JP3279005B2 - Actinic radiation sensitive polymer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive polyimide coating composition and, more particularly, to a novel photosensitive polyimide composition.

[0002]

2. Description of the Related Art As a photosensitive polyimide composition, a polyamic acid which can be dimerized or polymerized by actinic radiation is used.
A composition to which a compound containing a carbon double bond and an amino group or a quaternary salt thereof is added (for example, JP-B-59-5282).
No. 2) or a polyimide precursor composition in which photosensitivity is introduced into a polyamic acid by an ester group (for example, US Pat.
No. 12 and US Pat. No. 4,408,831) are known.

[0003] However, in such a conventional composition, as a developer, a polar solvent such as N-methyl-2-pyrrolidone and an organic solvent such as methanol, ethanol, toluene and xylene are usually used in combination. For this reason, the flash point of the developer is low, and it is necessary to take measures such as explosion proof.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel photosensitive polyimide composition which can be developed with an aqueous alkali solution or the like without using an organic solvent as a developer.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
This is achieved by adopting the following configuration.

That is, it comprises a polymer having a structural unit represented by the following general formula [1], a compound represented by the following general formula [2], and an electron-donating photoamine generation auxiliary. Actinic radiation sensitive polymer composition.

[0007]

Embedded image (R ¹ is a trivalent or tetravalent organic group having at least 2 carbon atoms, R ² is a divalent organic group having at least 2 carbon atoms, R ³ is hydrogen, an alkali metal ion, Represents an ammonium ion or an organic group having 1 to 20 carbon atoms, and n is 1 or 2.) (R ⁴ —OCO—NH) _m —R ⁵ [2] [R ⁴ is at least one in the molecule. Is represented by the following general formula [3],

Embedded image (R ⁶ represents hydrogen or an organic group having 1 to 10 carbon atoms.
l is an integer of 0-3. ), And the others represent organic groups having 1 to 20 carbon atoms. R ⁵ represents one or more monovalent to tetravalent organic group having a carbon number. m is an integer of 1 to 4. As the polymer having the structural unit represented by the general formula [1] in the present invention, the polymer having the structure represented by the above general formula, and an imide ring,
Other examples include polymers that can become polymers having a cyclic structure (hereinafter, referred to as “polyimide polymers”).

In the above general formula [1], R ¹ is at least 2
Is a trivalent or tetravalent organic group having three carbon atoms.
In view of the heat resistance of the polyimide polymer, R ¹ is preferably a trivalent or tetravalent group containing an aromatic ring or an aromatic heterocyclic ring and having 6 to 30 carbon atoms. Preferred specific examples of R ¹ include a pyromellitic acid residue, 3,3 ′, 4,4′-
Benzophenonetetracarboxylic acid residue, 3,3 ', 4
4′-biphenyltetracarboxylic acid residue, 3,3 ′,
4,4′-diphenylethertetracarboxylic acid residue,
Examples include, but are not limited to, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid residue, butanetetracarboxylic acid residue, and cyclopentanetetracarboxylic acid residue.

In the polymer of the present invention, R ¹ may be composed of one of these, or may be a copolymer composed of two or more.

In the above general formula [1], R ² is at least 2
It is a divalent organic group having two carbon atoms. Like R ¹ , R ² is preferably a divalent group containing an aromatic ring or an aromatic hetero ring and having 6 to 30 carbon atoms from the viewpoint of the heat resistance of the polyimide polymer. Preferred specific examples of R ² include a diaminodiphenyl ether residue, a diaminodiphenylsulfide residue, a diaminodiphenylmethane residue,
Examples include, but are not limited to, diaminodiphenylsulfone residues, phenylenediamine residues, benzidine residues, bisaminophenoxypropane residues, and the like.

In the polymer of the present invention, R ² may be composed of one of these, or may be a copolymer composed of two or more.

Further, in order to improve the adhesiveness of the polyimide-based polymer, it is possible to copolymerize an aliphatic group having a siloxane bond as R ² as long as the heat resistance is not reduced. Preferred specific examples include bis (3-aminopropyl) tetramethyldisiloxane.

In the above general formula [1], R ³ is hydrogen, an alkali metal ion, an ammonium ion, or a compound having 1 to 1 carbon atoms.
Represents 20 organic groups, and n is 1 or 2.

In the polymer of the present invention, R ³ may be composed of one of these, or may be a copolymer composed of two or more.

The polymer in the present invention has the general formula [1]
Or a copolymer or a blend with other structural units. At that time, it is preferable that the content of the structural unit represented by the general formula [1] is 90% or more. It is desirable that the type and amount of the structural unit used for copolymerization or blending be selected within a range that does not significantly impair the heat resistance of the polyimide-based polymer obtained by the final heat treatment.

Specific examples of the polymer in the present invention include pyromellitic dianhydride and 4,4'-diaminodiphenyl ether, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether. 4'-diaminodiphenyl ether, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether, pyromellitic dianhydride and 3,3' (or 4,4 ') -Diaminodiphenyl sulfone, pyromellitic dianhydride and 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 3,3' (or 4,4
') -Diaminodiphenyl sulfone, 3,3', 4,4
'-Benzophenonetetracarboxylic dianhydride and 3,3
'(Or 4,4')-diaminodiphenyl sulfone,
3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and 3,3 ′ (or 4,4 ′)-diaminodiphenyl sulfone, pyromellitic dianhydride and 4,4′-diaminodiphenyl sulfide, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and 4,4'-diaminodiphenyl sulfide, 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 4,4'- Diaminodiphenyl sulfide, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and paraphenylenediamine, 3,3', 4,4'-biphenyltetracarboxylic dianhydride and paraphenylenediamine, pyromellitus Acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride and paraphenylenediamine, pyromellitic dianhydride and 3 , 3 ', 4,4'-biphenyltetracarboxylic dianhydride and paraphenylenediamine, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether, 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride and paraphenylenediamine, butanetetracarboxylic dianhydride and 1,3-bis (3-aminophenoxy) benzene, cyclopentanetetracarboxylic dianhydride and 4 , 4'-diaminodiphenylmethane,
Polyamic acid synthesized from pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, bis (3-aminopropyl) tetramethyldisiloxane and the like is preferably used.

The actinic radiation polymer composition of the present invention contains a photoamine generator as an essential component. The photoamine generator refers to a compound that generates an amine upon irradiation with light. When an amine is formed in the system by light irradiation, remarkable effects are obtained, such as imidization is promoted, and the carboxylic acid in the polymer reacts with the amine to form a crosslink, thereby insolubilizing the polymer.

Preferred photoamine generators in the present invention include:
A system composed of a combination of a compound represented by the following general formula [2] and an electron-donating photoamine generation aid can be given.

(R ⁴ -OCO-NH) _m -R ⁵ [2] In the general formula [2], R ⁴ is a group capable of photoelimination reaction in the presence of an electron-donating photoamine generating auxiliary. And R ⁴ is
At least one in the molecule has the following general formula [3]:

Embedded image (R ⁶ represents hydrogen or an organic group having 1 to 10 carbon atoms.
l is an integer of 0-3. ), And the others represent organic groups having 1 to 20 carbon atoms.

Specific examples of the group represented by the general formula [3] include p-nitrobenzyl, 2,4-dinitrobenzyl, 3,4-dinitrobenzyl, 2,4,6-trinitrobenzyl Group, (α-methyl) p-nitrobenzyl group, (α-methyl) 2,4-dinitrobenzyl group, (α
-Methyl) 3,4-dinitrobenzyl group, (α-methyl) 2,4,6-trinitrobenzyl group and the like.

R ⁵ is a monovalent to tetravalent organic group having 1 or more carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group, a phenyl group, a naphthyl group, an anthryl group, a benzyl group. Group, methylene group, poly (methylene) group, phenylene group, methylphenylene group, methanediphenylene group, triphenylmethane group and the like. m is an integer of 1 to 4.

Specific examples of the compound represented by the general formula [2] include [p-nitrobenzyloxycarbonyl]
Cyclohexylamine, [2,4-dinitrobenzyloxycarbonyl] cyclohexylamine, [3,4-dinitrobenzyloxycarbonyl] cyclohexylamine, [2,4,6-trinitrobenzyloxycarbonyl] cyclohexylamine, [(α-methyl ) P-Nitrobenzyloxycarbonyl] cyclohexylamine,
[(Α-methyl) 2,4-dinitrobenzyloxycarbonyl] cyclohexylamine, [(α-methyl) 3
4-dinitrobenzyloxycarbonyl] cyclohexylamine, [(α-methyl) 2,4,6-trinitrobenzyloxycarbonyl] cyclohexylamine, bis [p-nitrobenzyloxycarbonyl] hexamethylenediamine, bis [2,4- Dinitrobenzyloxycarbonyl] hexamethylenediamine, bis [3,4-dinitrobenzyloxycarbonyl] hexamethylenediamine, bis [2,4,6-trinitrobenzyloxycarbonyl] hexamethylenediamine, bis [(α-methyl) p -Nitrobenzyloxycarbonyl] hexamethylenediamine, bis [(α-methyl) 2,4-dinitrobenzyloxycarbonyl] hexamethylenediamine,
Bis [(α-methyl) 3,4-dinitrobenzyloxycarbonyl] hexamethylenediamine, bis [(α-methyl) 2,4,6-trinitrobenzyloxycarbonyl] hexamethylenediamine, bis [p-nitrobenzyloxy Carbonyl] methylphenylenediamine, bis [2,4-dinitrobenzyloxycarbonyl] methylphenylenediamine, bis [3,4-dinitrobenzyloxycarbonyl] methylphenylenediamine, bis [2,4,6-trinitrobenzyloxycarbonyl]
Methylphenylenediamine, bis [(α-methyl) p-
Nitrobenzyloxycarbonyl] methylphenylenediamine, bis [(α-methyl) 2,4-dinitrobenzyloxycarbonyl] methylphenylenediamine, bis [(α-methyl) 3,4-dinitrobenzyloxycarbonyl] methylphenylenediamine, bis [(Α-methyl) 2,4,6-trinitrobenzyloxycarbonyl] methylphenylenediamine, bis [p-nitrobenzyloxycarbonyl] methanediphenylenediamine,
Bis [2,4-dinitrobenzyloxycarbonyl] methanediphenylenediamine, bis [3,4-dinitrobenzyloxycarbonyl] methanediphenylenediamine, bis [2,4,6-trinitrobenzyloxycarbonyl] methanediphenylenediamine Bis [(α-methyl) p-nitrobenzyloxycarbonyl] methanediphenylenediamine, bis [(α-methyl) 2,4-dinitrobenzyloxycarbonyl] methanediphenylenediamine, bis [(α-methyl) 3, 4-dinitrobenzyloxycarbonyl] methanediphenylenediamine,
Bis [(α-methyl) 2,4,6-trinitrobenzyloxycarbonyl] methanediphenylenediamine; and the like.

Among the above, particularly preferred are:
Bis [p-nitrobenzyloxycarbonyl] hexamethylenediamine, bis [2,4-dinitrobenzyloxycarbonyl] hexamethylenediamine, bis [3,4
-Dinitrobenzyloxycarbonyl] hexamethylenediamine, bis [2,4,6-trinitrobenzyloxycarbonyl] hexamethylenediamine, bis [(α-
Methyl) p-nitrobenzyloxycarbonyl] hexamethylenediamine, bis [(α-methyl) 2,4-dinitrobenzyloxycarbonyl] hexamethylenediamine, bis [(α-methyl) 3,4-dinitrobenzyloxycarbonyl] hexa Methylenediamine, bis [(α
-Methyl) 2,4,6-trinitrobenzyloxycarbonyl] hexamethylenediamine, and the like.

The compound represented by the general formula [2] can be usually synthesized by a condensation reaction between a benzyl alcohol derivative and an isocyanate compound.

The compound represented by the general formula [2] alone does not substantially generate an amine even when irradiated with light, but is effective only when combined with an electron-donating photoamine generating auxiliary. Becomes an amine generator.

Examples of the electron-donating photoamine generating aid include anthracenes, xanthenes, triphenylmethanes, phthalocyanines, porphyrins, and acridines. It is preferable that these photoamine generation aids contain one or more electron-donating substituents. Specific examples of the electron donating substituent include a hydroxy group, an alkoxy group having 1 to 20 carbon atoms, a phenoxy group, an amino group, and a substituted amino group. Furthermore, in order to improve compatibility with the polymer, a nitro group, a sulfone group, a chloro group, a fluoro group, a bromo group,
An iodine group, a carboxyl group, a chloromethyl group, a bromomethyl group, a hydroxymethyl group, or the like may be introduced.

Among these electron-donating photoamine generating aids, preferred are anthracenes represented by the following general formula [4].

[0028]

Embedded image In the above general formula [4], R ⁷ and R ⁸ are organic groups having 1 to 20 carbon atoms. Preferred specific examples of R ⁷ and R ⁸ include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a benzyl group and a phenyl group. It may contain a cyano group, a carboxyl group or the like. R ⁷ and R ⁸ may be the same or different.

R ⁹ is hydrogen, an organic group having 1 to 20 carbon atoms,
A nitro group, an amino group, a hydroxyl group, a sulfonic acid group or a halogen, specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group,
Benzyl, phenyl, chloromethyl, bromomethyl, hydroxymethyl, chloro, fluoro, bromo, iodo and the like. p is an integer of 1 to 3.

Specific examples of the anthracene represented by the general formula [4] include 2-carboxy-9,10-dimethoxyanthracene, 2-nitro-9,10-dimethoxyanthracene, 2-amino-9,10- Dimethoxyanthracene, 2-hydroxy-9,10-dimethoxyanthracene, 9,10-dimethoxyanthracene-2-sulfonic acid, 2-chloro-9,10-dimethoxyanthracene, 2-methyl-9,10-dimethoxyanthracene,
2-bromomethyl-9,10-dimethoxyanthracene, 2-carboxy-9,10-diethoxyanthracene, 2-nitro-9,10-diethoxyanthracene,
2-amino-9,10-diethoxyanthracene, 2-
Hydroxy-9,10-diethoxyanthracene, 9,
10-diethoxyanthracene-2-sulfonic acid, 2-
Chloro-9,10-diethoxyanthracene, 2-methyl-9,10-diethoxyanthracene, 2-bromomethyl-9,10-diethoxyanthracene, and the like.

The above-mentioned electron-donating photoamine generating auxiliary is
It is preferable to add 1 to 200% by weight, preferably 5 to 100% by weight to the compound represented by the general formula [3]. If the ratio is outside this range, care must be taken because amine may not be effectively generated.

The photoamine generator of the present invention has the general formula [3]
The total amount of the compound represented by the formula (1) and the electron-donating photoamine generating aid is 1 to 200% by weight, preferably 3 to 100% by weight, based on the polymer. Care must be taken because if it is out of this range, an image cannot be formed or the mechanical properties of the film may be deteriorated.

A photoinitiator or a sensitizer can be added to the composition of the present invention, if necessary.

The photoinitiator suitable for the present invention includes aromatic amines such as N-phenyldiethanolamine, N-phenylglycine and Michler's ketone, 3-phenyl-5-
Cyclic oxime compounds represented by isoxazolone, 1
Examples include, but are not limited to, cyclic oxime compounds represented by -phenylpropanedione-2- (O-ethoxycarbonyl) oxime.

Examples of sensitizers suitable for the present invention include coumarin compounds such as aromatic monoazides such as azidoanthraquinone and azidobenzalacetophenone, and 3,3'-carbonylbis (diethylaminocoumarin); benzanthrone and phenanthrenequinone. In some cases, aromatic ketones such as those generally used for photocurable resins and those used as charge transfer agents for electrophotography can be preferably used.

The photoinitiator and the sensitizer are used in an amount of 0.1 to the polymer.
It is preferable to add in the range of -5% by weight. If the ratio is outside this range, the photosensitivity is reduced and the mechanical properties of the polymer are reduced. These photoinitiators and sensitizers can be used alone or in combination of two or more.

In order to improve the adhesion between the coating film of the composition of the present invention or the polyimide film after the heat treatment and the support, an adhesion aid may be appropriately used.

Examples of the adhesion promoter include oxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-
Organosilicon compounds such as methacryloxypropyltrimethoxysilane; or aluminum chelate compounds such as aluminum monoethylacetoacetate diisopropylate and aluminum tris (acetylacetonate); or titanium bis (acetylacenate)
Titanium chelate compounds and the like are preferably used.

As other additives, a copolymer monomer or an adhesion improver with a substrate may be contained within a range where sensitivity and heat resistance are not significantly reduced.

An example of the method for producing the composition of the present invention will be described. First, a diamine compound and an acid dianhydride are reacted in a solvent to obtain a polymer having a structural unit represented by the general formula [1] as a main component. Next, a composition is obtained by dissolving and mixing a photoamine generator (a compound represented by the general formula [3] and an electron-donating photoamine generation auxiliary) with this solution and other additives as necessary. . As the above-mentioned polymer, a solid polyamic acid polymer or a polymer separated and purified from a solution after the reaction may be used after being dissolved again.

As the solvent used in the above production method, a polar solvent is preferably used in view of the solubility of the polymer, and an aprotic polar solvent is particularly preferable. Examples of aprotic polar solvents include N-methyl-2-pyrrolidone, N, N-
Dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorotriamide, γ-butyrolactone and the like are preferably used.

Next, the method of using the composition of the present invention will be described. The composition of the present invention can be patterned by a known fine processing technique using actinic radiation.

First, the composition of the present invention is coated on a suitable support. Examples of the material of the support include metal, glass, semiconductor, metal oxide insulator, silicon nitride, and the like.

As a coating method, means such as spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating are possible. The coating thickness can be adjusted by the coating means, the solid content concentration of the composition, and the viscosity, but it is usually applied so as to be in the range of 1 to 30 μm.

Next, the composition of the present invention formed into a coating film on the support is irradiated with actinic radiation in a desired pattern. Examples of the actinic ray include X-rays, electron beams, ultraviolet rays, and visible rays, but ultraviolet rays and short-wavelength visible rays, that is, 200 to 500 nm in a wavelength range are preferable.

After exposure, an imidization reaction and a cross-linking reaction are performed by baking. The temperature is 60 to 160
C. is preferred. If the ratio is outside this range, the reaction may not proceed or all the regions may not be dissolved.

Next, a relief pattern is obtained by dissolving and removing the unirradiated portion with a developing solution. A suitable developer can be selected according to the structure of the polymer.
An alkaline aqueous solution of ammonia, tetramethylammonium hydroxide, diethanolamine or the like can be preferably used. Further, N-methyl-2-pyrrolidone and N-acetyl-2, which are solvents of the present composition, are used.
-Pyrrolidone, N, N-dimethylformamide, N, N
-Dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide or the like alone or a mixture of a composition such as methanol, ethanol, isopropyl alcohol, water, methyl carbitol, ethyl carbitol, toluene and xylene with a non-solvent is also preferably used. can do.

The development can be carried out by spraying the above-mentioned developing solution on the coating film surface, dipping in the developing solution, or applying ultrasonic waves while dipping.

Next, it is desirable to wash the relief pattern formed by development with a rinsing liquid. As the rinsing liquid, water is preferably used when developing with an aqueous alkali solution. When rinsing with an organic solvent, methanol, ethanol,
Isopropyl alcohol, butyl acetate and the like are preferably used.

The polymer of the relief pattern obtained by the above treatment is a precursor of a polyimide-based polymer having heat resistance, and becomes a heat-resistant polymer having an imide ring or another cyclic structure by heat treatment. As the heat treatment temperature,
It is preferably performed at 135 to 400 ° C. Heat treatment is usually
The heating is performed stepwise or continuously.

The actinic radiation-sensitive polymer composition of the present invention can be used for a passivation film of a semiconductor, a buffer coat film of a passivation film, an interlayer insulating film of a multilayer integrated circuit, an interlayer insulating film or a surface protective film of a hybrid integrated circuit, a printed circuit. To form a soldering protective film, an alignment film for liquid crystal, an interlayer insulating film of a mounting substrate, and the like. Further, it is also possible to apply a metal as a highly heat-resistant photoresist or a dry etching process. It can be applied to other known uses of polyimide.

[0052]

EXAMPLES Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.

<Synthesis of Photoamine Generator><< Synthesis of Compound Represented by General Formula [3] >> Synthesis of (p-nitrobenzyloxycarbonyl) cyclohexylamine 15.3 g of p-nitrobenzyl alcohol was dissolved in 50 ml of tetrahydrofuran. I let it. Here, cyclohexyl isocyanate was added dropwise, and a reaction was carried out at 30 ° C. for 2 hours using dibutyl dilauryl tin as a catalyst. The reaction product was poured into water and collected to obtain (p-nitrobenzyloxycarbonyl) cyclohexylamine. This is designated as photoamine generator (1).

Synthesis of (3,4-dinitrobenzyloxycarbonyl) cyclohexylamine 19.8 g of 3,4-dinitrobenzyl alcohol was dissolved in 50 ml of tetrahydrofuran. Here, cyclohexyl isocyanate was added dropwise, and a reaction was carried out at 30 ° C. for 2 hours using methyllithium as a catalyst. The reaction product was poured into water and collected to obtain (3,4-dinitrobenzyloxycarbonyl) cyclohexylamine. This is designated as photoamine generator (2).

Synthesis of bis (p-nitrobenzyloxycarbonyl) hexamethylenediamine 15.3 g of p-nitrobenzyl alcohol was dissolved in 50 ml of tetrahydrofuran. Here, hexamethylene diisocyanate was added dropwise, and a reaction was carried out at 30 ° C. for 2 hours using dibutyl dilauryl tin as a catalyst. The reaction product was poured into water and collected to obtain bis (p-nitrobenzyloxycarbonyl) hexamethylenediamine. This is designated as photoamine generator (3).

<< Synthesis of Electron Donating Photoamine Generation Aid >> Synthesis of 2-carboxy-9,10-dimethoxyanthracene 2-carboxy-9,10-anthraquinone 25.2
g, zinc 10 g and ethanol 40 ml were mixed at room temperature. To this was added 200 ml of 20% sodium hydroxide, and the mixture was heated under reflux for 1 hour. To this solution, 117 g of methyl p-toluenesulfonate was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction solution was allowed to cool to room temperature, filtered, and the filtrate was treated with dilute hydrochloric acid to precipitate a solid. This was separated by filtration and collected to obtain 2-carboxy-9,10-dimethoxyanthracene. This is designated as photoamine generation aid (1).

<Synthesis of Polyimide Stock Solution> 100.1 g of 4,4′-diaminodiphenyl ether
Was dissolved in 670 g of N-methyl-2-pyrrolidone at room temperature, and 157.5 g of 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride was added together with 103 g of N-methyl-2-pyrrolidone, followed by vigorous stirring. Was. At this time, the liquid temperature rises rapidly and reaches 50 ° C., but then becomes a steady state. The reaction was continued at 30 ° C. for 1 hour,
Then, the solution temperature was raised and the reaction was carried out for 4 hours to obtain a polyamic acid solution (A).

100.1 g of 4,4'-diaminodiphenyl ether was dissolved in 670 g of N-methyl-2-pyrrolidone at room temperature, and 108.2 g of pyromellitic anhydride was added together with 80 g of N-methyl-2-pyrrolidone, followed by vigorous stirring. Was done. At this time, the liquid temperature rises rapidly and reaches 50 ° C., but then becomes a steady state. The reaction was continued at 30 ° C. for 1 hour, and the reaction temperature was further raised to 60 ° C. for 4 hours to obtain a polyamic acid solution (B).

124.3 g of 3,3'-diaminodiphenylsulfone was dissolved in 600 g of N-methyl-2-pyrrolidone at room temperature, and 146.5 g of 3,3 ', 4,4'-biphenyltetracarboxylic anhydride was added to N -Methyl-2-pyrrolidone was added together with 100 g, followed by vigorous stirring.
At this time, the liquid temperature rises rapidly and reaches 50 ° C., but then becomes a steady state. Thereafter, the reaction was carried out at 50 ° C. for 1 hour, the liquid temperature was further raised to 60 ° C., and the reaction was carried out for 4 hours to obtain a polyamic acid solution (C).

Example 1 Photoamine generator (1) 5 g, Photoamine generation auxiliary (1) 2
g, Michler's ketone 0.5 g and polyamic acid solution (A)
Was mixed. This solution was spin-coated on a 4-inch silicon wafer. Next, heat treatment was performed at 100 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). At this time, the film thickness was 5 μm.

After the heat treatment, 800 mJ / cm ² (measured at 365 nm) using a contact aligner (PLA-501 manufactured by Canon) and a gray scale as a mask.
Was exposed.

After the exposure, a heat treatment was performed at 130 ° C. for 2 minutes. At this time, the film thickness was 4.3 μm.

Subsequently, an alkaline developer (NMD manufactured by Tokyo Ohka)
-3) for 1 minute for development.

An image remained at an exposure amount of 320 mJ / cm ² or more. The film thickness at an exposure amount of 800 mJ / cm ² was 3.9 μm.

Example 2 5 g of photoamine generator (2), photoamine generation aid (1) 2
g, 0.5 g of N-phenylglycine and 0.2 g of benzanthrone were mixed with the polyamic acid solution (B). This solution was spin-coated on a 4-inch silicon wafer.
Then hot plate (SCW manufactured by Dainippon Screen Mfg. Co., Ltd.)
-636) to perform a heat treatment at 100 ° C. for 2 minutes.
At this time, the film thickness was 5 μm.

After the heat treatment, 600 mJ / cm ² (measured at 365 nm) using a contact aligner (PLA-501 manufactured by Canon Inc.) and a gray scale as a mask.
Was exposed.

After the exposure, a heat treatment was performed at 130 ° C. for 2 minutes. At this time, the film thickness was 4.3 μm.

Subsequently, an alkaline developer (NMD manufactured by Tokyo Ohka)
-3) for 1 minute for development.

An image remained when the exposure amount was 240 mJ / cm ² or more. The film thickness at an exposure amount of 600 mJ / cm ² was 3.8 μm.

Example 3 5 g of photoamine generator (3), photoamine generation aid (1) 2
g, 3,3′-carbonylbis (diethylaminocoumarin) 0.3 g and the polyamic acid solution (C) were mixed. This solution was spin-coated on a 4-inch silicon wafer. Next, use a hot plate (D-Nippon Screen Manufacturing S
Heat treatment was performed at 100 ° C. for 2 minutes using CW-636). At this time, the film thickness was 5 μm.

After the heat treatment, 600 mJ / cm ² (measured at 365 nm) using a contact aligner (PLA-501 manufactured by Canon Inc.) and a gray scale as a mask.
Was exposed.

After the exposure, a heat treatment was performed at 130 ° C. for 2 minutes. At this time, the film thickness was 4.3 μm.

Subsequently, an alkaline developer (NMD manufactured by Tokyo Ohka)
-3) for 1 minute for development.

An image remained when the exposure amount was 150 mJ / cm ² or more. The film thickness at an exposure amount of 600 mJ / cm ² was 3.7 μm.

Comparative Example 5 g of triethylamine and a polyamic acid solution (A) were mixed. This solution was spin-coated on a 4-inch silicon wafer. Next, heat treatment was performed at 100 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). At this time, the film thickness was 5 μm.

After the heat treatment, 600 mJ / cm ² (measured at 365 nm) using a contact aligner (PLA-501 manufactured by Canon Inc.) and a gray scale as a mask.
Was exposed.

After the exposure, a heat treatment was performed at 130 ° C. for 2 minutes. At this time, the film thickness was 4.3 μm.

Subsequently, an alkali developer (NMD manufactured by Tokyo Ohka)
-3) was immersed for 1 minute to develop, but did not dissolve at all.

[0079]

According to the present invention, a novel photosensitive polyimide which can be developed with an alkaline aqueous solution or the like without using an organic solvent as a developer can be obtained.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI G03F 7/031 G03F 7/031 7/037 501 7/037 501 H01L 21/027 H01L 21/312 B 21/312 H05K 3/28 D H05K 3/28 H01L 21/30 502R (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F 7/038 504 CA (STN) REGISTRY (STN)

Claims (3)

(57) [Claims] 1. A polymer having a structural unit represented by the following general formula [1], a compound represented by the following general formula [2], and an electron-donating photoamine generating auxiliary. Actinic radiation sensitive polymer composition. Embedded image (R ¹ is a trivalent or tetravalent organic group having at least 2 carbon atoms, R ² is a divalent organic group having at least 2 carbon atoms, R ³ is hydrogen, an alkali metal ion, Represents an ammonium ion or an organic group having 1 to 20 carbon atoms, and n is 1 or 2.) (R ⁴ —OCO—NH) _m —R ⁵ [2] [R ⁴ is at least one in the molecule. Is represented by the following general formula [3]: (R ⁶ represents hydrogen or an organic group having 1 to 10 carbon atoms.
l is an integer of 0-3. ), And the others represent organic groups having 1 to 20 carbon atoms. R ⁵ represents one or more monovalent to tetravalent organic group having a carbon number. m is an integer of 1 to 4. ] 2. The method according to claim 1, wherein the electron-donating photoamine generating auxiliary is at least one selected from the group consisting of anthracenes, xanthenes, triphenylmethanes, phthalocyanines, porphyrins and acridines. Item 1
The actinic radiation-sensitive polymer composition according to the above. 3. The actinic ray-sensitive polymer composition according to claim 2, wherein the electron donating photoamine generating auxiliary is an anthracene represented by the following general formula [4]. Embedded image (R ⁷ and R ⁸ represent an organic group having 1 to 20 carbon atoms. R ⁹ represents hydrogen, an organic group having 1 to 20 carbon atoms, a nitro group, an amino group,
Represents a hydroxyl group, a sulfonic acid group or a halogen. p is 1 to
It is an integer of 3. )