JPS63226639A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To obtain a photosensitive resin compsn. having superior solubility and transparency and capable of forming a thick film by blending a photosensitive adduct comprising a polyimide precursor having prescribed repeating units and an isocyanate compd. having a prescribed structure, a photopolymn. initiator and an org. solvent or by further adding a polymerizable unsatd. compd. CONSTITUTION:A photosensitive adduct comprising a polyimide precursor having repeating units represented by formula I and an isocyanate compd. represented by formula II is blended with a photopolymn. initiator and an org. solvent. In the formula I, R1 is a quatervalent aliphat. or alicyclic group and R2 is a bivalent arom., alighat. or alicyclic group or an organosiloxane group. In the formula II, each of R3-R5 is H atom or methyl group and R6 is a bivalent hydrocarbon compd. group. A photosensitive resin compsn. having superior solubility and transparency and capable of forming a thick film can be obtd.

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.

A photosensitive material with excellent solubility and light transmittance and capable of forming thick films, suitable as a forming material for insulating films and passivation films for solid-state devices in the semiconductor industry, interlayer insulating materials for semiconductor integrated circuits, multilayer glint wiring boards, etc. The present invention relates to a synthetic resin composition.

(Prior Art) In recent years, in the semiconductor industry, organic materials have been used for interlayer insulation, which was conventionally 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 factory, there is a desire for a heat-resistant photosensitive material that can be used as an insulating material by leaving a pattern intact after exposure and development.

One example of these materials is photosensitive polyimide.

Heat-resistant photosensitive materials using cyclized polybutadiene as a base polymer have been proposed, and photosensitive polyimide has attracted particular attention due to its excellent heat resistance and ease of removing impurities.
There is.

As a photosensitive polyimide, a system consisting of a polyimide precursor and a dichromate was first proposed (Japanese Patent Publication No. 49-1989).
17374), this material has advantages such as practical photosensitivity and high film-forming ability, but has disadvantages such as lack of 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
74), since a dehydrochloride reaction is involved when introducing a photosensitive group, chloride ultimately remains, 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 (#Kaisho 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.

From the viewpoint of its heat resistance, aromatic polyimide precursors are used as base polymers. 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 making a photosensitive polyimide by dissolving an aromatic polyimide precursor and a compound having a photosensitive group, 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 teeth,
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, most photosensitive resins, including photosensitive polyimides, are chemically or structurally activated within one molecule or between molecules because the light energy absorbed by the coexisting photopolymerization initiator acts as a trigger for the reaction. This is because the absorption wavelength of most current photopolymerization initiators is 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, in order to avoid such problems in solubility and light transmittance, a method of mixing a compound having a photosensitive group with an aliphatic polyimide precursor (Japanese Unexamined Patent Application Publication No. 5-11711) has been proposed.
9-131927), but these polyimide precursors are susceptible to hydrolysis due to the presence of an extremely large number of carboxyl groups adjacent to amide bonds, and are susceptible to hydrolysis if stored for a long period of time. It has the disadvantage that the molecular weight of the aliphatic polyimide precursor decreases significantly due to hydrolysis. Additionally, a method has been developed in which a compound having a photosensitive group is mixed into an adduct solution prepared by adding an epoxy compound having a polymerizable unsaturated bond to an aliphatic polyimide precursor (4? Japanese Patent Publication No. 1983-68332). However, there is a problem in that it is difficult to obtain the desired adduct due to the low reactivity between the epoxy compound and the polyimide precursor.

C) Problems to be Solved by the Invention) The present invention solves the problems of the prior art shown above, and provides a photosensitive material that has excellent solubility and light transmittance and can be formed into a thick film, which is suitable for the above-mentioned uses. A resin composition is provided.

(Means for Solving the Problems) The present invention provides formula 9 (1) (wherein R1 is a tetravalent aliphatic group or alicyclic group and LR
x is a divalent aromatic group, aliphatic group, alicyclic group, or organosiloxane group. ) and a polyimide precursor having a repeating unit represented by the formula (2, in which HRs I R
a and Rs are a hydrogen atom or a methyl group, and R6 is a divalent group of a hydrocarbon compound) A photosensitive adduct with an incyanate compound, a photopolymerization initiator, an organic solvent, and optionally a polymerizable The present invention relates to a photosensitive resin composition containing an unsaturated compound.

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.

Examples of aliphatic or alicyclic tetracarboxylic acids or anhydrides thereof include butane, pentane, hexane, cyclopentane, and bicyclohexene.

Cyclopropane, cyclobutane, cyclopentane
, cyclohexane-, methyl-cyclohexene-, ethylene- and other tetracarboxylic acids or their anhydrides; 2.
3.5-) Licarboxycyclopentyl acetic acid or its anhydride, bicyclo-(Z2.2)-octo7ene-2. λ5,6-tetracarboxylic acid or its anhydride, tetrahydrofuran-2,34,5-tetracarboxylic acid or its anhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1 , 2-dicarboxylic acid or its anhydride, 3,5.6-)licarboxy2-carboxymethylnorbornane-2:3,5
: 6 or its anhydride, 5.5'-thiobis(norbonane-2,3-dicarboxylic acid) or its anhydride, 5.5'-
Methylene dithiobis (norbonane-2,3-dicarboxylic acid) or its anhydride, he5'-ethylene dithiobis (norbonane-43-dicarboxylic acid) or its anhydride.

5'-propylene dithiobis(norbonane-3-dicarboxylic acid) or its anhydride, 45'-sulfonylbis(norbonane-2,3-dicarboxylic acid) or anhydride of tt, 5,5'-methylenedisulfonyl bis( norbonane-2,3-dicarboxylic acid) or its anhydride, 5.5
'-ethylenedisulfonylbisCnorbonane-'2.3
-dicarboxylic acid) or its anhydride, to 5'-propylenedisulfonylbisC norbonane-λ3-dicarboxylic acid)
or its anhydride. 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 singly or in combination of two or more.

In addition, as a diamine compound which reacts with the above-mentioned tetracarboxylic acid or its anhydride to give a polyimide precursor, 2
Examples include compounds represented by formula (3) % formula % (3) (wherein & is a divalent aromatic group, aliphatic group, alicyclic group, or organosiloxane group). Preferred R in the formula (3) is 1, for example.

Xs X3 X
4 (n x O or an integer of 1) (In the formula, XhXs, Xs and X4 may be the same or different and represent a hydrogen atom, a monovalent group of a hydrocarbon compound or a substituted product thereof -t', s, Y is -CHz-, -C
4+.

).

-(CH*Notification-(m is an integer from 2 to 50).

& Rδ Ru R+ (in the formula, R7 and Ell (1 is a divalent organic group, 几8.R.

'Rot and R1 are monovalent groups of the same or different hydrocarbon compounds or substituted products thereof, t and k are 0 or integers of 1 to 20).

Specific examples of the diamine compound represented by the above formula (3) include p-phenide diamine, 9m-phenide diamine, and 44'-diaminodiphenylmethane.

4.4'-Diaminodiphenylethane, pendici/.

44'-diaminodiphenylsulfone)', 44'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, 3,3'-diaminobenzophenone.

4.4'-diaminobenzophenone, 1,5-diaminonaphthalene &3/-dimethyl-4,4'-diaminobiphenyl,λ4'-diaminodiphenyl ether.

22-di(p-aminophenyl)hexafluoropropane, &4'-diaminobenzanilide, m-xylylenediamine, p-xylylenediamine, ethylenediamine,
1.3-propanediamine, tetramethylenediamine,
Pentamethylene diamine.

Hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, 44'
-dimethyl hebutamethylene diamine.

1.4-diaminocyclohexane, tetrahydrodicyclopentadienylenediamine, hexahydro-IL7-
Methanoindanilene symethylenediamine.

Tricyclo(6121190”)-landecylenedimethyldiamine.

(In both formulas, lJ:H or CHs; in both formulas, R' is H, CHs, C1t or Br). These diamine compounds alone can produce 2
More than one type 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 0 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 it in a ratio of 2/1 (molar ratio), and it is particularly preferable to use it in equimolar amounts.

The organic solvent used in the above reaction is generally preferably a polar solvent that completely dissolves the polyimide precursor to be produced, such as 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, there are also 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 ethyl acetate. , butyl acetate.

Diethyl oxalate, diethyl malonate, r-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, )IJtrichloroethane, chlorobenzene, 0 -Dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene:
/41! 'I can do something. 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 amount of this organic solvent used is 10 to 950 to 9 in the photosensitive resin composition.
5% by weight, preferably 3°0 to 80% by weight.

In the present invention, the polyimide precursor has the above formula (2).
A photosensitive adduct is obtained by adding an incyanate compound represented by:

In the present invention, the reaction between the polyimide precursor and the isocyanate compound is carried out in the organic solvent used in the synthesis of the polyimide precursor, usually at 0 to 100°C.

It is preferably carried out at a temperature of 20 to 70°C. The ratio of the isocyanate compound to the polyimide precursor is usually 0.1 to 0.1 to 1 equivalent of carboxyl group in the polyimide precursor, from the viewpoint of sensitivity of the composition and heat resistance of the coating film.
g equivalent, preferably 0.4 to 0.8 equivalent.

Furthermore, the reaction between the isocyanate compound and the polyimide precursor can be performed using triethylamine, 1,4-diazobicyclo (Z2
．． 2) It is facilitated by using amines such as octane, tin compounds such as cyphytyltin dilaurate, and dibutyltin diacetate. These can usually be used in an amount of about 0.5 to 25% by weight based on the incyanate compound.

As for the isocyanate compound represented by formula (2),
Incyanate ethyl acrylate, Incyanate propyl acrylate, Incyanate butyl acrylate, Incyanate pentyl acrylate, Incyanate hexyl acrylate, Incyanate octyl acrylate, Incyanate decyl acrylate, Incyanate octadecyl isocyanate, Incyanate ethyl methacrylate, Incyanate propyl methacrylate. , Incyanate butyl acrylate, Incyanate pentyl methacrylate, Incyanate hexyl methacrylate, Incyanate octyl methacrylate, Incyanate decyl acrylate, Incyanate octadecyl methacrylate, Incyanate ethyl crotonate, Incyanate propyl crotonate.

Examples include incyanate hexyl crotonate.

A commercially available product is IBM (Incyanate Ethyl Methacrylate) manufactured by Dow Chemical Company.

Furthermore, these incyanate compounds can be used alone or in combination of two or more.

There are various types of polymerizable unsaturated compounds that can be used as needed in the present invention, and acrylic acid compounds, methacrylic acid compounds, and the like are practical. Specific acrylic acid compounds include acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, inglovir acrylate, n-butyl acrylate, inbutyl 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, penta Erythritol monoacrylate, trimethylolpropane monoacrylate, allyl acrylate, 1,3-glopylene gelicol diacrylate, 1,4-butylene glycol diacrylate, 1,6-hexane glycol diacrylate, neopentyl glycol diacrylate, cyclopyrene Glycol diacrylate, 2,2-bis-(4-
Acryloxyjethoxyphenyl)propane, z2-bis-(4-acryloxypropylxyphenyl)propane.

Trimethylolpropane diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, triacryl formal.

Tetramethylolmethanetetraacrylate, Tris(
Acrylic ester of 2-hydroxyethyl)in cyanuric acid.

(n is an integer of 1 to 30) Hm (n, m are integers where n-4-m is 2 to 30) HzBr, etc., and examples of methacrylic acid compounds include methacrylic acid, methyl methacrylate, Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, inbutyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, octyl methacrylate, ethylhexyl methacrylate V-), 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, 1.6-hexane glycol diacrylate, neopentyl glycol Dimethacrylate, 2-bis-(
4-methacryloxyjethoxyphenyl)propane.

Trimethylolpropane dimethacrylate, pentaerythritol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate, tetramesololmethanetetramethacrylate, methacrylic acid ester of tris(2-hydroxyethyl)in cyanuric acid, and others (n is 1 to 30) Integers) (n, m are integers where n+m is 1 to 30) CH Br 0 Br Br etc., 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-arylmethacrylamide, 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 alcohol, styrene derivatives such as styrene divinylbenzene with substituents such as alkyl groups, alkoxy groups, norogens, carboxyl groups, and allyl groups at the ortho and hhala positions, allyloxyethanol , diallyl ester of dicarboxylic acid, N-vinyloxazolidone, N-vinylimidazole, N-vinylpyrrolidone, N-vinylcarbazole, etc. These may be used alone or as a mixture.

As the photopolymerization initiator, various compounds that are generally used as photopolymerization initiators for ultraviolet curable paints can be used. For example, Michler's ketone, benzine, 2-methylbenzoin, pentuine methyl ether, benzoin ethyl ether, pentuine isopropyl ether, pensy/butyl ether, 2-1-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, anthraquinone , butylanthraquinone, 4,4'-bis(diethylamino)benzophenone, acetophenone.

Benzophenone, thioxanto, t, s-acenaphthene, 2+2-dimethoxy-2-722-2-2-2-2-2-acetophenone, 1-hydroxycyclohexylphenylketone, 2-
Methyl-(4-(methylthio)phenyl)-2-morpholino-1-propanone.

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

The amount of these photopolymerization initiators used is usually 0 per 100 parts by weight of the photosensitive adduct or 100 parts by weight of the photosensitive adduct and the polymerizable unsaturated compound from the viewpoint of sensitivity of the composition and heat resistance of the coating film. .01-30 parts by weight preferably ld 0.1-1
0 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, chloranil, naphthylamine, β-naphthol, and 2.6-sheet t-7'thyl-p-cresol. , pyridine, nitrobenzene, p-toluidine, methylene blue.

Examples include s-τ-methylenebis (4-methyl-6-t-butylphenol), s-τ-methylenebis (4-ethy-6-1-butylphenol), etc., and the amount used is 100 parts by weight of the photosensitive adduct or It is usually preferable to use 0.001 to 10 parts by weight per 100 parts by weight of the compound and the polymerizable unsaturated compound.

The photosensitive resin composition of the present invention contains an organic solvent, and this organic solvent may be the organic solvent used in the above reaction, or the nine organic solvents used in the nine reactions may be the nine organic solvents described above. You may change it to an organic solvent.

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

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 photosensitive resin composition of the present invention is applied to a base material such as a steel-clad laminate or a silicon wafer by an appropriate means and dried. In this case, the photosensitive adduct, which is the backbone of the photosensitive resin composition of the present invention, has very good solubility and light transmittance, and even in the presence of the 9-polymerizable unsaturated compound, the coating is uniform and has excellent transmittance Vζ. Give a membrane.

By irradiating actinic light from above a mask with a desired pattern drawn on this coating film, polymerization occurs in the irradiated areas, and the solubility is greatly reduced compared to the non-irradiated areas. In some cases, irradiation with ionizing radiation such as electron beams or radiation can also provide a similar effect.

Thus, a desired thick resin pattern can be obtained by developing and removing the non-irradiated areas using an appropriate organic solvent or aqueous Bukary solution as a developer. As the organic solvent, the above-mentioned synthetic solvent for the polyimide precursor is used. Also.

When using such an organic solvent, water may be added to the organic solvent when development remains. The amount of water used is usually 1 to 100 parts per 1003 parts of organic solvent.
Parts by weight, preferably 5 to 50 parts by weight.

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

Carbonates, 9 bicarbonates, silicates, phosphates, birophosphates, acetates, amines, etc. are used. Specific examples of these include lithium hydroxide, sodium hydroxide, potassium hydroxide, and ammonium hydroxide.

Trimethylbenzylammonium 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 0.00 parts by weight per 100 parts by weight of water.
01 to 30 parts by weight, preferably 0 to 5 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 alkaline aqueous solution.

The resulting nine-thick resin pattern can be converted into an interlayer insulating film for semiconductors, multilayer printed wiring boards, etc. having excellent heat resistance through subsequent baking, that is, post-curing. Things.

It is very useful mainly in the field of microfabrication as mentioned above.

(Effects of the Invention) The photosensitive resin composition of the present invention is a photosensitive resin composition that is excellent in solubility and light transmittance, and is suitable for the above-mentioned uses capable of forming a thick film.

(Example) Example 1 A thermometer, a nitrogen gas inlet, and a stirring device were installed.
5-(λ5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1 in a four-bottom Oml flask.
, 2-dicarboxylic anhydride (manufactured by Dainippon Ink & Chemicals) (5284 g (0.2 mol)) and 250 ml of N,N-dimethylacetamide were added, and the mixture was stirred at room temperature under dry nitrogen gas flow. Next, 40.05 g (0.2 mol) of 4,4'-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. Furthermore, at room temperature under the exclusion of light,
Incyanate ethyl methacrylate (Dow Chemical Co. IEMI 15.59 (0.1 mol) was added to 24
Stir for hours. Carbon dioxide was evolved during the reaction.

Add tetraethylene glycol diacrylate (
(manufactured by Shin Nakamura Chemical Co., Ltd.) was added, and under light shielding, 5.4 g of benzophenone and 0.69 g of 4,4'-bis(diethylamino)benzophenone were processed and mixed, followed by filtration with a filter to obtain a photosensitive resin composition. Obtained.

This composition was applied to steel-clad laminates (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 surface was pattern masked,
After irradiating with ultraviolet rays of mJ/<-, it was washed with N-methylpyrrolidone and rinsed with ethyl alcohol.
A clear resin pattern was obtained. This resin pattern coating is.

After post-curing by heating at 250°C for 1 hour, thermogravimetric analysis was performed, and the temperature at which the weight decreased by 10 cm was 415°C, indicating good heat resistance.

Example 2 As in Example 1, 1. “I-Butanetetracarboxylic anhydride (manufactured by Mitsui Toatsu Fine Co., Ltd.) 39.63g
(0,2 mol) and N,N-dimethylacetamide 25
0 ml was added thereto, and 4,4'-diaminodiphenyl ether 4o, osg (0.2 mol) was added in the same manner as in Example 1 to obtain a viscous polyimide precursor. Furthermore, Example 1
In the same manner as above, 15.59 g of incyanate ethyl methacrylate (Dow Chemical Company, IBM) was added at room temperature, and the mixture was stirred for 24 hours.

Add trimethylolpropane triacrylate (
79.6 g of Shin Nakamura Chemical Co., Ltd. was added, and 429 g of benzyl dimethyl ketal (manufactured by Ciba Geigy) was added under light shielding. After stirring and mixing, the mixture 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.

When this coating film was irradiated with 300 mJ/am'', prepared 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 using the method described in Example 1, the temperature at which the resin pattern decreased by 10 cm was #1''.
It had good heat resistance of 432°C.

Example 3 In the same manner as in Example 1, 5-(Z5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-
Add 1,2-dicarboxylic anhydride 5SL849 (0.2 mol) and 250 ml of N,N-dimethylacetamide, and add 44'-diaminodiphenyl ether 40.05 (0.29) in the same manner as in Example 1. A viscous polyimide precursor was obtained. Furthermore, in the same manner as in Example 1, incyanate ethyl methacrylate (Dow Chemical Co., IBM) xs and sg were added at room temperature and stirred for 24 hours.

Add A-BPE-10 (Shin Nakamura Chemical Co., Ltd. z2) to this solution.
- Add 929 g of benzophenone (bis(4-acryloxypentaethoxyphenyl)propane) and
．． 4 g and 44'-bis(diethylamino)benzophenone o, ag were added, stirred and mixed, and filtered through a filter to obtain a photosensitive resin composition.

This composition was applied in the same manner as in Example 1, and a transparent 50%
A coating film with a thickness of μm was obtained. When this coating film was irradiated with 300 mJ/an'', developed with Kl as in Example 1, and rinsed, a clear resin pattern was obtained.

When this resin pattern coating film was subjected to thermogravimetric analysis using the method described in Example 1, it was found that the weight decreased by 101 points just above the temperature i412.
℃ and has good heat resistance.

Example 4 As in Example 1, 1. 39.63 (0.2 mol) of λ4-butanetetracarboxylic dianhydride and N,
250ml of N-dimethylacetamide! Then, in the same manner as in Example 1, a viscous polyimide precursor was obtained using 05 g (0.2 mol) of 44'-diaminodiphenyl ether. Furthermore, in the same manner as in Example 1, incyanate ethyl methacrylate was prepared at room temperature. (manufactured by Dow Chemical Company)
15.59 g of IEM) was added and stirred for 24 hours.

This solution KFA-731A (Tris(2) manufactured by Hitachi Chemical Co., Ltd.
-acryloylethyl)in cyanurate) 79.6g
and benzophenone 5.4s and 44' under light exclusion.
-Bis(diethylamino)benzophenone (0.69 g) was added and mixed with stirring, followed by filtration with a filter to obtain a photosensitive resin composition. This composition was applied in the same manner as in Example 1, and a transparent coating film with a thickness of 50 μm was obtained. This coating K 300 r
When irradiation was carried out at a rate of nJ/an'', development and rinsing were carried out 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 using the method described in Example 1, it was found that the temperature was 428°C, just above the 10% weight loss temperature.
It had good heat resistance.

Example 5 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid mhydrate szsg (0.2 mol) was placed in a flask in the same manner as in Example 1.
and 250 ml of N,N-dimethylacetamide! was added and stirred at room temperature under dry nitrogen gas flow. Next, silicone diamine having the following structural formula (manufactured by Shin-Etsu Chemical Co., Ltd.)
Add LP-103>49.6 B (0.2 mol).

This solution was stirred at room temperature for 8 hours to obtain a viscous polyimide precursor. Further, in the same manner as in Example 1.

Incyanate ethyl methacrylate (IEMI 15.59 (manufactured by Dow Chemical Company) (0.1 mol) was added and stirred for 24 hours. Carbon dioxide was generated during the reaction. Tetraethylene glycol diacrylate (Shin Nakamura Chemical Company, Ltd.) was added to this solution. 9,299 added.

5.4 g of benzophenone and 0.69 g of 4,4'-bis(diethylamino)benzophenone were processed under light exclusion.

After stirring and mixing, the mixture was filtered through a filter to obtain a photosensitive resin composition. This composition was coated in the same manner as in Example 1, and
The coating was dried by heating for 30 minutes to obtain a transparent coating film with a thickness of 59 gn.

This coating surface was pattern masked and irradiated with ultraviolet rays at 300 mJ/am'', developed and rinsed in the same manner as in Example 1, resulting in a clear resin pattern. Thermogravimetric analysis was conducted using the method described in 1 (1), and the weight loss temperature was 411° C., indicating good heat resistance.

Examples 6 to 14 The photosensitive resin composition obtained in Example 1 was applied to a copper-clad laminate (
Coated onto MCL-E-61 (manufactured by Hitachi Chemical Co., Ltd.) using a bar coater to a dry thickness of 50 μm.
C. for 30 minutes, then pattern-masked the coating surface, irradiated with 300 mJ/an'' ultraviolet rays, developed with an alkaline aqueous solution shown in Table 1 below, and rinsed with water.

A clear resin pattern was obtained.

Below is Kinpaku Table 1 Relationship between type and concentration of developer and development time □□□□
□□

Claims (1)

[Claims] 1. Formula (1) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) (In the formula, R_1 is a tetravalent aliphatic group or alicyclic group, and R_2 is a divalent A polyimide precursor having a repeating unit represented by an aromatic group, an aliphatic group, an alicyclic group, or an organosiloxane group, and a polyimide precursor having a repeating unit represented by the formula (2) ▲ Numerical formula, chemical formula, table, etc. ▼ (2) (in the formula , R_3, R_4 and R_5 are hydrogen atoms or methyl groups, R_6 is a divalent group of a hydrocarbon compound), a photopolymerization initiator, an organic solvent and optionally A photosensitive resin composition containing a polymerizable unsaturated compound.