JPH0365954A - Photosensitive resin composition and photosensitive element - Google Patents

Abstract

PURPOSE:To obtain the photosensitive resin compsn. which has a high sensitivity and excellent heat resistance, solvent resistance, etc., and can form a coating film having a high residual film rate of development by incorporating the photosensitive adduct of a polymer having a specific repeating unit and a specific isocyanate compd. and a photoinitiator into the compsn. CONSTITUTION:This photosensitive resin compsn. is constituted by incorporating the photosensitive adduct of the polymer having the repeating unit expressed by formula I and the isocyanate compd. expressed by formula II and the photoinitiator into the compsn. In the formula I, R1 is a quadrivalent org. group which does not contain fluorine atoms and R2 is a bivalent org. group which does not contain a fluorine atom. In the formula II, Z denotes a hydrogen atom or methyl group. The photosensitive resin compsn. which has the high sensitivity, heat resistance, solvent resistance, etc., and can form the coated film having the high residual film rate of development is obtd. in this way.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a photosensitive resin composition, more specifically, a coating film that has excellent heat resistance and electrical and mechanical properties, and is suitable for use in multilayer wiring boards and semiconductor devices. The present invention relates to a photosensitive resin composition suitable for surface protection films, interlayer insulating films, etc., and a photosensitive element using the same.

[Conventional technology]

Conventionally, heat-resistant polymers such as polyimide have excellent electrical and mechanical properties as well as heat resistance, so they have been used as insulating films and surface protective films for semiconductor devices, and also for wiring boards. It is also widely used in the field of glabellar insulating films for multilayer wiring boards. By the way, pattern formation of surface protective films and interlayer insulating films of semiconductor elements and multilayer wiring boards has conventionally involved forming films on the surface of the base material, exposing predetermined areas to light, removing unnecessary areas by etching, etc., and cleaning the surface of the base material. Because the process was complicated and involved a wide variety of processes, it is desirable to develop a heat-resistant photosensitive material that can be used with the necessary parts left intact as an insulating material even after pattern formation by exposure and development. ing.

As these materials, heat-resistant photosensitive materials based on, for example, photosensitive polyimide and cyclized polybutadiene have been proposed, and photosensitive polyimide in particular has attracted attention because of its excellent heat resistance and mechanical properties. As such photosensitive polyimide, for example, Japanese Patent Publication No. 49-173
A system consisting of a polyimide precursor and dichromate was first proposed in Publication No. 74, but while this material has advantages such as practical photosensitivity and good pattern formation, it is difficult to store. It lacked 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, but since acid chloride is used as a raw material, chlorine Ions remain in the system,
It has been found to hinder the usefulness of polyimide.

[Problems to be solved by the invention] The present invention has been made in view of the above problems, and
By using an isocyanate compound represented by the general formula (II) with high reactivity, a photosensitive adduct can be easily obtained, and it has excellent sensitivity, heat resistance, solvent resistance, etc., and a high rate of residual film after development. The present invention provides a photosensitive resin composition capable of forming a coating film and a photosensitive element using the same.

[Means to solve the problem]

The present invention provides (A) general formula (I) [wherein R6 is a tetravalent organic group that does not contain a fluorine atom, and R2 is a divalent organic group that does not contain a fluorine atom]
A polymer having a repeating unit represented by the formula (n) and an isocyanate compound represented by the general formula (n) H2C=C-C-NC01 (n) [wherein Z is a hydrogen atom or a methyl group] The present invention relates to a photosensitive resin composition containing a photosensitive adduct and (B) a photoinitiator, and a photosensitive element formed by laminating this photosensitive resin composition on a base material.

The polymer having a repeating unit represented by the general formula (1) used as component (A) of the present invention is obtained by a known method using a tetracarboxylic acid anhydride and an amine compound as starting materials.

-i The tetracarboxylic acid anhydride used in the production of the polymer having the repeating unit represented by formula (1) is an aromatic or aliphatic tetracarboxylic acid anhydride that does not contain a fluorine atom, such as pyrocarbon Mellitic acid dianhydride, 3.
3', 4.4'-hensiphenotetracarboxylic dianhydride, 3.3'4.4'-biphenyltetracarboxylic dianhydride, m-terphenyl-3,3", 4.4"
-Tetracarboxylic dianhydride, p-terphenyl-3゜3'', 4.4''-Tetracarboxylic dianhydride, 2゜3.
6.7-Naphthalenetetracarboxylic dianhydride, bis(
3,4-dicarboxyphenyl)ether dianhydride, 2
．． 2-bis(3,4-dicarboxyphenyl)propanihydride, 1,4.5゜8-naphthalenetetracarboxylic dianhydride, 3゜4.9.10-perylenetetracarboxylic dianhydride, 4. 4'-Sulfonyl siphthalic dianhydride, butanetetracarboxylic dianhydride, pentanetetracarboxylic dianhydride, -, xanetetracarboxylic dianhydride, cyclopenkune tetracarboxylic dianhydride, cyclohexanetetracarboxylic dianhydride Acid dianhydride, methyl-cyclohexenetetracarboxylic dianhydride, ethylenetetracarboxylic dianhydride, 2゜3.5-tricarboxy-cyclopentyl acetic anhydride, bicyclo-(2,2,2)-
Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, Tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1
, 2-dicarboxylic acid anhydride, ethylene bistrimelitate dianhydride, trimethylene bistrimelitate dianhydride, tetramethylene bistrimelitate dianhydride, pentamethylene bistrimelitate dianhydride, hexamethylene bistrimelitate dianhydride octamethylene bistrimelitate dianhydride, decamethylene bistrimelitate dianhydride, 3,5.6-)licarboxy2carboxymethylnorbornane-2:5,5:6 anhydride, 5.5'
- anhydride of thiobis(norbornane-2,3-dicarboxylic acid), anhydride of 5,5'-methylenedithiobis(norbornane-2,3-dicarboxylic acid), anhydride of 5,5'-ethylenedithiobis(norbornane-2,3-dicarboxylic acid), ,3-dicarboxylic acid)
anhydride, 5.5'-propylenedithiobis(norbornane-2,3-dicarboxylic acid) anhydride, 5゜5'-sulfonylbis(norbornane-2,3-dicarboxylic acid)
Anhydride of 5.5'-methylenedisulfonylbis(norbornane-2,3-dicarboxylic acid), 5.5'
-ethylenedisulfonylbis(norbornane-2,3-
dicarboxylic acid), 5,5'-propylene disulfonyl bis(norbornane-2,3-dicarboxylic acid)
anhydride, biscyclohexane-3,3', 4,4'
As the amine compound used in the production of tetracarboxylic dianhydride, a polymer having a repeating unit represented by the above general formula (1), various amine compounds that do not contain a fluorine atom can be used, For example, 4,4'-diaminodiphenyl ether,
4.4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4.4'-diaminodiphenylsulfide, benzidine, m-phenylenediamine,
P-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2.2bis(4-(4
-aminophenoxy)phenyl]propane, and the like. These tetracarboxylic acid anhydrides are
One type or a combination of two or more types can be used.

CHs CHy HEN-(CHz)3 5i-OSi (CHz)3
NHzCH,CHI CzHs CzHs H2N (CHI)3 Si OSi (C
H2) Diamine compounds such as 3NHzCzHs CzHs, 4.4'-diaminodiphenyl ether-3-sulfonamide, 3.4'diaminodiphenyl ether-4-sulfonamide, 3.4'-diaminodiphenyl ether-3'sulfonamide, 3, 3'
-diaminodiphenyl ether-4-sulfonamide,
4.4'-diaminodiphenylmethane-3-sulfonamide, 3.4'-diaminodiphenylmethane-4-sulfonamide, 3.4'-diaminodiphenylmethane-
3'-sulfonamide, 3,3'-diaminodiphenylmethane-4-sulfonamide, 4,4'-diaminodiphenylsulfone-3-sulfonamide, 3,4'-diaminodiphenylsulfone 4-sulfonamide, 3,4'
-Diaminodiphenylsulfone-3'-sulfonamide, 3,3'-diaminodiphenylsulfone-4-sulfonamide, 4,4'-diaminodiphenylsulfide-3-sulfonamide, 3,4'-diaminodiphenylsulfide-4- Sulfonamide, 3°3'-diaminodiphenyl sulfide-4-sulfonamide, 3.
4'-diaminodiphenyl sulfide-3'-sulfonamide, ■, 4-diaminobenzene-2-sulfonamide, 4,4'-diaminodiphenyl ether-3-carbonamide, 3,4'-diaminodiphenyl ether 4-carbonamide Amide, 3,4'-diaminodiphenyl ether-3'-carbonamide, 3,3'-diaminodiphenyl ether-4-carbonamide, 4,4'-diaminodiphenylmethane-3carbonamide, 3,4'
-diaminodiphenylmethane-4-carbonamide, 3
．． 4'-diaminodiphenylmethane-3'-carbonamide, 3,3'-diaminodiphenylmethane-4-carbonamide, 4,4'-diaminodiphenylsulfone-
3-carbonamide, 3.4'-diaminodiphenylsulfone-4-carbonamide, 3゜4'-diaminodiphenylsulfone-3'-carbonamide, 3.3'-diaminodiphenylsulfone-4-carbonamide, 4,
4'-Diaminodiphenylsulfide-3-carbonamide, 3.4'-Diaminodiphenylsulfide-
4=carbonamide, 3.3'-diaminodiphenylsulfide-4-carbonamide, 3.4'-diaminodiphenylsulfide-3'-carbonamide, 1.
4-Sia, minobenzene-2-carbonamide, 4,4
'-Diaminodiphenyl ether-3,3'-sulfonamide, 3,4'diaminodiphenyl ether-4,5
'-#y carbonamide, 3,3'-diaminodiphenyl ether-4,4'-sulfonamide, 4,4'-diaminodiphenyl ether-3,3'-carbonamide, 3,4'-diaminodiphenylmethane-4゜5' - Triamine compounds such as sulfonamides and the like.

Preference is given to using diamine compounds.

These amine compounds can be used alone or in combination of two or more.

The reaction between the above tetracarboxylic acid anhydride and the above amine compound is usually carried out at 0 to 100°C in an inert organic solvent.
It is preferably carried out at a temperature of 5 to 60°C, and more preferably carried out at a temperature of 5 to 60°C, and it can be obtained as an organic solvent solution of a polymer having a repeating unit represented by -CI).

In the reaction, the above-mentioned tetracarboxylic acid anhydride and the above-mentioned amine compound were mixed at a ratio of 0.8/1 to 1.2 of the former/latter.
It is preferable to use the ratio of /1 (molar ratio), and it is more preferable to use the equimolar amount.

As a solvent in the above reaction, for example, N-methyl-
2-pyrrolidone, N-acetyl-2-pyrrolidone, N-
Benzyl-2-pyrrolidone, NN-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, hexamethylenephosphoramide, N-acetyl-
ε-caprolactam, tetramethylene sulfone, p-chlorophenol, p~dibromoenol, dimethylimidazolidinone, N, N-dimethylpropylene urea, N,
Examples include N-dimethylethylene urea.

In addition to the above polar solvents, - alcohols, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons such as methyl alcohol, ethyl alcohol, methyl cellosolve,
Ethyl cellosolve, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, γ-butyrolactone, diethyl ether,
Ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, O-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, etc. are also used. be able to. The amount of these organic solvents used is preferably 50 to 1500 parts by weight, and 100 to 1
000 parts by weight is more preferred.

In the present invention, by adding an isocyanate compound represented by general formula (II) to the above polymer (
Obtain the photosensitive adduct which is component A).

-Isocyanate compounds represented by (II) include H2C=C)l-C-NCO and 1CH.

Examples include H,C=C-C-NC01. These are known compounds, and are produced, for example, by the reaction of methacryloylamide and oxalyl halide or the reaction of dehydrohalogenating the reaction product of acrylamide and oxalyl halide (JP-A-60-115557). Publication, JP 61-12225
Publication No. 7).

In the present invention, the reaction between the polymer and the isocyanate compound represented by general formula (II) is preferably carried out at 0 to 100°C in the organic solvent used in the synthesis of the polymer, and at 20 to 70°C. More preferably, it is carried out at °C.

From the viewpoint of sensitivity of the photosensitive resin composition and heat resistance of the coating film, the ratio of the isocyanate compound represented by the general formula (n) to the polymer is 0.05 per equivalent of carboxyl group in the polymer. It is preferable to use ~00g equivalent, and 0.
It is more preferable to use 1 to 0.8 equivalents.

Furthermore, the reaction between the isocyanate compound represented by (II) and the polymer can be performed using amines such as triethylamine, 1,4-diazobicyclo(2,2,2)octane, tin esters such as dibutyltin dilaurate, dibutyltin diacetate, etc. This is facilitated by using a compound as a catalyst. These can be used in an amount of about 0.1 to 10% by weight based on the isocyanate compound represented by -kill (n).

Examples of the photoinitiator as component (B) used in the present invention include Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-7' Tylanthraquinone, 1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis(
diethylamino)benzophenone, acetophenone, benzophenone, thioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 1,5
-Acenaphthene, 2.2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1=[4-(methylthio)phenyl]-2-morpholino-1-propanone, diacetyl, benzyl, benzyl Dimethyl ketal, benzyl diethyl ketal, diphenyl disulfide, anthracene, 3,3'-carbonylbis(7-dinithylamino)
Examples include coumarin, 2,6-bis(p-N,N-diethylaminobenzylidene)-4-methyl-4-azacyclohexanone, and the like.

The amount of these photoinitiators to be used is determined from the viewpoint of sensitivity of the photosensitive resin composition and heat resistance of the coating film, and the solid content of the photosensitive adduct is 10%.
It is preferable to use 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight relative to 0 parts by weight.

These photoinitiators can be used in combination with amines, which are known photoinitiators. Examples of amines include N
-Phenylglycine, N-(p-chlorophenyl)glycine, N-(p-bromophenyl)glycine, N-(p-
-cyanophenyl)glycine, ethyl p-diethylaminobenzoate, ethyl p-dimethylaminobenzoate, p-
Examples include isoamyl dimethylaminobenzoate and isoamyl p-diethylaminobenzoate.

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, t-butylcatechol, pyrogallol, phenothiazine, chloranil, naphthylamine, β
-naphthol, 2,6 di-butyl-p-cresol, pyridine, nitrobenzene, p-)lyidine, methylene blue 2,2'-methylenebis(4-methyl-6-t
-butylphenol), 2,2'-methylenebis(4
-ethyl-6-t-butylphenol), etc.
The amount used is preferably 1 to 10 parts by weight of O,OO per 100 parts by weight of the solid content of the photosensitive adduct.

In the present invention, a polymerizable unsaturated compound can also be used if necessary. Practical examples include acrylic acid compounds and methacrylic acid compounds.

Examples of acrylic acid compounds include acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, cyclohexyl acrylate, benzyl acrylate, carpitol acrylate, methoxyethyl acrylate, Ethoxyethyl acrylate, butoxyethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, butylene glycol monoacrylate, N,
N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, pentaerythritol monoacrylate, trimethylolpropane monoacrylate, allyl acrylate, 1,3-propylene glycol diacrylate, 1.4- Butylene glycol diacrylate, 1,6-hexane glycol diacrylate, neopentyl glycol diacrylate, dipropylene glycol diacrylate, 2.2-
Bis-(4-acryloxyjethoxyphenyl)propane, 2,2-bis(4-acryloxypropyloxyphenyl)propane, trimethylolpropane diacrylate, trimethylolpropane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , triacrylic formal, tetramethylolmethanetetraacrylate, acrylic ester of tris(2-hydroxyethyl)isocyanuric acid, I Hz C= CHC-(-o CHt CH2 〇-(in the formula, n and m are n+m) Indicates an integer selected from 2 to 30.) CH! B r etc. can be mentioned.

Examples of methacrylic acid compounds include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, octyl methacrylate, ethylhexyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, butoxyethyl methacrylate,
Hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate, N,N-dimethylamino methacrylate, N,N-diethylamino methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, methacryloxypropyltrimethoxysilane, allyl methacrylate, tri Methylolpropane monomethacrylate, pentaerythritol monomethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexane gelicold dimethacrylate, neopentyl glycol dimethacrylate, 2
．． 2-bis-(4-methacryloxyjethoxyphenyl)propane, trimethylolpropane dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, tetramethylolmethanetetramethacrylate, tris(2-hydroxyethyl) methacrylic acid ester of isocyanuric acid, (wherein n is 1 to 3
Indicates an integer of 0. )1+CH2CH20)-C-C=CH2H3 (In the formula, n and m represent integers selected such that n+m is 2 to 30.) CH3CHzBr CH:1 etc. can be mentioned.

Moreover, when the photosensitive resin composition of the present invention is used as a material for forming a relief pattern, it can be used as a solution dissolved in an organic solvent.

The organic solvent used at this time is preferably the polar solvent used in the above reaction from the viewpoint of solubility, such as N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-acetyl-2-pyrrolidone,
-benzyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, N-acetyl-ε-caprolactam, tetramethylenesulfone,
p-chlorophenol, P-7'lomophenol, N,
Examples include N-dimethylpropylene urea, N,N-dimethylpropylene urea, dimethylimidazolidinone, and the like.

In addition to the above polar solvents, - boat fishing organic solvents such as ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and methyl acetate. , ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane,
1,4-dichlorobutane, trichloroethane, chlorobenzene, 0-dichlorobenzene, hexane, heptane,
Octane, benzene, toluene, xylene, etc. can also be used.

From the viewpoint of film-forming properties, the blending ratio of the organic solvent is preferably 100 to 100 parts by weight per 100 parts by weight of the solid content of the photosensitive adduct.
Toooo parts by weight, more preferably 200 to 5000 parts by weight.

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

When applying the photosensitive resin composition of the present invention onto a support substrate such as a glass substrate, silicon wafer, or copper-clad laminate, methods such as spin coating using a spinner, dipping, and spray printing are used. The applied coating film can be adjusted by the coating means, the solid content concentration of the varnish of the photosensitive resin composition of the present invention, the viscosity, etc.

A relief pattern is obtained by irradiating the photosensitive resin composition of the present invention, which has formed a film on a support substrate through a drying process, with a light source, and then dissolving and removing the unexposed portions with a developer. At this time, the light source used is ultraviolet rays, visible light, radiation, or the like.

Alternatively, a photosensitive element may be prepared by coating, drying, and laminating a photosensitive resin composition or a solution thereof onto a substrate such as a polyethylene terephthalate film or a polyimide film by a knife coating method or a roll coating method. If necessary, a cover sheet such as a polyethylene film may be further provided on the coated and dried photosensitive composition), and the photosensitive element is laminated under heat and pressure on the supporting substrate using a hot roll or the like. (If a cover sheet is used, the cover sheet is removed and then laminated) to form a film of the photosensitive resin composition of the present invention.

Examples of the developer include N-methyl-2-pyrrolidone,
N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphorotriamide, dimethylimidazuridinone, N-benzyl-2-pyrrolidone, N-acetyl ε - An aprotic polar solvent such as caprolactam is used alone or as a mixture with, for example, methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, methyl cellosolve, water, a basic compound, an aqueous solution of a basic compound, etc. .

Basic compounds include monoethanolamine, jetanolamine, triethanolamine, tetraethylammonium hydroxide, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, trimethylbenzylammonium hydroxide. , tetramethylammonium hydroxide, sodium hydrogen carbonate, sodium silicate, sodium birophosphate, sodium acetate, sodium phosphate and the like. When preparing an aqueous solution of a basic compound, the amount of the basic compound used is 0 to 100 parts by weight of water.
．． It is preferable to use 0001 to 30 parts by weight, and 0.0
It is more preferable to use 5 to 5 parts by weight.

Next, the relief pattern formed by development is washed with a rinse solution to remove the developing solvent. As the rinsing liquid, a solvent having good miscibility with the developer can be used, and examples thereof include methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, methyl cellosolve, and water.

The relief pattern obtained by the above process is 150
The heat treatment at .degree. C. to 400.degree. C. results in a relief pattern of a heat-resistant polymer having imide rings.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited thereby.

Example 1 500d equipped with thermometer, nitrogen gas inlet and stirring device
In the fourth flask, add 3.3',4.4'-benzophenonetetracarboxylic dianhydride (manufactured by Aldrich) 3
2.2 g (0.1 mol) and 1301 d of N-methyl-2-pyrrolidone were added, and the mixture was stirred at room temperature under dry nitrogen gas flow.

Next, 20.0 g (0.1 mol) of 4,4'-diaminodiphenyl ether (manufactured by Mitsui Toatsu Chemical Co., Ltd.) was added to this solution, and the mixture was stirred at room temperature for 8 hours to obtain a viscous polymer solution.

Furthermore, 5.55 g of methacryloyl isocyanate (manufactured by Nippon Paint Co., Ltd.) (
0.05 mol) was added and stirred for 10 hours.

During the reaction, carbon dioxide was evolved.

The obtained photosensitive adduct solution (solid content 30.7%) was
It was named I-IJ. The solid content was determined from the nonvolatile content of the photosensitive adduct solution (210°C for 12 hours) by gravimetric method.

Example 2 In addition to 3.3' and 4.4' benzophenonetetracarboxylic dianhydride, 1.3-
Bis(3,4-dicarboxyphenyl)-1,1,3,
3-Tetramethyldisiloxane dianhydride (manufactured by Organic Synthetic Yakuhin Co., Ltd.) was used. The ratio in that case is 3.3', 4.4'
-benzophenonetetracarboxylic dianhydride 22.5
g (0.07 mol), and 12.8 g (0.03 mol) of 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride. A photosensitive adduct solution was obtained in the same manner as in Example 1 except for the above. This photosensitive adduct solution (solid content 31.8%) was mixed with PI-
It was named 2.

Example 3 3.3′-, 4.4′-benzophenone tetracarboxylic dianhydride was used as the acid component in Example 1.
',4.4'-Biphenyltetracarboxylic dianhydride (29.4 g (0.1 mol)) was used to prepare 4.4'-biphenyltetracarboxylic dianhydride.
2.2- instead of 4'-diaminodiphenyl ether
41.0 g (0.1 mol) of bis(4-(4-aminophenoxy)phenyl)propane was used.Other than that, a photosensitive adduct solution was obtained in the same manner as in Example 1.This photosensitive adduct The solution (36.8% solids) was named PI-3.

Examples 4-12 Photosensitive adduct solutions 1 of PI-1, PI-2 and PI-3
Each photoinitiator and polymerizable unsaturated compound shown in Table 1 were added to 00 g in the indicated weights and mixed with stirring to obtain a uniform photosensitive resin composition.

Each of the photosensitive resin compositions was passed through a filter and added dropwise onto a silicon wafer at a rotation speed of 1500 to 2500 rpm.
Spin code was performed for 30 seconds.

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 100 μm, an ultra-high pressure mercury lamp (8 mW/CTA) was used to
Exposure for seconds.

Thereafter, development was performed with a mixed solution consisting of 1 volume of N,N-dimethylacetamide, 4 volumes of ethanol, and 4 volumes of 1% aqueous tetramethylammonium hydroxide solution, followed by rinsing with water and drying with air spray.

The cured state of the pattern was determined 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)×100%.

In addition, the coating film was heat-treated at 350°C for 1 hour in a nitrogen atmosphere to produce a film, and the temperature at which the thermal decomposition started was measured using sample 10. (examined by differential thermal balance).

The results obtained are shown in Table 1.

Comparative Example 1 A polymer solution (
182g of glycidyl methacrylate (solid content 28.6%)
) 6.3 g (0.05 mol) was added and stirred at 80°C for 10 hours, resulting in a photosensitive adduct solution (solid content 30.8
%) was named rPI-4.

Comparative Examples 2 to 5 Each photoinitiator and polymerizable unsaturated compound shown in Table 2 was added to 100 g of a photosensitive adduct solution of PI-4 to obtain a uniform photosensitive resin composition.

The obtained photosensitive resin composition was applied onto a silicone wafer in the same manner as in Examples 4 to 12, the coating film was dried, and the film thickness was measured.

Furthermore, the characteristics of this coating film were investigated in the same manner as in Examples 4-12.

The results are shown in Table 2.

In Tables 1 and 2, the symbols mean the following.

K-1: 2.6-bis(p-N, N-diethylaminobenzylidene)-4-methyl-4-azacyclohexanone NPG: For solvents such as N-(p-cyanophenyl)glycindoamide and dimethyl sulfoxide Since it also has excellent durability, it is particularly effective in application to the glabella insulating film of a multilayer wiring board.

A-4G: Tetraethylene glycol diacrylate A-BPE-10 = 2,2-bis(4-acryloxypentaethoxyphenyl)propane [Effects of the invention]

Claims (1)

[Claims] 1. (A) General formula (I) ▲ Includes mathematical formulas, chemical formulas, tables, etc. ▼ (I) [In the formula, R_1 is a tetravalent organic group that does not contain a fluorine atom, and R_2 is is a divalent organic group that does not contain a fluorine atom] and a polymer having a repeating unit represented by the general formula (
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) A photosensitive adduct with an isocyanate compound represented by [In the formula, Z is a hydrogen atom or a methyl group] and (B) a photoinitiator. A photosensitive resin composition comprising: 2. A photosensitive element obtained by laminating the photosensitive resin composition according to claim 1 on a base material.