JPH11218932A - Developer for polimido type photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developer for the polyimido type photosensitive resin composition small in swelling in patterned parts in the developing and superior in resolution and prevented from film frilling in the developing and small in an effect on physical properties after hardening. SOLUTION: A photosensitive layer formed by using this polyimido type photosensitive resin composition containing a polyamic acid is patternwise exposed and developed with the developing solution composed of an aqueous solution of alkali containing a basic compound represented by the formula in which X<2> is N<+> or P<+> ; R is a 1-20C alkyl or 6-10C aryl group; Y<-> is a univalent anion; (m) is 0 or 1; (n) is 3 or 4; m+n=4; when m=0, n=4, and R is an alkyl group, the number of the total carbon atoms of the 4 alkyl groups is >=13, and when m=1, n=3, and R is an alkyl group, the total carbon number of the 3 alkyl groups is >=6.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a developer for a polyimide-based photosensitive resin composition, and more particularly to a developer comprising an alkaline aqueous solution containing a basic compound. The developer of the present invention is used for developing a photosensitive layer formed from a polyimide photosensitive resin composition containing a polyamic acid, after exposing the photosensitive layer in a pattern.

[0002]

2. Description of the Related Art In the process of manufacturing a semiconductor device, generally, a photoresist is peeled off when its role is finished in a process such as etching. However, when a photoresist film is used as a surface protective film or an interlayer insulating film of a semiconductor device, it is required to have high electrical and mechanical properties because it is left as a permanent film. Further, such a film is required to withstand high temperatures applied in a semiconductor manufacturing process.

In recent years, a film of a polyimide-based photosensitive resin composition has been used for such applications. Polyimide resin has excellent electrical properties, mechanical properties, and heat resistance, and is used for surface protection films and interlayer insulating films of semiconductor devices.A polyimide resin film is selectively applied to fine parts. For this purpose, it is convenient to use a polyimide-based photosensitive resin composition containing a polyamic acid (that is, a polyimide precursor). Forming a photosensitive layer by applying a polyimide-based photosensitive resin composition on a substrate and drying, then, after exposing in a pattern from the top of the photosensitive layer, by developing,
The pattern is formed by removing the non-exposed portions. The formed pattern is heat-treated, if necessary, to ring-close the polyamic acid and make it into a polyimide.

Conventionally, a developing solution used in the step of developing a polyimide-based photosensitive resin composition includes, for example, N
Aprotic polar solvent such as -methyl-2-pyrrolidone to which a lower alcohol such as methanol or water is added as a poor solvent (JP-A-58-66940;
Japanese Unexamined Patent Publication (Kokai) No. 2-127938) and a non-protonic polar solvent such as N-methyl-2-pyrrolidone to which an aromatic hydrocarbon such as xylene is added (JP-A-2-255988) are used. These developing solutions are mainly composed of an organic solvent. In recent years, it has been pointed out that when an organic solvent is used as a developer, development costs are high, explosion-proof equipment is required, there is a danger to the health of workers, and there is an adverse effect on the natural environment. Therefore, a polyamic acid or polyimide photosensitive resin composition that can be developed with an alkali developing solution, particularly a developing solution composed of an alkaline aqueous solution, instead of the organic solvent, has attracted attention.

[0005] Polyamic acids which have hitherto been reported as an alkali developing type or an alkaline aqueous solution developing type include, for example, those in which a protecting group removable under acid or alkali conditions is introduced into a carboxyl group or a phenolic hydroxyl group. [(J. Macrom. Sc
i. Chem. , A24, 10, 1407, 198
7), JP-A-1-259351, JP-A-4-36
No. 3361]. However, these polyamic acids require the introduction of a substituent having a large steric hindrance to the main chain carboxyl group or the side chain hydroxyl group via a covalent bond, so that the synthesis method becomes complicated and the curing temperature is high. There are problems such as the need for temperature and the deterioration of physical properties of the film.

[0006] A dihydropyridine derivative as a photobase generator is blended with polyamic acid, and the effect of accelerating imidization of the base formed by exposure is promoted by PEB (heat treatment after exposure), and the solubility difference due to imidization is utilized. A method of developing with an alkali developing solution has been proposed (JP-A-5-5-5).
995, JP-A-5-281717). However, these methods require PEB processing,
There are problems such as a low degree of exposure and a large amount of exposure.

Using a photosensitive resin composition obtained by adding a specific photopolymerizable monomer to a polyamic acid as a crosslinking aid,
A method of developing with an alkali developer or an aqueous alkali solution has been proposed (JP-A-63-183439, JP-A-5-100424). In these methods, a special polymerizable unsaturated compound such as one having an isocyanate structure and one having a urethane structure is used as a photopolymerizable monomer. Further, since the polyamic acid used in this method has no photopolymerizable group in its structure, there is a problem that sensitivity and resolution are not sufficient.

It has been proposed to use an aqueous alkali solution containing an amino alcohol and an alkali other than the amino alcohol as a developer for a photosensitive polyimide precursor (Japanese Patent Application Laid-Open No. 6-301217). This publication discloses, as alkalis other than amino alcohols, for example, tetramethylammonium hydroxide, choline, sodium hydroxide and the like. The invention described in this publication is
It is characterized in that it provides a developer that is more basic than a developer used for a positive resist containing a novolak resin as a resin component. By using this developer as a developer for the positive photosensitive polyimide precursor, it is said that it is advantageous for controlling the developing speed and forming fine patterns. However, in this developer, when a carboxyl group having a salt forming ability is present in the pattern forming portion of the photosensitive polyimide precursor, the dissolving power is too strong, and the resin swells in the pattern forming portion, and the resolution is reduced. This causes a decrease in the residual film ratio, and in a severe case, a pattern may not be formed.

In forming a pattern using a photosensitive heat-resistant polymer composition containing a polyamic acid having a photosensitive group introduced into a repeating unit, a sensitizer and a sensitizing aid, a method of developing with an aqueous alkali solution is known. It has been proposed (Japanese Unexamined Patent Publication No.
-180505). By this method, a wiring structure having a surface protective film formed of a cured product of the photosensitive heat-resistant polymer composition is manufactured. However, when an alkali aqueous solution containing tetramethylammonium hydroxide or the like specifically shown in the publication is used as a developing solution, it is difficult to sufficiently suppress swelling of a resin portion remaining as a pattern, resulting in poor resolution. Insufficient, and the strength of the obtained film is reduced.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to reduce swelling of a pattern-formed portion at the time of development, to have excellent resolution, not to cause peeling of the film at the time of development, and to have little effect on the physical properties of the film after curing. An object of the present invention is to provide a developer for a polyimide-based photosensitive resin composition. The present inventors have conducted intensive studies to overcome the problems of the prior art, and as a result, as a basic compound (alkali), a specific quaternary ammonium salt or a quaternary phosphonium salt having a bulky substituent is used. It has been found that when the contained alkaline aqueous solution is used as a developing solution, swelling of the resin portion remaining as a pattern is suppressed, and as a result, sensitivity and resolution are greatly improved. In addition, since the infiltration of the alkali component into the resin portion remaining as a pattern is suppressed, the deterioration of the film strength, particularly, the surface adhesion strength is effectively suppressed.

Further, together with the specific basic compound,
By using other basic compounds in combination, developability, resolution, surface adhesion strength of the film and the like can be highly balanced. When an organic solvent or a surfactant is added to the developer of the present invention, resolution, film peeling margin during development, development time, and the like can be further improved. As the polyimide-based photosensitive resin composition, those containing a polyamic acid having a photopolymerizable functional group in the molecular chain (particularly at both ends) are preferable. The polyamic acid preferably has a structure having a carboxyl group capable of forming a salt with an alkali. The present invention has been completed based on these findings.

[0012]

According to the present invention, there is provided a developer used for developing a photosensitive layer formed from a polyimide-based photosensitive resin composition containing a polyamic acid, after exposing the photosensitive layer in a pattern. The developer is represented by the formula (1)

[0013]

Embedded image [Wherein X ⁺ = N ⁺ or P ⁺ , R = C 1-20
An alkyl group or an aryl group having a nuclear carbon atom having 6 to 10 carbon atoms, Y ⁻ = a monovalent anion, m = 0 or 1, n = 3 or 4, and m + n = 4. Where m =
When 0, n = 4, and R = alkyl group, the total number of carbon atoms of the four alkyl groups is 13 or more. Also, m = 1, n
= 3, R = alkyl group, the total number of carbon atoms of the three alkyl groups is 6 or more. And a developing solution for a polyimide-based photosensitive resin composition, comprising an aqueous alkali solution containing a basic compound (A) represented by the formula:

Further, according to the present invention, a photosensitive layer is formed on a substrate using a polyimide-based photosensitive resin composition containing a polyamic acid, and then the photosensitive layer is exposed in a pattern and then developed. In the pattern forming method including the step, in the developing step, the formula (1)

[0015]

Embedded image [Wherein X ⁺ = N ⁺ or P ⁺ , R = C 1-20
An alkyl group or an aryl group having a nuclear carbon atom having 6 to 10 carbon atoms, Y ⁻ = a monovalent anion, m = 0 or 1, n = 3 or 4, and m + n = 4. Where m =
When 0, n = 4, and R = alkyl group, the total number of carbon atoms of the four alkyl groups is 13 or more. Also, m = 1, n
= 3, R = alkyl group, the total number of carbon atoms of the three alkyl groups is 6 or more. Wherein the alkaline aqueous solution containing the basic compound (A) is used as a developer.

Further, according to the present invention, the following preferred embodiments are provided. 1. When the basic compound (A) represented by the formula (1) is a tetraalkylammonium salt, a tetraalkylphosphonium salt, a benzyltrialkylammonium salt, a benzyltrialkylphosphonium salt, a benzyltriarylammonium salt, or a benzyltriarylphosphonium salt The developer as described above. 2. When the basic compound (A) represented by the formula (1) is a monovalent anion Y ⁻ , OH ⁻ , or Cl ⁻ , Br ⁻ , F ⁻ ,
And the above-mentioned developer containing a halogen anion selected from I ⁻ and I ⁻ .

3. The above developer comprising an alkaline aqueous solution containing, in addition to the basic compound (A) represented by the formula (1), another basic compound (B). 4. Other basic compound (B) is a tetraalkylammonium salt having a total number of carbon atoms of 4 or less of 10 or less, choline, a tertiary aliphatic amine having 1 to 5 carbon atoms of the alkyl group, 4. The developer according to item 3, which is at least one selected from the group consisting of pyridines and inorganic base compounds. 5. Basic compound (A) and other basic compounds (B)
And the third molar ratio is within the range of 2:98 to 99: 1.
Item 5. The developer according to item 4 or 4.

6. The above developer wherein the pH of the aqueous alkaline solution is 10.0 or more. 7. The above developer, wherein the alkaline aqueous solution contains, as a medium, 51% by weight or more of water and 49% by weight or less of at least one selected from the group consisting of an organic solvent and a surfactant. 8. 8. The developer according to item 7, wherein the organic solvent is at least one oxygen-containing compound selected from the group consisting of monohydric alcohols, polyhydric alcohols, ketones, and esters. 9. The above developer, wherein the polyamic acid has a photopolymerizable functional group in a molecular chain.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION <Developer> The basic compound (A) used in the present invention is a compound represented by the above formula (1), wherein 3 or 4 R's each represent They may be the same or different from each other. The basic compound (A) is represented by the formula (2)

[0020]

Embedded image [Wherein the symbols have the same meanings as in equation (1). And a counter ion anion component (Y ⁻ ). Specific examples of the basic compound (A) include compounds represented by the formula (3)

[0021]

Embedded image Wherein R ₁ is an alkyl group having 1 to 20 carbon atoms. However, the total number of carbon atoms of the four alkyl groups is 13
The number is preferably 16 or more. Further, the four alkyl groups may be the same or different from each other. A tetraalkylammonium salt represented by the formula (4):

[0022]

Embedded image Wherein R ₁ is an alkyl group having 1 to 20 carbon atoms. However, the total number of carbon atoms of the three alkyl groups is 6 or more. Further, the three alkyl groups may be the same or different from each other. A benzyltrialkylammonium salt represented by the formula (5):

[0023]

Embedded image [In the formula, Ar is an aryl group having a nuclear carbon atom having 6 to 10 carbon atoms. A benzyltriarylammonium salt represented by the formula (6):

[0024]

Embedded image Wherein R ₁ is an alkyl group having 1 to 20 carbon atoms. However, the total number of carbon atoms of the four alkyl groups is 13
That is all. Further, the four alkyl groups may be the same or different from each other. A tetraalkylphosphonium salt represented by the formula (7):

[0025]

Embedded image Wherein R ₁ is an alkyl group having 1 to 20 carbon atoms. However, the total number of carbon atoms of the three alkyl groups is 6 or more. Further, the three alkyl groups may be the same or different from each other. A benzyltrialkylphosphonium salt represented by the formula (8):

[0026]

Embedded image [In the formula, Ar is an aryl group having a nuclear carbon atom having 6 to 10 carbon atoms. And the like.

The anion (Y ⁻ ) is not particularly restricted but includes, for example, hydroxy anion (OH ⁻ ), C
^{l -, Br -, F -} , I - and a halogen anion, such as. Of these, OH ^- is preferred. More specifically, examples of the basic compound (A) include tetrabutylammonium hydroxide, cetyltrimethylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, benzyltriethylammonium hydroxide, and benzyltriphenylammonium. Hydroxide,
Examples include tetrabutylphosphonium hydroxide, benzyltriethylphosphonium hydroxide and the like. Among these, tetrabutylammonium hydroxide and benzyltriethylammonium hydroxide are particularly preferred. These basic compounds (A) can be used alone or in combination of two or more.

Basic compound (A) in alkaline aqueous solution
Is usually 0.025 to 30% by weight, preferably 0.1 to 15% by weight. The content of the basic compound (A) is such that the pH of the aqueous alkali solution is usually 10.0 or higher, preferably 10.0 to 13.8, more preferably 11.0 to
It is desirable to adjust so as to be 13.0. When the content of the basic compound (A) is too small,
Is less than 10.0, the development speed may be slow depending on the type of polyamic acid, and the swelling of the resin surface remaining as a pattern may not be sufficiently suppressed, resulting in poor resolution. In particular, when the film thickness of the polyimide-based photosensitive resin composition is large, the development is difficult to proceed, the development time becomes extremely long, and problems such as film peeling during the development are likely to occur.

When the content of the basic compound (A) is excessive and the pH of the aqueous alkali solution exceeds 13.8, the developing speed becomes too high, and it becomes difficult to control the developing time or control the pattern formation. If the content of the basic compound (A) is too large, the carboxyl group of the polyamic acid and the cation component represented by the formula (2) may form on the surface of the film to be developed using an aqueous alkali solution (developer). Since a hydrophobic salt is generated to suppress the seepage of the developing solution more than necessary, the resolution is also deteriorated.

In the present invention, the basic compound (A) may be used alone, but another basic compound (B) may be used in combination. As the other basic compounds, those conventionally used in alkaline developers can be used. Other basic compounds (B) include, for example, tetraalkylammonium salts in which the total number of carbon atoms in four alkyl groups is 12 or less, choline, and tertiary aliphatics having 1 to 5 carbon atoms in the alkyl group. Examples include amines, pyridines, and inorganic base compounds. Preferred basic compounds (B) include, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, sodium hydroxide, potassium hydroxide, barium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, barium carbonate, Lithium carbonate and the like. Among them, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline and the like are particularly preferable. These basic compounds (B)
Can be used alone or in combination of two or more.

Basic compound (B) in alkaline aqueous solution
Is usually 0.025 to 30% by weight, preferably 0.1 to 15% by weight. However, the content of the basic compound (A) and the basic compound (B) is such that the pH of the alkaline aqueous solution is usually 10.0 or more, preferably 10.0 to
It is desirable to adjust so as to be 13.8, more preferably 11.0 to 13.0. If the content of the basic compound is excessive, the resin portion which should be left at the time of development is also dissolved, and it becomes difficult to form a pattern.

When the basic compound (A) represented by the formula (1) and another basic compound (B) are used in combination, the molar ratio (A) :( B) of the two is usually 2:98 to 99: 1, preferably 5:95 to 90:10, more preferably 10:
90-90: 10, particularly preferably 30: 70-75:
25. It is desirable to use both of them within these ranges, because the developability, the resolution, the surface adhesion strength of the film and the like are highly balanced. Here, the mole% is calculated based on the cation component.

The basic compound (A) represented by the formula (1)
Has a substituent consisting of a bulky (bulky) hydrophobic hydrocarbon group such as a butyl group, a cetyl group, a pentyl group, a hexyl group, a benzyl group, and a phenyl group. When the contained aqueous solution is used as a developer, the carboxyl group of the polyamic acid and the cation component represented by the formula (2) form a salt on the surface of the resin film remaining as a pattern during development, whereby the hydrophobic film is formed. It is considered to form As a result, it is estimated that unnecessary penetration of the alkaline aqueous solution can be suppressed, and swelling of the remaining film portion is suppressed. On the other hand, the basic compound (B) represented by tetramethylammonium hydroxide forms a salt having high solubility in water with a carboxyl group in the film component removed by development and a salt highly soluble in water. This has the effect of increasing the dissolution rate during development.
Therefore, when these two basic compounds are effectively combined, optimization of development time and resolution can be achieved,
Excellent sensitivity and resolution can be achieved.

The alkaline aqueous solution used as the developer in the present invention contains, as a medium, at least 51% by weight of water and at least 49% by weight of at least one selected from the group consisting of an organic solvent and a surfactant. You may. When an organic solvent or a surfactant is added to the developer, film peeling during development can be suppressed, and the degree of penetration of the developer into the developed film can be adjusted. as a result,
This is effective for expanding the development margin of pattern formation by stable resolution and suppressing film peeling during development.

Examples of the organic solvent include oxygen-containing compounds such as monohydric alcohols, polyhydric alcohols, ketones, esters, and mixtures thereof. Specific examples of the organic solvent include monohydric alcohols such as methanol, ethanol, isopropyl alcohol and cyclopentanol; ketones such as cyclopentanone and methyl ethyl ketone; polyhydric alcohols such as propylene glycol and glycerin; ethyl acetate and lactic acid Esters such as ethyl; These organic solvents are used in a proportion of preferably 1 to 40% by weight, more preferably 3 to 30% by weight in the total medium.

The surfactant is not particularly limited, and commercially available products include, for example, Surfynol 440, Surfynol 465, Pluronic L-62, Adecitol LO-7, and the like. These surfactants can adjust the developing speed by improving the wettability of water on the film surface and improving the initial seepage of the developer. The surfactant has an improving effect even in a small amount of about 0.01 to 1% by weight, and it is particularly preferable to use the surfactant together with the organic solvent. The developing solution of the present invention may contain various additional components as needed, as long as the object of the present invention is not impaired.

<Polyimide photosensitive resin composition> Examples of the polyimide photosensitive resin composition that can be suitably developed using the developer of the present invention include, for example, a photopolymerizable functional group (chemical Photosensitive resin composition containing a polyamic acid having a linear functional group (for example, JP-A-8-8)
2931, JP-A-8-95247, JP-A-4-77741, JP-A-5-86154), a photosensitive resin containing a polyamic acid having a photopolymerizable functional group in a diamine structure. Composition (for example, JP-A-9-90629), a photosensitive resin composition in which a photopolymerizable monomer is mixed with polyamic acid (for example,
JP-A-9-90630).

The polyamic acid is used in a developing step after exposure,
It is preferable that the carboxyl group in the film-forming resin in the exposed part and the unexposed part is capable of forming a salt with the cation component. As the polyamic acid, those having a photopolymerizable functional group in a molecular chain are preferable, and those having a photopolymerizable functional group at both ends are more preferable. These polyimide-based photosensitive resin compositions contain, if necessary, a photosensitizer, a photopolymerization initiator, and the like, and each component is uniformly dissolved or dispersed in an organic solvent.

Among the polyimide-based photosensitive resin compositions,
JP-A-8-82931 and JP-A-8-95247
Japanese Patent Application Laid-Open Publication No. H10-207, which contains a polyamic acid having actinic radiation functional groups introduced at both ends, adjusts the molecular structure of the main chain, and can facilitate development with an aqueous alkaline solution, preferable. Such a polyamic acid having actinic radiation functional groups introduced at both ends is represented by the formula (9) in the main chain.

[0040]

Embedded image (Wherein, R ¹ is a tetravalent organic group, and R ² is a divalent organic group.)
Equation (10)

[0041]

Embedded image (Wherein X is a single bond, -O-, -CO-, -COO
-, - OCO -, - OCOO -, - COCH 2 O -, -
S -, - SO -, - SO ₂ -, or -SO ₂ are ^{O-, R 3, R 4,} R 5, R 6, and R ⁷ are photopolymerizable carbon - carbon double bonds A substituent, m is 0 or 1, and n is an integer in the range of 1-3. Groups Z ¹ represented by), and (11)

[0042]

Embedded image (Wherein, R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are substituents having a photopolymerizable carbon-carbon double bond, and m is 0
Or 1. )), And polyamic acid (A) having at least one actinic radiation functional group selected from the group consisting of groups Z ² at both ends. here,
When the repeating unit represented by the formula (9) is defined as a unit molecular weight, the monomer component (diamine) is adjusted so that the value of the unit molecular weight per one carboxyl group (unit molecular weight / -COOH) is in the range of 200 to 300. It is preferable to select a compound or a tetracarboxylic dianhydride. As such a polyamic acid, a compound represented by the formula (12) having an actinic radiation functional group Z ¹ represented by the formula (10) at both terminals

[0043]

Embedded image [Wherein, R ¹ is a tetravalent organic group, R ² is a divalent organic group, k is an integer in the range of 5 to 10,000, and Z ¹ is a group represented by the formula (10) Is an actinic radiation functional group represented by A polyamic acid (A1) represented by the formula:
Formula (13) having actinic radiation functional groups Z ² represented by 1) at both ends

[0044]

Embedded image [Wherein, R ¹ is a tetravalent organic group, R ² is a divalent organic group, k is an integer in the range of 5 to 10,000, and Z ² is a group represented by the formula (11) Is an actinic radiation functional group represented by And the polyamic acid (A2) represented by the formula:

The polyamic acid (A1) is usually prepared by adding a tetracarboxylic acid or an acid anhydride thereof to a mixture of a diamine compound and an aminobenzene such as p-aminobenzoic acid [tris (methacryloyl) pentaerythritol] ester. It can be obtained by a condensation reaction in a conventional manner. Polyamic acid (A2) is a diamine compound,
It is obtained by adding a trimellitic acid derivative such as trimellitic anhydride [tris (methacryloyl) pentaerythritol] ester and tetracarboxylic acid or an anhydride thereof, and subjecting the mixture to a condensation reaction by a conventional method.

As the diamine compound, for example, 4,
4'-diaminobenzanilide, 3,4'-diaminobenzanilide, 3,3'-diaminobenzanilide,
4,3'-diaminobenzanilide, 3,3'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,
2'-ditrifluoromethyl-4,4'-diaminobiphenyl, 2,2'-di (p-aminophenyl) -6,
6'-bibenzoxazole, 2,2'-di (p-aminophenyl) -5,5'-bibenzoxazole, m-
Phenylenediamine, 1-isopropyl-2,4-phenylenediamine, p-phenylenediamine, 4,4'-
Diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylethane, 4,4'-
Diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,
4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether,
1,4-bis (4-aminophenoxy) benzene, benzidine, 4,4 ″ -diamino-p-terphenyl, 3,
3 "-diamino-p-terphenyl, bis (p-aminocyclohexyl) methene, bis (p-β-amino-t-
Butylphenyl) ether, bis (p-β-methyl-δ)
-Aminopentyl) benzene, p-bis (2-methyl-
4-aminopentyl) benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4
-Bis (β-amino-t-butyl) toluene, 2,4-
Diaminotoluene, m-xylene-2,5-diamine,
aromatic diamines such as p-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine; 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1, Heterocyclic diamines such as 3,4-oxadiazole; alicyclic diamines such as 1,4-diaminocyclohexane; piperazine, methylene diamine, ethylene diamine, propylene diamine;
2,2-dimethylpropylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, 3
-Methoxyhexamethylenediamine, heptamethylenediamine, 2,5-dimethylheptamethylenediamine, 3
-Methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, octamethylenediamine, nonamethylenediamine, 5-methylnonamethylenediamine,
2,5-dimethylnonamethylenediamine, decamethylenediamine, 1,10-diamino-1,10-dimethyldecane, 2,11-diaminododecane, 1,12-diaminooctadecane, 2,12-diaminooctadecane,
Aliphatic diamines such as 2,17-diaminoicosane; diaminosiloxane, 2,6-diamino-4-carboxylic benzene, 3,3'-diamino-4,4 '
-Dicarboxylic benzidine and the like. These diamine compounds may be used alone or in combination.
More than one species can be used in combination. Equation (9)
R ^{2 in the above} is a divalent organic group derived from a diamine compound such as an aromatic diamine, a heterocyclic diamine, an alicyclic diamine, or an aliphatic diamine.

Examples of the tetracarboxylic acid or its acid anhydride include pyromellitic dianhydride, 3,3 ',
4,4'-benzophenonetetracarboxylic dianhydride,
Benzene-1,2,3,4-tetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride Anhydride, naphthalene-2,3,6,7
-Tetracarboxylic dianhydride, naphthalene-1,2,2
5,6-tetracarboxylic dianhydride, naphthalene-1,
2,4,5-tetracarboxylic dianhydride, naphthalene-
1,2,5,8-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,
8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6 , 7-Hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,4
5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,
4,5,8-tetracarboxylic dianhydride, 1,4,5
8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic dianhydride, 2,2', 3,3'-diphenyl Tetracarboxylic dianhydride, 2,3,3 ', 4'
Diphenyltetracarboxylic dianhydride, 2,3 ″,
4,4 "-p-terphenyltetracarboxylic dianhydride, 2,2", 3,3 "-p-terphenyltetracarboxylic dianhydride, 2,3,3", 4 "-p-ter Phenyltetracarboxylic dianhydride, 2,2-bis (2,3-
Dicarboxyphenyl) -propane dianhydride, 2,2-
Bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2 3-dicarboxyphenyl)
Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-
Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, perylene-2,3,8,9-tetracarboxylic dianhydride,
Perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride Phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,2
6,7-tetracarboxylic dianhydride, phenanthrene-
Aromatic tetracarboxylic dianhydride such as 1,2,9,10-tetracarboxylic dianhydride and its water additive; cyclopentane-1,2,3,4-tetracarboxylic dianhydride, cyclobutanetetraanhydride Carboxylic acid dianhydride, bicyclo [2,2,2] oct-7-en-2-exo, 3-exo, 5-exo, 6-exotetracarboxylic acid 2,
3: 5,6-dianhydride, bicyclo [2,2,1] heptane-2-exo, 3-exo, 5-exo, 6-exotetracarboxylic acid 2,3: 5,6-dianhydride and the like Alicyclic acid dianhydride; pyrazine-2,3,5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4 And heterocyclic derivative acid dianhydrides such as 1,5-tetracarboxylic dianhydride. R ¹ in the formula (9) is derived from a tetracarboxylic acid such as an aromatic tetracarboxylic dianhydride and a water additive thereof, an alicyclic acid anhydride and a heterocyclic derivative acid anhydride or an acid anhydride thereof. Is a tetravalent organic group.

[0048] by reacting with the carboxyl groups of tetracarboxylic acid or anhydride thereof, as a compound which gives a substituent Z ¹ of the amino benzenes, preferably used aminobenzene carboxylic acid ester. Specific examples of aminobenzenecarboxylic acid esters include o-aminobenzoic acid [tris (methacryloyl) pentaerythritol]
Esters, o-aminobenzoic acid [tris (acryloyl) pentaerythritol] ester, m-aminobenzoic acid [tris (methacryloyl) pentaerythritol] ester, m-aminobenzoic acid [tris (acryloyl) pentaerythritol] ester, p-amino Benzoic acid [tris (methacryloyl) pentaerythritol] ester, p-aminobenzoic acid [tris (acryloyl) pentaerythritol] ester, 5-amino-
Isophthalic acid [tris (methacryloyl) pentaerythritol] diester, 5-amino-isophthalic acid [tris (acryloyl) pentaerythritol] diester, o-aminobenzoic acid [pentakis (methacryloyl) dipentaerythritol] ester, o-aminobenzoic acid [ Pentakis (acryloyl) dipentaerythritol] ester, m-aminobenzoic acid [pentakis (methacryloyl) dipentaerythritol] ester, m-aminobenzoic acid [pentakis (acryloyl)]
Examples thereof include dipentaerythritol] ester, p-aminobenzoic acid [pentakis (methacryloyl) dipentaerythritol] ester, and p-aminobenzoic acid [pentakis (acryloyl) dipentaerythritol] ester. Among these, p-aminobenzoic acid [tris (methacryloyl) pentaerythritol] ester is particularly preferable because it is excellent in synthesis cost, operability, high sensitivity, high resolution and the like.

In order to synthesize a polyamic acid (A1) having an actinic radiation functional group Z ¹ represented by the formula (10) at both ends, a mixture of a diamine compound and an aminobenzene is prepared by adding
Tetracarboxylic acid or its anhydride is added, and a condensation reaction is performed by a conventional method. More specifically, in order to synthesize a polyamic acid having actinic ray functional groups introduced at both ends, a diamine compound is usually used in an amount of 0.850 to 0.990 mol per 1 mol of a tetracarboxylic acid or an anhydride thereof. Preferably, it is used in a ratio of 0.900 to 0.970 mol, and aminobenzenes are usually added in an amount of 0.1 to 1 mol of the diamine compound.
400-0.020 mol, preferably 0.110-0.
040 moles, more preferably 0.100 to 0.050 moles, and the total amount of the diamine compound and the aminobenzenes is usually 1 to 1 mole of the tetracarboxylic acid or its anhydride. It is used in a proportion of 100 to 0.900 mol, preferably 1.100 to 0.950 mol, more preferably 1.060 to 0.990 mol.
The condensation reaction is carried out according to a conventional method for synthesizing a polyamic acid.
The components may be reacted in a polar organic solvent such as dimethylacetamide. The reaction is usually carried out at a reaction temperature of -20 ° C.
The reaction is carried out at a temperature in the range of ~ 80 ° C and a reaction time of 0.5-80 hours. When the solubility of the monomer in the reaction system is low, a treatment may be performed in which the temperature is raised to a temperature at which the monomer can be dissolved, and a preliminary reaction is carried out until the monomer becomes a soluble oligomer in the reaction system.

A trimellitic acid derivative having a specific structure is used as a compound that provides a substituent Z ² represented by the formula (11) at both ends of the polyamic acid. As trimellitic acid derivatives, for example, trimellitic anhydride [tris (acryloyl) pentaerythritol] ester, trimellitic anhydride [tris (methacryloyl) pentaerythritol] ester, and the like, synthesis cost, operability, high sensitivity, It is excellent in terms of high resolution and the like, and is particularly preferable.

In order to synthesize a polyamic acid (A2) having an actinic radiation functional group Z ² represented by the formula (11) at both ends, a trimellitic acid derivative and a tetracarboxylic acid or an anhydride thereof are added to a diamine compound. And a condensation reaction is carried out by a conventional method. Alternatively, a tetracarboxylic acid or an anhydride thereof may be added to a mixture of a diamine compound and a trimellitic acid derivative, and a condensation reaction may be performed by a conventional method. More specifically, in order to synthesize a polyamic acid having actinic radiation functional groups introduced at both ends, tetracarboxylic acid or its anhydride is usually used in an amount of 0.850 to 1 mol of the diamine compound.
It is used in an amount of 0.990 mol, preferably 0.900 to 0.970 mol, and the trimellitic acid derivative is usually added in an amount of 0.4 mol per mol of tetracarboxylic acid or its anhydride.
00 to 0.020 mol, preferably 0.110 to 0.0
It is used in a proportion of 40 mol, more preferably 0.100 to 0.050 mol, and further, the total amount of tetracarboxylic acid or its anhydride and trimellitic acid derivative is usually 1 to 1 mol of the diamine compound. .100 to 0.900
Mole, preferably 1.100 to 0.990 mole, more preferably 1.060 to 1.020 mole. In the condensation reaction, each component may be reacted in a polar organic solvent such as dimethylacetamide according to a conventional method for synthesizing a polyamic acid. The reaction is usually carried out at a reaction temperature of -2.
The reaction is carried out at a temperature of 0 ° C to + 80 ° C and a reaction time of 0.5 to 80 hours. When the solubility of the monomer in the reaction system is low, a treatment may be performed in which the temperature is raised to a temperature at which the monomer can be dissolved, and a preliminary reaction is carried out until the monomer becomes a soluble oligomer in the reaction system.

The polyamic acid (A) comprises a photosensitive auxiliary (B) having a photopolymerizable functional group, and a photopolymerization initiator (C).
And uniformly mixed in the solvent (D) to obtain a polyimide-based photosensitive resin composition. The photosensitive assistant (B) is not particularly limited as long as it is generally known as a photocurable monomer. Representative examples of the photosensitizer include (meth) acrylic acid compounds such as pentaerythritol triacrylate. The photosensitizer is used in an amount of usually 10 to 50 parts by weight, preferably 15 to 50 parts by weight, based on 100 parts by weight of the polyamic acid.
It is used in a proportion of ４０40 parts by weight, more preferably 20-35 parts by weight.

Examples of the photopolymerization initiator (C) include Michler's ketone, benzoin, 2-methylbenzoin,
Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butylanthraquinone, 1,2-
Benzo-9,10-anthraquinone, anthraquinone,
Methylanthraquinone, 4,4'-bis- (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, 2,2-
Dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl- [4
-(Methylthio) phenyl] -2-morpholino-1-
Propanone, diacetylbenzyl, benzyldimethylketal, benzyldiethylketal, diphenyldisulfide, anthracene, phenanthrenequinone, riboflavin tetrabutyrate, acrylic orange, erythrosine, phenanthrenequinone, 2-isopropylthioxanthone, 2,6-bis (p -Diethylaminobenzylidene) -4-methyl-4-azacyclohexanone, 6-
Bis (p-dimethylaminobenzylidene) -cyclopentanone, 2,6-bis (p-diethylaminobenzylidene) -4-phenylcyclohexanone, aminostyryl ketone, 3-ketocoumarin compound, biscoumarin compound, N-phenylglycine, N- Examples thereof include phenyldiethanolamine and 3,3 ', 4,4'tetra (t-butylperoxycarbonyl) benzophenone. The amount of the photopolymerization initiator used is 100 parts of polyamic acid.
The amount is usually 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 1 to 5 parts by weight with respect to parts by weight.

As the solvent, for example, N-methyl-2-
Pyrrolidone, N, N-dimethylacetamide, N, N-
Examples include polar solvents such as dimethylformamide, dimethylsulfoxide, tetramethylurea, hexamethylphosphoric triamide, and γ-butyrolactone. The amount of the solvent used is an amount sufficient to uniformly dissolve each component. In particular, it is used in an amount ratio sufficient to dissolve the polyamic acid.
The proportion of the solvent used depends on the type of the solvent and the polyamic acid, but is usually 3 to 25 times (weight ratio), preferably 5 to 20 times, more preferably 6 to 10 times the amount of the polyamic acid. Within range.

Various additives such as an adhesion aid, a leveling agent, and a polymerization inhibitor can be used in the polyimide-based photosensitive resin composition, if necessary. Among various additives,
By adding 1H-tetrazole such as 1H-tetrazole, 5,5'-bis-1H-tetrazole and derivatives thereof, corrosion of copper and copper alloy is prevented, and thus adhesion of polyimide film to substrate is improved. Of the photosensitive film and prevention of the remaining photosensitive film. 1
H-tetrazole and derivatives thereof include unsubstituted 1H-tetrazole; 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-amino-
5-substituted-1H-tetrazole such as 1H-tetrazole; monosubstituted-1 such as 1-methyl-1H-tetrazole
H-tetrazole; 1-phenyl-5-mercapto-1
1-substituted-5-substituted-1H-tetrazole such as H-tetrazole; and the like. One of these
H-tetrazole and pentasubstituted-1H-tetrazole are particularly preferred.

1H-tetrazole is usually used in an amount of 0.1 part by weight based on 100 parts by weight of the polyamic acid (A) (solid basis).
It is used in an amount of 0.5 to 20 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.3 to 3.0 parts by weight. If the compounding ratio is too small, the effect of addition is small, and if it is too large, the effect is saturated. 1H-tetrazoles are usually added to a solution of polyamic acid to form a resin composition (solution), and the obtained composition is used for application to a substrate or the like to form a film. Of course, the polyimide-based photosensitive resin composition to which the developer of the present invention can be applied is not limited to the resin composition containing the polyamic acid (A) having the specific actinic radiation functional group. As long as it can be developed with the developer of the above, it can be applied to a polyimide-based photosensitive resin composition containing as a resin component a polyamic acid into which various photopolymerizable functional groups (actinic radiation functional groups) are introduced. .

<Pattern Forming Method> As a typical method of forming a pattern with the developing solution of the present invention, a polyimide photosensitive resin composition (varnish) is applied onto a substrate such as a silicon wafer by a method such as spin coating. After applying, drying on a hot plate or oven to form a film, and then performing a predetermined amount of exposure through a photomask,
There is a method of performing development. Examples of the developing method include immersion development in which the substrate is immersed in a developer bath, ultrasonic immersion development in which ultrasonic waves are applied by immersion development, and the like. After development, the film is usually washed with a rinse solution to remove the developer. As the rinsing liquid, a water-miscible solvent such as water, methanol, ethanol, isopropyl alcohol, acetone, methyl cellosolve, and ethyl cellosolve is used. Further, toluene, xylene and the like can be used. Preferably, water is good. Then, heat treatment (200-450)
C.) to convert to polyimide to obtain a final film.

[0058]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Reference Examples, Examples, and Comparative Examples. However, the present invention is not limited to only these Examples.

[Reference Example 1] Polyimide photosensitive resin composition
In a reactor equipped with a stirrer and a drying gas introduction tube,
45.9 g of 4'-diaminobenzanilide (0.202
mol) and 811 g of dimethylacetamide, and 5
Stir at 0 ° C. to dissolve. To this solution, 22.9 g (0.105 mol) of pyromellitic dianhydride, 3,3 ′,
4,4'-benzophenonetetracarboxylic dianhydride 3
3.8 g (0.105 mol) was reacted at a reaction temperature of 50 ° C. for 3 hours. Then, after cooling to 10 ° C. or lower, 9.8 g (0.045 mol) of pyromellitic dianhydride, 3,
14.5 g (0.045 mol) of 3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 25.1 g (0.04 mol of 1,4-bis (4-aminophenoxy) benzene
86 mol), and 11.02 g (0.024 mol) of p-aminobenzoic acid [tris (methacryloyl) pentaeristol] ester as a terminal-modified amine were added as a powder, and the mixture was stirred with ice-cooling for 3 hours and room temperature with stirring for 24 hours to obtain polyamic acid. Was synthesized. To 597 parts by weight of the polyamic acid thus obtained (100 parts by weight in solid content),
2 parts by weight of 3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone (λmax = 340 ηm, manufactured by NOF Corporation), 2 parts by weight of N-phenylglycine,
0.5 parts by weight of H-tetrazole and 32 parts by weight of triethylene glycol diacrylate (3EG-A, manufactured by Kyoeisha Chemical Co., Ltd.) as a photosensitizer are added and dissolved at room temperature to obtain a polyimide-based photosensitive resin composition (varnish). ) Got.

Example 1 <Resolution of Various Developing Solutions> The polyimide photosensitive resin composition obtained in Reference Example 1 was applied on various substrates by a spinner,
Dry on a hot plate at 70 ° C for 6 minutes, thickness about 15μ
m of film was formed. The substrate on which this film is formed is exposed using PLA-501F (manufactured by Canon Inc.) using a step tablet mask manufactured by Toppan Printing Co., Ltd. (exposure amount: 1000 mj; converted to g-line), and then ultrasonically immersed in various developing solutions. Development was performed and the development effect was compared and studied.
The results are shown in Table 1. <Measurement of Mechanical Strength of Film Surface: Evaluation of Adhesion Strength with Sputtered Chromium Film> The varnish synthesized in Reference Example 1 was applied to a silicon wafer substrate by the above method, dried to form a prebaked film, and then exposed to the entire surface. (Exposure amount: 1000 mj; g-line conversion). Next, ultrasonic immersion development was performed for 5 minutes with various developing solutions. After rinsing with water, under nitrogen atmosphere,
Heat treatment was performed for a time to form a polyimide film. On this film, a chromium film was formed by a sputtering method.
The strength of the adhesion between the polyimide film and the chromium film was measured by the Sebastian method. The results are shown in Table 1.

[0061]

[Table 1]

(Footnote) (1) Film thickness at development = about 15 μm, film thickness after curing = about 7.8
μm (2) Solvent composition = water: isopropyl alcohol = 8
5:15 (% by weight) (3) Symbol of alkali component (basic compound) TPAH: Tetra-n-propylammonium hydroxide TMAH: Tetramethylammonium hydroxide TBAH: Tetrabutylammonium hydroxide BTEAH: Benzyltriethylammonium hydroxide CMAH: Cetyltrimethylammonium hydroxide (4) Alkaline component (basic compound) concentration Experiment No. 2: TMAH concentration = 0.15% (weight ratio to solvent) Experiment Nos. 3 to 8: When TMAH = 0.15% by weight TMA
The molar ratio of TMAH: TBAH (the total amine molar amount is
0.15% TMAH weight). Experiment Nos. 9 to 11: unified to the same molar amount as the amount of TMAH amine in Experiment No. 2

<Evaluation> In Table 1, Experiment Nos. 1-2
Is a comparative example. TPAH (Experiment No. 1) and TMAH (Experiment No. 2) as alkali components (basic compounds)
TBA having a bulky substituent as compared with the case where
H (Experiment No. 9), BTEAH (Experiment No. 10), CM
Use of AH (Experiment No. 11) greatly improves the resolution. Further, by using TMAH and TBAH together (Experiment Nos. 3 to 8), it is possible to prevent the development time from becoming long while maintaining good resolution. effective.

Example 2 <Effects of Adding Organic Solvent> Developers of various compositions were prepared by adding an organic solvent (oxygen-containing compound) to various alkaline aqueous solutions, and the effects during development were compared. This experiment was carried out in accordance with the test of <Resolution of Various Developers> in Example 1. The results are shown in Table 2.

[0065]

[Table 2]

(Footnotes) (1) Film thickness at development = about 15 μm, film thickness after curing = about 7.8
μm (2) × mark indicates that the dissolution rate was insufficient and a pattern could not be formed.
This indicates that a film was left. (3)-indicates that the dissolution rate was increased and the residual film was reduced, and thus was not evaluated as data. (4) The development time is the time until a pattern can be formed. (5) The film peeling margin at the time of development is a margin time during which the pattern is maintained when overdeveloping after forming the pattern. The longer the time, the wider the margin and the easier to use. (6) pH Measurement Conditions Using a HORIBA PH Meter F-8L (pH meter manufactured by Horiba), the pH was measured at 23 ° C. one minute after the developer was brought into contact with the detector.

<Evaluation> From the results in Table 2, it can be seen that the addition of an organic solvent (oxygen-containing compound) improves the resolution and shortens the development time. When isopropyl alcohol was added to the combined system of TMAH and TBAH (Experiment No. 1)
3 to 17), it can be seen that excellent resolution and a wide development margin can be obtained. TBAH (Experiment No. 23) and BT
When isopropyl alcohol is added to EAH (Experiment No. 25), effects such as a reduction in development temperature, an improvement in resolution, a reduction in development time, and an increase in development margin can be obtained.

Example 3 <Effect of Addition of Surfactant> A developer was prepared by adding a surfactant to an aqueous alkali solution. The effects during development were examined. This experiment was conducted in the same manner as in Example 1 <Resolution of Various Developers>
The test was performed according to the test. The results are shown in Table 3.

[0069]

[Table 3]

(Footnotes) (1) Adecitol LO-7: a surfactant manufactured by Asahi Denka Co., Ltd. <Evaluation> From the results in Table 3, it can be seen that the development time can be reduced by adding a surfactant.

[0071]

According to the present invention, when a developer comprising an aqueous alkali solution of the present invention is used, the resolution can be greatly improved when a pattern is formed using a polyimide photosensitive resin composition, and a fine pattern can be formed. Becomes Since an alkaline aqueous solution is used as the developing solution, explosion-proof equipment in the developing equipment is not required, so that the cost of the developing solution and the cost of treating the waste liquid can be reduced, which greatly contributes to safety for workers and the natural environment.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Kei Sakamoto 1-2-1, Yasuko, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Within the Zeon Corporation General Development Center (72) Inventor Yasuhiro Yoneda Kami-Odanaka, Nakahara-ku, Kawasaki-shi, Kanagawa 4-1-1 1-1 Fujitsu Limited (72) Inventor Takao Yokouchi 4-1-1, Kamidadanaka, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture Fujitsu Limited

Claims (4)

[Claims] 1. A developer used for developing a photosensitive layer formed from a polyimide-based photosensitive resin composition containing a polyamic acid after patternwise exposing the photosensitive layer, wherein the developer is represented by the formula (1) ) [Wherein X ⁺ = N ⁺ or P ⁺ , R = C 1-20
An alkyl group or an aryl group having a nuclear carbon atom having 6 to 10 carbon atoms, Y ⁻ = a monovalent anion, m = 0 or 1, n = 3 or 4, and m + n = 4. Where m
= 0, n = 4, and R = alkyl group, the total number of carbon atoms of the four alkyl groups is 13 or more. Also, m = 1,
When n = 3 and R = alkyl group, the total number of carbon atoms of the three alkyl groups is 6 or more. ] A developer for a polyimide-based photosensitive resin composition, comprising an alkaline aqueous solution containing a basic compound (A) represented by the formula: 2. The basic compound (A) represented by the formula (1)
Is a tetraalkylammonium salt, a tetraalkylphosphonium salt, a benzyltrialkylammonium salt,
The developer according to claim 1, which is a benzyltrialkylphosphonium salt, a benzyltriarylammonium salt, or a benzyltriarylphosphonium salt. 3. A basic compound (A) represented by the formula (1)
But monovalent anion Y ^- as OH ^- or Cl, ^-, B
The developer according to claim 1, wherein the developer contains a halogen anion selected from r ⁻ , F ⁻ , and I ⁻ . 4. A pattern forming method comprising: forming a photosensitive layer on a substrate using a polyimide photosensitive resin composition containing a polyamic acid, exposing the photosensitive layer in a pattern, and then developing. In the developing step, the formula (1) [Wherein X ⁺ = N ⁺ or P ⁺ , R = C 1-20
An alkyl group or an aryl group having a nuclear carbon atom having 6 to 10 carbon atoms, Y ⁻ = a monovalent anion, m = 0 or 1, n = 3 or 4, and m + n = 4. Where m =
When 0, n = 4, and R = alkyl group, the total number of carbon atoms of the four alkyl groups is 13 or more. Also, m = 1, n
= 3, R = alkyl group, the total number of carbon atoms of the three alkyl groups is 6 or more. ], Wherein an alkaline aqueous solution containing the basic compound (A) is used as a developer.