JPH02154263A - 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 a thick film on a base material by incorporating a polymer having specified recurrent units and a specified photoinitiator into the compsn. CONSTITUTION:A polymer having recurrent units expressed by the formula I and a photoinitiator are contained in a photosensitive resin compsn. The compsn. is laminated on a flexible base body such as polyester film by coating and drying. Thus, a photosensitive element having a sandwich structure is prepd. previously by providing, if necessary a cover sheet comprising polyethylene, etc. on the lamination. The cover sheet is removed thereafter, thus, a coating film is formed on a base body. The thickness of the coating film can be adjusted by selecting a coating means, solid content and the viscosity of an varnish, etc. Thus, a thick film is formed on the surface of the base body.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a photosensitive resin composition that has excellent light transmittance and solubility and is capable of forming a thick film on a substrate surface, and a photosensitive resin composition using the same. Regarding elements.

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

Due to its excellent heat resistance, electrical and mechanical properties, it is used as a forming material for insulating films and passivation 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 substrates, or as an interlayer insulation material.

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 desired.

However, heat-resistant photosensitive materials using base polymers such as photosensitive polyimide, cyclized polybutadiene, etc. have been proposed as these materials, and the amount thereof is 1%.

, photosensitive polyimide has attracted particular attention because of its excellent 1 m 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 this material has advantages such as practical photosensitivity and high film-forming ability. On the other hand.

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, Japanese Patent Publication No. 55-30207 proposes a photosensitive polyimide precursor in which a photosensitive group is introduced into a polyimide precursor through an ester bond. Because it involves a hydrochloric acid reaction, chloride remains in the end.

The loss of this chloride has become a problem.

In order to avoid such problems, for example,
According to Japanese Patent No. 109828, a method of mixing a compound having a photosensitive group with a polyimide precursor.

Also, 1% Publication No. 56-24343,! Kaisho 60-1
No. 00143 and the like propose a method of imparting photosensitivity by reacting a functional group in a polyimide precursor with a functional group of a compound having a photosensitive group.

However, these photosensitive polyimides.

An aromatic polyimide precursor is used as the base polymer to ensure heat resistance, and as a result, it has an essential gap in solubility and also has low light transmittance in the ultraviolet region, forming a thick film. There are problems such as difficulty in

In this way, when an aromatic polyimide precursor is used as a base polymer, it is difficult to form a thick film, so when used as an insulating material, problems remain in flattening the two circuits and lowering the dielectric constant. Improvements are desired.

For example, when a photosensitive polyimide is prepared by dissolving an aromatic polyimide precursor and a compound having a photosensitive group, most of the good solvent evaporates during the drying process of forming a coating film from this solution.

The dried coating film is composed of an aromatic polyimide precursor and a compound having a photosensitive group.

And what about compounds that have such photosensitive groups?

Since it is generally a poor solvent for aromatic polyimide precursors, aromatic polyimide precursors become insolubilized and cause a whitening phenomenon in the coating film, making it difficult to use them in the exposure process due to such solubility problems. .

In addition, in most photosensitive resins, including photosensitive polyimides, the light energy absorbed by the coexisting photopolymerization initiator triggers the reaction, causing chemical or structural changes between the molecules. Most current photopolymerization initiators have an absorption wavelength in the ultraviolet region, so a base polymer using an aromatic polyimide precursor with low light transmittance in this region is used. This makes it difficult to form a thick film.

In this way, with photosensitive polyimide that uses an aromatic polyimide precursor as a base polymer, the film thickness is limited due to the whitening phenomenon and poor light transmittance, making it extremely difficult to form thick film patterns. There is a problem with that.

(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, and has excellent light transmittance and solubility, as well as the ability to form a thick film on the surface of a substrate. The present invention provides a possible photosensitive resin composition and a photosensitive element using the same.

(Means for Solving the Problems) The present invention relates to a photosensitive resin composition containing a photoinitiator and a polymer having a repeating unit generally represented by 2m.

is an alicyclic group, R2 represents a divalent aromatic group, and Y is an organic group having a monovalent ethylenically unsaturated group.

n is 0 or 1. nl is 1 or 2, and n-4-m
In addition, in the present invention, the photosensitive resin composition is coated on a substrate with Ht
=Relating to a photosensitive element comprising:

The polymer having a repeating unit represented by a monomorphic number used in the present invention can be obtained, for example, by polycondensing a compound represented by a general 2 (II) or (machi) with an aromatic diamine.

(However, in formula 1, X is a halogen atom or a hydroxyl group, Y is an organic group having a monovalent ethylenically unsaturated group, and the symbol → represents isomerization) - Format (II) or [
The reaction between the compound represented by I[l) and the aromatic diamine is preferably carried out in an inert organic solvent at a temperature of 0 to 100°C, more preferably at a temperature of 5 to 60°C. preferable.

-Form [111 or (ml) Compound and aromatic diamine are generally 2 (Ill and compound represented by (III)/aromatic diamine are 0.8/1 to 1.
It is preferably used in a ratio of 2/1 (molar ratio), and more preferably in a molar equivalent to 2%.

In addition, the reaction between a compound represented by the -format tUt or (In) and an aromatic diamine can be carried out using a carbodiimide-type dehydration condensing agent 2, such as dicyclohexylcarbodiimide, or a dehalogenating agent 2 such as amines.

This is promoted by using pyridine, triethylamine, etc.

As the organic solvent used in the above reaction, it is generally preferable to use a polar solvent that completely dissolves the produced polymer having a repeating unit represented by a monomorphic mountain.

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.

The photosensitive resin composition of the present invention can contain an organic solvent as described above. In such a case, the amount of the organic solvent used is preferably 10 to 95:[i% of the photosensitive resin composition, and more preferably 30 to 80 wtS.

The compound represented by the above-format (IIl or (I[Il) is.

For example, a novel dicyclohexyl-84. expressed by the quadratic formula N). z 4'-tetracarboxylic dianhydride.

By fully or partially ring-opening with a hydroxy compound having an ethylenically unsaturated group and half-esterifying it,
Furthermore, it can be obtained from K by acid halogenating this product with thionyl chloride, phosphorus pentachloride, or the like.

The reaction between dicyclohexyl-3,4,x 4'-tetracarboxylic dianhydride and a hydroxy compound having an ethylenically unsaturated group is promoted by adding 2, for example, pyridine, dimethylaminopyridine, etc. .

This dicyclohexyl-a, 4.14'-tetracarboxylic dianhydride is a novel compound obtained by the present inventors, and can be obtained, for example, by the method described in (V) below. Can be done.

Side light, a, 4. 4'-Biphenyltetracarboxylic acid tetramethyl ester is subjected to a hydrogenation reaction using a rhodium catalyst, and an aqueous solution containing a mineral acid catalyst is added thereto and heated for 7 lux to perform hydrolysis.

Dicyclohexyl-3,4,3:4'-tetracarboxylic dianhydride can be obtained by subsequently heating or adding acetic anhydride.

In addition, when obtaining a polymer having a repeating unit represented by the form (1>), dicyclohexyl-3,4,3:4'-tetracarboxylic dianhydride may be In addition to compounds represented by the general formula (II) or (I[1) obtained from compounds, aromatic tetracarboxylic dianhydrides may also be used, for example, with hydroxy compounds having dimerizable or polymerizable unsaturated groups. By fully or partially ring-opening and half-esterification, and further acid halogenation of this product with thionyl chloride, phosphorus pentoxide, etc., it can be obtained by general formula (■) or (VTJ) Can be used in combination with compounds.

Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3; 4,4'-benzophenonetetracarboxylic dianhydride, a, a; 4,4'-biphenyltetracarboxylic dianhydride; Acid dianhydride, meta-terphenyl & r 4. (-tetracarboxylic dianhydride, hala-terphenyl-3+ to 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-naphthalenetetracarboxylic dianhydride, 3,4,9.10- Examples include perylenetetracarboxylic dianhydride, 4,4'-sulfonylsiphthalic dianhydride, and the like.

Examples of the hydroxy compound having an ethylenically unsaturated group include trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, and trimethylolethane diacrylate.

Trimethylol ethane dimethacrylate, pentane j7
Thritol triacrylate, pentaerythritol trimethacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate.

2-hydroxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate.

2-hydroxy-3-phenoxypropyl methacrylate, allyl alcohol, glycerin diallyl ether,
Trimethylolpropane diallyl ether, trimethylolethane diallyl ether.

Pentaerythritol diallyl ether, x-1-lengellicol monoallyl ether, diethylene glycol monoallyl ether, dicrycerol triallyl ether, crotyl alcohol, vinylphenol, cinnamyl alcohol, allylphenol, 0-cinnamylphenol.

(R is H or C mountain) (R is H or C mountain) etc.

These hydroxy compounds can be used alone or in combination with 2a.

Examples of aromatic diamines which give a polymer having a repeating unit represented by the general formula (Ill) by polycondensation with a compound represented by the above -format (It) or -format (I[[3) include 9, for example, 4.4' -diaminodiphenyl ether, 3.4'-diaminodiphenyl ether, 4.4'
-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl nulphide, benzidine, meta-phenylenediamine, para-
phenylenediamine, 1,5-naphthalenediamine, 2
．． 6-naphthalenediamine, λ2-bis(4-aminophenoxyphenyl)bronosine.

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 (1), diaminosiloxane can be used in combination to the extent that heat resistance is not reduced.

Examples of this compound include 1.

zHs ■ zHs 2H8 C,H.

CH3 CI(1 CH3 C,1(S c.H.

CH3CHI CH3CH3Ci too Examples include.

In addition, in the case of isolating 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 in the reaction, adding it to alcohol or water, and reprecipitating it.

Photoinitiators used in the present invention include, for example, Michler's ketone, benzoin, 2-methylbenzoyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, z-t-butylanthraquinone, 1,2-benzo-
9,1O-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis(diethylamino)benzophenone, acetophenone, benzophenone, thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 1,5-acenaphthene.

2-dimethoxy 2-phenylacetophenone.

1-Hydroxycyclohexylphenyl ketone.

2-Methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, diacetyl.

Benzyl, benzyl dimethyl ketal, benzyl diethyl ketal, diphenyl disulfide, anthracene,
2.6-bis(p-diethylaminobenzylidene)-4
-Aza-4-methylcyclonanone, 2,6-bis(
Examples include p-diethylaminobenzylidene)-4-oxocyclohexanone and slow bis(p-diethylaminobenzylidene)-4-theacyclohexanone.

From the viewpoint of the sensitivity of the composition and the heat resistance of the coating film, the amount of these photoinitiators used is usually 0.01 parts by weight per 100 parts by weight of the photosensitive resin composition excluding the organic solvent and photoinitiator.
It is preferable to use 30 parts by weight, and more preferably 0.1 to 10 parts by weight.

Furthermore, a small amount of amines, which are photoinitiation aids, can also be used in combination with these photoinitiators.

Examples of amines include ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, and isoamyl p-dimethylaminobenzoate.

Isoamyl p-diethylaminobenzoate, benzoic acid-2
-(dimethylamino)ethyl, p-dimethylaminobenzaldehyde, p-dimethylaminobenzaldehyde,
Ethyl N,N-diethylanthranilate, p-dimethylaminobenzonitrile.

p-diethylaminobenzonitrile, N,N-dimethylaminonaphthalene, N-phenylglycine.

N-(p-cyanophenyl)glycine, N-(p-chlorophenyl)lycine, N-(p-bromophenyl)
Examples include glycine and the like.

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

Examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallolnitrobenzene, p-
Toluidine, methylene blue, 42'-methylenebis(
4-methyl-6-t-butylphenol), 2.2'-
Examples include methylenebis(4-ethyl-6-1-butylphenol), and the amount of t used is usually 0'6. It is preferable to set it as oot~10 parts by weight.

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

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

n-7' acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, benzyl acrylate, carpitol acrylate.

Methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, diglobylene glycol diacrylate, 2,2-bis-(
4-acryloxyjethoxyphenyl)propane, 2.
2-bis-(4-7cryloxybrobylxophenyl)
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).

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

→C gift CH, 0 → -C-CH=C city (n, m are integers selected so that n0m is 2 to 30).

CH2B r ■ OCHaBr 0 HtC=CH-C-0-CH2-CH-CH20Br
Br methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, λ2-bis(4-
(methacryloxyjethoxyphenyl)propane, trimethylolpropane dimethacrylate, pentaerythritol dimethacrylate.

(n is an integer from 1 to 30).

1+-CH5CHzO-+-C-C-CHzCHz (n, m are integers selected such that n+m is 1 to 30).

CHz B r HI 0 CH2B r CR3 H2C=CHC-0-CHz-CH-C) (20Br
Br In the present invention, a photocrosslinking agent can be used if necessary.

Examples of photocrosslinking agents include 1.

etc. can be mentioned.

The photosensitive resin composition of the present invention can be patterned using a conventional microfabrication technique.

In addition, 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 spray printing, and dried to form a coating film. It can be done.

The thickness of the coating film depends on the coating means 1, solid content concentration, viscosity, etc. of the face of the photosensitive polymer composition of the present invention! It can be adjusted.

In addition, the photosensitive resin composition is applied onto a flexible substrate 2 such as a polyester film, dried and laminated, and a BOLIETEL 4 cover sheet is provided on top of this to form a sandwich-structured photosensitive element in advance. It is also possible to peel off the cover sheet of the photosensitive element and form a coating on the supporting substrate to be coated.

A relief pattern is obtained by irradiating the coating on the support substrate with a light source, and then dissolving and removing the unexposed portions with a developer.

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

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-ε-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 cellosolve, water, a basic compound, a basic aqueous solution, etc.

Examples of basic compounds include monoethanolamine, jetanolamine, triethanolamine, tetramethylammonium hydroxide, sodium carbonate, potassium carbonate, and sodium phosphate.

The amount used is usually 0.000 parts by weight per 100 parts by weight of water.
It is preferable to use 1 to 30 parts by weight.

It is more preferable to use 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.

) Polyamic acid non-solvents having good miscibility with the developing solution are used as the liquid solution, such as methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, and methyl cellosolve.

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.

Reference example: Synthesis example of dicyclohexyl-3,4,4'-tetracarboxylic acid and its anhydride (1) Dicyclohexyl-3,4,4'-tetracarboxylic acid and its anhydride. a 4'-Tetracarboxylic acid tetramethyl ester In a 500 m1 autoclave with a capacity of 500 m1 equipped with an electromagnetic vertical stirring device (Model 5E-50 electromagnetic vertical stirring autoclave manufactured by Hanshita Kagakukiki ■), 3.4° 3:4' -Biphenyltetracarboxylic acid tetramethyl ester 38.69 (
0,100 mol), 193 g of tetrahydrofuran, and 3.869 g of a catalyst (manufactured by Nippon Engelhardt Co., Ltd.) in which 5-fold ik tyrodium was supported on activated carbon, and the hydrogen pressure was 30
The hydrogenation reaction was carried out at a reaction temperature of 100°C.

Hydrogen consumption stopped after a reaction time of 3.5 hours, and the amount of hydrogen consumed, calculated from the amount of decrease in hydrogen pressure in the pressure accumulator at that time, was 98.7 inches of the theoretical amount of hydrogen consumption (0.60 mol). Ta.

After removing the rhodium catalyst supported on activated carbon in the reaction solution by filtration, the solvent tetrahydrofuran was removed by evaporation, and a white waxy dicyclohexyl a,
4.3: 36.879 (0,0925 mol) of 4'-tetracarboxylic acid tetramethyl ester was obtained.

As a result of analysis by Super H-NMR (Hitachi R-250 Nuclear Magnetic Resonance Spectrometer), no benzene nuclear hydrogen or hydrogen attached to carbon-carbon double bonds were found, and no hydrogenation reaction was detected. It turned out to be complete.

(2) Production of dicyclohexyl-3,4,3:4'-tetracarboxylic acid In a No. 11 eggplant-shaped flask equipped with a cooling tube, add 29 g of dicyclohexyl-3,4,3:4'-tetracarboxylic acid tetramethyl ester. .99 (0,075 mol) and added 200 g of methanol to make a homogeneous solution, then 10%
The mixture was quenched with 200 g of sodium hydroxide solution, placed in an oil bath at 100°C, and refluxed for 6 hours.

After this, methanol is distilled off by evaporation.
Concentrate until the amount of reaction liquid becomes 140 g.

48 ml of 36% hydrochloric acid was added to this to adjust the pH to 1.

At pH 4 to 5, the liquid became cloudy, and at pH 1, fine white powder precipitated.

The precipitate was removed by filtration, then washed with water and dried.
g white fine powder crystals of dicyclohexyl-3,4,3
:4'-tetracarboxylic acid was obtained (0.052 mol)
.

Infrared absorption spectrum of this crystal (measured by KBr method using Hitachi Model 260-30 infrared spectrophotometer manufactured by Hitachi, Ltd.)
is shown in Figure 1, and its "H-NMR spectrum is shown in Figure 2. In Figure 2, the absorption at Z50ppm is due to the solvent d
, - absorption based on dimethyl sulfoxide fi,
The absorption at 3.35 ppm is due to water contained in the solvent.

In the absorption excluding these two, there is an absorption based on carboxyl group protons of 11.95 ppm.

The integrated intensity ratio of absorption based on cyclohexane ring protons of 0.87 to a, o o ppm is 29 for the former: for the latter.
:132 (=4:18.2), the theoretical value is clear◇弗→
→It matched now.

The melting point of this crystal is 219-222°C, and as a result of nine element analysis, it is 56.24% carbon and 6.53% hydrogen, and the calculated value is 56.13% carbon.

It corresponded to 6.48 h of hydrogen.

(3) Production of dicyclohexyl-3,4,z4'-tetracarboxylic dianhydride A 300 ml eggplant-shaped flask K equipped with a cooling tube.

15.09 (0,044 mol) of dicyclohexyl-3,4,1+'-tetracarboxylic acid and 180 g of acetic anhydride were charged, placed in an oil bath at 150°C, and refluxed for 1 hour.

After this, when filtration was performed while hot and the 1M solution was allowed to cool,
White crystals precipitated. These crystals are removed by filtration,
The amount of crystals after drying for 2 hours at a pressure of 30 mmHg and a temperature of ioo°C was 10.89 (0,035 mol).

Further, the melting point of this crystal was 231 to 234°C, which was in good agreement with the theoretical values (samurai compound) of carbon 6z74 and hydrogen 5°92.

The infrared absorption spectrum of this crystal is shown in FIG.

The 'H-NMR spectrum is shown in FIG. In Fig. 4, it can be seen that there is no absorption of carboxylic acid protons in a low magnetic field of 110-13 pp, indicating that it is an anhydride.

Example 1 30.99 (0.1 mol) of dicyclohexyl-3,4,3:4'-tetracarboxylic dianhydride was added
200 ml of 2-pyrrolidone and 26.09 (0.2 mol) of 2-hydroxyethyl methacrylate were added and 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.

Thereafter, the mixture was stirred at room temperature for 4 hours.

Add 20.0 g (o) of diaminodiphenyl ether to this solution.
, t mol) and stirred at room temperature for 8 hours.

Furthermore, when this solution was slowly poured into water in No. 51, thread-like solid matter was precipitated.

After filtration and thorough washing with ethanol and water.

By drying, a polymer having a repeating unit represented by the general formula m was obtained.

The obtained polymer is designated as rpl-IJ.

Example 2 N-methyl-
200 mj' of 2-pyrrolidone and 59.69 (0.1 mol) of pentaerythritol triacrylate were added and stirred at room temperature for 12 hours. While cooling this solution with water, thionyl chloride 359 was added dropwise over 1 hour.

Thereafter, the mixture was stirred at room temperature for 4 hours.

This -c'M'tc diaminodiphenyl ether20.
0 (0.1 mol) was added thereto, and the mixture was stirred at room temperature for 8 hours.

Furthermore, when this solution was slowly poured into water of 5e, thread-like solid matter was precipitated.

After filtration and thorough washing with ethanol and water.

By drying, a polymer having repeating units represented by general formula (1) was obtained.

The obtained polymer is referred to as rPI-2J.

Examples 3 to 8 To the polymers of PI-1 and PI-2, the indicated weights of each photoinitiator and polymerizable unsaturated compound shown in Table 1 were further added to form a homogeneous product for use in Examples 3 to 8. A solution was obtained.

Each of these solutions was filtered and dropped onto a silicon wafer, and spin-coded for 30 seconds at two revolutions of 200 Orpm.

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

Next, using a line-and-space photomask with a coating film of 80 μm, it was exposed to ultra-high pressure mercury lamp (8 mW/am 2 ) for 70 seconds.

After that, development was carried out with a mixed solution consisting of 1 volume of N,N-dimethylacetamide, 4 volumes of ethyl alcohol, and 4 volumes of 1% tetramethylammonium hydroxide aqueous solution, rinsed with water, and dried by air spray. A clear pattern was obtained.

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

Further, the coating film was heat-treated at 350° C. for 1 hour in a nitrogen atmosphere to prepare a film, and the following physical property tests (1) and (2) were conducted to obtain the results shown in Table 1.

(1) Thermal decomposition start temperature qllc Coat a photosensitive i-type parabolite on a glass substrate.

After drying, heat treatment was performed at 300°C for 1 hour to create a film.
The film was peeled off from the glass substrate.

It was measured.

(2) Weight reduction rate Above film 8 Air 300℃/3 Empty using the same equipment as (1) using 0 mg. Measure weight loss rate after holding for 0 minutes did.

Comparative Examples 1 to 3 Dicyclohexyl-3,4,3:4'- used in Examples
Using 32.2 g (0.1 mol) of benzophenone tetracarboxylic dianhydride instead of tetracarboxylic dianhydride, 200 ml of N-methyl-2-pyrrolidone and 2
-Hydroxyethyl methacrylate 26.09 (0,2
mol) and stirred at room temperature for 12 hours. Thionyl chloride 359 was added dropwise to this solution over 1 hour under ice cooling, and then stirred at room temperature for 4 hours.

Add 20% of diaminodiphenyl ether to this solution. .

9 (0.1 mol) was added and stirred at room temperature for 8 hours.

This solution was slowly poured into water of 5j in the same manner as in Example 1, and then washed with ethanol and water and dried to obtain a polymer. The obtained polymer is referred to as rPI-3J.

The indicated weights of each photoinitiator and polymerizable unsaturated compound shown in Table 1 were added to this polymer to obtain a homogeneous solution used in Comparative Examples 1 to 3iC.

Each of the solutions was filtered, dropped onto a silicon wafer, and spin coded at 9 rotations of 200 Orpm 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 3-8.

(Effect of the invention) The photosensitive polymer composition of the present invention and the photosensitive element using the same have excellent light transmittance and solubility, and
It is possible to form a thick film on the surface of the base material.

[Brief explanation of the drawing]

Figure 1 shows the infrared absorption spectrum of dicyclohexyl-3,4,3:4'-tetracarboxylic acid, which is an intermediate produced in the reference example, Figure 2 shows its 'H-NMR spectrum, and Figure 3 is for reference. Dicyclohexyl-3,4,3 prepared in Example
: Infrared absorption spectrum of 4'-tetracarboxylic anhydride; FIG. 4 shows its 'H-NMR spectrum.

Claims (1)

[Claims] 1. A photosensitive resin composition containing a repeating polymer represented by general formula (1) and a photoinitiator. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, R_1 is a tetravalent alicyclic group represented by ▲There are mathematical formulas, chemical formulas, tables, etc.), R_2 is a divalent aromatic group, and 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 is selected) 2 The photosensitive resin composition according to claim 1 A photosensitive element made by layering materials on a substrate.