TWI850462B - Radiation sensitive resin composition - Google Patents

Abstract

The object of the present invention is to provide a radiation-sensitive resin composition that can form a resin film with suppressed top loss of a line pattern and excellent heat flow resistance. The radiation-sensitive resin composition of the present invention comprises a cycloolefin polymer (A) having a protonic polar group, a cresol novolac resin (B) having a softening point of 140°C or higher, an acid generator (C) and a crosslinking agent (D).

Description

Radiation sensitive resin composition

The present invention relates to radiation sensitive resin compositions.

Various resin films are provided on electronic components such as integrated circuit components, solid-state imaging components, color filters, various display components (e.g., organic EL components, liquid crystal display components), and black matrices, such as surface protection films to prevent degradation or damage, planarization films to planarize component surfaces or wiring, and interlayer insulation films to insulate wiring arranged in layers.

For the formation of such a resin film, a radiation-sensitive resin composition (hereinafter sometimes abbreviated as "resin composition") containing, for example, a resin component and an acid generator that generates an acid by irradiation with active radiation (for example, ultraviolet rays (including single-wavelength ultraviolet rays such as g-rays and i-rays), KrF excimer laser light, and ArF excimer laser light; for example, a particle beam such as an electron beam) has been used. Specifically, a resin film having a desired pattern shape depending on the application can be obtained by irradiating the radiation-sensitive film obtained using the resin composition with active radiation, removing the exposed portion of the obtained exposed film with a developer (development), etc.

Furthermore, conventionally, a cycloolefin polymer having a protonic polar group has been used as a resin component of such a resin composition (see, for example, Patent Documents 1 and 2).

『Patent Document』 《Patent Document 1》: Japanese Patent Publication No. 2016-508759 《Patent Document 2》: International Patent Publication No. 2015/141719

However, when a conventional resin composition including a cycloolefin polymer having a protonic polar group is used to form a resin film having a pattern shape with fine line width and line spacing, the height of the line pattern formed by the unexposed portion is sometimes reduced compared to the height of the unexposed portion without a pattern (i.e., top loss of the line pattern occurs).

In general, when a resin film is formed using a resin composition, a heat treatment is sometimes performed for the purpose of heat curing after exposure and development. However, during such heat treatment, the desired pattern shape formed by exposure and development may be damaged. Therefore, it is required that the resin film formed using the resin composition has a property (heat flow resistance) that can maintain the desired pattern shape even when formed by heat treatment.

Therefore, an object of the present invention is to provide a radiation sensitive resin composition that can form a resin film with suppressed top loss of a line pattern and excellent heat flow resistance.

The inventors of the present invention have conducted intensive research with the purpose of solving the above-mentioned problems. Then, the inventors of the present invention have found that if a resin film is formed using a resin composition that "in addition to a cycloolefin polymer having a protonic polar group, contains a cresol novolac resin having a softening point above a specified value as a resin component, and further contains an acid generator and a crosslinking agent", it is possible to suppress the top loss of the line pattern while improving the heat flow tolerance, thereby completing the present invention.

That is, the present invention aims to solve the above-mentioned problems. The radiation-sensitive resin composition of the present invention is characterized in that it contains a cycloolefin polymer (A) having a protonic polar group, a cresol novolac resin (B) having a softening point of 140°C or higher, an acid generator (C) and a crosslinking agent (D). By using the resin composition containing the components (A) to (D) described above, a resin film can be formed in which the top loss of the line pattern is suppressed and the heat flow resistance is excellent.

In addition, in the present invention, the "softening point" can be measured by the global method described in JIS K 6910:2007.

Here, the radiation-sensitive resin composition of the present invention preferably comprises the cresol novolac resin (B) comprising a cresol skeleton and a xylenol skeleton. If the cresol novolac resin (B) comprising a skeleton derived from cresol and a skeleton derived from xylenol is used, the heat flow resistance of the resin film can be further improved.

Furthermore, the radiation-sensitive resin composition of the present invention preferably has the acid generator (C) being a quinone diazide compound. If a quinone diazide compound is used as the acid generator (C), the resolution of the line width and line spacing pattern formed on the resin film can be improved.

Furthermore, the radiation-sensitive resin composition of the present invention preferably has the crosslinking agent (D) selected from at least one of the group consisting of a polyfunctional epoxy compound, a polyfunctional alkoxymethyl compound and a polyfunctional hydroxymethyl compound. If a polyfunctional epoxy compound, a polyfunctional alkoxymethyl compound and/or a polyfunctional hydroxymethyl compound is used as the crosslinking agent (D), the chemical resistance of the resin film can be improved while further improving the heat flow tolerance.

In addition, the radiation sensitive resin composition of the present invention preferably has a ratio of the cycloolefin polymer (A) to the total of the cycloolefin polymer (A) and the cresol novolac resin (B) of 10 mass % or more and 90 mass % or less. If the cycloolefin polymer (A) and the cresol novolac resin (B) are used in the above-mentioned amount ratio, the relative dielectric constant of the resin film can be reduced and the top loss of the line pattern formed on the resin film can be further suppressed.

Furthermore, the radiation-sensitive resin composition of the present invention preferably has a molar ratio (i.e., m/p ratio) of the content of the meta-skeletal to the content of the para-skeletal in the skeleton derived from cresols contained in the aforementioned cresol novolac resin (B) of 5.0 or less. If a cresol novolac resin (B) is used in which "the content of the skeleton derived from the meta-skeletal to the content of the skeleton derived from the para-skeletal in the skeleton derived from cresols is less than 5.0 on a molar basis", the top loss of the line pattern on the resin film can be further suppressed while the heat flow tolerance can be further improved.

In addition, in the present invention, the "m/p ratio" can be measured by a known method such as nuclear magnetic resonance (eg ¹³ C-NMR).

According to the present invention, a radiation sensitive resin composition can be provided which can form a resin film having suppressed top loss of a line pattern and excellent heat flow resistance.

The following is a detailed description of the implementation of the present invention.

The radiation-sensitive resin composition of the present invention can be used to form a resin film, and the resin film can be used as, for example, a surface protection film, a planarization film, an interlayer insulation film, etc. in electronic parts manufactured by wafer-level packaging technology.

The radiation sensitive resin composition of the present invention contains a cycloolefin polymer (A) having a protonic polar group, a cresol novolac resin (B) having a softening point of 140°C or higher, an acid generator (C) and a crosslinking agent (D), and optionally contains a solvent or other doping agents.

Furthermore, since the radiation-sensitive resin composition of the present invention contains the above-mentioned cycloolefin polymer (A) and cresol novolac resin (B) as resin components and also contains an acid generator (C) and a crosslinking agent (D), when the resin composition is used, a resin film having a suppressed top loss of a line pattern and excellent heat flow resistance can be formed.

〈Cycloolefin polymer (A)〉

The cycloolefin polymer (A) is a polymer having a protonic polar group and a cycloolefin skeleton.

Protonic Polar Radicals

The cycloolefin polymer (A) has protonic polar groups and is soluble in developer (especially alkaline developer described later). Furthermore, during thermal curing, the protonic polar groups react with the crosslinking agent (D), and the cycloolefin polymer (A) and other resin components can form a strong crosslinking structure, thereby giving the resin film excellent heat flow resistance and chemical resistance.

Here, the so-called protonic polar group refers to a group containing an atom belonging to Group 15 or Group 16 of the periodic table directly bonded to a hydrogen atom. The atom belonging to Group 15 or Group 16 of the periodic table is preferably an atom belonging to the second or third period of Group 15 or Group 16 of the periodic table, more preferably an oxygen atom, a nitrogen atom or a sulfur atom, and particularly preferably an oxygen atom.

Specific examples of such protonic polar groups include polar groups having oxygen atoms such as hydroxyl, carboxyl (hydroxycarbonyl), sulfonic acid, and phosphoric acid groups; polar groups having nitrogen atoms such as primary amine, secondary amine, primary amide, and secondary amide (imide); and polar groups having sulfur atoms such as hydroxyl. Among these, polar groups having oxygen atoms are preferred, carboxyl and hydroxyl groups are more preferred, and carboxyl groups are more preferred.

The cycloolefin polymer (A) may have only one type of protonic polar group or may have two or more types.

Composition

Furthermore, the method for introducing the above-mentioned protonic polar group into the cycloolefin polymer (A) is not particularly limited. That is, the cycloolefin polymer (A) may be, for example, a polymer comprising repeating units derived from a cycloolefin monomer (a) having a protonic polar group and optionally comprising repeating units derived from another monomer (b), or a polymer obtained by introducing a protonic polar group into a cycloolefin polymer having no protonic polar group using a modifier, but the former is preferred.

[Cycloolefin monomer having a protonic polar group (a)]

The cycloalkene monomer (a) having a protonic polar group is not particularly limited as long as it has the protonic polar group and cycloalkene structure as described above, but suitable examples include cycloalkene monomers having a carboxyl group and cycloalkene monomers having a hydroxyl group.

―Cycloolefin monomers with carboxyl groups―

Examples of cycloolefin monomers having a carboxyl group include 2-hydroxycarbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-hydroxycarbonylbicyclo[2.2.1]hept-5-ene, 2-carboxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-methoxycarbonylmethylbicyclo[2.2 .1]hept-5-ene, 2-hydroxycarbonyl-2-ethoxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-propoxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-butoxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-pentyloxycarbonylmethylbicyclo[2.2.1]hept-5-ene Cyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-hexyloxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-cyclohexyloxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-phenoxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-naphthalene Oxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-biphenyloxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-benzyloxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-2-hydroxyethoxycarbonylmethylbicyclo[2.2.1]hept-5-ene, ,3-dihydroxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-methoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-ethoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-propoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3- Butoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-pentyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-hexyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-cyclohexyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-phenoxy Carbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-naphthyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-biphenyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-benzyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-hydroxyethoxy Carbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyl-3-hydroxycarbonylmethylbicyclo[2.2.1]hept-5-ene, 3-methyl-2-hydroxycarbonylbicyclo[2.2.1]hept-5-ene, 3-hydroxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hept-5-ene, 2-hydroxycarbonyltricyclo[5.2.1.0 ^2,6 ]dec-3,8-diene, 4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene, 4-methyl-4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene, 4,5-dihydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene, 4-carboxymethyl-4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-9-ene, N-(hydroxycarbonylmethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(hydroxycarbonylethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(hydroxycarbonylpentyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(dihydroxycarbonylethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(di 2-(4-Hydroxyphenyl)-1-(hydroxycarbonyl)ethyl]bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(hydroxycarbonylphenyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide.

―Cycloolefin monomers having a hydroxyl group―

Examples of the cycloolefin monomer having a hydroxyl group include 2-(4-hydroxyphenyl)bicyclo[2.2.1]hept-5-ene, 2-methyl-2-(4-hydroxyphenyl)bicyclo[2.2.1]hept-5-ene, 4-(4-hydroxyphenyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene, 4-methyl-4-(4-hydroxyphenyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-9-ene, 2-hydroxybicyclo[2.2.1]hept-5-ene, 2-hydroxymethylbicyclo[2.2.1]hept-5-ene, 2-hydroxyethylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-hydroxymethylbicyclo[2.2.1]hept-5-ene, 2,3-dihydroxymethylbicyclo[2.2.1]hept-5-ene, 2-(hydroxyethoxycarbonyl)bicyclo[2.2.1 ]hept-5-ene, 2-methyl-2-(hydroxyethoxycarbonyl)bicyclo[2.2.1]hept-5-ene, 2-(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)bicyclo[2.2.1]hept-5-ene, 2-(2-hydroxy-2-trifluoromethyl-3,3,3-trifluoropropyl)bicyclo[2.2.1]hept-5-ene, 3-hydroxytricyclo[5.2.1.0 ^2,6 ]deca-4,8-diene, 3-hydroxymethyltricyclo[5.2.1.0 ^2,6 ]deca-4,8-diene, 4-hydroxytetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene, 4-hydroxymethyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene, 4,5-dihydroxymethyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene, 4-(hydroxyethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene, 4-methyl-4-(hydroxyethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-9-ene, N-(hydroxyethyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(hydroxyphenyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide.

Among these, from the viewpoint of improving the solubility in a developer (especially an alkaline developer described later) and enhancing the adhesion of the resin film to metal, a cycloolefin monomer having a carboxyl group is preferred, and 4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene is more preferred. The cycloolefin monomer (a) may be used alone or in combination of two or more.

―Content ratio―

Furthermore, the content ratio of the repeating units derived from the cycloolefin monomer (a) in the cycloolefin polymer (A) is preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 30 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less, and more preferably 70 mol% or less, when all the repeating units are 100 mol%. If the ratio of the repeating units derived from the cycloolefin monomer (a) is 10 mol% or more, the heat flow tolerance of the resin film can be further improved, and if it is 90 mol% or less, the relative dielectric constant of the resin film can be reduced.

[Other monomers (b)]

The other monomer (b) is not particularly limited as long as it is a monomer copolymerizable with the above-mentioned cycloolefin monomer (a). Examples of monomers copolymerizable with the cycloolefin monomer (a) include cycloolefin monomers (b1) having a polar group other than a protic polar group, cycloolefin monomers (b2) having no polar group, and monomers other than cycloolefins (b3).

―Monomer (b1)―

Examples of the cycloalkene monomer (b1) having a polar group other than a protonic polar group include cycloalkene monomers having an N-substituted imide group, an ester group, a cyano group, an acid anhydride group or a halogen atom.

Examples of the cycloolefin monomer having an N-substituted imide group include a monomer represented by the following formula (1) and a monomer represented by the following formula (2).

『Chemistry 1』 [In formula (1), ^R2 represents an alkyl group or an aryl group having 1 to 16 carbon atoms, and n represents 1 or 2.]

"Chemistry 2" [In formula (2), R ³ represents a divalent alkylene group having 1 to 3 carbon atoms, and R ⁴ represents a monovalent alkyl group having 1 to 10 carbon atoms or a monovalent halogenated alkyl group having 1 to 10 carbon atoms. In addition, two R ⁴ groups may be the same or different.]

In formula (1), the alkyl group having 1 to 16 carbon atoms as ^R2 may be, for example, a linear alkyl group such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, and n-hexadecyl; a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, , norinthyl, iodine, isothyl, decahydronaphthyl, tricyclodecyl, adamantyl and other cycloalkyl groups; 2-propyl, 2-butyl, 2-methyl-1-propyl, 2-methyl-2-propyl, 1-methylbutyl, 2-methylbutyl, 1-methylpentyl, 1-ethylbutyl, 2-methylhexyl, 2-ethylhexyl, 4-methylheptyl, 1-methylnonyl, 1-methyltridecyl, 1-methyltetradecyl and other branched alkyl groups.

In the formula (1), examples of the aryl group for ^R2 include benzyl.

Among these, from the viewpoint of improving the solubility of the cycloolefin polymer (A) in the solvent and further improving the heat flow resistance of the resin film, an alkyl group or an aryl group having 4 to 14 carbon atoms is preferred, and an alkyl group or an aryl group having 6 to 10 carbon atoms is more preferred.

Specific examples of the monomer represented by formula (1) include bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-phenylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-ethylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboximide, N-propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-butylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-cyclohexylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-adamantylbicyclo[2. 2.1]hept-5-ene-2,3-dicarboximide, N-(1-methylbutyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(2-methylbutyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(1-methylpentyl)bicyclo[2.2.1]hept-5-ene-2,3 -dimethimide, N-(2-methylpentyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethimide, N-(1-ethylbutyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethimide, N-(2-ethylbutyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethimide, N-(1-methyl N-(2-methylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(3-methylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(1-butylpentyl)bicyclo[2.2.1 ]hept-5-ene-2,3-dimethoxyimide, N-(2-butylpentyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethoxyimide, N-(1-methylheptyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethoxyimide, N-(2-methylheptyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethoxyimide Imides, N-(3-methylheptyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(4-methylheptyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(1-ethylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(2-ethylhexyl) )Bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(3-ethylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(1-propylpentyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(2-propylpentyl)bicyclo[2.2.1]hept-5 -ene-2,3-dimethoxyimide, N-(1-methyloctyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethoxyimide, N-(2-methyloctyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethoxyimide, N-(3-methyloctyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethoxyimide 、N-(4-methyloctyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide、N-(1-ethylheptyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide、N-(2-ethylheptyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide、N-(3-ethylheptyl)bicyclo [2.2.1]hept-5-ene-2,3-dicarboximide, N-(4-ethylheptyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(1-propylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(2-propylhexyl)bicyclo[2.2.1]hept-5-ene- 2,3-dimethacrylamide, N-(3-propylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethacrylamide, N-(1-methylnonyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethacrylamide, N-(2-methylnonyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethacrylamide, N-( 3-methylnonyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(4-methylnonyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(5-methylnonyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(1-ethyloctyl)bicyclo[2. 2.1]hept-5-ene-2,3-dimethacrylamide, N-(2-ethyloctyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethacrylamide, N-(3-ethyloctyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethacrylamide, N-(4-ethyloctyl)bicyclo[2.2.1]hept-5-ene-2,3 -dimethimide, N-(1-methyldecyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethimide, N-(1-methyldodecyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethimide, N-(1-methylundecyl)bicyclo[2.2.1]hept-5-ene-2,3-dimethimide, N-(1 -methyltridecyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(1-methyltetradecyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-(1-methylpentadecayl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide, N-phenyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene-4,5-dicarboximide, N-(2,4-dimethoxyphenyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene-4,5-dicarboximide.

In formula (2), the divalent alkylene group having 1 or more and 3 or less carbon atoms as R ³ may be exemplified by methylene, ethylene, propylene and isopropylene. Of these, methylene and ethylene are preferred because of their good polymerization activity.

In formula (2), examples of the monovalent alkyl group having 1 to 10 carbon atoms as ^R4 include methyl, ethyl, propyl, isopropyl, butyl, dibutyl, tertiary butyl, hexyl and cyclohexyl.

In formula (2), examples of the monovalent halogenated alkyl group having 1 to 10 carbon atoms as ^R4 include fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoropropyl, perfluorobutyl and perfluoropentyl.

Among them, from the viewpoint of improving the solubility of the cycloolefin polymer (A) in the solvent, R ⁴ is preferably a methyl group or an ethyl group.

In addition, the monomers represented by formula (1) and (2) can be obtained by, for example, an imidization reaction of the corresponding amine and 5-northene-2,3-dicarboxylic anhydride. Furthermore, the obtained monomers can be isolated with high efficiency by separating and purifying the reaction solution of the imidization reaction by a known method.

Examples of the cycloolefin monomer having an ester group include 2-acetyloxybicyclo[2.2.1]hept-5-ene, 2-acetyloxymethylbicyclo[2.2.1]hept-5-ene, 2-methoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-ethoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-propoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-butoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-cyclohexyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-methoxycarbonylbicyclo[2.2.1]hept-5-ene, 5-ene, 2-methyl-2-ethoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-propyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-butoxycarbonylbicyclo[2.2.1]hept-5-ene, 2-methyl-2-cyclohexyloxycarbonylbicyclo[2.2.1]hept-5-ene, 2-(2,2,2-trifluoroethoxycarbonyl)bicyclo[2.2.1]hept-5-ene, 2-methyl-2-(2,2,2-trifluoroethoxycarbonyl)bicyclo[2.2.1]hept-5-ene, 2-methoxycarbonyltricyclo[5.2.1.0 ^2,6 ] dec-8-ene, 2-ethoxycarbonyl tricyclo[5.2.1.0 ^2,6 ] dec-8-ene, 2-propoxycarbonyl tricyclo[5.2.1.0 ^2,6 ] dec-8-ene, 4-acetyloxytetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-9-ene, 4-methoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca- ⁹ -ene, 4-ethoxycarbonyltetracyclo[6.2.1.1 3,6 .0 ^2,7 ] dodeca-9-ene, 4-propoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-9-ene, 4-butoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-9-ene, 4-methyl-4-methoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-9-ene, 4-methyl-4-ethoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-9-ene, 4-methyl-4-propoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-9-ene, 4-methyl-4-butoxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-9-ene, 4-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-9-ene, 4-methyl-4-(2,2,2-trifluoroethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-9-ene.

Examples of the cycloolefin monomer having a cyano group include 4-cyanotetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodec-9-ene, 4-methyl-4-cyanotetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodec-9-ene, 4,5-dicyanotetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodec-9-ene, 2-cyanobicyclo[2.2.1]hept-5-ene, 2-methyl-2-cyanobicyclo[2.2.1]hept-5-ene, and 2,3-dicyanobicyclo[2.2.1]hept-5-ene.

Examples of the cycloolefin monomer having an acid anhydride group include tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodecan-9-ene-4,5-dicarboxylic anhydride, bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic anhydride, and 2-carboxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hept-5-ene anhydride.

Examples of the cycloolefin monomer having a halogen atom include 2-chlorobicyclo[2.2.1]hept-5-ene, 2-chloromethylbicyclo[2.2.1]hept-5-ene, 2-(chlorophenyl)bicyclo[2.2.1]hept-5-ene, 4-chlorotetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene, and 4-methyl-4-chlorotetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene.

―Monomer (b2)―

Examples of the cycloolefin monomers (b2) having no polar groups include bicyclo[2.2.1]hept-2-ene (also called "norbenzene"), 5-ethylbicyclo[2.2.1]hept-2-ene, 5-butylbicyclo[2.2.1]hept-2-ene, 5-ethylenebicyclo[2.2.1]hept-2-ene, 5-methylenebicyclo[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, tricyclo[5.2.1.0 ^2,6 ]deca-3,8-diene (common name: dicyclopentadiene), tetracyclo[10.2.1.0 ^2,11 .0 ^4,9 ]pentadeca-4,6,8,13-tetraene, tetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene (also known as "tetracyclododecene"), 9-methyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-ethyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-methylenetetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-ethylenetetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-4-ene, 9-vinyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, 9-propenyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, pentacyclo[9.2.1.1 ^3,9 .0 ^2,10 .0 ^4,8 ] pentadeca-5,12-diene, cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cycloheptene, cyclooctene, cyclooctadiene, indene, 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene, 9-phenyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ] dodeca-4-ene, tetracyclo[9.2.1.0 ^2,10 .0 ^3,8 ]tetradeca-3,5,7,12-tetraene, pentacyclo[9.2.1.1 ^3,9 .0 ^2,10 .0 ^4,8 ]pentadeca-12-ene.

―Single body (b3)―

Examples of the monomer (b3) other than cycloolefins include ethylene; α-olefins having 3 or more and 20 carbon atoms, such as 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, and 1-eicosene; and non-conjugated dienes, such as 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene, and their derivatives.

The monomers (b1) to (b3) and other monomers (b) mentioned above may be used alone or in combination of two or more. Among them, from the viewpoint of further improving the heat flow resistance of the resin membrane, the cycloolefin monomer (b1) having a polar group other than a protonic polar group is preferred, and the cycloolefin monomer having an N-substituted imide group is more preferred.

―Content ratio―

Furthermore, the content ratio of the repeating units derived from the other monomers (b) in the cycloolefin polymer (A) is preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 30 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less, and more preferably 70 mol% or less, when all the repeating units are 100 mol%. If the ratio of the repeating units derived from the other monomers (b) is 10 mol% or more, the relative dielectric constant of the resin film can be reduced, and if it is 90 mol% or less, the heat flow tolerance of the resin film can be further improved.

《Preparation Method》

The method for preparing the cycloolefin polymer (A) having a protonic polar group is not particularly limited, and examples thereof include the following methods (i) and (ii): (i) a method of polymerizing a monomer composition comprising a cycloolefin monomer (a) having a protonic polar group and any other monomer (b) used and optionally subjecting the monomer composition to a hydrogenation reaction, or (ii) a method of modifying a cycloolefin polymer having no protonic polar group using a modifier having a protonic polar group. Among these, method (i) is preferred.

[Preparation method (i)]

The method for polymerizing the monomer composition containing the cycloolefin monomer (a) and any other monomer (b) is not particularly limited, and a known method can be used. As a specific polymerization method, for example, ring-opening polymerization and addition polymerization can be listed, but ring-opening polymerization is preferred. That is, the cycloolefin polymer (A) is preferably a ring-opening polymer or an addition polymer, and a ring-opening polymer is more preferred.

In addition, as a method of ring-opening polymerization, for example, a ring-opening metathesis polymerization in which a cycloolefin monomer (a) having a protonic polar group and other monomers (b) used as required are polymerized in the presence of a metathesis catalyst can be cited. As a method of ring-opening metathesis polymerization, for example, the method described in International Patent Publication No. 2010/110323 can be adopted.

Furthermore, when ring-opening polymerization is used in the preparation of the cycloolefin polymer (A), the obtained ring-opening polymer is further subjected to a hydrogenation reaction to obtain a hydrogenated product in which the carbon-carbon double bonds contained in the main chain are hydrogenated. When the cycloolefin polymer (A) is a hydrogenated product, the ratio of hydrogenated carbon-carbon double bonds (hydrogenation rate) is preferably 50% or more, more preferably 70% or more, more preferably 90% or more, and particularly preferably 95% or more from the viewpoint of further improving the heat resistance of the resin film.

Furthermore, in the present invention, the "hydrogenation rate" can be measured using ¹ H-NMR spectroscopy.

[Preparation method (ii)]

The method for preparing the cycloolefin polymer without protonic polar groups is not particularly limited. For example, the cycloolefin polymer without protonic polar groups can be obtained by polymerizing at least one of the monomers (b1) and (b2) described above in any combination as needed with the monomer (b3) using a known method. Furthermore, the method of modifying the obtained polymer using a modifier having a protonic polar group can be carried out according to a general method, usually in the presence of a free radical generator.

Furthermore, as the modifier having a protonic polar group, a compound having both a protonic polar group and a reactive carbon-carbon unsaturated bond can be used. Specifically, a compound described in International Patent Publication No. 2015/141717 can be used.

Weight average molecular weight

The weight average molecular weight of the cycloolefin polymer (A) is preferably 1,000 or more, more preferably 3,000 or more, more preferably 5,000 or more, and preferably 100,000 or less, more preferably 50,000 or less, and more preferably 30,000 or less. If the weight average molecular weight of the cycloolefin polymer (A) is 1,000 or more, the heat flow resistance of the resin film can be further improved while the top loss of the line pattern on the resin film is further suppressed. In addition, the chemical resistance of the resin film can be improved. On the other hand, if the weight average molecular weight of the cycloolefin polymer (A) is 100,000 or less, the solubility of the cycloolefin polymer (A) in the solvent can be fully ensured.

In the present invention, the "weight average molecular weight" and "number average molecular weight" of the cycloolefin polymer (A) are values obtained in the form of polystyrene conversion values by gel permeation chromatography (GPC) using tetrahydrofuran or the like as a solvent.

Furthermore, the weight average molecular weight and number average molecular weight of the cycloolefin polymer (A) can be controlled by adjusting the synthesis conditions (for example, the amount of the molecular weight regulator).

Molecular Weight Distribution

Furthermore, the molecular weight distribution (weight average molecular weight/number average molecular weight) of the cycloolefin polymer (A) is preferably 4 or less, more preferably 3 or less, and even more preferably 2.5 or less. When the molecular weight distribution of the cycloolefin polymer (A) is 4 or less, the top loss of the line pattern on the resin film can be further suppressed and the heat flow resistance can be further improved. In addition, the chemical resistance of the resin film can be improved.

The molecular weight distribution of the cycloolefin polymer (A) can be reduced by, for example, the method described in Japanese Patent Publication No. 2006-307155.

〈Cresol Novolac Resin (B)〉

The resin composition of the present invention contains, in addition to the above-mentioned cycloolefin polymer (A), a cresol novolac resin (B) having a softening point of 140°C or higher as a resin component. When the resin composition contains the cresol novolac resin (B), a resin film having a line pattern with suppressed top loss can be formed.

Here, the cresol novolac resin (B) is a resin obtained by condensing phenols including cresols with aldehydes.

《Phenols including cresols》

The phenols used in the preparation of the cresol novolac resin (B) are not particularly limited as long as they include cresols, and may be cresols alone, or cresols and phenols other than cresols (hereinafter referred to as "other phenols") may be used in combination.

- Cresols -

The so-called cresols refer to a group of compounds in which at least one of the five hydrogen atoms on the benzene ring of phenol (C ₆ H ₅ OH) is substituted with a methyl group and the remaining hydrogen atoms are unsubstituted. Examples of cresols include cresols (o-cresol, m-cresol, p-cresol), xylenols (2,5-xylenol (2,5-dimethylphenol), 3,5-xylenol (3,5-dimethylphenol), etc.), and trimethylols (2,3,5-trimethylphenol, etc.). These can be used alone or in combination of two or more. Among these, from the viewpoint of further improving the heat flow resistance of the resin film, it is preferred to use cresols and xylenols together, and it is more preferred to use m-cresol, p-cresol and 3,5-xylenol together. In other words, the cresol novolac resin (B) preferably contains a cresol skeleton and a xylenol skeleton as skeletons derived from cresols, and more preferably contains a m-cresol skeleton, a p-cresol skeleton and a 3,5-xylenol skeleton as skeletons derived from cresols.

Furthermore, when the meta-former (meta-cresol, 3,5-xylenol (meta-xylenol)) and the para-former (p-cresol) are used in combination as the cresols, the molar ratio (m/p ratio) of the content of the meta-former skeleton (meta-cresol skeleton, 3,5-xylenol skeleton) to the content of the para-former skeleton (p-cresol skeleton) in the skeleton derived from the cresols contained in the cresol novolac resin (B) is preferably 0.5 or more, more preferably 1.0 or more, more preferably 2.0 or more, particularly preferably 2.2 or more, and is preferably 5.0 or less, preferably 4.0 or less, more preferably 3.0 or less, and particularly preferably 2.5 or less. If the m/p ratio is within the above-mentioned range, the heat flow tolerance can be further improved while further suppressing the top loss of the line pattern on the resin film.

Furthermore, the ratio of cresols in the phenols used in the preparation of the cresol novolac resin (B) is preferably 50 mass % or more, more preferably 95 mass % or more, further preferably 97 mass % or more, and particularly preferably 100 mass % (that is, only cresols are used as phenols), when the total amount of phenols is 100 mass %.

―Other phenols―

As phenols other than the cresols mentioned above that can be used in the preparation of the cresol novolac resin (B), there can be listed: monovalent phenol compounds, divalent or higher valent phenol compounds (polyvalent phenol compounds). In addition, the other phenols may be used alone or in combination of two or more.

As monovalent phenolic compounds, for example, phenol; 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2,5-diethylphenol, 3,5-diethylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol, 2-tert-butyl-3-methylphenol, 2,3,5-triethylphenol, Alkylphenols such as 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol and the like; arylphenols such as 2-phenylphenol, 3-phenylphenol, 4-phenylphenol and the like; alkenylphenols such as 2-isopropenylphenol, 4-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-isopropenylphenol and the like; etc.

Examples of divalent or higher phenolic compounds include resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-methoxyresorcinol, 4-methoxyresorcinol; hydroquinone; o-catechin, 4-tert-butyl o-catechin, 3-methoxy o-catechin; 4,4′-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane; 1,2,3-benzenetriol; 1,3,5-benzenetriol; and the like.

《Aldehydes》

Examples of the aldehydes to be used in the condensation reaction with the phenols included in the cresols mentioned above include aliphatic aldehydes, alicyclic aldehydes and aromatic aldehydes.

―Aliphatic aldehydes―

Examples of aliphatic aldehydes include formaldehyde, trioxane (trioxymethylene), polyoxymethylene, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, trimethylacetaldehyde, n-hexanal, acrolein, 2-butenal, and the like.

―Alicyclic aldehydes―

Examples of the alicyclic aldehydes include cyclopentanal, cyclohexanal, furfural, furanyl acrolein, and the like.

―Aromatic aldehydes―

Examples of the aromatic aldehydes include benzaldehyde, o-benzylaldehyde, m-benzylaldehyde, p-benzylaldehyde, p-ethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, 3,4-dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-anisaldehyde, m-anisaldehyde, p-anisaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, and cinnamaldehyde.

The aldehydes mentioned above may be used alone or in combination of two or more. Among them, aliphatic aldehydes are preferred, and formaldehyde is more preferred.

《Preparation Method》

The cresol novolac resin (B) can be prepared by subjecting the phenols included in the cresols mentioned above to a condensation reaction with aldehydes. This condensation reaction can be carried out, for example, by a known method using an acidic catalyst. Examples of the acidic catalyst used include hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid, and the like.

Softening Point

The softening point of the cresol novolac resin (B) must be 140°C or higher, preferably 150°C or higher, and more preferably 160°C or higher. If the softening point is less than 140°C, the heat flow resistance of the resin film cannot be ensured.

The upper limit of the softening point of the cresol novolac resin (B) is not particularly limited, but is preferably 300° C. or lower from the viewpoint of handling properties.

Furthermore, the softening point of the cresol novolac resin (B) can be controlled by adjusting the types of phenols and aldehydes used in the condensation reaction or the conditions of the condensation reaction.

Weight average molecular weight

The weight average molecular weight of the cresol novolac resin (B) is preferably 1,000 or more, more preferably 3,000 or more, more preferably 6,000 or more, and preferably 20,000 or less, more preferably 15,000 or less, and more preferably 10,000 or less. If the weight average molecular weight is 1,000 or more, the softening point can be increased, and the heat flow resistance of the resin film can be further improved. In addition, the top loss of the line pattern on the resin film can be further suppressed. On the other hand, if the weight average molecular weight is 20,000 or less, the solubility of the cresol novolac resin (B) in the solvent can be fully ensured.

In the present invention, the "weight average molecular weight" of the cresol novolac resin (B) is a value obtained in terms of polystyrene by gel permeation chromatography (GPC) using tetrahydrofuran or the like as a solvent.

Furthermore, the weight average molecular weight of the cresol novolac resin (B) can be controlled by adjusting the types of phenols and aldehydes used in the condensation reaction or the conditions of the condensation reaction.

<Ratio of content of cycloolefin polymer (A) and cresol novolac resin (B)>

Here, the proportion of the cycloolefin polymer (A) in the total amount of the cycloolefin polymer (A) and the cresol novolac resin (B) is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and more preferably 75% by mass or less, when the total amount of the cycloolefin polymer (A) and the cresol novolac resin (B) is 100% by mass. If the proportion of the cycloolefin polymer (A) in the total of the cycloolefin polymer (A) and the cresol novolac resin (B) is 10 mass % or more, the relative dielectric constant of the resin film can be sufficiently reduced, and if it is 90 mass % or less, the top loss of the line pattern on the resin film can be further suppressed.

〈Acid generator (C)〉

The acid generator (C) is a compound that decomposes upon exposure to active radiation to generate an acid component such as carboxylic acid. When the radiation sensitive film formed using the resin composition of the present invention containing the acid generator (C) is exposed to active radiation, the alkali solubility of the exposed portion increases.

Here, the acid generator (C) may include, for example, azide compounds, onium salt compounds, halogenated organic compounds, α,α′-disulfonyldiazomethane compounds, α-carbonyl-α′-sulfonyldiazomethane compounds, sulfonium compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds, acetophenone compounds, and triarylsilonium salts. However, from the viewpoint of excellent resolution of the obtained pattern of line width and line spacing, azide compounds are preferred, and quinonediazide compounds are more preferred.

As the quinonediazide compound that can be suitably used as the acid generator (C), for example, an ester compound of "quinonediazide sulfonyl halide" and "a compound having a phenolic hydroxyl group" can be used. Here, as specific examples of the quinonediazide sulfonyl halide, there can be listed: 1,2-naphthoquinonediazide-5-sulfonyl chloride, 1,2-naphthoquinonediazide-4-sulfonyl chloride, 1,2-benzoquinonediazide-5-sulfonyl chloride, etc. In addition, specific examples of compounds having a phenolic hydroxyl group include 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4′-(1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylidene)bisphenol, 2,3,4-trihydroxydiphenyl ketone, 2,3,4,4′-tetrahydroxy phenyl ketone, 2-bis(4-hydroxyphenyl)propane, tris(4-hydroxyphenyl)methane, 1,1,1-tris(4-hydroxy-3-methylphenyl)ethane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, oligomers of novolac resins, oligomers obtained by copolymerizing a compound having one or more phenolic hydroxyl groups with dicyclopentadiene, and the like.

Among them, the acid generator (C) is preferably an ester compound (condensate) of 1,2-naphthoquinonediazide-5-sulfonyl chloride and 4,4′-(1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylene)bisphenol.

The acid generator (C) may be used alone or in combination of two or more.

"content"

The content of the acid generator (C) in the resin composition of the present invention is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, more preferably 25 parts by mass or more, and particularly preferably 30 parts by mass or more, and is preferably 100 parts by mass or less, more preferably 70 parts by mass or less, and more preferably 50 parts by mass or less, based on 100 parts by mass of the total of the cycloolefin polymer (A) and the cresol novolac resin (B). If the content of the acid generator (C) is 10 parts by mass or more, based on 100 parts by mass of the total of the cycloolefin polymer (A) and the cresol novolac resin (B), the solubility of the exposed portion in the alkaline developer can be sufficiently improved. Furthermore, when using the resin composition to form a pattern with fine line width and line spacing, sometimes the unexposed part is also exposed to some active radiation and the top loss of the line pattern occurs. However, if the content of the acid generator (C) is 100 parts by weight or less when the total of the cycloolefin polymer (A) and the cresol novolac resin (B) is 100 parts by weight, the solubility of the unexposed part in the alkaline developer will not be undesirably increased, and the top loss of the line pattern formed by the unexposed part can be further suppressed.

〈Crosslinking agent (D)〉

The crosslinking agent (D) is a compound that undergoes a crosslinking reaction with the protonic polar group of the cycloolefin polymer (A), the hydroxyl group of the cresol novolac resin (B), and/or the aromatic ring of the cresol novolac resin (B). When the resin composition contains the crosslinking agent (D), the heat flow resistance and chemical resistance of the obtained resin film can be improved.

Here, the crosslinking agent (D) is not particularly limited as long as it is a compound having two or more functional groups that can react with the protonic polar group of the cycloolefin polymer (A) and/or the hydroxyl group of the cresol novolac resin (B) in one molecule, but examples thereof include polyfunctional epoxy compounds (compounds having two or more epoxy groups), polyfunctional alkoxymethyl compounds (compounds having two or more alkoxymethyl groups), and polyfunctional hydroxymethyl compounds (compounds having two or more hydroxymethyl groups).

The crosslinking agent (D) may be used alone or in combination of two or more.

《Polyfunctional Epoxides》

Examples of the polyfunctional epoxy compound include tris(2,3-epoxypropyl)isocyanate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris(p-(2,3-epoxypropyloxy)phenyl)propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ether, 4,4′-methylenebis(N,N-diepoxypropylaniline), 3,4-epoxyepoxyhexanecarboxylic acid-3,4-epoxyepoxyhexyl methyl ester, trihydroxymethylethane triepoxypropyl ether, bisphenol A diepoxypropyl ether, neopentylthritol polyepoxypropyl ether, epoxybutanetetracarboxylic acid tetra(3-cyclohexenyl methyl ester) modified ε-caprolactone and 1,2-epoxy-4-(2-epoxyethylene)cyclohexane adduct of 2,2-di(hydroxymethyl)-1-butanol, etc.

In addition, commercially available products of multifunctional epoxy compounds include, for example, EPOLEAD (registered trademark) GT401, EPOLEAD PB3600, EPOLEAD PB4700, Celloxide (registered trademark) 2021, Celloxide 3000, EHPE3150 (all made by DAICEL); jER1001, jER1002, jER1003, jER1004, jER1007, jER1009, jER1010, jER828, jER871, jER872, jER180S75, jER807, jER152, jER154 (all made by Mitsubishi Chemical); EPPN201, EPPN202, EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (all made by Nippon Kayaku Co., Ltd.); EPICLON (registered trademark) 200, EPICLON 400 (all manufactured by DIC Corporation); DENACOL (registered trademark) EX-611, DENACOL EX-612, DENACOL EX-614, DENACOL EX-622, DENACOL EX-411, DENACOL EX-512, DENACOL EX-522, DENACOL EX-421, DENACOL EX-313, DENACOL EX-314, DENACOL EX-321 (all manufactured by Nagase ChemteX Corporation); TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.), etc.

《Multifunctional alkoxymethyl compounds》

Examples of the polyfunctional alkoxymethyl compound include a phenol compound in which two or more alkoxymethyl groups are directly bonded to an aromatic ring, a melamine compound in which an amino group is substituted with two or more alkoxymethyl groups, and a urea compound in which two or more alkoxymethyl groups are substituted.

Examples of phenol compounds in which two or more alkoxymethyl groups are directly bonded to an aromatic ring include dimethoxymethyl-substituted phenol compounds, tetramethoxymethyl-substituted biphenyl compounds, and hexamethoxymethyl-substituted triphenyl compounds.

More specifically, they include: 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 3,3′,5,5′-tetramethoxymethyl-4,4′-dihydroxybiphenyl (e.g., product name "TMOM-BP", manufactured by Honshu Chemical Industry Co., Ltd.), 1,1-bis[3,5-bis(methoxymethyl)-4-hydroxyphenyl]-1-phenylethane, 4,4′,4″-(dimethoxymethyl)-4-hydroxyphenyl]-1-phenylethane, 4,4′-[1-(4-{1-[4-hydroxy-3,5-di(methoxymethyl)phenyl]-1-methylethyl}phenyl)ethylidene]bis[2,6-di(methoxymethyl)phenol] (e.g., product name "HMX-PA", manufactured by Asahi Chemical Industries, Ltd.), etc.

Examples of the melamine compound in which the amino group is substituted with two or more alkoxymethyl groups include N,N′-dimethoxymethyl melamine, N,N′,N″-trimethoxymethyl melamine, N,N,N′,N″-tetramethoxymethyl melamine, N,N,N′,N′,N″-pentamethoxymethyl melamine, N,N,N′,N′,N″,N″-hexamethoxymethyl melamine (e.g., product name “NIKALAC (registered trademark) MW-390LM”, product name “NIKALAC MW-100LM”, both manufactured by Sanwa Chemical Co., Ltd.) or polymers thereof.

Examples of urea compounds substituted with two or more alkoxymethyl groups include the product names "NIKALAC MX270", "NIKALAC MX280", and "NIKALAC MX290" (all manufactured by Sanwa Chemical Co., Ltd.).

《Multifunctional Hydroxymethyl Compounds》

Examples of the polyfunctional hydroxymethyl compound include phenol compounds in which two or more hydroxymethyl groups are directly bonded to an aromatic ring.

In addition, examples of phenolic compounds in which two or more hydroxymethyl groups are directly bonded to an aromatic ring include 2,4-dihydroxymethyl-6-methylphenol, 2,6-di(hydroxymethyl)-p-cresol, 4-tert-butyl-2,6-di(hydroxymethyl)phenol, bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane (product name "DM-BIPC-F", manufactured by Asahi Organic Materials Co., Ltd.), bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane (product name "DM-BIOC-F", manufactured by Asahi Organic Materials Co., Ltd.), and 2,2-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane (product name "TM-BIP-A", manufactured by Asahi Organic Materials Co., Ltd.).

Among the crosslinking agents (D) mentioned above, from the viewpoint of further improving the heat flow resistance of the resin film and enhancing the chemical resistance, it is preferred to use at least one of a polyfunctional epoxy compound and a polyfunctional alkoxymethyl compound, and it is more preferred to use both a polyfunctional epoxy compound and a polyfunctional alkoxymethyl compound.

Furthermore, as the polyfunctional epoxy compound, from the viewpoint of improving the chemical resistance of the resin film, it is preferred to include at least one selected from the group consisting of a polyfunctional epoxy compound having an alicyclic structure such as EPOLEAD GT401 (substance name: epoxide butane tetracarboxylic acid tetra(3-cyclohexenyl methyl ester) modified ε-caprolactone) and an epoxidized polybutadiene having a terminal H such as EPOLEAD PB4700, and a polyfunctional epoxy compound having an alicyclic structure such as EPOLEAD GT401 and an epoxidized polybutadiene having a terminal H such as EPOLEAD PB4700. Preferably, at least one of the group consisting of epoxidized polybutadiene having a terminal H of an epoxypropyl ether structure in the main chain such as PB4700 is used, and more preferably, at least epoxidized butanetetracarboxylic acid tetra(3-cyclohexenylmethyl ester)-modified ε-caprolactone is used.

[content]

The content of the crosslinking agent (D) in the resin composition of the present invention is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and particularly preferably 40 parts by mass or more, and is preferably 120 parts by mass or less, more preferably 80 parts by mass or less, more preferably 60 parts by mass or less, and particularly preferably 50 parts by mass or less, based on 100 parts by mass of the total of the cycloolefin polymer (A) and the cresol novolac resin (B). If the content of the crosslinking agent (D) is 15 parts by mass or more when the total amount of the cycloolefin polymer (A) and the cresol novolac resin (B) is 100 parts by mass, the heat flow tolerance and chemical resistance of the resin film can be further improved. If it is 120 parts by mass or less, a pattern with excellent line width and line spacing can be formed.

Furthermore, when "polyfunctional epoxy compound" and "at least one of polyfunctional alkoxymethyl compound and polyfunctional hydroxymethyl compound (polyfunctional alkoxymethyl compound and/or polyfunctional hydroxymethyl compound)" are used together, the mass ratio of polyfunctional epoxy compound to polyfunctional alkoxymethyl compound and/or polyfunctional hydroxymethyl compound (polyfunctional epoxy compound: polyfunctional alkoxymethyl compound and/or polyfunctional hydroxymethyl compound) is preferably in the range of 1:1 to 1:0.1, and more preferably in the range of 1:0.5 to 1:0.25. If the ratio of polyfunctional epoxy compound: polyfunctional alkoxymethyl compound and/or polyfunctional hydroxymethyl compound is within the above range, a resin film having an excellent balance of line width and line spacing pattern resolution, heat flow tolerance and chemical resistance can be formed.

〈Solvent〉

The resin composition of the present invention may also contain a solvent. That is, the resin composition of the present invention may also be a radiation-sensitive resin liquid prepared by dissolving and/or dispersing a cycloolefin polymer (A) having a protonic polar group, a cresol novolac resin (B) having a softening point of 140°C or higher, an acid generator (C), a crosslinking agent (D), and other optional added admixtures in a solvent.

The solvent is not particularly limited, and examples of the solvent known as a resin composition include: linear ketones such as acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone; alcohols such as n-propanol, isopropanol, n-butanol, cyclohexanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dioxane; alcohol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether; esters such as propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate ; cellulose acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl lactate, ethyl lactate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl lactate, ethyl lactate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl lactate, ethyl lactate, ethyl lactate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl acetate, ethyl lactate ... Cellulose esters such as methylcellulose acid, ethylcellulose acetate, propylcellulose acetate, and butylcellulose acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether; diethylene glycol such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether; saturated γ-lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octanolactone; halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene; other polar solvents such as dimethylacetamide, dimethylformamide, and N-methylacetamide.

The solvent may be used alone or in combination of two or more.

〈Other additives〉

The resin composition of the present invention may also contain a blending agent other than the above-mentioned components. Examples of other blending agents include resin components other than cycloolefin polymer (A) and cresol novolac resin (B), silane coupling agents, compounds having acidic groups or heat-latent acidic groups, dissolution promoters, surfactants, antioxidants, sensitizers, light stabilizers, defoaming agents, pigments, dyes, and fillers. In addition, other blending agents may be used alone or in combination of two or more.

〈Method for preparing radiation sensitive resin composition〉

The method for preparing the resin composition of the present invention is not particularly limited, as long as the components constituting the resin composition are mixed.

Specifically, the resin composition of the present invention is preferably obtained by mixing the cycloolefin polymer (A), the cresol novolac resin (B), the acid generator (C), the crosslinking agent (D) and any other admixtures used in the above-mentioned solvent and dissolving or dispersing them in the solvent. By this operation, the resin composition can be obtained in the form of a solution or dispersion (that is, in the form of a radiation-sensitive resin liquid).

The mixing is not particularly limited and can be performed using a known mixer. Furthermore, filtering can be performed using a known method after mixing.

Furthermore, the solid content concentration of the radiation-sensitive resin liquid, which is the resin composition of the present invention, is usually 1 mass % or more and 70 mass % or less, preferably 5 mass % or more and 60 mass % or less, and more preferably 10 mass % or more and 50 mass % or less. If the solid content concentration is within the above-mentioned range, the dissolution stability and coating properties of the radiation-sensitive resin liquid and the film thickness uniformity and flatness of the resin film to be formed can be highly balanced.

〈Resin film formation method〉

The radiation-sensitive resin composition of the present invention can be used to form a resin film on a substrate such as a silicon wafer on which a semiconductor device is mounted.

Furthermore, the method for forming the resin film on the substrate is not particularly limited. The resin film, for example, can be manufactured by a process of forming a radiation-sensitive film on the substrate using a radiation-sensitive resin composition (i.e., a radiation-sensitive resin liquid) containing a solvent (radiation-sensitive film forming process), irradiating the radiation-sensitive film with active radiation to obtain an exposed film (exposure process), developing the exposed film to obtain a developed film (development process), and curing the developed film to obtain a resin film (curing process).

《Radiation sensitive film formation process》

The method of forming a radiation sensitive film on a substrate using a radiation sensitive resin liquid is not particularly limited, and methods such as a coating method or a thin film stacking method can be used.

[Painting method]

The coating method is a method of forming a radiation sensitive film by coating a radiation sensitive resin liquid on a substrate and then removing the solvent by heating and drying. As a method of coating the radiation sensitive resin liquid, various methods such as spray coating, spin coating, roller coating, die coating, doctor blade coating, slit coating, rod coating, screen printing, inkjet coating, etc. can be used. The heating and drying conditions vary depending on the type or blending ratio of each component, but the heating temperature is usually 30 to 150°C, preferably 60 to 130°C, and the heating time is usually 0.5 to 90 minutes, preferably 1 to 60 minutes, and more preferably 1 to 30 minutes.

[Thin film stacking method]

The thin film stacking method is a method in which a radiation-sensitive resin liquid is applied to a substrate (resin film or metal film, etc.) for forming a radiation-sensitive film, and then the solvent is removed by heat drying to obtain a radiation-sensitive film, and then the obtained radiation-sensitive film is stacked on a substrate. The heating and drying conditions can be appropriately selected according to the type or blending ratio of each component, but the heating temperature is usually 30 to 150°C, and the heating time is usually 0.5 to 90 minutes. The stacking of the radiation-sensitive film on the substrate can be carried out using a laminating machine such as a pressure laminating machine, a press, a vacuum laminating machine, a vacuum press, and a roll laminating machine.

The thickness of the radiation sensitive film formed on the substrate using any of the above methods is not particularly limited, and can be appropriately set according to the application. It is preferably 0.1-100 μm, more preferably 0.5-50 μm, and even more preferably 0.5-30 μm.

《Exposure process》

Then, the radiation sensitive film formed in the above-mentioned radiation sensitive film forming step is irradiated with active radiation to obtain an exposed film having a latent pattern.

[Active Radiation]

The active radiation is not particularly limited as long as it can activate the acid generator (C) contained in the radiation sensitive film to increase the solubility of the resin component in the exposed part in the developer (especially in the alkaline developer). Specifically, examples of light that can be used include ultraviolet rays (including single-wavelength ultraviolet rays such as g-rays and i-rays), KrF excimer lasers, and ArF excimer lasers; particle beams such as electron beams; and the like.

Furthermore, when light is used as active radiation, it may be light of a single wavelength or light of mixed wavelengths.

[Exposure conditions]

As a method for selectively irradiating the active radiation described above into a pattern to form a latent pattern, it is sufficient to follow a general method, for example, a method of irradiating ultraviolet rays, KrF excimer laser light, ArF excimer laser light, etc. through a desired mask pattern through a reduced projection exposure device, or a method of drawing through a particle beam such as an electron beam.

The irradiation conditions are appropriately selected according to the active radiation used, but when using light with a wavelength of 200 to 450 mm, for example, the irradiation dose is usually 10 to 5,000 mJ/cm ² , preferably in the range of 50 to 1,500 mJ/cm ² , depending on the irradiation time and illumination.

In addition, after irradiation with active radiation, the obtained exposed film may be subjected to a heat treatment at a temperature of about 60 to 150° C. for about 1 to 10 minutes as required.

《Development Process》

Next, the latent pattern formed on the exposure film in the above-mentioned exposure step is developed by a developer to obtain a developed film.

[Developer]

As the developer, an alkaline developer can be used. The alkaline developer can be obtained by dissolving an alkaline compound in an aqueous medium.

As the alkaline compound, for example, alkaline metal salts, amines, and ammonium salts can be used. The alkaline compound can be an inorganic compound or an organic compound. Specific examples of alkaline compounds include alkaline metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, and sodium metasilicate; ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and choline; alcoholamines such as dimethylethanolamine and triethanolamine; cyclic amines such as pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5-diazabicyclo[4.3.0]non-5-ene, and N-methylpyrrolidone. These alkaline compounds may be used alone or in combination of two or more.

As the aqueous medium of the alkaline developer, water or a water-soluble organic solvent such as methanol or ethanol can be used.

Furthermore, the alkaline developer may be one to which an appropriate amount of surfactant is added.

[Development method]

As a method for contacting the exposed film with the latent pattern with the developer, for example, a stirring method, a spraying method, an immersion method, etc. can be used. In addition, the developing temperature is usually appropriately selected in the range of 0 to 100°C, preferably 5 to 55°C, and more preferably 10 to 30°C, and the developing time is usually appropriately selected in the range of 30 to 180 seconds.

The developed film having the target pattern formed thereon may be washed with a washing liquid to remove the development residue as required. After the washing treatment, the residual washing liquid is preferably removed by compressed air or compressed nitrogen.

Furthermore, the developer film may be irradiated with active radiation to inactivate the acid generator (C) remaining in the developer film as required. The irradiation with active radiation may be carried out by the method described in the "exposure process" above. In addition, the developer film may be heated simultaneously with or after the irradiation with active radiation. As a heating method, for example, a method of heating electronic parts in a heating plate or an oven may be cited. The heating temperature is usually in the range of 80 to 300°C, preferably 100 to 200°C.

《Curing process》

Then, the developed film patterned in the above-mentioned developing step is cured to obtain a patterned resin film.

The curing method can be selected appropriately according to the type of crosslinking agent (D) contained in the radiation-sensitive resin liquid, but is usually carried out by heating.

The heating method can be carried out using, for example, a heating plate, an oven, etc. The heating temperature is usually 150 to 250°C, and the heating time is appropriately selected according to the area or thickness of the developer film, the equipment used, etc. For example, when a heating plate is used, it is usually 5 to 120 minutes, and when an oven is used, it is usually in the range of 30 to 150 minutes. In addition, heating can also be carried out in an inert gas environment as required. As an inert gas, any gas that does not contain oxygen and does not oxidize the developer film can be used, for example: nitrogen, argon, helium, neon, xenon, krypton, etc. Among these, nitrogen and argon are preferred, and nitrogen is particularly preferred. In particular, an inert gas having an oxygen content of 0.1 volume % or less, preferably 0.01 volume % or less, particularly nitrogen is suitable. Such inert gases may be used alone or in combination of two or more.

『Implementation example』

The present invention is specifically described below based on embodiments, but the present invention is not limited to these embodiments.

In the embodiments and comparative examples, relative dielectric constant, top loss, heat flow resistance and chemical resistance were evaluated as follows.

〈Relative dielectric constant〉

The prepared resin composition was applied by spin coating on a 4-inch silicon wafer with a 50 nm thick aluminum film formed using a sputtering device (manufactured by SHIBAURA ELETEC CORPORATION, product name "i-Miller CFS-4EP-LL"), and then dried (pre-baked) at 120°C for 2 minutes using a hot plate to form a radiation sensitive film. The film was cured by heating it at 230°C in nitrogen for 1 hour to obtain a silicon wafer with a 10 μm thick cured film. The aluminum was etched by immersing it in a 0.1 mol% hydrochloric acid aqueous solution for 12 hours, and the cured film was peeled off from the silicon wafer. This cured film was cut into strips with a width of 2 mm and a length of 50 mm to make test pieces. The relative dielectric constant of this test piece was measured at 10 GHz using the cavity resonator method and evaluated using the following criteria. A: Relative dielectric constant less than 2.85 B: Relative dielectric constant greater than 2.85 and less than 3.00 C: Relative dielectric constant greater than 3.00

〈Top Loss〉

The prepared resin composition was applied on a silicon wafer by spin coating, and then dried (pre-baked) at 120°C for 2 minutes using a hot plate to form a radiation sensitive film (film thickness 3.0 μm). Subsequently, a reticle capable of forming a pattern with a line width and line spacing of 1.0 μm was installed on an i-line stepper (NIKON, product name "NSR2005i9C"), and the exposure amount was changed from 100 to 2000 mJ/cm ² to perform an exposure process. The obtained exposed film was developed using a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. After that, after rinsing with ultrapure water and spin drying, a stack of a developer film with a line width and line spacing pattern and a silicon wafer was obtained. Then, a scanning electron microscope (SEM) was used to observe the cross-section of the line width and line spacing pattern portion of the obtained stack, and the film thickness of the line width portion was measured under an exposure dose of 1:1 between the line width and the line spacing. In addition, the film thickness of the unexposed portion where the line width and line spacing pattern was not formed was also measured by SEM. Then, the top loss was calculated using the formula: Top loss (%) = (film thickness of the unexposed portion - film thickness of the line width portion) / (film thickness of the unexposed portion) × 100, and evaluated using the following criteria. A: Top loss less than 25% B: Top loss more than 25% but less than 40% C: Top loss more than 40%

〈Heat flow tolerance〉

The resin composition prepared by spin coating was applied on a silicon wafer, and then heated and dried (pre-baked) at 120°C for 2 minutes using a heating plate to form a radiation sensitive film (film thickness 3.0 μm). Subsequently, an exposure process was performed by changing the exposure amount from 100 to 2000 mJ/cm ² using a mask capable of forming a 2.0 μm via pattern. The obtained exposed film was developed for 60 seconds using a 2.38 mass% tetramethylammonium hydroxide aqueous solution. After that, it was rinsed with ultrapure water and dried by spin drying to obtain a stack of a developed film with 2.0 μm via holes and a silicon wafer. In addition, the length was measured by optical microscope observation, confirming that a 2.0 μm via pattern was opened. The obtained stack was heated from 50°C to 110°C at 2°C/min in nitrogen, kept at 110°C for 30 minutes, then heated to 230°C at 3°C/min, and further kept at 230°C for 1 hour to cure the developed film and obtain a resin film. Then, the length of the via hole on the resin film with a 2.0 μm via hole pattern before curing was measured with an optical microscope. The reduction ratio of the via hole diameter caused by curing was calculated using the formula: Reduction ratio of via hole diameter (%) = (via hole diameter before curing - via hole diameter after curing) / (via hole diameter before curing) × 100, and the evaluation was performed using the following criteria. A: The reduction in the via diameter is less than 5% B: The reduction in the via diameter is more than 5% and less than 10% C: The reduction in the via diameter is more than 10%

〈Chemical resistance〉

The resin composition prepared by spin coating was applied on a silicon wafer, and then dried (pre-baked) at 120°C for 2 minutes using a hot plate to form a radiation sensitive film. Subsequently, the temperature was raised from 50°C to 110°C at 2°C/min in nitrogen, and after being kept at 110°C for 30 minutes, the temperature was raised to 230°C at 3°C/min, and further kept at 230°C for 1 hour, thereby curing the radiation sensitive film to obtain a cured film. Immerse in monoethanolamine/dimethyl sulfoxide = 7/3 (mass ratio) at 23°C for 15 minutes, and use the formula: Film thickness change ratio (%) = | Film thickness before immersion - Film thickness after immersion | / (Film thickness before immersion) × 100 to calculate the film thickness change ratio caused by immersion, and evaluate it according to the following criteria in combination with the results of visual observation of the cured film (whether there are cracks or peeling). A: The film thickness change ratio is less than 10%, and there are no cracks or peeling B: The film thickness change ratio is more than 10% and less than 20%, and there are no cracks or peeling C: The film thickness change ratio is more than 20%, and/or there is at least one of cracks and peeling

(Example 1)

<Preparation of Cycloolefin Polymer (A-1)>

100 parts by mass of a monomer mixture consisting of 40 mol% of N-phenylbicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (NBPI) and 60 mol% of 4-hydroxycarbonyltetracyclo[6.2.1.1 ^3,6 .0 ^2,7 ]dodec-9-ene (TCDC), 2.0 parts by mass of 1,5-hexadiene, dichloro[1,3-bis(1,3,5-trimethylphenyl)imidazolin-2-ylidene](tricyclohexylphosphine)benzylideneruthenium (known as "Org. 1, p. 953, 1999) and 200 parts by mass of diethylene glycol methyl ethyl ether were placed in a nitrogen-substituted glass pressure reactor and reacted at 80° C. for 4 hours while stirring to obtain a polymerization reaction solution.

Then, the obtained polymerization reaction liquid was placed in an autoclave and stirred at 150°C and a hydrogen pressure of 4 MPa for 5 hours to carry out a hydrogenation reaction, thereby obtaining a polymer solution containing a cycloolefin polymer (A-1) having a protonic polar group. The obtained cycloolefin polymer (A-1) had a polymerization conversion of 99.7% by mass, a weight average molecular weight (polystyrene conversion) of 7,200, a number average molecular weight of 4,700, a molecular weight distribution of 1.53, and a hydrogenation rate of 99.7%. In addition, the solid content concentration of the obtained cycloolefin polymer (A-1) polymer solution was 34.4% by mass.

〈Preparation of radiation-sensitive resin composition (radiation-sensitive resin liquid)〉

75 parts of a polymer solution of a cycloolefin polymer (A-1) (equivalent to the amount of the solid content), 25 parts of a cresol novolac resin (B-1) (produced by Asahi Organic Materials Co., Ltd., product name "TMR30B35G", weight average molecular weight: 7000, softening point: 163°C, a condensation product of m-cresol/p-cresol/m-xylenol = 60/30/10 (molar ratio) and formaldehyde, m/p ratio: about 2.3), and an acid generator were added. (C-1) (Toyo Gosei Co., Ltd., product name "TS250", condensation product of quinone diazide compound (4,4′-(1-{4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl}ethylene)bisphenol (1.0 mol) and 1,2-naphthoquinone diazide-5-sulfonyl chloride (2.5 mol))) 30 parts, crosslinking agent (D-1) (Daicel Co., Ltd., product name "EPOLEAD GT401", a multifunctional epoxy compound having an alicyclic structure) 30 parts, a crosslinking agent (D-4) (manufactured by Sanwa Chemical Co., Ltd., product name "NIKALAC MW-100LM", N,N,N′,N′,N″,N″-hexamethoxymethylmelamine) 10 parts and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. In addition, the amount of diethylene glycol methyl ethyl ether used was determined to be an amount that gave a solid component concentration of 40% by mass. Subsequently, the obtained solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. The results are shown in Table 1.

(Example 2)

Cycloolefin polymer (A-1) and resin composition were prepared in the same manner as in Example 1, except that the amount of cycloolefin polymer (A-1) was changed from 75 parts to 55 parts (equivalent to the amount of solid components), the amount of cresol novolac resin (B-1) was changed from 25 parts to 45 parts, and the amount of crosslinking agent (D-1) was changed from 30 parts to 35 parts during the preparation of the resin composition, and various evaluations were performed. The results are shown in Table 1.

(Example 3)

The cycloolefin polymer (A-1) and the resin composition were prepared in the same manner as in Example 1, except that the amount of the cycloolefin polymer (A-1) was changed from 75 parts to 30 parts (equivalent to the amount of the solid component) and the amount of the cresol novolac resin (B-1) was changed from 25 parts to 70 parts during the preparation of the resin composition, and various evaluations were performed. The results are shown in Table 1.

(Example 4)

〈Preparation of Cycloolefin Polymer (A-2)〉

A cycloolefin polymer (A-2) having a protonic polar group was prepared in the same manner as the cycloolefin polymer (A-1) except that the NBPI was adjusted to 31.5 mol% and the TCDC was adjusted to 68.5 mol%. The polymerization conversion rate of the obtained cycloolefin polymer (A-2) was 99.8% by mass, the weight average molecular weight (polystyrene conversion) was 7300, the number average molecular weight was 4800, the molecular weight distribution was 1.52, and the hydrogenation rate was 99.9%. In addition, the solid content concentration of the polymer solution of the obtained cycloolefin polymer (A-2) was 34.3% by mass.

〈Preparation of radiation-sensitive resin composition (radiation-sensitive resin liquid)〉

50 parts of a polymer solution of a cycloolefin polymer (A-2) (equivalent to the amount of the solid content), 50 parts of a cresol novolac resin (B-2) (produced by Asahi Organic Materials Co., Ltd., product name "TMR30B25G", weight average molecular weight: 9000, softening point: 167°C, a condensation product of m-cresol/p-cresol/m-xylenol = 60/30/10 (molar ratio) and formaldehyde, m/p ratio: about 2.3), 30 parts of an acid generator (C-1), 37 parts of a crosslinking agent (D-1), 10 parts of a crosslinking agent (D-5) (manufactured by Honshu Chemical Industry Co., Ltd., product name "HMOM-TPHAP", 4,4',4"-(ethylene)tris[2,6-bis(methoxymethyl)phenol]) and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. The amount of diethylene glycol methyl ethyl ether used was set to an amount that gave a solid content concentration of 40 mass %. Subsequently, the obtained solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. The results are shown in Table 1.

(Example 5)

<Preparation of Cycloolefin Polymers (A-1) and (A-2)>

A cycloolefin polymer (A-1) was prepared according to Example 1, and a cycloolefin polymer (A-2) was prepared according to Example 4.

〈Preparation of radiation-sensitive resin composition (radiation-sensitive resin liquid)〉

25 parts (equivalent to the amount of solid components) of a polymer solution of a cycloolefin polymer (A-1), 30 parts (equivalent to the amount of solid components) of a polymer solution of a cycloolefin polymer (A-2), 45 parts of a cresol novolac resin (B-2), 30 parts of an acid generator (C-1), 35 parts of a crosslinking agent (D-1), 10 parts of a crosslinking agent (D-4), and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. The amount of diethylene glycol methyl ethyl ether used was determined to be an amount at which the solid content concentration was 40% by mass. The obtained solution was then filtered through a polytetrafluoroethylene filter having a pore size of 0.45 μm to prepare a resin composition. The obtained resin composition was used for various evaluations. The results are shown in Table 1.

(Example 6)

<Preparation of Cycloolefin Polymer (A-1)>

According to Example 1, a cycloolefin polymer (A-1) was prepared.

〈Preparation of radiation-sensitive resin composition (radiation-sensitive resin liquid)〉

60 parts of the polymer solution of the cycloolefin polymer (A-1) (equivalent to the amount of the solid content), 20 parts of a cresol novolac resin (B-2), 20 parts of a cresol novolac resin (B-3) (manufactured by Asahi Organic Materials Co., Ltd., product name "SE3010", weight average molecular weight: 5000, softening point: 155°C, condensation product of m-cresol/p-cresol = 70/30 (molar ratio) and formaldehyde, m/p ratio: about 2.3), 30 parts of an acid generator (C-1), 30 parts of a crosslinking agent (D-1), 15 parts of a crosslinking agent (D-6) (manufactured by Asahi Organic Materials Co., Ltd., product name "HMX-PA", 4,4′-[1-(4-{1-[4-hydroxy-3,5-bis(methoxymethyl)phenyl]-1-methylethyl}phenyl)ethylidene]bis[2,6-bis(methoxymethyl)phenol]) and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. The amount of diethylene glycol methyl ethyl ether used was determined to be an amount that gave a solid content concentration of 40% by mass. The obtained solution was then filtered through a polytetrafluoroethylene filter having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. The results are shown in Table 1.

(Example 7)

〈Preparation of Cycloolefin Polymer (A-3)〉

A cycloolefin polymer (A-3) having a protonic polar group was prepared in the same manner as the cycloolefin polymer (A-1) except that NBPI was not used, N-(2-ethylhexyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboximide (NEHI) was adjusted to 40 mol % and TCDC was adjusted to 60 mol %. The polymerization conversion of the obtained cycloolefin polymer (A-3) was 99.8% by mass, the weight average molecular weight (polystyrene conversion) was 8500, the number average molecular weight was 5800, the molecular weight distribution was 1.47, and the hydrogenation rate was 99.9%. In addition, the solid content concentration of the polymer solution of the obtained cycloolefin polymer (A-3) was 34.3% by mass.

<Preparation of Cycloolefin Polymer (A-4)>

100 parts by mass of a monomer mixture consisting of 16 mol% of NBPI, 16 mol% of NEHI and 68 mol% of TCDC, 1.0 part by mass of 1-hexene, 0.06 part by mass of dichloro[1,3-bis(1,3,5-trimethylphenyl)imidazolin-2-ylidene](tricyclohexylphosphine)benzylideneruthenium and 300 parts by mass of diethylene glycol methyl ethyl ether were placed in a nitrogen-purged glass pressure reactor and reacted at 80°C for 4 hours while stirring to obtain a polymerization reaction solution.

Then, the obtained polymerization reaction liquid was placed in an autoclave and stirred at 150°C and a hydrogen pressure of 4 MPa for 5 hours to carry out a hydrogenation reaction, thereby obtaining a polymer solution containing a cycloolefin polymer (A-4) having a protonic polar group. The obtained cycloolefin polymer (A-4) had a polymerization conversion of 99.3% by mass, a weight average molecular weight (polystyrene conversion) of 20,600, a number average molecular weight of 11,500, a molecular weight distribution of 1.79, and a hydrogenation rate of 99.8%. In addition, the solid content concentration of the obtained cycloolefin polymer (A-4) polymer solution was 25.3% by mass.

〈Preparation of radiation-sensitive resin composition (radiation-sensitive resin liquid)〉

20 parts (equivalent to the amount of solid content) of a polymer solution of a cycloolefin hydrocarbon polymer (A-3), 30 parts (equivalent to the amount of solid content) of a polymer solution of a cycloolefin hydrocarbon polymer (A-4), 50 parts of a cresol novolac resin (B-4) (produced by Asahi Organic Materials Co., Ltd., product name "EP4050G", weight average molecular weight: 7600, softening point: 156°C, m-cresol/p-cresol = 60/40 (molar ratio) and formaldehyde condensation product, m/p ratio: 1.5), and an acid generator (C-1) were added. 30 parts, 15 parts of a crosslinking agent (D-1), 15 parts of a crosslinking agent (D-2) (manufactured by Nissan Chemical Industries, Ltd., product name "TEPIC-S", tris(2,3-epoxypropyl)isocyanurate (tris(epoxypropyl)isocyanurate)) 15 parts, 10 parts of a crosslinking agent (D-7) (manufactured by Honshu Chemical Industries, Ltd., product name "TMOM-BP", 3,3',5,5'-tetramethoxymethyl-4,4'-dihydroxybiphenyl), and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. The amount of diethylene glycol methyl ethyl ether used was set to an amount that the solid content concentration was 40 mass %. Subsequently, the obtained solution was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare a resin composition. The obtained resin composition was used to perform various evaluations. The results are shown in Table 1.

(Example 8)

<Preparation of Cycloolefin Polymers (A-2) and (A-4)>

A cycloolefin polymer (A-2) was prepared according to Example 4, and a cycloolefin polymer (A-4) was prepared according to Example 7.

〈Preparation of radiation-sensitive resin composition (radiation-sensitive resin liquid)〉

30 parts (equivalent to the amount of the solid content) of a polymer solution of a cycloolefin polymer (A-2), 30 parts (equivalent to the amount of the solid content) of a polymer solution of a cycloolefin polymer (A-4), 40 parts of a cresol novolac resin (B-1), 30 parts of an acid generator (C-1), 15 parts of a crosslinking agent (D-1), 15 parts of a crosslinking agent (D-3) (manufactured by DAICEL, product name "EHPE3150", 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-di(hydroxymethyl)-1-butanol), 10 parts of a crosslinking agent (D-6) and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. In addition, the amount of diethylene glycol methyl ethyl ether used was set to an amount in which the solid content concentration was 40 mass %. Subsequently, the obtained solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. The results are shown in Table 1.

(Example 9)

The cycloolefin polymer (A-1) and the resin composition were prepared in the same manner as in Example 1, except that the amount of the cycloolefin polymer (A-1) was changed from 75 parts to 15 parts (equivalent to the amount of the solid component) and the amount of the cresol novolac resin (B-1) was changed from 25 parts to 85 parts during the preparation of the resin composition, and various evaluations were performed. The results are shown in Table 2.

(Example 10)

Cycloolefin polymer (A-2) and resin composition were prepared in the same manner as in Example 4, except that the amount of cycloolefin polymer (A-2) was changed from 50 parts to 85 parts (corresponding to the amount equivalent to the solid component), the amount of cresol novolac resin (B-2) was changed from 50 parts to 15 parts, and the amount of crosslinking agent (D-1) was changed from 37 parts to 35 parts during the preparation of the resin composition, and various evaluations were performed. The results are shown in Table 2.

(Comparison Example 1)

<Preparation of Cycloolefin Polymer (A-1)>

According to Example 1, a cycloolefin polymer (A-1) was prepared.

〈Preparation of radiation-sensitive resin composition (radiation-sensitive resin liquid)〉

100 parts (relative to the amount of solid components) of a polymer solution of a cycloolefin polymer (A-1), 28 parts of an acid generator (C-1), 35 parts of a crosslinking agent (D-1), 15 parts of a crosslinking agent (D-4) and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. In addition, the amount of diethylene glycol methyl ethyl ether used was determined to be an amount that gave a solid component concentration of 40% by mass. Subsequently, the obtained solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.45 μm to prepare a resin composition. The obtained resin composition was used for various evaluations. The results are shown in Table 2.

(Comparison Example 2)

100 parts of cresol novolac resin (B-4), 25 parts of acid generator (C-1), 30 parts of crosslinking agent (D-1), 10 parts of crosslinking agent (D-7) and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. In addition, the amount of diethylene glycol methyl ethyl ether used was determined to be an amount that the solid content concentration was 40% by mass. Subsequently, the obtained solution was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. The results are shown in Table 2.

(Comparison Example 3)

〈Preparation of Cycloolefin Polymer (A-3)〉

According to Example 7, a cycloolefin polymer (A-3) was prepared.

〈Preparation of radiation-sensitive resin composition (radiation-sensitive resin liquid)〉

50 parts of a polymer solution of a cycloolefin polymer (A-3) (in terms of the amount of the solid content), 50 parts of a cresol novolac resin (B-5) (manufactured by Asahi Organic Materials Co., Ltd., product name "EP6040A", weight average molecular weight: 2600, softening point: 130°C, a condensation product of m-cresol/p-cresol = 40/60 (molar ratio) and formaldehyde, m/p ratio: about 0.67), 28 parts of an acid generator (C-1), 35 parts of a crosslinking agent (D-1), 10 parts of a crosslinking agent (D-3), 10 parts of a crosslinking agent (D-6), and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. The amount of diethylene glycol methyl ethyl ether used was set to an amount in which the solid content concentration was 40% by mass. Subsequently, the obtained solution was filtered through a polytetrafluoroethylene filter with a pore size of 0.45 μm to prepare a resin composition. The obtained resin composition was used to perform various evaluations. The results are shown in Table 2.

(Comparison Example 4)

<Preparation of Cycloolefin Polymer (A-1)>

According to Example 1, a cycloolefin polymer (A-1) was prepared.

〈Preparation of radiation-sensitive resin composition (radiation-sensitive resin liquid)〉

50 parts of a polymer solution of a cycloolefin polymer (A-1) (equivalent to the amount of the solid component), 50 parts of a cresol novolac resin (B-1), 30 parts of an acid generator (C-1) and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. In addition, the amount of diethylene glycol methyl ethyl ether used was determined to be an amount that gave a solid component concentration of 40% by mass. Subsequently, the obtained solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.45 μm to prepare a resin composition. The obtained resin composition was used for various evaluations. The results are shown in Table 2.

(Comparison Example 5)

<Preparation of Cycloolefin Polymer (A-1)>

According to Example 1, a cycloolefin polymer (A-1) was prepared.

〈Preparation of radiation-sensitive resin composition (radiation-sensitive resin liquid)〉

60 parts (equivalent to the amount of solid content) of a polymer solution of a cycloolefin polymer (A-1), 40 parts of a phenol novolac resin (manufactured by Asahi Organic Materials Co., Ltd., product name "PAPS-PN4", Mw: 1300, softening point: 110°C), 30 parts of an acid generator (C-1), 30 parts of a crosslinking agent (D-2), 10 parts of a crosslinking agent (D-7), and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. The amount of diethylene glycol methyl ethyl ether used was determined to be an amount in which the solid content concentration was 40% by mass. The obtained solution was then filtered through a polytetrafluoroethylene filter having a pore size of 0.45 μm to prepare a resin composition. The obtained resin composition was used to perform various evaluations. The results are shown in Table 2.

(Comparison Example 6)

〈Preparation of radiation-sensitive resin composition (radiation-sensitive resin liquid)〉

50 parts of cresol novolac resin (B-1), 50 parts of polyvinyl phenol resin (manufactured by Maruzen Petrochemical Co., Ltd., product name "S-2P"), 28 parts of acid generator (C-1), 30 parts of crosslinking agent (D-1), 10 parts of crosslinking agent (D-5) and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. In addition, the amount of diethylene glycol methyl ethyl ether used was determined to be an amount that the solid content concentration was 40% by mass. Subsequently, the obtained solution was filtered with a polytetrafluoroethylene filter having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. The results are shown in Table 2.

In addition, in Tables 1 to 2 shown below, "mC/pC/mX" represents m-cresol/p-cresol/m-xylenol (molar ratio), "mC/pC" represents m-cresol/p-cresol (molar ratio), "epoxy" represents a polyfunctional epoxy compound, and "methoxymethyl" represents a polyfunctional methoxymethyl (alkoxymethyl) compound.

『Table 1』 Embodiment 8 ― 30 ― 30 40 ― ― ― ― ― ― 30 15 ― 15 ― ― 10 ― A A A A Embodiment 7 ― ― 20 30 ― ― ― 50 ― ― ― 30 15 15 ― ― ― ― 10 A A A B Embodiment 6 60 ― ― ― ― 20 20 ― ― ― ― 30 30 ― ― ― ― 15 ― A A A A Embodiment 5 25 30 ― ― ― 45 ― ― ― ― ― 30 35 ― ― 10 ― ― ― A A A A Embodiment 4 ― 50 ― ― ― 50 ― ― ― ― ― 30 37 ― ― ― 10 ― ― A A A A Embodiment 3 30 ― ― ― 70 ― ― ― ― ― ― 30 30 ― ― 10 ― ― ― A A A A Embodiment 2 55 ― ― ― 45 ― ― ― ― ― ― 30 35 ― ― 10 ― ― ― A A A A Embodiment 1 75 ― ― ― 25 ― ― ― ― ― ― 30 30 ― ― 10 ― ― ― A A A A Softening point[℃] 163 167 155 156 130 110 Relative dielectric constant Top loss Chemical resistance Heat flow resistance Mw [－] 7200 7300 8500 20600 7000 9000 5000 7600 2600 1300 m/p ratio [-] 2.3 2.3 2.3 1.5 0.67 (A-1) (A-2) (A-3) (A-4) mC/pC/mX =60/30/10 mC/pC=70/30 mC/pC=60/40 mC/pC=40/60 Phenol novolac resin Polyvinyl phenol resin (C-1) Epoxy Methoxymethyl (B-1) (B-2) (B-3) (B-4) (B-5) (D-1) (D-2) (D-3) (D-4) (D-5) (D-6) (D-7) Cycloolefin polymer (A) Cresol Novolac Resin (B) Acid generator (C) Crosslinking agent (D)

Table 2 Comparative Example 6 ― ― ― ― 50 ― ― ― ― ― 50 28 30 ― ― ― 10 ― ― A B A C Comparison Example 5 60 ― ― ― ― ― ― ― ― 40 ― 30 ― 30 ― ― ― ― 10 A C A C Comparison Example 4 50 ― ― ― 50 ― ― ― ― ― ― 30 ― ― ― ― ― ― ― A A C C Comparison Example 3 ― ― 50 ― ― ― ― ― 50 ― ― 28 35 ― 10 ― ― 10 ― A B A C Comparison Example 2 ― ― ― ― ― ― ― 100 ― ― ― 25 30 ― ― ― ― ― 10 C A A C Comparison Example 1 100 ― ― ― ― ― ― ― ― ― ― 28 35 ― ― 15 ― ― ― A C A A Embodiment 10 ― 85 ― ― ― 15 ― ― ― ― ― 30 35 ― ― ― 10 ― ― A B A A Embodiment 9 15 ― ― ― 85 ― ― ― ― ― ― 30 30 ― ― 10 ― ― ― B A A A Softening point[℃] 163 167 155 156 130 110 Relative dielectric constant Top loss Chemical resistance Heat flow resistance Mw [－] 7200 7300 8500 20600 7000 9000 5000 7600 2600 1300 m/p ratio [-] 2.3 2.3 2.3 1.5 0.67 (A-1) (A-2) (A-3) (A-4) mC/pC/mX =60/30/10 mC/pC=70/30 mC/pC=60/40 mC/pC=40/60 Phenol novolac resin Polyvinyl phenol resin (C-1) Epoxy Methoxymethyl (B-1) (B-2) (B-3) (B-4) (B-5) (D-1) (D-2) (D-3) (D-4) (D-5) (D-6) (D-7) Cycloolefin polymer (A) Cresol Novolac Resin (B) Acid generator (C) Crosslinking agent (D)

As shown in Tables 1 to 2, when the resin composition of Examples 1 to 10 including a cycloolefin polymer (A) having a protonic polar group, a cresol novolac resin (B) having a softening point of 140°C or higher, an acid generator (C) and a crosslinking agent (D) is used, a resin film having a suppressed top loss of a line pattern and excellent heat flow resistance can be formed. In addition, it can be seen that in Examples 1 to 10, a resin film having a low relative dielectric constant and excellent chemical resistance can be formed.

On the other hand, the following can be seen from Comparative Examples 1 to 6 in Table 2.

It is found that in Comparative Example 1 using a resin composition not containing cresol novolac resin (B), the top loss of the line pattern on the resin film cannot be suppressed.

It is found that in Comparative Example 2 using a resin composition not containing a cycloolefin polymer (A), the relative dielectric constant of the resin film increases and the heat flow resistance decreases.

It is found that in Comparative Example 3 using a resin composition including a cresol novolac resin but having a softening point of less than 140° C., the heat flow resistance of the resin film is reduced.

It is found that in Comparative Example 4 using a resin composition not containing a crosslinking agent (D), the chemical resistance and heat flow resistance of the resin film are reduced.

It is found that in Comparative Example 5 using a resin composition containing a phenol novolac resin but not containing a cresol novolac resin (B), the top loss of the line pattern on the resin film cannot be suppressed and the heat flow resistance of the resin film is reduced.

It is found that in Comparative Example 6 using a resin composition containing a polyvinylphenol resin but not containing a cycloolefin polymer (A), the heat flow resistance of the resin film is reduced.

According to the present invention, a radiation sensitive resin composition can be provided which can form a resin film having suppressed top loss of a line pattern and excellent heat flow resistance.

without.

without.

without.

Claims (5)

A radiation-sensitive resin composition, comprising a cycloolefin polymer (A) having a protonic polar group, a cresol novolac resin (B) having a softening point of 140°C or higher, an acid generator (C) and a crosslinking agent (D), wherein the proportion of the cycloolefin polymer (A) in the total of the cycloolefin polymer (A) and the cresol novolac resin (B) is 10% by mass or more and 75% by mass or less. The radiation-sensitive resin composition as described in claim 1, wherein the aforementioned cresol novolac resin (B) comprises a cresol skeleton and a xylenol skeleton. The radiation-sensitive resin composition as described in claim 1, wherein the acid generator (C) is a quinone diazide compound. The radiation-sensitive resin composition as described in claim 1, wherein the crosslinking agent (D) is at least one selected from the group consisting of a polyfunctional epoxy compound, a polyfunctional alkoxymethyl compound and a polyfunctional hydroxymethyl compound. A radiation-sensitive resin composition as described in any one of claims 1 to 4, wherein the molar ratio of the content of the meta-skeletal to the content of the para-skeletal in the skeleton derived from the cresol contained in the aforementioned cresol novolac resin (B) is 5.0 or less.