl group, pyridinecarbonyl Group, thiazolecarbonyl group, trifluoroacetyl group, etc.), thioacyl group (thioformyl group, thioacetyl group, thiobenzoyl group, pyridinethiocarbonyl group, etc.), sulfi Acid group and salt thereof, sulfonic acid group and salt thereof, sulfinyl group (methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, etc.), sulfonyl group (mesyl group, ethylsulfonyl group, phenylsulfonyl group, pyridylsulfonyl group, tosyl) Group, tauryl group, trifluoromethylsulfonyl group, sulfamoyl group, methylsulfamoyl group, sulfanilyl group, acetylsulfanylyl group, etc., oxysulfonyl group (methoxysulfonyl group, ethoxysulfonyl group, phenoxysulfonyl group, acetaminophenoxy group) Sulfonyl group, pyridyloxysulfonyl group, etc., thiosulfonyl group (methylthiosulfonyl group, ethylthiosulfonyl group, phenylthiosulfonyl group, acetaminophenylthiosulfonyl group, pyridyl O sulfonyl group), aminosulfonyl group (sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, phenylsulfamoyl group, acetaminophenylsulfamoyl group) , Pyridylsulfamoyl group), ammonio group (trimethylammonio group, ethyldimethylammonio group, dimethylsulfenylammonio group, pyridinio group, quinolinio group, etc.), azo group (phenylazo group, pyridylazo group,
Thiazolylazo group, etc.), azoxy group, halogenated alkyl group (chloromethyl group, bromomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group Etc.), hydrocarbon groups (alkyl groups, aryl groups, alkenyl groups, alkynyl groups, etc.), heterocyclic groups, organosilicon groups (silyl groups, disilanyl groups, trimethylsilyl groups, triphenylsilyl groups, etc.) and the like. .

The above-mentioned pyridinequinonediazide compound or quinolinequinonediazide compound has a thermosetting acceleration ability (dehydration cyclization reaction accelerating ability) before light irradiation. It is a compound that deactivates (promoting ability). Specifically, by irradiating such a compound with light, first, a denitrification reaction occurs to generate a ketene compound. The ketene compound reacts with surrounding water to form a pyrrole carboxylic acid compound or a cyclopentapyridine carboxylic acid compound, so that the thermosetting ability is deactivated. For example, quinoline-3,4-quinone-3
-Diazide is a compound that has a good ability to accelerate heat curing before light irradiation, but when this compound is irradiated with light, it reacts with the surrounding water via the ketene compound and changes to indole-3-carboxylic acid. Deactivates the ability to accelerate heat curing.

By adding these photosensitive thermosetting accelerators to a thermosetting polymer resin precursor solution that is dehydrated and cyclized by heating such as a polyimide precursor (polyamic acid), coating, exposure, PEB ( The post-exposure bake) and development steps give a positive photosensitive polymer resin composition capable of forming a fine pattern.

These photosensitive thermosetting accelerators may be used alone or in admixture of two or more, and are added in an amount of 0.1 molar equivalent or more per 1 molar equivalent of the repeating unit of the photosensitive polymer resin. It is preferable. The blending amount of the photosensitive thermosetting accelerator is more preferably 0.1 to 4.0 molar equivalents, and most preferably 0.1 to 2.0 molar equivalents. If the blending amount of the photosensitive heat-curing accelerator is too small, the photosensitivity of the resin layer is insufficient and sufficient resolution cannot be obtained. On the other hand, if the blending amount of the photosensitive curing accelerator is too large, the film loss may be large, or it may be difficult to form a clean thin film.

The fourth photosensitive thermosetting accelerator is a nitrogen-containing compound obtained by substituting the hydroxy group of a condensed or non-condensed substituted or unsubstituted 2-hydroxypyridine compound with a protective substituent capable of leaving by irradiation with light. It is a heterocyclic compound.

The condensed or non-condensed unsubstituted 2-hydroxypyridine compound which can be used here is, for example, 2
-Hydroxypyridine, 2-hydroxyquinoline, 1-
Hydroxyisoquinoline, 3-hydroxyisoquinoline, 6-hydroxyphenanthridine, 2-hydroxybenzo [f] quinoline, 2-hydroxybenzo [g] quinoline, 2-hydroxybenzo [h] quinoline, 1-hydroxybenzo [f] isoquinoline , 1-hydroxybenzo [g] isoquinoline, 1-hydroxybenzo [h]
At least one nitrogen-containing heterocyclic compound selected from the group consisting of isoquinoline, 3-hydroxybenzo [f] isoquinoline, 3-hydroxybenzo [g] isoquinoline, and 3-hydroxybenzo [h] isoquinoline.

Examples of the substituent introduced into the nitrogen-containing heterocyclic compound as described above to constitute the substituted nitrogen-containing heterocyclic compound include di-substituted amino groups (dimethylamino group, diethylamino group, dibutylamino group, ethylmethyl group). Amino group, butylmethylamino group, diamylamino group, dibenzylamino group, diphenethylamino group, diphenylamino group, ditolylamino group, dixylylamino group, methylphenylamino group, benzylmethylamino group, etc.), monosubstituted amino group ( Methylamino group, ethylamino group, propylamino group, isopropylamino group, tert.-butylamino group, anilino group, anisidino group, phenetidino group, toluidino group, xylidino group, pyridylamino group,
Thiazolylamino group, benzylamino group, benzylideneamino group, etc.), cyclic amino group (pyrrolidino group, piperidino group, piperazino group, morpholino group, 1-pyrrolyl group, 1-pyrazolyl group, 1-imidazolyl group, 1-triazolyl group, etc.) , Acylamino group (formylamino group, acetylamino group, benzoylamino group, cinnamoylamino group, pyridinecarbonylamino group, trifluoroacetylamino group, etc.), sulfonylamino group (mesylamino group, ethylsulfonylamino group, phenylsulfonylamino group) , Pyridylsulfonylamino group, tosylamino group, taurylamino group, trifluoromethylsulfonylamino group, sulfamoylamino group, methylsulfamoylamino group, sulfanylamino group, acetylsulfanylamino group Etc.), amino group, hydroxyamino group, ureido group, semicarbazide group, carbazide group, disubstituted hydrazino group (dimethylhydrazino group, diphenylhydrazino group, methylphenylhydrazino group, etc.), monosubstituted hydrazino group (methylhydrazino group) Group, phenylhydrazino group, pyridylhydrazino group, benzylidenehydrazino group, etc.), hydrazino group, amidino group,
Hydroxy group, oxime group (hydroxyiminomethyl group, methoxyiminomethyl group, ethoxyiminomethyl group, hydroxyiminoethyl group, hydroxyiminopropyl group, etc.), alkoxyalkyl group (hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, etc.) , Cyano group, cyanato group, thiocyanato group, nitro group, nitroso group, oxy group (methoxy group, ethoxy group,
Propoxy group, butoxy group, hydroxyethoxy group, phenoxy group, naphthoxy group, pyridyloxy group, thiazolyloxy group, acetoxy group, etc.), thio group (methylthio group, ethylthio group, phenylthio group, pyridylthio group, thiazolylthio group, etc.), mercapto group , Halogen group (fluoro group, chloro group, bromo group, iodo group), carboxyl group and salts thereof, oxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, pyridyloxycarbonyl group, etc.), aminocarbonyl group ( Carbamoyl group, methylcarbamoyl group, phenylcarbamoyl group, pyridylcarbamoyl group, carbazoyl group, allofanoyl group, oxamoyl group, succinamoyl group, etc.), thiocarboxyl group and salts thereof, dithio Ruboxyl group and its salts, thiocarbonyl group (methoxythiocarbonyl group, methylthiocarbonyl group, methylthiothiocarbonyl group, etc.), acyl group (formyl group, acetyl group, propionyl group, acryloyl group, benzoyl group, cinnamoyl group, pyridinecarbonyl group , Thiazolecarbonyl group, trifluoroacetyl group, etc.), thioacyl group (thioformyl group,
Thioacetyl group, thiobenzoyl group, pyridinethiocarbonyl group, etc.), sulfinic acid group and its salt, sulfonic acid group and its salt, sulfinyl group (methylsulfinyl group, ethylsulfinyl group, phenylsulfinyl group, etc.), sulfonyl group (mesyl group) , Ethylsulfonyl group, phenylsulfonyl group, pyridylsulfonyl group, tosyl group, tauryl group, trifluoromethylsulfonyl group, sulfamoyl group, methylsulfamoyl group, sulfanilyl group, acetylsulfanilyyl group, etc.), oxysulfonyl group (methoxy Sulfonyl group, ethoxysulfonyl group, phenoxysulfonyl group, acetaminophenoxysulfonyl group, pyridyloxysulfonyl group, etc., thiosulfonyl group (methylthiosulfonyl group, ethylthiosulfonyl group) Phenylthiosulfonyl group, acetaminophenylthiosulfonyl group, pyridylthiosulfonyl group, etc.), aminosulfonyl group (sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, Phenylsulfamoyl group, acetaminophenylsulfamoyl group, pyridylsulfamoyl group, etc.), Ammonio group (trimethylammonio group, ethyldimethylammonio group, dimethylsulfenylammonio group, pyridinio group, quinolinio group, etc.) , Azo group (phenylazo group, pyridylazo group, thiazolylazo group, etc.), azoxy group, halogenated alkyl group (chloromethyl group, bromomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, difluoromethyl , Trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group), hydrocarbon group (alkyl group, aryl group, alkenyl group, alkynyl group, etc.), heterocyclic group, organosilicon group (silyl group, disilanyl group, Trimethylsilyl group, triphenylsilyl group, etc.) and the like.

Further, as the protective substituent which can protect the hydroxy group of the above-mentioned substituted or unsubstituted specific nitrogen-containing heterocyclic compound and which is eliminated by irradiation of light, for example, a substituted substituent is substituted with a nitro group. Benzyl group (2-nitrobenzyl group, 4-nitrobenzyl group, 2,4-dinitrobenzyl group, etc.), acyl group (formyl group, acetyl group, benzoyl group, nitrobenzoyl group, pyridinecarbonyl group, trifluoroacetyl group, etc.) ), An acylmethyl group (acetonyl group, phenacyl group, nitrophenacyl group,
Pyridinecarbonylmethyl group), substituted or unsubstituted alkoxycarbonyl group (benzyloxycarbonyl group, 2-phenylisopropoxycarbonyl group, 2-
Nitrobenzyloxycarbonyl group, 4-nitrobenzyloxycarbonyl group, 2,4-dinitrobenzyloxycarbonyl group, 2-cyanomethylisopropoxycarbonyl group, 2-methylsulfonylisopropoxycarbonyl group, etc.), sulfonyl group (mesyl group, Phenylsulfonyl group, tosyl group, pyridylsulfonyl group, trifluoromethylsulfonyl group, diazophenolsulfonyl group, diazonaphtholsulfonyl group, etc., sulfonylmethyl group (phenylsulfonylmethyl group, tosylmethyl group, pyridylsulfonylmethyl group, trifluoromethylsulfonyl group) (Eg, a methyl group).

The 2-hydroxypyridine compound in which the hydroxy group is substituted with the protective substituent capable of leaving by irradiation with light as described above has a thermosetting acceleration ability (dehydration cyclization reaction acceleration ability) before the light irradiation. However, it is a compound that deactivates the thermosetting acceleration ability (dehydration cyclization reaction acceleration ability) by light irradiation. Specifically, by irradiating such a compound with light,
First, the protective substituent is eliminated, and a hydroxy group is generated at the nuclear carbon atom adjacent to the nuclear nitrogen atom. Then, the thermosetting ability is inactivated by cyclic amidation due to tautomerism.

By adding these photosensitive thermosetting accelerators to a thermosetting polymer resin precursor solution which is dehydrated and cyclized by heating such as a polyimide precursor (polyamic acid), curing, coating, exposure, PEB ( The post-exposure bake) and development steps give a positive photosensitive polymer resin composition capable of forming a fine pattern.

These photosensitive thermosetting accelerators may be used alone or in admixture of two or more, and are added in an amount of 0.1 molar equivalent or more per 1 molar equivalent of the repeating unit of the photosensitive polymer resin. It is preferable. The blending amount of the photosensitive thermosetting accelerator is more preferably 0.1 to 4.0 molar equivalents, and most preferably 0.1 to 2.0 molar equivalents. If the blending amount of the photosensitive heat-curing accelerator is too small, the photosensitivity of the resin layer is insufficient and sufficient resolution cannot be obtained. On the other hand, if the blending amount of the photosensitive curing accelerator is too large, the film loss may be large, or it may be difficult to form a clean thin film.

In the photosensitive polymer resin composition of the present invention, a sensitizer may be added, if necessary, in order to increase the sensitivity of the photosensitive curing accelerator. Specific examples of the sensitizer include acetophenone, benzophenone, benzoin, 2-methylbenzoin, benzoin isopropyl ether, anthrone, 1,9-benzanthrone, anthracene, phenanthrenequinone and pyrene-.
1,6-quinone, 9-fluorenone, 1,2-benzanthraquinone, anthanthrone, 2-chlorobenzanthraquinone, 2-bromobenzanthraquinone, 2-
Chloro-1,8-phthaloylnaphthalene, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, benzoin methyl ether, benzyl dimethyl ketal, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino- 1-propanone, 1-hydroxycyclohexyl phenyl ketone, ethyl N, N-dimethylaminobenzoate, acridine, cyanoacridine,
Examples include nitropyrene, 1,8-dinitropyrene, 5-nitroacenaphthene, 2-nitrofluorene, 2-tert-butyl-9,10-anthraquinone, and N-phenylmaleimide.

These sensitizers can be used alone or in admixture of two or more. The blending amount is preferably 0.01 molar equivalent or more, more preferably 0.1 molar equivalent or more, and most preferably 0.1 to 5 molar equivalent with respect to 1 molar equivalent of the repeating unit of the photosensitive polymer resin. If it deviates from this range, developability and film formability may be adversely affected.

Further, in the photosensitive polymer resin composition of the present invention, a dye, a surfactant, an alkali-soluble resin and the like may be added if necessary.

The photosensitive polymer resin composition of the present invention is prepared by dissolving a thermosetting polymer resin precursor, such as polyamic acid, which undergoes cyclodehydration by heating in an organic solvent.
It can be easily prepared by adding a photosensitive heat curing accelerator which deactivates the heat curing accelerating ability by light irradiation. At this time, you may dilute with a suitable organic solvent as needed.
In some cases, a sensitizer, a dye, a surfactant, an alkali-soluble resin and the like are added to the obtained mixed solution, and if desired, fine impurities are removed by a method such as filtration to prepare a mixture. That is, the photosensitive polymer resin composition of the present invention,
It can be easily prepared without any complicated steps, and impurities are not mixed in the obtained composition.

At this time, examples of the organic solvent used include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N,
N-dimethoxyacetamide, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-
2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphortriamide, N-methyl-
ε-caprolactam, N-acetyl-ε-caprolactam, 1,2-dimethoxyethane, 1,2-diethoxyethane, bis (2-methoxyethyl) ether, bis (2
-Ethoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, bis [2- (2-methoxyethoxy) ethyl] ether, 1-acetoxy-2-methoxyethane, 1-acetoxy-2-ethoxyethane , (2
-Acetoxyethyl) (2-methoxyethyl) ether, (2-acetoxyethyl) (2-ethoxyethyl)
Ether, methyl 3-methoxypropionate, tetrahydrofuran, 1,3-dioxane, 1,3-dioxolane, 1,4-dioxane, pyrroline, pyridine, picoline, dimethylsulfoxide, sulfolane, γ-butyrolactone, propylene carbonate, phenol, cresol , Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetonyl acetone, etc., and these organic solvents may be used alone or in combination of two or more kinds.

Next, the pattern forming method using the positive photosensitive polymer resin composition of the present invention will be described in detail.

First, the positive type photosensitive polymer resin composition prepared as described above is applied to the surface of a substrate by a spin coating method or the like, and heated by a hot plate to give 180 ° C. or lower, preferably 120 ° C. or lower. The resin layer is formed by drying at the temperature of. Since the photosensitive polymer resin composition of the present invention contains a photosensitive thermosetting accelerator having a curing accelerating ability when unexposed, the entire resin layer is cured when heated at a temperature exceeding this upper limit temperature. As a result, the resolution will decrease.

Next, the resin layer thus formed is exposed to energy rays such as visible light, infrared light, ultraviolet light, EB or X-ray through a photomask having a desired pattern. Irradiation is performed to expose a desired region of the resin layer. As the exposure method in this case, either contact exposure or projection exposure may be used.

By performing the exposure as described above, the heat curing accelerating ability of the photosensitive heat curing accelerator is deactivated in the exposed portion of the resin layer. Therefore, even if the heat treatment is performed after the exposure, the resin layer in the exposed portion remains. It is prevented from hardening. The first to the fourth
The mechanism for deactivating the heat-curing acceleration ability of each of the photosensitive heat-curing accelerators is as described above.

Then, the exposed resin layer is heated at 50 to 200 ° C., preferably 80 to 1 by using a hot plate or the like.
Heat treatment at 60 ° C. is performed. By this heat treatment process, in the unexposed portion of the resin layer, the thermosetting by the dehydration cyclization of the polyamic acid as the polyimide precursor proceeds due to the action of the curing accelerator, and the polyimide is formed. On the other hand, in the exposure unit,
As described above, since the curing accelerating ability of the photosensitive heat curing accelerator is deactivated by the exposure, the heat curing hardly progresses, and as a result, there is a large difference in the solubility between the exposed portion and the unexposed portion. In addition, when the resin layer is heated below a predetermined temperature, the curing acceleration ability of the photosensitive thermosetting accelerator cannot be sufficiently exerted, so that the thermal curing of the unexposed portion hardly progresses. On the other hand, when the resin layer is heated at a temperature higher than the predetermined temperature, the heat curing will considerably proceed even in the exposed portion. In either case, the resolution is lowered and it becomes difficult to form a fine pattern. The heat treatment time, which depends on the heat treatment temperature, is usually about 0.5 to 60 minutes, more preferably about 0.5 to 30 minutes. This is because if the heat treatment time is too short, the heat curing of the unexposed area hardly progresses, and conversely if the heat treatment time is too long, the heat curing of the exposed area considerably progresses. Is caused, and it becomes difficult to form a fine pattern.

The resin layer after the heat treatment is subjected to a developing treatment using an appropriate developing solution by a dipping method, a spray developing method, a paddle developing method or the like. Examples of the developer that can be used here include organic solvent-based developers and alkaline aqueous solution-based developers. Examples of the organic solvent-based developer include N, N-dimethylformamide, N, N-dimethylacetamide,
N, N-diethylacetamide, N, N-dimethoxyacetamide, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-benzyl-2-pyrrolidone,
Aprotic polar solvents such as 1,3-dimethyl-2-imidazolidinone, hexamethylphosphortriamide, dimethylsulfoxide, N-methyl-ε-caprolactam, N-acetyl-ε-caprolactam can be used. These solvents may be used alone or in methanol,
Ethanol, isopropanol, benzene, toluene,
It may be used as a mixed solution of a polymer resin such as xylene, methyl cellosolve and water with a poor solvent.

Further, as the alkaline aqueous solution type developing solution,
For example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, propylamine, butylamine, monoethanolethylenediamine, trimethylenediamine, trimethylammonium hydroxide, hydrazine, organic alkaline aqueous solution such as trimethylhydroxyethylammonium hydroxide,
Alternatively, an inorganic alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, ammonium carbonate, potassium hydrogen carbonate, ammonium phosphate, or ammonia can be used. In these aqueous solutions, methanol, ethanol, acetone, 2-propanol, ethylene glycol, ethyl cellosolve, butyl cellosolve, diethylene glycol, diethylene glycol monoethyl ether, N-methylpyrrolidone, N, N-dimethylformamide, N,
A mixture of organic solvents such as N-dimethylacetamide and dimethyl sulfoxide may also be used. Although developing with an organic solvent has an advantage of less inclusion of metallic impurities, it is desirable to use an alkaline aqueous solution as a developing solution from the viewpoint of safety, hygiene and environment. Furthermore, when developed with an alkaline aqueous solution, swelling of the obtained polyimide film pattern can be avoided.

By such development processing, the resin layer in the exposed portion is dissolved and removed, and a positive type polyimide film pattern is formed. In particular, in the photosensitive polymer resin composition of the present invention, due to the fact that a photosensitive thermosetting accelerator whose curing accelerating ability is deactivated by irradiation of light is blended, the resin layer of the resin layer can be formed by heat treatment after exposure. Only in the unexposed area, a dehydration cyclization reaction of polyamic acid occurs selectively to form a polyimide.
On the other hand, in the exposed portion of the resin layer, since the heat curing accelerating ability of the curing accelerator is deactivated, curing does not proceed and the polyamic acid remains as it is.

That is, by performing post-exposure heating under appropriate conditions, polyimide is formed in the unexposed area of the resin layer, while polyamic acid remains in the exposed area. A great difference can be provided in the solubility in the developing solution. Therefore, only the exposed portion is selectively dissolved and removed during the development process, and it becomes possible to form a fine pattern with high resolution.

The resin layer after development is preferably rinsed with water, alcohol, acetone or the like for the purpose of removing developer residue and the like. further,
120 to 40 in order to dry the developing solution or the rinse solution and to complete the curing of the partially uncured portion in the resin.
It is desirable to perform heat treatment or vacuum heat treatment within the range of 0 ° C.

According to the method of the present invention, a patterned polyimide film can be formed without separately using a photoresist, and since it can be developed with an alkaline aqueous solution, it is safe and environmentally friendly. The problem of is also avoided.

The polyimide film on which the pattern is formed as described above is used for various electronic parts such as semiconductor elements such as LSI elements, high-density printed wiring boards, thin film magnetic heads, magnetic bubble memories, solar cells, thermal heads, etc. In, it can be applied as an insulating member such as an interlayer insulating film or a wiring insulating film between conductors or semiconductors, or a protective member such as a passivation film. Furthermore, as an optical member such as an optical waveguide of an optical element or a liquid crystal alignment film of a liquid crystal element,
It is also possible to apply the polyimide film pattern formed by the method of the present invention. In any case, in addition to the characteristics such as heat resistance and low dielectric constant of the polyimide itself, the adhesiveness and adhesiveness between the polyimide film pattern and the substrate and the like are good, so that the reliability of electronic components can be improved. it can.

Further, in the present invention, the above-mentioned positive type pattern can be applied to a fine processing technique utilizing photolithography. Specifically, using the positive photosensitive polymer resin composition of the present invention, after forming a pattern on a predetermined substrate, the substrate is processed by dry etching or a wet etching agent according to a conventional method using this as an etching mask. To do. Incidentally, the dry etching method is preferable especially when performing fine processing of 3 μm or less.

As the wet etching agent at this time, an aqueous solution of hydrofluoric acid, an aqueous solution of ammonium fluoride, or the like is used when the silicon oxide film is to be etched.
An aqueous solution of phosphoric acid, an aqueous solution of acetic acid, an aqueous solution of nitric acid or the like is used when aluminum is an etching target, and an aqueous solution of cerium ammonium nitrate or the like is used when a chromium-based film is an etching target. The gas for dry etching is CF ₄ , C ₂ F ₆ , CCl ₄ , BCl ₃ , C.
L ₂ , HCl, H _{2 and the} like can be mentioned, and these gases are used in combination as necessary. The etching conditions include the concentration of the wet etching agent in the reaction tank, the concentration of the dry etching gas, the reaction temperature, the reaction time, etc., based on the combination of the type of substance on which the fine pattern is formed and the photosensitive polymer resin composition. It is determined, but the method is not particularly limited. After this etching, the pattern formed by using the photosensitive polymer resin composition of the present invention remaining on the substrate may be removed by using a release agent (for example, hydrazine aqueous solution) or oxygen gas plasma.

In the pattern forming method of the present invention, the polyamic acid is insolubilized in the developing solution without being cross-linked to form a positive type pattern, so that the film reduction due to the volume contraction of the film can be avoided sufficiently. It is possible to ensure pattern accuracy. Moreover, since there is no particular restriction on the structure of the polyamic acid as the polyamide precursor, a polyimide film pattern excellent in electrical characteristics, thermal characteristics, adhesion, etc. can be easily formed, which is very advantageous. Therefore,
INDUSTRIAL APPLICABILITY The photosensitive polymer resin composition of the present invention is useful not only as an insulating film for various electronic components as described above, but also when performing fine processing on a predetermined member.

[0120]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

First, the polyamic acid was synthesized in the following manner using the raw materials shown in the following Table 1 at a predetermined compounding ratio (expressed in molar equivalent). First, under a argon gas atmosphere, a separable flask cooled to −5 ° C. to 5 ° C. with a refrigerant was filled with N,
Into 50 ml of N-dimethylacetamide, a predetermined amount of tetracarboxylic dianhydride was added and dissolved while stirring. A solution obtained by dissolving a predetermined amount of a diamine compound in 50 ml of N, N-dimethylelacetamide was slowly added dropwise to this solution using a dropping funnel equipped with a pressure balancing tube, and the mixture was stirred for 4 hours. Furthermore, it stirred at room temperature for 4 hours, and obtained polyamic acid PAA1-PAA5.

0.5 of each polyamic acid synthesized
The inherent viscosity of the wt% -N-methyl-2-pyrrolidone solution was measured at 30 ° C. The results are shown in Table 1.

Here, the abbreviations of tetracarboxylic dianhydride, diamine compound and solvent shown in Table 1 represent the following compounds.

(Tetracarboxylic acid dianhydride) PMA: Pyromellitic acid dianhydride BNTA: 3,3'4,4'-benzophenone tetracarboxylic acid dianhydride 6FTA: 1,1,1,3,3,3- Hexafluoro-2,2-propylidene-4,4'-diphthalic acid dianhydride (diamine compound) ODA: oxy-4,4'-dianiline SNDA: sulfonyl-3,3'-dianiline TSDA: 1,3-bis (3-Aminopropyl) -1,1,3,3-tetramethyldisiloxane (solvent) DMAC: N, N-dimethylacetamide

[Table 1]

Using the polyamic acid obtained as described above, the positive photosensitive polymer resin composition of the present invention was prepared as follows.

Example I In this example, the azomethine compound represented by the general formula (2) was blended as a photosensitive thermosetting accelerator to prepare a positive photosensitive polymer resin composition, and its characteristics I checked. First, the abbreviations of the azomethine compounds, which are the photosensitive thermosetting accelerators used in this example, are summarized below.

PYX: 2-pyridinealdoxime QNX: 2-quinoline aldoxime IMX: 4-imidazole aldoxime IX: 2-benzimidazole aldoxime PPX: phenyl-2-pyridylketoxime PPH: 2-pyridinecarbaldehyde = 2 -Pyridylhydrazone PAH: 2-pyridinecarbaldehyde = acetylhydrazone PSC: 2-pyridinecarbaldehyde = semicarbazone As shown in Tables 2 to 5 below, the polyamic acid solution synthesized in the above steps was exposed at a predetermined compounding ratio. Heat curing accelerator was added, and the mixture was stirred and mixed at room temperature so as to be uniform. The present invention (Examples I-1 to I-40) was obtained by filtering this with a membrane filter having a pore size of 0.5 μm.
A photosensitive polymer resin composition was prepared.

Further, the obtained photosensitive polymer resin composition was patterned to examine the resolution, and the results are shown in Tables 2 and 3 below. In addition, a polyimide film was formed to evaluate adhesion and heat resistance, and the results are summarized in Tables 4 and 5 below.

The resolution, adhesion and heat resistance were evaluated as follows.

(Evaluation of Resolution) First, a solution of each photosensitive polymer resin composition was applied on a silicon wafer having a diameter of 4 inches by spin coating, and heated (prebaked) on a hot plate at 90 ° C. for 10 minutes. As a result, a resin layer having a film thickness of about 5 μm was formed. Next, an exposure device (Cannon: PL
A-501FA) was used to expose the resin layer through a quartz mask for resolving power test with a predetermined light irradiation amount.

After the exposure, the silicon wafer was heated (PEB) on a hot plate at 140 ° C. for 5 minutes to promote thermosetting by dehydration cyclization of the polyamic acid in the unexposed portion of the resin layer.

Then, the silicon wafer was immersed in an alkali developing solution (1.19 wt% tetramethylammonium hydroxide aqueous solution) for 120 seconds to carry out a developing treatment to selectively dissolve and remove the exposed portion of the resin layer. 20
It was washed with water for 2 seconds.

Finally, the silicon wafer on which the resin film pattern after development was formed was heated on a hot plate at 250 ° C. for 30 minutes to form a positive type polyimide pattern film. The cross section of the pattern film thus formed was observed with an electron microscope (SEM) to determine the resolution.

(Evaluation of Adhesion) First, a solution of each photosensitive polymer resin composition was applied onto a silicon wafer having a diameter of 4 inches by a spin coating method, and heated (prebaked) on a hot plate at 90 ° C. for 10 minutes. A resin layer having a film thickness of about 5 μm was formed. Next, the silicon wafer is heated to 250 ° C.
The sample was heated for 30 minutes on a hot plate to prepare a sample polyimide film. Furthermore, this wafer is 2
After heating in saturated steam at atmospheric pressure at 120 ° C. for 24 hours,
Adhesion was evaluated by a goose eye test method.

(Evaluation of Heat Resistance) First, each photosensitive polyimide resin composition was applied onto a silicon wafer having a diameter of 4 inches by a spin coating method, followed by 1 on a hot plate at 90 ° C.
By heating (pre-baking) for 0 minutes, a resin layer having a film thickness of about 5 μm was formed. Next, the silicon wafer was heated on a hot plate at 250 ° C. for 30 minutes to prepare a sample polyimide film. Then, the resin layer was peeled off from the wafer with a razor, and the 3 wt% weight loss temperature (in a nitrogen stream) of the resin layer was measured by thermogravimetric analysis (TGA).

[0136]

[Table 2]

[0137]

[Table 3]

[0138]

[Table 4]

[0139]

[Table 5]

Example II In this example, the nitrogen-containing heterocyclic compound represented by the general formula (3) was blended as a photosensitive thermosetting accelerator to prepare a positive photosensitive polymer resin composition. , Its characteristics were investigated. First, the nitrogen-containing compound (PY, which is the photosensitive thermosetting accelerator used in this example, is used.
1), (PY2), (PY3), (QN1) and (Q
N2) is summarized below.

[0141]

[Chemical 14]

As shown in Tables 6 to 9 below, a photosensitive thermosetting accelerator was added to the polyamic acid solution synthesized in the above step at a predetermined mixing ratio, and the mixture was stirred and mixed so as to be uniform at room temperature. By filtering this with a membrane filter having pores of 0.5 μm, the present invention (Example II-1 to
The photosensitive polymer resin composition of II-30) was prepared.

Further, the obtained photosensitive polymer resin composition was subjected to patterning under the same conditions as above to examine the resolution, and the results are shown in Tables 6 and 7 below. In addition, a polyimide film was formed and adhesion and heat resistance were evaluated in the same manner as described above, and the results are summarized in Tables 8 and 9 below.

[0144]

[Table 6]

[0145]

[Table 7]

[0146]

[Table 8]

[0147]

[Table 9]

Example III In this example, a condensed or non-condensed substituted or unsubstituted pyridinequinone diazide compound or quinoline quinone diazide compound was used as a photosensitive thermosetting accelerator in a positive photosensitive polymer resin composition. Was prepared and its characteristics were investigated. First, the abbreviations of the photosensitive thermosetting accelerators used in this example are summarized below.

QNQD: Quinoline-3,4-quinone-3
-Diazide 7PQD: 7-phenylquinoline-3,4-quinone-3
-Diazide DMQD: 5,8-dimethoxyquinoline-3,4-quinone-3-diazide 2HQD: 2-hydroxyquinoline-3,4-quinone-
3-diazide BQQD: benzo [g] quinoline-3,4-quinone-3
-Diazide As shown in Tables 10 to 13 below, a photosensitive thermosetting accelerator was added to the polyamic acid solution synthesized in the above step at a predetermined mixing ratio, and the mixture was stirred and mixed so as to be uniform at room temperature. By filtering this with a membrane filter having pores of 0.5 μm, the present invention (Examples III-1 to III-
The photosensitive polymer resin composition of 30) was prepared.

Further, the obtained photosensitive polymer resin composition was subjected to patterning under the same conditions as described above to examine the resolution, and the results are shown in Tables 10 and 11 below. In addition, a polyimide film was formed and adhesion and heat resistance were evaluated by the same method as described above, and the results are summarized in Tables 12 and 13 below.

[0151]

[Table 10]

[0152]

[Table 11]

[0153]

[Table 12]

[0154]

[Table 13]

Example IV In this example, the hydroxy group of a condensed or non-condensed substituted or unsubstituted 2-hydroxypyridine compound is substituted with a protective substituent which is eliminated by irradiation with light. A positive type photosensitive polymer resin composition was prepared using a nitrogen-containing heterocyclic compound as a photosensitive thermosetting accelerator, and its characteristics were investigated. First, the abbreviations of the photosensitive thermosetting accelerators used in this example are summarized below.

2NBP: 2- (2-nitrobenzyloxy) pyridine 2NBQ: 2- (2-nitrobenzyloxy) quinoline 1NBI: 1- (2-nitrobenzyloxy) isoquinoline 2DNP: 2- (2-diazo-1-) Naphthol-4-ylsulfonyloxy) pyridine 2DNQ: 2- (2-diazo-1-naphthol-4-ylsulfonyloxy) quinoline NTFP: 5-nitro-2- (trifluoromethanesulfonyloxy) pyridine 2TFQ: 2- (trifluoro Rmethanesulfonyloxy) quinoline 1TFI: 1- (trifluoromethanesulfonyloxy) isoquinoline As shown in Tables 14 to 17 below, the photosensitive thermosetting accelerator was added to the polyamic acid solution synthesized in the above step at a predetermined mixing ratio. In addition, stir to mix evenly at room temperature. It was. The present invention (Examples IV-1 to IV-4) was obtained by filtering this with a membrane filter having pores of 0.5 μm.
The photosensitive polymer resin composition of 0) was prepared.

Further, the obtained photosensitive polymer resin composition was subjected to patterning under the same conditions as described above to examine the resolution, and the results are shown in Tables 14 and 15 below. Further, a polyimide film was formed and the adhesion and heat resistance were evaluated by the same method as described above, and the results are summarized in Tables 16 and 17 below.

[0158]

[Table 14]

[0159]

[Table 15]

[0160]

[Table 16]

[0161]

[Table 17]

Further, using the photosensitive polymer resin composition prepared without blending the photosensitive thermosetting accelerator, patterning was carried out under the same conditions as in the above-mentioned Examples to examine the resolution,
The results are summarized in Table 18 below as Comparative Examples (1 to 5).

[0163]

[Table 18]

A polyimide film was formed by a high temperature heating process (150 ° C. for 1 hour, 250 ° C. for 1 hour, 350 ° C. for 1 hour), and adhesion and heat resistance were examined in the same manner, and a comparative example ( 6 to 10) and summarized in Table 19 below.

[0165]

[Table 19]

As shown in the above results, each of the photosensitive polymer resin compositions of the present invention containing a photosensitive thermosetting accelerator whose curing promoting ability is lowered by irradiation of light is 15
The line width is 2.0 to 3. at an irradiation dose of 0 to 400 mJ / cm ² .
A good positive pattern having a line and space of 5 μm is formed. Therefore, it is suggested that the photosensitive polymer resin composition of the present invention has good resolution for a passivation film, a wiring insulating film and the like.

Moreover, the polyimide film formed using the photosensitive polymer resin composition of the present invention does not peel off at all, and has sufficient adhesiveness between the resin layer and the silicon wafer. The polyimide films formed by using the photosensitive polymer resin composition of the present invention showed no reduction in weight due to thermal decomposition up to 450 ° C., and thus the polyimide films of Comparative Examples (6 to 10) prepared by a high temperature heating process were used. It was confirmed that it has high heat resistance equivalent to that of a polyimide film.

On the other hand, the resin compositions containing no photosensitive heat curing accelerator (Comparative Examples 1 to 5) had 1000 mJ.
A pattern cannot be formed at all even if the exposure is performed at a dose of / cm ² .

Further, using the polyimide film pattern obtained by patterning the resin film made of the positive photosensitive polymer resin composition of the present invention, various electronic parts shown in FIGS.

FIG. 1 is a sectional view of a semiconductor device having a passivation film made of a photosensitive polymer according to the method of the present invention. Here, the photosensitive polymer resin composition of Example (III-14) was used, and a polyimide film patterned as described below was used as a passivation film.

First, a pnp type transistor is constructed,
The photosensitive polymer resin composition is applied onto a silicon substrate having a thermal oxide film and electrodes formed thereon, and the composition is applied at 90 ° C. for 10 hours.
It was prebaked for a minute to form a resin layer having a film thickness of about 10 μm. Next, an exposure apparatus (PLA-501F manufactured by Canon Inc.)
According to A), the surface of the resin layer was exposed to light through a quartz mask for resolution test at a dose of 300 mJ / cm ² . After the exposure, the silicon wafer was heated on a 140 ° C. hot plate for 5 minutes. After that, the silicon substrate is immersed in an alkaline developer (1.19 wt% tetramethylammonium hydroxide aqueous solution) for 120 seconds to selectively dissolve and remove the resin layer in the exposed portion, and further 20
It was washed with water for 2 seconds. Finally, on a hot plate at 250 ° C, do 3
The polyimide pattern film was formed by heating for 0 minutes.

In FIG. 1, L placed on the tab 13
A bonding pad 12 is provided on the SI chip 11, and a passivation film 15 made of a patterned polyimide film is further formed. Note that L
The bonding pad 12 on the SI chip 11 is connected to the lead frame 17 by a bonding wire 16 and these are sealed with a sealant 18.

A polyimide film pattern obtained from the photosensitive polymer resin composition of the present invention is formed into a passivation film 15.
When used for, a highly reliable semiconductor element can be obtained and there are almost no defects in the manufacturing process. Moreover, since the PEP process is not required, the manufacturing process is simplified and there is no problem with safety.

FIG. 2 is a sectional view showing a part of a multichip module having an interlayer insulating film made of the photosensitive polymer resin composition according to the present invention. Here, the example (IV
Using the photosensitive polymer resin composition of -4), a polyimide film patterned by the same method as described above was used as an interlayer insulating film.

In FIG. 2, a thermal oxide film 22 is formed on a silicon substrate 21. On the thermal oxide film 22, a copper wiring 23 and an interlayer insulating film 2 made of a polyimide film are formed.
4, a copper wiring 25, and an interlayer insulating film 26 made of a polyimide film are sequentially formed. Further, a contact hole is opened in a part of the upper interlayer insulating film 26, and the copper wiring 23
Pb / Sn electrode 27 and BLM (Ball Limi
ting metallization) 28 is formed.

The above-mentioned interlayer insulating film 24 is formed by spin-coating a solution containing polyamic acid and then hardening it.
The step due to the copper wiring can be greatly alleviated and flattened, and a highly reliable wiring structure can be obtained.

FIG. 3 is a sectional view of an embedded type optical waveguide having a polymer core layer made of a photosensitive polymer according to the present invention. Here, the photosensitive polymer resin composition of Example (II-12) was used, and the polyimide film pattern formed by the same method as described above was used as the interlayer insulating film.

In FIG. 3, P is formed on the silicon substrate 31.
A lower clad layer 32 made of a thermosetting film of AA1 is formed. On the lower clad layer 32, a polymer core layer 33 and an upper clad layer 34 made of a thermosetting film of PAA1 are sequentially formed.

The above-mentioned polymer core layer 33 can be formed easily and accurately by using the photosensitive polymer resin composition of the present invention, so that there is an advantage that the PEP step is unnecessary and the productivity is improved.

FIG. 4 is a sectional view of a semiconductor device having a multilayer wiring structure having an interlayer insulating film made of a polyimide film obtained by curing the photosensitive polymer resin composition according to the present invention. Here, the photosensitive polymer resin composition of Example (I-5) was used, and the polyimide film pattern formed by the same method as described above was used as the interlayer insulating film.

In FIG. 4, a thermal oxide film 42 is formed on the surface of the silicon substrate 41 on which the element portion 47 is formed. A contact hole is opened in a part of the thermal oxide film 42, and the first-layer Al wiring 43 is formed thereon. An interlayer insulating film 44 made of a polyimide film is formed on the Al wiring 43. A contact hole is opened in a part of the interlayer insulating film 44, and a first layer of Al is formed on the contact hole.
A second-layer Al wiring 45 connected to the wiring 43 is formed. An interlayer insulating film 46 made of a polyimide film is further formed on the Al wiring 45.

The above-mentioned interlayer insulating film 44 is formed by spin-coating a solution containing polyamic acid and then hardening it.
It is possible to form a multi-layered Al wiring in a state where the surface steps are alleviated and the surface is flattened, and a highly reliable wiring structure can be obtained.

[0183]

As described above in detail, since the photosensitive polymer resin composition of the present invention contains a photosensitive thermosetting accelerator, a photoresist can be separately prepared by using such a resin composition. A fine pattern can be formed without using it. Moreover, since development is possible using an alkaline aqueous solution, all safety, hygiene and environmental problems are avoided. Furthermore, when the photosensitive polymer resin composition of the present invention is used, a polyimide film pattern having excellent resolution, adhesion and heat resistance is provided as an insulating member, a protective film member, a liquid crystal member or an optical waveguide, It is possible to provide high electronic components.

Therefore, in particular, the wiring insulating film of the LSI, L
Moisture resistant protective film of SI, α ray blocking film of LSI, passivation film of semiconductor, wiring insulating film of multi-chip module, thin film magnetic head wiring insulating film, magnetic bubble memory device wiring insulating film, optical element, liquid crystal orientation of liquid crystal display element It is useful for membranes.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a semiconductor device having a passivation film obtained by patterning a film made of a photosensitive polymer resin composition according to the present invention.

FIG. 2 is a cross-sectional view of a multi-chip module having an interlayer insulating film obtained by patterning a film made of a photosensitive polymer resin composition according to the present invention.

FIG. 3 is a sectional view of an optical waveguide having a polymer core layer obtained by patterning a film made of a photosensitive polymer resin composition according to the present invention.

FIG. 4 is a cross-sectional view of a semiconductor device having a multilayer wiring structure having an interlayer insulating film obtained by patterning a film made of the photosensitive polymer resin composition according to the present invention.

[Explanation of symbols]

11 ... LSI chip 12 ... Bonding pad 13 ... Tab 15 ... Passivation film made of polyimide film 16 ... Bonding wire 17 ... Lead frame 18 ... Sealing agent 21 ... Silicon substrate 22 ... Thermal oxide film 23, 25 ... Copper wiring 24, 26 ... Interlayer insulating film made of polyimide film 27 ... Pb / Sn electrode 28 ... BLM (Ball Limiting Metallization) 31 ... Silicon substrate 32 ... Lower clad 33 ... Polymer core layer 34 ... Upper clad 41 ... Silicon substrate 42 ... Thermal oxide film 43, 45 ... Al wiring 44, 46 ... Interlayer insulating film made of polyimide film 47 ... Element part

─────────────────────────────────────────────────── --- Continuation of the front page (56) References JP-A-4-168441 (JP, A) JP-A-6-324492 (JP, A) JP-A-5-11451 (JP, A) JP-A-6- 295063 (JP, A) JP 8-54736 (JP, A) JP 3-97733 (JP, A) JP 3-209478 (JP, A) JP 5-197148 (JP, A) JP-A-5-5996 (JP, A) JP-A-7-333851 (JP, A) JP-A-63-13032 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03F 7/00-7/42

Claims (5)

(57) [Claims] 1. A repeat represented by the following general formula (1):
Contains a thermosetting polymer resin precursor that is dehydrated and cyclized by heating, comprising a polyimide precursor having units, and a photosensitive thermosetting accelerator that deactivates the thermosetting acceleration ability by light irradiation.
However, the photosensitive heat that deactivates the thermosetting acceleration ability by the light irradiation.
The curing accelerator is an azomethyene represented by the following general formula (2).
Compound; nitrogen-containing heterocycle represented by the following general formula (3)
Compounds; fused or non-fused pyridinequinonediazides
A compound or a quinoline quinonediazide compound;
Ringed or non-fused, substituted or unsubstituted 2-hydroxy
Removal of hydroxy group of cypyridine compound by light irradiation
Consisting of a nitrogen-containing heterocyclic compound substituted with a protective substituent
A positive photosensitive polymer resin composition, which is at least one selected from the group . [Chemical 1] (In the general formula (1), φ is a tetravalent organic group, and Ψ is a divalent organic group.
Indicates an organic group. ) [Chemical 2] (In the general formula (2), Ar ¹¹ is a pyridine-type nuclear nitrogen source.
Nucleus having a child (-N =) and being adjacent to the nuclear nitrogen atom
Substituted or unsubstituted nitrogen-containing having a bond at a carbon atom
It is an aromatic heterocyclic group, and R ¹¹ is a substituted or unsubstituted aromatic group.
Aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, alicyclic group
It is a hydrocarbon group, an acyl group or a hydrogen atom, and R ¹² is
-OH group, -NH-R ¹³ group (R ¹³ is a substituted or unsubstituted
Aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, fat
Cyclic hydrocarbon group, acyl group, thioacyl group or carba
It is a moyl group. ), Or a —COOH group. ) [Chemical 3] (In the general formula (3), Ar ²¹ is a pyridine-type nuclear nitrogen source.
Substituted or unsubstituted nitrogen-containing aroma having a child (-N =)
Is a group heterocyclic group, and R ²⁰ is selected from the group shown below.
It is an organic group. ) [Chemical 4] (In the above general formula, R ²¹ and R ²² are substituted or unsubstituted.
Aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group, fat
Cyclic hydrocarbon group, alkoxy group, hydroxyl group or
It is a hydrogen atom, and R ²¹ and R ²² are bonded to each other to form an alicyclic group.
It may form a hydrocarbon group. R ²³ , R ²⁴ , R ²⁵ ,
R ³⁰ and R ^31, substituted or unsubstituted Kaoru aromatic hydrocarbons
Group, heterocyclic group, aliphatic hydrocarbon group, alicyclic hydrocarbon group
Or a hydrogen atom; R ²⁶ , R ²⁷ and R ²⁸ are substituted or non-substituted.
Substituted aromatic hydrocarbon group, heterocyclic group, aliphatic hydrocarbon group
Or an alicyclic hydrocarbon group; R ²⁹ is a substituted or unsubstituted aromatic group
Aromatic hydrocarbon group or aromatic heterocyclic group; X is a halogen group
And Z is a cyclic amino group. ) 2. The heat curing accelerating ability is deactivated by the light irradiation.
The photosensitive thermosetting accelerator is a substituted or unsubstituted pyridinium
-3,4-quinone-3-diazide, quinoline-3,4
-Quinone-3-diazide, quinoline-3,4-quinone-
4-diazide, quinoline-5,6-quinone-5-diazi
De, quinoline-5,6-quinone-6-diazide, quinoli
-7,8-quinone-8-diazide, quinoline-7,8
-Quinone-7-diazide, benzo [f] quinoline-3,
4-quinone-3-diazide, benzo [g] quinoline-
3,4-quinone-3-diazide, and benzo [h] quino
From the group consisting of Norrin-3,4-quinone-3-diazide
The positive photosensitive polymer resin composition according to claim 1, which is at least one selected . 3. The 2-hydroxypyridine compound is
2-hydroxypyridine, 2-hydroxyquinoline, 1
-Hydroxyisoquinoline, 3-hydroxyisoquinoline
6-hydroxyphenanthridine, 2-hydroxy
Benzo [f] quinoline, 2-hydroxybenzo [g] ki
Norrin, 2-hydroxybenzo [h] quinoline, 1-hi
Droxybenzo [f] isoquinoline, 1-hydroxy ester
Nzo [g] isoquinoline, 1-hydroxybenzo [h]
Isoquinoline, 3-hydroxybenzo [f] isoquinoli
And 3-hydroxybenzo [g] isoquinoline, and
Is it a group consisting of 3-hydroxybenzo [h] isoquinoline?
The positive photosensitive polymer resin composition according to claim 1, which is at least one nitrogen-containing heterocyclic compound selected from the group consisting of: 4. The method according to any one of claims 1 to 3.
The photosensitive polymer resin composition of
Step of forming a resin layer by heating and drying at a temperature of 0 ° C. or lower
And irradiating light to a predetermined area of the resin layer to perform exposure.
Step and the resin layer after the exposure at a temperature of 50 to 200 ° C.
The process of heat treatment with and the exposed part of the resin layer after heat treatment are developed
And a developing process.
Turn-shaped formation method. 5. The method according to any one of claims 1 to 3.
The layer containing the positive photosensitive polymer resin composition of
The polymer resin film obtained by
Material, optical member or liquid crystal alignment film
Electronic components to collect.