JP2540927B2 - Photosensitive resin composition and photosensitive element using the same - Google Patents

Description

Detailed Description of the Invention << Field of Industrial Application >> The present invention has excellent heat resistance, electrical and mechanical properties,
The present invention relates to a photosensitive resin composition suitable as an insulating film for a solid element in the semiconductor industry, a material for forming a passivation film, an interlayer insulating material for semiconductor integrated circuits, multilayer printed wiring boards and the like, and a photosensitive element using the same.

<< Prior Art >> In recent years, in the semiconductor industry, an organic material is used for interlayer insulation instead of a conventional inorganic material by utilizing its characteristics, and a material having excellent heat resistance such as a polyimide resin is mainly used. However, since a complicated step is required for pattern formation, it is desired to develop a heat-resistant photosensitive material that can be used as an insulating material by leaving it as it is even after pattern formation by exposure and development.

As these materials, for example, photosensitive polyimides, heat-resistant photosensitive materials based on cyclized polybutadiene as a base polymer, and the like have been proposed, and in particular, photosensitive polyimides have been particularly attracting attention because of their excellent heat resistance and easy exclusion of impurities. There is.

As a photosensitive polyimide, a system consisting of a polyimide precursor and a dichromate was first proposed (Japanese Patent Publication No. Sho 49-1).
No. 7374), this material has practical photosensitivity and has advantages such as high film-forming ability, but on the other hand, it lacks storage stability.
In addition, there is a defect that chromium ions remain in the polyimide, and it has not been practically used.

As another example, a photosensitive polyimide precursor in which a photosensitive group is introduced into a polyimide precursor by an ester bond has been proposed (Japanese Patent Publication No. 55-30207), but a dehydrochlorination reaction occurs when the photosensitive group is introduced. Because of the inclusion, the chloride finally remains, and this removal is a problem.

In order to avoid such problems, a method of mixing a compound having a photosensitive group with a polyimide precursor (JP-A-54-10982).
No. 8) or a method of introducing a photosensitive group by reacting a functional group in a polyimide precursor with a functional group of a compound having a photosensitive group (JP-A-56-243434). Sho 60-100143).

<< Problems to be Solved by the Invention >> However, in the photosensitive polyimide as described above, an aromatic polyimide precursor is used as a base polymer from the viewpoint of importance of heat resistance.

Such an aromatic polyimide precursor has an essential problem in solubility and has a low light transmittance in the ultraviolet region, which makes it difficult to form a thick film. Since it is difficult to form a thick film in this way, when it is used as an insulating material, there remain problems in flattening the circuit and lowering the dielectric constant, and improvement thereof is desired.

For example, when an aromatic polyimide precursor and a compound having a photosensitive group are dissolved as a photosensitive polyimide, most of the good solvent is volatilized in the drying step for forming a coating film from this solution, and the coating film after drying is dried. Is composed of an aromatic polyimide precursor and a compound having a photosensitive group.
Since the compound having such a photosensitive group is generally a poor solvent for the aromatic polyimide precursor, the aromatic polyimide precursor is insolubilized and a whitening phenomenon occurs in the coating film. Therefore, it becomes difficult to use the exposure process.

Also, in most photosensitive resins including photosensitive polyimide, the light energy absorbed by the coexisting photopolymerization initiator triggers the reaction, causing chemical or structural changes within or between molecules. Since most of the current photopolymerization initiators have an absorption wavelength in the ultraviolet region, the base polymer using an aromatic polyimide precursor with a small light transmittance in this region is a thick film. Difficult to form.

Therefore, in the photosensitive polyimide using the aromatic polyimide precursor as the base polymer, the film thickness is limited due to the whitening phenomenon and poor light transmission, and it is extremely difficult to form a thick film pattern. .

In order to avoid such problems of solubility and light transmission, a method of mixing a compound having a photosensitive group into an adduct solution obtained by adding an epoxy compound having a polymerizable unsaturated bond to an aliphatic polyimide precursor. (JP-A-59-68332) has also been developed, but there is a problem that an adduct is difficult to obtain due to low reactivity between an epoxy compound epoxy group and a polyimide precursor.

In view of the above problems, it is an object of the present invention to provide a photosensitive resin composition that has excellent solubility and light transmission properties and that can form a thick film.

<< Means for Solving the Problem >> The present invention relates to a photosensitive resin composition containing an ethylenically unsaturated group-containing polyamic acid having a repeating unit represented by the following general formula (I) and a photoinitiator.

(However, in the formula, R ₁ is Which is a tetravalent alicyclic group represented by R ₂ and R ₂ is a divalent aromatic group having an ethylenically unsaturated group) Further, in the present invention, the photosensitive resin composition is laminated on a substrate. To a photosensitive element.

The ethylenically unsaturated group-containing polyamic acid used in the present invention is, for example, a novel dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride represented by the following formula (II): It is obtained by reacting a diamine containing an ethylenically unsaturated group in an organic solvent.

This acid anhydride is a novel compound and is obtained by the reaction of the following formula (III).

For example, biphenyl-3,4,3 ', 4'-tetracarboxylic acid tetramethyl ester is hydrogenated using a rhodium catalyst, and an aqueous solution containing a mineral acid catalyst is added to this to heat reflux to hydrolyze. Do.

Then, by heating or adding acetic anhydride, dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride can be obtained.

When obtaining an ethylenically unsaturated group-containing polyamic acid, an aromatic tetracarboxylic acid dianhydride may be used in combination to the extent that solubility and light transmittance are not deteriorated.

Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, and 3,3', 4,4'-biphenyltetracarboxylic acid. Acid dianhydride, meta-ta-phenyl-3,
3 ″, 4,4 ″ -tetracarboxylic dianhydride, para-phenyl-3,3 ″, 4,4 ″ -tetracarboxylic dianhydride, 1,
2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7
-Naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylene Examples thereof include tetracarboxylic dianhydride and 4,4′-sulfonyldiphthalic dianhydride.

Examples of the diamine containing an ethylenically unsaturated group used in the present invention include, for example, 4,4′-diaminochalcone,
3,4'-diaminochalcone, 4,4'-diaminodibenzalacetone, 3,4'-diaminodibenzalacetone, 3,5-
Diaminobenzoic acid ethyl acrylate, 3,5-diaminobenzoic acid ethyl methacrylic acid ester, 3,5-diaminobenzoic acid glycidyl acrylate, 3,5-
Glycidyl methacrylic acid diaminobenzoate, 3,
5-Diaminobenzoic acid cinnamic acid ester, 2,4-diaminobenzoic acid ethyl acrylate, 2,4-diaminobenzoic acid ethyl methacrylic acid ester, 2,4-diaminobenzoic acid glycidyl acrylate, 2,4- Diaminobenzoic acid glycidyl methacrylic acid ester, 2,4-diaminobenzoic acid cinnamic acid ester, 4-acrylamide-
3,4'-diaminodiphenyl ether, 3,4'-diacrylamide-3,4'-diaminodiphenyl ether, 4-
Cinnamamide-3,4'-diaminodiphenyl ether, 3,5-diaminobenzyl acrylate, 3,5-diaminobenzyl methacrylate, 2,4-diaminobenzyl acrylate, 2,4-diaminobenzyl methacrylate,
And diamines represented by the following formulas.

Further, when obtaining the polyamic acid containing an ethylenically unsaturated group, another diamine or diaminoamide compound containing no ethylenically unsaturated group may be used in combination to the extent that the sensitivity of the composition is not deteriorated.

Examples of the diamine containing no ethylenically unsaturated group include, for example, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl sulfide, Benzidine, meta-phenylenediamine, para-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4-aminophenoxyphenyl)
Aromatic diamines such as sulfones may be mentioned.

In addition, the following general formula (IV) (Wherein R ₃ is a divalent hydrocarbon group, R ₄ is a monovalent hydrocarbon group, and m is an integer of 1 or more), and a diaminosiloxane represented by the formula can be used. Is, for example, Etc.

Examples of the diaminoamide compound containing no ethylenically unsaturated group include, for example, 4,4′-diaminodiphenyl ether-3-sulfonamide, 3,4′-diaminodiphenyl ether-4-sulfonamide and 3,4′-diamino. Diphenyl ether-3'-sulfonamide, 3,4 '
-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 ′
-Diaminodiphenyl sulfide-3-sulfonamide, 3,3'-diaminodiphenyl sulfide-4-sulfonamide, 3,4'-diaminodiphenyl sulfide-3'-sulfonamide, 1,4-diaminobenzene-
2-sulfonamide, 4,4'-diaminodiphenyl ether-3-carbonamide, 3,4'-diaminodiphenyl ether-4-carbonamide, 3,4'-diaminodiphenyl ether-3'-carbonamide, 3,3'diamino Diphenyl ether-4-carbonamide, 4,4 '
-Diaminodiphenylmethane-3-carbonamide, 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'-diaminodiphenyl sulfide-3-carbonamide,
3,4'-diaminodiphenyl sulfide-4-carbonamide, 3,3'-diaminodiphenyl sulfide-
4-carbonamide, 3,4'-diaminodiphenyl sulfide-3'-sulfonamide, 1,4-diaminobenzene-2-sulfonamide and the like can be mentioned.

Incidentally, when using an aromatic tetracarboxylic acid dianhydride, a diamine containing no ethylenically unsaturated group, a diaminocycloxane represented by the general formula (IV) and a diaminoamide compound containing no ethylenically unsaturated group, The ethylenically unsaturated group-containing polyamic acid can contain a repeating unit different from the repeating unit represented by the general formula (I).

The polyamic acid in the present invention is, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-
Dimethylformamide, dimethyl sulfoxide, N, N-
After dissolving the above diamine component in a highly polar organic solvent such as dimethylpropyleneurea, N, N-dimethylethyleneurea, hexamethylenephosphoramide, tetramethylenesulfone, p-chlorophenol, p-bromophenol, dicyclohexyl- It can be obtained by adding 3,4,3 ', 4'-tetracarboxylic dianhydride or an acid component containing the same 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.

Examples of the photoinitiator 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-butylanthraquinone, 1,2-benzo-9, 1
0-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-hydroxycyclohexyl phenyl ketone, 2-methyl- [4- (methylthio) phenyl] -2-morpholino-1-propanone, diacetyl, benzyl, benzyl dimethyl ketal, benzyl diethyl ketal, diphenyl disulfide, 3, Examples thereof include 3'-carbonylbis (7-diethylamino) coumarin, 2,6-bis (PN, N-diethylaminobenzylidene) -4-methyl-4-azacyclohexanone and anthracene.

The amount of these photoinitiators used, from the viewpoint of the sensitivity of the photosensitive resin composition and the heat resistance of the coating film, may be 0.01 to 30 parts by weight relative to 100 parts by weight of the ethylenically unsaturated group-containing polyamic acid. It is more preferably 0.1 to 10 parts by weight.

A small amount of known photoinitiators amines can be used in combination with these photoinitiators.

Specific examples of such amines include ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, isoamyl p-dimethylaminobenzoate, isoamyl p-diethylaminobenzoate, and 2- (dimethylamino) ethyl benzoate. p-dimethylaminobenzaldehyde, p-diethylaminobenzaldehyde, ethyl N, N-diethylanthranilate, p-dimethylaminobenzonitrile, p-diethylaminobenzonitrile, N-
Phenylglycine, N- (P-chlorophenyl) glycine, N- (P-cyanophenyl) glycine, N- (P-
Bromophenyl) glycine, N, N-diethylaminonaphthalene and the like can be mentioned.

Further, in order to improve the thermal stability of the photosensitive resin composition, a known thermal polymerization inhibitor can coexist.

Examples of the thermal polymerization inhibitor include p-methoxyphenol, hydroquinone, t-butylcatechol, pyrogallol, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di-t-butyl-p.
-Cresol, pyridine, nitrobenzene, p-toluidine, methylene blue, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), etc. The amount used is preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the polyamic acid containing an ethylenically unsaturated group.

In the present invention, a polymerizable unsaturated compound may be used if necessary, and acrylic acid compounds and methacrylic acid compounds are practical.

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, carbitol 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 Acrylate, dipropylene glycol diacrylate, 2,2-bis- (4-
Acryloxydiethoxyphenyl) propane, 2,2-bis- (4-acryloxypropyloxyphenyl) propane, trimethylolpropane diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, triacrylformal , Tetramethylolmethane tetraacrylate, acrylic acid ester of tris (2-hydroxyethyl) isocyanuric acid, Etc. can be mentioned.

Examples of the methacrylic acid compound 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, Methacryloxy propyl trimethoxy silane, allyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexane glycol dimethacrylate, neopentyl glycol dimethacrylate, 2,2
Bis- (4-methacryloxydiethoxyphenyl) propane, trimethylolpropane dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, tetramethylolmethane tetramethacrylate, tris (2-hydroxyethyl) isocyanuric acid Of methacrylic acid ester, Etc. can be mentioned.

The photosensitive resin composition of the present invention can be brought into a solution state by dissolving the ethylenically unsaturated group-containing polyamic acid and the photoinitiator in a suitable organic solvent. As this organic solvent, the organic solvent used in the reaction for producing the polyamic acid may be used, or another organic solvent may be used. In such a case, the amount of the organic solvent used is preferably 20 to 95% by weight of the photosensitive resin composition, and more preferably 40 to 90% by weight.

The photosensitive resin composition of the present invention can be patterned by a usual fine processing technique.

The photosensitive resin composition of the present invention can be applied on a supporting substrate such as a glass substrate or a silicon wafer by means of spin coating using a spinner, dipping, spray printing, etc. and dried to form a coating film. The thickness of the coating film can be adjusted by the coating means, the solid content concentration and viscosity of the varnish of the photosensitive resin composition of the present invention.

In addition, a photosensitive resin composition is applied on a flexible substrate, for example, a polyester film, dried and laminated, and a cover sheet of polyethylene or the like is provided on the substrate to preliminarily prepare a photosensitive element having a sandwich structure. It is also possible to peel off the cover sheet of the photosensitive element and form a coating on the substrate to be coated. The cover sheet does not necessarily have to be used.

A relief pattern can be obtained by imagewise irradiating the coating film on the supporting substrate with actinic rays and then dissolving and removing the unexposed portion with a developing solution. At this time, ultraviolet light, visible light, radiation or the like can be used as the light source.

Examples of developers include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortriamide, and dimethylimidazolidinone. , N-benzyl-2-pyrrolidone,
An aprotic polar solvent such as N-acetyl-ε-caprolactam is used alone or as a non-solvent for a polyamic acid, for example, methanol, ethanol, isopropyl alcohol, benzene, toluene, xylene, cyclohexanone, cyclopentanone, acetone, methyl ethyl ketone, It is used as a mixed solution with methyl cellosolve, water, a base, a basic aqueous solution and the like.

Examples of the base include monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate and the like. When preparing a basic aqueous solution, the amount of the base used is preferably 0.0001 to 30 parts by weight, and 0.05 to 5 parts by weight, relative to 100 parts by weight of water.
More preferably, it is parts by weight.

Then, the relief pattern formed by the development can be washed with a rinse liquid to remove the developing solvent.

As the rinse liquid, a non-solvent of polyamic acid having good miscibility with the developer is used, and examples thereof include methanol, ethanol, isopropyl alcohol, benzene, and toluene.
Examples include xylene, methyl cellosolve, water and the like.

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

<< Example >> Hereinafter, the present invention will be described with reference to Examples, Comparative Examples and Reference Examples.

Reference example Synthesis example of dicyclohexyl-3,4,3 ', 4'-tetracarboxylic acid and its anhydride (1) Production of dicyclohexyl-3,4,3', 4'-tetracarboxylic acid tetramethyl ester Biphenyl-3,4,3,3 ', 4' in a 500 ml autoclave (SE-50 type electromagnetic vertical stirring autoclave manufactured by Sakashita Chemical Co., Ltd.) equipped with a stirrer
-Tetracarboxylic acid tetramethyl ester 38.6 g (0.100
Mol), 193 g of tetrahydrofuran, and 3.86 g of a catalyst (made by Nippon Engelhard Co., Ltd.) in which activated carbon is loaded with 5 wt% rhodium, hydrogen pressure of 30 kg / cm ² , reaction temperature of 100 ° C.
The hydrogenation reaction was carried out. The hydrogen consumption stopped at the reaction time of 3.5 hours, and the hydrogen consumption amount calculated from the decrease amount of the hydrogen pressure in the accumulator at that time was 9 times the theoretical hydrogen consumption amount (0.60 mol).
It was 8.7%.

After removing the activated carbon-supported rhodium catalyst in the reaction solution by filtration, the solvent tetrahydrofuran was removed by evaporation, and white waxy dicyclohexyl-3,4,4,
36 'of 3', 4'-tetracarboxylic acid tetramethyl ester.
87 g (0.0925 mol) was obtained. ^{As a result of 1} H-NMR (Hitachi Ltd. Hitachi R-250 type nuclear magnetic resonance spectrometer) analysis, hydrogen on the benzene nucleus hydrogen and carbon-carbon double bond was not found, and the hydrogenation reaction It turned out to be complete.

(2) Production of dicyclohexyl-3,4,3 ', 4'-tetracarboxylic acid Dicyclohexyl-3,4,3', 4'-tetracarboxylic acid methyl ester 2 was placed in a round-bottomed flask equipped with a cooling tube.
After adding 9.9 g (0.075 mol) and adding 200 g of methanol to this to make a homogeneous solution, 200 g of 10% sodium hydroxide solution was added, and the mixture was placed in an oil bath at 100 ° C. and refluxed for 6 hours. Then, methanol was distilled off by evaporation, the reaction solution was concentrated to 140 g, and 48 ml of 36% hydrochloric acid was added to adjust the pH to 1. The solution becomes cloudy at pH 4 to 5, pH 1
Then, a white fine powder was precipitated. The precipitate was filtered off, washed with water and dried to obtain 17.8 g of white fine powdery crystals of dicyclohexyl-3,4,3 ', 4'-tetracarboxylic acid (0.052 mol).

Infrared absorption spectrum of this crystal (measured by KBr method using Hitachi 260-30 type infrared spectrophotometer manufactured by Hitachi, Ltd.)
Is shown in FIG. ¹ , and its ¹ H-NMR spectrum is shown in FIG.

In FIG. 2, the absorption at 2.50 ppm is absorption based on the solvent d ₆ -dimethyl sulfoxide, and the absorption at 3.35 ppm is absorption due to water contained in the solvent. In the absorption excluding these two, the integrated intensity ratio of the absorption based on the carboxyl group proton of 11.95 ppm and the absorption based on the cyclohexane ring proton of 0.87 to 3.00 ppm is 29: 1 for the former: the latter.
32 (= 4: 18.2), which was in agreement with the theoretical value (compound of formula (I)).

The melting point of this crystal was 219 to 222 ° C., and as a result of elemental analysis, it was 56.24% carbon and 6.53% hydrogen, which were in agreement with the calculated values of 56.13% carbon and 6.48% hydrogen for the compound of formula (I).

(3) Preparation of dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride In a 300 ml eggplant-shaped flask equipped with a cooling tube, dicyclohexyl-3,4,3', 4'-tetracarboxylic acid 15.0 was added. g (0.04
4 mol) and 180 g of acetic anhydride were charged and put in an oil bath at 150 ° C. for reflux for 1 hour.

Thereafter, filtration was performed while heating, and the filtrate was allowed to cool, whereby white crystals were precipitated. The crystals were taken out by filtration and dried at a pressure of 30 mmHg and a temperature of 100 ° C. for 2 hours to give 10.8 g (0.035 mol) of crystals.

The melting point of the crystal was 231 to 234 ℃. Elemental analysis showed that the carbon was 62.59% and hydrogen was 6.01%, which were in good agreement with the theoretical values (compound of formula (II)) carbon 62.74% and hydrogen 5.92%.

The infrared absorption spectrum of this crystal is shown in FIG. 3, and the ¹ 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 10 to 13 ppm, and the substance is an anhydride.

Example 1 A diamine solution was prepared by dissolving 11.9 g (0.05 mol) of 4,4'-diaminochalcone in 70 g of N-methyl-2-pyrrolidone under a nitrogen stream.

Next, while maintaining this solution at a temperature of about 15 ° C. with water cooling, dicyclohexyl-3, obtained in Reference Example, was stirred under stirring.
15.4 g (0.05 mol) of 4,3 ', 4'-tetracarboxylic dianhydride was added, and stirring was continued at room temperature for 8 hours to obtain a polyamic acid solution.

Irgacure 907 (2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one manufactured by Ciba-Geigy) was added to 20 g of this polyamic acid solution.
1 g and 0.01 g of 2-isopropylthioxanthone (manufactured by Ward Brekinsop Co., Ltd.) were added, and then pressure filtration was performed using a filter having a pore size of 1 μm to obtain a photosensitive resin composition.

Then, this composition was applied onto a silicon wafer with a spinner and dried at 80 ° C. for 10 minutes to obtain a photosensitive film having a thickness of 20.5 μm. This coating was contact-exposed using a 80-μm line-and-space striped photomask and irradiated with a 500 W ultra-high pressure mercury lamp at 600 mJ / cm ² . After exposure, N-methyl-2
-Pyrrolidone, ethanol and 2% tetramethylammonium hydroxide aqueous solution (N-methyl-2
-Pyrrolidone / ethanol / 20% tetramethylammonium hydroxide aqueous solution = 1/4/5 (weight ratio)), and then rinsed with ethanol to obtain a relief pattern.

Then, heat treatment was performed at 180 ° C. for 30 minutes and 300 ° C. for 60 minutes in a nitrogen atmosphere to obtain a polyimide relief pattern having a film thickness of 11.5 μm. At this time, the pattern firmly adhered to the substrate, and the pattern of the photomask was faithfully transferred.

Example 2 Instead of the 4,4'-diaminochalcone used in Example 1, 9.6 g (0.05 mol) of 3.5-diaminobenzyl acrylate was dissolved in 70 g of N-methyl-2-pyrrolidone, then dicyclohexyl-3, A solution of polyamic acid was synthesized by adding 15.4 g (0.05 mol) of 4,3 ', 4'-tetracarboxylic dianhydride.

To 20 g of this polyamic acid solution, 0.2 g of Irgacure 907
And 0.05 g of 2-isopropylthioxanthone are added,
Then, pressure filtration was performed using a filter having a pore size of 1 μm to obtain a photosensitive resin composition.

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

Example 3 In place of 4,4′-diaminochalcone used in Example 1, 3,5-diaminobenzoic acid ethyl acrylate 1
2.5 g (0.05 mol) was dissolved in 65 g N-methyl-2-pyrrolidone, then 12.3 g (0.04 mol) dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride and 3,3' ,Four,
2.94 g of 4'-biphenyltetracarboxylic dianhydride (0.01
Mol) was added to synthesize a polyamic acid solution.

To 20 g of this polyamic acid solution, 3.0 g of ethyl N, N-diethylaminobenzoate (manufactured by Wako Pure Chemical Industries, Ltd.) and 2.0 g of 2,4-diethylthioxanthone (manufactured by Nippon Kayaku Co., Ltd.) were added, and then a filter having a pore size of 1 μm was added. It pressure-filtered using and obtained the photosensitive resin composition.

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

Example 4 Under nitrogen stream, 4,4'-diaminochalcone 9.52 g (0.04 mol) and 4,4'-diaminodiphenyl ether 2.0 g
(0.01 mol) was dissolved in 70 g of N-methyl-2-pyrrolidone, and then 15.4 g (0.05 mol) of dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride was added, The solution was synthesized.

To 20 g of this polyamic acid solution, 0.15 of Irgacure 907 was added.
g and 2-isopropylthioxanthone 0.05 g,
Then, pressure filtration was performed using a filter having a pore size of 1 μm to obtain a photosensitive resin composition.

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

Example 5 3,5'-Diaminobenzyl acrylate under nitrogen stream
9.12 g (0.045 mol) and 1,3-bis (γ-aminopropyl) -1,1,3,3-tetramethyldisiloxane 1.24 g (0.
(005 mol) (LP-103 manufactured by Shin-Etsu Chemical Co., Ltd.) was dissolved in 70 g of N-methyl-2-pyrrolidone, and then 15.4 g of dicyclohexyl-3,4,3 ', 4'-tetracarboxylic dianhydride.
(0.05 mol) was added to synthesize a polyamic acid solution.

To 20 g of this polyamic acid solution, 0.2 g of Irgacure 907
And 0.05 g of 2-isopropylthioxanthone are added,
Then, pressure filtration was performed using a filter having a pore size of 1 μm to obtain a photosensitive resin composition.

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

Example 6 To 20 g of the polyamic acid solution obtained in Example 5, FA-731A was added.
(Hitachi Chemical Co., Ltd., tris (2-acryloylethyl (isocyanurate) 1.0 g, ethyl N, N-diethylaminobenzoate 3.0 g and 2,4'-diethylthioxanthone 2.0 g) were added, and then a filter having a pore size of 1 μm was added. It pressure-filtered using and obtained the photosensitive resin composition.

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

Comparative Example 1 Journal of Organic Chemistry (J.
Org. Chem.) Vol. 31, p. 3438 (1966), 1,2,4,5-cyclohexanetetracarboxylic acid was synthesized and dehydrated and ring-closed by using acetic anhydride. , 2,4,
5-Cyclohexanecarboxylic acid dianhydride was obtained. Using 15.692 g (70 mmol) of this acid anhydride, 14.28 g (70 mmol) of 4,4'-diaminochalcone and 69.321 g of N-methyl-2-pyrrolidone, a polyamic acid solution was synthesized in the same manner as in Example 1. did.

Next, when patterning was performed by the same operation as in Example 1, cracks were generated in the pattern after development, and image formation was not possible.

Comparative Example 2 Dicyclohexyl-3,4,3 ', 4'- used in Example 1
Instead of tetracarboxylic dianhydride, 14.7 g (0.05 mol) of biphenyltetracarboxylic dianhydride was dissolved in 100 g of N-methyl-2-pyrrolidone, and then 9.6 g (0.05 mol of 3,5-diaminobenzyl acrylate). ) Was added to synthesize a polyamic acid solution.

To 20 g of this polyamic acid solution, 0.2 g of Irgacure 907
And 0.05 g of 2-isopropylthioxanthone are added,
Then, pressure filtration was performed using a filter having a pore size of 1 μm to obtain a photosensitive resin composition.

Next, patterning was performed by the same operation as in Example 1. As a result, after development, cracks were generated in the pattern, and it was not possible to form an image.

<< Effects of the Invention >> The photosensitive resin composition and the photosensitive element using the same according to the present invention are excellent in solubility and light transmittance and can provide an interlayer insulating material capable of forming a thick film.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of dicyclohexyl-3,4,3 ', 4'-tetracarboxylic acid, which is an intermediate produced in Reference Example, FIG. 2 is its ¹ H-NMR spectrum, and FIG. 3 is Reference Example. The infrared absorption spectrum of the dicyclohexyl-3,4,3 ', 4'-tetracarboxylic acid anhydride prepared in ^1. is the ¹ H-NMR spectrum.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Takayuki Saito, 4-13-1, Higashimachi, Hitachi, Ibaraki Prefecture, Ibaraki Laboratory, Hitachi Chemical Co., Ltd. (72) Toshiaki Ishimaru, 4-13, Higashimachi, Hitachi, Ibaraki No. 1 Hitachi Chemical Co., Ltd. in Ibaraki Research Center (72) Inventor Nobuyuki Hayashi 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. in Ibaraki Research Center (72) Inventor Mitsumasa Kojima 4 Higashimachi, Hitachi City, Ibaraki Prefecture 13-13-1 Hitachi Chemical Co., Ltd. Yamazaki factory (56) References JP-A-60-72925 (JP, A) JP-A-58-55926 (JP, A)

Claims (2)

(57) [Claims] 1. A photosensitive resin composition comprising an ethylenically unsaturated group-containing polyamic acid having a repeating unit represented by the following general formula (I) and a photoinitiator. (However, in the formula, R ₁ is Is a tetravalent alicyclic group represented by and R ₂ is a divalent aromatic group having an ethylenically unsaturated group) 2. A photosensitive element obtained by laminating the photosensitive resin composition according to claim 1 on a substrate.