JPH01118514A - Photosensitive polymer composition - Google Patents

Abstract

PURPOSE:To obtain the subject compsn. being capable of giving a high concn. and a low viscosity in a soln. state and giving a final cured film having excellent heat resistance and flexibility, by compounding a polyamic acid contg. an ethylenically unsatd. group of a specified structural unit and a photo-polymn. initiator. CONSTITUTION:A polyamic acid of formula I (wherein R1 is a tetravalent arom. group of formula II; R2 is a divalent arom. group having an ethylenically unsatd. group) by dissolving a diamine contg. an ethylenically unsatd. group (e.g., 4,4'- diaminochalcone) in a polar solvent (e.g., N-methyl-2-pyrrolidone) and reacting p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride therewith. 100pts.wt. this polyamide acid, 0.01-30pts.wt. photo-polymn. initiator (e.g., 2-isopropylthioxanthone) and, if necessary, a sensitizing aid, a thermal polymn. inhibitor etc. are compounded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides a photosensitive resin composition, specifically, a coating film obtained that has excellent heat resistance, electrical and mechanical properties.

The present invention relates to a photosensitive resin composition suitable as a forming material for insulating films and passivation films for solid-state devices in the semiconductor industry, and as a glabella insulating material for semiconductor integrated circuits, multilayer printed wiring boards, etc.

(Conventional technology) Conventionally, as surface protection films and interlayer insulating films for semiconductor devices, etc., films are easy to form, can be flattened, have high heat resistance, and have excellent electrical and mechanical properties. For these reasons, polyimide is widely used.

Furthermore, recently, many studies have been conducted to develop photosensitive resin compositions that also have the function of photoresists, with the aim of streamlining the film forming process using polyimide.

As an example, it has been proposed to react a tetracarboxylic dianhydride with a diamine having an ethylenically unsaturated group to form a polyamic acid containing an ethylenically unsaturated group and obtain a polyimide with excellent needle heat resistance after curing. (Unexamined Japanese Patent Publication No. 55-1
Publication No. 35139).

This polyamic acid has an ethylenically unsaturated group.

The solution is applied to a substrate and dried, and after forming a coating film, it is exposed to light using a predetermined mask, developed to form a pattern, firstly cured at a temperature of 200 to 400°C, and finally used as a polyimide.

For polyamic acids with ethylenically unsaturated groups.

Some have excellent solubility, some have excellent heat resistance after curing, and some have excellent removability. for example.

Formula obtained from pyromellitic dianhydride and 5-diaminodiphenylstyryl ketone (ethylenic unsaturated group-containing polyamic acid having a structural unit expressed in ml,
The ethylenically unsaturated group-containing polyamic acid represented by the formula (fill) obtained from z 4,4'-, phenyltetracarboxylic dianhydride, and 3,5-diaminophenylstyryl ketone is.

Although it has excellent flexibility and heat resistance after curing, it has poor solubility in solvents, making it difficult to prepare a solution with high concentration and low viscosity.

Next, in order to improve the solubility of the polyamic acid,
3: When an ethylenically unsaturated group-containing polyamic acid having a structural unit represented by the formula obtained from 4.4'-benzophenone tetracarboxylic dianhydride and 3.5-diaminophenyl styryl ketone was used, flexible Although it has excellent properties, it has the disadvantage that the heat resistance of the polyimide after curing decreases because it contains a carbonyl group that is easily thermally cleaved between the benzene rings in the main chain.

(Problems to be Solved by the Invention) The present invention provides high concentration and low viscosity in a solution state, good viscosity stability, which could not be obtained with the above-mentioned polyamic acid, and furthermore, when formed into a final cured film. The present invention provides a photosensitive resin composition using an ethylenically unsaturated group-containing polyamic acid having properties such as heat resistance and flexibility.

(Means for solving the problem) The present invention provides a photosensitive material containing an ethylenically unsaturated group-containing polyamic acid having a structural unit represented by the following general formula (1) and a photopolymerization initiator. The present invention relates to a resin composition.

The ethylenically unsaturated group-containing polyamic acid used in the present invention consists essentially of the following two groups. Novel para-terphenyl-a, f represented by formula (V)
: 4.4'-tetracarboxylic dianhydride.

It is obtained by reacting a diamine containing an ethylenically unsaturated group in an organic solvent.

This acid anhydride is a novel compound obtained by the present inventors, and is obtained by a double cross-coupling reaction as shown in the formula (■) shown below.

(However, in formula 2, X1. IJ phenylphosphine) Tetramethyl-para-terphenyl is obtained by double cross-coupling reaction with meta-dihalogenobenzene in the presence of a nickel metal complex catalyst such as nickel. Next, add this to permanganate.

Nitric acid, liquid phase air oxidation to para-terphenyltetracarboxylic acid, followed by heating or addition of acetic anhydride to give para-terphenyl-λ4. ．． ('
It can be 4'-tetracarboxylic dianhydride.

Further, when obtaining the ethylenically unsaturated group-containing polyamic acid, other tetracarboxylic dianhydrides may be used in combination. For example, pyromellitic dianhydride, 3:44'-benzophenoneteto2carboxylic dianhydride, turtle &'4+'
-biphenyltetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2.5.6-naphthalenetetracarboxylic dianhydride, λ to 6.7-naphthalenetetracarboxylic dianhydride, 2. 3.5.6-Biricinthitracarboxylic dianhydride, 1,4,5.8-naphthalenetetracarboxylic dianhydride, 3,4,9.10
-perylenetetracarboxylic dianhydride, 4,4'-sulfonylsiphthalic dianhydride, butane, pentane, hexane, cyclopentane, bicyclohexene, cyclopropane, cyclobutane, cyclopentane,
Tetracarboxylic anhydrides such as cyclohexane, methyl-cyclohexene, and ethylene, bicyclo-(2,
2,2)-Octo-7dyne-2.3.5.6-tetracarboxylic dianhydride, tetrahydrofuran-2,3,4,
5-tetracarboxylic dianhydride $5-(2°5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5.6-)ricacyboxy-2- Carboxymethyl norbornane-2:
3,5:6 anhydride, 5.5'-thiobis(norbonane-λ3-dicarboxylic acid) dianhydride, 45'-methylenedithiobis(norbonane-2,3-dicarboxylic acid) dianhydride, 5.5'-ethylene Dithiobis (norbonane-2.3
-dicarboxylic acid) dianhydride 9 5'-Propylene dithiobis(norponanose 3-dicarboxylic acid) dianhydride, 5
．． 5'-sulfonylbis(norbonane-λ3-dicarboxylic acid) dianhydride, 5,5'-methylenedisulfonylbis(norbonane-2,3-dicarboxylic acid) dimhydrate.

5.5'-ethylenedisulfonylbis(norbonane-3-dicarboxylic acid) dianhydride, he5'-propylenedisulfonylbis(norbonane-λ3-dicarboxylic acid) dianhydride, and the like are used.

When other tetracarboxylic dianhydrides are used in combination, the polyamic acid will contain structural units different from the above structural units. meta-terphenyl-a, t 44'
- Tetracarboxylic dianhydride and other tetracarboxylic dianhydrides are preferably used in a ratio of 9515 to 40/60 (molti) of the former/latter.

Examples of the diamine containing an ethylenically unsaturated group used in the present invention include 9, 4,4'-diaminochalcone, 3
．． 4'-diaminochalcone, 4.4'-diaminodibenzalacetone, 4'-diaminodibenzalacetone,
λ5-diaminobenzoic acid ethyl acrylate, λ
5-diaminobenzoic acid ethyl methacrylate, 5-diaminobenzoic acid glycidyl acrylate,
5-diaminobenzoic acid glycidyl methacrylate, 5-diaminobenzoic acid cinnamate ester, 2
．． 4-diaminobenzoic acid ethyl acrylate, 4-diaminobenzoic acid ethyl methacrylate.

4-diaminobenzoic acid glycidyl acrylate, 2,4-diaminobenzoic acid glycidyl methacrylate, λ4-diaminobenzoic acid cinnamate, 4
-Acrylamide-tortoise 4'-diaminodiphenyl ether, λ4'-diacrylamide 44'-diaminodiphenyl ether, 4-cinnamamide-tortoise 4'-diaminodiphenyl ether, 5-diaminobenzyl acrylate, 3.5-diaminobenzyl methacrylate, Su 4 -diaminobenzyl acrylate, 4-diaminobenzyl methacrylate, diamines represented by the following formulas, and the like are used.

N OH COOCH to CHCH Examples of diamines include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 44'
-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, benzidine, meta-phenylenediamine, baraf 2-diamine, 1,5-naphthalenediamine, muro-naphthalenediamine, λ2-bis(
4-aminophenoxyphenyl)propane, bis(4-
Aromatic diamines such as aminophenoxyphenyl) sulfone are used.

In addition, there are diamino acids represented by the 9th general formula (Vli) (wherein Rs is a divalent hydrocarbon group, 4 is a monovalent hydrocarbon group, and 1m is an integer of 1 or more). Siloxane can be used, and examples of this compound include CHs CHs C5Hs C5Hs.

General formula (However, Ar is an aromatic group, Y represents Sow or CO.

A diaminoamide compound represented by one amino group and Y (NHx are positioned ortho to each other) can also be used. Examples of this compound include 44'-diaminodiphenyl ether-3-sulfonamide, zig-diaminodiphenyl ether-4-sulfonamide, 3.4'-
diaminodiphenyl ether-3'-sulfonamide,
λ3'-diaminodiphenyl ether-4-sulfonamide e4(-cyminodiphenylmethane-3-sulfonamide), 3゜4'-diaminodiphenylmethane-4-sulfonamide, 3.4'-diaminodiphenylmethane-3'-sulfone Amide, 3.3'-diaminodiphenylmethane-4-sulfonamide, 4.4'-diaminodiphenylsulfone-3-sulfonamide, Kame 4
'-Diaminodiphenylsulfone-4-sulfonamide, a4'-diaminodiphenylsulfone-31-sulfonamide, turtle 3'-diaminodiphenylsulfone-4-
Sulfonamide, 4. Diaminodiphenyl sulfide-3-sulfonamide, tome 4'-diaminodiphenyl sulfide-4-sulfonamide.

Tortoise 3'-diaminodiphenyl sulfide-4-sulfonamide, a<-diaminodiphenyl sulfide-3
'-Sulfonamide, 1,4-diaminobenzene-2-
Sulfonamide, 44'-diaminodiphenyl ether-3-carbonamide, 3,4-diaminodiphenyl ether-4-carbonamide, 24'-diaminodiphenyl ether-3'-carbonamide, tortoise 3'-diaminodiphenyl ether-4-carbonamide, 4.4
'-diaminodiphenylmethane-3-carbonamide,
a, <-diaminodiphenylmethane-4-carbonamide, 4'-diaminodiphenylmethane-3'-carbonamide, &3''-diaminodiphenylmethane-4-carbonamide, 44'-diaminodiphenylsulfone-
3-Carbonamide, Tortoise 4'-diaminodiphenylsulfone-4-carbonamide, Tortoise 4'-diaminodiphenylsulfone-31-carbonamide, Tortoise 3'-diaminodiphenylsulfone-4-carbonamide, 4.4'-
Diaminodiphenyl sulfide-3-carbonamide, 3.4''-diaminodiphenyl sulfide-4-carbonamide, turtle 3'-diaminodiphenyl sulfide-4-carbonamide, turtle 4'-diaminodiphenyl sulfide-3'-sulfonamide, Examples include 1,4-diaminobenzene-2-carbonamide.

In addition, the general formula circle (In the formula, Ar represents an aromatic group, and Y represents SO! or CO.

Diaminodiamide compounds represented by one amino group and one Y-Nl (the groups are positioned ortho to each other as a pair) can also be used, such as 44'-diaminodiphenyl ether-torto3' -sulfonamide, 3,4'-diaminodiphenyl ether-4,5
'-Carbonamide, 3.3'-diaminodiphenyl ether-44'-sulfonamide, 4゜4゛-diaminodiphenylmethane-tortoise 3'-carbonamide, 3.4''
-diaminodiphenylmethane-4,5'-sulfonamide and the like.

When other diamines containing no ethylenically unsaturated groups are used together, the resulting polyamic acid will contain structural units different from the above-mentioned structural units. The diamine containing an ethylenically unsaturated group and the other above-mentioned nine amino compounds are preferably used in a ratio of 90/10 to 20/80 (mol %) of the former/latter.

The polyamic acid in the present invention is 9, for example, N-methyl-2
-pyrron-171'n, N,N-dimethylacetamide,
N,N-dimethylformamide, dimethyl sulfoxide, hexamethylene phosphoramide, tetramethylene sulfone, p-chlorophenol.

After dissolving the diamine component described above in a polar solvent such as p-bromophenol, meta-terphenyl-&4. f
It can be obtained by adding 4'-tetracarboxylic dianhydride or an acid component containing it and reacting with stirring at a temperature of 80° C. or lower, preferably around room temperature or lower. The acid component and the diamine component are preferably used in equimolar amounts. - As the photopolymerization initiator in the present invention, various compounds that are generally used as photopolymerization initiators for ultraviolet curable coatings can be used. For example, Michler Sketon. Benzoin, 2-methylbenzoin,
Benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether.

pent-in-butyl ether, 2-t--/f anthraquinone, 1,2-benzo-9,10-acetophenone,
Anthraquinone, methylanthraquinone.

4.4'-bis(diethylamino)benzophenone.

Acetophenone, benzophenone, thioxanthone, 2
．． 4-diethylthioxanthone, 2-isopropylthioxanthone, 1,5-a7naphthene, λ2-dimethoxy 2-phenylacetophenone.

1-Hydroxycyclohexylphenyl ketone.

2-Methyl-(4-(methylthio)phenylcy 2-morpholino-1-propanone, diacetyl.

Examples include benzyl, benzyl dimethyl ketal, benzyl diethyl ketal, diphenyl disulfide, and anthracene. The amount of these photopolymerization initiators to be used is usually 0.01 to 30 parts by weight per 100 parts by weight of the ethylenically unsaturated group-containing polyamic acid from the viewpoint of sensitivity of the composition and heat resistance of the coating film. The amount is 0.1 to 10 parts by weight. A small amount of amines, which are known sensitizing aids, can also be used in combination with these photopolymerization initiators. Further, in order to improve the thermal stability of the composition, it is preferable to coexist a known thermal polymerization inhibitor.

Specific examples of thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, phenothiazine, floranil, 7-tylamine, β-naphthol, a6-di-t-butyl-p-cresol, and pyridine. , nitrobenzene, p-toluidine, methylene blue.

2.7-methylenebis(4-methyl-6-t-7'tylphenol), 2.2'-methylenebis(4-ethyl-
6-t-butylphenol), etc., and the amount used is 100% of ethylenically unsaturated group-containing polyamic acid! ift
The amount is usually 0.001 to 10 parts by weight.

In the present invention, polymerizable unsaturated compounds can also be used as necessary. Acrylic acid compound.

Practical examples include methacrylic acid compounds. Specific 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-bis-
(4-acryloxyjethoxyphenyl)furopane, 2-bis-(4-acryloxypropylxyphenyl)
Acrylic acid esters of propane, trimethylolpropane diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, triacryl formal, tetramethylolmethanetetraacrylate, tris(2-hydroxyethyl)isocyanuric acid.

(n is an integer of 1 to 30) 1 → CHxCH Xue Ian C-CH 2 C mountain (n, m are integers where n -4-m is 2 to 30) CH mushroom Br 0 CHsBr O etc. can. 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, and 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, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, 1,3-butylene glycol dimethacrylate, l,6-hexane gelicoldimethacrylate, neopentyl Glycol dimethacrylate, 2.2-
Bis-(diphenyl)propane in 4-methacryloxyshed.

Trimethylolpropane dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, tetramethylolmethanetetramethacrylate, methacrylic acid ester of tris(2- and droxyethyl)isocyanuric acid.

(n is an integer from 1 to 30) (n, m is an integer where n+m is 1 to 30) CH Tomi Br CHs OCH Tomi Br OCHso
Examples include Br Br and the like. Also butyl crotonate.

Glycerin monoclonate, vinyl butyrate.

Vinyl trimethyl acetate, vinyl caproate, vinyl chloroacetate, vinyl lactate.

Vinyl benzoate, divinyl succinate, divinyl phthalate, methacrylamide, N-methylmethacrylamide, N-ethylmethacrylamide.

N-esterylmethacrylamide, N-hydroxyethyl-N-methylmethacrylamide, acrylamide, N-
t-butylacrylamide, N-methylolacrylamide, N-imbutoxymethylacrylamide, N-butoxymethylacrylamide, diaseptone acrylamide, hexyl vinyl ether, ethylhexyl vinyl ether.

Vinyl tolyl ether, polyvinyl ether of polyhydric alcohols, styrene derivatives with substituents such as alkyl groups, alkoxy groups, norogen, carboxyl groups, and allyl groups in the ortho and para positions, divinylbenzene, allyloxyethanol , diallyl ester of dicarboxylic acid.

N-vinyl oxazolide/, N-vinylimidazole,
N-vinylpyrrolidone, N-vinylcarbazole, etc. can also be used. These may be used alone or as a mixture.

The photosensitive resin composition of the present invention is made into a solution state by dissolving the ethylenically unsaturated group-containing polyamic acid and a photopolymerization initiator in a suitable solvent.

The organic solvent used in this case is preferably an aprotic polar solvent from the viewpoint of solubility.
-pyrrolidone, N-acetyl-2-virolitone, N-benzyl-2-pyrrolidone.

Examples include N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphortriamide, N-acetyl-ε-caprolactam, dimethylimidazolidinone, and the like.

In addition to these polar solvents, common organic solvents such as ketones, esters, lactones, ethers, halogenated hydrocarbons, and hydrocarbons such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, and acetic acid are also used. Ethyl, butyl acetate, diethyl oxalate, diethyl malonate, r-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloromethane fi7.
1.4-C/Rolbutan, trichloroethane.

Chlorobenzene, 0-dichlorobenzene, hexane, heptane, octane, benzene, toluene.

Xylene and the like can also be used. In order to completely dissolve the polyimide precursor, it is desirable to use these general organic solvents in combination with the above-mentioned polar solvent.

The blending ratio of the organic solvent is preferably 100-10.0 parts by weight based on 100 parts by weight of the polyamic acid from the viewpoint of film-forming properties.
00 parts by weight, more preferably 200 to s, ooo parts by weight.

The photosensitive polymer composition of the present invention can be patterned using conventional microfabrication techniques.

When applying the photosensitive polymer composition of the present invention onto a supporting substrate such as a glass substrate or a silicon wafer, methods such as spin coating using a spinner, dipping, and spray printing are used. The coating film thickness depends on the coating method.

It can be adjusted by adjusting the solid content concentration, viscosity, etc. of the photosensitive polymer composition of the present invention.

By irradiating the photosensitive polymer 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.

A relief pattern is obtained. At this time, the light source is ultraviolet light,
Visible light, radiation, etc. are used.

As a developer, 9 such as N-methyl-2-pyrrolidone,
N-acetyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorotriamide, dimethylimidazolidinone, N-benzyl-2-pyrrolidone,
Aprotic polar solvents such as N-7 cetyl-e-caglolactam.

Non-solvents of polyamic acid alone or 9 such as methanol, ethanol, isoflovir alcohol.

It is used as a mixed solution with benzene, toluene, xylene, methyl cellosolve, water, aqueous alkaline solution, etc.

As a suitable base for use in alkaline aqueous solutions.

Monoethanolamine, tetraethylammonium hydroxide, sodium carbonate, potassium carbonate.

Examples include sodium phosphate. What is its usage?

The amount is usually 0.0001 to 30 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of water.

Next, the relief pattern formed by development is washed with a rinsing solution to remove the developing solvent. As the rinsing liquid, a polyamic acid non-solvent having good miscibility with the developer is used, such as methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, and methyl cellosolve.

Examples include water.

The relief pattern polymer obtained by the above treatment is a precursor of polyimide, and by heat treatment at 150 to 450° C., it becomes a relief pattern of a heat-resistant polymer having imide rings and other cyclic groups.

(Examples) The present invention will be described below using nine examples, reference examples, and comparative examples.

Reference example para(p)-terphenyl-tortoise 4. Synthesis example of K 4'-tetracarboxylic acid and its anhydride (1) Production of Grignard reagent 21 four-bottle flasks equipped with an Allene condenser, 9 dropping funnels, a thermometer, and a stirring device were thoroughly dried under an argon gas atmosphere. After that, 1o was dehydrated with metallic sodium.
o ml of tetrahydrofuran.

9.729 of magnesium metal and 10.09 of bromo-ortho-xylene (Aldrich, a mixture of 75 liters of 4-bromo-ortho-xylene and 2!L of 3-bromo-ortho-xylene) were added.

When the reaction solution started to take K and the GuIJ Niillard reagent started to be produced, a mixed solution of 64.09 mj of promo-ortho-xylene and 100 mj of tetrahydro-7rane was added dropwise from the dropping funnel over a period of 1 hour. During this time.

Since it is an exothermic reaction, the reaction temperature is 'i4' while cooling in a water bath.
It was kept at 0°C. Since metallic magnesium remained even after the dropwise addition was completed, it was heated in an oil path and stirred for 5 hours at a temperature of 40° C. to completely react the metallic magnesium to form a Grignard reagent.

(2) Production of 4 g of 4'-tetramethyl-m-terphenyl Next, in a flask, add 37 g of dichloro(1,2-bis(diphenylphosphine)ethane) nickel catalyst (to the total amount of the above pro-ortho-xylene). A solution of 29.49 (0,200 mol) of hala-dichlorobenzene dissolved in 85 mI! of tetrahydro7rane was added dropwise from the dropping funnel over 1 hour.

During this time, the reaction temperature was kept at 35°C. After the dropwise addition was completed, stirring was continued while maintaining the temperature at 35° C. for another 1 hour to complete the double cross coupling reaction.

Add 300 ml of toluene to the reaction solution! was added, and while stirring, 150 mj t" of ion-exchanged water was gradually added over 1 hour. After removing the lower aqueous layer using a separating funnel, the upper toluene layer was dried up using a rotary evaporator and released. After cooling, the precipitated crystals were taken out, washed three times with ethanol, and dried under reduced pressure.
．． 49 colorless plate-like crystals were obtained. The melting point of this crystal is 72
~73°C.

This crystal is shown in Figure 1 by proton nuclear magnetic resonance (IH-
NMR) spectrum and carbon nuclear magnetic resonance ("c") spectrum in Figure 2.
-NMR) spectrum analysis results are shown. In Figure 1, the integrated intensity ratio of absorption based on methyl group protons and absorption based on benzene ring protons at 2.29 ppm and zszppm is 180:150 (=12:10) for the former:
), which is in good agreement with the theoretical value.In Figure 2, only 10 peaks appear, indicating that the obtained compound (theoretical carbon number 22) has a symmetrical structure.

Furthermore, the absorptions 1 to 8 in Fig. 2 are in good agreement with the predicted chemical shifts of the benzene ring carbons with carbon numbers ■ to ■ of the compound represented by formula (X) according to the Savitsky rule. has appeared.

From the above, the above crystal is z43:4'-tetramethyl-p
- Confirmed to be terphenyl.

(3) p-terphenyl-tortoise4. f Production of 4'-tetracarboxylic acid x4t4'-tetramethyl-p-terphenyl 14.3
9 (50 mmol), pyridine 2009, and 200 g of ion-exchanged water, and a cooling tube, thermometer, and stirring device were installed. Pour 4 into a round flask, and fill the flask with 8
Heat to 0℃ and add 11α7g (70℃) of potassium permanganate.
0 mmol) was gradually added over 3 hours, and then the mixture was kept at 80° C. and stirred for an additional 5 hours. Precipitation of manganese oxide produced in the reaction was removed by t-filtration, distilled off using a pyridi7fo-Tali evaporator in solution F, and precipitated with 36-thihydrochloric acid to precipitate white fine crystals. The pH of the solution at this time was 1. After repeating filtration and washing with water twice, it was dried under reduced pressure to obtain 11.69 g of white powdery crystals.

The melting point of this crystal was 296-298°C.

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

For 0.4 g of this crystal, 50 ml of methanol and 9
Add 2 ml of 7% sulfuric acid and reflux for 8 hours.

The above crystals were methyl esterified. The results of the IH-NMR spectrum of the obtained methyl ester compound were
As shown in the figure. In Figure 4, 191 ppm and 3.94
Absorption based on ppm methyl group protons and 7.71-7
．． The integrated intensity ratio of the absorption based on the benzene ring proton of 95 PI)m is 180:151 (=12:
10.07) and p-terphenyl-3,43:4
It was in good agreement with the theoretical value of the methyl ester compound of '-tetracarboxylic acid.

Further, the results of elemental analysis of the above crystal were as follows.

Actual value Carbon: 59.67chi, Hydrogen: 415% Theoretical value Carbon: 65.03chi, Hydrogen: 3.47chi (However,
The theoretical value is the value determined as p-terphenyl-3,4,4'-tetracarboxylic acid. ) Results of elemental analysis,
Because the actual value and the theoretical value are different.

When the above crystal was analyzed at 160°C, 230°C and 310°C,
There was an endothermic peak at °C. 17 at 160℃ and 230℃
A decrease in weight of - was observed.

The endothermic peak at 310°C is due to the melting point, while the endothermic peaks at 160°C and 230°C are due to dehydration. If p-terphenyl-3,4,4'-tetracarboxylic acid simply undergoes dehydration and ring closure by heating during differential thermal analysis to form the corresponding acid anhydride, the weight loss would be 9. From this, it is thought that the obtained crystals contain water of crystallization, and the actual values of the above elemental analysis are p-
Theoretical value of carbon 59.7 in elemental analysis when two molecules of water of crystallization are hydrated in terphenyl-atto'-tetracarboxylic acid
3, hydrogen 4109bK matches very well.

From the above, the above crystal is p-terphenyl-kame 4,3:
It was confirmed that it was 4'-tetracarboxylic acid and had two molecules of water of crystallization.9.

(4) Production of p-terphenyl-kame 4g41-tetracarboxylic acid-λ4.3:4'-dianhydride The resulting p-terphenyl-3,4(4-tetracarboxylic acid 10.09
and 400 g of acetic anhydride! The mixture was placed in an eggplant-shaped flask, heated under reflux for 30 minutes to dissolve, filtered hot, and allowed to cool, resulting in the precipitation of light colored powdery microcrystals. It was filtered and dried under reduced pressure to obtain 6.9 g of powdered crystals. The infrared absorption spectrum and H-NMR spectrum of this powdered crystal are shown in FIGS. 5 and 6, respectively.

The melting point of this crystal is 311-313°C, and as a result of two-element analysis, it is 71.28% carbon and 176% hydrogen, and the theoretical value is 71.3696% carbon. It matches well with hydrogen 272, p
-terphenyl-kame 4s: 4'-tetracarboxylic acid-&
4. It was confirmed that it was i4'-dianhydride.

Example 1 4,4'-di'aminochalcone 11.99 under nitrogen flow
(O, OS mol) was dissolved in 15αOg of N-methy/l/-2-pyrrolidone to prepare a diamine solution.

Next, this solution was stirred while maintaining the temperature at about 16°C by water cooling, and the para-terphenyl-3 obtained in the reference example was stirred.
, 43:4'-tetracarboxylic dianhydride 1 & 59 (0
, 05 mol) was added thereto, and stirring was continued for 8 hours at room temperature to obtain a polyamic acid solution. The resulting polyamic acid solution had a nonvolatile content of 17% by weight and a viscosity of 950 poise at 25°C. Next, this polyamic acid solution is heated at a temperature of around 70°C,
When the viscosity was adjusted, the viscosity decreased to 11 poise in 5 hours, and a low viscosity ethylenically unsaturated group-containing polyamic acid solution was obtained.

Irgacure 907 (2-methyl-1-[4-(methylthio) manufactured by Ciba Geigy) was added to this polyamic acid solution 209.
phenyl2-morpholino-propan-1-one)
0.19 and 2-improvirthioxanthone (manufactured by Ward Prekinsop) 0.019 were added to give a 1 μm diameter at the 9th order.
A photosensitive resin composition (non-volatile content: 16% by weight) was obtained by pressure filtration using a pore filter.

Next, this composition was applied onto a silicon wafer using a spinner and dried at 80° C. for 10 minutes to obtain a photosensitive film with a thickness of 10.5 μm. This film was closely exposed using a photomask with a 20 μm line and space striped pattern, and
The film was irradiated with 600 mJ/cm" using a high-pressure mercury lamp. After exposure, it was developed with a mixture of 4 volumes of N-methyl-2-pyrrolidone and 1 volume of ethanol, and then rinsed with ethanol to obtain a relief/(turn).

30 minutes at 180℃ under nitrogen atmosphere, 60 minutes at 400℃
A polyimide relief pattern with a film thickness of 46 μm was obtained. At this time, the pattern firmly adheres to the substrate,
The photomask pattern was faithfully transferred.

Example 2 Instead of 4, diaminochalcone used in Example 1, 3,5-diaminobenzyl acrylate 9.69 (0
, 05 mol) was dissolved in N-methyl-2-pyrrolidone 709, and then 1 & 5 g (0.05 mol) of bara-terphenyl-kame 4.3:4'-tetracarboxylic dianhydride (0.05 mol) were added. A solution was synthesized. The obtained polyamic acid solution had a nonvolatile content of 29% by weight and a viscosity of 1100 poise (
25°C). Next, this polyamic acid solution was heated at 70°C.
When the viscosity was adjusted by heating at a similar temperature, the viscosity decreased to 18 poise in 8 hours, yielding a polyamic acid solution containing ethylenically unsaturated groups with high concentration and low viscosity.

To this polyamic acid solution 209, 0.2 g of Irgacure 907 and 2-isopropylthioxanthone o, os
Then, the mixture was filtered under pressure using a filter with 1 μm pores to obtain a photosensitive resin composition (non-volatile content: 27 es by weight).

Next, patterning was performed in the same manner as in Example 1, and a clear pattern could be obtained.

Example 3 Instead of the 4,4'-diaminochalcone used in Example 1, 3,5-diaminobenzoic acid ethyl acrylate tzsg (o, os mol) was dissolved in N-methyl-2-pyrrolidone 659. 9th varataphenyl-z43
:+'-Tetracarboxylic dianhydride 14.89 (0,0
4 mol) and 3'44'-biphenyltetracarboxylic dianhydride 2.949 (0.01 mol) t-added to synthesize a solution of polyamic acid. The resulting polyamic acid solution had a nonvolatile content of 30% by weight and a viscosity of 1.250 poise (25
℃). Next, this polyamic acid solution was heated at a temperature around 70°C to adjust the viscosity.
An ethylenically unsaturated group-containing polyamic acid solution with a high concentration and low viscosity was obtained.

Irgacure 907f was added to this polyamic acid solution 206.
:0.21 and 2-isopropylthioxanthone 0.0
59 was added and filtered under pressure using a filter with 1 μm pores to obtain a photosensitive resin composition (non-volatile content 27% by weight).
I got it.

Next, patterning was performed in the same manner as in Example 1, and a clear pattern could be obtained.

Example 4 441-diaminochalcone 9.529 (0
0.04 mol) and 20 G (0.01 mol) of 4'-diaminodiphenyl ether were dissolved in 70 g of N-methyl-2-pyrrolidone.
．． f 4'-tetracarboxylic dianhydride 18.59 (
0.05 mol) was added to synthesize a polyamic acid solution.

The resulting polyamic acid solution had a nonvolatile content of 30% by weight and a viscosity of 1,400 poise (at 25°C). Next, this polyamic acid solution was heated at a temperature around t-70°C to adjust the viscosity, and the viscosity decreased to 14 poise in 8 hours.
A highly concentrated and low viscosity ethylenically unsaturated polyamic acid solution was obtained.

To this polyamic acid solution 209, 0.159 of Irgacure 907 and 0.0 of 2-isopropylthioxanthone were added.
59 was added thereto and then filtered under pressure using a filter-e with 1 μm pores to obtain a photosensitive resin composition (non-volatile content: 26% by weight).

Next, patterning was performed in the same manner as in Example 1, and a clear pattern could be obtained.

Example 5 Tortoise 5'-diaminobenzyl acrylate 9 under nitrogen flow
．． No. 12 (0,045 mol) and 1,3-bis(r-aminopropyl)-1,1,3,3-tetramethyldisiloxane 1.249 (0,005 mol) (Shin-Etsu Chemical ■
LP-103) to N-methyl-2-pykylidone 709
9th para-terphenyl-a dissolved in 4. f
4'-Tetracarboxylic dianhydride 18.59 (0,05
mol) to combine the polyamic acid solution.

accomplished. The resulting polyamic acid solution had a nonvolatile content of 29% by weight and a viscosity of 1.400 poise (25°C). Next, this polyamic acid solution is heated at a temperature of around 70°C,
When the viscosity was adjusted, it decreased to 15 poise in 8 hours, and a polyamic acid solution containing ethylenically unsaturated groups with high concentration and low viscosity was obtained.

To this polyamic acid solution 209, 0.2 g of Irgacure 907 and 0.05 g of 2-isopropylthioxanthone were added.
sft was added, followed by pressure filtration using a filter with 1 μm pores to obtain a photosensitive resin composition (non-volatile content: 27% by weight).

Next, patterning was performed in the same manner as in Example 1, and a clear pattern could be obtained.

Example 6 To the polyamic acid solution 209 obtained in Example 5.

FA-731A (Tris (2-acryloylethyl (isocyanurate) manufactured by Hitachi Chemical Co., Ltd.) 1.0 g.

Irgacure 9071-0.29 and 2-isopropylthioxanthone 0.59 were added and filtered under pressure using a 9-order filter with 1 μm pores to obtain a photosensitive resin composition (nonvolatile content 31% by weight, viscosity 19 poise (25°C)). ) was obtained.

Next, when patterning was performed in the same manner as in Example 1, a clear pattern could be obtained.

Comparative Example 1 9.6 g of 3.5-diaminobenzyl acrylate (0,
05 mol), pyromellitic dianhydride 10.99 (0,
05 mol), N-methyl-2-pyrrolidone 499, the non-volatile content was 30% by weight, the viscosity was 1.
．． A 700 poise (25°C) polyamic acid solution was obtained.

This polyamic acid solution was heated at a temperature of around 80°C to adjust its viscosity.

An ethylenically unsaturated group-containing polyamic acid solution whose poise was reduced to 42 poise in 30 hours was obtained.

Add 0.2c of Irgacure 907 and 0.05g of 2-isopropylthioxanthone to this polyamic acid solution No. 20.
9 was added and filtered under pressure using a filter with 1 μm pores to obtain a photosensitive polymer composition (non-volatile content: 27% by weight). Next, patterning was performed in the same manner as in Example 1, and a clear pattern could be obtained.

Comparative example 2 3.5-diaminobenzyl acrylate 9.6 g (0,
05 mol), 3.3:44'-biphenyltetracarboxylic dianhydride 14.79 (0.05 mol), N-methyl-2-pyrrolidone 70 i1'! i- was synthesized in the same manner as in Example 1, with a nonvolatile content of 30% by weight and a viscosity of 4.
A polyamic acid solution of 300 poise (25° C.) was obtained. Next, this polyamic acid solution was heated at a temperature of around 80°C to adjust the viscosity.

The viscosity stopped decreasing and became constant around 170 poise, and when heating was continued, the solution began to become cloudy.

On the contrary, the viscosity increased and a low viscosity solution could not be obtained.

Comparative Example 3 3.5-diaminobenzyl acrylate 9.69 (O,
OS soru), &3S44'-benzophenonetetracarboxylic dianhydride x ax a (0,05 mol).

With N-methyl-2-pyrrolidone 60.99.

It was synthesized in the same manner as in Example 1 to obtain a polyamic acid solution with a nonvolatile content of 30% by weight and a viscosity of 1,800 poise (25°C). When this polyamic acid solution was heated at a temperature around 80°C to adjust the viscosity, it became 45 poise (25°C) in 20 hours.
A polyamic acid solution containing ethylenically unsaturated groups was obtained.

Next, Irgacure 9 was added to this polyamic acid solution 209.
07tO,29,2-isopropylthioxanthone o,
osg was added and filtered under pressure using a 1 μm pore filter to obtain a photosensitive polymer composition (non-volatile content: 24 qb by weight). Next, patterning was performed in the same manner as in Example 1, and a clear pattern could be obtained.

Next, Examples 1 to 6. After applying the photosensitive polymer compositions obtained in Comparative Examples 1 to 3 to a glass substrate and drying.

A film was created by heat treatment at 400°C for 1 hour.

The film was peeled off from the glass substrate and the film properties after curing were evaluated by the test method shown below.

Test method (1) Weight loss start temperature Measured using 10 mg of the above film using a differential thermal balance in air at a heating rate of 10° C./min.

(2) Weight loss rate Using the above film 80cm, the weight loss rate after being held in air at 460°C for 30 minutes was measured using the same apparatus as in (1).

(3) Elastic modulus The elastic modulus was measured using a viscoelasticity measuring device using a strip-shaped test piece of the above film 5 mm x 50 m+a.

In addition, changes in the viscosity (measured at 25° C.) of the photosensitive polymer composition were monitored.

The above results are shown in Table 1.

(Effects of the Invention) The photosensitive polymer composition of the present invention can have high concentration and low viscosity in a solution state, has good storage stability, and has good heat resistance in the final cured product.

It has excellent membrane properties such as flexibility.

[Brief explanation of the drawing]

Figure 1 shows the intermediate produced in Reference Example a, 4.3:
'H-NMR of 4'-tetramethyl-p-terphenyl
Figure 2 is the IIC-NMR spectrum of λ43:4'-tetramethyl-p-terphenyl. Figure 3 shows p-terphenyl-turtle c3 produced in reference example.
: Infrared absorption spectrum of 4'-tetracarboxylic acid,
Figure 4 shows the p-tar 7 enyl 3.4 produced in the reference example.
．． 3: IH-NMR spectrum of 4'-tetracarboxylic acid tetramethyl ester, Figure 5 shows p produced in the reference example.
-terphenyl-tortoise4. g 4'-Tetracarboxylic acid- & t a# The infrared absorption spectrum of 4#-dianhydride and Figure 6 show the p-terphenyl-kame c produced in the reference example.
The IH-NMR spectrum of a'i'-tetracarboxylic acid-&4K4'-dianhydride is shown. Procedural amendment (spontaneous) Date of May 22, 1985 Mr. Commissioner of the Patent Office Person name (us
1st Go Kasei Kogyo Co., Ltd. 4th Director (Telephone: Tokyo 346-3111 + Main Representative) - I will submit the tracing drawing as attached. that's all

Claims (1)

[Scope of Claims] A photosensitive resin composition comprising an ethylenically unsaturated group-containing polyamic acid having a structural unit represented by the following general formula (1) and a photopolymerization initiator. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (However, in the formula, R_1 is a tetravalent aromatic group represented by ▲There are mathematical formulas, chemical formulas, tables, etc.), and R_2 is an ethylenically unsaturated group. is a divalent aromatic group having