JP2001188343A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition capable of easily forming a micro-patterned thin film excellent in low dielectric property as well as in various properties such as flatness, heat resistance, transparency and chemical resistance. SOLUTION: The photosensitive resin composition contains an alkali-soluble alicyclic olefin polymer obtained by modifying an alicyclic olefin polymer with a compound having an acid derivative type residue such as an amido or carboxyl group, a crosslinking agent such as an alkocymethylated melamine or an alkoxymethylated glycol uryl and a photo-acid generating agent such as a halogen-containing triazine compound.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive composition. More specifically, it is suitable as a material for forming a protective film or the like used for electronic parts, or an interlayer insulating film, particularly as a material for forming an interlayer insulating film of a liquid crystal display element, an integrated circuit element, a solid-state imaging element, or the like. And a low-dielectric photosensitive resin composition.

[0002]

2. Description of the Related Art Generally, liquid crystal display devices, integrated circuit devices,
For electronic components such as solid-state imaging devices and color filters for liquid crystal displays, a protective film to prevent deterioration and damage, a flattening film to flatten the device surface and wiring, and to maintain electrical insulation. Insulating film and the like are provided. Further, a thin film transistor (hereinafter referred to as “TFT”) type liquid crystal display element or an integrated circuit element is provided with an interlayer insulating film in order to insulate between wirings arranged in layers. However, when a conventionally known thermosetting material for forming an insulating film for electronic parts is used to form an interlayer insulating film, for example, the number of steps for obtaining an interlayer insulating film having a required pattern shape However, since there is a problem that an interlayer insulating film having a large amount and having sufficient flatness cannot be obtained, development of a new photosensitive insulating film forming material capable of fine patterning has been demanded. Further, in recent years, with the increase in density of wirings and devices, low dielectric properties have been required for these materials.

As a device that can meet such requirements,
Ring-opening polymerization of an ester group-containing norbornene-based monomer,
A composition containing an alkali-soluble cyclic olefin polymer obtained by hydrolyzing an ester group portion after hydrogenation, a cross-linking agent, and a radiation-sensitive acid generator has been proposed (JP-A-11-52574). .. However, even when this resin composition was used, the unexposed portion could not be sufficiently removed in the development after exposure, and high-density patterning was difficult.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to easily form a fine patterned thin film excellent in flatness, heat resistance, transparency, chemical resistance, and various other properties, and also in low dielectric property. Another object of the present invention is to provide a photosensitive resin composition. The present inventors, as a result of studies to achieve the above objects, an alkali-soluble alicyclic olefin polymer obtained by modifying a compound having an acidic group to an alicyclic olefin polymer, and a specific cross-linking agent, It was found that the object of the present invention can be achieved by using a composition containing a photo-acid generator, and the present invention has been completed based on this finding.

[0005]

[In the formula (1), R ¹ is a hydrogen atom or an alkyl group. n is 1 or 2 (when n is 1, it becomes a divalent functional group). ]

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The photosensitive composition of the present invention contains an alkali-soluble alicyclic olefin polymer, a cross-linking agent and a photo-acid generator.

The alkali-soluble alicyclic olefin polymer preferably used in the present invention is obtained by modifying the alicyclic olefin polymer with a compound having an acidic group or a compound having an acid derivative type residue. It is a thing. The alicyclic olefin polymer is a polymer of olefin having an alicyclic structure. Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure, and a cycloalkane structure, particularly a norbornane structure, is preferable from the viewpoint of mechanical strength and heat resistance. Further, examples of the alicyclic structure include a monocyclic ring, a polycyclic ring, a condensed polycyclic ring, a bridging ring, and a polycyclic ring having a combination thereof. The number of carbon atoms constituting the alicyclic structure is not particularly limited, but when it is in the range of usually 4 to 30, preferably 5 to 20, and more preferably 5 to 15, the mechanical strength, Heat resistance and moldability are highly balanced and suitable. The alicyclic olefin polymer used in the present invention is usually thermoplastic.

The alicyclic olefin polymer usually contains a repeating unit derived from an olefin having an alicyclic structure (hereinafter sometimes referred to as an alicyclic olefin). The proportion of repeating units derived from an alicyclic olefin in the alicyclic olefin polymer is appropriately selected according to the purpose of use,
It is usually 30 to 100% by weight, preferably 50 to 100% by weight, more preferably 70 to 100% by weight. If the proportion of repeating units derived from an alicyclic olefin is too small, the heat resistance becomes poor, which is not preferable. The repeating unit other than the repeating unit derived from an alicyclic olefin is not particularly limited and is appropriately selected according to the purpose of use.

Examples of the alicyclic olefin polymer used in the present invention include those having a polar group. Examples of the polar group include a hydroxyl group, a carboxyl group, an alkoxyl group, an epoxy group, a glycidyl group, an oxycarbonyl group, a carbonyl group, an amino group, an ester group, and a carboxylic acid anhydride group.

The alicyclic olefin polymer is usually obtained by subjecting an alicyclic olefin to addition polymerization or ring-opening polymerization, and optionally hydrogenating an unsaturated bond portion, or addition polymerization of an aromatic olefin. , And the aromatic ring portion of the polymer is hydrogenated.

Examples of the alicyclic olefin used for obtaining the alicyclic olefin polymer include bicyclo[2.2.
1]-hept-2-ene (conventional name: norbornene), 5
-Methyl-bicyclo[2.2.1]-hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]-hept-2-ene, 5-ethyl-bicyclo[2.2.1] ] −
Hept-2-ene, 5-butyl-bicyclo [2.2.
1]-Hept-2-ene, 5-hexyl-bicyclo[2.2.1]-hept-2-ene, 5-octyl-bicyclo[2.2.1]-hept-2-ene, 5-octadecyl -Bicyclo[2.2.1]-hept-2-ene,
5-ethylidene-bicyclo[2.2.1]-hept-2
-Ene, 5-methylidene-bicyclo[2.2.1]-hept-2-ene, 5-vinyl-bicyclo[2.2.1]
-Hept-2-ene,

5-Propenyl-bicyclo[2.2.1]
-Hept-2-ene, 5-methoxy-carbinyl-bicyclo[2.2.1]-hept-2-ene, 5-cyano-
Bicyclo[2.2.1]-hept-2-ene, 5-methyl-5-methoxycarbonyl-bicyclo[2.2.1]
-Hept-2-ene, 5-ethoxycarbonyl-bicyclo[2.2.1]-hept-2-ene, bicyclo[2.
2.1]-Hept-5-enyl-2-methylpropionate, bicyclo[2.2.1]-hept-5-enyl-
2-methyl octanate,

Bicyclo[2.2.1]-hept-2-ene-5,6-dicarboxylic acid anhydride, 5-hydroxymethylbicyclo[2.2.1]-hept-2-ene, 5,6
-Di(hydroxymethyl)-bicyclo[2.2.1]-
Hept-2-ene, 5-hydroxy-i-propylbicyclo[2.2.1]-hept-2-ene, 5,6-dicarboxy-bicyclo[2.2.1]-hept-2-ene, Bicyclo[2.2.1]-hept-2-ene-5,
6-dicarboxylic acid imide, 5-cyclopentyl-bicyclo[2.2.1]-hept-2-ene, 5-cyclohexyl-bicyclo[2.2.1]-hept-2-ene, 5
-Cyclohexenyl-bicyclo[2.2.1]-hept-2-ene, 5-phenyl-bicyclo[2.2.1]-
Hept-2-ene,

Tricyclo[4.3.0.1 ^2,5 ]deca-3,7-diene (conventional name: dicyclopentadiene), tricyclo[4.3.0.1 ^2,5 ]deca-3
-Ene, tricyclo[4.4.0.1 ^2,5 ]undeca-3,7-diene, tricyclo[4.4.0.
1 ^2,5] undec-3,8-diene, tricyclo [4.4.0.1 ^2,5] undec-3-ene, tetracyclo ^{[7.4.0.1 10,13.} 0 ^2,7 ]-trideca-2,4,6-11-tetraene (alias: 1,4
- methano -1,4,4a, 9a- tetrahydrofluorene), tetracyclo ^{[8.4.0.1 11,14.} 0
^3,8 ]-Tetradeca-3,5,7,12-11-tetraene (also known as 1,4-methano-1,4,4a,5,1)
0,10a-hexahydroanthracene),

Tetracyclo[4.4.0.1 ^2,5 . 1
^7,10 ]-Dodeca-3-ene (conventional name: tetracyclododecene), 8-methyl-tetracyclo[4.4.0.
1 ^{2 , 5} . 1 ^7,10 ]-dodec-3-ene, 8-ethyl-tetracyclo[4.4.0.1 ^2,5 .
1 ^7,10 ]-dodeca-3-ene, 8-methylidene-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, 8-ethylidene-tetracyclo[4.
4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene,
8-Vinyl-tetracyclo[4.4.0.1 ^2,5 . 1
^7,10 ]-dodeca-3-ene, 8-propenyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10] - dodeca-3-ene, 8-methoxycarbonyloxy - tetracyclo [4.4.0.1 ^2, 5. 1 ^7,10 ]-dodeca-3-
Ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^{7, 10} ]-Dodeca-
3-ene, 8-hydroxymethyl-tetracyclo[4.
4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene,
8-carboxy-tetracyclo [4.4.0.
1 ^2,5 . 1 ^{7 , 10} ]-dodeca-3-ene,

8-cyclopentyl-tetracyclo[4.
4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene,
8-cyclohexyl-tetracyclo[4.4.0.1
^2,5 . 1 ^7,10 ]-dodec-3-ene, 8-cyclohexenyl-tetracyclo[4.4.0.1 ^2,5 . 1
^7,10 ]-dodeca-3-ene, 8-phenyl-tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]-dodeca-3-ene, pentacyclo[6.5.1.1 ^3,6 . 0
^2,7 . 0 ^{9, 13]} pentadeca-3,10-diene,
Pentacyclo[7.4.0.1 ^3,6 . 1 ^{10, 13} .
0 ^2,7 ]-pentadeca-4,11-diene,

5-phenylbicyclo[2.2.1]hept-2-ene, tetracyclo[6.5.0.1 ^2,5 .
0 ^8,13] Torideka 3,8,10,12- tetraene (1,4 methanol: Synthesis of 1,4,4, also referred 9a- tetrahydrofluorene), tetracyclo [6.6.0.
1 ^2,5 . 1 ^8,13] Tetoradeka 3,8,10,1
2-tetraene (1,4-methanoe 1,4,4a,5,
Norbornene-based monomer such as 10,10a-hexahydroanthracene);

Cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, cyclooctene, 3a,5,6,7a-tetrahydro-4,7- Monocyclic cycloalkenes such as methano-1H-indene and cycloheptene; vinyl-based alicyclic hydrocarbon-based monomers such as vinylcyclohexene and vinylcyclohexane; alicyclic-conjugated diene-based monomers such as cyclopentadiene and cyclohexadiene; Is mentioned.

Aromatic olefins include styrene and α
-Methylstyrene, divinylbenzene, vinylnaphthalene, vinyltoluene and the like.

The alicyclic olefins and/or aromatic olefins may be used alone or in combination of two or more.

The alicyclic olefin polymer may be obtained by copolymerizing the alicyclic olefin and/or aromatic olefin with a monomer copolymerizable therewith. Monomers copolymerizable with alicyclic olefins or aromatic olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-
Butene, 3-methyl-1-pentene, 3-ethyl-1-
Pentene, 4-methyl-1-pentene, 4-methyl-1
-Hexene, 4,4-dimethyl-1-hexene, 4,4
-Dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene. Such as C2-C20 ethylene or α-olefin; 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-
Non-conjugated dienes such as methyl-1,4-hexadiene and 1,7-octadiene; and the like. These monomers can be used alone or in combination of two or more.

The method for polymerizing the alicyclic olefin and/or the aromatic olefin and the method for hydrogenation, if necessary, are not particularly limited and can be carried out according to known methods.

Specific examples of the alicyclic olefin polymer include, for example, a ring-opening polymer of a norbornene-based monomer and its hydrogenated product, an addition polymer of a norbornene-based monomer, a norbornene-based monomer and vinyl. Addition polymers with compounds, monocyclic cycloalkene polymers, alicyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers and their hydrogenated products, aromatic ring hydrogenated products of aromatic olefin polymers, etc. Can be mentioned. Among these, ring-opening polymers of norbornene-based monomers and hydrogenated products thereof, addition polymers of norbornene-based monomers, addition polymers of norbornene-based monomers and vinyl compounds, aromatic olefin polymers Aromatic ring hydrogenated products are preferred, and hydrogenated products of ring-opening polymers of norbornene-based monomers are particularly preferred. The alicyclic olefin polymer,
Each can be used alone or in combination of two or more.

The acidic group-containing compound or acid derivative type residue-containing compound used in the present invention is a compound having an acidic group or acid derivative type residue. Examples of the acidic group or acid derivative-type residue include a carboxyl group, an ester group, an amide group, and an intramolecular or intermolecular carboxyl group dehydrated and condensed (hereinafter referred to as an acid anhydride group). Among these, those having a carboxyl group or an amide group, particularly a carboxyl group and an amide group coexist, are preferable.

Specific examples of the compound having an acidic group or an acid derivative type residue include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, endocis-bicyclo[2.2.1]. ] Hept-5
Unsaturated carboxylic acid compounds such as ene-2,3-dicarboxylic acid, methyl-endocis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid and their esters or amides; maleic anhydride Unsaturated carboxylic acid anhydrides such as chloromaleic anhydride, butenyl succinic anhydride, tetrahydrophthalic anhydride and citraconic anhydride. Of these, maleic anhydride is preferred.

The modification reaction between the alicyclic olefin polymer and the compound having an acidic group or an acid derivative type residue can be carried out by a known method. The modification reaction is usually carried out by allowing an alicyclic olefin polymer and a compound having an acidic group or an acid derivative type residue to coexist in the presence of a radical initiator.

As the radical initiator, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide,
2,5-Dimethyl-2,5-di(peroxide benzoate) hexyne-3,1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2, 5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(tert
-Butyl peroxy)hexane, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl perisobutyrate, tert-
Butyl per-sec-octoate, tert-butyl perpiperate, cumyl per piperate, tert-butyl perdiethyl acetate, etc. can be mentioned. Furthermore, in the present invention, an azo compound can be used as a radical initiator. Specific examples of the azo compound include azobisisobutyronitrile and dimethylazoisobutyrate. Of these radical initiators, organic peroxides and organic peresters are preferably used.

These radical initiators may be used alone or in combination of two or more. The use ratio of the radical initiator is usually 0.001 to 50 parts by weight, preferably 0.01 to 40 parts by weight, and more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the alicyclic olefin polymer. It is a range.

The conditions of the modification reaction are not particularly limited, and the reaction temperature is usually 0 to 400° C., preferably 60 to 400° C.
The reaction time is usually 1 minute to 24 hours, preferably 30 minutes to 10 hours at 300°C, more preferably 80 to 200°C.

The modification rate is such that the polymer exhibits alkali solubility. In order to exhibit alkali solubility, it is usually 10 to 200 based on the total number of monomer units in the polymer.
It is in the range of mol %, preferably 30 to 150 mol %, more preferably 50 to 100 mol %, and particularly preferably 60 to 80 mol %. When the modification rate is within this range, properties such as low dielectric property, transparency, heat resistance, solvent resistance, developability and surface hardness properties are highly balanced and suitable.

The modification rate is expressed by the following equation. Modification rate (mol %)=(X/Y)×100 X: Total number of moles of modified group in polymer by compound having acidic group or acid derivative type residue Y: Total number of monomer units of polymer X Is the total number of moles of modified residues in the alkali-soluble alicyclic olefin polymer, and thus can be measured by ¹ H-NMR. Y is the weight average molecular weight of the polymer (M
w)/equal to the molecular weight of the monomer. In the case of copolymerization, the molecular weight of the monomer is the average molecular weight of the monomer mixture.

When the alkali-soluble alicyclic olefin polymer used in the present invention is obtained by modifying the compound having an acid anhydride group or the compound having an ester group into an alicyclic olefin polymer, It is preferable to hydrolyze or amidate the acid anhydride group or ester group introduced in the modification reaction.

Examples of the compound used for promoting hydrolysis or amidation include potassium hydroxide, sodium hydroxide; trimethylamine, triethylamine, tributylamine and the like. Of these, metal hydroxides are preferred. Examples of the compound used for hydrolysis or amidation include water; methylamine, ethylamine, butylamine, pentylamine, allylamine, diallylamine, vinylamine; amines such as dimethylamine and dipropylamine. Of these, primary amines, especially primary amines having unsaturated carbon-carbon bonds, are preferred.

The molecular weight of the alkali-soluble alicyclic olefin polymer used in the present invention is appropriately selected according to the purpose of use, but toluene, tetrahydrofuran (TH
F), a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using either chloroform or chloroform as a solvent, and usually 3,000 to 500,000, preferably 5,000 to
100,000, more preferably 7,000 to 50,000
The range is 00. When the weight average molecular weight (Mw) of the ring structure-containing polymer is within this range, the developability, flatness, solvent resistance, heat resistance and strength characteristics are particularly excellent and suitable.

The glass transition temperature of the ring structure-containing polymer used in the present invention is not particularly limited, but is usually 50° C. or higher, preferably 80° C. or higher, and more preferably 100° C. or higher. It is excellent and suitable.

The crosslinking agent used in the present invention is a compound having a group represented by the formula (1). —CH _n OR ¹ (1) In the formula (1), R ¹ is a hydrogen atom or an alkyl group. The alkyl group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. Further, n is 1 or 2, and preferably 2. When n is 1, it becomes a divalent functional group.
In addition, when the compound having a group represented by the formula (2) is used, it is not limited to the alkali-soluble alicyclic olefin polymer obtained by the modification reaction, and other methods (for example, Japanese Patent Laid-Open No. It is also applicable to the alkali-soluble alicyclic olefin polymer obtained in No. 52574). >CHOR ¹ (2) In formula (2), R ¹ is a hydrogen atom or an alkyl group.

The cross-linking agent suitable for the present invention is one having at least two groups of the formula (1) in the molecule. Further, a compound in which the group of the formula (1) is bonded to a nitrogen atom, that is, a compound containing an N-methylol group and/or an N-alkoxymethyl group is preferable. When there are two or more groups of formula (1) in one molecule, R ^{1 s} of those groups may be the same or different.

Specific examples of the cross-linking agent include N, N, N',
Alkoxymethylated melamine such as N′,N″,N″-(hexaalkoxymethyl)melamine; N,N′,
Alkoxymethylated glycoluril, such as N″,N″′-(tetraalkoxymethyl)glycoluril;
1,4-di-(hydroxymethyl)cyclohexane,
1,4-di(hydroxymethyl)norbornane; 1,
3,4-trihydroxycyclohexane etc. are mentioned. Of these, N, N, N', N', N", N"-
(Hexamethoxymethyl)melamine or N,N',
N″,N″′-(tetraalkoxymethyl)glycoluril is preferred.

It is also possible to use a mixture of an alkoxymethylated melamine and an alkoxymethylated glycoluril from the viewpoint that a cured product having an excellent photocrosslinkability, heat resistance and solvent resistance and a low dielectric constant can be obtained. In this case, the weight ratio [alkoxymethylated melamine/alkoxymethylated glycoluril] is usually 5/95 to 95/5, preferably 10/90 to 90/10.

The amount of the cross-linking agent is usually 10 to 50 relative to 100 parts by weight of the alkali-soluble alicyclic olefin polymer.
Parts by weight, preferably 5 to 50 parts by weight, particularly preferably 10 to 40 parts by weight. If too little crosslinking agent is used,
The cross-linking density of the exposed area becomes insufficient, and as a result, the formed pattern swells or peels off, and the resolution decreases. Further, the cured product after high temperature crosslinking may have poor solvent resistance and heat resistance. On the other hand, if the amount is too large, the crosslinking reaction may proceed even in the unexposed portion, and the pattern properties formed may deteriorate.

The photo-acid generator used in the present invention is a substance which produces a Bronsted acid or a Lewis acid in response to light. For example, onium salts, halogenated organic compounds, quinonediazide compounds, α,α-bis(sulfonyl)diazomethane compounds, α-carbonyl-α-sulfonyl-diazomethane compounds, sulfone compounds, organic acid ester compounds, organic acid amide compounds, organic acids It is selected from imide compounds and the like.

Specific examples of onium salts include diazonium salts, ammonium salts, iodonium salts, sulfonium salts, phosphonium salts, arsonium salts, oxonium salts and the like, and include alkyl groups, alkenyl groups, aralkyl groups, aromatic groups and heterocyclic groups. The thing which has is mentioned. The counter anion of these onium salts is not particularly limited, and examples thereof include boric acid, arsenic acid, phosphoric acid, antimonic acid, sulfonic acid, carboxylic acid, and halides thereof.

Specific examples of the halogenated organic compound include:
Halogen-containing oxadiazole compound, halogen-containing triazine compound, halogen-containing acetophenone compound,
Halogen-containing benzophenone compounds, halogen-containing sulfoxide compounds, halogen-containing sulfone compounds, halogen-containing thiazole compounds, halogen-containing oxazole compounds, halogen-containing triazole compounds, halogen-containing 2-pyrone compounds, halogen-containing aliphatic hydrocarbon compounds, halogen-containing aromatic carbonization Examples thereof include a hydrogen compound, a halogen-containing heterocyclic compound, and a sulfenyl halide compound.

Further, as the halogenated organic compound,
Tris(2,3-dibromopropyl)phosphate, tris(2,3-dibromo-3-chloropropyl)phosphate, chlorotetrabromoethane, hexachlorobenzene, hexabromobenzene, hexabromocyclododecane, hexabromobiphenyl, tribromophenyl Allyl ether, tetrachlorobisphenol A, tetrabromobisphenol A, bis(bromoethyl ether) tetrabromobisphenol A, bis(chloroethyl ether) tetrachlorobisphenol A, tris(2,3-dibromopropyl) isocyanurate, 2,
2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxyethoxy-3,5-dibromophenyl)propane; dichlorodiphenyltrichloroethane, benzenehexachloride,
Pentachlorophenol, 2,4,6-trichlorophenyl-4-nitrophenyl ether, 2,4-dichlorophenyl-3'-methoxy-4'-nitrophenyl ether, 2,4-dichlorophenoxyacetic acid, 4,5,6 , 7
-Tetrachlorophthalide, 1,1-bis(4-chlorophenyl)ethanol, 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethanol, ethyl-
4,4-dichlorobenzylate, 2,4,5,4'-tetrachlorodiphenyl sulfide, 2,4,5,4'-
Examples include tetrachlorodiphenyl sulfone.

Specific examples of the quinonediazide compound include:
1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,2-naphthoquinonediazide-6-sulfonic acid Ester, 2,1-naphthoquinonediazide-4-
Sulfonate, 2,1-naphthoquinonediazide-
Sulfonic acid esters of quinonediazide derivatives such as 5-sulfonic acid ester and 2,1-naphthoquinonediazide-6-sulfonic acid ester; 1,2-benzoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfone Acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2
-Naphthoquinonediazide-6-sulfonic acid chloride,
Examples thereof include sulfonic acid chlorides of quinonediazide derivatives such as 2,1-naphthoquinonediazide-4-sulfonic acid chloride, 2,1-naphthoquinonediazide-5-sulfonic acid chloride and 2,1-naphthoquinonediazide-6-sulfonic acid chloride. .. These photo-acid generators can be used alone or in combination of two or more kinds.

The amount of the photo-acid generator is usually 0.5 with respect to 100 parts by weight of the alkali-soluble alicyclic olefin polymer.
To 20 parts by weight, preferably 1 to 15 parts by weight, particularly preferably 1 to 10 parts by weight. If the photoacid generator is too small, crosslinking by light irradiation may be insufficient,
As a result, the formed pattern swells or dissolves,
It may peel off. On the other hand, if the amount is too large, the crosslinking reaction may proceed even in the unirradiated area, and as a result, the unexposed area may not be dissolved and the pattern may not be developed.

Further, the photosensitive composition of the present invention may contain a surfactant for the purpose of preventing striation (after coating streaks) and improving the developability. Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether and other polyoxyethylene alkyl ethers; polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether and other polyoxyethylene alkyl ethers. Ethylene aryl ethers; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; F-top EF301,
303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), Megafac F171, F172, F173 (manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-430, FC
-431 (Sumitomo 3M Limited), Asahi Guard A
G710, Surflon S-382, SC-101, SC-102, SC-103, SC-104, S
Fluorine-based surfactants such as C-105 and SC-106 (manufactured by Asahi Glass Co., Ltd.); organosiloxane polymer KP3
41 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 5
7, (95) (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) and the like (meth)acrylic acid copolymer type surfactants. The above-mentioned surfactant is optionally used in an amount of 2 parts by weight or less, preferably 1 part by weight or less, relative to 100 parts by weight of the solid content of the photosensitive composition.

The photosensitive composition of the present invention may contain a thermal acid generator for the purpose of improving heat resistance and chemical resistance. The thermal acid generator used in the present invention is a substance that generates an acid when heated. Examples thereof include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts and phosphonium salts. Among these, sulfonium salts and benzothiazolium salts are preferable.

Specific examples of the sulfonium salt include 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate and dimethyl-4-.
(Benzyloxycarbonyloxy)phenylsulfonium hexafluoroantimonate, dimethyl-4-
(Benzoyloxy)phenylsulfonium hexafluoroantimonate, dimethyl-4-(benzoyloxy)phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate and other alkylsulfonium salts; benzyl-4 -Hydroxyphenylmethylsulfonium hexafluoroantimonate,
Benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-
2-Methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4
-Hydroxyphenylmethylsulfonium benzylsulfonium salts such as hexafluorophosphate;

Dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyldibenzylsulfonium hexafluoroantimonate, dibenzyl-4-methoxyphenylsulfonium hexafluoroantimonate, Dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-
tert-Butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl-
Dibenzylsulfonium salt such as 4-hydroxyphenylsulfonium hexafluorophosphate; p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-chloro Benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-
Hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3-chloro-4
A substituted benzylsulfonium salt such as hydroxyphenylmethylsulfonium hexafluoroantimonate;
Is mentioned.

Specific examples of the benzothiazonium salt include:
3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, 3-(p-methoxybenzyl)benzothiazolium hexafluoroantimonate , 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5-
Examples include benzylbenzothiazolium salts such as chlorobenzothiazolium hexafluoroantimonate.

Of these, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, benzyl-4-hydroxyphenylmethylsulfonium
Hexafluoroantimonate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, 4-acetoxyphenylbenzylsulfonium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluoroantimonate Nate and the like are preferably used. These thermal acid generators can be used alone or in combination of two or more kinds.

The photosensitive composition of the present invention may contain an adhesion aid for the purpose of improving the adhesion to the substrate.
Examples of such an adhesion aid include a functional silane coupling agent and the like. Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycid. Examples include xypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. The amount of the adhesion aid is usually 20 parts by weight or less, preferably 0.05 to 10 parts by weight, particularly preferably 1 to 10 parts by weight, based on 100 parts by weight of the alkali-soluble alicyclic olefin polymer. ..

The photosensitive composition of the present invention may further contain a sensitizer, an antistatic agent, a storage stabilizer, a defoaming agent, a pigment, a dye and the like, if necessary.

Examples of the sensitizer include benzophenone, anthraquinone, 1,2-naphthoquinone, 1,4-naphthoquinone, benzanthrone, p,p'-tetramethyldiaminobenzophenone, carbonyl compounds such as chloranil; nitrobenzene, p-dinitrobenzene. , Nitro compounds such as 2-nitrofluorene; aromatic hydrocarbons such as anthracene and chrysene; sulfur compounds such as diphenyl disulfide; nitroaniline, 2-chloro-4-nitroaniline, 5-nitro-2-aminotoluene, tetracyano Nitrogen compounds such as ethylene are mentioned.

As storage stabilizers, hydroquinone, methoxyphenol, pt-butylcatechol, 2,6-
Hydroxy aromatic compounds such as di-t-butyl-p-cresol; quinone compounds such as benzoquinone and p-toluquinone; amine compounds such as phenyl-α-naphthylamine; 4,4′-thiobis(6-t-butyl-3)
-Methylphenol), sulfur compounds such as 2,2'-thiobis(4-methyl-6-t-butylphenol);
Is mentioned.

The photosensitive composition of the present invention can be easily prepared by uniformly mixing the above components, and is usually dissolved in a suitable solvent and used in a solution state. Examples of the solvent include alcohols such as methanol, ethanol, propanol and butanol; cyclic ethers such as tetrahydrofuran and dioxane; cellosolve esters such as methyl cellosolve acetate and ethyl cellosolve acetate; ethylene glycol monomethyl ether and ethylene glycol monoethyl. Glycol ethers such as ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether and propylene glycol monomethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate;

Aromatic hydrocarbons such as benzene, toluene, xylene; methyl ethyl ketone, cyclohexanone,
Ketones such as 2-heptanone and 4-hydroxy-4-methyl-2-pentanone; ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate,
Ethyl ethoxy acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3
-Esters such as ethyl ethoxypropionate, methyl 3-ethoxypropionate, ethyl acetate, butyl acetate, ethyl lactate;

Dimethylformamide, N-methyl-2-
Examples include aprotic polar solvents such as pyrrolidone. N
-Methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethylether, dihexylether, acetonylacetone, isophorone, Caproic acid, caprylic acid, 1-octanol, 1
It is also possible to use solvents such as nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate and phenyl cellosolve acetate. Of these solvents, ketones, glycol ethers or amides are preferably used because of their solubility and ease of forming a coating film.

The photosensitive composition of the present invention is not particularly limited by the solid content concentration, but is usually 5 to 40% by weight.
Further, the photosensitive composition solution prepared as described above is preferably used after being filtered using a filter or the like.

The photosensitive composition of the present invention can be applied as a solution to the surface of a substrate and subjected to the removal of the solvent by heating to form a coating film. As a method of applying the photosensitive composition solution to the surface of the substrate, various methods such as a spray method, a roll coating method and a spin coating method can be adopted. This coating is then heated (Pre-Bak
e) be done. By heating, the solvent volatilizes and a coating film having no fluidity is obtained. The heating conditions vary depending on the type of each component, the mixing ratio, etc., but are usually 60 to 120.
It is about 10 to 600 seconds at 0°C.

Next, the heated coating film is irradiated with light through a mask having a predetermined pattern, and then heated (Post E
xposure Bake) and develop with a developer to remove unnecessary parts. By performing Post Exposure Bake, pattern reproducibility may be improved.

After irradiating with light, the pattern is developed using a developing solution. Examples of the developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; diethylamine, diamine -Secondary amines such as -n-propylamine; tertiary amines such as triethylamine, methyldiethylamine, N-methylpyrrolidone; alcohol amines such as dimethylethanolamine, triethanolamine; tetramethylammonium hydroxide, tetraethyl Quaternary ammonium salts such as ammonium hydroxide, tetrabutylammonium hydroxide and choline; pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene,1,5-diazabicyclo[4.3. It is possible to use an alkaline aqueous solution containing alkalis of cyclic amines such as 0]-5-nonane. Further, an aqueous solution prepared by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like to the above alkaline aqueous solution can be used as a developing solution.

The developing time is usually 30 to 180 seconds. Further, the developing method may be a paddle method, a puddle method, a dipping method, or the like. After the development, washing with running water is performed, and drying with compressed air or compressed nitrogen removes water on the substrate to form a patterned coating film. Thereafter, the patterned coating film is entirely irradiated with a light beam from a high pressure mercury lamp or the like. Then, by a heating device such as a hot plate or an oven, at a predetermined temperature, for example, 150 to 250° C., for a predetermined time, for example, 5 to 30 minutes on a hot plate, or 30 to 90 minutes in an oven.
A patterned crosslinked coating can be obtained. The heat treatment is
It is preferably performed in a low oxygen atmosphere, specifically, in an atmosphere having an oxygen concentration of 10 ppm or less. The heat treatment in the low oxygen atmosphere is not limited to the photosensitive resin composition of the present invention,
It is also applicable to a photosensitive resin composition containing another alkali-soluble alicyclic olefin polymer.

The cured product of the photosensitive composition of the present invention is used as an insulating material for electronic devices such as semiconductor devices, light emitting diodes, and various memories; hybrid ICs, MCMs, printed wiring boards or electronic parts. It is preferably used for an overcoat material such as; an interlayer insulating film of a multilayer circuit board; an insulating layer of a liquid crystal display.

[0066]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. In the examples, "parts" means "parts by weight" unless otherwise specified. <Test and Evaluation Method> (1) Hydrolysis Rate The hydrolysis rate of the modified product of the alicyclic olefin polymer after hydrolysis was measured by FT-IR. The hydrolysis rate of the alicyclic olefin polymer having an ester group is ¹ H-NM
It was measured by R. (2) Molecular weight The weight average molecular weight (Mw) was measured as a polystyrene conversion value by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent. (3) Modification ratio The hydrogenation ratio of the alicyclic olefin polymer main chain and the graft modification ratio of the alicyclic olefin polymer were measured by ¹ H-NMR. (4) Dielectric constant The dielectric constant (ε) at 1 MHz (room temperature) was measured according to JIS C6481.

(5) Heat-resistant dimensional stability A silicon substrate on which a patterned thin film is formed is heated in an oven at 220° C. for 60 minutes, and the ratio of the film thickness after heating to the film thickness before heating is 95% or more. Case: ○, 90%
When it is above 95%, it is indicated as Δ, and when it is less than 90%, it is indicated as x. (6) Flatness A solution of a photosensitive resin composition was applied onto a silicon oxide film substrate having a step of 1.0 μm, and then this substrate was heated on a hot plate at 200° C. for 30 minutes. The maximum step difference (d) of this thin film was measured using a contact-type film thickness measuring device, and was evaluated as ◯ when 5%>d and x when 5%≦d. (7) A glass substrate with a coating film was obtained in the same manner as above except that the transparent glass substrate "Corning 7059" (manufactured by Corning) was used. Then, the transmittance of the obtained glass substrate was measured for the minimum light transmittance (t) at a wavelength of 400 to 800 nm using an ultraviolet-visible near-infrared spectrophotometer (V-570) manufactured by JASCO Corporation, and 95 When %≦t, the evaluation was evaluated as ◯, when 93%≦t<95% was evaluated as Δ, and when 93%>t was evaluated as x. (8) Heat discoloration resistance The above glass substrate with a coating film was heated in an oven at 220° C. for 60 minutes.
After heating for a minute, the transmittance of this glass substrate is adjusted to the above (7).
Measurement is carried out in the same manner as above, and the rate of change (T) before and after heating is calculated.
%>T: ○, 5%≦T<10%: Δ, 10
The case where %≦T was evaluated as x.

(9) Solvent resistance The glass substrate on which the patterned thin film was formed was dipped in dimethyl sulfoxide at 70° C. for 15 minutes to measure the film thickness change rate (S). ○, 5%≦S<10
% Was evaluated as Δ, and 10%≧S was evaluated as x. (10) Resolution The minimum pattern in which line-and-space is formed with a line width of 1:1 by observing a 3.0 μm-thick patterned thin film formed on a glass substrate with a scanning electron microscope. When the dimension (W) is 5 μm or less, ◎, 5 μm<W≦1
When 0 μm was evaluated as ◯, when 10 μm<W≦15 μm was evaluated as Δ, and when W>15 μm was evaluated as x. (11) Developability The minimum pattern size expressed as resolution was observed with a scanning electron microscope, and the case where there was no scum or undeveloped residue was evaluated as ◯, and the case where they were present was evaluated as x.

Example 1 A polymerization catalyst composed of tungsten hexachloride, triisobutylaluminum and isobutyl alcohol and 1-hexene as a molecular weight modifier were used.
By a known method, 8-ethyltetracyclo[4.4.1]
2,5.17,10.0]-3-dodecene (hereinafter referred to as ET
Abbreviated as D. ) Was subjected to ring-opening polymerization. The obtained ring-opening polymer,
Hydrogenation was carried out using a hydrogenation catalyst of nickel acetylacetonate and triisobutylaluminum respectively to obtain a hydrogenated product of a ring-opening polymer having a hydrogenation rate of 99% or more. Then
100 parts of hydrogenated ring-opening polymer, 200 parts of maleic anhydride, and 400 parts of t-butylbenzene in an autoclave.
And 500 parts of anisole were mixed and the temperature was raised to 135°C. 1 part of 20 parts of dicumyl peroxide was added to this reaction vessel.
The solution was divided into 0 parts, added sequentially at 12-minute intervals, and further reacted for 3 hours. Then add 400 parts of water into the reaction vessel,
The reaction was carried out for 10 hours. The reaction liquid was dropped into a large amount of isopropanol, coagulated and dried to obtain a modified polymer. The physical properties of the modified polymer are shown in Table 1.

20 parts of a cross-linking agent (N,N,N',N',N",N"-(hexamethoxymethyl)melamine: CYMEL300 manufactured by Mitsui Cytec Co., Ltd.) and acid generation per 100 parts of the modified polymer. Agent (2-piperonyl bis (4
5 parts of 6-trichloromethyl)-S-triazine: manufactured by Midori Kagaku Co., Ltd. and 0.05 parts of a surfactant (Megafuck F172 manufactured by Dainippon Ink and Chemicals Co., Ltd.), and the mixture amount was 2
It was dissolved in cyclohexanone to be 0% by weight. The prepared solution was filtered with a 0.45 μm Millipore filter, spin-coated on each of a silicon substrate, a glass substrate, and a silicon oxide film substrate having a step of 1 μm, and then a hot plate at 90° C. for 2 minutes Prebaking was performed on the above to form a coating film having a film thickness of 3.0 μm. A mask having a predetermined pattern was placed on the obtained coated silicon substrate, and the wavelength was 365 nm and the light intensity was 5 mW/cm.
The ultraviolet ray of ² was irradiated in the air so that the energy amount was 50 mJ/cm ² . After the irradiation, Post Exposure Bake treatment was performed on a hot plate at 110° C. for 2 minutes. Next, development processing was performed at 25° C. for 60 seconds using a 0.3 wt% tetramethylammonium aqueous solution. afterwards,
A rinse treatment was performed with ultrapure water for 1 minute. Thus, a thin film having a negative pattern was formed. By heating the silicon substrate on which this pattern is formed and the glass substrate with a coating film that has not been developed at 200° C. for 30 minutes on a hot plate, the pattern and the coating film are post-baked to form a patterned thin film. The formed silicon substrate, coated glass substrate, and coated silicon oxide film substrate having a step of 1 μm were obtained. Using the various substrates obtained, dielectric constant, transparency, heat discoloration resistance, flatness, heat dimensional stability,
The solvent resistance, resolution and developability were evaluated, and the results are shown in Table 2.

[0071]

[Table 1]

Example 2 The amount of maleic anhydride was set to 150.
Parts, a modified polymer was obtained in the same manner as in Example 1 except that the amount of dicumyl peroxide was changed to 15 parts. Using this modified polymer, a silicon oxide film substrate and the like were obtained in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

Example 3 The amount of maleic anhydride was adjusted to 80
Parts, and modified polymer was obtained in the same manner as in Example 1 except that the amount of dicumyl peroxide was changed to 8 parts. Using this modified polymer, a silicon oxide film substrate and the like were obtained in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

Example 4 A modified polymer was obtained in the same manner as in Example 1 except that the amount of 1-hexene used in the ring-opening polymerization was changed to 1/10. Using this modified polymer, a silicon oxide film substrate and the like were obtained in the same manner as in Example 1. Table 1
The evaluation results are shown in Table 2.

Example 5 A modified polymer was obtained in the same manner as in Example 1 except that the amount of 1-hexene used in the ring-opening polymerization was changed to 1/20. Using this modified polymer, a silicon oxide film substrate and the like were obtained in the same manner as in Example 1. Table 1
The evaluation results are shown in Table 2.

Example 6 The amount of maleic anhydride was adjusted to 80
Parts, and modified polymer was obtained in the same manner as in Example 1 except that the amount of dicumyl peroxide was changed to 8 parts. Using this modified polymer, a silicon oxide film substrate and the like were obtained in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

Example 7 ETD used in ring-opening polymerization
Was changed to ETD/tricyclo[4.3.0.1 ^2,5 ]deca-3,7-diene <weight ratio 80/20> to obtain a modified polymer in the same manner as in Example 1. Using this modified polymer, a silicon oxide film substrate and the like were obtained in the same manner as in Example 1. The evaluation results are shown in Tables 1 and 2.

Example 8 A modified polymer was obtained in the same manner as in Example 2 except that 400 parts of water was changed to 400 parts of allylamine. Example 1 using this modified polymer
A silicon oxide film substrate and the like were obtained in the same manner as in. The evaluation results are shown in Tables 1 and 2.

[Comparative Example 1] 8-Methyl-8-methoxycarbonyltetracyclo[4.4.0.1 ^2,5 . 1
^7,10 ]-3-dodecene was subjected to ring-opening polymerization to obtain a ring-opening polymer having a weight average molecular weight of 16,000. Next, the ring-opening polymer is hydrogenated and hydrolyzed to give a hydrolysis rate of 96%.
A hydrolyzed polymer of A silicon oxide film substrate and the like were obtained in the same manner as in Example 1 using the hydrolyzed polymer. The evaluation results are shown in Tables 1 and 2.

[Comparative Example 2] 8-Methyl-8 as a monomer
-Methoxycarbonyltetracyclo[4.4.0.1
^2,5 . 1 ^7,10 ]-3-dodecene and bicyclo[2.
2. 1] The weight average molecular weight of the ring-opening polymer was 13,000 in the same manner as in Comparative Example 1 except that a mixture (80/20 molar ratio) with hept-2-ene (hereinafter abbreviated as NB) was used.
A hydrolyzed polymer having a hydrolysis rate of 0 and a hydrolysis rate of 95% was obtained. A silicon oxide film substrate and the like were obtained in the same manner as in Example 1 using the hydrolyzed polymer. The evaluation results are shown in Tables 1 and 2.

[0081]

[Table 2]

From Table 2, the present invention (Examples 1 to 8) has low dielectric properties, heat resistant dimensional stability, flatness, heat discoloration resistance, transparency, solvent resistance, resolution and developability. Also proves to be excellent. In particular, when a polymer obtained by decomposing a maleic anhydride group with a primary amine was used (Example 8), it was found that the dielectric constant was extremely low. Further, when a modified polymer having a weight average molecular weight of 40,000 or less and a modification ratio of 60 mol% to 80 mol% is used (Examples 1, 2, 4 and 7), the modification ratio is relatively low. It can be seen that the resolution is superior to the polymer or the modified polymer having a relatively high weight average molecular weight (Examples 3 and 5). Furthermore, the molecular weight of the modified polymer is 1
It can be seen that those having a low molecular weight of about 10,000 have excellent resolution as compared with those having a high molecular weight (comparison between Example 3 and Example 6, and Example 4 and Example 5). On the other hand, when a hydrolysis polymer is used (Comparative Examples 1 and 2), all have excellent low dielectric properties, heat-resistant dimensional stability, flatness, heat discoloration resistance, transparency, and solvent resistance. Also, it is understood that the developability is poor.

[0083]

INDUSTRIAL APPLICABILITY The photosensitive composition of the present invention has various properties such as flatness, heat resistance, transparency, and chemical resistance by being coated and dried on a silicon substrate, subjected to pattern exposure, and then developed. In addition to being excellent, it is possible to easily form a fine patterned thin film having excellent low dielectric properties. The thin film obtained by the photosensitive composition of the present invention, as an insulating material,
For example, electronic elements such as semiconductor elements, light-emitting diodes, and various memories; overcoat materials for hybrid ICs, MCMs, printed wiring boards or electronic parts;
An interlayer insulating film of a multilayer circuit board; suitable for use as an insulating layer of a liquid crystal display.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 51/08 C08L 51/08 65/00 65/00 G03F 7/004 501 G03F 7/004 501 7/032 7/032 H01L 21/027 H01L 21/30 502R F term (reference) 2H025 AA00 AA06 AA07 AA08 AA10 AA20 AB16 AB17 AC01 AD01 BE00 CB08 CB42 CB52 CC20 FA03 FA12 FA17 EJ037 EJ077370 EJ077370 BK0 BN001 EU167 EU186 EU227 EV197 EV217 EV237 EV247 EV297 EV327 EW057 EW177 FD030 FD146 FD310 GP03

Claims (3)

[Claims] 1. An alkali-soluble alicyclic olefin polymer obtained by subjecting an alicyclic olefin polymer to a modification reaction of a compound having an acidic group or a compound having an acid derivative type residue, which is represented by the formula (1). A photosensitive resin composition containing a cross-linking agent having a group and a photo-acid generator. —CH _n OR ¹ (1) [In the formula (1), R ¹ is a hydrogen atom or an alkyl group. n is 1 or 2 (when n is 1, it becomes a divalent functional group). ] 2. A photosensitive resin composition comprising an alkali-soluble alicyclic olefin polymer, a cross-linking agent having a group represented by the formula (2), and a photo-acid generator. >CHOR ¹ (2) [In the formula (2), R ¹ is a hydrogen atom or an alkyl group. ] 3. An insulating film obtained by curing the photosensitive resin composition according to claim 1.