JP2524705B2 - Photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel photosensitive composition, more specifically,
The present invention relates to a photosensitive composition which can be converted into a heat resistant polymer compound by heat treatment.

Conventionally, heat-resistant polymer compounds typified by polyimide have been used in the fields of electricity, automobiles, aircraft, space, nuclear power, etc., by taking advantage of their heat resistance and electrical characteristics, and are structural members, printed circuit board materials, and heat-resistant insulating materials. Widely used for.

Photosensitive polymer compounds, on the other hand, are widely used in applications such as paints and printing plates, and recently, taking advantage of their lithographic properties, they have recently been used in printed circuit resists, metal plate etching resists, and semiconductor device manufacturing. It is well known that remarkable progress has been made in materials for fine processing such as resists.

In recent years, polymer materials having two useful functions of heat resistance and photosensitivity have been actively developed, especially for electronic materials and optical materials. For example, a passivation film, an α-ray shielding film, and a jank Applications such as a surface protective film such as a film coat film, an insulating film for a semiconductor device such as an interlayer insulating film for multi-layer wiring, an alignment film for a liquid crystal display device, an insulating film for a thin film magnetic head, etc. are being studied. Functional Materials "July issue, pages 9-19 (1983) and" Photographic Science and Engineering "
Pages 303-309 (see 1979).

[Conventional technology]

Conventionally, as the heat-resistant photosensitive composition, for example, a polymer in which an active functional group such as a double bond is introduced into the ester side chain of a polyamic acid that is a precursor of polyimide is added with a photosensitizer or a photopolymerizable monomer. In addition, a composition capable of forming a crosslinked structure by light irradiation is known (Japanese Patent Publication No. 55-30207 and Japanese Patent Publication No. 55-41422). This is a basic composition of a heat-resistant polymer material for lithography, which is typified by so-called photosensitive polyimide, but its photosensitivity is low and it is insufficient for practical use.

On the other hand, a photosensitive composition containing a mixture of a polyamic acid and an amine compound having an active functional group such as a double bond as a main component has been proposed (JP-A-57-168942 and JP-A-5-168942).
4-145794, JP-A-59-160140).

However, since the viscosity of this solution is extremely high, it is necessary to handle it with a lower concentration solution, and when a spin coater commonly used for film formation on the surface of a semiconductor device is used, a thick film is formed. Is difficult. As a heat-resistant photosensitive composition having high sensitivity in a wide film thickness range in which these drawbacks are improved, a composition obtained by adding a photopolymerization initiator having a specific structure and a sensitizer to a polymer having a photosensitive group is It has been proposed (Japanese Patent Application No. 60-267395, Japanese Patent Application No. 61-25791).

[Problems to be solved by the invention]

These compositions can give higher photosensitivity by increasing the degree of polymerization of the polymer having a photosensitive group as the main component, but with the increase of the degree of polymerization, the resolution of the pattern and the group There is a problem that the adhesiveness with the material decreases. In view of these circumstances, the present inventors have earnestly conducted research to provide a heat-resistant photosensitive composition having high photosensitivity, excellent resolution and adhesiveness to a substrate.

[Means for solving problems]

As a result, it was found that a composition containing a photopolymerization initiator can be suitable for the purpose in a mixture of a polymer having a methacryloxy group and a polymer having an acryloxy group in photosensitivity, and based on this finding The present invention has been completed. That is, the present invention provides (a) a polymer having a viscosity number of 15 to 50 and having a repeating unit represented by the following general formula (1):
~ 5.9% by weight, (b) the following general formula (2) with a viscosity number of 2-20
The present invention provides a novel photosensitive resin composition comprising 5.9 to 94% by weight of a polymer having the repeating unit shown by and (c) 0.1 to 30% by weight of a photopolymerization initiator.

[Wherein X is a (2 + n) -valent carbocyclic or heterocyclic group, Y is a (2 + m) -valent carbocyclic or heterocyclic group, Z
Is Or ▲ R ^* ₁ ▼ is a group containing a methacryloxy group, ▲ R ^* ₂ ▼ is a group containing an acryloxy group, W is -COO ▲ R ^* ₁ ▼ by heat treatment
And a group capable of reacting with a carbonyl group of -COO ▲ R ^* ₂ ▼ to form a ring, n is 1 or 2, m is 0, 1 or 2, and COO ▲ R ^* ₁ ▼ and COO ▲ R ^* ₂ ▼ and Z are in the ortho position or the peri position with respect to each other.] In the composition of the present invention, the polymers used as the component (a) and the component (b) have the general formulas (1) and (2).
And has a repeating unit represented by
Is a trivalent or tetravalent carbocyclic group or a heterocyclic group, and such X is, for example, a benzene ring, a condensed polycyclic aromatic ring such as a naphthalene ring or an anthracene ring, pyridine,
Heterocyclic groups such as thiophene, and general formula (I ₁ ). [Wherein X ₁ is CH _{2 l} , -S-, -O-, Or 1 is 0 or 1, and X ₂ is CH ₃ or CF ₃ ] and the like. Among them, carbon number 6
An aromatic hydrocarbon group of -14, X ₁ is CH _{2 l} (l is 0 or 1), -O- or The group represented by the general formula (I ₁ ) is preferable. Are preferred.

Y in the general formulas (1) and (2) is a divalent, trivalent or tetravalent carbocyclic group or heterocyclic group, and examples of such a group include carbon numbers derived from naphthalene, anthracene and the like. Heterocyclic group and formula derived from 10-18 divalent aromatic hydrocarbon ring, pyridine, imidazole, etc. [Wherein Y ₁ is H, CH ₃ , (CH ₃ ) ₂ CH, OCH ₃ , COOH, a halogen atom or SO ₃ H, Y ₂ is CH _{2 p} (where p is 0 or 1
, -SO _2- , -CH = CH-, -O-, -S-, Y ₃ and Y ₄ are H, CH ₃ , C ₂ H ₅ , OCH ₃ , halogen atom, COO
H, SO ₃ H or NO ₂ , Y ₅ and Y ₆ are H, CN, halogen atom, CH
₃ , OCH ₃ , SO ₃ H or OH] and the like. Among them, carbon number 10
A divalent aromatic hydrocarbon ring of -14, Y ₂ is CH _{2 p} (where p is 0 or 1), A group represented by the formula (I ₆ ) in which —SO ₂ —, —O— or —S— and both Y ₃ and Y ₄ are hydrogen atoms is preferable, and The group represented by is preferable.

W in the general formulas (1) and (2) is a group capable of reacting with a carbonyl group of -COO ▲ R ^* ₁ ▼ and -COO ▲ R ^* ₂ ▼ to form a ring by heat treatment. For example, Is preferred. Further, n is preferably 2.

Further, in the above general formula (1), ▲ R ^* ₁ ▼ is a group containing a methacryloxy group, and as such a group, for example, [In the formula, R ′ represents an alkylene group having 1 to 3 carbon atoms, and α represents 2 to 9] and the like.

An example of (II ₁ ) is As an example of (II ₂ ), An example of (II ₃ ) is Etc., but in addition to this, It may be polyfunctional. Moreover, it is not limited to these.

In the above general formula (2), ▲ R ^* ₂ ▼ is a group containing an acryloxy group, and examples of such groups include: [Wherein R ′ and α in the formula have the same meanings as described above] and the like.

As an example of (III ₁ ), As an example of (III ₂ ), As an example of (III ₃ ), Etc., but in addition to this, It may be polyfunctional. Moreover, it is not limited to these.

In the composition of the present invention, the viscosity number (ηsp / C) of the polymer used as the component (a) is 0.15 to 0.50, preferably 0.20 to 0.40. The viscosity number (ηsp / C) of the polymer used as component (b) is 0.02 to 0.20, preferably 0.05 to 0.15. Here, the viscosity number of the above-mentioned polymer can be determined as follows. That is, 1 g of the polymer is dissolved in 100 ml of N-methylpyrrolidone. 10 ml of this solution was measured with an Ostwald viscometer, the measurement temperature was 30 ° C or less, and the flow-down time was measured.
[Sec]. In addition, 10 ml of N-methylpyrrolidone alone is similarly measured in an Ostwald viscometer, and the flow-down time is measured, which is defined as η ₀ [sec]. At this time, the viscosity number is Since it is defined as, it is calculated based on this formula.

The photopolymerization initiator used as the component (c) in the composition of the present invention is well known, and examples thereof include 2-ethylanthraquinone, 2-t-butylanthraquinone and 1,2.
-Benzanthraquinone, 2,3-diphenylanthraquinone, benzyl, benzophenone, valerophenone, γ
-Phenylbutyrophenone, dibenzosuberone, 4-morpholinobenzophenone, benzoin, α-phenylbenzoin, 10-thioxanthenone, 2-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indanone, Thioxanthen-9-one, xanthene-9-one, benzanthrone, 2,6-di (4 '
-Diazidobenzal) -4-methylcyclohexanone,
2,6-di (4'-diazidobenzal) cyclohexanone, and 1-phenyl- as an oxime type initiator
1,2-butanedione-2- (o-methoxycarbonyl)
Oxime, 1-phenyl-propanedione-2- (o-
Ethoxycarbonyl) oxime, 1-phenyl-propanedione-2- (o-benzoyl) oxime, 1,2-diphenyl-ethanedione-1- (o-benzoyl) oxime, 1,3-diphenyl-propanetrione-2- ( o
-Ethoxycarbonyl) oxime, 1,3-diphenyl-
Propanetrione-2- (o-benzoyl) oxime,
1,3-Diphenyl-propanetrione-2- (o-acetyl) oxime, 1-phenyl-3-ethoxy-propanetrione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxy-propanetrione-
2- (o-benzoyl) oxime and the like can be mentioned, and an oxime type initiator is preferable from the viewpoint of photosensitivity.

Further, a general sensitizer can be added to the composition of the present invention. This sensitizer can improve the photosensitivity of the composition by adding, for example, Michler's ketone, 4,4'-bis- (diethylamino) -benzphenone, 2,5-bis- (4'- Diethylaminobenzal)
-Cyclopentanone, 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-dimethylaminocinnamylideneindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylvinylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) -Isonaphthothiazole, 1,3-
Bis- (4'-dimethylaminobenzal) -acetone,
1,3-bis- (4'-diethylaminobenzal) -acetone, 3,3'-carbonyl-bis- (7-diethylaminocoumarin), diethanolaniline, tolyldiethanolamine and the like, but are not limited thereto. is not.

If necessary, a compound having a carbon-carbon double bond can be added to the composition of the present invention. This carbon
The compound having a carbon double bond is a compound that facilitates a photopolymerization reaction by being added. Examples of such a compound include 2-ethylhexyl acrylate and 2-ethylhexyl acrylate.
Hydroxyethyl acrylate, N-vinyl-2-pyrrolidone, carbitol acrylate, tetrahydrofurfuryl acrylate, isobornyl acrylate, 1,6
-Hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol diacrylate, polyethylene glycol diacrylate, pentaerythritol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, Examples thereof include tetraethylene glycol diacrylate, nonaethylene glycol diacrylate, methylenebisacrylamide, N-methylolacrylamide, and those obtained by replacing the above acrylate or acrylamide with methacrylate or methacrylamide, and among these, preferable one is 2 It is a compound having one or more carbon-carbon double bonds.

Further, by adding a mercaptan compound to the composition of the present invention, the photosensitivity can be further improved.
Examples of mercaptan compounds include, for example, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 1-phenyl-5-mercapto-1H-tetrazole, 2-mercaptothiazoline, 2-mercapto-4-.
Phenylthiazole, 2-amino-5-mercapto-1,
3,4-thiadiazole, 2-mercaptoimidazole,
2-mercapto-5-methyl-1,3,4-thiadiazole, 5-mercapto-1-methyl-1H-tetrazole,
2,4,6-trimercapto-s-triazine, 2-dibutylamino-4,6-dimercapto-s-triazine, 2,5-
Dimercapto-1,3,4-thiadiazole, 5-mercapto-1,3,4-thiadiazole, 1-ethyl-5-mercapto-1,2,3,4-tetrazole, 2-mercapto-6
Nitrothiazole, 2-mercaptobenzoxazole, 4-phenyl-2-mercaptothiazole, mercaptopyridine, 2-mercaptoquinoline, 1-methyl-
2-mercaptoimidazole, 2-mercapto-β-naphthothiazole and the like can be mentioned.

If desired, a functional dialkoxysilane compound may be added to the composition of the present invention or precoated on a substrate for use. This dialkoxysilane compound is a compound that improves the adhesiveness of the interface between the heat-resistant polymer film of the composition of the present invention and the substrate Si and the inorganic insulating film. Examples of these compounds include, for example, , Γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, dimethoxy-3-
Mercaptopropylmethylsilane, 3-methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-
Examples thereof include piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) succinimide and the like. Regarding the use method and effects of these dialkoxysilane compounds, see, for example, Japanese Patent Application No. 60-38242 (Japanese Patent Application Laid-Open No. 61-198634).
Issue). In order to improve the storage stability of the solution of the composition of the present invention, a polymerization inhibitor may be added. Examples of the polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-te.
Examples include rt-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, and 2,6-di-tert-butyl-p-methylphenol. However, it is not limited thereto.

The content ratio of the polymer of the component (a) and the component (b) in the present invention is 94 to 5.9% by weight and 5.9 to 94% by weight, respectively, and preferably 90 to 30.9% by weight of the component (a) and (b). The component is 9.9 to 69% by weight. Further, the content ratio of the component (c) photogravimetric initiator in the present invention is 0.1 to 30% by weight. It is preferably 0.1 to 20% by weight. The sensitizer is used in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the polymers of the components (a) and (b).

The amount of the compound having a carbon-carbon double bond is,
It is preferably 20% by weight or less with respect to the polymers of the components (a) and (b). The addition amount of the mercaptan compound is preferably 10% by weight or less, and more preferably 5% by weight or less, based on the polymers of the components (a) and (b). When the functional dialkoxysilane compound is added and used, the addition amount is 0.05 to 10% by weight, preferably 0.1 to 10% by weight based on the polymers of the components (a) and (b).
It is 4% by weight.

The polymerization inhibitor is used by adding 5% by weight or less, preferably 0.5% by weight or less, to the polymers of the components (a) and (b).

The polymers used as the component (a) and the component (b) in the composition of the present invention are, for example, the following general formulas (3) and (4), respectively. And a compound represented by the general formula By polycondensation or polyaddition with the compound represented by Examples of Z ₁ in the general formulas (3) and (4) and Z ₂ in the general formula (5) include —COOH.
(A), - COCl (B ), - NCO (C), - NH 2 (D), -
OH (E) is mentioned. In addition, X, ▲ R ^* ₁ ▼, ▲ R
^* ₂ ▼, Y and W have the same meaning as above.

By the polycondensation or polyaddition reaction of the compounds represented by the general formulas (3) and (4) with the compound represented by the general formula (5), -Z ₁ and Z _2- are reacted to form a bonded chain Z. To be done. The following table collectively shows preferable combinations of Z ₁ and Z ₂ , the type of Z to be produced, and the ring structure name produced when the obtained polymer is heat-treated.

The polymers of component (a) and component (b) can also be produced by the following method. That is, the general formula [Wherein X has the same meaning as described above] is reacted with a compound represented by the general formula (5-C) or (5-D). Here, the general formula (5-
C) and (5-D) are compounds in which Z _{2 in the} general formula (5) corresponds to the formulas (C) and (D), respectively,
The following combinations have the same meaning.

The carboxyl group of the product thus obtained,
The following general formulas (9) and (10) The polymer can be obtained by reacting with an epoxy compound represented by the formula: ▲ R ^* ₁ ▼ and ▲ R ^* ₂ ▼ have the same meanings as described above.

Incidentally, these reactions are described in, for example, JP-A-56-32524 and JP-A-60-194444.

The compounds represented by the general formulas (3-A) and (4-A) are, for example, The acid anhydride represented by ▲ R ^* ₁ ▼ OH and ▲ R ^* ₂ ▼ OH (▲
R ^* ₁ ▼ and ▲ R ^* ₂ ▼ have the same meanings as described above, and are obtained by ring opening. Examples of the acid anhydride (6) include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl ether. Tetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 2,3, 6,7-naphthalene tetracarboxylic acid anhydride, thiophene-2,3,4,5
-Tetracarboxylic acid anhydride, 2,2-bis- (3,4-biscarboxyphenyl) propane anhydride, etc. are mentioned, and as alcohol ▲ R ^* ₁ ▼ OH, 2-hydroxyethyl methacrylate, 2-hydroxy Propyl methacrylate,
The alcohol ▲ R ^* ₂ ▼ OH, 2- hydroxyethyl acrylate, 2-but-hydroxypropyl acrylate, and the like, but is not limited thereto.

In these anhydride (6) is reacted with an alcohol ▲ R ^* ₁ ▼ OH and ▲ R ^* ₂ ▼ OH, pyridine, dimethylaminopyridine, the reaction is accelerated by the addition of triethylenediamine and the like. The combination of the numbers 1 and 1'in Table 1 above is an example of the preferred embodiment, and the diamine represented by the general formula (5-D) used in this combination is, for example, 4,4'-diamino. Diphenyl ether, 4,4'-diaminobiphenyl, 2,4 '
-Diaminotoluene, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl sulfone, phenylindanediamine, 4,4'-diaminodiphenylmethane,
p-phenylenediamine, m-phenylenediamine, 1,
5-diaminonaphthalene, 3,3'-dimethoxy-4,4'-
Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, o-toluidine sulfone, 2,2-bis (4-aminophenoxyphenyl) propane, bis (4
-Aminophenoxyphenyl) sulfone, bis (4-aminophenoxyphenyl) sulfide, 1,4-bis (4
-Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 3,4'-diaminodiphenyl ether, 9,9-bis (4-aminophenyl) anthracene- (10), 9,9-bis (4 -Aminophenyl) fluorenone, 3,3'-diaminodiphenylsulfone, 4,4 '
-Di- (3-aminophenoxy) diphenyl sulfone,
4,4'-diaminobenzanilide, 3,4'-diaminodiphenyl ether, 4,4 '-[1,3-phenylenebis (1-
Methylethylidene)], 4,4 ′-[1,4-phenylenebis (1-methylethylidene)], 4,4 ′-(m-phenylenediisopropylidene) bis (m-toluidine), 4,
4 '-(p-phenylenediisopropylidene) bis (m
-Toluidine).

Among this combination, general formulas (3-A) and (4-
The reaction of the compound represented by A) with the compound represented by the general formula (5-D) can be carried out using a carbodiimide type dehydration condensation agent, for example, dicyclohexylcarbodiimide.

The compounds represented by the general formulas (3-B) and (4-B) are obtained by reacting the half-ester represented by the general formulas (3-A) and (4-A) with thionyl chloride or phosphorus pentachloride. Can be obtained.

For the methods of these reactions, see, for example, Japanese Patent Application No. 59-1.
93737 (JP-A 61-92022), JP-A-60-9918 (JP-A 61-170731), JP-A 59-238545 (JP-A 61-11842)
No. 3) etc.

The composition of the present invention is used by dissolving it in a solvent capable of dissolving all components in the composition and coating it on a predetermined substrate. At this time, the dialkoxysilane compound may be pre-coated on the substrate for use in order to enhance the adhesion to the substrate.

The solvent is preferably a polar solvent, and examples thereof include dimethylformamide, N-methylpyrrolidone, dimethylacetamide, diglyme, isobutyl acetate and cyclopentanone. Further, solvents such as alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like can be added within the range where components are not precipitated. As a method of coating on the substrate, after the solution obtained as described above is passed through a filter, for example, a method of coating the substrate by a spin coater, a bar coater, a blade coater, a screen printing method, etc. A method of immersing in the solution, a method of spraying the solution onto a substrate, and the like can be used.

As the substrate, for example, a heat resistant material such as metallic glass, a silicon semiconductor, a metal oxide insulator, or silicon nitride is preferable, and when heat treatment is not performed, a material such as a copper clad glass epoxy laminated plate can be used.

Next, the coating film thus obtained is dried by an appropriate method such as air drying, heat drying, or vacuum drying, and then exposed through a normal photomask. At this time, the actinic rays used include, for example, ultraviolet rays, X-rays, electron beams, and among these, ultraviolet rays are preferable, and examples of the light source thereof include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and halogen lamps. And so on. Among these light sources, an ultra-high pressure mercury lamp is preferred. Further, the exposure is preferably performed in a nitrogen atmosphere.

After exposure in this manner, development is performed using an immersion method, a spray method, or the like to remove unirradiated portions. Examples of the developing solution used at this time include N-methylpyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide,
An aprotic polar solvent such as N-benzyl-2-pyrrolidone or γ-butyrolactone may be used alone, or as the second component thereof, for example, alcohol such as ethanol or tosopropanol, toluene, xylene, etc. Aromatic hydrocarbon compounds, ketones such as methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate and methyl propionate, solvents such as tetrahydrofuran and ethers such as dioxane may be mixed and used. Further, it is preferable to rinse immediately after the development with a solvent as described as the second component.

Further, if a method of performing heat treatment after exposure and before development is used, a pattern with good resolution can be obtained in a shorter exposure time. The conditions for this heat treatment are 40 to 90 ° C and 30
~ 5 minutes is preferred, and this method is described in Japanese Patent Application No. 60-661.
It is described in detail in JP-A No. 61-165754.

The image thus obtained is dried, and then heated in a temperature range of 150 to 450 ° C., so that an imide ring, an isoindoloquinazolinedione ring, an oxazinedione ring, a quinazolinedione ring, etc. Is converted to

〔The invention's effect〕

The compositions of the present invention have many advantages over the compositions disclosed in the prior art. The advantage is that high photosensitivity was achieved.
It can also be mentioned that the resolution, which is regarded as important as the characteristics of the photoresist, has been remarkably improved. That is, although the conventional photopolymerizable composition comprising a high-sensitivity polymer containing a methacryloxy group has high photosensitivity, there was a problem in terms of resolution, whereas the photopolymerizable composition of the present invention had a low photosensitivity. It exhibits ideal characteristics as a photosensitive composition that exhibits high resolution at an exposure dose. Further, the composition of the present invention has an advantage that the adhesiveness at the interface with silicon, copper or the like which is a base material of the pattern obtained after exposure and development is excellent as compared with the conventional composition. In addition, good storage stability of the composition solution is also mentioned as an advantage.

INDUSTRIAL APPLICABILITY When the composition of the present invention is used for an interlayer insulating film or a surface protective film for a semiconductor element, a multilayer wiring board, etc., the exposure time is shortened by reflecting the above-mentioned characteristics, and it has high resolution and adheres to the board. It exhibits features such as the ability to form a pattern having excellent heat resistance and good heat resistance.

〔Example〕

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The names of polymers, photopolymerization initiators, sensitizers, compounds having a carbon-carbon double bond (monomer), mercaptan compounds, functional dialkoxysilane compounds, polymerization inhibitors, etc. The results are shown in Table 1.

Example 1 P-1 60 g and P-7 40 g as polymers, polymerization initiator
As X-38g, as sensitizer S-14g, as monomer
M-1 12 g, mercaptan compound T-3 3 g, heavy
As a compound inhibitor, Z-1 0.1g is N-methylpyrrolidone 138g
Was dissolved. This solution is spun onto a silicone wafer.
Coating and drying at 70 ° C. to obtain a 20 μ coating film. this
Using a PLA501F (manufactured by Canon Inc.) under a nitrogen stream,
It is exposed through a specified photomask and exposed at 70 ° C for 20 minutes.
Heat treated. This is N-methylpyrrolidone 60 volumes, xyle
A sharp pattern is obtained by spray development using a 40 volume developer.
Got In this pattern, a 20μ square
Was resolved. In addition, a 1.5 mm square goggle pattern
Tape peeling test (Scotch manufactured by Sumitomo 3M) Mendeingte
The pattern also remained in 100%. this
Is heat treated at 400 ° C for 1 hour,
The pattern of Mid was obtained. In addition, the same composition solution was added to a copper clad laminate.
After coating on the top and patterning in the same way,
A sharp pattern having good adhesion was obtained after development.
Also, grayscale (Photographic Step by Kodak)
Through Tablet No. 2), expose and develop for 5 minutes as above
Sensitivity of each step of gray scale depending on the curing state
When calculated as the number of stages, it was 9 stages.

Comparative Example 1 A silicone wafer was spin-coated with the same composition solution as in Example 1 except that P-2 (100 g) was used, and the coating was dried at 70 ° C. to obtain a 20 μm coating film. This was exposed and developed in the same manner as in Example 1, but a 20 μm square via hole was not resolved. Also, in the 1.5 mm square goggles pattern tape test, only 10% of the pattern remained. Further, the same composition solution was coated on a copper clad laminate and patterned by the same method.
The pattern peeled from the substrate.

Examples 2 to 5 By the same method as in Example 1, coating films of the compositions shown in Table 2 were obtained on the silicone wafer. This was exposed and developed in the same manner as in Example 1, and the sensitivity was determined as the number of steps.
The results obtained are shown in Table 2.

Comparative Examples 2 to 4 Table 3 shows the results of the compositions shown in Table 3 as in Examples 2 to 5.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 61-243447 (JP, A) JP 62-279696 (JP, A) JP 61-198634 (JP, A)

Claims (1)

(57) [Claims] (A) A polymer having a repeating unit represented by the following general formula (1) having a viscosity number (ηsp / C) of 0.15 to 0.50.
94-5.9% by weight, (b) Polymer having a repeating unit represented by the following general formula (2) having a viscosity number (ηsp / C) of 0.02-0.20 5.9-94
%, (C) A novel photosensitive resin composition comprising 0.1 to 30% by weight of a photopolymerization initiator. [Wherein X is a (2 + n) -valent carbocyclic or heterocyclic group, Y is a (2 + m) -valent carbocyclic or heterocyclic group, Z
Is ▲ R ^* ₁ ▼ is a group containing a methacryloxy group, ▲ R ^* ₂ ▼ is a group containing an acryloxy group, and W is -COO ▲ R ^* ₁ by heat treatment.
A group capable of forming a ring by reacting with the carbonyl group of ▼ and -COO ▲ R ^* ₂ , n is 1 or 2, m is 0, 1 or 2,
Also, COO ▲ R ^* ₁ ▼, COO ▲ R ^* ₂ ▼ and Z are in an ortho position or a periposition with respect to each other].