JPH03192155A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. with a high sensitivity, excellent heat resistance, etc., by compounding a specific polyimide resin with specified amts. of a biscoumarin compd. linked at the 3,3'-positions through a carbonyl group and an oxazolone compd. CONSTITUTION:The title compsn., suitable for a protective coating film, interlayer insulating film, etc., of a semiconductor element, is prepd. by compounding, as the essential components, 100 pts.wt. polymer mainly comprising the structural units of formula I (wherein R1 and R2 are each an arom. cyclic group; R3 is H, CH3, or C2H5; R4 is H, CH3, C2H5, CH2OH, or C6H5; (n) is 1 or 2; and (m) is 0. 1. or 2); 1-10 pts.wt. biscoumarin compd. of formula II (wherein R5 and R6 are each H, alkoxy,or dialkylamino) linked at the 3,3'- positions through a carbonyl group; and 1-20 pts.wt. oxazolone compd. of formula III (wherein R7 is a group of formula IV or V; R8 is H, 1-4C alkyl, C6H5, OH, etc.).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a photosensitive polyimide resin composition with high sensitivity and high heat resistance.

[Prior art] Conventionally, surface protection films of semiconductor elements, glabella insulating films, etc.
Polyimide resin is used because it has excellent heat resistance and outstanding electrical and mechanical properties. However, in recent years, semiconductor devices have become more highly integrated and larger, sealing resin packages have become thinner and smaller, and solder With the shift to surface mounting methods using reflow, there is a demand for significant improvements in heat cycle resistance, heat shock resistance, etc., and conventional polyimide resins have
It has become difficult to respond.

On the other hand, technology that imparts photosensitivity to polyimide resin itself has recently attracted attention.

Using polyimide resins that have been given these photosensitizers not only simplifies the pattern creation process compared to polyimide resins that have not been given photosensitivity, but also eliminates the need for highly toxic etching solutions, making them safer. It is also excellent in terms of pollution, and photosensitization of polyimide resin is expected to become an important technology in the future.

As the photosensitive polyimide resin, for example, a polyimide precursor composition to which a photosensitive group is added with an ester group having a structure as shown in the following formula () (Japanese Patent Publication No. 55-41422) or a polyimide precursor composition as shown in the following formula (V) A composition in which a compound containing a carbon-carbon double bond and an amino group or a quaternized salt thereof that can be dimerized or polymerized by actinic radiation is added to a polyamic acid having a structure (for example, Japanese Patent Publication No. 59-52822 Public bulletin) etc. are known.

All of these are dissolved in a suitable organic solvent, applied as a varnish, dried, exposed to ultraviolet light through a photomask, developed and rinsed to obtain the desired pattern, and then heat-treated to form a polyimide. It is a coating.

However, such conventional compositions have the following drawbacks. That is, the composition shown by the formula (IV) is manufactured through an extremely complicated process of first causing an esterification reaction between a tetracarboxylic dianhydride and an alcohol having a photosensitive group, and then performing an amidation reaction with a diamine. Therefore, it was difficult to stabilize the product. In the composition shown by the formula (V), the manufacturing process is extremely simple because it is only necessary to add and mix the photosensitive agent to the polyamic acid, but the ionic bonding force between the polyamic acid and the photosensitive agent is extremely weak. ,(
Spray development (a method of rapidly developing in a short period of time by spraying a developing solution), which is possible with the composition shown in the formula (mV), was not possible.

[Problems to be Solved by the Invention] An object of the present invention is to provide a highly sensitive heat-resistant photosensitive polyimide resin composition that has a simple manufacturing process, is consistent in product quality, can be spray developed, and is highly sensitive. There is something to do.

[Means to solve the problem] The present invention relates to the following general formula (I) Polymer (A) whose main component is a structural unit represented by and the following general formula (II) (In the formula, Rs, Rs: H, alkoxy group.

A biscoumarin compound (B) substituted with carbonyl at the 3-position represented by dialkylamino group) and the following general formula (m) (in the formula R1, R2:
Aromatic cyclic group.

R3: H, CH3, -C2Hs R4 H, -CH3, -C2H5゜-CH20H, Ce Hs n: 1-29m: 0-2) Re H, -CH3, -CzHs, -C3H7, -C
4H9゜-CeHs, -OH, -0CH3, -0C2H
5° -0C3H7, -0C4H9, -OC5Hs.

-CH2CeHrs, -CH2CH2CeHs.

-CH2oH, -CHxcH20H.

-CH2CH3, -CH(CH3)2. -C(CH3)
3゜-COCR3, -COC2H5, -OCOCR3゜-OCOC2H5, -CH2N R2゜-CH2CH2
N R2, -CON R2゜-CONHCH3, -CO
N(CH3)2゜-CON HC2H5,-C0N(C
2H5)2°-NHCH3,-N(CH3)2. -N(
The oxacylone compound (C) represented by C2H5)2) is an essential component, and (B) 1% per 100 parts by weight of (A).
-10 parts by weight and (C) t -20 parts by weight.

[Function] The polymer (A) used in the present invention is synthesized, for example, by the following method.

That is, the following general formula (VI) L VIノ The acid shown by and the following general formula [■] (COOH).

An amine represented by H2N-R2NR2... [■] and an N-methylolacrylamide represented by the following general formula [■]0H2C \
It is synthesized by reacting I) with [■], then adding [■] and further reacting. The reaction between (Vl) and [■] is usually completed in several hours at room temperature, and the reaction with [■] is completed in half an hour to several hours at 50 to 100°C. The reaction will complete more quickly if a catalyst is used, but it will proceed satisfactorily even without a catalyst. In this way, the reaction can be completed extremely easily and consistently.

In general formula (Vl), as the acid having an aromatic cyclic group in R1, tricarboxylic acid anhydride with n=1, tetracarboxylic dianhydride with n=2, etc. are used, and there is only one type of acid anhydride component. However, a mixture of two or more types may be used.

The types of acid anhydrides used include, for example, trimellitic anhydride, pyromellitic dianhydride, benzene-1
, 2,3,4-tetracarboxylic dianhydride, 3.3'
, 4.4'-benzophenone tetracarboxylic dianhydride, 2.2', 3.3'-benzophenone tetracarboxylic dianhydride, 2,3.3''.

4'-benzophenone tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride,
Naphthalene-1,2,5,6-tetracarboxylic dianhydride, Naphthalene-1,2,4,5-tetracarboxylic dianhydride, Naphthalene-1,4,5,8-tetracarboxylic dianhydride , naphthalene-1,2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,
6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,
3,5,6,7-hexahytronaphthalene-2.3,6
．． 7-tetracarboxylic dianhydride, 2,6-cyclonaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-cyclonaphthalene-1,4,5,8-tetracarboxylic Acid dianhydride, 2,3,6.7-titrachloronaphthalene-1.4,5.8-tetracarboxylic dianhydride, 1,4.5°8-tetrachloronaphthalene-2,
3,6,7-tetracarboxylic dianhydride, 3.3',
4.4'-diphenyltetracarboxylic dianhydride, 2.
2', 3.3'-diphenyltetracarboxylic dianhydride, 2,3.3', 4'-diphenyltetracarboxylic dianhydride, 3.3", 4.4"-p-terphenyltetracarboxylic dianhydride Acid dianhydride, 2.2", 3.3"-p-terphenyltetracarboxylic dianhydride, 2,3°3",
4”-p-terphenyltetracarboxylic dianhydride, 2
．． 2-bis(2,3-dicarboxyphenyl)-brovani anhydride, 2,2-bis(3,4-dicarboxyphenyl)-propani anhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, Bis(3,4-dicarboxyphenyl)ether dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-
dicarboxyphenyl)methanihydride, bis(2,3
-dicarboxyphenyl)sulfonic anhydride, bis(3
, 4-dicarboxyphenyl)sulfone dianhydride, 1.
1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)
Ethanide anhydride, perylene-2,3,8,9-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10,11
-tetracarboxylic dianhydride, perylene-5,6,11
, 12-tetracarboxylic dianhydride, phenanthrene-
1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride,
Phenanthrene-1,2゜9,1O-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2゜3.5.6-tetracarboxylic dianhydride pyrrolidine-2゜3.4.5-tetracarboxylic dianhydride, thiophene-2゜3.4.5
Examples include, but are not limited to, -tetracarboxylic dianhydride.

In the general formula [■], as the amine having an aromatic cyclic group for R2, diamine with m = 0, diaminocarboxylic acid with m = 1, diaminodicarboxylic acid with m = 2, etc. are used, and there is only one type of amine component. However, a mixture of two or more types may be used. Examples of the types of amines used include m
-phenylene-diamine, 1-isopropyl-2,4-
Phenylene diamine, p-phenylene diamine, 4
．． 4'-Diamino-diphenylpropane, 3.3'-diamino-diphenylpropane, 4,4'-diamino-diphenylethane, 3.3'-diamino-diphenylethane, 4.4'-diamino-diphenylmethane, 3.3 ′
-diamino-diphenylmethane, 4,4'-diamino-
Diphenylsulfide, 3,3'-diamino-diphenylsulfide, 4,4'-diamino-diphenylsulfone, 3,3'-diamino-diphenylsulfone, 4,4
'-Diamino-diphenyl ether, 3.3'-diamino-diphenyl ether, benzidine, 3.3'-diamino-biphenyl, 3.3'-dimethyl-4,4'-diamino-biphenyl, 3,3'-dimethoxy-benzidine , 4.4"-diamino-p-terphenyl, 3.3"
Diamino-p-terphenyl, bis(p-amino-cyclohexyl)methane, bis(p-β-amino-t-butylphenyl)ether, bis(p-β-methyl-δ-aminopentyl)benzene, p-bis (2-methyl-4-
aminopentyl)benzene, p-bis(1,1-dimethyl-diamino-pentyl)benzene, 1,5-diamino-naphthalene, 2,6-cyamitunaphthalene, 2,
4-bis(β-amino-1-butyl)toluene, 2,4
-diamino-toluene, m-xylene-2,5-diamine, p-xylene-2゜5-diamine, I-xylylene-diamine, p-xylylene-diamine, 2,6-cyamitopyridine, 2,5-diamino -pyridine, 2.5
-Diamino-1,3,4-oxadiazole, 1,4-
Diamino-cyclohexane, piperazine, methylene-diamine, ethylene-diamine, propylene-diamine,
2,2-dimethyl-propylene-diamine, tetramethylene-diamine, pentamethylene-diamine, hexamethylene-diamine, 2゜5-dimethyl-hexamethylene-diamine, 3-methoxy-hexamethylene-diamine, heptamethylene-diamine, 2,5-dimethyl-hebutamethylene-diamine, 3-methyl-hebutamethylene-
Diamine, 4,4-dimethyl-hebutamethylene-diamine, octamethylene-diamine, nonamethylene-diamine, 5-methynodononamethylene-diamine, 2,5-dimethyl-nonamethylene-diamine, decamethylene-diamine, 1,10-diamino -1,10-dimethyl-decane, 2,11-diamino-dodecane, 1,12-diamino-octadecane, 2,12-diamino-octadecane, 2,17-diaminosiloxane, diaminosiloxane, 2,6-diamino-4- carboxylic benzene,
Examples include, but are not limited to, 3,3'-diamino-4,4'-dicarboxylic benzidine.

Examples of the N-methylol acrylamide represented by the general formula [■] include N-methylol acrylamide, N-methylol methacrylamide, N,N-dimethylol acrylamide, N,N-dimethylol methacrylamide,
-Methylol-N-methylacrylamide, N-methylol-N-methylmethacrylamide, N-methylol-
Examples include, but are not limited to, N-ethylacrylamide and N-methylol-N-ethylmethacrylamide.

The sensitizer of component (B) used in the present invention has the following formula (II) (wherein R=, Rs: -H, alkoxy group).

It is a biscouman compound substituted with carbonyl at the 3-position represented by a dialkylamino group.

As this biscoumarin compound, for example, 3.3'-
Carbonyl-bis(7-dinithylaminocoumarin), 3
．． Examples include, but are not limited to, 3'-carbonyl-bis(5,7-simethoxycarbonylcoumarin).

Sensitizers used in the photosensitive resin composition include benzophenone, acetophenone, anthrone, p, ρ'-tetramethyldiaminobenzophenone (Michler ketone),
Phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, N-acetyl-p-nitroaniline, p-nitroaniline, 2-ethylanthraquinone, 2-tert-butylanthraquinone, N~acetyl-4-nitro-1- Naphthylamine, biclamide, 1,2-benzanthraquinone, 3-methyl-1,3
-Diaza-1,9-benzanthrone, p,p'-tetraethyldiaminobenzophenone, 2-chloro-4-nitroaniline, dibenzalacetone, 1,2-naphthoquinone, 2,5-bis-(4'-diethylamino benzal)-cyclopentane, 2,6-bis-(4'-diethylaminobenzal)-cyclohexanone, 2,6-bis-
(4'-dimethylaminobenzal)-4-methyl-cyclohexanone, 2,6-bis-(4'-diethylaminobenzal)-4-methyl-cyclohexanone, 4.4'
-bis-(dimethylamino)-chalcone, 4.4'-bis-(diethylamino)-chalcone, p-dimethylaminobenzylideneindanone, 1.3-bis-(4'-dimethylaminobenzal)-acetone, 1 .3-bis=(
Examples include 4'-diethylaminobenzal)-acetone, N-phenylene/L-jetanolamine, N-p-tolyl-diethylamine, etc., but the biscoumarin compound discovered in the present invention can be used as an initiator in the present invention. It shows a surprisingly excellent sensitizing effect only when used in combination with the oxacylone compound used. The reason for this surprising synergistic effect is not yet clear.

The amount of biscoumarin compound is 1 to 1 polyamic acid.
It is most preferably 1 part by weight or more and 10 parts by weight or less per 00 parts by weight, and sensitizers other than biscoumarin compounds may also be used in combination.

When the amount of the biscoumarin compound is less than 1 part by weight,
If it exceeds 10 parts by weight, the amount of light energy transmitted will be insufficient and photocuring in deep areas will not progress rapidly, which is not preferable.

The initiator of component (C) used in the present invention has the following formula (In) Reney H, -CH3, -C2H5, -C3H7, -C
4H9゜-CeHs, -OH, -0CH3, -0C2H
5゜-0CaH, -OC4Hs, -OC8H! 1゜-
CH2C0sH5, -CH2CH2C0Hs.

-CH20H, -CH2CH20H.

-CH2CH3, -CH(CH3)2. -C(CH3)
3゜-COCH:+, -COC2Hs, -0COCH3
゜-OCOC2H5,-CH2N H2゜-CH2CH
2N H2,-CON H2゜-CONHCH3,-C
ON(CH3)2゜-CONHC2H+s,-CON(
C2H5)2°-N HCH3,-N (CH3)2.
-N (C2H5)2) It is an oxacylone compound having an aromatic group represented by (C2H5)2).

As an initiator used in the photosensitive resin composition, 2.2-
Dimethoxy-2-phenyl-acetophenone, 1-hydroxy-cyclohexyl-phenylketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propane, 3.3', 4.4'- Tetra (t
-butylperoxycarbonyl)benzophenone, benzyl, benzoin-isopropyl ether, benzoin-isobutyl ether, 4,4'-dimethoxybenzyl, 1,4-dibenzoylbenzene, 4-benzoylbiphenyl, 2-benzoylnaphthalene, methyl-〇- Benzoylbenzoate, 2,2'-bis(0-chlorophenyl)-4,4', 5,5'-tetraphenyl-1,
2'-biimidazole, lO-butyl-2-chloroacridone, ethyl) L-4-dimethylaminobenzoate,
Dibenzoylmethane, 2,4-diethylthioxanthone, 3,3-dimethyl-4-methoxy-benzophenone,
2-Hydroxy-2-methyl-1-phenylpropane-
1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-
dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-phenyl-1,2-butanedione-2-(0-methoxycarbonyl)oxime, 1-phenyl-propanebutanedione-2-(O- benzoyl)
Oxime, 1,2-diphenyl-ethanedione-1-(
0-benzoyl)oxime, 1,3-dipheny/Iwpropanetrione-2-(O-benzoyl)oxime, l
-phenyl-3-ethoxy-propanetrione-2-(
Oxacilone compound discovered in the present invention can be used in combination with a biscoumarin compound as a sensitizer.
It showed a remarkable photoreaction initiation effect compared to other initiators.

The reason for how this surprising effect is expressed is currently not clear.

The amount of the oxacylone compound to be blended is essentially 1 to 20 parts by weight per 100 parts by weight of the polyamic acid, and initiators other than the oxacylone compound may also be used in combination.

If the amount of the oxacylone compound used as an initiator is less than 1 part by weight, the photosensitivity will be insufficient, which is not preferable.

Moreover, if it exceeds 20 parts by weight, the film properties after heat treatment and curing will deteriorate.

An adhesion aid, a leveling agent, and various other fillers may be added to the heat-resistant, photosensitive resin composition of the present invention.

The method for using the photosensitive resin composition according to the present invention is to first apply the composition to a suitable support such as a silicon wafer or a ceramic substrate. The 2i method includes rotation coating using a spinner, spray coating using a spray coater,
This can be done by dipping, printing, roll coating, etc. next,
After pre-baking at a low temperature of 60-80°C and drying the coating,
Actinic radiation is applied to the desired pattern shape. As the actinic radiation, X-rays, electron beams, ultraviolet rays, visible light, etc. can be used, but those having a wavelength of 200 to 500 nm are preferable.

Next, a relief pattern is obtained by dissolving and removing the unirradiated areas with a developer. As a developer, N-methyl-2
-pyrrolidone, N,N-dimethylacetamide, N,N
-Dimethylformamide, methanol, isopropyl alcohol, water, toluene, xylene, etc. are used alone or in combination. Development methods include spray,
Although paddle, immersion, and ultrasonic methods are possible, spray development is the most preferred, as it has the shortest development time, can be incorporated in-line into the process, and provides the cleanest finished pattern. In spray development, the developer is sprayed under considerable pressure, so unless the coating film has zero or extremely low solubility in the irradiated areas, it will dissolve together with the unirradiated areas, leaving no relief pattern. Put it away. Although many conventional compositions cannot be spray developed, the composition according to the present invention can be developed and can be directly incorporated into an in-line process.

Next, the relief pattern formed by development is rinsed. As the rinsing liquid, methanol, ethanol, isopropyl alcohol, butyl acetate, etc. are used. Next, heat treatment is performed to form imide rings and obtain a final pattern with high heat resistance.

The photosensitive resin composition according to the present invention is useful not only for semiconductor applications but also as an interlayer insulating film for multilayer circuits, a cover coat for flexible copper clad boards, a solder resist film, a liquid crystal alignment film, and the like.

The present invention will be specifically explained below using Examples.

Example 1 A mixture of 57 g of 3.3', 4.4'-benzophenone tetracarboxylic dianhydride, 33 g of 4.4'-diaminodiphenyl ether as an amine, and 10 g of silicone diamine represented by the following formula was N-
The mixture was poured into methylpyrrolidone and reacted at 20°C for 6 hours.

60 g of N-methylolacrylamide was added to the obtained polyamic acid and reacted at 80°C for 1 hour. The molecular weight of the obtained polymer was 23,500, which was as expected.

Next, 3,3'-carbonyl-bis(7-
dinitylaminocoumarin) and 6 g of 3-phenyl-5-isoxacilone as an initiator were added and mixed and dissolved at room temperature to obtain a photosensitive resin composition.

The obtained composition was applied onto an aluminum plate using a spinner and dried at 65°C for 1 hour using a dryer.

This film is coated with Kodak's Photographic Step Tablet No. 2.21 Step (in this gray scale, as the number of steps increases, the amount of transmitted light is 1/1 of that of the previous step).
f2, so the larger the residual stage after development, the better the sensitivity).

Next, this was set in a spray developing machine and developed using a developer containing 60% by weight of N-methylpyrrolidone and 40% by weight of xylene. When the pattern was further rinsed with isopropyl alcohol, up to 14 levels of the pattern remained, showing high sensitivity. I found out something.

Development time was only 30 seconds.

Next, the coating was applied onto a silicon wafer in the same manner as described above, the entire surface was exposed, development and rinsing steps were performed, and then
5G and heat curing at 250.350° C. for 30 minutes each.

For the adhesion test, 100 pieces were cut into 1 mg square pieces and an attempt was made to peel them off using cellophane tape, but not a single piece came off, indicating that they had high adhesion.

Separately, it was coated on an aluminum plate, exposed to light over the entire surface, developed, rinsed, and cured with heat, and then the aluminum plate was removed by etching to obtain a film.

Tensile strength of the obtained film (JIS K-6760)
was as large as 16 Kg/mm'' (the larger the better), and the thermal decomposition initiation temperature was as high as 420°C (the higher the better).

Volume resistivity of the obtained film (JISC-6481)
was as large as 3X10"Ω・Cm (the larger the better), and the dielectric constant was as low as 3.2 (IMH2) (the lower the better)
.

Comparative Examples 1 to 6 The same experiments as in Example 1 were carried out by changing the types and amounts of the sensitizer and initiator, and the results shown in Table 1 were obtained.

In Comparative Example 1, the amount of initiator added was 0.6 parts by weight, and the photosensitivity was extremely low.

In Comparative Example 2, the amount was 26 parts by weight, contrary to Comparative Example 1, and in this case, the initiator remained in the film, resulting in a low thermal decomposition initiation temperature.

Comparative Example 3 used an initiator other than the one according to the invention, had low photosensitivity, and was not practical.

In Comparative Example 4, the amount of sensitizer added was 0.3 parts by weight, and in this case, the photosensitivity was extremely low and the crosslinking was insufficient.

In Comparative Example 5, the amount of sensitizer was 23 parts by weight, and in this case, the amount of light transmitted to the deep part was insufficient, curing in the deep part was insufficient, voids were generated, and a uniform film was not obtained. .

Comparative Example 6 used a sensitizer other than the one of the present invention and had low photosensitivity, making it impractical.

Comparative Example 7 After dissolving 57 g of 3.3', 4.4'-benzophenone tetracarboxylic dianhydride and 48 g of 2-hydroxyethyl methacrylate in γ-butyrolactone, 30 gm of pyridine was added as a catalyst, and the mixture was heated at 20°C for 24 hours. react,
An esterified product was obtained. Next, 73 g of dicyclohexylcarbodiimide was added as an amidation catalyst, and then 33 g of 4,4'-diaminodiphenyl ether and 10 g of the silicone diamine described in Example 1 were added and reacted at 20°C for 8 hours. Next, this slurry was filtered, and the filtrate was
The mixture was added dropwise to 0 liter of ethanol with vigorous stirring to precipitate a polymer, and then allowed to stand for 12 hours. The precipitate was filtered off, dried and ground. The resulting polymer (formula (IV
The molecular weight of the photosensitive resin) was 6,500, which was much smaller than expected. Therefore, a polymer was synthesized again using the same method, but the molecular weight remained at 12,000 in this case as well. It was found that this method not only requires a long and complicated process, but also has large variations.

Next, this polymer was dissolved in N-methyl-2-pyrrolidone, and the same sensitizer and initiator as in Example 1 were added to obtain a photosensitive resin composition, which was then coated, exposed, and developed in the same manner. did.

In this case, spray development is possible, and the development time is 30 seconds.
The sensitivity was as high as 10 steps.

However, when an attempt was made to heat-treat and evaluate the film in the same manner as in Example 1, the tensile strength of the film was 3K.
g/+am2 or less, and other properties could not be evaluated.

(to form a photosensitive resin of formula (V)). Next, Example 1
The same amounts of the same sensitizer and initiator as above were added to obtain a photosensitive resin composition. An attempt was made to apply this composition to a silicon wafer, expose it to light, and develop it, but during spray development, not only the unexposed areas but also the exposed areas were dissolved, and no relief pattern could be obtained.

Comparative Example 8 60 g of diethylamino methacrylate was added to the polyamic acid in Example 1 and mixed at room temperature [Effects of the Invention] The present invention provides a photosensitized material that can directly exhibit the excellent properties inherent to polyimide resin that is rich in heat resistance. It is now possible to obtain a composition that

Moreover, since the method is simple, there is no variation, and since spray development is possible during the processing process, it has excellent processability and can be flowed in-line.

Furthermore, they discovered a special combination of sensitizer and initiator that has extremely high photosensitivity, making it possible to obtain good patterns with a small irradiation dose (which speeds up the process).

Claims (1)

[Claims] (1) Polymer (A) whose main component is the structural unit represented by the following formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼・・・(I) (In the formula, R_1, R_2: aromatic cyclic group , R_3:-H, -CH_3, -C_2H_5R_4:-
H_, -CH_3, -C_2H_5, -CH_2OH,
-C_6H_5 n: 1-2, m: 0-2) Biscoumarin compound (B) with carbonyl substitution at the 3-position represented by the following formula [II] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼・・・・・・(II) (In the formula, R_5, R_6: -H, alkoxy group, dialkylamino group) Oxazolone compound represented by the following formula [IV] ) (R_7 in the formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ R_8: -H, -CH_3, -C_2H_5, -C_3
H_7, -C_4H_9, -C_6H_5, -OH, -
OCH_3, -OC_2H_5, -OC_3H_7, -
OC_4H_9, -OC_6H_5, -CH_2C_6
H_5, -CH_2CH_2C_6H_5, -CH_2
OH, -CH_2CH_2OH, -CH_2CH_3,
-CH(CH_3)_2, -C(CH_3)_3, -C
OCH_3, -COC_2H_5, -OCOCH_3,
-OCOC_2H_5, -CH_2NH_2, -CH_
2CH_2NH_2, -CONH_2, -CONHCH
_3, -CON(CH_3)_2, -CONHC_2H
_5, -CON(C_2H_5)_2, -NHCH_3
, -N(CH_3)_2, -N(C_2H_5)_2)
is an essential component, and (B) 1 per 100 parts by weight of (A)
~10 parts by weight and (C) 1 to 20 parts by weight.