JPH10307388A - Radiation sensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the radiation sensitive resin composition superior in various performances, such as electric nonconductance, flatness, heat resistance, transparence, and resistance to chemicals, and capable of easily forming a patternwise thin film low in dielectric constant by incorporating a 1,2-quinonediazido compound and a cross-linking agent capable of reacting with a specified resin and forming bridges between each resin molecule. SOLUTION: This radiation sensitive resin composition contains (A) an alkali- soluble cyclic polyolefin resin, (B) the 1,2quinonediazido compound, and (C) the cross-linking agent having a functional group capable of forming bridges between each molecule of the resin (A). The resin (A) can be embodied by the hydrolyzate of the ring-opening polymer or copolymer or the like made from a monomer represented by the formula in which each of R<1> and R<3> is, independently, an H atom or a hydrocarbon group or a polar group except a hydrocarbon group; and each of (m) and (p) is an integer of 0-3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a radiation-sensitive resin composition. More specifically, a material for forming a protective film or the like used for an electronic component, or an interlayer insulating film,
In particular, the present invention relates to a low dielectric radiation-sensitive resin composition suitable as a material for forming an interlayer insulating film of a liquid crystal display device, an integrated circuit device, a solid-state image sensor, and the like.

[0002]

2. Description of the Related Art Generally, liquid crystal display devices, integrated circuit devices,
An electronic component such as a solid-state imaging device is provided with a protective film for preventing its deterioration and damage, a flattening film for flattening the device surface, an insulating film for maintaining electrical insulation, and the like. In addition, 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 for insulating between wirings arranged in layers.

However, in the case where an interlayer insulating film is formed using a material for forming a thermosetting insulating film for electronic parts which is conventionally known, it is necessary to obtain an interlayer insulating film having a required pattern shape. Since there is a problem that an interlayer insulating film having many steps and having sufficient flatness cannot be obtained, development of a photosensitive insulating film forming material that can be patterned has been demanded. In recent years, as the density of wirings and devices has increased, low dielectric properties of these materials have been required.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and its object is to provide:
To provide a radiation-sensitive resin composition having excellent properties such as insulation, flatness, heat resistance, transparency, and chemical resistance and capable of easily forming a patterned thin film having excellent low dielectric properties. It is in. Another object of the present invention is to reduce the dielectric constant of the obtained film while maintaining good photosensitivity, developability with an aqueous alkali solution after exposure, heat resistance, solvent resistance and transparency of the obtained film. An object of the present invention is to provide a radiation-sensitive resin composition of the present invention as described above, which overcomes difficult problems. Still other objects and advantages of the present invention will become apparent from the following description.

[0005]

According to the present invention, the above objects and advantages of the present invention are as follows: [A] an alkali-soluble cyclic polyolefin resin, [B] a 1,2-quinonediazide compound and a [C] resin [A]. And a crosslinking agent having a functional group capable of forming a crosslinking between the resins [A] by reacting with the radiation-sensitive resin composition.

Hereinafter, first, each component contained in the radiation-sensitive resin composition according to the present invention will be described. In the present invention, the term “radiation” is used in a concept including ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ-rays, synchrotron radiation, proton beam lines, and the like.

The alkali-soluble cyclic polyolefin resin used in the present invention includes the following polymer hydrolysates. A ring-opening (co) polymer of a monomer represented by the following formula (1) (hereinafter, referred to as a specific monomer), a ring-opening copolymer of a specific monomer and a copolymerizable monomer, Hydrogenated polymer of ring-opening (co) polymer, <Specific monomer>

[0008]

Embedded image

In the formula, R ¹ and R ³ are each independently a hydrogen atom or a hydrocarbon group, and R ² and R ⁴ are each independently a hydrogen atom, a hydrocarbon group or a polar group other than a hydrocarbon group. Where m is an integer from 0 to 3 and p is 0 to
It is an integer of 3. However, at least one of R ² and R ⁴ is a polar group other than a hydrocarbon.

Among the specific monomers represented by the above formula (1), preferred are those in which R ¹ and R ³ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. ,
At least one of R ² and R ⁴ is a polar group other than a hydrocarbon group, m is an integer of 0 to 3, and p is 0 to 3
Is an integer. Preferably m + p is 0-4,
Particularly preferred is 0 to 2, especially 1. Of specific monomers, polar group is particularly formula - (CH ₂₎ a specific polar group represented by _n COOR specific monomer is preferred sensitivity of the radiation-sensitive resin composition obtained becomes particularly good . In the above formula showing the specific polar group, R is a group having 1 to 1 carbon atoms.
2 hydrocarbon groups, preferably alkyl groups. Also,
n is usually 0-5.

Specific examples of the specific monomer represented by the above formula (1) include the following compounds. 5-acetoxybicyclo [2.2.1] hept-2-ene, 5-
Methoxycarbonylbicyclo [2.2.1] hept-2-
Ene, 5-methyl-5-methoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyanobicyclo [2.2.1] hept-2-ene, 8-acetoxytetracyclo [4.4 .0.1 ^{2,5.1 7,10} ] -3-dodecene, 8
-Methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .
1 ^7,10] -3-dodecene, 8-ethoxycarbonyl tetracyclo ^{[4.4.0.1 2,5 .1 7, 10]} -3- dodecene,
8-n-propoxycarbonyltetracyclo [4.4.
0.1 ^2,5 .1 ^7,10] -3-dodecene, 8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10]
3-dodecene, 8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-
Methyl-8-methoxycarbonyltetracyclo [4.4.
0.1 ^{2,5.1 7,10} ] -3-dodecene, 8-methyl-8-
Ethoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5} .1
^7,10] -3-dodecene, 8-methyl -8-n-propoxycarbonyl tetracyclo [4.4.0.1 ^{2, 5} .1 ^7,10]
3-dodecene, 8-methyl-8-isopropoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
Dodecene, 8-methyl -8-n-butoxycarbonyl tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene, 8-methyl-8- (2,2,2-trifluoroethoxy-carbonyl) tetracyclo [4.4.0.1 ^2,5.1
7,10 ] -3-dodecene. Among them, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0., Which gives a radiation-sensitive resin composition having a good balance between sensitivity and dielectric constant.
1 ^2,5 .1 ^7,10] -3-dodecene is particularly preferred.

<Copolymerizable Monomer> The alkali-soluble cyclic polyolefin-based resin may be a homopolymer obtained by ring-opening polymerization of the above-mentioned specific monomer alone. A copolymer obtained by ring-opening copolymerization with a monomer may be used. As the copolymerizable monomer used in this case,
An unsubstituted cycloolefin or a cycloolefin substituted with a hydrocarbon group, a halogenated hydrocarbon group or a halogen atom is preferably used. Of these, those having 4 to 20 carbon atoms in the cycloolefin moiety are preferred, and those having 5 to 21 carbon atoms are more preferred. The cycloolefin moiety is preferably a mono-, bi-, tri-, tetra-, penta- or hexa-cyclo compound.

Specific examples of such a copolymerizable monomer include:
Bicyclo [2.2.1] hept-2-ene, tricyclo [5.2.1.0 ^2,6 ] -8-decene, tetracyclo [4.
4.0.1 ^2,5 .1 ^7,10] -3-dodecene, pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene, pentacyclo [7 .4.0.1 ^2,5 .1 ^9,12 .0 ^8,13] -
3-pentadecene, tricyclo [4.4.0.1 ^2,5 ] -3
-Undecene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-
2-ene, dimethanooctahydronaphthalene, ethyl tetracyclododecene, 6-ethylidene-2-tetracyclododecene, tri methanolate octahydronaphthalene, pentacyclo [8.4.0.1 ^2,5 .1 ^9,12 .0 ^8,13] -3-hexadecene, heptacyclo [8.7.0.1 ^3,6 .1 ^10,17 .1
^12,15 .0 ^2,7 .0 ^11,16] -4-eicosene, heptacyclo ^{[8.8.0.1 4,7 .1 11,18 .1 13,16 .0} 3,8 .0 12, ¹⁷ ]
-5-heneicosen,

5-ethylidenebicyclo [2.2.1] hept-2-ene, 8-ethylidenetetracyclo [4.4.
0.1 ^2,5 .1 ^7,10] -3-dodecene, 5-phenyl-bicyclo [2.2.1] hept-2-ene, 8-phenyl-tetracyclo [4.4.0.1 ^2,5 .1, ^7,10 ] -3-dodecene;
5-fluorobicyclo [2.2.1] hept-2-ene,
5-fluoromethylbicyclo [2.2.1] hept-2-
Ene, 5-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5-pentafluoroethylbicyclo [2.2.1] hept-2-ene, 5,5-difluorobicyclo [2.2 .1] Hept-2-ene, 5,6-difluorobicyclo [2.2.1] hept-2-ene, 5,5-
Bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5-methyl-5
-Trifluoromethylbicyclo [2.2.1] hept-2
-Ene, 5,5,6-trifluorobicyclo [2.2.1]
Hept-2-ene, 5,5,6-tris (fluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,5,
6,6-tetrafluorobicyclo [2.2.1] hept-
2-ene, 5,5,6,6-tetrakis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5.5
-Difluoro-6,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,6-difluoro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] ] Hept-2-ene, 5,5,6-trifluoro-5-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5-fluoro-5-pentafluoroethyl-6,6-bis (Trifluoromethyl) bicyclo [2.
2.1] Hept-2-ene, 5,6-difluoro-5-heptafluoro-iso-propyl-6-trifluoromethylbicyclo [2.2.1] hept-2-ene, 5-chloro-5, 6,6-trifluorobicyclo [2.2.1] hept-2-ene, 5,6-dichloro-5,6-bis (trifluoromethyl) bicyclo [2.2.1] hept-2-ene, 5,5,6-trifluoro-6-trifluoromethoxybicyclo [2.2.1] hept-2-ene, 5,5,6-
Trifluoro-6-heptafluoropropoxybicyclo [2.2.1] hept-2-ene,

8-fluorotetracyclo [4.4.0.1
^2,5.1^7,10] -3-Dodecene, 8-fluoromethyltet
Lacyclo [4.4.0.1^2,5.1^7,10-3-dodecene,
8-difluoromethyltetracyclo [4.4.0.1^2,5.
1^7,10] -3-dodecene, 8-trifluoromethyltet
Lacyclo [4.4.0.1^2,5.1^7,10-3-dodecene,
8-pentafluoroethyltetracyclo [4.4.0.1
^2,5.1^7,10] -3-dodecene, 8,8-difluorotet
Lacyclo [4.4.0.1^2,5.1^7,10-3-dodecene,
8,9-difluorotetracyclo [4.4.0.1^2,5.1
^7,10] -3-dodecene, 8,8-bis (trifluoromethyl
Tyl) tetracyclo [4.4.0.1^2,5.1^7,10] -3-
Dodecene, 8,9-bis (trifluoromethyl) tetra
Cyclo [4.4.0.1^2,5.1^7,10] -3-dodecene, 8
-Methyl-8-trifluoromethyltetracyclo [4.
40.1^2,5.1^7,10] -3-dodecene, 8,8,9-tri
Fluorotetracyclo [4.4.0.1^2,5.1^7,10] -3
-Dodecene, 8,8,9-tris (trifluoromethyl)
Tetracyclo [4.4.0.1^2,5.1^7,10] -3-Dodece
8,8,9,9-tetrafluorotetracyclo [4.
40.1^2,5.1^7,10-3-Dodecene, 8,8,9,9-
Tetrakis (trifluoromethyl) tetracyclo [4.
40.1^2,5.1^7,10] -3-Dodecene, 8,8-diflu
Oro-9,9-bis (trifluoromethyl) tetracyclic
B [4.4.0.1^2,5.1^7,10] -3-dodecene, 8,9-
Difluoro-8,9-bis (trifluoromethyl) tetra
Lacyclo [4.4.0.1 ^2,5 .1^7,10-3-dodecene,
8,8,9-trifluoro-9-trifluoromethyltet
Lacyclo [4.4.0.1^2,5.1^7,10-3-dodecene,
8,8,9-trifluoro-9-trifluoromethoxy
Toracyclo [4.4.0.1^2,5.1^7,10] -3-Dodece
, 8,8,9-trifluoro-9-pentafluoropro
Poxytetracyclo [4.4.0.1^2,5.1^7,10] -3-
Dodecene, 8-fluoro-8-pentafluoroethyl-
9,9-bis (trifluoromethyl) tetracyclo [4.
40.1^2,5.1^7,10] -3-Dodecene, 8,9-diflu
Oro-8-heptafluoroiso-propyl-9-tri
Fluoromethyltetracyclo [4.4.0.1^2,5.
1^{7,1 0}] -3-dodecene, 8-chloro-8,9,9-tri
Fluorotetracyclo [4.4.0.1^2,5.1^7,10] -3
-Dodecene, 8,9-dichloro-8,9-bis (trifur
Oromethyl) tetracyclo [4.4.0.1^2,5.1^7,10]
-3-dodecene, cyclopentene, cycloheptene,
Crooctene, tricyclo [5.2.1.0^2,6] -3-de
Sen, 5-ethylidene-2-norbornene, dicyclope
Antadiene and the like.

Further, polybutadiene, polyisoprene,
Unsaturated hydrocarbon polymers containing a carbon-carbon double bond in the main chain, such as styrene-butadiene copolymer, ethylene-nonconjugated diene copolymer, and polynorbornene, are also copolymerizable monomers. Can be used as
In this case, the copolymer is produced by subjecting a specific monomer to ring-opening polymerization in the presence of such a polymer.

<Unsaturated Double Bond-Containing Compound> In order to obtain a cyclic olefin-based polymer which is a saturated copolymer, the unsaturated double bond-containing compound used together with the specific monomer may have 2 carbon atoms. -12, preferably 2-8 olefinic compounds are used. Such compounds include, for example, ethylene, propylene and butene.

<Polymerization Catalyst> In the present invention, the ring-opening polymerization reaction for producing the above-mentioned ring-opening (co) polymer and ring-opening copolymer which are alkali-soluble cyclic polyolefin compounds is carried out in the presence of a metathesis catalyst. . This metathesis catalyst comprises (a) at least one selected from compounds of W, Mo and Re, and (b) a periodic table IA of Deming.
Group II elements (eg, Li, Na, K, etc.), Group IIA elements (eg, Mg, Ca, etc.), Group IIB elements (eg, Zn, C, etc.)
d, Hg, etc.), a group IIIA element (eg, B, Al, etc.), a group IVA element (eg, Si, Sn, Pb, etc.) or a group IVB element (eg, Ti, Zr, etc.) and at least one of the elements A catalyst comprising a combination with a compound having a carbon bond and / or the element-hydrogen bond. In this case, to increase the activity of the catalyst,
It may contain the additive (c) described below.
Representative examples of W, Mo or Re compounds suitable as the component (a) include WCl ₆ , MoCl ₅ , and ReOCl.
_And the compounds described in JP-A-1-240517. Specific examples of the component (b) include n
_{-C 4 H 9 Li, (C} 2 H 5) 3 Al, (C 2 H 5) 2 AlC
1, (C ₂ H ₅ ) _1.5 AlCl _1.5 , (C ₂ H ₅ ) AlC
l _2, methyl alumoxane, LiH, etc. JP-1-24
Compounds described in JP-A-0517 can be mentioned.
As a typical example of the component (c) which is an additive, alcohols, aldehydes, ketones, amines and the like can be preferably mentioned.
No. 517 can also be used.

The amount of the metathesis catalyst used is such that the molar ratio of the component (a) to the monomer is such that “component (a): monomer” is usually 1: 500 to 1: 50,000. It is preferably in the range of 1: 1,000 to 1: 40,000. The ratio of the component (a) to the component (b) is such that the ratio of the component (a) to the component (b) is 1: 1 to 1:50, preferably 1: 2 to 1:30, in terms of metal atom ratio. . The molar ratio of the component (a) to the component (c) is 0.005: 1 to 15: 1, preferably 0.05: 1, for the component (c): the component (a).
７7: 1.

<Solvent for Ring-Opening Polymerization Reaction> Examples of the solvent used in the above-mentioned ring-opening polymerization reaction (solvent constituting the molecular weight modifier solution, solvent for the monomer and / or metathesis catalyst) include, for example, pentane, hexane, heptane , Alkanes such as octane, nonane and decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and cumene; chlorobutane, bromohexane and chloride Halogenated alkanes or aryl halides such as methylene, dichloroethane, hexamethylene dibromide, chlorobenzene, chloroform, tetrachloroethylene, etc .: ethyl acetate, n-butyl acetate, iso-butyl acetate, methyl propionate, dipropionate Saturated carboxylic acid esters such as Tokishietan; and dibutyl ether, tetrahydrofuran, and the like can be illustrated ethers such as dimethoxyethane, they can be used singly or in combination. Of these, aromatic hydrocarbons are preferred. The amount of the solvent to be used is such that the “solvent: monomer (weight ratio)” is usually 1: 1 to 10: 1, preferably 1: 1 to 5: 1.

<Molecular Weight Control Agent> The molecular weight of the ring-opened polymer and the ring-opened polymer can be controlled by the polymerization temperature, the type of catalyst, and the type of solvent. In the present invention, the molecular weight control agent coexists in the reaction system. It is particularly preferable to adjust the temperature by performing the adjustment. Suitable molecular weight regulators include, for example, ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,
Α-olefins such as -decene and styrene. Of these, 1-butene and 1-hexene are particularly preferred. These molecular weight regulators can be used alone or in combination of two or more. The amount of the molecular weight modifier used is preferably 0.005 to 5.0 mol per 1 mol of the monomer subjected to the ring-opening polymerization reaction,
More preferably, it is 0.02 to 2.5 mol.

The molecular weight of the cyclic olefin polymer used in the present invention is such that the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is 2,000 to 30,000, and the weight average molecular weight (Mw) ) (Hereinafter simply referred to as number average molecular weight and weight average molecular weight) is preferably in the range of 5,000 to 100,000.

<Hydrogenation catalyst> The ring-opened polymer obtained as described above can be hydrogenated using a hydrogenation catalyst.
The above hydrogenated polymer is provided. The hydrogenation reaction is carried out in a usual manner, that is, a hydrogenation catalyst is added to a solution of the ring-opening polymer, and the solution is added at normal pressure to 300 atm, preferably 3
Hydrogen gas at a pressure of 0 to 200 ° C., preferably 2 to 200 atm.
It is performed by operating at 0 to 180 ° C. As the hydrogenation catalyst, those used in ordinary hydrogenation reactions of olefinic compounds can be used. As the hydrogenation catalyst, a heterogeneous catalyst and a homogeneous catalyst are known.

Examples of the heterogeneous catalyst include a solid catalyst in which a noble metal catalyst such as palladium, platinum, nickel, rhodium and ruthenium is supported on a carrier such as carbon, silica, alumina and titania. it can. Examples of the homogeneous catalyst include nickel / triethylaluminum naphthenate, nickel acetylacetonate / triethylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum monochloride, rhodium acetate, and chlorotris (triphenylphosphine). Rhodium, dichlorotris (triphenylphosphine) ruthenium, chlorohydrocarbonyltris (triphenylphosphine) ruthenium, dichlorocarbonyltris (triphenylphosphine) ruthenium and the like can be mentioned. The form of these catalysts may be powder or granular.

These hydrogenation catalysts are used in such a ratio that the weight ratio of the ring-opening polymer to the hydrogenation catalyst is from 1: 1 × 10 ^-6 to 1: 2. As described above, the hydrogenated polymer obtained by hydrogenation has excellent thermal stability, and its characteristics are not deteriorated by heating when used as a product. Here, the hydrogenation rate is usually 50% or more, preferably 70% or more, and more preferably 90% or more.

<Hydrolysis> An alkali-soluble cyclic polyolefin-based resin can be obtained by hydrolyzing the above (co) polymer. The method of hydrolysis is not particularly limited, and ordinary alkali and acid hydrolysis can be used.

Examples of the reaction 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; ethylene glycol Glycol ethers such as monoethyl 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 and xylene; methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2
Ketones such as -pentanone; ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate,
Esters such as methyl hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl acetate and butyl acetate; dimethylformamide, N Aprotic polar solvents such as -methyl-2-pyrrolidone. N-
Methylformamide, N, N-dimethylformamide,
N-methylformanilide, N-methylacetamide,
N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether,
Dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-
Nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,
γ-butyrolactone, ethylene carbonate, propylene carbonate,
Solvents such as phenyl cellosolve acetate and water can be used alone or as a mixture. The hydrolysis rate of the polymer can be arbitrarily changed by adjusting the reaction temperature, the reaction time, the amount of the acid and the amount of the alkali.

[B] 1,2-quinonediazide compound As the 1,2-quinonediazide compound used in the present invention, an esterified product of a hydroxy compound and 1,2-quinonediazidesulfonic acid is used. As the 1,2-quinonediazide compound, a compound in which all or a part of the hydroxyl groups of the hydroxy compound is esterified with 1,2-quinonediazidesulfonic acid can be used, and specifically, 20 to 100 of the hydroxyl groups of the hydroxy compound can be used. % Is 1,
Compounds esterified with 2-quinonediazidesulfonic acid can be used.

Specific examples of such 1,2-quinonediazide compounds include 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone. -1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,4,6-trihydroxybenzophenone-1,
2-naphthoquinonediazide-4-sulfonic acid ester,
2,4,6-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, etc.
Esterified product of trihydroxybenzophenone and 1,2-quinonediazidosulfonic acid;

2,2 ', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2', 4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide −5-
Sulfonate 2,2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4
-Sulfonic acid ester, 2,3,4,3'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-
5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphtho Quinonediazide-5-sulfonic acid ester, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,
4,2'-tetrahydroxy-4'-methylbenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-
Methoxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone-1,2-
Esterified products of tetrahydroxybenzophenone and 1,2-naphthoquinonediazidosulfonic acid, such as naphthoquinonediazide-5-sulfonic acid ester;

2,3,4,2 ', 6'-pentahydroxybenzophenone-1,2-naphthoquinonediazido-4-sulfonic acid ester, 2,3,4,2', 6'-pentahydroxybenzophenone-1, 2-naphthoquinonediazide-
5-sulfonic acid ester, 3,4,5,2 ', 4'-pentahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,4,5,2', 4'-
Esterified products of pentahydroxybenzophenone and 1,2-naphthoquinonediazidesulfonic acid, such as pentahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester;

2,4,6,3 ', 4', 5'-Hexahydroxybenzophenone-1,2-naphthoquinonediazide
4-sulfonic acid ester, 2,4,6,3 ', 4', 5'-
Hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,4,5,3 ',
4'5'-hexahydroxybenzophenone-1,2-
Naphthoquinonediazide-4-sulfonic acid ester, 3,
Hexahydroxybenzophenone, such as 4,5,3 ′, 4 ′, 5′-hexahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonate, and 1,1
Esterified product with 2-naphthoquinonediazidesulfonic acid;

Bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,4-dihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester Such as bisdihydroxyphenylmethane and 1,
Esterified product with 2-naphthoquinonediazidosulfonic acid; bis (p-hydroxyphenyl) methane-1,2-
Esterified products of bishydroxyphenylmethane and 1,2-naphthoquinonediazidesulfonic acid, such as naphthoquinonediazide-4-sulfonic acid ester and bis (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester Tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-4
Esterified products of trihydroxyphenylmethane with 1,2-naphthoquinonediazidesulfonic acid, such as sulfonic acid esters and tri (p-hydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester;

1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2- Esterified products of trihydroxyphenylethane and 1,2-naphthoquinonediazidosulfonic acid, such as naphthoquinonediazide-5-sulfonic acid ester; bis (2,3,4-trihydroxyphenyl)
Bistrihydroxyphenylmethane such as methane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,3,4-trihydroxyphenyl) methane-1,2-naphthoquinonediazide-5-sulfonic acid ester Esterified with 2,2-naphthoquinonediazidosulfonic acid;

2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide
Bistrihydroxyphenylpropane and 1,2-naphthoquinonediazide such as 4-sulfonic acid ester, 2,2-bis (2,3,4-trihydroxyphenyl) propane-1,2-naphthoquinonediazide-5-sulfonic acid ester Esterified product with sulfonic acid; 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-
Phenylpropane-1,2-naphthoquinonediazide-4
Tris (dimethylhydroxyphenyl) such as sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-5-sulfonic acid ester ) Esterified products of phenylpropane and 1,2-naphthoquinonediazidosulfonic acid;

4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester 4 '-[1- [4-
[1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-
Esterified products of hydroxyphenylmethylethylphenylethylidene bisphenol and 1,2-naphthoquinonediazidesulfonic acid, such as naphthoquinonediazide-5-sulfonic acid ester; bis (2,5-dimethyl-4
-Hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide-4-sulfonic acid ester, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane-1,2-naphthoquinonediazide Esterified product of bis (dimethylhydroxyphenyl) hydroxyphenylmethane and 1,2-naphthoquinonediazidosulfonic acid, such as -5-sulfonic acid ester; 3,3,3 ′, 3′-tetramethyl-1,
1'-spiroindene-5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 3,3,3 ', 3'-tetramethyl-1 ,
Tetramethylspiroindenehexanol and 1,2-naphthoquinonediazide, such as 1'-spiroindene-5,6,7,5 ', 6', 7'-hexanol-1,2-naphthoquinonediazide-5-sulfonic acid ester Esterified product with sulfonic acid; 2,2,4-trimethyl-7,2 ′,
4'-Trihydroxyflavan-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2
And esterified products of trimethyltrihydroxyflavan and 1,2-naphthoquinonediazidesulfonic acid, such as -naphthoquinonediazide-5-sulfonic acid ester.

Of these, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-
Sulfonic acid ester, 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfone Acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-5-sulfonic acid ester, 3,4,5,2 ', 4'-pentahydroxybenzophenone-1,2-naphtho Quinonediazide
4-sulfonic acid ester, 1,1,3-tris (2,5-
Dimethyl-4-hydroxyphenyl) -3-phenylpropane-1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,1,3-tris (2,5-dimethyl-4)
-Hydroxyphenyl) -3-phenylpropane-1,
2-naphthoquinonediazide-5-sulfonic acid ester,
4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol-1,2-naphthoquinonediazide-4-sulfonic acid ester, 4,4'- [1- [4- [1- [4-
Hydroxyphenyl] -1-methylethyl] phenyl]
[Ethylidene] bisphenol-1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-
Naphthoquinonediazide-4-sulfonic acid ester, 2,
2,4-trimethyl-7,2 ', 4'-trihydroxyflavan-1,2-naphthoquinonediazide-5-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2- Naphthoquinonediazide-4-sulfonic acid ester, 1,1,1-tri (p-hydroxyphenyl) ethane-1,2-naphthoquinonediazide-5-sulfonic acid ester and the like are preferably used. These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

The above-mentioned 1,2-quinonediazidosulfonic acid esters can be obtained, for example, by esterifying a halide of 1,2-quinonediazidesulfonic acid with a corresponding hydroxy compound in the presence of a base catalyst. . In such an esterification reaction, a halide of 1,2-quinonediazidesulfonic acid is usually used in an amount of 10 to 120 mol% based on all hydroxyl groups of the hydroxy compound.
It is desirable to use. These 1,2-quinonediazide compounds [B] are preferably 5 to 100 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the polymer [A].
It is desirable to include parts by weight.

If the amount of the 1,2-quinonediazide compound in the radiation-sensitive resin composition is less than 5 parts by weight based on 100 parts by weight of the polymer [A], the coating film formed from the composition will The solubility difference between the irradiated part and the unirradiated part may be so small that patterning by development may be difficult. On the other hand, if it exceeds 100 parts by weight, the 1,2-quinonediazide compound will be insufficient in short-time irradiation. It may not be decomposed and the sensitivity may decrease. [C] a cross-linking agent having a functional group capable of forming a cross-link between the resins [A] by reacting with the resin [A]; a functional group capable of forming a cross-link between the resins [A] by reacting with the resin [A]; Examples of the crosslinking agent include melamines represented by the following formula (2) (hereinafter, referred to as “melamines”), glycolurils represented by the following formula (3), and at least two epoxy groups in the molecule. Compounds having no radical polymerizability are preferred.

[0041]

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[Wherein the six Rs are the same or different;
An alkyl group, preferably an alkyl group having 1 to 4 carbon atoms], such as an alkoxymethylated melamine such as N, N, N ', N', N ", N"-(hexaalkoxymethyl) melamine .

[0043]

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[Wherein the four Rs are the same or different;
Which is the same as the definition of equation (2)].
Alkoxymethylated glycolurils such as N ″, N ′ ″-(tetraalkoxymethyl) glycoluril. As melamines, for example, hexamethylol melamine,
Examples thereof include hexabutyrol melamine, partially methylolated melamine and its alkoxyalkylated melamine, tetramethylol benzoguanamine, partially methylolated benzoguanamine and its alkylated product, and the like. Of these, alkoxyalkylated melamines are preferred, and alkoxymethylated melamines are particularly preferred.

The amount of these melamines and glycoluril to be used is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the alkali-soluble cyclic polyolefin resin [A]. When the addition amount is less than 1 part by weight, the crosslinking of the system is insufficient, and the patterning tends to be difficult. On the other hand, if the amount exceeds 100 parts by weight, the alkali solubility of the entire composition becomes too high, so that the problem that the residual film ratio after development decreases tends to occur.

The non-radical polymerizable compound having at least two epoxy groups in the molecule includes, for example, Epicoat 1001, 1002, 1003 and 10
04, 1007, 1009, 1010, 828
Bisphenol A type epoxy resin such as (trade name; Yuka Shell Epoxy Co., Ltd.); bisphenol F type epoxy resin such as Epicoat 807 (trade name; Yuka Shell Epoxy Co., Ltd.); Epicoat 152, 154 ( Product name: Yuka Shell Epoxy Co., Ltd.), EPPN20
Phenol novolak type epoxy resins such as 1, 202 (trade name; manufactured by Nippon Kayaku Co., Ltd.); EOCN102, 103S, 104S, 1020, 1025, 1027
(Trade name; manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S7
Cresol novolak type epoxy resin such as 5 (trade name; Yuka Shell Epoxy Co., Ltd.); Epicoat 1032
Polyphenol type epoxy resins such as H60 and XY-4000 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), C
Y-175, 177, 179, Araldite CY-
182, 192, 184 (trade names; manufactured by Ciba-Geigy Corporation), ERL-4234, 4299, 4221,
4206 (trade name; manufactured by UCC), Shodyne 50
9 (trade name; manufactured by Showa Denko KK), Epicron 200,
400 (trade name; manufactured by Dainippon Ink Co., Ltd.), Epicoat 871, 872 (trade name; manufactured by Yuka Shell Epoxy Co., Ltd.), ED-5661, and 5662 (trade name: Celanese Coating Co., Ltd.) And aliphatic polyglycidyl ethers such as Epolite 100MF (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) and Epiol TMP (manufactured by NOF Corporation).

These compounds having no radical polymerizability include the alkali-soluble cyclic polyolefin resin [A] 1
It is preferably used in an amount of 1 to 50 parts by weight, based on 00 parts by weight.

Other components that may be contained in the radiation-sensitive resin composition The radiation-sensitive resin composition according to the present invention contains a sensitizer for the 1,2-quinonediazide compound for the purpose of further improving the sensitivity. You may go out. Examples of such a sensitizer include 2H-pyrido- (3,2-b) -1,4-oxazin-3 (4H) -ones and 10H-pyrido- (3,
2-b) 1,4-benzothiazines, urazoles,
Hydantoins, barbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, maleimides and the like are preferred. The sensitizer is used, if necessary, in an amount of usually 100 parts by weight or less, preferably 10 parts by weight or less based on 100 parts by weight of the 1,2-quinonediazide compound [B].

Further, the radiation-sensitive resin composition of the present invention comprises
For the purpose of preventing striation (after coating streaks) and improving developability, a surfactant can be added.
Examples of the surfactant include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether,
Polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyoxyethylene dilaurate and polyoxyethylene distearate Nonionic surfactants such as oxyethylene dialkyl esters; F-Top EF301, 303 and 352 (Shin-Akita Chemical Co., Ltd.)
Manufactured), Mega Fac F171, F172, F173
(Manufactured by Dainippon Ink and Chemicals, Inc.), Florard FC-
430, FC-431 (manufactured by Sumitomo 3M Limited),
Asahi Guard AG710, Surflon S-382, S
C-101, SC-102, SC-103, SC
-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants; organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 57, 95 (Kyoeisha) (Meth) acrylic acid copolymer-based surfactants such as Yushi Kagaku Kogyo Co., Ltd.).

The surfactant is used in an amount of 2 parts by weight or less, preferably 1 part by weight or less, as needed, based on 100 parts by weight of the solid content of the radiation-sensitive resin composition. The radiation-sensitive resin composition of the present invention may contain a latent acid generator for the purpose of improving heat resistance and chemical resistance. The latent acid generator used in the present invention is a cationic polymerization catalyst that generates an acid by heating, and an onium salt such as a sulfonium salt, a benzothiazolium salt, an ammonium salt, and a phosphonium salt is used. Among them, sulfonium salts and benzothiazolium salts are preferred.

Specific examples of the above sulfonium salt include, for example, 4-acetophenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate Alkyl such as dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate Sulfonium salt; benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4 -Hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenylmethylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate Benzylsulfonium salts such as benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenylmethylsulfonium 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 salts 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
Substituted benzylsulfonium salts such as -hydroxyphenylmethylsulfonium hexafluoroantimonate and o-chlorobenzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate; sulfonium salts represented by the following formulas (4) to (10) Is mentioned.

[0053]

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Specific examples of the benzothiazonium salt include 3-benzylbenzothiazolium hexafluoroantimonate, 3-benzylbenzothiazolium hexafluorophosphate, 3-benzylbenzothiazolium tetrafluoroborate, (P-methoxybenzyl) benzothiazolium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazolium hexafluoroantimonate, 3-benzyl-5
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 Nates and the like are preferably used. These commercial products include Sun-Aid SI-L85,
-L110, SI-L145, SI-L150, and SI-L160 (manufactured by Sanshin Chemical Industry Co., Ltd.).

These compounds can be used alone or in combination of two or more. In addition, the radiation-sensitive resin 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. Specific examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycid Xypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned. The use ratio of the adhesion aid is usually 20 parts by weight or less, preferably 0.1 part by weight, per 100 parts by weight of the resin [A] component.
05 to 10 parts by weight, particularly preferably 1 to 10 parts by weight. Further, the radiation-sensitive resin composition according to the present invention may contain an antistatic agent, a storage stabilizer, an antifoaming agent, a pigment, a dye, and the like, if necessary.

Preparation of Radiation-Sensitive Resin Composition The radiation-sensitive resin composition of the present invention can be easily prepared by uniformly mixing the above-mentioned components, and is usually dissolved in a suitable solvent. Used in solution. For example, resin [A] is dissolved in a solvent, and 1,2-
The radiation-sensitive resin composition can be prepared in a solution state by mixing the quinonediazide compound [B], the crosslinking agent [C], and other components as required at a predetermined ratio.

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; Glycol ethers such as monoethyl 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 and xylene; methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2
Ketones such as -pentanone; ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate,
Esters such as methyl hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, ethyl acetate and butyl acetate; dimethylformamide, N Aprotic polar solvents such as -methyl-2-pyrrolidone. N-
Methylformamide, N, N-dimethylformamide,
N-methylformanilide, N-methylacetamide,
N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether,
Dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-
Nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate,
γ-butyrolactone, ethylene carbonate, propylene carbonate,
A solvent such as phenyl cellosolve acetate can also be used.

Among these solvents, ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 4-hydroxy-4-methyl-2-pentanone and ethylene glycol monoethyl are preferred in view of solubility and ease of forming a coating film. Glycol ethers such as ether and propylene glycol monomethyl ether are preferably used.

The radiation-sensitive resin composition of the present invention is applied to a substrate as a solution dissolved in a solvent so that the solid content concentration is preferably 10 to 40% by weight. The radiation-sensitive resin composition solution prepared as described above is preferably used after being filtered using a filter having a pore size of about 0.5 μm. The radiation-sensitive resin composition solution thus prepared is excellent in long-term storage stability.

Method for Using Radiation-Sensitive Resin Composition The radiation-sensitive resin composition solution of the present invention can be applied to the surface of a substrate, and the solvent can be removed by heating to form a coating film. As a method of applying the radiation-sensitive resin composition solution to the substrate surface, various methods such as a spray method, a roll coating method, and a spin coating method can be employed. The coating is then heated (prebaked). By heating, the solvent is volatilized, and a coating film having no fluidity is obtained. The heating conditions vary depending on the type of each component, the mixing ratio, and the like, but are usually 1 to 60 ° C to 120 ° C.
It is about 0 to 600 seconds.

Next, the heated coating film is irradiated with radiation through a mask having a predetermined pattern, and then developed with a developing solution.
Remove unnecessary parts. Examples of the developing solution 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 and diamine. Secondary amines such as n-propylamine; tertiary amines such as triethylamine, methyldiethylamine and N-methylpyrrolidone; alcohol amines such as dimethylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethyl Quaternary ammonium salts such as ammonium hydroxide and choline; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0]
-7-undecene, 1,5-diazabicyclo [4.3.
An alkaline aqueous solution composed of alkalis of cyclic amines such as [0] -5-nonane can be used. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like to the above-mentioned alkaline aqueous solution can also be used as a developer.

The development time is usually 30 to 180 seconds. Further, the developing method may be any of a puddle method and a dipping method. After the development, the substrate is washed with running water for 30 to 90 seconds and air-dried with compressed air or compressed nitrogen to remove moisture on the substrate and form a patterned film. Then, the entire surface of the patterned film is irradiated with radiation from a high-pressure mercury lamp, etc.
Completely decompose the quinonediazide compound. Subsequently, 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, and 30 to 30 minutes in an oven.
By performing the heat treatment for 90 minutes, a patterned crosslinked film can be obtained.

[0065]

Hereinafter, embodiments of the present invention will be described.
The present invention is not limited by these.
In the examples, "parts" means "parts by weight".

Synthesis Example 1 The following formula (11) as a monomer

[0067]

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[0068] 8-methyl-8-methoxycarbonyl represented by tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3-
250 parts of dodecene, 180 parts of 1-hexene and 750 parts of toluene were charged into a reaction vessel purged with nitrogen,
Heated. To this, triethylaluminum (1.5
Mol / l) of a toluene solution of 0.62 parts, tert-C ₄ H
Denatured with ₅ OH / CH ₃ OH (tert-C ₄ H ₉ OH / CH
_{3 OH / W = 0.35 / 0.3} / 1; molar ratio) was WCl ₆
3.7 parts of a solution (concentration of 0.05 mol / l) was added, and the mixture was heated and stirred at 80 ° C. for 3 hours to obtain a ring-opened polymer solution. The polymerization conversion in this polymerization reaction was 90%, and the weight average molecular weight of the polymer was 17,000.

4,000 parts of the obtained polymer solution was
Into a clave and add RuHCl (CO) [P (C₆
H_Five)_Three30.48 parts and hydrogen gas pressure of 100 kg
/ Cm ^TwoThe mixture was heated and stirred at a reaction temperature of 165 ° C for 3 hours.
Was. After cooling the resulting reaction solution, release hydrogen gas
Thus, a hydrogenated polymer solution (b) was obtained. Thus obtained
Pour the hydrogenated polymer into a large amount of methanol
The body solidified. The water of the hydrogenated polymer thus obtained is
The degree of priming was substantially 100%. Obtained hydrogenation weight
100 parts, 100 parts N-methylpyrrolidone, propyle
500 parts of glycol, potassium hydroxide (85%) 8
4.5 parts were charged into a reactor and heated and stirred at 190 ° C for 4.5 hours.
did. A large amount of water and tetrahydrofuran
The hydrolyzate by pouring it into a mixed solution of hydrochloric acid and hydrochloric acid.
Was. The coagulated polymer is washed with water, dried and hydrolyzed polymer (A
-1) was obtained. The hydrolysis rate of the obtained hydrolyzed polymer is
95%.

Synthesis Example 2 As monomers, 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.12,5.17,10] -3-dodecene and 5-methyl-5-methoxycarbonylbicyclo [ 2.2.1] mixture with hept-2-ene (80/20
(Molar ratio)), except that ring-opening polymerization reaction, hydrogenation reaction, and hydrolysis were performed in the same manner as in Synthesis Example 1 to obtain a hydrolyzed polymer (A-2). Synthesis Example 3 8-Methyl-8-methoxycarbonyltetracyclo [4.4.0.12,5.17,10] -3-dodecene and bicyclo [2.2.1] hept-2-ene as monomers Synthesis Example 1 except that a mixture (80/20 (molar ratio)) was used.
The ring-opening polymerization reaction, the hydrogenation reaction, and the hydrolysis were carried out in the same manner as in the above to obtain a hydrolyzed polymer (A-3).

Synthesis Example 4 A ring-opening polymerization reaction, a hydrogenation reaction and hydrolysis were carried out in the same manner as in Synthesis Example 1 except that 1-hexene was used in an amount of 60 parts to obtain a hydrolyzed polymer (A-4). Synthesis Example 5 A ring-opening polymerization reaction, a hydrogenation reaction, and hydrolysis were carried out in the same manner as in Synthesis Example 1 except that the hydrolysis time was 1.5 hours, to obtain a hydrolyzed polymer (A-5). Table 1 shows the polymerization conversion, the weight-average molecular weight, and the hydrolysis in Synthesis Examples 1 to 5. The hydrogenation rate of the hydrogenated polymer in Synthesis Examples 1 to 5 was substantially 100%. Weight average molecular weight is GP
It is a molecular weight in terms of polystyrene measured using C (gel permeation chromatography) (HLC-8020 manufactured by Tosoh Corporation).

[0072]

[Table 1]

Preparation of Radiation-Sensitive Resin Composition Example 1 100 parts by weight of the hydrolyzed polymer (A-1) obtained in Synthesis Example 1, 550 parts by weight of cyclohexanone as a solvent, 1,2
-1,1,3-tris (2,
20% by weight of a condensate ([B-1]) of 5-dimethyl-4-hydroxyphenyl-3-phenyl) propane (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (1.9 mol) Part and CYME as crosslinking agent
25 parts of L300, 5 parts of γ-glycidoxypropyltrimethoxysilane as an adhesion aid, and Megafac F172 as a surfactant (manufactured by Dainippon Ink and Chemicals, Inc.)
After mixing and dissolving 0.05 part, a radiation-sensitive resin composition solution was prepared by filtration through a 0.45 μm pore size Millipore filter.

[Formation of Coating Film] A spinner was formed on a silicon substrate.
Using the above, the obtained resin composition solution was applied.
Then, pre-bake on a hot plate at 90 ° C for 120 seconds
As a result, a coating film having a thickness of 3.0 μm was formed. [Radiation treatment and development treatment]
Light at 365 nm through a fixed pattern mask
Strength 5mW / cm^TwoUV light in the air for 40 seconds
Irradiated. Then, tetramethyl ammonium hydroxide
Developing with 0.3% by weight aqueous solution of Sid for 60 seconds at 25 °
Rinsing with ultrapure water for 1 minute
A pattern was formed. Then, the entire surface is set to 365 nm.
Light intensity of 5mW / cm ^TwoUV rays in the air 6
Irradiated for 0 seconds.

[Post-baking] The silicon substrate on which the pattern was formed was heated on a hot plate at 200 ° C. for 30 minutes to post-bake the pattern to obtain a silicon substrate on which a patterned thin film was formed. Measurement of Dielectric Constant It was measured at room temperature and 10 KHz. Table 1 shows the results. [Evaluation of Heat-Resistant Dimensional Stability] After the silicon substrate on which the patterned thin film was formed was heated in an oven at 220 ° C. for 60 minutes, a change in the thickness of the patterned thin film was measured. 、, 9 when the film thickness after heating exceeds 95% of the film thickness before heating.
The case where it was in the range of 0 to 95% was rated as Δ, and the case where it was less than 90% was rated as x. Table 2 shows the results.

[Evaluation of Flatness] A patterned thin film was formed in the same manner as described above except that a silicon oxide film substrate having a step of 1.0 μm was used instead of the silicon substrate. The step of the patterned thin film was measured using a measuring instrument, and the case where the maximum value of the step was less than 5% was evaluated as ○.
And 5% or more was evaluated as x. Table 2 shows the results. [Evaluation of Transparency] A glass substrate having a patterned thin film was obtained in the same manner as described above except that a glass substrate “Corning 7059 (manufactured by Corning)” was used instead of the silicon substrate. Next, the transmittance of the obtained glass substrate was measured at a wavelength of 400 to 800 nm using a spectrophotometer “150-20 double beam (manufactured by Hitachi, Ltd.)”.
場合, 90% when the minimum transmittance exceeds 90%
When the value was less than the above, it was evaluated as x. Table 2 shows the results.

[Evaluation of Thermal Discoloration Resistance] After the glass substrate on which the patterned thin film was formed was heated in an oven at 220 ° C. for 60 minutes, the transmittance of the glass substrate was measured using a spectrophotometer “150”.
Measurement was performed at a wavelength of 400 to 800 nm using a “-20 type double beam” to determine the change in transmittance after the heat treatment. ○ when the change rate of the transmittance is less than 5%, 5 to 10%
And the case exceeding 10% was evaluated as x. Table 2 shows the results. [Evaluation of Solvent Resistance] The glass substrate on which the patterned thin film was formed was immersed in dimethyl sulfoxide at 70 ° C. for 15 minutes, and the change in film thickness was measured. The film thickness change of 10% or less was evaluated as ○, the case of exceeding 10% was evaluated as △, and the state of large swelling and peeling from the substrate was evaluated as ×. Table 2 shows the results.

Example 2 A radiation-sensitive resin composition solution was prepared in the same manner as in Example 1, except that the hydrolysis polymer was changed to (A-2). Table 2 shows the results of the formation and evaluation of the coating film and the heat-cured film. Example 3 A radiation-sensitive resin composition solution was prepared in the same manner as in Example 1, except that the hydrolysis polymer was changed to (A-3). Table 2 shows the results of the formation and evaluation of the coating film and the heat-cured film.

Example 4 A radiation-sensitive resin composition solution was prepared in the same manner as in Example 1, except that the hydrolysis polymer was changed to (A-4). Table 2 shows the results of the formation and evaluation of the coating film and the heat-cured film. Example 5 A radiation-sensitive resin composition solution was prepared in the same manner as in Example 1, except that the hydrolysis polymer was changed to (A-5). Table 2 shows the results of the formation and evaluation of the coating film and the heat-cured film.

Example 6 In Example 1, 1,2-quinonediazide compound was converted to 4,
4 '-[1- [4- [1- [4-hydroxyphenyl]
-1-methylethyl] phenyl] ethylidene] The reaction was carried out in the same manner as in Example 1 except that a condensate of bisphenol (1 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2 mol) was used. A radiation resin composition solution was prepared. Table 2 shows the results of the formation and evaluation of the coating film and the heat-cured film. Example 7 In Example 1, the 1,2-quinonediazide compound was replaced with 2,2
3,4-trihydroxybenzophenone (1 mol) and 1,
A radiation-sensitive resin composition solution was prepared in the same manner as in Example 1, except that the condensate with 2-naphthoquinonediazide-5-sulfonic acid chloride (2.6 mol) was used. Table 2 shows the results of formation and evaluation of coating films and heat-cured films.
Shown in

Example 8 A radiation-sensitive resin composition solution was prepared in the same manner as in Example 1, except that the crosslinking agent was changed to Epicoat 828. Table 2 shows the results of the formation and evaluation of the coating film and the heat-cured film. Example 9 In Example 1, a sun aid SI-L150 was further added.
(Sanshin Chemical Industry Co., Ltd.) (3 parts) was added, and a radiation-sensitive resin composition solution was prepared in the same manner as in Example 1. Table 2 shows the results of formation and evaluation of coating films and heat-cured films.
Shown in

[0082]

[Table 2]

[0083]

According to the radiation-sensitive resin composition of the present invention, a patterned thin film which is excellent in various properties such as insulating properties, flatness, heat resistance, transparency and chemical resistance, and is also excellent in low dielectric properties. Can be easily formed.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI H01L 21/027 H01L 21/30 502R 21/768 21/90 S (72) Inventor Masayuki Endo 2-11 Tsukiji, Chuo-ku, Tokyo 24 Nippon Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. A functional group capable of reacting with [A] an alkali-soluble cyclic polyolefin-based resin, [B] a 1,2-quinonediazide compound and [C] a resin [A] to form a crosslink between the resins [A]. A radiation-sensitive resin composition comprising a crosslinking agent.