JPS63175854A - Image producing method - Google Patents

Abstract

PURPOSE:To obtain an image having superior heat resistance and a thick film by forming a photosensitive layer with a photosensitive resin compsn. contg. a polyimide precursor having specified repeating units, a polymerizable unsatd. compd., a photopolymn. initiator and an org. solvent. CONSTITUTION:A photosensitive layer is formed on a base with a photosensitive resin compsn. contg. a polyimide precursor having repeating units represented by the formula, a polymerizable unsatd. compd., a photopolymn. initiator and an org. solvent. In the formula, R1 is a quatervalent aliphat. or alicyclic group and R2 is a bivalent arom., aliphat. or alicyclic group or an organosiloxane group. The polyimide precursor is easily obtd. with aliphat. or alicyclic tetracarboxylic acid or anhydride thereof and a diamine compd. as starting materials. The aliphat. or alicyclic tetracarboxylic acid or anhydride thereof may be butanetetracarboxylic acid or pentanetetracarboxylic acid. When the photosensitive layer is used, an image having superior heat resistance and a thick film can be obtd. with safety in working environment.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing a thick ll1Ii image with excellent heat resistance. Excellent material for forming insulating films and pansivation films for solid-state devices in the semiconductor industry.

Image production using a photosensitive resin composition suitable as an interlayer insulation material for semiconductor integrated circuits, multilayer printed wiring boards, etc.
#Relating to construction methods.

(Prior Art) In recent years, in the semiconductor industry, organic materials have been used for interlayer insulation, which was previously performed using inorganic materials.

It is used to take advantage of its characteristics, and materials with excellent heat resistance, such as polyimide resin, are mainly used.

However, since pattern formation requires a complicated process, there is a desire for a heat-resistant photosensitive material that can be used as an insulating material by leaving the pattern intact after exposure and development.

Two examples of these materials are photosensitive polyimide.

Heat-resistant photosensitive materials using cyclized polyfridiene as a pace polymer have been proposed, and 2% photosensitive polyimide is attracting particular attention because of its excellent heat resistance and ease of removing impurities.

As a photosensitive polyimide, a system consisting of a polyimide precursor and a dichromate was first proposed (Japanese Patent Publication No. 49-1989).
Although this material has advantages such as practical photosensitivity and high film-forming ability, it has disadvantages such as poor storage stability and residual chromium ions in the polyimide.

It was not put into practical use. As another example, a photosensitive polyimide precursor has been proposed in which a photosensitive group is introduced into the polyimide precursor through an ester bond (Japanese Patent Publication No. 55-3020
No. 7), since a dehydrochloric acid reaction is involved when introducing a photosensitive group, chloride remains in the end, and its removal poses a problem.

In order to avoid such problems, a method of mixing a compound having a photosensitive group with a polyimide precursor (Japanese Patent Laid-Open No. 54-1
09828) and 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 has also been developed (Japanese Patent Laid-Open No. 56-24343).
(Japanese Unexamined Patent Publication No. 1988-100143).

However, these photosensitive polyimides.

An aromatic polyimide precursor is used as a base polymer from the viewpoint of its heat resistance. Such aromatic polyimide precursors have an essential problem in solubility and further have low light transmittance in the ultraviolet region, making it difficult to form a thick film. Because it is difficult to form a thick film, problems remain in flattening the circuit and lowering the dielectric constant when used as an insulating material.

Improvement is desired. For example, when an aromatic polyimide precursor and a compound having a photosensitive group are dissolved to form a photosensitive polyimide, most of the good solvent evaporates during the drying process to form a coating film from this solution, and the coating film after drying is ,
It is composed of an aromatic polyimide precursor and a compound having a photosensitive group. Compounds having such photosensitive groups are generally poor solvents for aromatic polyimide precursors, so the aromatic polyimide precursor becomes insolubilized and causes a whitening phenomenon in the coating film. It becomes difficult to subject the film to the exposure process.

In addition, in most photosensitive resins, including photosensitive polyimides, the light energy absorbed by the coexisting photopolymerization initiator triggers the reaction, causing chemical or structural changes within or between molecules. This is because most of the current photopolymerization initiators have absorption wavelengths in the ultraviolet region.

With a base polymer using an aromatic polyimide precursor having low light transmittance in this region, it is difficult to form a thick film. For this reason, with photosensitive polyimide using an aromatic polyimide precursor as a base polymer, the film thickness is limited due to the whitening phenomenon and poor light transmittance, making it extremely difficult to form a thick film pattern.

In addition, a method using an aliphatic polyimide precursor to improve solubility and light transmittance (Japanese Unexamined Patent Publication No. 59-154
49, JP-A-59-100135) and a method of adding an epoxy compound having a polymerizable unsaturated bond to an aliphatic polyimide precursor (JP-A-59-13192).
However, since these methods use an organic bath agent during development, workers may inhale solvent vapor during development, causing odors to build up in the work area. There are problems in that it is harmful to the environment, there is a risk of ignition if a flammable solvent is used, and a treatment device is required if the developer waste solution contains a high concentration of organic matter.

(Problems to be Solved by the Invention) The present invention solves the problems of the prior art shown above, and
This provides a method for producing a thick film image with excellent 1 liter heat resistance.

(Means for Solving the Problems) The present invention provides (1) two formulas (1) (wherein r
tt is a tetravalent aliphatic group or alicyclic group, and 几2 is 2
These are aromatic groups, aliphatic groups, alicyclic groups, or organosiloxane groups. ) A step of forming a photosensitive layer from a photosensitive resin composition containing a polyimide precursor 1 polymerizable unsaturated compound, a photopolymerization initiator, and an organic solvent.

The present invention relates to a method for producing an image, which includes (2) imagewise exposing a photosensitive layer to actinic light and (3) developing with an alkaline aqueous solution.

The polyimide precursor having a repeating unit represented by the above formula (1) in the present invention is already a known compound,
It can be easily obtained using an aliphatic or alicyclic tetracarboxylic acid or its anhydride and a diamine compound as starting materials.

Aliphatic or alicyclic tetracarboxylic acids or anhydrides thereof include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, cyclopentanetetracarboxylic acid, bicyclohexenetetracarboxylic acid,
Cyclopropane tetracarboxylic acid, cyclobutane tetracarboxylic acid.

Tetracarbo/acids such as cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, methyl-cyclohexenetetracarboxylic acid, ethylenetetracarboxylic acid or anhydride thereof, 2,3.5-)'J carboxycyclopentyl acetic acid or anhydride thereof.

Bicyclo-(2.2)-oct-7ene-2.35°6-tetracarboxylic acid or its anhydride, Tetrahydrofuran-2,3,4,5-tetracarboxylic acid or its anhydride, 5-(2, 5-dioxotetrahydrofuryl)-3
-Methyl-3-cyclohexene-1,2-dicarboxylic acid or its anhydride, 3,5,6-dolycarboxy-2-carboxymethylnorbornane-2:3.5:6 or its anhydride, 5.5'- Thiobis(norponane-2,3-dicarboxylic acid) or its anhydride, 5,5'-methylenedithiobis(norbote/-43-dicarboxylic acid) or its anhydride, j5'-ethylenedithiobis(norponane-2.
3-dicarboxylic acid) or its anhydride, 5,5'-propylenedithiobis(norbonane-2,3-dicarboxylic acid)
or its anhydride, s,s'-sulfonylbis(norbonanth-3-dicarboxylic acid) or its anhydride, 5.5'
-methylenedisulfonylbis(norponane-2,3-dicarboxylic acid) or its anhydride, 5,5'-ethylenedisulfonylbis(norponane-2,3-dicarboxylic acid) or its anhydride, 5,5'-propylenedisulfonyl Examples include bis(norbonanth-3-dicarboxylic acid) or anhydride thereof. Of course, the skeleton of these tetracarboxylic acids or their anhydrides may be substituted with a substituent such as an alkyl group. These tetracarboxylic acids or their anhydrides can be used alone or in combination of two or more.

In addition, the diamine compound which reacts with the above-mentioned tetracarboxylic acid or its anhydride to give a polyimide precursor is 1
Examples include compounds represented by formula (2) % formula % (2) (in the formula, 114 is a divalent aromatic group, aliphatic group, alicyclic group, or organosiloxane group). A preferable horse in formula (2) is 1, for example.

I (wherein Xs, Xs, Xs and X4 may be the same or different and represent a hydrogen atom, a monovalent group of a hydrocarbon compound or a substitute thereof, and Y is -CHz -C2H<).

OCHs CFs is -CONH- l -(CHz)m (m is 2
~5° integer) (CHz)3C(CHsn, -9Hs R4R4 R@horse (in the formula, Rs and R6 are divalent organic groups, R4,
Rse islands and mountains are monovalent groups of the same or different hydrocarbon compounds or substituents thereof, /, is O or 1 to 2
is an integer of 0).

Specific examples of the diamine compound represented by the above formula (2) include p-phenylene diamine, m-phenylene diamine, and 4,4'-diaminodiphenylmethane.

4.4'-Diaminodiphenylethane, benzidine.

4.4'-diaminodiphenyl sulfide, 4.4'-
Diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone.

4.4'-Diaminobenzopheno7.1.5-diaminonaphthalene, 3.3'-dimethyl-4,4'-diaminobiphenyl, 3.4'-diaminodiphenyl ether.

2.2-di(p-aminophenyl)fluoropropane, 3.4'-diaminobenzanilide, m-xylylenediamine, p-xylylenediamine, ethylenediamine, 1.3-propanediamine, tetramethylenediamine , pentamethylene diamine.

Hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, 4.4
'-Dimethylhebutamethylenediamine.

1.4-diaminocyclohexane, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-
Metanoing nylene dimethylene diamine.

Tricyclo(6,2,1,O'']-Urandecylenedimethyldiamine R,R (In both formulas, 几 is H or CH3) (In both formulas, R' is H, CHs, C1l or Br)C
Examples include Hs CH3 and the like. These diamine compounds are
One type can be used alone or two or more types can be used in combination.

The reaction between an aliphatic or alicyclic tetracarboxylic acid or its anhydride and a diamine compound is usually carried out in an inert organic solvent.
It is usually carried out at a temperature of θ to 100°C, preferably 5 to 60°C, and is obtained as a solution of the polyimide precursor in an organic solvent. The ratio of the aliphatic or alicyclic tetracarboxylic acid or its anhydride and the diamine compound is 0.8/1 to 1.
It is preferable to use them in a ratio of 2/1 (molar ratio), and it is particularly preferable to use them in equimolar amounts.

As the organic solvent used in the above reaction, it is generally preferable to use a polar solvent that completely dissolves the produced polyimide precursor.
For example, N-methyl-2-pyrrolidone.

N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, tetramethylurea,
Examples include hexamethylphosphoric acid triamide, r-butyrolactone, and the like. In addition to these polar solvents, alcohols are common organic solvents.

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, r-butyrolact/, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane.

1,2-dichloroethane, 1,4-dichlorobutane.

Triqual ethane, chlorpenzea, O-dical benzene, hexane, heptane, octane, benzene,
Toluene, xylene, etc. 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 needle used for this organic solvent is 1 in the photosensitive resin composition.
It is 0 to 95% by weight, preferably 30 to 80% by weight.

There are various types of polymerizable unsaturated compounds used in the present invention, and acrylic acid compounds, methacrylic acid compounds, and the like are practical. A specific example of an acrylic acid compound is acrylic acid.

Methyl acrylate, ethyl acrylate, n-propyl acrylate, improvil acrylate, n-butyl acrylate, inbutyl acrylate, cyclohexyl acrylate, benzyl acrylate, carpitol acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate,
and droxyethyl acrylate, hydroxypropyl acrylate, petite/glycol monoacrylate.

N, N-dimethylaminoethyl acrylate), N, N-
Diethylaminoethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, pentaerythritol monoacrylate.

Trimethylolpropane monoacrylate, Oriru acrylate, 1.3-propylene glycol diacrylate, 1.4-butylene glycol diacrylate, 1.
6-hexane glycol diacrylate, neopentyl glycol diacrylate.

Diglobylene glycol diacrylate, 2-bis-
(4-acryloxyjethoxyphenylphenyl, 2-bis-(4-acryloxypropylxphenyl)
Acrylic acid of propane, trimethylolpropane diacrylate, be/taerythritol diacrylate, trimethylalpropane triacrylate, pentaerythritol triacrylate, triacryl formal, tetramethylolmethanetetraacrylate, tris(2-hydroxyethyl)isocyanuric acid ester.

(n is an integer from 1 to 30 j
Examples of methacrylic acid compounds include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, cyclohe Xyl methacrylate, benzyl methacrylate, octyl methacrylate, ethylhexyl methacrylate, methoxyethyl methacrylate.

ethoxyethyl methacrylate, butoxyethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxybentyl 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, neobenchi 2,2-bis-(4-methacryloxyjethoxyphenyl)propane, trimethylolpropane dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, tetramethylolmethanetetramethacrylate, Methacrylic acid ester of tris(2-hydroxyethyl)incyanuric acid.

(n is an integer of 1 to 30 → CH*Cl1zO←CC= CH2 CH3 (n, m are integers where n-4-m is 1 to 30) HzBr etc. Butyl crotonate, glycerin monochrome, etc. nate, vinyl butyrate, vinyl trimethyl acetate, vinyl caproate.

Vinyl chloroacetate, vinyl lactate, vinyl benzoate, divinyl succinate, divinyl phthalate,
Methacrylamide, N-methylmethacrylamide, N-
Ethyl methacrylamide, N-aryl methacrylamide, N-hydroxyethyl-N-methyl methacrylamide, 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 alcohol, alkyl groups in ortho and para positions.

Styrene derivatives with substituents such as alkoxy groups, halogens, carboxyl groups, allyl groups, divinylbenzene, allyloxyethanol, diallyl esters of dicarboxylic acids, N-vinyloxazolidone, N-vinylimidazole, N-vinylpyrrolidone, N-vinyl Polymerizable unsaturated compounds such as carbazole can also be used. These may be used alone or two or more types of -ti may be used.

As the photopolymerization initiator, various compounds that are generally used as photopolymerization initiators for ultraviolet curable paints can be used. For example, Michlerskaton, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, pensoy/impropyl ether, benzoin butyl ether, 2-1-butyl anthraquino/
, l,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis(diethylamino)benzophenone, acetophenone.

Benzophenone, Thioxa 7ton, 1.5-A7naphthene, 2.2-dimethoxy-2-phenylacetophenone, 1-Hydroxynchlorohexyl722ketone, 2-
Methyl-(4-(methylthio)phenyl)-2-morphoIJ/-1-7'lovanone.

Examples include diacetyl, benzyl, benzyl dimethyl ketal, benzyl diethyl ketal, diphenyl disulfide, anthracene, and the like.

The amount of these photopolymerization initiators to be used is preferably 0.01 to 30 parts by weight per 100 parts by weight of the polymerizable unsaturated compound from the viewpoint of photocurability of the photosensitive resin composition and heat resistance of the coating film. More preferably, it is in the range of 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, chloraniel unaphthylamine, β-naphthol, 2,6-di-t-butyl-p-cresol, Pyridine, nitrobenzene, p-)luidine, methylene blue.

42'-methylenebis(4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethy6-
(1-butylphenol) etc., and the amount used is usually 0.001 parts by weight per 100 parts by weight of the polymerizable unsaturated compound.
It is preferable to set it as 10 parts by weight.

The photosensitive resin composition of the present invention contains an organic solvent, but the organic solvent used in the above reaction may be used, or the organic solvent used in the 9 reactions may be used in addition to those described above. You may change it to an organic solvent.

The amount of organic solvent to be used is preferably 10 to 95% by weight of the photosensitive resin composition, and preferably 30 to 80% by weight from the viewpoint of the viscosity of the composition.
The range of

The photosensitive resin composition of the present invention contains the above-mentioned components, but there are no particular restrictions on the order, mixing method, etc. of these components.

The present invention necessarily includes a step of forming a photosensitive layer from the above-described photosensitive resin composition on a base material such as a metal plate, a copper-clad laminate, or a silicon wafer. The step of forming the photosensitive layer on the substrate to be coated is carried out in a conventional manner. For example, the photosensitive resin composition is applied onto a substrate by a dip coating method, a 70-coating method, etc., and the organic solvent is dried.

The photosensitive resin composition is not directly coated on the substrate, but is coated and dried on the support film by a known method such as knife coating or roll coating, and the photosensitive resin composition is coated on the support film. After manufacturing a photosensitive element having
It is also possible to form a photosensitive layer on the substrate by laminating the photosensitive element on the substrate by a known method under pressure.

The present invention necessarily includes a step of imagewise exposing the photosensitive layer to active light. A high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or the like is used as a light source in the imagewise exposure process, and at this time, irradiation is performed through a negative mask. It is also possible to imagewise scan a laser beam or the like focused on a minute cross-sectional area.

The present invention necessarily includes a step of developing with an alkaline aqueous solution after imagewise exposure.

Suitable bases for use in alkaline aqueous solutions include hydroxides of alkali metals and quaternary ammonium.

Carbonates, bicarbonates, silicates, phosphates, picrates, acetates, amines, etc. are used. Specific examples of these include lithium hydroxide, sodium hydroxide, potassium hydroxide, and ammonium hydroxide.

Trimethylpendylammonium hydroxide.

Tetramethylammonium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate.

Examples include sodium silicate, sodium phosphate, sodium pyrophosphate, sodium acetate, monoethanolamine, jetanolamine, triethanolamine, and the like. The amount used is usually o or oo per 100 parts by weight of water.
oi~30 parts by weight, preferably o, o oi~10
Parts by weight.

Further, if such an alkaline aqueous solution causes residual development, an organic solvent can be added to the alkaline aqueous solution. As the organic solvent, the polar solvent used in the synthesis of the polyimide precursor described above is generally preferred. In addition to this polar solvent, the above-mentioned general organic solvents can also be used. The amount of organic solvent used is usually 0.1 to 100 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the aqueous alkaline solution.

After the photosensitive resin composition of the present invention is developed.

By heat treatment at 80 to 400°C and, if necessary, irradiation with active light, it can be converted into a glabella insulating film material with excellent heat resistance, and is extremely useful mainly in the field of microfabrication as mentioned above. Useful.

(Effects of the Invention) According to the present invention, it is possible to obtain thick images that are safe in the working environment and have excellent heat resistance.

(Examples) Next, the present invention will be explained by examples, but the present invention is not limited to these examples.

Example 1 500r equipped with a thermometer, nitrogen gas inlet and stirring device
5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexe/- in a four-bottle flask of rLe
1,2-dicarboxylic anhydride (manufactured by Dainippon Ink & Chemicals) 5L849 (0.2 mol) and 250 g of N,N-dimethylacetamide were added.

The mixture was stirred at room temperature under a stream of dry nitrogen gas. Next 4°4'
40.059 (0.2 mol) of -diaminodiphenyl ether (manufactured by Mitsui Toatsu Chemical Co., Ltd.) was added, and the solution was stirred at room temperature for 8 hours to obtain a viscous polyimide precursor.

Add tetraethylene glycol diacrylate (
(manufactured by Shin Nakamura Chemical Co., Ltd.) was added, and under light shielding, 5.4 g of benzophenone and 0.6 g of 4,4'-bis(diethylamino)benzophenone were added, stirred and mixed, and filtered through a filter to form a photosensitive resin. I got something.

This composition was applied to a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd.).
MCL-E-61) was coated with a bar coater to a dry thickness of 50 μm, heated and dried at 80°C for 30 minutes, and then the above coated film was pattern masked.
After irradiating with ultraviolet rays of 0 mJ/cm'', it was developed with a double FFI% IJ aqueous solution.

When rinsed with water, a clear resin turn was obtained. When this resin pattern coating film was subjected to thermogravimetric analysis after being post-cured by heating at 250°C for 1 hour, it was found to have good heat resistance with a 10% weight loss in temperature of 425°C.

Example 2 Similarly to Example 1, 1.2.3.4-butanetetracarboxylic anhydride (manufactured by Mitsui Toatsu Fine Co., Ltd.) 39.
639 (0.2 mol) and 250 ml of N,N-dimethylacetamide were added, and 4.4'
- Diaminodiphenyl ether 40.059 (0.2 mol) was added to obtain a viscous polyimide precursor.

Add F'A-73LA (Tris manufactured by Hitachi Chemical Co., Ltd.) to this solution.
2-acryloylethyl isocyanurate) at 79.
In addition, 4.2 g of benzyl dimethyl ketal (manufactured by Ciba Geigy) was added under light shielding, and the mixture was stirred and mixed, followed by filtration with a filter to obtain a photosensitive resin composition. This composition was applied in the same manner as in Example 1 to obtain a transparent coating film with a thickness of 50 μm. When this coating film was irradiated with 300 mJ/cm'', developed and rinsed in the same manner as in Example 1, a clear resin pattern was obtained.

When thermogravimetric analysis was performed on this resin pattern coating film in the evaluation described in Example 1, it was found that the weight loss was 10% at a temperature of 452°C.
It had good heat resistance.

Example 3 In the same manner as in Example 1, 52.849 (0.2 mol) of 5-(2,5-dioquintetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride and 250 ml of N,N-dimethylacetamide was added, and in the same manner as in Example 1, a viscous polyimide precursor was obtained using 40.05 (0.2 g) of 4,4'-diaminodiphenyl ether.

To this solution, add 192.89 g of FA-731A () lis(2-acryloylethyl)in cyanurate, add 5.49 g of benzophenone and 0.6 g of 4,4'-bis(diethylamino)benzophenone under light shielding, and mix with stirring. Thereafter, it was filtered through a filter to obtain a photosensitive resin composition. This composition was applied in the same manner as in Example 1 to obtain a transparent coating film with a thickness of 50 μm. This coating film was irradiated at 300 mJ/am'', developed with a 1% by weight triethanolamine aqueous solution, and rinsed with water to obtain a clear resin pattern.

When this resin pattern coating film was subjected to thermogravimetric analysis according to the evaluation described in Example 1, the 10 inch weight loss temperature was 430°C.
It had good heat resistance.

Example 4 In the same manner as in Example 1, 39.63 (0.2 mol) of 1.2.3.4-butanetetracarboxylic dianhydride and 250 mA' of N,N-dimethylacetamide were added to the flask.
A viscous polyimide precursor was obtained in the same manner as in Example 1 using 40.059 (0.2 mol) of 4,4'-diaminodiphenyl ether.

To this solution, 79°6 g of A-BPE-10 (S2-bis(4-acryloxypentaethoxyphenyl)propane manufactured by Shin-Nakamura Chemical Co., Ltd.) was added, and 5.4 g of benzophenone was added under light shielding.
g and 0.6 g of 4,4'-bis(diethylamino)benzophenone were added and mixed with stirring.

A photosensitive resin composition was obtained by filtration with a filter.

This composition was applied in the same manner as in Example 1, and a transparent 50%
A coating film with a thickness of μ was obtained. This coating film was irradiated with 300 mJ/Cm' and developed in the same manner as in Example 3.

After rinsing, a clear resin pattern was obtained.

When thermogravimetric analysis was performed on this resin pattern coating film in the evaluation described in Example 1, it was found that the weight loss was 10% and the temperature was 439°C.
It had good heat resistance.

Example 5 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-fuclohexene-1,2-dicarboxylic anhydride 5289 (0.2 mol) was placed in a flask in the same manner as in Example 1.
and 250 ml of N,N-dimethylacetamide were added, and the mixture was stirred at room temperature under dry nitrogen gas flow. Next, silicone diamine having the following structural formula (manufactured by Shin-Etsu Chemical Co., Ltd.)
LP-103) 49.69 (0.2 mol) was added.

The solution was stirred at room temperature for 8 hours to obtain a viscous polyimide precursor. Add 9L99 of tetraethylene glycol diacrylate (manufactured by Shin Nakamura Chemical Co., Ltd.) to this solution, add 5.49 L of benzophenone and 0.69 L of 4,4'-bis(diethylamino)benzophenone under light shielding, stir and mix, and filter through a filter. A photosensitive resin composition was obtained. This composition was coated in the same manner as in Example 1 and dried by heating at 80° C. for 30 minutes to obtain a transparent coating film with a thickness of 50 μm. This coated film surface was pattern masked and irradiated with ultraviolet rays at 300 mJ/cm 2 , and developed and rinsed in the same manner as in Example 1 to obtain a clear resin pattern. When the coating film of this resin pattern was subjected to thermogravimetric analysis using the method described in Example IK, it was found that the resin pattern showed good heat resistance, with a 10% weight loss in temperature change of 423°C.

Claims (1)

[Claims] 1. (1) On the base material, there is a formula (1) ▲ mathematical formula, chemical formula, table, etc. ▼ (1) (in the formula, R_1 is a tetravalent aliphatic group or alicyclic group and R_2 is a divalent aromatic group, aliphatic group, alicyclic group, or organosiloxane group), a polymerizable unsaturated compound, a photopolymerization initiator, and an organic An image forming method comprising: (2) forming a photosensitive layer from a photosensitive resin composition containing a solvent; (2) imagewise exposing the photosensitive layer to actinic light; and (3) developing with an alkaline aqueous solution. Manufacturing method.