JPS5962661A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To prepare the titled composition having excellent solution stability and solubility, free from the problems of exposure hindrance caused by e.g. whitening of the coating film, and having high heat resistance and high sensitivity, by adding a polymerizable unsaturated compound and a photo-polymerization initiator to a polyamide precursor containing an aliphatic tetracarboxylic acid. CONSTITUTION:The objective composition is prepared by compounding (A) a solution containing a polyimide precursor having an intrinsic viscosity of >=0.1 and composed essentially of the recurring unit of formula I (R is aliphatic tetracarboxylic acid residue; R' is bivalent organic residue) and a recurring unit of formula II (Ar is aromatic tetracarboxylic acid residue), wherein the amount of the recurring unit of formula I in whole recurring units is >=3wt%, with (B) 10-500pts.wt., based on 100pts.wt. of the precursor, of a polymerizable unsaturated compound (e.g. acrylic acid) and (C) 0.05-30wt%, based on the polymerizable unsaturated compound, of a photo-polymerization initiator (e.g. benzoin). The dried coating film is highly transparent to light, and gives high photosensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel photosensitive Jjit resin composition, and more specifically, its stability in a solution state and bath-disintegrability (scrubbing, exposure to light due to whitening of the photosensitive resin composition). +iIl harm etc. is f, c<,
Partial t that can provide heat resistance, photosensitivity, etc. that are superior to practicality.
The present invention relates to a polyimide-based photosensitive 4FF fat composition containing residual aliphatic detracarboxylic acid as a repeating unit, and a method for producing the same.

recent years,? Densification of nji 1 roaster, jj4. : Reliability,
Significant changes are being seen in small light vehicles (I-electrification, etc.).

Photoresist materials for circuit formation are functional materials that greatly contribute to these efforts, and have realized so-called microfabrication. Furthermore, in the field of IC and LSI, the use of organic materials for interlayer insulation, which was conventionally performed using inorganic materials, has become widespread by adding such microfabrication.
), heat-resistant materials such as polyimide resin have come into use.However, this material still requires photoresist to process patterns such as through holes, and this photoresist process takes a long time. Since this requires a complicated process, it is highly desirable to develop a heat-resistant photoresist that can be used as an insulating material, leaving the resist as it is even after forming a circuit through exposure and development.
I'm at t.

These materials are based on photosensitive polyimide and cyclized polybutadiene (such as heat-resistant photoresists, etc.), and in particular, photosensitive polyimide has a polyimide skeleton characteristic (m). It is attracting attention because of its wearability and ease of removing impurities. As in the case of ordinary polyimides, photosensitive polyimides are subjected to processing in the form of a precursor (polyamic acid) to achieve post-cure imidization.

As a photosensitive polyimide, a system consisting of a polyimide precursor and a small chromate was first proposed (Japanese Patent Publication No. 1973-
No. 17374), this photosensitive composition has an extremely short pot life! In addition to the critical drawbacks, there were also drawbacks such as the development process being complicated and long, and chromium ions remaining in the polyimide film, so it was not put into practical use. In addition, as another example, a photosensitive polyimide pre-lζ112 body has been proposed in which a photosensitive group is introduced into a polyimide pre-l body through an ester bond (Japanese Patent Publication No. 30207/1983); Since the dehydrochlorination reaction involves a dehydrochloric acid reaction, chlorine ions remain in the solution (1), and their removal poses a problem.

In order to avoid such problems such as impurities, it is necessary to select a method of mixing a polyimide precursor (this is a directly photosensitive compound) and a functional group of a compound having a photosensitive group and an inorganic functional group of a polyimide compound. A method has also been developed in which a photosensitive group is introduced through a reaction.A method for obtaining a photosensitive polyimide precursor using a monomer having a photosensitive group at i is also known.

However, from the viewpoint of heat resistance, these photosensitive polyimides are based on the aromatic polyimide precursor 149 synthesized from, for example, pyromellitic acid difluoride monohydrate and 4,4'-diamino phenyl ether. 1), these series of photosensitive polyimides include the drawbacks of conventional aromatic polyimide precursors. That is, the solution containing the above precursor has a fundamental R problem in solubility1), and also has a practical problem in stability as a solution, such as insolubilization due to partial imifization of FG during storage. C) has a defect, and its improvement is significant.

For example, even if a solution is prepared in which an aromatic polyimide precursor and a compound having a photosensitive group are uniformly dissolved as a photosensitive polyimide, in the drying process of forming a coating film from this solution, Most of the good solvent has evaporated, and when drying and recoating, the nji k14 body and the photosensitive thread are removed.
+l^ is formed from a compound that is Qtx. Compounds having such a photosensitive group generally cause the precursor (on the other hand, a poor medium, and the whitening phenomenon caused by the insolubilization of the precursor causes dry coating) 19, and the exposure process This makes me feel embarrassed. Furthermore, according to the observations and speculations of the present inventors, it has been found that the compound having a photosensitive group dissolves in the 3-film formation special number during drying.
At the same time, (there was no phenomenon of thick whitening, but a strange phenomenon of photosensitivity burning out was also found)' (Therefore, it was found that a compound with a photosensitive group that can be used; I
ll/I! M! &, #: +1 from the point of compatibility, especially 7
7t-++ (e.g. expensive or malodorous compounds)
Currently, it is limited to.

Under these circumstances, the present inventors have determined that the stability and solubility in a solution state are uncertain7, that there are no exposure problems such as whitening during the formation of a photosensitive coating film, and that it has a highly practical heat resistance and photosensitivity. As a result of intensive studies to develop a photosensitive resin composition, surprisingly, by introducing a predetermined amount of repeating units containing a residual aliphatic tetracarboxylic acid into the backbone polymer of the polyimide precursor, 5) We discovered a unique phenomenon in which not only the solubility or compatibility is greatly improved and the stability in the solution state is improved, but also the whitening of the dried coating film is reduced and the volatilization of compounds with photosensitive groups is suppressed. , which led to the present invention.

That is, the present invention provides repeating units CI represented by (wherein R is an aliphatic tetracarboxylic acid residue and R' is a divalent organic group) and the formula (wherein Ar is an aromatic tetracarboxylic acid residue) residue, R/
represents a divalent organic group) (n)
A polymerizable unsaturated compound and a photopolymerizable compound are added to a solution containing a polyimide precursor which consists essentially of repeating units [■] in an amount of at least 3% of all repeating units, and has an intrinsic viscosity of 0.1 or more. The present invention provides a novel photosensitive resin composition in which an initiator is blended and the coating film after drying substantially allows light to pass through and provides active photosensitivity.

The polyimide precursor used in the present invention uses as starting materials a predetermined ratio of aliphatic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, and diamines for these, and substantially contains an inert carboxylic acid dianhydride. Examples of dianhydrides include tetracarboxylic dianhydrides such as boudan, pentane, hexane, cyclopentane, and bicyclohexene, 5-(2,5-dioxotetrahydrofuryl)-3
-Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, bicyclo-(2,2,2)-octene-2,3
-5,6-tetracarboxylic dianhydride is mentioned. Of course, the skeleton of these tetracarboxylic acids may be substituted with a substituent such as an alkyl group, and it is also possible to use partially side aliphatic dicarboxylic acids, tricarboxylic acids, or anhydrides thereof.

Further, examples of the aromatic tetracarboxylic dianhydride for adding an aromatic tetracarboxylic acid residue to the repeating unit (n) include pyromellitic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, Bis(3,4-dicarboxyphenyl)ether, bis(3,4-;)hlupoxyphenyl)sulfone, 3,3',4,47-benzophenonetetracarboxylic acid, 3,3',4,4' -Biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 2,2',6,6'-biphenyltetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2・3,6,7-naphthalenetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1
・There are dianhydrides such as 3-bis(3,4-dicarboxyphenyl)hexafluoropronone.

The diamine to be reacted with these predetermined ratios of aliphatic and aromatic tetracarboxylic dianhydrides is a diamine represented by the general formula H2H-R'-NH2, and R
′ is a divalent organic group (ζ), aromatic, aliphatic, alicyclic, ~terocyclic, etc., or a combination thereof, or these are oxygen, nitrogen, sulfur, phosphorus, It can be a group bonded with silicon fr, etc. In this case R'
It may have a substituent that does not react in place under the reaction conditions to an amino group or an acid anhydride. This is because these groups can impart desirable properties such as solubility, processability, or adhesiveness to the resulting precursor.

Further, υ1, which is a triamine commonly used in am, can also be used in combination with a tetraamine.

Aromatic diamines are desirable as diamines, but specific examples of diamines used in the present invention include meta-phenylene diamine, para-phenylene diamine, and 4,4'-
Diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 4,4'-diaminodiphenylmethane,
Benzidine, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenylsulfone, 3,3'-
Diaminodiphenylsulfone, para-bis-(4-aminophenoxy)benzene, medarpis-(4-aminophenoxy)benzene, 4,4'-diaminodiphenyl ether, 1,5-diaminonaphthalene, 3,3'-dimethyl-4. 4'-diaminopiphenyl, 3,4'-diaminobenzanilide, 4-(para-aminophenoxy)
-4-aminobenzanilide, 3,4-diaminodiphenyl ether, 3,3'dimethoxybenzidine, 2,4
-bis(β-amino-tert-butyl)toluene,
Bis(para-β-amino-tert-butylphenyl) ether, meta-xylylene diamine, para-xylylene diamine, di(para-amino-tert-butylphenyl)methane, hexamethylene diamine, hexamethylene diamine,
Okudamethylene diamine, nonamethylene diamine, 4.
4-dimethylhebutamethylenediamine, 3-methoxyhebutamethylenediamine, 2,11-diaminododecane, 1,4-diaminocyclohexane, 2,2'-diaminodiethyl ether, 2,2'-diaminodiethylthionythyl , 3,3'-diaminodipropoxyethane, 2
・6-diamitubiridine, guanamine, 2,5-diamino-1,3,4-oky-1)diazo-1,2-(3
'-aminophenyl)-5-aminopenzoxanol, bis-(4-aminophenyl)phosphine oxide, bis-(4-amino-phenyl)diethylsilane, etc., which may be used alone or as a mixture. can be used.

The reaction between aliphatic and aromatic tetracarboxylic dianhydrides and diamines in the present invention is usually carried out in an organic solvent. This reaction is an exothermic reaction (1), and the reaction temperature can be preferably controlled by some cooling means during the reaction. It is preferable to add one of these components to an organic solvent, and then add the other component by an appropriate amount of h1'. (If the reaction is sufficiently controlled) (There is no problem even if both components coexist. Usually 0
The polyimide precursor BoIJ amic acid can be prepared at an anti-Lr temperature of ~100°C.

The aromatic tetracarboxylic dianhydride component may be reacted with the diamine. The reaction between the anhydride and the diamine can be carried out under even stricter conditions. For example, 80°C or higher, the ?Iti point of the solvent.

The rebaimide ring-closing reaction was also carried out by adopting temperature conditions up to 411
A boIJ imide precursor having a partially imide ring-closed repeating unit of an aliphatic tetracarboxylic acid is also obtained. In this case, since the aliphatic tetracarboxylic acid skeleton has a solubility of 1T, even if the repeating unit of the aliphatic tetracarboxylic acid is partially bent and ring-closed, it can be used as the polyimide precursor of the present invention. You can also do that.

Furthermore, by selecting a molar ratio of 1:1 for the ratio of tetracarboxylic dianhydride to diamine, the highest polymer layer can be obtained.

In the present invention, according to the above formula, it is necessary that the tetracarboxylic acid residues contain at least 3% or more, preferably 5% or more, of aliphatic tetracarboxylic acid residues. At 3% or less, aliphatic tetracarboxylic acid residues (no effects on improving solubility and compatibility are observed, resulting in exposure problems due to whitening of the dried paint film or the effect of inhibiting volatilization of polymerizable unsaturated compounds). is no longer observed, and a coating film with active photosensitivity cannot be obtained.Furthermore, in the present invention, the polyimide precursor having 28! repeating units has an intrinsic viscosity of 0.1 or more. The intrinsic viscosity is a value measured at 30° C. using an N-methylpyrrolibin solution with a precursor concentration of 0.5 g/100 d.

Misfire +11. ．． In this case, if the polyimide precursor has an intrinsic viscosity of 0.1 or less, the baking of the resin pattern after exposure and development is likely to cause paint film defects due to foaming. ) Because the mechanical strength of the resulting coating film is poor,
2. Should be avoided.

The solvents used in the reaction of the aliphatic and aromatic tetracarboxylic dianhydrides with diamines include N-N-dimethylformamide, N-N-diethylformamide, N-N-diethylformamide, and
-N-dimethylacetamide, N-methyl-2-pyrrolidone, N-medylcabrolacdam, dimethyl sulfoxide, tetramethylene sulfone, tetramethylurea, hexamethylposboamide, pyridine, quinoline, γ-butyllaritone, N- Examples include acetyl-2-pyrrolidone, phenol, cresol i, tl, glycols, cellosolves, carpitols, and the like. The amount of organic solvent used is 20 to 95% by weight of the reaction system, but in some cases it is possible to carry out the reaction in the coexistence of polymerizable unsaturated compounds and initiators. The amount to be used may be appropriately determined so as to obtain a C degree indicating viscosity.

There are various types of polymerizable unsaturated compounds in the composition of the present invention, and acrylic acid compounds, methacrylic acid compounds, compounds having an allyl group, etc. are practical. Specific acrylic acid compounds include acrylic acid, methyl agellylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, imbutyl acrylate, cyclohexyl agellylate, benzyl acrylate, and 2-ethylhexyl. Acrylate, Carbi I-ru acrylate, Methgyne ethyl acrylate, Ethgyne ethyl acrylate, Butoxyethyl acrylate, Hydroxyethyl acrylate, Hydrogine propyl acrylate, Butylene glycol monoacrylate, N-N-dimethylaminoethyl acrylate, N-N- Diethylaminoethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl agellylate, allyl acrylate, 1.
3-butylene glycol diacrylate, 1,4-butylene glycol diacrylate, 1,6-hexane glycol diacrylate, neopenotyl glycol diacrylate, dipropylene glycol diacrylate, 2
・2-bis-(4-acrylogycydiethoxyphenyl)
Propane, 2,2-bis-(4-acryloxyprobyloxyphenyl)propane, trimethylolpropane diacrylate, pentaerythritol diacrylate, trimethylolpropane triaglylate, penta
eris litor tria riri
Acrylic formal, tetramethylolmethanetetraacrylate, etc., and methacrylic acid compounds include methacrylic acid, fluoric acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate. , ncrohexyl methacrylate, benzyl methacrylate, ogtyl methacrylate, ethylhexyl methacrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, butoxyethyl methacrylate hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl, nodacrylate, hydroxyethyl acrylate, N- N
-Dimethylaminomethacrylate, N-N-diethylaminomethacrylate, glycidyl acrylate, tetrahydrofurfuryl agerylate, methacrylokinepropyltrimethoxysilane, allyl methacrylate, trimethylolpropane triaglylate, diethylene glycol monomethacrylate, pentaerythritol mono Methacrylate, ethylene glycol dimethac! JL/-
), 1,3-butylene gelicoldimethacrylate, 1
・6-hexane glycol dimedaglylate, neopentyl glycol dimethacrylate, 2,2-bis-(4
-methacryloxyethoxyphenyl)propane, 2.2
-bis-(4-methacryloxyethoxyphenyl)propane, trimethylolpropane trimethacrylate, etc.Other butyl crotonate, glycerin monoclonate,
Vinyl butyrate, vinyl trimethyl acetate, vinyl caproate, vinyl gloracetate, vinyl lactate, vinyl benzoate, divinyl succinate, divinyl phthalate, metagrilamide, N-methylmethacryl 7'mide, N-ethylmethacrylamide, N-7+
1-lumecrylamide, N-hydroxyethyl-N-
Methyl methacrylamide, acrylamide, N-dashalybutyl acrylamide, N-methylol acrylamide, N-butogine methyl acrylamide, N-isobutogine methyl acrylamide, diaseptone acrylamide, hegizyl vinyl ether, ethylhexyl vinyl ether, vinyl trilone del, poly(+ih polyvinylny'7' /l/ of alcohol, styrene derivatives such as alkyl in ortho and/or para position, 1.Hl:, alkoxy y > r=, halogen, carboxyl group, allyl group j ``Styrene with which substitution Jk, divinylbenzene, allyloxyethanol, diallyl ester of dicarboxylic acid, N-vinyloxazolidone, N-vinylimitazole, N-vinylpyrrolidone,
Examples include N-vinylcarbazole, which may be used alone or in mixtures.

The amount L1 of these polymerizable unsaturated compounds used is 10 to 500 parts by weight, preferably 20 to 200 parts by weight, based on 100 parts by weight of the resin content of the polyimide precursor.

If the amount is less than 10 parts by weight, the curing due to polymerization of the polymerizable unsaturated compound will be insufficient (ζ), and if it is more than 500 parts by weight, the heat resistance of the coating film will be reduced due to the influence of the residue during post-curing. The amount used depends on the activity of each polymerizable unsaturated compound, as well as the relationship between the amount of each compound used in the composition, that is, the amount that remains during drying and exhibits hardening nodes. It is desirable to make a decision by considering the following.

These polymerizable unsaturated compounds can be treated with various photopolymerization initiators that are generally used as initiators and sensitizers for UV-curable φ materials.

Examples are benzoin, benzoin methyl ether, and benzoin methyl ether.

Pentwin isopropyl ether, benzoin butyl ether, 2-methylbenzoin, benzophenone, Michler's ketone, benzyl, benzyl dimethyl ketal,
Examples include benzyl diethyl ketal, anthraquinone, methylanthraquinone, diacetyl, acetophenone, diphenyl disulfide, and anthracene. The amount of these photopolymerization initiators used t11 is usually 0.05 to 30 parts, preferably 0.1 to 10 parts per 100 parts by weight of the polymerizable unsaturated compound. It is also possible to use conventionally known sensitizing aids such as amines in the year of photopolymerization initiation. Further, in order to improve the thermal stability of the composition, it may be effective to coexist with a known thermal polymerization inhibitor.

Specific examples of the thermal polymerization inhibitor 1 include paramethoxyphenol, hydroquinone, dasibutylcatechol, pyrogallol, phenothiazine, floranil, naphthylamine, β-naphthol, 2,6-di-tert-butyl-valacresol, pyridine, nitrobenzene, Examples include para-toluidine and methylene blue, and the amount used is usually 0.01 to 5 parts by weight per 100 parts by weight of the polymerizable unsaturated compound.

The photosensitive resin composition thus obtained is applied by an appropriate means, and dried. At this time, the HO1J imide precursor obtained from the aliphatic and aromatic tetracarboxylic dianhydride and diamine, which is the backbone of the composition of the present invention, contains 3% or more of repeating units containing aliphatic tetracarboxylic acid residues. Because of this, it has very good solubility, and even among polymerizable unsaturated compounds after solvent volatilization during dry coating, it provides a uniform coating film that can actually allow light to pass through. The desired )(
By irradiating actinic light from above the patterned mask (), the irradiated area is exposed to a photopolymerization initiator. ), polymerization of the polymerizable unsaturated compound occurs ζ), and the solubility in the non-irradiated area is greatly reduced. In some cases, irradiation with ionizing radiation such as electron beams or radiation can also provide a similar effect.

Thus, by selecting an appropriate solvent system, 1)
By removing the non-irradiated areas through development, 1) a desired resin pattern can be obtained.

The resulting resin pattern can be converted into an insulating layer with improved heat resistance through subsequent baking or post-curing. It's very useful.

The present invention will be explained below using examples.

Example 1 Using a 500cc four-hole flask equipped with a thermometer, N2 gas inlet, cooling tube with tiger knob, and stirring device,
In Table 1 (each formulation shown) 4., the following reaction was carried out to obtain a polyimide v11 precursor solution, and a polymerizable unsaturated compound and a photopolymerization initiator were added to the photosensitive resin I] The results of these evaluations are also shown in Table 1.

That is, 1,2,3,4-butanetetracarboxylic dianhydride (abbreviated as BTCA), pyromellitic dianhydride (abbreviated as PMDA), and N/N-dimethylformamide (abbreviated as DMF) are placed in a flask. ) and stirred on a water bath under dry N2 gas flow.

When the contents were at about 5°C, 4,4'-diaminodiphenyl ether (abbreviated as DDE) was added little by little while monitoring the degree of heat generation. This addition (this takes about 30 minutes, and the temperature of the reactant rises to about 15°C. After the addition, the water bath is removed, and stirring is continued at room temperature for about 2 hours). 2
A viscous polyimide precursor solution having an intrinsic viscosity of 14 or more is prepared.

2-ethylhexyl acrylate was added as a polymerizable unsaturated compound to this solution, and Irgakinear 651 (manufactured by Chipa Geigy Chemical Co., Ltd., benzyldimethylkecool) was added as a photopolymerization initiator under light shielding, and after stirring and mixing, 1μ It was filtered through a filter to obtain a photosensitive resin composition.

These compositions were then spun onto a glass plate at 300 rpm using a spinner. Apply at a rotation speed of 90
After drying at ℃ for 10 minutes, uniform coating films of sample numbers 1 to 8 were obtained. A mask pattern was installed on this coating film, and 300mJ
/cJ After irradiating with ultraviolet rays, observe the coating surface,
The presence or absence of photosensitivity was examined. Those with photosensitivity were developed with a mixed solvent of DMF-benzene and rinsed with benzene to obtain a clear resin pattern.

These resin pattern coatings were post-keyed by baking at 350°C for 2 hours, and then subjected to thermogravimetric analysis at a heating rate of 5°C/min in air.
.

Sample numbers 1 to 3 in Table 1 show comparative test examples, and sample numbers 4 to 8 show examples according to the present invention. Sample No. 1 is a case where a wholly aromatic polyimide precursor is used, and the dried coating film is severely whitened by the polymerizable unsaturated compound which is a poor solvent, and has no photosensitivity at all. It is. Sample numbers 2 to 811 are examples in which polyimide precursors contain aliphatic detracarboxylic acid residues derived from BTCA, and sample numbers 2 to 3, which contain a small amount of BTCA-containing U, have almost no difference from sample number 1. However, when the mole % BTCA content exceeds 3%, the sample Nos. 4 to 8 exhibit photosensitivity. By the way, as the molar percentage of BTCA increases, there is a tendency for heat resistance to decrease. However, for vine applications where a decrease in heat resistance is acceptable, the content may be up to about 95%.

Example 2 In a flask similar to Example 1, a polyimide precursor solution was obtained by reacting with each formulation shown in Table 2, and a polymerizable unsaturated compound and a photopolymerization initiator were added thereto. A Q photosensitive resin composition was used to form a resin/4 durn, and the evaluation results (i) are also listed in Table 2.

That is, flaskona cyclobenkune tetracarboxylic dianhydride (abbreviated as CPTA), PMD A and D
MF was 210, and DDE was added and reacted in the same manner as in Example 1 to obtain a viscous polyimide precursor solution having an intrinsic viscosity of 0.25 or more.

Ethylcarpitol acrylate (abbreviated as ECA) was added to this solution as a polymerizable unsaturated compound, and then Irgacure 651 was added as a photoinitiator under light shielding. A resin composition was obtained.

Thereafter, coating, drying, and ultraviolet irradiation were carried out in the same manner as in Example 1, and the surface of the coating film was observed and detected, and the presence or absence of photosensitivity was examined. We conducted a vehicle stiffness analysis. These results are also listed in Table 2.

Sample No. 9 in Table 2 is a wholly aromatic polyimide precursor, similar to Sample No. 1 in Table 1 of Example 1, but the dry coating film (whitening was not observed in this case). However, ECA evaporates and has no photosensitivity at all (
Even if irradiated with ultraviolet rays of 300mJ/c4 or more, no changes will be caused.)

Although the phenomenon is different from that in Example 1 due to the difference in the polymerizable unsaturated compound, as in sample numbers 12 to 16, <CPT
Those with a mole % content of A exceeding 3% have photosensitivity, and the tendency is the same as in Example 1. ,
A photosensitive composition is obtained.

Example 3 In a flask similar to Example 1, 26.49 (0.1 mol) of 5-(2,5-diogysotetrahydrocryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, PMDA 21.8g (0.1 mol) and 0MF
205.8. Add @, same as implementation 0111 (then D
DE 40.0.9 (0.2 mol) was added and reacted to obtain a viscous polyimide precursor solution with an intrinsic viscosity of 0.3.

Add ethylcarpitol acrylate s 8.2 to this solution.
1.9 g of Irgakia-651 was added under light shielding, and after stirring and mixing, the mixture was filtered through a 1 μm filter to obtain a photosensitive resin composition.

This composition was coated on a glass plate in the same manner as in Example 1 and dried to obtain a uniform coating film with a thickness of 5.5 μm. Example 1
After developing and rinsing using the same method as above, a clear resin pattern was obtained.

The coating film of this resin pattern was evaluated as 400 as described in Example 1.
There was no noticeable reduction in temperature up to ℃, and the result was good.

Example 4 Same as Example 1 (2) B T CA 19.
8 g (0,1 mol), 3,3',4,4'-benzophenonetetracarboxylic dianhydride 32.2 g (0,1
mol) and 214.7 g of DMF were added, and 40.0 p (0.2 mol) of DDE was reacted in the same manner as in Example 1 to obtain a viscous polyimide precursor solution with an intrinsic viscosity of 0.35. Ta.

Add this solution to 920 g of 2-ethylhexylagelylate.
of Irgacure (i51) under light shielding.
．． After adding 60g and stirring and mixing, the mixture was filtered through a 1μ filter to obtain a ready-made photosensitive resin.

This composition was applied to glass spray 1-h in the same manner as in Example 1, dried to obtain a transparent coating film with a thickness of 48 μm, and this coating film was irradiated at 300 m and T/J.

When developing and rinsing was performed in the same manner as in Example 1,
IIl, ¥ (March 4; jr IJ!-f pattern was obtained.

In the evaluation described in Example 1, no significant decrease was observed in this (h·t Jli pattern φ film) up to 410° C., indicating good heat resistance.

patent applicant E” Tokyo Electric Industry Co., Ltd. Representative Hijikata Ohbe

Claims (1)

[Claims] (In the formula, il is an aliphatic tetracarboxylic acid residue, R' is 2
Repeating unit [■] with a value h) 1L)
and (wherein, Ar is an aromatic tetracarboxylic acid residue, R' is 2
(indicating a valent organic group) [Essentially from LD (
Contains at least 3% of I) and has a hardness of 0.1 or more
3; A polymerizable unsaturated compound and a photopolymerization 114 initiator are blended into a solution containing a polyimide precursor for forming 11M]), and after drying, the solution contains substantially no light transmission. A photosensitive resin composition that provides acceptable and active photosensitivity.