KR20220069932A - Radiation-sensitive resin composition - Google Patents

Abstract

An object of the present invention is to provide a radiation-sensitive resin composition capable of forming a resin film excellent in heat flow resistance while suppressing the top loss of a line pattern. The radiation-sensitive resin composition of the present invention contains a cyclic olefin polymer having a protonic polar group (A), a cresol novolac resin (B) having a softening point of 140°C or higher, an acid generator (C), and a crosslinking agent (D) do.

Description

Radiation-sensitive resin composition

The present invention relates to a radiation-sensitive resin composition.

In electronic components, such as an integrated circuit element, a solid-state image sensor, a color filter, various display elements (for example, organic electroluminescent element, liquid crystal display element), and a black matrix, the surface protection film for preventing the deterioration and damage, element surface However, various resin films such as a planarization film for flattening the wiring and an interlayer insulating film for insulating the wirings arranged in layers are formed.

Formation of such a resin film includes, for example, a resin component and a light beam exemplified by an actinic radiation (ultraviolet rays (including ultraviolet rays of a single wavelength such as g-ray or i-ray), KrF excimer laser light, and ArF excimer laser light; A radiation-sensitive resin composition (hereinafter, sometimes abbreviated as "resin composition") containing an acid generator that generates an acid upon irradiation with a particle beam exemplified by an electron beam has been conventionally used. Specifically, the radiation-sensitive film obtained by using the resin composition is irradiated with actinic radiation, and the exposed portion of the obtained exposure film is removed (developed) with a developer, etc., and the resin film having a desired pattern shape according to the use can be obtained

And conventionally, as a resin component of such a resin composition, the cyclic olefin polymer which has a protonic polar group is used (for example, refer patent documents 1-2).

Japanese Patent Laid-Open No. 2016-508759 International Publication No. 2015/141719

However, when a resin film having a fine line-and-space pattern shape is formed using a conventional resin composition comprising a cyclic olefin polymer having a protonic polar group, the height of the line pattern composed of the unexposed portion is not a pattern-free minnow. There were cases where it became smaller than the miner's height (that is, a top loss of the line pattern occurred).

In general, in forming a resin film using a resin composition, heat treatment is sometimes performed for the purpose of thermal curing after exposure and development, but in such heat treatment, the desired pattern shape formed by exposure and development This may be damaged. Therefore, it was calculated|required by the resin film formed using the resin composition to improve the property (thermal flow resistance) which maintains a desired pattern shape even when it forms through heat processing.

Accordingly, an object of the present invention is to provide a radiation-sensitive resin composition capable of forming a resin film excellent in heat flow resistance while suppressing the top loss of a line pattern.

MEANS TO SOLVE THE PROBLEM This inventor earnestly examined for the purpose of solving the said subject. The present inventors, as a resin component, in addition to the cyclic olefin polymer having a protonic polar group, contain a cresol novolac resin having a softening point of a predetermined value or more, and use a resin composition further containing an acid generator and a crosslinking agent. When the resin film was formed, it was discovered that heat flow resistance could be improved while suppressing the top loss of the line pattern, and the present invention was completed.

That is, this invention aims at solving the said subject advantageously, and the radiation-sensitive resin composition of this invention is a cyclic olefin polymer (A) which has a protonic polar group, and a cresol novolak whose softening point is 140 degreeC or more. It is characterized in that it contains a resin (B), an acid generator (C), and a crosslinking agent (D). When the resin composition containing the components of (A)-(D) mentioned above is used, while the top loss of a line pattern is suppressed, the resin film excellent in heat flow resistance can be formed.

In addition, in this invention, "softening point" can be measured by the ring-ball method described in JISK6910:2007.

Here, in the radiation-sensitive resin composition of the present invention, it is preferable that the cresol novolac resin (B) contains a cresol skeleton and a xylenol skeleton. When the cresol novolac resin (B) containing a skeleton derived from cresol and a skeleton derived from xylenol is used, the thermal flow resistance of the resin film can be further improved.

Moreover, in the radiation-sensitive resin composition of this invention, it is preferable that the said acid generator (C) is a quinonediazide compound. When a quinonediazide compound is used as the acid generator (C), the resolution of the line-and-space pattern formed in the resin film can be improved.

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

Incidentally, in the radiation-sensitive resin composition of the present invention, the ratio of the cyclic olefin polymer (A) in the total of the cyclic olefin polymer (A) and the cresol novolac resin (B) is 10 mass% or more and 90 It is preferable that it is mass % or less. When the cyclic olefin polymer (A) and the cresol novolac resin (B) are used in the above-mentioned ratio, the top loss of the line pattern formed on the resin film can be further suppressed while reducing the dielectric constant of the resin film.

Further, in the radiation-sensitive resin composition of the present invention, in the skeleton derived from the cresols contained in the cresol novolac resin (B), the molar ratio of the content of the meta skeleton to the content of the para-body skeleton (that is, m /p ratio) is preferably 5.0 or less. In the skeleton derived from cresols, when a cresol novolac resin (B) in which the ratio of the content derived from the meta body to the content of the skeleton derived from the para body is 5.0 or less on a molar basis is used, the line in the resin film Thermal flow resistance can be further improved while further suppressing the top loss of a pattern.

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

ADVANTAGE OF THE INVENTION According to this invention, while suppressing the top loss of a line pattern, the radiation-sensitive resin composition which can form the resin film excellent in heat flow resistance can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

The radiation-sensitive resin composition of the present invention can be used for the formation of a resin film, and the resin film is, for example, used as a surface protective film, a planarization film, an interlayer insulating film, etc. in an electronic component manufactured by wafer level packaging technology. can

The radiation-sensitive resin composition of the present invention contains a cyclic olefin polymer having a protonic polar group (A), 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, a solvent or other compounding agent.

And, the radiation-sensitive resin composition of the present invention contains, as a resin component, an acid generator (C) and a crosslinking agent (D) while including the above-mentioned cyclic olefin polymer (A) and cresol novolac resin (B). Therefore, when the said resin composition is used, while the top loss of a line pattern is suppressed, the resin film excellent in heat flow resistance can be formed.

<Cyclic Olefin Polymer (A)>

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

<<Protonic polar group>>

Cyclic olefin polymer (A) has solubility with respect to a developing solution (particularly, the alkali developing solution mentioned later) by providing a protonic polar group. In addition, since the protonic polar group reacts with the crosslinking agent (D) during thermal curing, and the resin component such as the cyclic olefin polymer (A) can take a strong crosslinked structure, the resin film has excellent thermal flow resistance and chemical resistance can be given

Here, the protonic polar group refers to a group containing an atom belonging to Group 15 or Group 16 of the periodic table to which a hydrogen atom is directly bonded. The atom belonging to Group 15 or 16 of the periodic table is preferably an atom belonging to the second or third period of Group 15 or 16 of the periodic table, more preferably an oxygen atom, a nitrogen atom or a sulfur atom; Especially preferably, it is an oxygen atom.

Specific examples of the protonic polar group include a polar group having an oxygen atom such as a hydroxyl group, a carboxyl group (hydroxycarbonyl group), a sulfonic acid group, and a phosphoric acid group; polar groups having a nitrogen atom, such as a primary amino group, a secondary amino group, a primary amide group, and a secondary amide group (imide group); and polar groups having a sulfur atom such as a thiol group. Among these, the polar group which has an oxygen atom is preferable, a carboxyl group and a hydroxyl group are more preferable, and a carboxyl group is still more preferable.

In addition, the cyclic olefin polymer (A) may have only 1 type of protonic polar group, and may have it 2 or more types.

<<Composition>>

In addition, the method of introduce|transducing the above-mentioned protonic polar group into the cyclic olefin polymer (A) is not specifically limited. That is, the cyclic olefin polymer (A) contains, for example, a repeating unit derived from a cyclic olefin monomer (a) having a protonic polar group, and optionally a repeating unit derived from another monomer (b). The polymer containing may be sufficient, and the polymer formed by introduce|transducing a protonic polar group using a modifier to the cyclic olefin polymer which does not have a protonic polar group may be sufficient, but the former is preferable.

[Cyclic olefin monomer (a) having a protic polar group]

The cyclic olefin monomer (a) having a protonic polar group is not particularly limited as long as it is a monomer having the above-described protonic polar group and a cyclic olefin structure. For example, a cyclic olefin monomer having a carboxyl group, a ring having a hydroxyl group A type olefin monomer is mentioned preferably.

-Cyclic olefin monomer having a carboxyl group-

Examples of the cyclic olefin monomer having a carboxyl group include 2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2-hydroxycarbonylbicyclo[2.2.1] Hepto-5-ene, 2-carboxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-methoxycarbonylmethylbicyclo[2.2.1 ]hepto-5-ene, 2-hydroxycarbonyl-2-ethoxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-propoxycarbonylmethylbicyclo [2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-butoxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-pentyloxycar Bornylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-hexyloxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl- 2-cyclohexyloxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-phenoxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2 -Hydroxycarbonyl-2-naphthyloxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-biphenyloxycarbonylmethylbicyclo[2.2.1]hepto -5-ene, 2-hydroxycarbonyl-2-benzyloxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-2-hydroxyethoxycarbonylmethylbicyclo [2.2.1]hepto-5-ene, 2,3-dihydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-methoxycarbonylbicyclo[2.2 .1]hepto-5-ene, 2-hydroxycarbonyl-3-ethoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-propoxycarbonylbicyclo [2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-butoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-pentyloxycarbo Nylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-hexyloxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-cyclohex Siloxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-phenoxycarbonylbicy Chlo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-naphthyloxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-biphenyl Oxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-benzyloxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3 -Hydroxyethoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarbonyl-3-hydroxycarbonylmethylbicyclo[2.2.1]hepto-5-ene, 3-methyl -2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 3-hydroxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-hydroxycarr Bornyltricyclo[5.2.1.0 ^2,6 ]deca-3,8-diene, 4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, 4-methyl -4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, 4,5-dihydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2 ,7} ]dodeca-9-ene, 4-carboxymethyl-4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, N-(hydroxycarbonyl methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(hydroxycarbonylethyl)bicyclo[2.2.1]hepto-5-ene-2,3-di Carboxyimide, N-(hydroxycarbonylpentyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(dihydroxycarbonylethyl)bicyclo[2.2.1] Hepto-5-ene-2,3-dicarboxyimide, N-(dihydroxycarbonylpropyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(hydroxy Carbonylphenethyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(2-(4-hydroxyphenyl)-1-(hydroxycarbonyl)ethyl)bi Cyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(hydroxycarbonylphenyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide can be heard

-Cyclic olefin monomer having a hydroxyl group-

Examples of the cyclic olefin monomer having a hydroxyl group include 2-(4-hydroxyphenyl)bicyclo[2.2.1]hepto-5-ene, 2-methyl-2-(4-hydroxyphenyl)bi Cyclo[2.2.1]hepto-5-ene, 4-(4-hydroxyphenyl)tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-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]hepto-5-ene, 2-hydroxymethyl Bicyclo[2.2.1]hepto-5-ene, 2-hydroxyethylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2-hydroxymethylbicyclo[2.2.1]hepto-5 -ene, 2,3-dihydroxymethylbicyclo[2.2.1]hepto-5-ene, 2-(hydroxyethoxycarbonyl)bicyclo[2.2.1]hepto-5-ene, 2-methyl -2-(Hydroxyethoxycarbonyl)bicyclo[2.2.1]hepto-5-ene, 2-(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) Bicyclo[2.2.1]hepto-5-ene, 2-(2-hydroxy-2-trifluoromethyl-3,3,3-trifluoropropyl)bicyclo[2.2.1]hepto-5- N, 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-hydro hydroxytetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, 4-hydroxymethyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, 4,5-dihydroxymethyltetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, 4-(hydroxyethoxycarbonyl)tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodeca-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]hepto-5-ene-2,3-dicarboxyimide, N-(hydroxyphenyl)bicyclo[2.2.1]hepto-5-ene-2,3- and dicarboxyimide.

Among these, a cyclic olefin monomer having a carboxyl group is preferable, and 4-hydroxycarbonyltetracyclo[ 6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene is more preferred. In addition, a cyclic olefin monomer (a) may be used individually by 1 type, and may be used in combination of 2 or more type.

-Content Ratio-

In addition, the content rate of the repeating unit derived from the cyclic olefin monomer (a) in the cyclic olefin polymer (A) is 100 mol% of all repeating units, It is preferable that it is 10 mol% or more, and it is 20 mol% More preferably, it is more preferably 30 mol% or more, more preferably 90 mol% or less, more preferably 80 mol% or less, and still more preferably 70 mol% or less. When the ratio of the repeating unit derived from the cyclic olefin monomer (a) is 10 mol% or more, the heat flow resistance of the resin film can be further improved, and when it is 90 mol% or less, the dielectric constant of the resin film can be reduced.

[Other monomers (b)]

As another monomer (b), if it is a monomer copolymerizable with the above-mentioned cyclic olefin monomer (a), it will not specifically limit. Examples of the monomer copolymerizable with the cyclic olefin monomer (a) include a cyclic olefin monomer having a polar group other than a protonic polar group (b1), a cyclic olefin monomer having no polar group (b2), and a monomer other than a cyclic olefin ( b3) can be mentioned.

-monomer (b1)-

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

Examples of the cyclic olefin 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).

[Formula 1]

[In formula (1), R ² represents an alkyl group or an aryl group having 1 to 16 carbon atoms, and n represents 1 or 2.]

[Formula 2]

[In formula (2), R ³ is a divalent alkylene group having 1 to 3 carbon atoms, R ⁴ is a monovalent alkyl group having 1 to 10 carbon atoms or monovalent halogenation having 1 to 10 carbon atoms represents an alkyl group. In addition, two R< ⁴ > may be same or different.]

In formula (1), as the C1-C16 alkyl group of R< ² >, For example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n -heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexa straight-chain alkyl groups such as a decyl group; Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cycloundecyl group, cyclododecyl group, norbornyl group, bornyl group, isobornyl group , a cyclic alkyl group such as a decahydronaphthyl group, a tricyclodecanyl group, and an adamantyl group; 2-propyl group, 2-butyl group, 2-methyl-1-propyl group, 2-methyl-2-propyl group, 1-methylbutyl group, 2-methylbutyl group, 1-methylpentyl group, 1-ethylbutyl group branched alkyl groups such as group, 2-methylhexyl group, 2-ethylhexyl group, 4-methylheptyl group, 1-methylnonyl group, 1-methyltridecyl group and 1-methyltetradecyl group;

In Formula (1), as an aryl group of R< ² >, a benzyl group is mentioned, for example.

Among these, from the viewpoint of improving the solubility of the cyclic olefin polymer (A) in a solvent and further improving the heat flow resistance of the resin film, an alkyl group and an aryl group having 4 or more and 14 or less carbon atoms are preferable, and the number of carbon atoms is preferable. 6 or more and 10 or less alkyl groups and aryl groups are more preferable.

And, as a specific example of the monomer represented by Formula (1), bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-phenyl-bicyclo[2.2.1]hepto- 5-ene-2,3-dicarboxyimide, N-methylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-ethylbicyclo[2.2.1]hepto-5- ene-2,3-dicarboxyimide, N-propylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-butylbicyclo[2.2.1]hepto-5-ene- 2,3-dicarboxyimide, N-cyclohexylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-adamantylbicyclo[2.2.1]hepto-5-ene- 2,3-Dicarboxyimide, N-(1-methylbutyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(2-methylbutyl)-bicyclo[ 2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(1-methylpentyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N- (2-Methylpentyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(1-ethylbutyl)-bicyclo[2.2.1]hepto-5-ene- 2,3-Dicarboxyimide, N-(2-ethylbutyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(1-methylhexyl)-bicyclo[ 2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(2-methylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N- (3-Methylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(1-butylpentyl)-bicyclo[2.2.1]hepto-5-ene- 2,3-Dicarboxyimide, N-(2-Butylpentyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(1-methylheptyl)-bicyclo[ 2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(2-methylheptyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N- (3-Methylheptyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(4-methylheptyl)-bicyclo[2.2.1]hepto-5-ene- 2,3-dicarboxyimide, N-(1-ethylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3- Dicarboxyimide, N-(2-ethylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(3-ethylhexyl)-bicyclo[2.2.1] Hepto-5-ene-2,3-dicarboxyimide, N-(1-propylpentyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(2-propyl Pentyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(1-methyloctyl)-bicyclo[2.2.1]hepto-5-ene-2,3- Dicarboxyimide, N-(2-methyloctyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(3-methyloctyl)-bicyclo[2.2.1] Hepto-5-ene-2,3-dicarboxyimide, N-(4-methyloctyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(1-ethyl Heptyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(2-ethylheptyl)-bicyclo[2.2.1]hepto-5-ene-2,3- Dicarboxyimide, N-(3-ethylheptyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(4-ethylheptyl)-bicyclo[2.2.1] Hepto-5-ene-2,3-dicarboxyimide, N-(1-propylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(2-propyl Hexyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(3-propylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3- Dicarboxyimide, N-(1-methylnonyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(2-methylnonyl)-bicyclo[2.2.1] Hepto-5-ene-2,3-dicarboxyimide, N-(3-methylnonyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(4-methyl Nonyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(5-methylnonyl)-bicyclo[2.2.1]hepto-5-ene-2,3- Dicarboxyimide, N-(1-ethyloctyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(2-ethyloctyl)-bicyclo[2.2.1] Hepto-5-ene-2,3-dicarboxyimide, N-(3-ethyloctyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyi Mead, N-(4-ethyloctyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(1-methyldecyl)-bicyclo[2.2.1]hepto- 5-ene-2,3-dicarboxyimide, N-(1-methyldodecyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(1-methylunde syl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(1-methyltridecyl)-bicyclo[2.2.1]hepto-5-ene-2,3 -dicarboxyimide, N-(1-methyltetradecyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(1-methylpentadecyl)-bicyclo[2.2 .1]hepto-5-ene-2,3-dicarboxyimide, N-phenyl-tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene-4,5-dicarboxyimide , N-(2,4-dimethoxyphenyl)-tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene-4,5-dicarboxyimide.

In Formula (2), as a C1-C3 divalent alkylene group of R< ³ >, a methylene group, an ethylene group, a propylene group, and an isopropylene group are mentioned. Among these, since polymerization activity is favorable, a methylene group and an ethylene group are preferable.

In formula (2), as a C1-C10 monovalent|monohydric alkyl group of R< ⁴ >, For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert- butyl group , a hexyl group and a cyclohexyl group are mentioned.

In the formula (2), the monovalent halogenated alkyl group having 1 to 10 carbon atoms for R ⁴ is, for example, a fluoromethyl group, a chloromethyl group, a bromomethyl group, a difluoromethyl group, a dichloromethyl group, a trifluoro and a methyl group, trichloromethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, heptafluoropropyl group, perfluorobutyl group and perfluoropentyl group.

Among these, from the viewpoint of improving the solubility of the cyclic olefin polymer (A) in a solvent, R ⁴ is preferably a methyl group and an ethyl group.

In addition, the monomer represented by Formula (1), (2) can be obtained by the imidation reaction of a corresponding amine and 5-norbornene-2,3-dicarboxylic acid anhydride, for example. In addition, the obtained monomer can be efficiently isolated by isolate|separating and refine|purifying the reaction liquid of an imidation reaction by a known method.

Examples of the cyclic olefin monomer having an ester group include 2-acetoxybicyclo[2.2.1]hepto-5-ene, 2-acetoxymethylbicyclo[2.2.1]hepto-5-ene, 2 -Methoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-ethoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-propoxycarbonylbicyclo[2.2.1] Hepto-5-ene, 2-butoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-cyclohexyloxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2 -Methoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2-ethoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2-propoxycar Bornylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2-butoxycarbonylbicyclo[2.2.1]hepto-5-ene, 2-methyl-2-cyclohexyloxycarbonylbicyclo [2.2.1]hepto-5-ene, 2-(2,2,2-trifluoroethoxycarbonyl)bicyclo[2.2.1]hepto-5-ene, 2-methyl-2-(2, 2,2-trifluoroethoxycarbonyl)bicyclo[2.2.1]hepto-5-ene, 2-methoxycarbonyltricyclo[5.2.1.0 ^2,6 ]deca-8-ene, 2-e Toxycarbonyltricyclo[5.2.1.0 ^2,6 ]deca-8-ene, 2-propoxycarbonyltricyclo[5.2.1.0 ^2,6 ]deca-8-ene, 4-acetoxytetracyclo[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-ethoxycar Bornyltetracyclo[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-pro Foxycarbonyltetracyclo[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; have.

Examples of the cyclic olefin monomer having a cyano group include 4-cyanotetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, 4-methyl-4-cyanotetra Cyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, 4,5-dicyanotetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, 2 -Cyanobicyclo[2.2.1]hepto-5-ene, 2-methyl-2-cyanobicyclo[2.2.1]hepto-5-ene, 2,3-dicyanobicyclo[2.2.1]hepto- 5-yen.

Examples of the cyclic olefin monomer having an acid anhydride group include tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene-4,5-dicarboxylic acid anhydride, bicyclo[ 2.2.1]hepto-5-ene-2,3-dicarboxylic acid anhydride and 2-carboxymethyl-2-hydroxycarbonylbicyclo[2.2.1]hepto-5-ene anhydride.

Examples of the cyclic olefin monomer having a halogen atom include 2-chlorobicyclo[2.2.1]hepto-5-ene, 2-chloromethylbicyclo[2.2.1]hepto-5-ene, 2- (Chlorophenyl)bicyclo[2.2.1]hepto-5-ene, 4-chlorotetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene, 4-methyl-4-chlorotetra cyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-9-ene.

-monomer (b2)-

As the cyclic olefin monomer (b2) having no polar group, for example, bicyclo[2.2.1]hepto-2-ene (also referred to as “norbornene”), 5-ethyl-bicyclo[2.2.1 ]hepto-2-ene, 5-butyl-bicyclo[2.2.1]hepto-2-ene, 5-ethylidene-bicyclo[2.2.1]hepto-2-ene, 5-methylidene-bicyclo[ 2.2.1]hepto-2-ene, 5-vinyl-bicyclo[2.2.1]hepto-2-ene, tricyclo[5.2.1.0 ^2,6 ]deca-3,8-diene (common name: dicyclopenta diene), 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} ]dodeca- 4-ene (also called “tetracyclododecene”), 9-methyl-tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-ethyl-tetracyclo[6.2. 1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-methylidene-tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-ethylidene-tetra Cyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-vinyl-tetracyclo[6.2.1.1 ^{3,6.0 2,7} ]dodeca-4-ene, 9-pro Phenyl-tetracyclo[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-phenyl-tetracyclo[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.

-monomer (b3)-

As a monomer (b3) other than a cyclic olefin, For example, ethylene; Propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl- 1-Hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1- ?-olefins having 3 or more and 20 or less carbon atoms, such as dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; 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 these derivatives of;

Other monomers (b), such as above-mentioned monomer (b1) - (b3), may be used individually by 1 type, and may be used in combination of 2 or more type. And among these, from the viewpoint of further improving the heat flow resistance of the resin film, the cyclic olefin monomer (b1) having a polar group other than the protonic polar group is preferable, and the cyclic olefin monomer having an N-substituted imide group is more preferable. .

-Content Ratio-

And the content rate of the repeating unit derived from the other monomer (b) in the cyclic olefin polymer (A) makes all repeating units 100 mol%, It is preferable that it is 10 mol% or more, and it is 20 mol% or more. More preferably, it is more preferably 30 mol% or more, more preferably 90 mol% or less, more preferably 80 mol% or less, and still more preferably 70 mol% or less. When the ratio of the repeating unit derived from the other monomer (b) is 10 mol% or more, the dielectric constant of the resin film can be reduced, and when it is 90 mol% or less, the heat flow resistance of the resin film can be further improved.

<<Preparation method>>

The method of preparing the cyclic olefin polymer (A) which has a protonic polar group is not specifically limited, For example, the method of the following (i) and (ii):

(i) a method in which a monomer composition comprising a cyclic olefin monomer (a) having a protonic polar group and another monomer (b) optionally used is polymerized and optionally hydrogenated; or

(ii) A method of modifying a cyclic olefin polymer having no protonic polar group using a modifier having a protonic polar group

can be heard Among these, the method of (i) is preferable.

[Preparation method (i)]

The method of superposing|polymerizing a cyclic olefin monomer (a) and the monomer composition which optionally contains another monomer (b) is not specifically limited, A well-known method can be used. As a specific polymerization method, although ring-opening polymerization and addition polymerization are mentioned, for example, ring-opening polymerization is preferable. That is, it is preferable that it is a ring-opened polymer or an addition polymer, and, as for the cyclic olefin polymer (A), it is more preferable that it is a ring-opened polymer.

On the other hand, as a method of ring-opening polymerization, for example, in the presence of a metathesis reaction catalyst, a ring-opening polymerization of a cyclic olefin monomer (a) having a protonic polar group and other monomers used as necessary (b). Metathesis polymerization is mentioned. As a method of ring-opening metathesis polymerization, the method described in International Publication No. 2010/110323 can be employ|adopted, for example.

In addition, when ring-opening polymerization is used for preparation of the cyclic olefin polymer (A), it is preferable that the obtained ring-opened polymer is further subjected to a hydrogenation reaction to obtain a hydrogenated product in which the carbon-carbon double bond contained in the main chain is hydrogenated. . When the cyclic olefin polymer (A) is a hydrogenated product, the ratio of hydrogenated carbon-carbon double bonds (hydrogenation rate) is preferably 50% or more, and more preferably 70% or more, from the viewpoint of further improving the heat resistance of the resin film. Preferably, it is more preferably 90% or more, and particularly preferably 95% or more.

In addition, in this invention, "hydrogenation rate" can be measured using ¹ H-NMR spectrum.

[Preparation method (ii)]

The method of preparing the cyclic olefin polymer which does not have a protonic polar group is not specifically limited. The cyclic olefin polymer having no protonic polar group can be prepared by, for example, at least one of the above-mentioned monomers (b1) and (b2) and, if necessary, optionally combining the monomer (b3) and polymerization by a known method. can be obtained And the method of modifying|denaturing the obtained polymer using the modifier which has a protonic polar group should just follow a normal method, and is normally performed in presence of a radical generating agent.

On the other hand, 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, and specifically, those described in International Publication No. 2015/141717 can be used.

<<weight average molecular weight >>

The weight average molecular weight of the cyclic olefin polymer (A) is preferably 1000 or more, more preferably 3000 or more, still more preferably 5000 or more, preferably 100000 or less, more preferably 50000 or less, more preferably 30000 or less. desirable. The heat flow resistance of the said resin film can further be improved, suppressing the top loss of the line pattern in a resin film as the weight average molecular weight of a cyclic olefin polymer (A) is 1000 or more. Moreover, the chemical-resistance of a resin film can be improved. On the other hand, when the weight average molecular weight of the cyclic olefin polymer (A) is 100000 or less, the solubility of the cyclic olefin polymer (A) in a solvent can be sufficiently ensured.

On the other hand, in the present invention, the "weight average molecular weight" and "number average molecular weight" of the cyclic olefin polymer (A) are determined by gel permeation chromatography (GPC) using a solvent such as tetrahydrofuran as an eluent. , a value obtained as a polystyrene conversion value.

In addition, the weight average molecular weight and number average molecular weight of a cyclic olefin polymer (A) are controllable by adjusting synthetic|combination conditions (for example, the quantity of a molecular weight modifier).

<<Molecular weight distribution>>

Further, the molecular weight distribution (weight average molecular weight/number average molecular weight) of the cyclic olefin polymer (A) is preferably 4 or less, more preferably 3 or less, and still more preferably 2.5 or less. Thermal flow tolerance can further be improved, suppressing the top loss of the line pattern in a resin film as molecular weight distribution of a cyclic olefin polymer (A) is 4 or less further. Moreover, the chemical-resistance of a resin film can be improved.

On the other hand, the molecular weight distribution of a cyclic olefin polymer (A) can be reduced by the method of Unexamined-Japanese-Patent No. 2006-307155, for example.

<Cresol novolac resin (B)>

The resin composition of this invention contains the cresol novolac resin (B) whose softening point is 140 degreeC or more in addition to the above-mentioned cyclic olefin polymer (A) as a resin component. When the resin composition contains cresol novolac resin (B), it is possible to form a resin film having a line pattern in which top loss is suppressed.

Here, the cresol novolak resin (B) is a resin obtained by condensing phenols containing cresols and aldehydes.

<<Phenols including cresols>>

The phenols used for preparation of the cresol novolak resin (B) are not particularly limited as long as cresols are contained, and may be only cresols, and cresols and phenols other than cresols (hereinafter referred to as "other phenols") .) may be used together.

-Cresols-

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 not substituted. As cresols, for example, cresol (o-cresol, m-cresol, p-cresol), xylenol (2,5-xylenol (2,5-dimethylphenol), 3,5-xyle nol (3,5-dimethylphenol, etc.) and trimethylphenol (2,3,5-trimethylphenol, etc.) are mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type. And among these, from the viewpoint of further improving the thermal flow resistance of the resin film, it is preferable to use cresol and xylenol together, and it is more preferable to use m-cresol, p-cresol, and 3,5-xylenol together. desirable. In other words, the cresol novolac resin (B) is a skeleton derived from cresols, and preferably contains a cresol skeleton and a xylenol skeleton, m-cresol skeleton, p-cresol skeleton, 3,5- It is more preferable to include a xylenol skeleton.

In addition, when meta-form (m-cresol, 3,5-xylenol (m-xylenol)) and para-form (p-cresol) are used together as cresols, the cresol novolac resin (B) The molar ratio (m/p ratio) of the content of the meta-body skeleton (m-cresol skeleton, 3,5-xylenol skeleton) to the content of the para-body skeleton (p-cresol skeleton) in the skeleton derived from the cresols included. ) is preferably 0.5 or more, more preferably 1.0 or more, still more preferably 2.0 or more, particularly preferably 2.2 or more, preferably 5.0 or less, more preferably 4.0 or less, still more preferably 3.0 or less, It is especially preferable that it is 2.5 or less. Heat flow tolerance can be further improved, suppressing the top loss of the line pattern in a resin film as m/p ratio is in the above-mentioned range.

On the other hand, the ratio of cresols in the phenols used for the preparation of the cresol novolak resin (B) is preferably 50 mass% or more, more preferably 95 mass% or more, with the total amount of phenols being 100 mass%, It is more preferable that it is 97 mass % or more, and it is especially preferable that it is 100 mass % (that is, use only cresols as phenols).

-Other phenols-

As phenols other than the cresols mentioned above which can be used for preparation of cresol novolak resin (B), a monovalent|monohydric phenol compound and a dihydric or more phenolic compound (polyhydric phenol compound) are mentioned. In addition, other phenols may be used individually by 1 type, and may be used in combination of 2 or more type.

As a monovalent phenol compound, For example, phenol; 2-ethylphenol, 3-ethylphenol, 4-ethylphenol, 2-propylphenol, 3-propylphenol, 4-propylphenol, 2-t-butylphenol, 3-t-butylphenol, 4-t-butylphenol , 2,5-diethylphenol, 3,5-diethylphenol, 2-t-butyl-4-methylphenol, 2-t-butyl-5-methylphenol, 2-t-butyl-3-methylphenol, alkylphenols such as 2,3,5-triethylphenol; 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxy alkoxyphenols such as phenol; arylphenols such as 2-phenylphenol, 3-phenylphenol, and 4-phenylphenol; alkenylphenols such as 2-isopropenylphenol, 4-isopropenylphenol, 2-methyl-4-isopropenylphenol, and 2-ethyl-4-isopropenylphenol; and the like.

Examples of the dihydric or higher phenol compound include resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-methoxyresorcinol, and 4-methoxyresorcinol. lecinol; hydroquinone; catechol, 4-t-butylcatechol, 3-methoxycatechol; 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane; pyrogallol; Phloroglucinol; and the like.

<<Aldehydes>>

Examples of the aldehydes subjected to the condensation reaction with phenols including cresols described above include aliphatic aldehydes, alicyclic aldehydes and aromatic aldehydes.

-aliphatic aldehyde-

The aliphatic aldehydes include, for example, formaldehyde, trioxane (metaformaldehyde), paraformaldehyde, acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, trimethylacetaldehyde, n-hexylaldehyde, acrolein, Crotonaldehyde etc. are mentioned.

-alicyclic aldehyde-

Examples of the alicyclic aldehyde include cyclopentanaldehyde, cyclohexanealdehyde, furfural, and furyl acrolein.

-aromatic aldehyde-

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

The above-mentioned aldehydes may be used individually by 1 type, and may be used in combination of 2 or more type. And among these, an aliphatic aldehyde is preferable and formaldehyde is more preferable.

<<Preparation method>>

The cresol novolak resin (B) can be prepared by subjecting the phenols and aldehydes containing the cresols described above to a condensation reaction. This condensation reaction can be performed, for example by a known method using an acid catalyst. Examples of the acid catalyst to be used include hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, and p-toluenesulfonic acid.

<<Softening Point>>

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

In addition, although the upper limit of the softening point of cresol novolak resin (B) is not specifically limited, From a viewpoint of handleability, it is preferable that it is 300 degrees C or less.

In addition, the softening point of cresol novolac resin (B) is controllable by adjusting the kind of phenols and aldehydes used for a condensation reaction, and conditions of a condensation reaction.

<<weight average molecular weight >>

The weight average molecular weight of the cresol novolak resin (B) is preferably 1000 or more, more preferably 3000 or more, still more preferably 6000 or more, preferably 20000 or less, more preferably 15000 or less, more preferably 10000 or less desirable. When the weight average molecular weight is 1000 or more, the softening point becomes high and the heat flow resistance of the resin film can be further improved. Moreover, the top loss of the line pattern in a resin film can be suppressed further. On the other hand, when the weight average molecular weight is 20000 or less, the solubility of the cresol novolac resin (B) in the solvent can be sufficiently ensured.

On the other hand, in the present invention, the "weight average molecular weight" of the cresol novolac resin (B) is calculated as a polystyrene conversion value by gel permeation chromatography (GPC) using a solvent such as tetrahydrofuran as an eluent. is a losing value.

In addition, the weight average molecular weight of cresol novolak resin (B) is controllable by adjusting the kind of phenols and aldehydes used for a condensation reaction, and conditions of a condensation reaction.

<Content Ratio of Cyclic Olefin Polymer (A) and Cresol Novolac Resin (B)>

Here, the ratio of the cyclic olefin polymer (A) in the total of the above-mentioned cyclic olefin polymer (A) and the above-mentioned cresol novolak resin (B) is the cyclic olefin polymer (A) and the cresol novolac resin ( The total amount of B) is 100% by mass, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, preferably 90% by mass or less, and 80% by mass or less It is more preferable, and it is still more preferable that it is 75 mass % or less. When the ratio of the cyclic olefin polymer (A) in the total of the cyclic olefin polymer (A) and the cresol novolac resin (B) is 10 mass % or more, the dielectric constant of the resin film can be sufficiently reduced, and 90 mass % or less If it is the back surface, the top loss of the line pattern in a resin film can be suppressed further.

<Acid generator (C)>

An acid generator (C) is a compound which decomposes|disassembles by irradiation of actinic radiation, and generate|occur|produces acid components, such as carboxylic acid. And when the radiation-sensitive film|membrane formed using the resin composition of this invention containing an acid generator (C) is irradiated with actinic radiation, alkali solubility of an exposure part will increase.

Here, as the acid generator (C), for example, an azide compound, an onium salt compound, a halogenated organic compound, an α,α′-bis(sulfonyl)diazomethane compound, α-carbonyl-α′- sulfonyldiazomethane compounds, sulfone compounds, organic acid ester compounds, organic acid amide compounds, organic acid imide compounds, acetophenone compounds, and triarylsulfonium salts, but from the viewpoint of excellent resolution of the resulting line and space pattern, An azide compound is preferable and a quinonediazide compound is more preferable.

As a quinonediazide compound suitably used as an acid generator (C), the ester compound of the compound which has a quinonediazidesulfonic acid halide and a phenolic hydroxyl group can be used, for example. Here, as specific examples of the quinonediazidesulfonic acid halide, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-benzoquinonedia Zide-5-sulfonic acid chloride etc. are mentioned. Moreover, as a specific example of the compound which has a phenolic hydroxyl group, 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-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone , 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, an oligomer of a novolak resin, an oligomer obtained by copolymerizing a compound having one or more phenolic hydroxyl groups with dicyclopentadiene; and the like.

Among them, as the acid generator (C), 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1- The ester compound (condensate) of methylethyl]phenyl]ethylidene]bisphenol is preferable.

In addition, an acid generator (C) may be used individually by 1 type, and may be used in combination of 2 or more type.

<<Content content>>

The content of the acid generator (C) in the resin composition of the present invention is preferably 10 parts by mass or more, and 15 parts by mass per 100 parts by mass in total of the cyclic olefin polymer (A) and the cresol novolac resin (B). It is more preferable that it is more than, it is more preferable that it is 25 mass parts or more, It is especially preferable that it is 30 mass parts or more, It is preferable that it is 100 mass parts or less, It is more preferable that it is 70 mass parts or less, It is still more preferable that it is 50 mass parts or less. When the content of the acid generator (C) is 10 parts by mass or more per 100 parts by mass in total of the cyclic olefin polymer (A) and the cresol novolac resin (B), the solubility of the exposed part in the alkaline developer can be sufficiently improved. In addition, in forming a fine line-and-space pattern using the resin composition, there is a case where a slight amount of active radiation is applied to an unexposed portion, thereby generating a top loss of the line pattern. However, if the content of the acid generator (C) is 100 parts by mass or less per 100 parts by mass of the total of the cyclic olefin polymer (A) and the cresol novolac resin (B), the solubility in the alkali developer of the unexposed part is unexpectedly increased. There is no work, and the top loss of the line pattern which consists of an unexposed part can be suppressed further.

<Crosslinking agent (D)>

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

Here, the crosslinking agent (D) is particularly limited if it is a compound having two or more functional groups capable of reacting with the protonic polar group of the cyclic olefin polymer (A) and/or the hydroxyl group of the cresol novolak resin (B) in one molecule. However, polyfunctional epoxy compounds (compounds having two or more epoxy groups), polyfunctional alkoxymethyl compounds (compounds having two or more alkoxymethyl groups), and polyfunctional methylol compounds (compounds having two or more methylol groups) can be heard

In addition, a crosslinking agent (D) may be used individually by 1 type, and may be used in combination of 2 or more type.

<<polyfunctional epoxy compound>>

Examples of the polyfunctional epoxy compound include tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, and 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-epoxypropoxy)phenyl ]Propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4- Epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol A diglycidyl ether, pentaerythritol polyglycidyl ether, epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) formula and the 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of ε-caprolactone and 2,2-bis(hydroxymethyl)-1-butanol.

In addition, as a commercial item of polyfunctional epoxy compound, For example, Epolide (trademark) GT401, Epolide PB3600, Epolide PB4700, Celoxide (trademark) 2021, Celoxide 3000, EHPE3150 (above, Daicel Corporation make) ); jER1001, jER1002, jER1003, jER1004, jER1007, jER1009, jER1010, jER828, jER871, jER872, jER180S75, jER807, jER152, jER154 (above, manufactured by Mitsubishi Chemical Corporation); EPPN201, EPPN202, EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, manufactured by Nippon Kayaku Co., Ltd.); Epiclone (registered trademark) 200, Epiclone 400 (above, manufactured by DIC); 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, and denacol EX-321 (above, manufactured by Nagase Chemtex); TEPIC-S (made by Nissan Chemical Industries, Ltd.) etc. are mentioned.

<<Polyfunctional Alkoxymethyl Compound>>

As the polyfunctional alkoxymethyl compound, for example, 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 two or more alkoxymethyl groups are substituted The urea compound which consists of is mentioned.

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

More specifically, 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 3,3',5,5'-tetramethoxymethyl-4,4 '-dihydroxybiphenyl (for example, product name "TMOM-BP", manufactured by Honshu Chemical Industries, Ltd.), 1,1-bis[3,5-di(methoxymethyl)-4-hydroxyphenyl]-1 -Phenylethane, 4,4',4''-(ethylidene)tris[2,6-bis(methoxymethyl)phenol] (for example, product name "HMOM-TPHAP", manufactured by Honshu Chemical Industry Co., Ltd.), 4 ,4'-[1-[4-[1-[4-hydroxy-3,5-bis(methoxymethyl)phenyl]-1-methylethyl]phenyl]ethylidene]bis[2,6-bis( methoxymethyl) phenol] (For example, product name "HMX-PA" manufactured by Asahi Organic Co., Ltd.) etc. are mentioned.

Examples of the melamine compound in which an amino group is substituted with two or more alkoxymethyl groups include N,N'-dimethoxymethylmelamine, N,N',N''-trimethoxymethylmelamine, N,N,N ',N''-Tetramethoxymethylmelamine, N,N,N',N',N''-Pentamethoxymethylmelamine, N,N,N',N',N'',N''- Hexamethoxymethylmelamine (For example, a product name "Nikalac (trademark) MW-390LM", a product name "Nikalac MW-100LM", both manufactured by Sanwa Chemical), these polymers, etc. are mentioned.

Examples of the urea compound substituted with two or more alkoxymethyl groups include a product name “Nikalac MX270”, a product name “Nikalac MX280”, and a product name “Nikalac MX290” (all manufactured by Sanwa Chemical).

<<Polyfunctional methylol compound>>

As a polyfunctional methylol compound, the phenol compound which two or more methylol groups couple|bond directly to an aromatic ring is mentioned, for example.

And, as a phenol compound formed by direct bonding of two or more methylol groups to an aromatic ring, 2,4-2,4-dihydroxymethyl-6-methylphenol, 2,6-bis(hydroxymethyl)-p -Cresol, 4-tertiary-2,6-bis(hydroxymethyl)phenol, bis(2-hydroxy-3-hydroxymethyl-5-methylphenyl)methane (product name "DM-BIPC-F", Asahi Organic Co., Ltd.), bis(4-hydroxy-3-hydroxymethyl-5-methylphenyl)methane (product name "DM-BIOC-F", manufactured by Asahi Organic Co., Ltd.), 2,2-bis(4-hydroxy-3) and 5-dihydroxymethylphenyl) propane (product name "TM-BIP-A", manufactured by Asahi Organic Co., Ltd.).

It is preferable to use at least one of a polyfunctional epoxy compound and a polyfunctional alkoxymethyl compound from a viewpoint of improving chemical-resistance while further raising the heat flow resistance of a resin film among the crosslinking agents (D) mentioned above, and polyfunctional epoxy It is more preferable to use both a compound and a polyfunctional alkoxymethyl compound.

In addition, as a polyfunctional epoxy compound, from a viewpoint of improving the chemical-resistance of a resin film favorably, Epolide GT401 (Material name: epoxidized butanetetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone) It is preferable to include at least one selected from the group consisting of a polyfunctional epoxy compound having an alicyclic structure such as Epolide PB4700, and epoxidized polybutadiene at the terminal H such as Epolide PB4700, and an alicyclic structure such as Epolide GT401 It is more preferable to include at least one selected from the group consisting of a polyfunctional epoxy compound having a polyfunctional epoxy compound and an epoxidized polybutadiene having a terminal H having a glycidyl ether structure in the main chain such as Epolide PB4700, and at least epoxidized butanetetra It is more preferable to include tetrakis(3-cyclohexenylmethyl)-modified ?-caprolactone of carboxylic acid.

[content]

The content of the crosslinking agent (D) in the resin composition of the present invention is preferably 15 parts by mass or more, and preferably 20 parts by mass or more, per 100 parts by mass in total of the cyclic olefin polymer (A) and the cresol novolac resin (B). More preferably, it is more preferably 30 parts by mass or more, particularly preferably 40 parts by mass or more, preferably 120 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less. It is especially preferable that it is less than part. When the content of the crosslinking agent (D) is 15 parts by mass or more per 100 parts by mass of the total of the cyclic olefin polymer (A) and the cresol novolac resin (B), the heat flow resistance and chemical resistance of the resin film can be further improved, and the If it is negative or less, a line-and-space pattern with excellent resolution can be formed.

Moreover, when using together a polyfunctional epoxy compound and at least one of a polyfunctional alkoxymethyl compound and a polyfunctional methylol compound (a polyfunctional alkoxymethyl compound and/or a polyfunctional methylol compound), a polyfunctional epoxy compound and a polyfunctional The mass ratio of the alkoxymethyl compound and/or the polyfunctional methylol compound (polyfunctional epoxy compound: polyfunctional alkoxymethyl compound and/or polyfunctional methylol compound) is preferably in the range of 1:1 to 1:0.1, 1 It is more preferable to exist in the range of :0.5-1:0.25. Polyfunctional epoxy compound: When the polyfunctional alkoxymethyl compound and/or the polyfunctional methylol compound are within the above ranges, it is possible to form a resin film excellent in the balance of line-and-space pattern resolution, thermal flow resistance, and chemical resistance.

<solvent>

The resin composition of this invention may contain the solvent. That is, the resin composition of the present invention contains, in a solvent, a cyclic olefin polymer having a protonic polar group (A), a cresol novolac resin (B) having a softening point of 140°C or higher, an acid generator (C), a crosslinking agent (D), And the radiation-sensitive resin liquid formed by dissolving and/or disperse|distributing other compounding agents optionally added may be sufficient.

It does not specifically limit as a solvent, As a solvent of a resin composition, a well-known thing, for example, acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-hep straight-chain ketones such as tanone, 4-heptanone, 2-octanone, 3-octanone, and 4-octanone; alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and cyclohexanol; ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and dioxane; alcohol ethers such as ethylene glycol monomethyl ether and 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, and ethyl lactate; cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, and butyl cellosolve acetate; propylene glycols such as propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monobutyl ether; diethylene glycols 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-caprylolactone; halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene; and other polar solvents such as dimethylacetamide, dimethylformamide, and N-methylacetamide.

A solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

<Other compounding agents>

The resin composition of this invention may contain compounding agents other than the above-mentioned component. Examples of other compounding agents include resin components other than the cyclic olefin polymer (A) and cresol novolac resin (B), a silane coupling agent, a compound having an acidic group or a heat latent acidic group, a dissolution accelerator, and a surfactant , an antioxidant, a sensitizer, a light stabilizer, an antifoaming agent, a pigment, a dye, and a filler. In addition, other compounding agents may be used individually by 1 type, and may be used in combination of 2 or more type.

<The preparation method of the radiation-sensitive resin composition>

The method of preparing the resin composition of this invention is not specifically limited, What is necessary is just to mix each component which comprises a resin composition.

Specifically, the resin composition of the present invention comprises a cyclic olefin polymer (A), a cresol novolak resin (B), an acid generator (C), a crosslinking agent (D), and other compounding agents optionally used. It is preferable to obtain by dissolving or dispersing in a solvent by mixing in the above-mentioned solvent. By this operation, the resin composition is obtained in the form of a solution or dispersion (that is, as a radiation-sensitive resin liquid).

The said mixing is not specifically limited, It is performed using a known mixer. Moreover, you may filter by a known method after mixing.

And the solid content concentration of the radiation-sensitive resin liquid which is the resin composition of this invention is 1 mass % or more and 70 mass % or less normally, Preferably it is 5 mass % or more and 60 mass % or less, More preferably, 10 mass % or more and 50 mass % or less. mass% or less. When the solid content concentration is within the above-mentioned range, the dissolution stability and applicability of the radiation-sensitive resin liquid, and the film thickness uniformity and flatness of the formed resin film can be highly balanced.

<Method of forming a resin film>

By using the radiation-sensitive resin composition of the present invention, a resin film can be formed on a substrate such as a silicon wafer on which a semiconductor element is mounted.

In addition, the method of forming a resin film on a board|substrate is not specifically limited. The resin film, for example, using a radiation-sensitive resin composition containing a solvent (that is, a radiation-sensitive resin solution), a step of forming a radiation-sensitive film on a substrate (radiation-sensitive film formation step), It can be manufactured through a process (exposure process) to obtain an exposure film by irradiating the radioactive film with actinic radiation, a process to obtain a developing film by developing the exposure film (development process), and a process (curing process) to obtain a resin film by curing the developing film. have.

<<Radiation-sensitive film formation process>>

The method of forming a radiation-sensitive film|membrane on a board|substrate using a radiation-sensitive resin liquid is not specifically limited, For example, methods, such as a coating method and a film lamination method, can be used.

[Applying method]

The coating method is a method of forming a radiation-sensitive film by applying a radiation-sensitive resin solution on a substrate and then removing the solvent by heating and drying. As a method of applying the radiation-sensitive resin liquid, for example, a spray method, a spin coat method, a roll coat method, a die coat method, a doctor blade method, a spin coating method, a slit coat method, a bar coating method, a screen printing method , various methods such as an inkjet method can be employed. Although heat-drying conditions change with the kind and mixing ratio of each component, a heating temperature is 30-150 degreeC normally, Preferably it is 60-130 degreeC, and a heating time is 0.5-90 minutes normally, Preferably it is 1- It is for 60 minutes, More preferably, it is for 1 to 30 minutes.

[Film Lamination Method]

In the film lamination method, a radiation-sensitive resin solution is applied on a substrate for forming a radiation-sensitive film (such as a resin film or a metal film), and then the solvent is removed by heating and drying to obtain a radiation-sensitive film, and then the obtained A method of laminating a radioactive film on a substrate. Although heat-drying conditions can be suitably selected according to the kind and mixing|blending ratio of each component, a heating temperature is 30-150 degreeC normally, and a heating time is 0.5 to 90 minutes normally. Lamination of the radiation-sensitive film onto the substrate can be performed using a press machine such as a pressure laminator, a press, a vacuum laminator, a vacuum press, or a roll laminator.

The thickness of the radiation-sensitive film formed on the substrate by any of the above methods is not particularly limited, and may be appropriately set according to the use, preferably 0.1 to 100 µm, more preferably 0.5 to 50 µm, More preferably, it is 0.5-30 micrometers.

<<Exposure process>>

Next, actinic radiation is irradiated to the radiation-sensitive film formed in the above-mentioned radiation-sensitive film forming step to obtain an exposure film having a latent image pattern.

[Active Radiation]

As the actinic radiation, the acid generator (C) contained in the radiation-sensitive film is activated to improve the solubility of the resin component in the developer (especially the solubility in the alkali developer) in the exposed portion, especially if it is not limited Specifically, light rays exemplified by ultraviolet rays (including ultraviolet rays having a single wavelength such as g-line and i-ray), KrF excimer laser light, and ArF excimer laser light; particle beams exemplified by electron beams; etc. can be used.

On the other hand, when using a light ray as actinic radiation, single-wavelength light may be sufficient, and mixed wavelength light may be sufficient.

[Exposure conditions]

As a method of selectively irradiating the above-described actinic radiation in a pattern shape to form a latent image pattern, a conventional method may be followed, for example, ultraviolet rays, KrF excimer laser light, and ArF excimer by a reduced projection exposure apparatus or the like. The method of irradiating light beams, such as a laser beam, through a desired mask pattern, or the method of drawing with particle beams, such as an electron beam, can be used.

Irradiation conditions are appropriately selected depending on the actinic radiation to be used. For example, when using a light beam having a wavelength of 200 to 450 nm, the irradiation amount is usually 10 to 5,000 mJ/cm ² , preferably 50 to 1,500 mJ/ It is in the range of cm ² and is determined by irradiation time and illuminance.

On the other hand, after irradiating actinic radiation, you may heat-process the obtained exposure film for about 1 to 10 minutes at the temperature of about 60-150 degreeC as needed.

<<Development process>>

Next, the latent image pattern formed in the exposure film in the above-mentioned exposure process is developed with a developing solution, and it is made visible, and a developing film is obtained.

[developer]

As a developing solution, an alkali developing solution can be used. An alkaline developer can be obtained by dissolving an alkaline compound in an aqueous medium.

As an alkaline compound, an alkali metal salt, an amine, and an ammonium salt can be used, for example. An inorganic compound may be sufficient as an alkaline compound, and an organic compound may be sufficient as it. Specific examples of the alkaline compound include alkali 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; alcohol amines such as dimethylethanolamine and triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, 1,5-diazabicyclo[4.3.0]nona-5-ene, N-methylpyrrolidone, etc. of cyclic amines; These alkaline compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the aqueous medium of the alkaline developer include water; Water-soluble organic solvents, such as methanol and ethanol, can be used.

Moreover, the alkali developing solution may add surfactant etc. in an appropriate amount.

[Development method]

As a method of making a developing solution contact the exposure film which has a latent image pattern, methods, such as a paddle method, a spray method, the dipping method, are used, for example. In addition, the developing temperature is normally selected from 0-100 degreeC, Preferably it is 5-55 degreeC, More preferably, it is suitably selected in the range of 10-30 degreeC, and the developing time is suitably selected normally in the range for 30 to 180 second. .

In this way, the developing film on which the target pattern has been formed can be rinsed with a rinsing liquid, if necessary, in order to remove the development residue. After the rinsing treatment, the remaining rinsing liquid is preferably removed with compressed air or compressed nitrogen.

In addition, if necessary, in order to deactivate the acid generator (C) remaining in the developing film, the developing film may be irradiated with actinic radiation. The method mentioned above in "exposure process" can be used for irradiation of actinic radiation. In addition, you may heat a developing film simultaneously with irradiation of actinic radiation or after irradiation of actinic radiation. As a heating method, the method of heating an electronic component in a hotplate or oven is mentioned, for example. Heating temperature is 80-300 degreeC normally, Preferably it is the range of 100-200 degreeC.

<<curing process>>

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

What is necessary is just to select a method suitably according to the kind of the crosslinking agent (D) made to contain the radiation-sensitive resin liquid as a method of hardening, However, Usually, it performs by heating.

The heating method can be performed using a hot plate, oven, etc., for example. The heating temperature is usually 150 to 250 ° C., and the heating time is appropriately selected depending on the area or thickness of the developing film, the equipment used, etc. For example, when using a hot plate, usually 5 to 120 minutes, using an oven In this case, it is usually in the range of 30 to 150 minutes. In addition, you may perform a heating in an inert gas atmosphere as needed. As an inert gas, what is necessary is just to not contain oxygen and not to oxidize a developing film, For example, nitrogen, argon, helium, neon, xenon, krypton, etc. are mentioned. Among these, nitrogen and argon are preferable, and nitrogen is especially preferable. In particular, an inert gas having an oxygen content of 0.1% by volume or less, preferably 0.01% by volume or less, particularly nitrogen, is suitable. These inert gases may be used individually by 1 type, and may be used in combination of 2 or more type.

[Example]

Hereinafter, the present invention will be specifically described based on Examples, but the present invention is not limited to these Examples.

In the Example and the comparative example, the dielectric constant, top loss, heat flow resistance, and chemical-resistance were evaluated as follows.

<Relative permittivity>

Using a sputtering device (manufactured by Shibaura Illetek, product name "i-Miller CFS-4EP-LL"), the prepared resin composition was applied by spin coating on a 4-inch silicon wafer on which an aluminum film having a thickness of 50 nm was formed. Then, it heat-dried (pre-baked) for 2 minutes at 120 degreeC using the hotplate, and formed the radiation-sensitive film|membrane. The film was cured by heating in nitrogen at 230°C for 1 hour to obtain a 10 µm-thick cured film-forming silicon wafer. The cured film was peeled from a silicon wafer by immersing this in 0.1 mol% hydrochloric acid aqueous solution for 12 hours and etching aluminum. The cured film was cut out into a rectangular shape having a width of 2 mm and a length of 50 mm to be a test piece, and the relative dielectric constant at 10 GHz was measured for this test piece by a cavity resonance technique, and the following criteria were evaluated.

A: The relative permittivity is less than 2.85

B: Relative permittivity of 2.85 or more and less than 3.00

C: Relative permittivity of 3.00 or more

<Top Loss>

On a silicon wafer, the prepared resin composition was applied by spin coating, followed by heating and drying (pre-baking) at 120° C. for 2 minutes using a hot plate to form a radiation-sensitive film (thickness of 3.0 µm). . Next, an exposure step was performed by setting a reticle capable of forming a line-and-space pattern of 1.0 μm on an i-line stepper (manufactured by Nikon Corporation, product name “NSR2005i9C”), and changing the exposure amount from 100 to 2000 mJ/cm ² . With respect to the obtained exposure film, the development process was performed for 60 second using the 2.38 mass % tetramethylammonium hydroxide aqueous solution. Then, it was rinsed with ultrapure water and drip-drying, and the laminated body which consists of a developing film which has a line-and-space pattern, and a silicon wafer was obtained. And using a scanning electron microscope (SEM), the cross section of the line-and-space pattern part of the obtained laminated body is observed, and the film thickness of the line part in the exposure amount which a line and a space becomes 1:1 is measured. did In addition, the film thickness of the unexposed part in which the line-and-space pattern was not formed was also measured by SEM. And using the formula: top loss (%) = (film thickness of unexposed part - film thickness of line part)/(film thickness of unexposed part) x 100, the top loss was computed, and the following reference|standard evaluated.

A: Top loss is less than 25%

B: Top loss is 25% or more but less than 40%

C: Top loss is 40% or more

<Heat flow resistance>

On a silicon wafer, the prepared resin composition was applied by spin coating, followed by heating and drying (pre-baking) at 120° C. for 2 minutes using a hot plate to form a radiation-sensitive film (thickness of 3.0 µm). . Next, the exposure process was performed by changing the exposure amount from 100 to 2000 mJ/cm ² using a mask capable of forming a via pattern of 2.0 µm. With respect to the obtained exposure film, the development process was performed for 60 second using the 2.38 weight% tetramethylammonium hydroxide aqueous solution. Thereafter, rinsing with ultrapure water and dropping-drying were performed to obtain a laminate comprising a developing film having a 2.0 µm via hole and a silicon wafer. On the other hand, it was observed and measured with an optical microscope, and it was confirmed that the via pattern of 2.0 micrometers was open. The resulting laminate was heated in nitrogen from 50°C to 110°C at 2°C/min, held at 110°C for 30 minutes, then heated to 230°C at 3°C/min, and further maintained at 230°C for 1 hour to develop The film was cured to obtain a resin film. Then, the via diameter at the exposure dose at which the 2.0 µm via pattern was opened before curing was measured with an optical microscope, and the formula: reduction ratio (%) of via diameter = (via diameter before curing - via diameter after curing)/ Using (via diameter before hardening) x 100, the reduction ratio of the via diameter by hardening was computed, and the following reference|standard evaluated.

A: The reduction ratio of the via diameter is less than 5%

B: The reduction ratio of the via diameter is 5% or more and less than 10%

C: The reduction ratio of the via diameter is 10% or more

<Chemical resistance>

On a silicon wafer, the prepared resin composition was apply|coated by the spin coating method, it heat-dried (prebaked) for 2 minutes at 120 degreeC using the hotplate, and formed the radiation-sensitive film|membrane. Then, the radiation-sensitive film was heated at 2° C./min from 50° C. to 110° C. in nitrogen, held at 110° C. for 30 minutes, then heated to 3° C./min to 230° C., and maintained at 230° C. for an additional hour. It hardened, and the cured film was obtained. This was immersed in monoethanolamine/dimethyl sulfoxide = 7/3 (mass ratio) for 15 minutes at 23° C., formula: rate of change in film thickness (%) = | film thickness before immersion - film thickness after immersion |/(before immersion) Using film thickness) x 100, the change ratio of the film thickness by immersion was computed, and it combined with the result of visual observation of a cured film (crack, peeling presence or absence), and evaluated by the following reference|standard.

A: The rate of change of the film thickness is less than 10%, and there is no crack or peeling

B: The rate of change of the film thickness is 10% or more and less than 20%, and there is no crack or peeling

C: The rate of change of the film thickness is 20% or more, and/or there is at least one of cracks and peeling

(Example 1)

<Preparation of Cyclic Olefin Polymer (A-1)>

40 mol% N-phenyl-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide (NBPI) and 4-hydroxycarbonyltetracyclo[6.2.1.1 ^{3,6.0 2, 7} ] 100 parts by mass of a monomer mixture comprising 60 mol% of dodeca-9-ene (TCDC), 2.0 parts by mass of 1,5-hexadiene, (1,3-dimethylimidazolin-2-ylidene) ( 0.02 parts by mass of tricyclohexylphosphine)benzylideneruthenium dichloride (synthesized by the method described in "Org. Lett., Vol. 1, page 953, 1999"), and 200 parts by mass of diethylene glycol methyl ethyl ether, It injected|threw-in to the glass internal pressure reactor which substituted nitrogen, and it was made to react at 80 degreeC for 4 hours, stirring, and the polymerization reaction liquid was obtained.

Then, the obtained polymerization reaction solution is placed in an autoclave, stirred at 150° C. and a hydrogen pressure of 4 MPa for 5 hours to perform a hydrogenation reaction, and a polymer solution containing a cyclic olefin polymer (A-1) having a protonic polar group is obtained. got it The polymerization conversion ratio of the obtained cyclic olefin polymer (A-1) was 99.7 mass %, the weight average molecular weight (polystyrene conversion) 7200, the number average molecular weight 4700, molecular weight distribution were 1.53, and the hydrogenation rate was 99.7 %. In addition, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-1) was 34.4 mass %.

<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>

75 parts (equivalent to solid content) of the polymer solution of the cyclic olefin polymer (A-1), cresol novolac resin (B-1) (manufactured by Asahi Organic Co., Ltd., product name "TMR30B35G", weight average molecular weight: 7000, softening point: 163°C , m-cresol/p-cresol/m-xylenol = 60/30/10 (molar ratio) and formaldehyde condensation polymer, m/p ratio: about 2.3) 25 parts, acid generator (C-1) (Toyo Synthesis Co., Ltd. product name "TS250", quinonediazide compound (4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol (1.0 30 parts by mole) and a condensate of 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mole parts)), a crosslinking agent (D-1) (manufactured by Daicel, product name “Epolide GT401”, alicyclic 30 parts of polyfunctional epoxy compound having a structure), crosslinking agent (D-4) (manufactured by Sanwa Chemical, product name "Nikalac MW-100LM", N,N,N',N',N'',N'' -Hexamethoxymethylmelamine) was mixed with 10 parts and diethylene glycol methyl ethyl ether as a solvent, and it was dissolved. In addition, the usage-amount of diethylene glycol methyl ethyl ether was made into the quantity used as 40 mass % of solid content concentration. Next, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 µm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. A result is shown in Table 1.

(Example 2)

When preparing the resin composition, the amount of the cyclic olefin polymer (A-1) is from 75 parts to 55 parts (equivalent to solid content), the amount of the cresol novolac resin (B-1) is from 25 parts to 45 parts, and the crosslinking agent Except having changed the quantity of (D-1) from 30 parts to 35 parts, it carried out similarly to Example 1, the cyclic olefin polymer (A-1) and the resin composition were prepared, and various evaluation was performed. A result is shown in Table 1.

(Example 3)

When preparing the resin composition, the amount of the cyclic olefin polymer (A-1) was changed from 75 parts to 30 parts (equivalent to solid content) and the amount of the cresol novolac resin (B-1) was changed from 25 parts to 70 parts, except that , It carried out similarly to Example 1, the cyclic olefin polymer (A-1) and the resin composition were prepared, and various evaluation was performed. A result is shown in Table 1.

(Example 4)

<Preparation of cyclic olefin polymer (A-2)>

A cyclic olefin polymer (A-2) having a protonic polar group was prepared in the same manner as for the cyclic olefin polymer (A-1) except that NBPI was 31.5 mol% and TCDC was 68.5 mol%. The polymerization conversion ratio of the obtained cyclic olefin polymer (A-2) was 99.8 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 cyclic olefin polymer (A-2) was 34.3 mass %.

<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>

50 parts (equivalent to solid content) of a polymer solution of cyclic olefin polymer (A-2), cresol novolac resin (B-2) (manufactured by Asahi Organic Co., Ltd., product name "TMR30B25G", weight average molecular weight: 9000, softening point: 167°C , m-cresol/p-cresol/m-xylenol = 60/30/10 (molar ratio) and formaldehyde condensation polymer, m/p ratio: about 2.3) 50 parts, acid generator (C-1) 30 parts of crosslinking agent (D-1), 37 parts of crosslinking agent (D-5) (manufactured by Honshu Chemical Industries, Ltd., product name "HMOM-TPHAP", 4,4',4''-(ethylidene)tris[2, 6-bis(methoxymethyl)phenol]) were mixed with 10 parts of diethylene glycol methyl ethyl ether as a solvent and dissolved. In addition, the usage-amount of diethylene glycol methyl ethyl ether was made into the quantity used as 40 mass % of solid content concentration. Next, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 µm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. A result is shown in Table 1.

(Example 5)

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

It carried out similarly to Example 1, and prepared the cyclic olefin polymer (A-1), it carried out similarly to Example 4, and prepared the cyclic olefin polymer (A-2), respectively.

<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>

25 parts (equivalent to solid content) of the polymer solution of cyclic olefin polymer (A-1), 30 parts (equivalent to solid content) of polymer solution of cyclic olefin polymer (A-2), cresol novolac resin (B-2) 45 parts, 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. . In addition, the usage-amount of diethylene glycol methyl ethyl ether was made into the quantity used as 40 mass % of solid content concentration. Next, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 µm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. A result is shown in Table 1.

(Example 6)

<Preparation of Cyclic Olefin Polymer (A-1)>

It carried out similarly to Example 1, and prepared the cyclic olefin polymer (A-1).

<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>

60 parts (equivalent to solid content) of a polymer solution of cyclic olefin polymer (A-1), 20 parts of cresol novolac resin (B-2), and cresol novolak resin (B-3) (manufactured by Asahi Organic Co., Ltd., product name " SE3010", weight average molecular weight: 5000, softening point: 155°C, m-cresol/p-cresol = 70/30 (molar ratio) and formaldehyde condensation polymer, m/p ratio: about 2.3) 20 parts, acid generator (C-1) 30 parts, crosslinking agent (D-1) 30 parts, crosslinking agent (D-6) (manufactured by Asahi Organic Co., Ltd., product name "HMX-PA", 4,4'-[1-[4-[ 15 parts of 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 was mixed and dissolved. In addition, the usage-amount of diethylene glycol methyl ethyl ether was made into the quantity used as 40 mass % of solid content concentration. Next, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 µm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. A result is shown in Table 1.

(Example 7)

<Preparation of cyclic olefin polymer (A-3)>

No NBPI, 40 mol% of N-(2-ethylhexyl)-bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide (NEHI) and 60 mol% of TCDC Except for that, it carried out similarly to the cyclic olefin polymer (A-1), and prepared the cyclic olefin polymer (A-3) which has a protonic polar group. The polymerization conversion ratio of the obtained cyclic olefin polymer (A-3) was 99.8 mass %, the weight average molecular weight (polystyrene conversion) was 8500, the number average molecular weight was 5800, 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 cyclic olefin polymer (A-3) was 34.3 mass %.

<Preparation of cyclic olefin 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 parts by mass of 1-hexene, (1,3-dimethylimidazolin-2-ylidene) (tricyclo 0.06 parts by mass of hexylphosphine) benzylidene ruthenium dichloride and 300 parts by mass of diethylene glycol methyl ethyl ether were put into a glass pressure-resistant reactor substituted with nitrogen, and reacted at 80° C. for 4 hours while stirring to obtain a polymerization reaction solution.

Then, the obtained polymerization reaction solution is placed in an autoclave, and hydrogenated by stirring at 150° C. and a hydrogen pressure of 4 MPa for 5 hours to obtain a polymer solution containing a cyclic olefin polymer (A-4) having a protonic polar group. got it The polymerization conversion ratio of the obtained cyclic olefin polymer (A-4) was 99.3 mass %, the weight average molecular weight (polystyrene conversion) was 20600, the number average molecular weight was 11500, molecular weight distribution was 1.79, and the hydrogenation rate was 99.8 %. In addition, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-4) was 25.3 mass %.

<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>

20 parts (equivalent to solid content) of a polymer solution of cyclic olefin polymer (A-3), 30 parts (equivalent to solid content) of a polymer solution of cyclic olefin polymer (A-4), cresol novolac resin (B-4) ( Asahi Organic 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 polymer, m/p ratio: 1.5) 50 parts, 30 parts of acid generator (C-1), 15 parts of crosslinking agent (D-1), crosslinking agent (D-2) (manufactured by Nissan Chemical Industries, Ltd., product name "TEPIC-S", tris (2,3-) Epoxypropyl) isocyanurate (triglycidyl isocyanurate)) in 15 parts, crosslinking agent (D-7) (manufactured by Honshu Chemical Industries, Ltd., product name "TMOM-BP", 3,3',5,5'- 10 parts of tetramethoxymethyl-4,4'-dihydroxybiphenyl) and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. In addition, the usage-amount of diethylene glycol methyl ethyl ether was made into the quantity used as 40 mass % of solid content concentration. Next, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 µm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. A result is shown in Table 1.

(Example 8)

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

It carried out similarly to Example 4, and prepared the cyclic olefin polymer (A-2), it carried out similarly to Example 7, and prepared the cyclic olefin polymer (A-4), respectively.

<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>

30 parts (equivalent to solid content) of a polymer solution of cyclic olefin polymer (A-2), 30 parts (equivalent to solid content) of a polymer solution of cyclic olefin polymer (A-4), cresol novolac resin (B-1) 40 parts, 30 parts of acid generator (C-1), 15 parts of crosslinking agent (D-1), crosslinking agent (D-3) (made by Daicel, product name "EHPE3150", 2,2-bis(hydroxymethyl) ) -1-butanol 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct) 15 parts, crosslinking agent (D-6) 10 parts, and diethylene glycol methyl ethyl ether as a solvent are mixed So, it was dissolved. In addition, the usage-amount of diethylene glycol methyl ethyl ether was made into the quantity used as 40 mass % of solid content concentration. Next, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 µm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. A result is shown in Table 1.

(Example 9)

When preparing the resin composition, the amount of the cyclic olefin polymer (A-1) was changed from 75 parts to 15 parts (equivalent to solid content) and the amount of the cresol novolac resin (B-1) was changed from 25 parts to 85 parts, except that , It carried out similarly to Example 1, the cyclic olefin polymer (A-1) and the resin composition were prepared, and various evaluation was performed. A result is shown in Table 2.

(Example 10)

When preparing the resin composition, the amount of the cyclic olefin polymer (A-2) is changed from 50 parts to 85 parts (equivalent to solid content), and the amount of the cresol novolac resin (B-2) is changed from 50 parts to 15 parts, and , A cyclic olefin polymer (A-2) and a resin composition were prepared in the same manner as in Example 4 except that the amount of the crosslinking agent (D-1) was changed from 37 parts to 35 parts, and various evaluations were performed. A result is shown in Table 2.

(Comparative Example 1)

<Preparation of Cyclic Olefin Polymer (A-1)>

It carried out similarly to Example 1, and prepared the cyclic olefin polymer (A-1).

<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>

100 parts (equivalent to solid content) of the polymer solution of the cyclic olefin 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) Diethylene glycol methyl ethyl ether was mixed and dissolved as a part and a solvent. In addition, the usage-amount of diethylene glycol methyl ethyl ether was made into the quantity used as 40 mass % of solid content concentration. Next, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 µm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. A result is shown in Table 2.

(Comparative Example 2)

Cresol novolac resin (B-4) 100 parts, acid generator (C-1) 25 parts, crosslinking agent (D-1) 30 parts, crosslinking agent (D-7) 10 parts, and diethylene as a solvent Glycolmethyl ethyl ether was mixed and dissolved. In addition, the usage-amount of diethylene glycol methyl ethyl ether was made into the quantity used as 40 mass % of solid content concentration. Next, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 µm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. A result is shown in Table 2.

(Comparative Example 3)

<Preparation of cyclic olefin polymer (A-3)>

In the same manner as in Example 7, a cyclic olefin polymer (A-3) was prepared.

<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>

50 parts (equivalent to solid content) of a polymer solution of the cyclic olefin polymer (A-3), cresol novolac resin (B-5) (manufactured by Asahi Organic Co., Ltd., product name "EP6040A", weight average molecular weight: 2600, softening point: 130 ° C. , m-cresol/p-cresol = 40/60 (molar ratio) and formaldehyde condensation polymer, m/p ratio: about 0.67) 50 parts, acid generator (C-1) 28 parts, crosslinking agent (D- 1) 35 parts, crosslinking agent (D-3) 10 parts, crosslinking agent (D-6) 10 parts, and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. In addition, the usage-amount of diethylene glycol methyl ethyl ether was made into the quantity used as 40 mass % of solid content concentration. Next, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 µm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. A result is shown in Table 2.

(Comparative Example 4)

<Preparation of Cyclic Olefin Polymer (A-1)>

It carried out similarly to Example 1, and prepared the cyclic olefin polymer (A-1).

<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>

50 parts (equivalent to solid content) of a polymer solution of cyclic olefin polymer (A-1), 50 parts of cresol novolac resin (B-1), 30 parts of acid generator (C-1), and diethylene as a solvent Glycolmethyl ethyl ether was mixed and dissolved. In addition, the usage-amount of diethylene glycol methyl ethyl ether was made into the quantity used as 40 mass % of solid content concentration. Next, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 µm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. A result is shown in Table 2.

(Comparative Example 5)

<Preparation of Cyclic Olefin Polymer (A-1)>

It carried out similarly to Example 1, and prepared the cyclic olefin polymer (A-1).

<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>

60 parts (equivalent to solid content) of the polymer solution of the cyclic olefin polymer (A-1), 40 parts of phenol novolac resin (manufactured by Asahi Organic 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. In addition, the usage-amount of diethylene glycol methyl ethyl ether was made into the quantity used as 40 mass % of solid content concentration. Next, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 µm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. A result is shown in Table 2.

(Comparative Example 6)

<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>

50 parts of cresol novolac resin (B-1), 50 parts of polyvinylphenol resin (manufactured by Maruzen Petrochemical, product name "S-2P"), 28 parts of acid generator (C-1), crosslinking agent (D 30 parts of -1), 10 parts of a crosslinking agent (D-5), and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. In addition, the usage-amount of diethylene glycol methyl ethyl ether was made into the quantity used as 40 mass % of solid content concentration. Next, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore diameter of 0.45 µm to prepare a resin composition. Various evaluations were performed using the obtained resin composition. A result is shown in Table 2.

On the other hand, in Tables 1-2 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,

"Methoxymethyl" represents a polyfunctional methoxymethyl (alkoxymethyl) compound.

From Tables 1 and 2, Example 1 comprising a cyclic olefin polymer having a protonic polar group (A), a cresol novolac resin (B) having a softening point of 140°C or higher, an acid generator (C), and a crosslinking agent (D) When the resin composition of -10 is used, while the top loss of a line pattern is suppressed, it turns out that the resin film excellent in heat flow resistance can be formed. Moreover, in Examples 1-10, it also turns out that a resin film excellent in a dielectric constant is low and chemical-resistance can be formed.

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

It turns out that the top loss of the line pattern in a resin film cannot be suppressed in the comparative example 1 using the resin composition which does not contain cresol novolak resin (B).

In the comparative example 2 using the resin composition which does not contain a cyclic olefin polymer (A), it turns out that the dielectric constant of a resin film rises and thermal flow tolerance falls.

Although cresol novolac resin is included, in the comparative example 3 using the resin composition whose softening point is less than 140 degreeC, it turns out that the heat flow resistance of a resin film falls.

It turns out that the chemical-resistance and thermal-flow resistance of a resin film fall in the comparative example 4 using the resin composition which does not contain a crosslinking agent (D).

In Comparative Example 5 using the resin composition containing the phenol novolac resin but not containing the cresol novolac resin (B), the top loss of the line pattern in the resin film cannot be suppressed, and the heat flow of the resin film It can be seen that the tolerance is lowered.

It turns out that the heat flow resistance of a resin film falls in the comparative example 6 using the resin composition which contains polyvinyl phenol resin and does not contain a cyclic olefin polymer (A).

[Industrial Applicability]

ADVANTAGE OF THE INVENTION According to this invention, while suppressing the top loss of a line pattern, the radiation-sensitive resin composition which can form the resin film excellent in heat flow resistance can be provided.

Claims (6)

A radiation-sensitive resin composition comprising a cyclic olefin 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). According to claim 1,
The radiation-sensitive resin composition, wherein the cresol novolak resin (B) comprises a cresol skeleton and a xylenol skeleton. 3. The method of claim 1 or 2,
The radiation-sensitive resin composition wherein the acid generator (C) is a quinonediazide compound. 4. The method according to any one of claims 1 to 3,
The radiation-sensitive resin composition, 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 methylol compound. 5. The method according to any one of claims 1 to 4,
The radiation-sensitive resin composition, wherein the proportion of the cyclic olefin polymer (A) in the total of the cyclic olefin polymer (A) and the cresol novolac resin (B) is 10 mass% or more and 90 mass% or less. 6. The method according to any one of claims 1 to 5,
The radiation-sensitive resin composition, wherein in the skeleton derived from cresols contained in the cresol novolac resin (B), the molar ratio of the content of the meta-body skeleton to the content of the para-body skeleton is 5.0 or less.