JPH02154262A - Photosensitive resin composition and photosensitive element using this photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive resin compsn. capable of providing a photosensitive element having high photosensitivity even in a form of thick film by incorporating a photoinitiating mixture contg. a specified polymer, a specified amino benzilidene carbonyl compd., and a specified N-aryl-alpha-amino acid into a compsn. CONSTITUTION:A polymer having recurrent units expressed by the formula I, an amino benzylidene carbonyl compd. expressed by the formula II, and an N-aryl-alpha-amino acid expressed by the formula III, are incorporated in a compsn. In the formula II, each R3-R6 is an alkyl group; each R7 and R8 is an H atom, or a cyano group, etc.; each R9-R16 is an H atom, Cl atom, etc.; X is an O atom or S atom, etc. In the formula III, each R17 and R21 is an H atom, cyano group, etc.; R22 is an H atom, alkyl group, etc.; each R23 and R24 is an H atom or an alkyl group. Thus, a photosensitive resin compsn. capable of providing a photosensitive element having high photosensitivity even in a form of thick film is obtd.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a photosensitive resin composition with excellent heat resistance that can have high photosensitivity even when used as a thick film, and a photosensitive resin composition using the same. Concerning photosensitive elements.

(Conventional technology) Conventionally, heat-resistant polymers typified by polyimide.

Heat-resistant,! Due to its excellent chemical and mechanical properties, it is used as a forming material for insulating films and insulating films for solid-state devices in the semiconductor industry, and as a resist material for forming semiconductor integrated circuits. In the field of printed wiring boards, it is also widely used as a resist material for forming circuit patterns on boards, or as an insulating material between the eyebrows.

In recent years, in the semiconductor industry, inorganic materials have traditionally been used as interlayer insulation materials.

Organic materials with excellent heat resistance, such as polyimide resin, have been mainly used to take advantage of their properties.

However, pattern formation of semiconductor integrated circuits and circuits on printed circuit boards involves forming a film of resist material on the surface of the base material, exposing predetermined areas to light, removing unnecessary areas by etching, etc.
Since pattern formation is performed through a complex and diverse process such as cleaning the surface of the base material, a heat-resistant resist material that can be used as an insulating material even after the pattern is formed by exposure and development. The development of photosensitive materials is aspirational.

As these materials, for example, heat-resistant photosensitive materials using a base polymer such as photosensitive polyimide or cyclized polybutadiene have been proposed.

Photosensitive polyimide has attracted particular attention because of its excellent heat resistance and the ease with which impurities can be removed.

Examples of such photosensitive polyimides include 9, for example,
9-17374, a system consisting of a polyimide precursor and a dichromate was first proposed, but while this material has advantages such as practical photosensitivity and high film-forming ability.

It lacked storage stability and had drawbacks such as residual chromium ions in the polyimide, so it was not put into practical use.

As another example, a photosensitive polyimide precursor has been proposed in which a photosensitive group is introduced into a polyimide precursor through an ester bond, according to 1% Publication No. 30207/1983. is low and insufficient for practical use.

On the other hand, according to Japanese Patent Application Laid-Open No. 168942/1983.

A photosensitive composition containing a mixture of a polyamic acid and an amine having a photoactive functional group as a main component has been proposed.

However, this photosensitive composition has the problem that as the film thickness increases, the photosensitivity decreases and the composition swells during development.

Furthermore, a photosensitive composition is proposed in JP-A-59-84936, in which a long-wavelength sensitizer is blended into a composition mainly composed of polyamic acid having a double bond in its side chain. However, similar to the above, this thick film had low photosensitivity and was insufficient for practical use.

(Problems to be Solved by the Invention) The present invention has been made in view of the problems of the prior art as described above. The present invention provides a photosensitive resin composition having excellent properties and a photosensitive element using the same.

(i!Means for solving the problem) The present invention is.

A polymer having a repeating unit represented by (formation + 1) (wherein R1 is a tetravalent aromatic group, R2 is a divalent aromatic group, and Y is a monovalent ethylenically unsaturated group). an organic group having the group nl''tO or 1°m is 1 or 2 and n −1−m = 2) and (aminobenzylidenecarbonyl represented by the Bl − form (If)) The compound is a dihydrogen atom, a cyano group, an alkoxycarbonyl group, an alkyl group, or an aryl group.

R2゜* no * Ru + R+s + R14e
R+s and aSS are each independently a hydrogen atom, a chlorine atom, and a bromine atom.

is an alkyl group, aryl group or alkoxy group, and
is an oxygen atom, a sulfur atom, or an alkyl group.

an aralkyl group, an aryl group, an aroyl group, an acyl group, or a nitrogen atom substituted with a hydrogen atom) and -form (N-aryl-α-amino acid represented by I[Il).

(In the formula, 几3.R4, R5 and R are each independently an alkyl group, and R7 and M are each independently a hydrogen group. an atom, a cyan group, an alkyl group, or a halogen atom, and R22 is a hydrogen atom, an alkyl group, a cycloalkyl group, or a hydroxyalkyl group.

Alkoxyalkyl group, aminoalkyl group or 71J
-R23 and R24 are each independently a hydrogen atom or an alkyl group.

The present invention also relates to a photosensitive element formed by laminating the photosensitive resin composition on a substrate.

The polymer having a repeating unit represented by the general formula (1) of component (1) used in the present invention is 9, for example, the following general 2 (2).
(2) It is obtained by polycondensing a compound represented by l- or (Vl) and an aromatic diamine.

(However, in Formula 1, R3 and Roll are tetravalent aromatic groups, and X is a halogen atom or a hydroxyl group.

(Y is an organic group having a monovalent ethylenically unsaturated group) The reaction between the compound represented by one form or (V) and the aromatic diamine is carried out at a temperature of 0 to 100°C in an inert organic solvent. The temperature is preferably 5 to 60°C, and more preferably 5 to 60°C.

- The compound represented by the form (!V) or (V) and the aromatic diamine are mixed in a ratio of 0.8/1 to 1.2/l (the compound represented by the form (!V) or (V)/aromatic diamine).
It is preferable to use a molar ratio), and it is more preferable to use an approximately equimolar amount.

In addition, the reaction between a compound represented by the -form (■) or (Vl) and an aromatic diamine can be carried out using a carbodiimide-type dehydration condensing agent 1, such as dicyclohexylcarbodiimide, and a dehalogenating agent such as amines, 9 such as pyridine or triethylamine. This is facilitated by using .

As the organic solvent used in the above reaction, the general formula (
Polar solvents that completely dissolve the polymer having repeating units represented by 1) are generally preferred.

For example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea.

Phoxamethyl phosphate triamide, r-butyrolactone,
N,N-dimethylpropyleneurea, N,N-dimethylethyleneurea, and the like.

Further, in order to isolate the polymer from the above-mentioned reaction mixture in some cases, it is preferable to add the reaction mixture to alcohol or water little by little.

The solid thus obtained can be purified by repeating dissolving it in the organic solvent used for the reaction, adding it to alcohol or water, and reprecipitating it.

The compound represented by the general formula (1v) or (V) is obtained by semi-esterifying an aromatic tetracarboxylic dianhydride by completely or partially ring-opening it with a hydroxy compound having an ethylenically unsaturated group. It can be obtained from K or further by acid halogenating the half-esterified product with thionyl chloride, phosphorus pentachloride, or the like. The reaction between an aromatic tetracarboxylic dianhydride and a hydroxy compound having an ethylenically unsaturated group can be performed using, for example, pyridine,
This can be promoted by adding dimethylaminopyridine or the like.

Examples of the aromatic tetracarboxylic dianhydride used in the present invention include 9, for example, pyromellitic dianhydride, 3.3
', 4.4'-hensiphenotetracarboxylic dianhydride, 3.3:4.4'-biphenyltetracarboxylic dianhydride, meta-terphenyl-3,a, "4.4"-tetra Carboxylic dianhydride, para-terphenyl-3,3
,"4.4"-tetracarboxylic dianhydride, 1,2,5
．． 6-naphthalenetetracarboxylic dianhydride, 2,3,
6゜7-naphthalenetetracarboxylic dianhydride, 2
,3゜5.6-pyridinetetracarboxylic dianhydride, 1
,4゜5.8-naphthalene/tetracarboxylic dianhydride,
3°4,9.10-perylenetetracarboxylic dianhydride.

4.4'-sulfonyl cyphthalic dianhydride and the like.

Examples of the hydroxy compound having an ethylenically unsaturated group used in the present invention include trimethylolpropane diacrylate, trimethyolpropane dimethacrylate, trimethylolethane diacrylate, trimethylolethane dimethacrylate, pentaerythritol triacrylate, Pentaerythritol trimethacrylate.

2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, allyl alcohol, glycerin diallyl ether , trimethylolpropane diallyl ether, trino'F-rollethane diallyl ether, pentaerythritol diallyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, dicrycerol triallyl ether, crotyl alcohol, vinylphenol, cinnamyl alcohol, allyl phenol,
0-Cinnamylphenol.

(RFiH or CHs).

(RFiH or CHs) etc.

These hydroxy compounds alone have 2f! It is also possible to use a combination of the above types.

An aromatic diamine which yields a polymer having a repeating unit represented by the general formula (1) by polycondensation with a compound represented by the above-mentioned form (Seki or one form) '-diaminodiphenyl ether, a-
1'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-cyaminocyphenylsulfide, benzidine, meta-phenylenediamine, para-phenylenediamine, 1,5-naphthalene /diamine, 2.6-naphthalene/diamine, 2.2-bis(4-aminophenoxyphenyl)furopane.

Bis(4-aminophenoxyphenyl)sulfone.

2.2-bis(p-aminophenyl)hexafluoropropane and the like are used.

These aromatic diamines can be used alone or in combination of two or more.

Furthermore, when obtaining the polyimide precursor represented by the -format (I), diaminosiloxane can be used in combination to the extent that heat resistance is not reduced.

Examples of this compound include 1.

Examples include.

In addition, diaminoamide compounds represented by one formula can also be used.

(However, pAr is an aromatic group, Z is Sox or CO, and one amino group and Z -NH3 are located in the ortho position to each other.) This compound includes 1, for example, 4,4'-diaminodiphenyl ether- 3-sulfonamide)', 3,4'-diaminodiphenyl ether-4-sulfonamide, containing 4
'-Diaminodiphenyl ether-3'-sulfonamide, &3'-diaminodiphenyl ether-4-sulfonamide, 4,4'-diaminodiphenylmethane-3-
Sulfonamide, 4'-diaminodiphenylmethane-
4-sulfonamide, 3゜4'-diaminodiphenylmethane-3'-sulfonamide, 3.3'-diaminodiphenylmethane-4-sulfonamide, 4.4'-diaminodiphenylsulfone-3-sulfonamide, 3.4
'-Diaminodiphenylsulfone-4-sulfonamide, a,4'-diaminodiphenylsulfone-3'-sulfonamide.

3,3'-diaminodiphenylsulfone-4-sulfonamide, 4,4'-diaminodiphenylsulfide-3-sulfonamide, 4'-diaminodiphenylsulfide-4-sulfonamide, &3'-diaminodiphenylsulfide-4- Sulfonamide, λ4'-
Diaminodiphenyl sulfide-3'-sulfonamide, 1,4-diaminobenzene-2-sulfonamide,
44'-diaminodiphenyl ether-3-carbonamide, 3.4'-diaminodiphenyl ether-4-carbonamide, 3゜4'-diaminodiphenyl ether-3'-carbonamide, 3'-diaminodiphenyl ether-4-carbonamide, 4.4'-diaminodiphenylmethane-3-carbonamide, 3.4'-diaminodiphenylmethane-4-carbonamide, 14'-
Diaminodiphenylmethane-3'-carbonamide, 3
゜3'-diaminodiphenylmethane-4-carbonamide, 4,4'-diaminodiphenylsulfone-3-carbonamide, 3,4'-diaminodiphenylsulfone-
4-carbonamide, 14'-diaminodiphenylsulfone-3'-carbonamide)'', a3'-diaminodiphenylsulfone-4-carbonamide.

4.4'-diaminodiphenyl sulfide-3-carbonamide, &4'-diaminodiphenyl sulfide-4-carbonamide, 13'-diaminodiphenyl sulfide-4-carbonamide, 4'-diaminodiphenyl sulfide-3'-sulfone Ryo Mido, 1,4
-diaminobenzene-2-carbonamide and the like.

In the photoinitiator system of component (B) used in the present invention, an aminobenzylidene carbonyl compound represented by the above-mentioned format (II) is used. ) No. 16
It can be easily synthesized by aldol-type condensation of a cyclohexanone derivative and p-aminobenzaldehyde according to the method detailed in Volumes I/c.

Examples of the aminobenzylidene carbonyl compound represented by one form + II) include 1, for example, slobis (p-N, N
-dimethylaminobenzylidene)-4-oxocyclohexanone, 2,6-bis(p-N,N-diethylaminobenzylidene)-4-oxocyclohexanone, z6-
Bis(p-N,N-dimethylaminobenzylidene)-
4-thiacyclohexanone, 2,6-bis(p Ne
N-diethylaminobenzylidene)-4-thiacyclohexanone, 2,6-bix(p-N,N-dimethylaminobenzylidene)-4-methyl-4-azacyclohexanone 12+6-his(p-N,N-diethylaminobenzylidene) )-4-methyl-4-azacyclohexanone, Z
6-bis(p-N,N-dimethylaminebenzylidene)
-4-Ethyl-4-azacyclohexanone, 2,6-bis(p-NUN-diethylaminobenzylidene)-4-
Ethyl-4-azasifhexanone, Z6-bis(4'
-N,N-diethylamino-2'-methoxybenzylidene)-4-oxocyclohexanone.

2.6-bis(4'-N,N-diethylamino-2'-
methylbenzylidene)-4-oxocyclohexanone,
Slow bis(4'-N, N-diethylamine-2'-methoxybenzylidene)-4-thiacyclohexanone, Slow bis < z -N, N-diethylamino-τ-methylbenzylidene)-4-+acyclohexanone, 2.6
-bis(4'-N, N-diethylamino-2'-methoxybenzylidene)-4-methyl-4-azacyclohexanone, slow bis(4'-N.

N-diethylamine-2'-methylbenzylidene)-4
-Methyl-4-azacyclohexanone, 2,6-bis(
4'-N,N-diethylamino-2'-methoxybenzylidene)-4-azacyclohexanone.

2.6-bis(4'=N, N-diethylamine-2'-
methylbenzylidene)-4-ethyl-4-azacyclohexanone, etc., but from the viewpoint of sensitivity, X in general formula (II) is an alkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms.
Compounds in which the nitrogen atom is substituted with 12 aralkyl groups are preferred.

The above aminobenzylidene carbonyl compound is.

They may be used alone or in combination of two or more.

The photoinitiator system of the CB+ component used in the present invention includes N-aryl-α represented by the above general formula (It).
The N-aryl-α-amino acid can be easily synthesized from the reaction of 2, for example, anilines and monochloroacetic acid.

As the N-aryl-α-amino acid, for example:

N-phenyl chrysin, N-methyl-N-phenyl chrysin. N-ethyl-N-phenylglycine.

N-(n-7'rovir)-N-phenylchrysine.

N-(n-butyl)-N-phenylglycine, N-(2
-methoxyethyl)-N-phenylglycine, N-methyl-N-phenylalanine, N-ethyl-N-phenylalanine, N-(n-7'robil)-N-phenylalanine, N-(n-7'fk)- N-phenylalanine, N-methyl-N-phenylvaline, N-methyl-
N-phenylleucine.

N-methyl-N-(p-tolyl)glycine, N-ethyl-N-(p-1lyl)glycine, N-(n-brobyl)
-N-(p-tolyl)glycine, N-(n-butyl)-
N-(p-4yl)glycine.

N-methyl-N-(p-chlorophenyl)glycine, N
-ethyl-N-(p-chlorophenyl)chrysin, N-
(p-chlorophenyl)ri+)syn.

N-(p-cyanophenyl)glycine, N-(p-bromophenyl)glycine, N-ethyl-N-(p-cyanophenyl)glycine, N-(n-propyl)-N-(p
-chlorophenyl)glycine.

N-methyl-N-(p-bromophenyl)glycine, N
-ethyl-N-(p-7'romophenyl)chrysin, N
-(n-butyl)-N-(p-bromophenyl)glycine, N,N-diphenylglycine.

Examples include N-methyl-N-(p-iodophenyl)glycine, but those having a cyano group or a phenyl group substituted with a halogen are preferred from the viewpoint of sensitivity and storage stability.

N-aryl-α represented by the above general formula (III)
-Amino acids may be used alone or in combination of two or more.

From the viewpoint of the sensitivity of the photosensitive resin composition and the heat resistance of the coating film, the amount of these photoinitiator systems to be used is determined based on 100 parts of the photosensitive resin composition excluding the organic solvent and photoinitiator system. 9 usually 0.01 to 301 parts, preferably 0.1
~10 parts by weight.

Further, in order to improve the thermal stability of the photosensitive resin composition, a known thermal polymerization inhibitor may be present.

Examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, phenothiazine, chloranyl unaphthylamine,
β-naphthol, z6-di-t-butyl-p-cresol, pyridine, nitrobenzene, p-toluidine, methylene blue 2.2'-methylenebis(4-methyl-6-
t-butylphenol), 2,2'-methylenebis(4
-ethyl-6-t-butylphenol) and the like.

In the present invention, a polymerizable unsaturated compound can be used as necessary.

Examples of polymerizable unsaturated compounds include acrylic acid, methyl acrylate, and ethyl acrylate.

n-propyl acrylate, inglovir acrylate, n-butyl acrylate, inbutyl acrylate,
Cyclohexyl acrylate, benzyl acrylate,
Calpitol acrylate.

Methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl IJL/-t,
Dipropylene glycol diacrylate #z2-bis-(4-acryloxyjethoxyphenyl)propane,
Z2-bis-(4-acryloxypropylxyphenyl)propane, trimethylolpropane diacrylate,
Pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, triacryl formal, tetramethylolmethanetetraacrylate, tris(2-hydroxyethyl)isocyanuric acid.

(n is an integer from 1 to 30) Methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, z2-bis-(4-
methacryloxyjethoxyphenyl) 7'opan, trimethylolpronochloride dimethacrylate, pentaerythritol dimethacrylate.

Trimethylolpropane triacrylate, pentaerythritol trimethacrylate, tetramethylolmethanetetramethacrylate, tris(2-hydroxyethyl)in cyanuric acid.

[1 1←CH2CH2O+FFr-C-CH=CHz.

(n, m are integers where n 10 m is 2 to 30) (n
is an integer from 1 to 30).

O -1+CHzCHzO-+FFV-CCCH, 2H3 (n and m are integers from 1 to 30).

HzBr etc. can be mentioned.

In the present invention, a photocrosslinking agent can be used as necessary.

For example, 1 as a photocrosslinking agent.

Examples include aromatic azide compounds such as.

The photosensitive resin composition of the present invention can contain an organic solvent.

Examples of such organic solvents include 1, for example, the above-mentioned general formula (
A solvent or the like that completely dissolves the polymer having the repeating unit represented by 1) can be used.

In such a case, the organic solvent used f is 10 to 95! of the photosensitive resin composition. It is preferable to set it as fit%, and 30
More preferably, the content is 80% by weight.

The photosensitive resin composition of the present invention can be patterned by conventional microfabrication techniques.

The photosensitive resin composition of the present invention is applied onto a support substrate such as a glass substrate, silicon wafer, or copper-clad laminate by means such as spin coating using a spinner, dipping, or spraying, and is dried to form a coating film. be able to.

The thickness of the coating film can be adjusted by adjusting the coating means 9, the solid content concentration of the phenol in the photosensitive polymer composition of the present invention, the viscosity, etc.

In addition, a photosensitive resin composition is applied to a flexible substrate 9, for example, a photosensitive element having a sandwich structure is prepared in advance, and the cover sheet of this photosensitive element is peeled off to form a coating film on the supporting substrate to be coated. It is also possible.

The coating film on the support substrate was then irradiated with a light source.

A relief pattern is obtained by dissolving and removing the unexposed areas with a developer.

At this time, as a light source, for example, ultraviolet rays, visible light, radiation, etc. can be used.

Examples of the developer include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, dimethylimidazolidinone. .

Polar solvents such as N-benzyl-2-pyrrolidone, N-acetyl-C-caprolactam alone or non-solvents of polyamic acids such as methanol, ethanol, isopropyl alcohol, benzene.

It can be used as a mixed solution with acetone, methyl ethyl ketone, cyclohexanone, cyclopentanone, toluene, xylene, methyl selon rub, water, a basic compound, a basic aqueous solution, etc.

As a basic compound, for example, monoethanolamine,
Jetanolamine, triethanolamine, tetramethylammonium hydroxide.

Examples include sodium carbonate, potassium carbonate, and sodium phosphate.

When preparing a basic aqueous solution, the amount of the basic compound used is usually 0.0001 to 3014 parts by weight per 100 parts by weight of water.
It is preferable to use 0.05 to 5 parts by weight, more preferably 0.05 to 5 parts by weight.

Next, the relief pattern formed by development is
The developer solution can be removed by cleaning with a rinse solution.

As the rinsing solution, a non-solvent of polyamic acid having good miscibility with the developer is used, such as methanol, ethanol, inglobil alcohol, benzene, toluene, cylene, and methyl cellosol.

Examples include water.

What is the relief pattern obtained by the above treatment?

It is a precursor of polyimide, and when heated at 150 to 450°C, it becomes a heat-resistant relief pattern with imide rings and other cyclic groups.

(Example) The present invention will be explained below using Examples, Reference Examples, and Comparative Examples. Chi means heavy f chi.

Reference Example 1 Synthesis of polymer having repeating unit gold represented by general formula (1) 2 g of benzophenone tetracarboxylic dianhydride 3Z (o
, imol) were added with 200 ml of NMP and 26.09 (0.2 mol) of 2-hydroxymethacrylate, and the mixture was stirred at room temperature for 12 hours. To this solution, 35 g of thionyl chloride was added dropwise over 1 hour while cooling with water, followed by stirring at room temperature for 2 hours. 20.09 (0.1 mol) of diaminodiphenyl ether was added to this solution and stirred for 8 hours.

Furthermore, 40 ml of ethanol was added and stirred for 4 hours.
Thereafter, when the mixture was slowly poured into water in No. 51, a thread-like solid substance was precipitated. This was designated as polymer PI-1.

Reference Example 2 λ6-bis(p-N,N-diethylaminobenzylidene)-4-methyl-4-azacyclohexanone (K-1)
Synthesis of N-methyl-4-piperide 72G<17.7mmol)
and p-N,N-diethylaminobenzaldehyde6.
Put 26 g (35.4 mmol) in a 100 ml eggplant-shaped flask, add 50 mj' of methanol in which 0.59 sodium hydroxide was dissolved, and add a magnetic stirrer and stir while turning on a reflux condenser. The mixture was heated under reflux for about 1 hour. After cooling, the precipitated orange crystals were separated and thoroughly washed with methanol. It was purified by recrystallization from benzene/chloroform solvent.

2.6-bis(p-diethylaminobenzylidene)-4
-Oxocyclohexanone (K-2) was also synthesized in the same manner.

The H'-NMII data of the aminobenzylidenecarbonyl compound thus synthesized (deuterated chloroform was used as the solvent and tetramethylsilane was used as the internal standard) and the UV-visible absorption characteristics in methanol are shown in Table 3 and Table 3, respectively. 4.

Examples 1 to 8 Polymer PI-1tog obtained in Reference Example 1 was converted into N-methyl-2
- Add pyrrolidone 259 to make a solution.

The indicated weights of each photoinitiator and photocrosslinking agent shown in Table 1 were added to obtain a homogeneous solution for use in Examples 1-8.

Each of these solutions was filtered, dropped onto a silicon wafer, and spin-coded for 30 seconds at a rotation speed of 1,500 to 2,500 rpm. The resulting coating film was dried at 80° C. for 10 minutes, and the thickness of the coating film was measured. Next, the coating film was exposed for 80 seconds to an ultra-high pressure mercury lamp (8 mW/cm'') using a through-hole test pattern manufactured by Dainippon Printing Co., Ltd.

After that, immersion development was performed with a mixed solution consisting of 3 volumes of N-methyl-2-pyrrolidone, 4 volumes of mefk alcohol, and 3 volumes of 1% aqueous tetramethylammonium hydroxide solution.
It was rinsed with water and dried with air sougere. The resolution was determined by measuring the maximum size of the through holes.

The cured state of the pattern was examined by the residual film rate of the coating film after development (thickness of the coating film after development÷thickness of the coating film before development×100).

Further, the coating film was heat-treated at 350° C. for 1 hour in a nitrogen atmosphere to produce a film, and its thermal decomposition onset temperature was investigated. The results obtained are shown in Table 1.

Comparative Examples 1 to 4 Each photoinitiator system and polymerizable unsaturated compound shown in Table 2 were added to the polymer PI-IK to obtain a uniform solution to be used in Comparative Examples 1 to 4. Each of these solutions.

Filter it and drop it onto a silicon wafer.

Spin code was performed at a rotation speed of 1500 rpm for 30 seconds.

The resulting coating film was dried at 80'C for 10 minutes, and the thickness of the coating film was measured.

The properties of this coating film were investigated in the same manner as in Examples 1-4.

The results obtained are shown in Table 2.　　　　　　.

Hereinafter, 5:1τ1 Table 4 Ultraviolet-visible absorption characteristics (in MeOH) (Effects of the invention) The photosensitive resin composition of the present invention and the photosensitive element using the same have high light absorption characteristics, especially when used as a thick film. It can be sensitive and has excellent heat resistance.

Claims (1)

[Claims] 1. (A) A polymer having a repeating unit represented by the general formula (I) ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (I) (However, in the formula, R_1 is a tetravalent aromatic group, R_2 is a divalent aromatic group, Y is an organic group having a monovalent ethylenically unsaturated group, n is 0 or 1, m is 1 or 2, and n+m=2. and (B) an aminobenzylidenecarbonyl compound represented by the general formula (II) ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_3, R_4, R_5 and R_6 are each independently an alkyl group. R_7 and R_8 are each independently a hydrogen atom, a cyano group, an alkoxycarbonyl group, an alkyl group, or an aryl group, and R_9, R_
1_0, R_1_1, R_1_2, R_1_3, R_1
_4, R_1_5 and R_1_6 are each independently a hydrogen atom, chlorine atom, bromine atom, alkyl group, aryl group or alkoxy group, and X is an oxygen atom, a sulfur atom or an alkyl group, an aralkyl group, an aryl group, an aroyl group, an acyl group. or a nitrogen atom substituted with a hydrogen atom) and an N-aryl-α-amino acid represented by the general formula (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R_1_7, R_1_8, R_1_9, R_2
_0 and R_2_1 are each independently a hydrogen atom, a cyano group, an alkyl group, or a halogen atom, and R_2_
2 is a hydrogen atom, an alkyl group, a cycloalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an aminoalkyl group or an aryl group, and R_2_3 and R_2_4 are each independently a hydrogen atom or an alkyl group). A photosensitive resin composition made of 2. A photosensitive element obtained by laminating the photosensitive resin composition according to claim 1 on a substrate.