JPH0488347A - Chemical ray sensitive polymer composition - Google Patents

Abstract

PURPOSE:To enhance development speed and resolution and adhesion to a silicon wafer by forming the composition comprising of a specified polymer and a (meth)acrylate having an aromatic ring and a photopolymerization initiator. CONSTITUTION:This polymer composition comprises 100pts.wt. of the polymer composed essentially of structural units each represented by formula I, 20 - 200pts.wt. of acrylate and/or methacrylate having the aromatic ring, and 0.1 - 10pts.wt. of the photopolymerization initiator. In formula I, R1 is a >=2 C tri- or tetra-valent organic group; R2 is a >=2 C divalent organic group; R3 is H, an alkali metal counter ion, or 1 - 3 C alkyl; and (n) is 1 or 2, thus permitting the development speed sensitivity and adhesion to the silicon wafer to be enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photosensitive polyimide coating agent composition, and more particularly to a photosensitive polyimide composition that can form good images in a short development time. It is something.

[Prior Art] A photosensitive polyimide composition is a composition in which a compound containing a carbon-carbon double bond and an amino group or a quaternized salt thereof that can be dimerized or polymerized by actinic radiation is added to a polyamic acid ( For example, Japanese Patent Publication No. 59-52822) or a polyimide precursor composition in which photosensitivity is introduced into polyamic acid with an ester group (for example, U.S. Pat. No. 3,957,512).
No. 4,040,831) is known.

However, polyamic acid contains a carbon-carbon double bond that can be dimerized or polymerized by actinic radiation, an amino group, or
Compositions containing compounds containing graded salts have high resolution, good heat resistance, and can be easily converted into polyimide, but due to relatively long development times, they are difficult to use on wafers in the production of semiconductor devices. The disadvantage is that the processing time per sheet is long.

In addition, polyimide precursor compositions in which photosensitivity is introduced into polyamic acid with ester groups can be developed in a relatively short time, but in the case of fine patterns, the image swells and connects with adjacent images, resulting in poor heat resistance. It has disadvantages such as being relatively poor, requiring high temperatures of 400 degrees or more when converting to polyimide, being easily affected by the heat treatment atmosphere, and having poor adhesion to silicon wafers.

Furthermore, a polyfunctional acrylate with a molecular weight of 500 or less and a sensitizer are added to a polyimide precursor containing 5 to 50% by weight of high molecular weight siloxane diamine, thereby creating a photosensitive polyimide precursor with a small elastic modulus and low water absorption. It has been proposed to obtain (Japanese Unexamined Patent Publication No. 2-50161).

However, in the case of this invention, since it contains high molecular weight siloxane diamine, a decrease in heat resistance (the temperature at which thermal decomposition starts is about 430°C at most) and a decrease in mechanical properties such as strength and elongation are unavoidable. However, there is a problem in that the high heat resistance and excellent mechanical properties inherent to polyimide are impaired.

On the other hand, in the case of the present invention, if high molecular weight siloxane diamine is not copolymerized, phase separation occurs due to poor compatibility between the polyimide precursor and the polyfunctional acrylate, making it unusable.

[Problems to be Solved by the Invention] Therefore, an object of the present invention is to solve the problem without the above-mentioned drawbacks.
The object of the present invention is to provide a photosensitive polyimide composition that can be developed in a short time, has high resolution, has excellent adhesion to silicon wafers, and can be converted into polyimide at a low temperature of 400 degrees or less.

[Means to solve the problem] This object of the present invention is achieved by the following configuration.

(a) General formula % Formula %] (However, in the formula, R1 is a trivalent or tetravalent organic group having at least 2 or more carbon atoms, and R2 is a divalent organic group having at least 2 or more carbon atoms. , R3 represents hydrogen, an alkali metal counterion, or an alkyl group having 1 to 3 carbon atoms. n is 1 or 2).
0 parts by weight (b) Acrylic ester and/or methacrylic ester having an aromatic ring [2 volumes 0-200
Part by weight (C) Photoinitiator [3 pieces 0. 1 to 10 parts by weight of an actinic radiation-sensitive polymer composition.

In the present invention, a polymer having one structural unit is a polymer having a structure represented by the above general formula and having an imide ring or its geographical structure by heating or a suitable catalyst.
Hereinafter, it can be referred to as a polyimide-based polymer).

In the above structural unit [1], R+ is a trivalent or tetravalent organic group having at least two or more carbon atoms. In view of the heat resistance of the polyimide polymer, it is preferable that R has a structure in which the bond to the carbonyl group in the main chain of the polymer is directly formed from an aromatic heterocycle. Therefore, for R+,
Contains an aromatic ring or an aromatic heterocycle, and has 6 to 3 carbon atoms
A trivalent or tetravalent group of 0 is preferred.

Preferred specific examples of R1 include -(ra, -(raX -()-CF 3 (wherein
is selected from -co--o--c F3 SO2- and -. In the formula, the bond represents a bond with the carbonyl group of the polymer main chain, and the carbonyl group is located at the ortho position to the bond, but this bond is not shown in the above structural formula). However, it is not limited to this.

Further, in the polymer having the structural unit [1], R1 may be composed of only one type among these, or may be a copolymer composed of two or more types.

In the above structural unit [1], R2 is a divalent organic group having at least two or more carbon atoms, but from the viewpoint of heat resistance when made into a polyimide polymer, it is necessary to bond with the amide group of the polymer main chain. It is preferable to have a structure in which is directly formed from an aromatic ring or an aromatic heterocycle. Therefore, R2 is preferably a divalent group containing an aromatic ring or an aromatic heterocycle and having 6 to 30 carbon atoms.

Preferred specific examples of R2 include 10)-, (D-0-Ctope10 ((Ra0-6-H3). In the formula, the bond represents a bond with the amide group of the main chain) Examples include.

Further, these may have a nuclear substituent such as an amino group, an azide group, a carboxyl group, or a sulfonamide group within a range that does not adversely affect the heat resistance of the polyimide polymer.

Particularly preferred examples of those having these nuclear substituents include: and the like.

In the polymer having one structural unit, R2 may be composed of only one of these, or may be a copolymer composed of two or more of these.

Furthermore, in order to improve the adhesiveness of the polyimide polymer, it is also possible to copolymerize an aliphatic group having a siloxane bond as R2 within a range that does not reduce the heat resistance.

A preferred specific example is Examples include.

Specific examples of polymers containing structural unit [1] as main components include pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and 3.3'',4.4-benzophenonetetracarboxylic dianhydride. and 4.4′-diaminodiphenyl ether, 3, 3-, 4. 4-biphenyltetracarboxylic dianhydride and 4.4′-diaminodiphenyl ether, 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, pyromellitic dianhydride and 3.3-
．． 4゜4゛-benzophenonetetracarboxylic dianhydride and paraphenylenediamine, pyromellitic dianhydride and 3.3-. 4゜4'-biphenyltetracarboxylic dianhydride and paraphenylenediamine, 3.3-. 4.4--Diphenyl ether tetracarboxylic dianhydride and 4,4'-diaminodiphenyl ether, 3, 3-, 4. 4. --Polyamic acid synthesized from diphenyl ether tetracarboxylic dianhydride and paraphenylene diamine, pyromellitic dianhydride, 4,4'-diaminodiphenyl ether, and bis(3-aminopropyl)tetramethyldisiloxane, etc. is preferable. used.

As a polymer having the structural unit [1], the structural unit [1]
], or may be a copolymer or blend with other structural units. The type and amount of structural units used in the copolymerization are desirably selected within a range that does not significantly impair the heat resistance of the polyimide polymer obtained by the final heat treatment.

Acrylic ester having an aromatic ring and/or methacrylic ester having an aromatic ring in the present invention [
2. When the double bond of the acrylic group or methacrylic group of the compound is dimerized or multiplied by actinic irradiation and insolubilized in the solvent, the polyamide precursor of 1 is incorporated into the insolubilized component, and the polyamide precursor of 1. From this point of view, it is preferable that the acrylic ester or methacrylic ester having an aromatic ring has two or more acrylic or methacrylic groups. .

More preferably, the number is 3 to 4. If the number of acrylic or methacrylic groups is 6 or more, problems such as gelation during standing may occur, which is not preferable.

In addition, the molecular weight of component [2] is preferably in the range of 200 to 800 from the viewpoint of scattering properties and prevention of deterioration of photosensitivity in the heat treatment step performed to obtain polyimide images. .

It is important that component [2] has an aromatic ring; if an acrylic ester or methacrylic ester that does not have an aromatic ring is used, the compatibility with the aromatic polyimide precursor will be extremely poor. This is not desirable.

The aromatic ring of the compound is an aromatic ring such as a naphthalene ring, anthracene ring, pyrene ring, biphenyl group, or terphenyl group, more preferably a benzene ring directly, or an alkylene group, or a hydroxyl group, a ketone group, or an ester. Any acrylic acid or methacrylic acid derivative may be indirectly bonded with an ester bond through a divalent organic group having a group, etc., but due to compatibility with the polymer, acrylic acid or methacrylic acid derivative is The number of carbon atoms in the organic groups bonded together is preferably 10 or less, more preferably 5 or less. Also,
Those having 1 to 4 polar groups such as ketone groups, ester groups, hydroxyl groups, and carboxyl groups are more preferable from the viewpoint of compatibility with the polyimide precursor.

The aromatic ring in the present invention preferably has 12 or less carbon atoms, and more preferably has 6 carbon atoms, from the viewpoint of volatility during conversion into polyimide by heat treatment.

The acrylic ester or methacrylic ester [2] having an aromatic ring preferably used in the present invention includes those having a structure represented by the following general formula (1) or (2).

(R+ is hydrogen, an alkyl group having 1 to 10 carbon atoms, or a monovalent organic group having at least one group selected from a hydroxyl group, a ketone group, and an ester group, R
2. R4 is an alkylene group having 1 to 5 carbon atoms, or a divalent organic group having at least one group selected from hydroxyl group, ketone group, and ester group, R3 is hydrogen or methyl group, and R5 is carbon number A monovalent organic group of 1 to 5 or -Ra -OCo CR3=CH, Re is hydrogen or a divalent organic group of 1 to 10 carbon atoms or -CH2-N -Ra -0-CO-CR3= CH2
selected from. ) Examples of acrylic esters having an aromatic ring used in the present invention include 2-hydroxy-3-phenoxypropyl acrylate, phenoxyethyl acrylate, 2-acryloyloxyethylphthalic acid, and 2-
Examples of methacrylic esters having an aromatic ring include acryloyloxyethyl-2-hydroxyethylphthalic acid, methacrylic esters, 2-hydroxyethylphthalic acid, etc.
hydroxy-3-phenoxypropyl methacrylate,
Phenoxyethyl methacrylate, 2-methacryloyloxyethyl phthalate, 2-methacryloyloxyethyl-2-hydroxyethylphthalic acid, condensate of benzylamine and 2 times the mole of glycidyl methacrylate, and 4 times the mole of 2,4-xylylenediamine Examples include, but are not limited to, condensates with molar glycidyl methacrylate.

Only one type of acrylic ester or methacrylic ester [2] having an aromatic group may be used, or two or more types may be used in combination.

The acrylic ester and/or methacrylic ester [2] having an aromatic group is preferably added in a total amount of 20% by weight or more, more preferably 50-150% by weight
It is best to add it in the proportion of If the amount is less than 20% by weight, sufficient photosensitive performance will not be obtained, and if the amount added exceeds 150% by weight, the composition may deteriorate due to compatibility with the polyimide precursor, dark reaction, etc., resulting in gelation when left. This is not preferable because it may cause stability problems, or it may remain in the polyimide film without being completely scattered when it is converted into polyimide by heat treatment after image formation, resulting in a decrease in heat resistance and mechanical properties.

As the photoinitiator [3], known ones can be used. Suitable photoinitiators are those that generate radicals with visible or ultraviolet light, and specific examples include benzophenone, benzoin isopropyl ether, Michler's ketone, 3.3''-carbonyl-bis-(7-diethylamino)coumarin, 7-diethylamino-3-benzoincmarine, N-phenyldiethanolamine, N-phenylglycine, 4.4-bis(diethylamino)benzophenone, 2.6-di(4'-azidobenzal)-4-
Carboxycyclohexanone, 2゜6-di(4-azidobenzal)-4-hydroxycyclohexanone, 4
-azidobenzalacetophenone and the like.

Examples include, but are not limited to, the following.

Only one type of photoinitiator [3] may be used, or two types may be used.
One or more types may be used in combination.

The photoinitiator [3] is desirably added in a total amount of 0.1 to 30% or more based on the weight of the polymer whose main component is 1 structural unit, more preferably 0.5% or more based on the weight of the polymer.
It is preferable to add it in a proportion of not less than 10% by weight.

If it is outside this range, it may adversely affect the developability and stability of the composition, so care must be taken.

Furthermore, in order to improve photosensitivity, amines with double bonds such as N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, or N, N-dimethylaminopropyl methacrylamide are used as structural units [1]. It can be added in an amount of 5 to 20% by weight based on the polymer having as a main component.

An example of the method for producing the composition of the present invention will be explained. First, a diamine compound and an acid dianhydride are reacted in a solvent to obtain a polymer containing the structural unit [1] as a main component. Next, compounds [2] and [3] and other additives as required are dissolved and prepared in this solution. In addition, as the above-mentioned polymer, a solid polyamic acid polymer or a polymer separated and purified from the solution after the reaction may be redissolved and used.

As the solvent used in the above production method, polar solvents are preferably used from the viewpoint of solubility of the polymer, and aprotic polar solvents are particularly suitable. As the aprotic polar solvent, N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorotriamide, γ-butyrolactone, etc. are preferably used. As other additives, a sensitizer, a copolymer monomer, or an adhesion improver with the substrate may be included as long as the sensitivity and heat resistance are not significantly reduced.

When the amount of compound [3] mixed is 1 to 5% by weight, 4,4'-bis(diethylamino)benzophenone is preferably used as the sensitizer.

The actinic radiation sensitivity of the composition of the invention can be further improved by adding a sensitizer.

It is also preferably used to add monomaleimide, polymaleimide, or substituted products thereof as copolymerizable monomers.

Furthermore, in order to further improve photosensitivity, an organic group having an alcoholic hydroxyl group on the amino group such as N-phenyldiethanolamine and an aromatic secondary or Addition of a tertiary amino compound is also preferably used.

Next, a method of using the composition of the present invention will be explained.

The compositions of the present invention can be patterned using well-known microfabrication techniques using actinic radiation.

First, the composition of the present invention is coated on a suitable support. Possible coating methods include spin coating using a spinner, spray coating using a spray coater, dipping, printing, and roll coating. The coating film thickness can be adjusted by the coating means, solid content concentration, and viscosity of the composition.

Examples of the material for the support to which the composition of the present invention is applied include metals, glass, semiconductors, metal oxide insulators, and silicon nitride.

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

As an adhesion aid, oxypropyltrimethoxysilane,
Organosilicon compounds such as γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, aluminum monoethylacetoacetate diisopropylate, aluminum tris (acetylacetonate), etc. Aluminum chelate compounds such as or titanium chelate compounds such as titanium bis(acetylacenate) are preferably used.

Next, the composition of the present invention, which has become a coating film on the support, is irradiated with actinic radiation in a desired pattern. Examples of actinic radiation include X-rays, electron beams, ultraviolet rays, visible light, etc., but ultraviolet rays and short-wavelength visible rays, that is, wavelengths in the range of 200 to 500 nm are preferred.

Then, a relief pattern is obtained by dissolving and removing the unirradiated areas with a developer. It is preferable to select an appropriate developer according to the structure of the polymer.

The developer contains N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorotriamide, etc., which are the solvents of this composition. It can be used alone or as a mixture with a non-solvent composition such as methanol, ethanol, isopropyl alcohol, water, methylcarpitol, ethylcarpitol, toluene, xylene, or the like. Furthermore, aqueous ammonia and other alkaline aqueous solutions can also be used.

Development can be done by spraying your own developing solution onto the coating surface, immersing it in the developer, or applying ultrasonic waves while immersing it.
This can be done by a method such as spraying a developer while rotating the substrate.

It is desirable that the relief pattern formed by development is then washed with a rinsing solution. As the rinsing liquid, methanol, ethanol, isopropyl alcohol, butyl acetate, xylene, toluene, etc., which have good miscibility with the developer, are preferably used.

The relief pattern polymer obtained by the above treatment is a precursor of a heat-resistant polyimide polymer,
Heat treatment results in a heat-resistant polymer having imide rings and other cyclic structures. The heat treatment temperature is 135-400°C. Heat treatment is usually performed while increasing the temperature stepwise or continuously.

The degree of actinic radiation sensitivity of the composition of the present invention is determined by the grayscale (Kodak Pho) coating formed on the supporting substrate.
tographic 5tep tablet No2
The film was irradiated with light from a high-pressure mercury lamp (215tepS), and then developed, and the film roughness and film loss after development were examined.

The developability of the composition of the present invention was determined by measuring the dissolution time of the unexposed area and determining the ease of development.

The actinic radiation-sensitive polymer composition of the present invention can be applied to passivation films for semiconductors, buffer coat films for passivation films, interlayer insulating films for multilayer integrated circuits, interlayer insulating films and surface protection films for hybrid integrated circuits, and soldering for printed circuits. is used for forming protective films, alignment films for liquid crystals, interlayer insulating films for mounting boards, etc. Furthermore, it can be used as a highly heat-resistant photoresist for metal adhesion and dry etching processes.

It can be applied to other known uses of polyimide.

[Effects of the Invention] Since the actinic radiation-sensitive polymer composition of the present invention is constructed as described above, it can be developed in a short time and exhibits high sensitivity, unlike conventional photosensitive polyimides.

[Example] Next, the present invention will be specifically explained based on Examples.

Example 1 192°2 g of 4.4'-diaminodiphenyl ether,
1.9.94 g of 3-bis(3-aminopropyl)tetramethyldisiloxane was dissolved in 18 g of N-methyl-2-pyrrolidone.
90g to prepare an amine solution. Add 315.7% of benzophenonetetracarboxylic anhydride to this amine solution.
g was added, reacted at 50°C for 3 hours, and heated to 150°C at 25°C.
Poise's polymer solution (A) was obtained. This polymer solution (A
) and 8.63 g of N-phenyldiethanolamine.

17.25 g of 4-azidobenzalacetophenone.

A solution of 300 g (57.9% by weight) of a condensate of 2.4-xylylene diamine and 4 times the mole of glycidyl methacrylate dissolved in 250 g of N-methyl-2-pyrrolidone was mixed and filtered to produce a photosensitive polyimide precursor varnish. I got it.

The obtained solution was spin-coated onto a silicon wafer using a spinner, and then dried at 100° C. for 2 minutes using a vacuum adsorption hot plate (Model SCW636, manufactured by Dainippon Screen Co., Ltd.). The film thickness of this coating film was 10μ. Next, the coating film was exposed using an exposure machine (PLA-50 manufactured by Canon Co., Ltd.).
1F) and gray scale (Kodak Ph.
otographicstep tablet No2
Exposure was carried out for 1 minute via 215 teps). The intensity of the ultraviolet rays at this time was 8 mW/cm2 (365 nm).

Development was performed using N-methylpyrrolidone (70 parts) and methanol (
Immersion development was performed using a mixed solvent of 30 parts). The dissolution time of this unexposed area was very short, 20 seconds.

Development was continued for an additional 10 seconds immediately after the unexposed areas were dissolved. It was then rinsed with isopropanol for 20 seconds and spun dry with a spinner. When the film thickness was measured after development, it was 8.7μ (film reduction amount = 1.3μ)
. Thereafter, the film was heat-treated at 200° C. and 350° C. for 30 minutes each, and the pattern was observed using an optical microscope. At an exposure dose of 96 mJ or more, a good pattern with no film roughness was shown.

Example 2 108.1 g of paraphenylenediamine was converted into N-methyl-2
- An amine solution was prepared by dissolving in 1600 g of pyrrolidone. 292 g of biphenyltetracarboxylic anhydride was added to this amine solution and reacted at 50°C for 4 hours.
A 350 poise polymer solution (B) was obtained.

To this polymer solution (B), 16.0 g of 4-azidobenzalacetophenone, 16.0 g of N-phenylglycine, and 400.0 g of phenoxyethyl acrylate (100,
A solution of 0% by weight) dissolved in 300 g of N-methyl-2-pyrrolidone was mixed and filtered to obtain a varnish of a photosensitive polyimide precursor.

The obtained solution was spin-coated onto a silicon wafer using a spinner, and then dried at 90°C and 95°C for 2 minutes each using the vacuum adsorption hot plate described above to form a coating film (thickness: 10μ). Obtained.

Next, this coating film was exposed in the same manner as in Example 1, and then N-methylpyrrolidone (50 parts) and dimethylformamide (2 parts) were added.
Immersion development was performed using a mixed solvent of 0 parts) and methanol (30 parts). The dissolution time of this unexposed area was very short, 30 seconds.

Development was continued for an additional 15 seconds immediately after the unexposed areas were dissolved. It was then rinsed with isopropanol for 20 seconds and spun dry with a spinner. When the film thickness was measured after development, it was 8.2μ (film reduction amount = 1.8μ)
. Thereafter, heat treatment was carried out at 200° C. and 350° C. for 30 minutes each, and the pattern was observed using an optical microscope. The film showed a good pattern with no film roughening at an exposure dose of 144 mJ or more.

Example 3 17.25% of 3,3-carbonylbis(7-cy-nithylaminocoumarin) was added to the polymer solution (A) prepared in Example 1.
A solution prepared by dissolving 500 g (96.6% by weight) of 2-methacryloyloxyethyl-2-hydroxyethylphthalic acid in 250 g of N-methyl-2-pyrrolidone was mixed and filtered.

The obtained solution was spin-coated onto a silicon wafer using a spinner, and then dried at 80° C. for 1 hour to obtain a coating film with a thickness of 10 μm. Next, after exposing this coating film under the same conditions as described above, N-methylpyrrolidone (70 parts) and methanol (
Immersion development was performed using a mixed solvent of 30 parts). The dissolution time of this unexposed area was very short, 50 seconds.

Development was continued for an additional 20 seconds immediately after the unexposed areas were dissolved. It was then rinsed with isopropanol for 20 seconds and spun dry with a spinner. When the film thickness was measured after development, it was 8.0μ (film reduction amount = 2.0μ)
. Thereafter, the film was heat-treated at 200° C. and 350° C. for 30 minutes each, and the pattern was observed using an optical microscope. At an exposure dose of 144 mJ or more, a good pattern with no film roughness was shown.

Example 4 To the polymer solution (A) obtained in Example 1 were added 8.63 g of N-phenyldiethanolamine, 17.25 g of 4-azidobenzalacetophenone, and 300 g of 2-hydroxy-3-phenoxypropyl methacrylate (57,9 (wt%), dimethylaminoethyl methacrylate 50g with N
A solution dissolved in 250 g of -methyl-2-pyrrolidone was mixed and filtered to obtain a photosensitive polyimide precursor varnish.

The obtained solution was spin-coated onto a silicon wafer using a spinner, and then dried at 100° C. for 2 minutes using a similar vacuum suction type hot plate to obtain a coating film (thickness: 10 μm). Next, after exposure in the same manner, immersion development was performed using a mixed solvent of N-methylpyrrolidone (70 parts) and methanol (30 parts). The dissolution time of this unexposed area is 3
It was very short at 0 seconds.

Development was continued for an additional 10 seconds immediately after the unexposed areas were dissolved. It was then rinsed with isopropanol for 20 seconds and spun dry with a spinner. When the film thickness was measured after development, it was 8.8μ (film reduction amount = 1.3μ)
. Thereafter, the film was heat-treated at 200° C. and 350° C. for 30 minutes each, and the pattern was observed using an optical microscope. At an exposure dose of 48 mJ or more, a good pattern with no film roughness was shown.

Comparative Example 1 Condensation of 8.63 g of N-phenyldiethanolamine, 17.25 g of 4-azidobenzalacetophenone, 2.4-xylindiamine and 4 times the mole of glycidyl methacrylate was added to the polymer solution (A) prepared in Example 1. 50g of stuff
(9.6% by weight) to N-methyl-2-pyrrolidone 250
A varnish of a photosensitive polyimide precursor was obtained by mixing and filtering the solution dissolved in g.

Using this solution, coating film formation, exposure, and development were performed in the same manner as in Example 1. The dissolution time of this unexposed area is 20
seconds, and the image disappeared shortly thereafter.

Comparative Example 2 To the polymer solution (A) used in Example 1 were added 17.25 g of 4-azidobenzalacetophenone, 17.25 g of N-phenylglycine, 1200 g of glycidyl methacrylate (231,7
% by weight) in 250 g of N-methyl-2-pyrrolidone was mixed and filtered to obtain a varnish of a photosensitive polyimide precursor.

The obtained solution was spin-coated onto a silicon wafer using a spinner, and then dried at 90°C for 1 hour to form a coating (thickness: 10μ).
), and then exposed in the same manner. Next, immersion development was performed using a mixed solvent of N-methylpyrrolidone (70 parts) and methanol (30 parts), but dissolution did not occur and development could not be performed.

Moreover, the obtained solution gelled after 3 days at room temperature.

Claims (2)

[Claims] (1) (a) General formula -[CO-R_1-CONH-R_2-NH]-(CO
OR_3)_n (However, in the formula, R_1 is a trivalent or tetravalent organic group having at least two or more carbon atoms, R_2 is a divalent organic group having at least two or more carbon atoms, and R_3 is hydrogen or alkali. 100 parts by weight of a polymer whose main component is a structural unit [1] (representing a metal counterion or an alkyl group having 1 to 3 carbon atoms, where n is 1 or 2) (b) having an aromatic ring An actinic radiation-sensitive polymer composition comprising 20 to 200 parts by weight of an acrylic ester and/or a methacrylic ester [2] (C) and 0.1 to 10 parts by weight of a photoinitiator [3]. (2) The actinic radiation-sensitive polymer composition according to claim 1, wherein the acrylic ester or methacrylic ester having an aromatic ring has a structure represented by the following general formula (1) or (2). thing. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (R_1 is hydrogen, an alkyl group with 1 to 10 carbon atoms, or a hydroxyl group, a ketone group, or an ester group) A monovalent organic group having at least one group selected from R_2
, R_4 is an alkylene group having 1 to 5 carbon atoms, or a divalent organic group having at least one group selected from a hydroxyl group, a ketone group, and an ester group, R_3 is hydrogen or a methyl group, and R_5 is a carbon number 1 ~5 monovalent organic group or -R_4-O-CO-CR_3=CH, R
_6 is selected from hydrogen, a divalent organic group having 1 to 10 carbon atoms, or ▲numerical formula, chemical formula, table, etc.▼. )