WO2021060060A1 - Radiation-sensitive resin composition - Google Patents

Radiation-sensitive resin composition Download PDF

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Publication number
WO2021060060A1
WO2021060060A1 PCT/JP2020/034791 JP2020034791W WO2021060060A1 WO 2021060060 A1 WO2021060060 A1 WO 2021060060A1 JP 2020034791 W JP2020034791 W JP 2020034791W WO 2021060060 A1 WO2021060060 A1 WO 2021060060A1
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WIPO (PCT)
Prior art keywords
cyclic olefin
ene
hept
group
radiation
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PCT/JP2020/034791
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French (fr)
Japanese (ja)
Inventor
隆志 堤
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日本ゼオン株式会社
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Application filed by 日本ゼオン株式会社 filed Critical 日本ゼオン株式会社
Priority to JP2021548823A priority Critical patent/JPWO2021060060A1/ja
Priority to CN202080064437.5A priority patent/CN114402258A/en
Priority to KR1020227008174A priority patent/KR20220069932A/en
Publication of WO2021060060A1 publication Critical patent/WO2021060060A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins

Definitions

  • the present invention relates to a radiation-sensitive resin composition.
  • Electronic components such as integrated circuit elements, solid-state imaging elements, color filters, various display elements (for example, organic EL elements and liquid crystal display elements), and black matrices have surface protective films and elements to prevent deterioration and damage.
  • Various resin films such as a flattening film for flattening the surface and wiring and an interlayer insulating film for insulating between the wiring arranged in layers are provided.
  • a radiation-sensitive resin composition (hereinafter, may be abbreviated as "resin composition") containing an acid generator that generates an acid by irradiation with an ultraviolet ray (such as a particle beam exemplified for an electron beam). It has been used conventionally. Specifically, the radiation-sensitive film obtained by using the resin composition is irradiated with active radiation, and the exposed portion of the obtained exposure film is removed (developed) with a developing solution, etc. A resin film having a desired pattern shape can be obtained. Conventionally, a cyclic olefin polymer having a protonic polar group has been used as a resin component of such a resin composition (see, for example, Patent Documents 1 and 2).
  • the height of the line pattern including the unexposed portion is high. In some cases, the height is less than the height of the unexposed portion having no pattern (that is, a top loss of the line pattern occurs).
  • heat treatment may be performed for the purpose of heat curing after exposure and development. However, during such heat treatment, the resin film is formed by exposure and development. The desired pattern shape may be impaired. Therefore, the resin film formed by using the resin composition is required to enhance the property (heat flow resistance) of maintaining the desired pattern shape even when it is formed through heat treatment.
  • an object of the present invention is to provide a radiation-sensitive resin composition capable of forming a resin film having excellent heat flow resistance while suppressing the top loss of the line pattern.
  • the present inventor conducted a diligent study for the purpose of solving the above problems. Then, the present inventor contains, as a resin component, a cresol novolac resin having a softening point of a predetermined value or more in addition to a cyclic olefin polymer having a protonic polar group, and further contains an acid generator and a cross-linking agent.
  • a resin component a cresol novolac resin having a softening point of a predetermined value or more in addition to a cyclic olefin polymer having a protonic polar group
  • an acid generator and a cross-linking agent e.g., a cross-linking agent
  • the present invention aims to advantageously solve the above problems, and the radiation-sensitive resin composition of the present invention has a cyclic olefin polymer (A) having a protonic polar group and a softening point. It is characterized by containing a cresol novolak resin (B) at 140 ° C. or higher, an acid generator (C), and a cross-linking agent (D).
  • a cresol novolak resin B
  • C an acid generator
  • D cross-linking agent
  • the resin composition containing the above-mentioned components (A) to (D) the top loss of the line pattern can be suppressed and a resin film having excellent heat flow resistance can be formed.
  • the "softening point" can be measured by the ring-and-ball method described in JIS K6910: 2007.
  • the cresol novolac resin (B) contains a cresol skeleton and a xylenol skeleton.
  • the heat flow resistance of the resin film can be further improved.
  • the acid generator (C) is a quinonediazide compound.
  • a quinone diazide compound is used as the acid generator (C)
  • the resolution of the line and space pattern formed on the resin film can be improved.
  • the cross-linking 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. Is preferable.
  • a polyfunctional epoxy compound, a polyfunctional alkoxymethyl compound, and / or a polyfunctional methylol compound is used as the cross-linking agent (D)
  • the chemical resistance of the resin film can be enhanced and the heat flow resistance can be further improved.
  • the ratio of the cyclic olefin polymer (A) to the total of the cyclic olefin polymer (A) and the cresol novolak resin (B) is 10% by mass. It is preferably 90% by mass or more.
  • the radiation-sensitive resin composition of the present invention has a molar ratio of the content of the meta-skeleton to the content of the para-skeleton in the skeleton derived from the cresols contained in the cresol novolak resin (B) (that is, The m / p ratio) is preferably 5.0 or less. If the cresol novolac resin (B) in which the ratio of the content derived from the meta form to the content of the skeleton derived from the para form in the skeleton derived from cresols is 5.0 or less on a molar basis, the resin is used. The heat flow resistance can be further improved while further suppressing the top loss of the line pattern in the film.
  • the "m / p ratio" can be measured by a known method such as nuclear magnetic resonance (for example, 13 C-NMR).
  • the present invention it is possible to provide a radiation-sensitive resin composition capable of forming a resin film having excellent heat flow resistance while suppressing the top loss of the line pattern.
  • the radiation-sensitive resin composition of the present invention can be used for forming a resin film, and the resin film can be used, for example, in electronic components manufactured by wafer level packaging technology, as a surface protective film, a flattening film, and interlayer insulation. It can be used as a film or the like.
  • the radiation-sensitive resin composition of the present invention comprises 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 cross-linking agent ( D) is contained, and optionally, a solvent and other compounding agents are contained.
  • the radiation-sensitive resin composition of the present invention contains the above-mentioned cyclic olefin polymer (A) and cresol novolac resin (B) as resin components, and also contains an acid generator (C) and a cross-linking agent (D). Therefore, if the resin composition is used, the top loss of the line pattern can be suppressed and a resin film having excellent heat flow resistance can be formed.
  • the cyclic olefin polymer (A) is a polymer having a protonic polar group and a cyclic olefin skeleton.
  • the cyclic olefin polymer (A) has a solubility in a developing solution (particularly, an alkaline developing solution described later) by having a protonic polar group. Further, since the protonic polar group reacts with the cross-linking agent (D) during thermosetting and the resin component such as the cyclic olefin polymer (A) can have a strong cross-linked structure, the resin film has excellent heat flow resistance. And chemical resistance can be imparted.
  • the protic 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 the 15th group or the 16th group of the periodic table the atom belonging to the 2nd or 3rd period of the 15th group or the 16th period of the periodic table is preferable, and an oxygen atom, a nitrogen atom or a sulfur atom is more preferable. , Particularly preferably an oxygen atom.
  • a protonic polar group examples 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; a primary amino group and a secondary amino group.
  • a polar group having a nitrogen atom such as a primary amide group and a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group;
  • a polar group having an oxygen atom is preferable, a carboxyl group and a hydroxyl group are more preferable, and a carboxyl group is further preferable.
  • the cyclic olefin polymer (A) may have only one type of protonic polar group, or may have two or more types.
  • the method for introducing the above-mentioned protonic polar group into the cyclic olefin polymer (A) is not particularly limited. That is, the cyclic olefin polymer (A) contains, for example, a repeating unit derived from the cyclic olefin monomer (a) having a protic polar group, and optionally, a repeating unit derived from another monomer (b). It may be a polymer containing a unit, or it may be a polymer in which a protonic polar group is introduced into a cyclic olefin polymer having no protonal polar group by using a modifier, but the former is preferable. ..
  • the cyclic olefin monomer (a) having a protonic polar group is not particularly limited as long as it is a monomer having the above-mentioned protonic polar group and a cyclic olefin structure, but for example, a cyclic olefin simple having a carboxyl group.
  • a cyclic olefin monomer having a metric or a hydroxyl group is preferably used.
  • cyclic olefin monomer having a carboxyl group examples include 2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene and 2-methyl-2-hydroxycarbonylbicyclo [2.2.1] hept-.
  • cyclic olefin monomer having a hydroxyl group examples include 2- (4-hydroxyphenyl) bicyclo [2.2.1] hept-5-ene and 2-methyl-2- (4-hydroxyphenyl) bicyclo [2]. .2.1] Hept-5-ene, 4- (4-hydroxyphenyl) tetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-ene, 4-methyl-4- (4-hydroxyphenyl) tetracyclo [6.2.1.1 3,6 .
  • a cyclic olefin monomer having a carboxyl group is preferable, and 4-hydroxy is preferable from the viewpoint of improving the solubility in a developing solution (particularly an alkaline developing solution described later) and improving the adhesion of the resin film to a metal.
  • Carbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-ene is more preferable.
  • the cyclic olefin monomer (a) may be used alone or in combination of two or more.
  • the content ratio of the repeating unit derived from the cyclic olefin monomer (a) in the cyclic olefin polymer (A) is preferably 10 mol% or more, preferably 20 mol, with the total repeating unit as 100 mol%. % Or more, more preferably 30 mol% or more, more preferably 90 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less. preferable. If the proportion 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 if it is 90 mol% or less, the relative permittivity of the resin film. Can be reduced.
  • the other monomer (b) is not particularly limited as long as it is a monomer copolymerizable with the above-mentioned cyclic olefin monomer (a).
  • Examples of the monomer copolymerizable with the cyclic olefin monomer (a) include a cyclic olefin monomer (b1) having a polar group other than the protonic polar group and a cyclic olefin monomer having no polar group (b1). Examples thereof include b2) and a monomer (b3) other than the cyclic olefin.
  • cyclic olefin monomer (b1) having a polar group other than the protonic polar group examples include an N-substituted imide group, an ester group, a cyano group, an acid anhydride group, or a cyclic olefin monomer having a halogen atom. Can be mentioned.
  • 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).
  • R 2 represents an alkyl group or an aryl group having 1 to 16 carbon atoms, and n represents 1 or 2.
  • R 3 is a divalent alkylene group having 1 or more and 3 or less carbon atoms
  • R 4 is a monovalent alkyl group having 1 or more and 10 or less carbon atoms or 1 or more and 10 or less carbon atoms. Represents a monovalent alkyl halide group.
  • the two R 4s may be the same or different.
  • examples of the alkyl group having 1 or more and 16 or less carbon atoms of R 2 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and an n-hexyl group.
  • Linear alkyl 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 Cyclic alkyl groups such as groups, decahydronaphthyl groups, tricyclodecanyl groups, adamantyl groups; 2-propyl groups, 2-butyl groups, 2-methyl-1-propyl groups, 2-methyl-2-propyl groups, 1 -Methylbutyl group, 2-methylbutyl group, 1-methylpentyl group, 1-ethylbutyl group, 2-methylhexyl group, 2-ethylhexyl group, 4-methylheptyl group, 1-methylnonyl group,
  • alkyl groups and aryl groups having 4 to 14 carbon atoms are preferable 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.
  • Alkyl groups and aryl groups having 6 or more and 10 or less carbon atoms are more preferable.
  • the monomer represented by the formula (1) include bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide and N-phenyl-bicyclo [2.2]. .1] Hept-5-en-2,3-dicarboxyimide, N-methylbicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N-ethylbicyclo [2.2] .1] Hept-5-en-2,3-dicarboxyimide, N-propylbicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N-butylbicyclo [2.2] .1] Hept-5-en-2,3-dicarboxyimide, N-cyclohexylbicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N-adamantylbicyclo [2.2] .1] Hept-5-en-2,3-dicarboxyimide, N- (1-methyl
  • examples of the divalent alkylene group having 1 or more and 3 or less carbon atoms of R 3 include a methylene group, an ethylene group, a propylene group and an isopropylene group. Among these, a methylene group and an ethylene group are preferable because the polymerization activity is good.
  • examples of the monovalent alkyl group having 1 or more and 10 or less carbon atoms of R 4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group and tert-butyl. Groups include groups, hexyl groups and cyclohexyl groups.
  • examples of the monovalent alkyl halide group having 1 to 10 carbon atoms of R 4 include fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group and trifluoro.
  • Examples thereof include a methyl group, a trichloromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a perfluorobutyl group and a perfluoropentyl group.
  • a methyl group and an ethyl group are preferable as R 4 from the viewpoint of improving the solubility of the cyclic olefin polymer (A) in a solvent.
  • the monomers represented by the formulas (1) and (2) can be obtained, for example, by an imidization reaction between the corresponding amine and 5-norbornene-2,3-dicarboxylic acid anhydride. Further, the obtained monomer can be efficiently isolated by separating and purifying the reaction solution of the imidization reaction by a known method.
  • Examples of the cyclic olefin monomer having an ester group include 2-acetoxybicyclo [2.2.1] hept-5-ene and 2-acetoxymethylbicyclo [2.2.1] hept-5-ene, 2 -Methoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-ethoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-propoxycarbonylbicyclo [2.2.1] hept-5 -En, 2-butoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-cyclohexyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-methyl-2-methoxycarbonylbicyclo [ 2.2.1] Hept-5-ene, 2-methyl-2-ethoxycarbonylbicyclo [2.2.1] Hept-5-ene, 2-methyl-2-propoxycarbonylbicyclo [2.2.1] Hept-5-ene, 2-methyl-2-butoxycarbonylbicy
  • Dodeca-9-en can be mentioned.
  • 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-cyanotetracyclo [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] hept-5-ene, 2-methyl-2-cyanobicyclo [2.2.1] hept-5-ene, 2 , 3-Dicyanobicyclo [2.2.1] Hept-5-ene.
  • cyclic olefin monomer having an acid anhydride group examples include tetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-ene-4,5-dicarboxylic acid anhydride, bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylic acid anhydride, 2-carboxymethyl-2- Hydroxycarbonylbicyclo [2.2.1] hept-5-ene anhydride can be mentioned.
  • Examples of the cyclic olefin monomer having a halogen atom include 2-chlorobicyclo [2.2.1] hept-5-ene and 2-chloromethylbicyclo [2.2.1] hept-5-ene, 2 -(Chlorophenyl) bicyclo [2.2.1] hept-5-ene, 4-chlorotetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-ene, 4-methyl-4-chlorotetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-en can be mentioned.
  • cyclic olefin monomer (b2) having no polar group include bicyclo [2.2.1] hept-2-ene (also referred to as “norbornene”) and 5-ethyl-bicyclo [2.2].
  • Dodeca-4-ene (also referred to as "tetracyclododecene"), 9-methyl-tetracyclo [6.2.1.1 3,6 . 0 2,7 ]
  • Monomer (b3) examples include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl.
  • -1-Pentene 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3 -Ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and other ⁇ -olefins with 3 to 20 carbon atoms; 1, Non-conjugated diene such as 4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadene, and derivatives thereof;
  • the other monomers (b) such as the above-mentioned monomers (b1) to (b3), one kind may be used alone or two or more kinds may be used in combination.
  • the cyclic olefin monomer (b1) having a polar group other than the protonic polar group is preferable, and the cyclic olefin single amount having an N-substituted imide group is preferable.
  • the body is more preferred.
  • the content ratio of the repeating unit derived from the other monomer (b) in the cyclic olefin polymer (A) is preferably 10 mol% or more, preferably 20 mol, with the total repeating unit as 100 mol%. % Or more, more preferably 30 mol% or more, more preferably 90 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less. preferable. If the proportion of the repeating unit derived from the other monomer (b) is 10 mol% or more, the relative permittivity of the resin film can be lowered, and if it is 90 mol% or less, the heat flow resistance of the resin film is increased. It can be further improved.
  • the method for preparing the cyclic olefin polymer (A) having a protonic polar group is not particularly limited, and for example, the following methods (i) and (ii): (I) A monomer composition containing a cyclic olefin monomer (a) having a protic polar group and another monomer (b) used arbitrarily is polymerized, and an optional hydrogenation reaction is carried out. The method to be carried out, or (ii) a method of modifying a cyclic olefin polymer having no protonic polar group with a modifier having a protonic polar group. Can be mentioned. Among these, the method (i) is preferable.
  • the method for polymerizing the cyclic olefin monomer (a) and the monomer composition optionally containing the other monomer (b) is not particularly limited, and a known method can be used. Specific examples of the polymerization method include ring-opening polymerization and addition polymerization, and ring-opening polymerization is preferable. That is, the cyclic olefin polymer (A) is preferably a ring-opening polymer or an addition polymer, and more preferably a ring-opening polymer.
  • ring-opening polymerization for example, a cyclic olefin monomer (a) having a protonic polar group and another monomer (b) used as needed in the presence of a metathesis reaction catalyst are used. Ring-opening metathesis polymerization that polymerizes can be mentioned.
  • a method for ring-opening metathesis polymerization for example, the method described in International Publication No. 2010/10123 can be adopted.
  • the obtained ring-opening polymer is further hydrogenated to hydrogenate the carbon-carbon double bond contained in the main chain. It is preferable to use a hydrogenated additive.
  • the ratio of hydrogenated carbon-carbon double bonds is 50% or more from the viewpoint of further improving the heat resistance of the resin film. It is preferably 70% or more, more preferably 90% or more, and particularly preferably 95% or more.
  • the "hydrogenation rate" can be measured using a 1 H-NMR spectrum.
  • the method for preparing a cyclic olefin polymer having no protonic polar group is not particularly limited.
  • the cyclic olefin polymer having no protic polar group is, for example, an optional combination of at least one of the above-mentioned monomers (b1) and (b2) and, if necessary, the monomer (b3).
  • the method of modifying the obtained polymer with a modifier having a protonic polar group may follow a conventional method, and is usually carried out in the presence of a radical generator.
  • 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, International Publication No. 2015/141717. Can be used as described in.
  • the weight average molecular weight of the cyclic olefin polymer (A) is preferably 1000 or more, more preferably 3000 or more, further preferably 5000 or more, preferably 100,000 or less, and preferably 50,000 or less. It is more preferably present, and further preferably 30,000 or less.
  • the weight average molecular weight of the cyclic olefin polymer (A) is 1000 or more, the top loss of the line pattern in the resin film can be further suppressed, and the heat flow resistance of the resin film can be further improved. In addition, the chemical resistance of the resin film can be improved.
  • the weight average molecular weight of the cyclic olefin polymer (A) is 100,000 or less, the solubility of the cyclic olefin polymer (A) in a solvent can be sufficiently ensured.
  • the "weight average molecular weight” and “number average molecular weight” of the cyclic olefin polymer (A) are converted into polystyrene by gel permeation chromatography (GPC) using a solvent such as tetrahydrofuran as an eluent. It is a value obtained as a value.
  • the weight average molecular weight and the number average molecular weight of the cyclic olefin polymer (A) can be controlled by adjusting the synthesis conditions (for example, the amount of the molecular weight modifier).
  • 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 even more preferably 2.5 or less. ..
  • the molecular weight distribution of the cyclic olefin polymer (A) is 4 or less, the heat flow resistance can be further improved while further suppressing the top loss of the line pattern in the resin film.
  • the chemical resistance of the resin film can be improved.
  • the molecular weight distribution of the cyclic olefin polymer (A) can be reduced by, for example, the method described in JP-A-2006-307155.
  • the resin composition of the present invention contains, as a resin component, a cresol novolac resin (B) having a softening point of 140 ° C. or higher, in addition to the cyclic olefin polymer (A) described above.
  • a cresol novolac resin (B) having a softening point of 140 ° C. or higher, in addition to the cyclic olefin polymer (A) described above.
  • the cresol novolak resin (B) is a resin obtained by condensing phenols including cresols with aldehydes.
  • Phenols including cresols are not particularly limited as long as they contain cresols, and may be only cresols, and phenols other than cresols and cresols (hereinafter, "" Other phenols ”) may be used in combination.
  • Cresols mean 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. To do.
  • cresols include cresol (o-cresol, m-cresol, p-cresol), xylenol (2,5-xylenol (2,5-dimethylphenol)), and 3,5-xylenol (3,5-dimethylphenol). ) Etc.), trimethylphenol (2,3,5-trimethylphenol, etc.). These may be used individually by 1 type, or may be used in combination of 2 or more type.
  • the cresol novolak resin (B) preferably contains a cresol skeleton and a xylenol skeleton as cresol-derived skeletons, and includes an m-cresol skeleton, a p-cresol skeleton, and a 3,5-xylenol skeleton. It is more preferable to include.
  • the molar ratio (m / p ratio) of the content of meta-body skeleton (m-cresol skeleton, 3,5-xylenol skeleton) to the content of para-body skeleton (p-cresol skeleton) in the skeleton derived from It is preferably 0.5 or more, more preferably 1.0 or more, further preferably 2.0 or more, particularly preferably 2.2 or more, and 5.0 or less.
  • the proportion of cresols in the phenols used for the preparation of the cresol novolak resin (B) is preferably 50% by mass or more, preferably 95% by mass or more, assuming that the total amount of the phenols is 100% by mass. Is more preferable, 97% by mass or more is further preferable, and 100% by mass (that is, only cresols are used as phenols) is particularly preferable.
  • phenols other than the above-mentioned cresols that can be used for the preparation of the cresol novolak resin (B) include monovalent phenol compounds and divalent or higher phenol compounds (polyphenol compounds). As for other phenols, one type may be used alone, or two or more types may be used in combination.
  • Examples of the monovalent phenol compound include 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?
  • Alkylphenols such as methylphenol, 2-t-butyl-5-methylphenol, 2-t-butyl-3-methylphenol, 2,3,5-triethylphenol; 2-methoxyphenol, 3-methoxyphenol, 4-methoxy Alkoxyphenols such as phenol, 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol; 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, etc.
  • Arylphenols; alkenylphenols such as 2-isopropenylphenol, 4-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-isopropenylphenol; and the like.
  • divalent or higher phenol compound examples include resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-methoxyresorcinol, 4-methoxyresorcinol; hydroquinone; catechol, 4-t-butylcatechol, 3 -Methoxycatechol; 4,4'-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane; pyrogallol; fluororesorcinol; and the like.
  • Aldehydes Examples of the aldehydes to be subjected to the condensation reaction with the phenols including the above-mentioned cresols include aliphatic aldehydes, alicyclic aldehydes and aromatic aldehydes.
  • aliphatic aldehyde examples include formaldehyde, trioxane (metaformaldehyde), paraformaldehyde, acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, trimethylacetaldehyde, n-hexylaldehyde, achlorine, and crotonaldehyde. ..
  • alicyclic aldehyde examples include cyclopentane aldehyde, cyclohexane aldehyde, furfural, and frill acrolein.
  • aromatic aldehydes include benzaldehyde, o-tolaldehyde, m-tolualdehyde, p-tolualdehyde, p-ethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, and 3,4-dimethylbenzaldehyde.
  • aldehydes may be used alone or in combination of two or more. Among these, aliphatic aldehydes are preferable, and formaldehyde is more preferable.
  • the cresol novolak resin (B) can be prepared by subjecting the above-mentioned phenols containing cresols and aldehydes to a condensation reaction.
  • This condensation reaction can be carried out, for example, by a known method using an acidic catalyst.
  • the acidic catalyst used include hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid and the like.
  • the softening point of the cresol novolak resin (B) needs to be 140 ° C. or higher, preferably 150 ° C. or higher, and more preferably 160 ° C. or higher. If the softening point is less than 140 ° C., the heat flow resistance of the resin film cannot be ensured.
  • the upper limit of the softening point of the cresol novolak resin (B) is not particularly limited, but is preferably 300 ° C. or lower from the viewpoint of handleability. Further, the softening point of the cresol novolak resin (B) can be controlled by adjusting the types of phenols and aldehydes used in the condensation reaction and the conditions of the condensation reaction.
  • the weight average molecular weight of the cresol novolak resin (B) is preferably 1000 or more, more preferably 3000 or more, further preferably 6000 or more, preferably 20000 or less, and preferably 15000 or less. More preferably, it is more preferably 10,000 or less.
  • the weight average molecular weight is 1000 or more, the softening point is increased and the heat flow resistance of the resin film can be further improved. In addition, the top loss of the line pattern in the resin film can be further suppressed.
  • the weight average molecular weight is 20000 or less, the solubility of the cresol novolak resin (B) in the solvent can be sufficiently ensured.
  • the "weight average molecular weight" of the cresol novolak resin (B) is a value obtained as a polystyrene-equivalent value by gel permeation chromatography (GPC) using a solvent such as tetrahydrofuran as an eluent. .. Further, the weight average molecular weight of the cresol novolak resin (B) can be controlled by adjusting the types of phenols and aldehydes used in the condensation reaction and the conditions of the condensation reaction.
  • the ratio of the cyclic olefin polymer (A) to the total of the above-mentioned cyclic olefin polymer (A) and the above-mentioned cresol novolac resin (B) is the cyclic olefin polymer (A) and the cresol novolac resin (B).
  • the total amount of B) is 100% by mass, it is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and 90% by mass or less. Is more preferable, 80% by mass or less is more preferable, and 75% by mass or less is further preferable.
  • the ratio of the cyclic olefin polymer (A) to the total of the cyclic olefin polymer (A) and the cresol novolak resin (B) is 10% by mass or more, the relative permittivity of the resin film can be sufficiently reduced. If it is 90% by mass or less, the top loss of the line pattern in the resin film can be further suppressed.
  • the acid generator (C) is a compound that decomposes by irradiation with active radiation to generate an acid component such as a carboxylic acid.
  • an acid component such as a carboxylic acid.
  • examples of the acid generator (C) include azide compounds, onium salt compounds, halogenated organic compounds, ⁇ , ⁇ '-bis (sulfonyl) diazomethane compounds, and ⁇ -carbonyl- ⁇ '-sulfonyl diazomethane compounds.
  • Sulphonic acid ester compound, organic acid amide compound, organic acid imide compound, acetophenone compound, triarylsulfonium salt, and azide compound is preferable from the viewpoint of excellent resolution of the obtained line and space pattern.
  • a quinone diazide compound is more preferred.
  • quinone diazide compound preferably used as the acid generator (C) for example, an ester compound of quinone diazido sulfonic acid halide and a compound having a phenolic hydroxyl group can be used.
  • specific examples of quinonediazide sulfonic acid halide include 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, and 1,2-benzoquinonediazide-5-sulfonic acid. Chloride and the like can be mentioned.
  • the compound having a phenolic hydroxyl group examples include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane and 4,4'-[1- [4- [4-]. [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2-bis (4-bis) Hydroxyphenyl) propane, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, Examples thereof include 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.
  • the acid generator (C) includes 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 4,4'-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl].
  • An ester compound (condensate) with phenyl] ethylidene] bisphenol is preferable.
  • the acid generator (C) may be used alone or in combination of two or more.
  • the content of the acid generator (C) in the resin composition of the present invention is preferably 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). It is more preferably 15 parts by mass or more, further preferably 25 parts by mass or more, particularly preferably 30 parts by mass or more, preferably 100 parts by mass or less, and 70 parts by mass or less. Is more preferable, and 50 parts by mass or less is further preferable.
  • the solubility of the exposed part in the alkaline developer is sufficient. Can be enhanced. Further, when forming a fine line-and-space pattern using the resin composition, the active irradiation line may slightly hit the unexposed portion and a top loss of the line pattern may occur. 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 novolak resin (B), the unexposed portion is alkaline-developed. The top loss of the line pattern composed of the unexposed portion can be further suppressed without increasing the solubility in the liquid.
  • the cross-linking agent (D) is a compound capable of cross-linking 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.
  • the resin composition contains the cross-linking agent (D)
  • the heat flow resistance and chemical resistance of the obtained resin film can be improved.
  • the cross-linking agent (D) has 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.
  • the compound is not particularly limited as long as it is a compound, but a polyfunctional epoxy compound (a compound having two or more epoxy groups), a polyfunctional alkoxymethyl compound (a compound having two or more alkoxymethyl groups), and a polyfunctional methylol compound (a methylol group). Compounds having two or more) can be mentioned.
  • the cross-linking agent (D) may be used alone or in combination of two or more.
  • polyfunctional epoxy compound examples include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, and glycerol triglycidyl ether.
  • Epolide registered trademark
  • GT401 Epolide PB3600
  • Epolide PB4700 Celoxide (registered trademark) 2021, Celoxide 3000, EHPE3150 (all manufactured by DIC CORPORATION); jER1001, jER1002, jER1003, jER1004, jER1007, jER1009, jER1010, jER828, jER871, jER872, jER180S75, jER807, jER152, jER154 (all manufactured by Mitsubishi Chemical Industries, Ltd.); EPPN201, EPPN202, EOCN-102, EOCN-103S, EOCN-104S 1020, EOCN-1025, EOCN-1027 (above, manufactured by Nippon Kayaku); Epicron (registered trademark) 200, Epicron 400 (above, manufactured by DIC); Denacol (registered trademark) EX-611, Denacol
  • polyfunctional alkoxymethyl compound examples include a phenol compound in which two or more alkoxymethyl groups are directly bonded to an aromatic ring, a melamine compound in which an amino group is substituted with two or more alkoxymethyl groups, and two or more.
  • the urea compound are substituted with the alkoxymethyl group of the above.
  • Examples of the phenol compound in which two or more alkoxymethyl groups are directly bonded to the aromatic ring include a dimethoxymethyl-substituted phenol compound, a tetramethoxymethyl-substituted biphenyl compound, and a hexamethoxymethyl-substituted triphenyl compound.
  • Examples of the melamine compound in which the 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''-Hexamethoxy Examples thereof include methyl melamine (for example, product name "Nikalac (registered trademark) MW-390LM", product name "Nikalac MW-100LM", all manufactured by Sanwa Chemical Co., Ltd.), or polymers thereof.
  • methyl melamine for example, product name "Nikalac (registered trademark) MW-390LM", product name "Nikalac MW-100LM", all manufactured by Sanwa Chemical Co., Ltd.
  • Examples of the urea compound substituted with two or more alkoxymethyl groups include the product name "Nikalac MX270", the product name “Nikalac MX280”, and the product name "Nikalac MX290” (all manufactured by Sanwa Chemical Co., Ltd.). Be done.
  • Polyfunctional methylol compound examples include a phenol compound in which two or more methylol groups are directly bonded to an aromatic ring.
  • Phenol compounds in which two or more methylol groups are directly bonded to the aromatic ring include 2,4-2,4-dihydroxymethyl-6-methylphenol and 2,6-bis (hydroxymethyl) -p-.
  • cross-linking agents (D) it is preferable to use at least one of a polyfunctional epoxy compound and a polyfunctional alkoxymethyl compound from the viewpoint of further improving the heat flow resistance of the resin film and improving the chemical resistance. It is more preferable to use both a functional epoxy compound and a polyfunctional alkoxymethyl compound.
  • the polyfunctional epoxy compound from the viewpoint of improving the chemical resistance of the resin film satisfactorily, Eporide GT401 (substance name: epoxidized butane tetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ⁇ -caprolactone) and the like are used.
  • the content of the cross-linking agent (D) in the resin composition of the present invention is preferably 15 parts by mass or more per 100 parts by mass in total of the cyclic olefin polymer (A) and the cresol novolac resin (B). It is more preferably parts by mass or more, more preferably 30 parts by mass or more, particularly preferably 40 parts by mass or more, preferably 120 parts by mass or less, and preferably 80 parts by mass or less. It is more preferably 60 parts by mass or less, and particularly preferably 50 parts by mass or less.
  • the content of the cross-linking 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 novolak resin (B), the heat flow resistance and chemical resistance of the resin film are further improved. If it is 120 parts by mass or less, a line-and-space pattern having excellent resolution can be formed.
  • the polyfunctional epoxy compound when used in combination with at least one of the polyfunctional alkoxymethyl compound and the polyfunctional methylol compound (polyfunctional alkoxymethyl compound and / or the polyfunctional methylol compound), the polyfunctional epoxy compound and the polyfunctional alkoxy
  • the mass ratio to the methyl compound and / or the polyfunctional methylol compound may be in the range of 1: 1 to 1: 0.1. It is preferably in the range of 1: 0.5 to 1: 0.25, more preferably.
  • Polyfunctional epoxy compound When the polyfunctional alkoxymethyl compound and / or the polyfunctional methylol compound is within the above range, a resin film having an excellent balance of line-and-space pattern resolution, heat flow resistance and chemical resistance is formed. be able to.
  • the resin composition of the present invention may contain a solvent. That is, the resin composition of the present invention contains 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 crosslink in a solvent.
  • the agent (D) and other compounding agents to be optionally added may be a radiation-sensitive resin solution in which the agent (D) and other compounding agents added optionally are dissolved and / or dispersed.
  • the solvent is not particularly limited, and known as a solvent for the resin composition, for example, acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2 -Straight chain ketones such as octanone, 3-octanone and 4-octanone; alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and cyclohexanol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dioxane and the like.
  • Alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate Esters such as: Cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene.
  • Alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether
  • propyl formate such as ethylene glycol monomethyl
  • Propropylene glycols such as 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; ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -capri Saturated ⁇ -lactones such as lolactone; halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene; other polar solvents such as dimethylacetamide, dimethylformamide and N-methylacetamide; .. As the solvent, one type may be used alone, or two or more types may be used in combination.
  • the resin composition of the present invention may contain a compounding agent other than the above-mentioned components.
  • compounding agents include, for example, resin components other than the cyclic olefin polymer (A) and the cresol novolak resin (B), a silane coupling agent, a compound having an acidic group or a thermopotential acidic group, a dissolution accelerator, and a surfactant. Examples include activators, antioxidants, sensitizers, light stabilizers, defoamers, pigments, dyes and fillers.
  • one type may be used alone, or two or more types may be used in combination.
  • the method for preparing the resin composition of the present invention is not particularly limited, and each component constituting the resin composition may be mixed.
  • the resin composition of the present invention includes a cyclic olefin polymer (A), a cresol novolac resin (B), an acid generator (C), a cross-linking agent (D), and others arbitrarily used. It is preferable to obtain by dissolving or dispersing in the solvent by mixing the compounding agent of the above in the above-mentioned solvent. By this operation, the resin composition is obtained in the form of a solution or a dispersion (that is, as a radiation-sensitive resin solution).
  • the above mixing is not particularly limited, and is carried out using a known mixer. Further, after mixing, filtration may be performed by a known method.
  • the solid content concentration of the radiation-sensitive resin liquid which is the resin composition of the present invention, is usually 1% by mass or more and 70% by mass or less, preferably 5% by mass or more and 60% by mass or less, and more preferably 10% by mass or more. It is 50% by mass or less.
  • the solid content concentration is within the above range, the dissolution stability and coatability of the radiation-sensitive resin liquid, the film thickness uniformity and flatness of the formed resin film, and the like can be highly balanced.
  • a resin film can be formed on a substrate such as a silicon wafer on which a semiconductor element is mounted.
  • the method of forming the resin film on the substrate is not particularly limited.
  • a step of forming a radiation-sensitive film on a substrate that is, a radiation-sensitive film forming step
  • a radiation-sensitive resin composition containing a solvent that is, a radiation-sensitive resin solution
  • a step of irradiating a radioactive film with active radiation to obtain an exposure film (exposure step), a step of developing the exposure film to obtain a development film (development step), and a step of curing the development film to obtain a resin film (exposure step). It can be manufactured through a curing step).
  • Radiation-sensitive film forming process The method for forming the radiation-sensitive film on the substrate using the radiation-sensitive resin liquid is not particularly limited, and for example, a coating method, a film lamination method, or the like can be used.
  • the coating method is a method in which a radiation-sensitive resin solution is applied onto a substrate and then the solvent is removed by heating and drying to form a radiation-sensitive film.
  • Examples of the method for applying the radiation-sensitive resin liquid include a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a rotary coating method, a slit coating method, a bar coating method, a screen printing method, and an inkjet method. Various methods such as, etc. can be adopted.
  • the heating and drying conditions differ depending on the type and blending ratio of each component, but the heating temperature is usually 30 to 150 ° C., preferably 60 to 130 ° C., and the heating time is usually 0.5 to 90 minutes. , Preferably 1 to 60 minutes, more preferably 1 to 30 minutes.
  • a radiation-sensitive resin solution is applied on a base material for forming a radiation-sensitive film (resin film, metal film, etc.), and then the solvent is removed by heat drying to obtain a radiation-sensitive film, and then a radiation-sensitive film is obtained.
  • This is a method of laminating the obtained radiation-sensitive film on a substrate.
  • the heating and drying conditions can be appropriately selected according to the type and blending ratio of each component, but the heating temperature is usually 30 to 150 ° C., and the heating time is usually 0.5 to 90 minutes. ..
  • the radiation-sensitive film can be laminated on the substrate by using a crimping 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-mentioned methods is not particularly limited and may be appropriately set according to the intended use, but is preferably 0.1 to 100 ⁇ m, more preferably 0.1 to 100 ⁇ m. It is 0.5 to 50 ⁇ m, more preferably 0.5 to 30 ⁇ m.
  • Exposure process the radiation-sensitive film formed in the above-mentioned radiation-sensitive film forming step is irradiated with active radiation to obtain an exposed film having a latent image pattern.
  • the acid generator (C) contained in the radiation-sensitive film is activated to improve the solubility of the resin component in the developing solution (particularly, the solubility in the alkaline developing solution) in the exposed portion.
  • the acid generator (C) contained in the radiation-sensitive film is activated to improve the solubility of the resin component in the developing solution (particularly, the solubility in the alkaline developing solution) in the exposed portion.
  • ultraviolet rays including ultraviolet rays having a single wavelength such as g-rays and i-rays
  • KrF excimer laser light KrF excimer laser light
  • light rays exemplified by ArF excimer laser light particle beams exemplified by electron beams; and the like.
  • light rays When light rays are used as the active radiation, it may be single wavelength light or mixed wavelength light.
  • Exposure conditions As a method of selectively irradiating the above-mentioned active radiation in a pattern to form a latent image pattern, a conventional method may be followed. For example, an ultraviolet ray, KrF excimer laser light, and ArF may be used by a reduced projection exposure device or the like. A method of irradiating a light beam such as excimer laser light through a desired mask pattern, or a method of drawing with a particle beam such as an electron beam can be used. The irradiation conditions are appropriately selected according to the active radiation to be used.
  • the irradiation amount is usually 10 to 5,000 mJ / cm 2 , preferably 50 to 1, The range is 500 mJ / cm 2 , and it depends on the irradiation time and illuminance.
  • the obtained exposure film may be heat-treated at a temperature of about 60 to 150 ° C. for about 1 to 10 minutes, if necessary.
  • An alkaline developer can be used as the developer.
  • the alkaline developer can be obtained by dissolving an alkaline compound in an aqueous medium.
  • alkaline compound for example, an alkali metal salt, an amine, or an ammonium salt can be used.
  • the alkaline compound may be an inorganic compound or an organic compound.
  • Specific examples of alkaline compounds 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; diethylamine and di.
  • alkaline compounds such as -n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Tertiary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline; dimethyl Alcohol amines such as ethanolamine and triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5-ene , N-Methylpyrrolidone and other cyclic amines; These alkaline compounds may be used alone or in combination of two or more.
  • the aqueous medium of the alkaline developer water; a water-soluble organic solvent such as methanol or ethanol can be used.
  • the alkaline developer may be one to which an appropriate amount of a surfactant
  • the developing temperature is usually appropriately selected in the range of 0 to 100 ° C., preferably 5 to 55 ° C., more preferably 10 to 30 ° C., and the developing time is usually appropriately selected in the range of 30 to 180 seconds.
  • the developing film on which the desired pattern is formed in this way can be rinsed with a rinsing solution, if necessary, in order to remove the developing residue. After the rinsing treatment, it is preferable to remove the remaining rinsing liquid with compressed air or compressed nitrogen. Further, if necessary, the developing film can be irradiated with active radiation in order to inactivate the acid generator (C) remaining in the developing film.
  • active radiation the method described above in the "exposure step" can be used.
  • the developing film may be heated at the same time as the irradiation of the active radiation or after the irradiation of the active radiation. Examples of the heating method include a method of heating an electronic component in a hot plate or an oven. The heating temperature is usually in the range of 80 to 300 ° C, preferably 100 to 200 ° C.
  • the curing method may be appropriately selected depending on the type of the cross-linking agent (D) contained in the radiation-sensitive resin liquid, but is usually carried out by heating.
  • the heating method can be performed using, for example, a hot plate, an oven, or the like.
  • the heating temperature is usually 150 to 250 ° C.
  • the heating time is appropriately selected depending on the area and thickness of the developing film, the equipment used, etc.
  • the oven is usually operated for 5 to 120 minutes. When used, it is usually in the range of 30-150 minutes. Further, heating may be performed in an inert gas atmosphere, if necessary.
  • the inert gas may be any gas that does not contain oxygen and does not oxidize the developing film, and examples thereof include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is particularly 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 preferable. These inert gases may be used alone or in combination of two or more.
  • the prepared resin composition was spin-coated on a 4-inch silicon wafer on which an aluminum film having a film thickness of 50 nm was formed using a sputtering device (manufactured by Shibaura Eletech Co., Ltd., product name "i-Miller CFS-4EP-LL"). It was applied and then heat-dried (prebaked) at 120 ° C. for 2 minutes using a hot plate to form a radiation-sensitive film. The film was cured by heating in nitrogen at 230 ° C. for 1 hour to obtain a silicon wafer with a cured film having a thickness of 10 ⁇ m.
  • a sputtering device manufactured by Shibaura Eletech Co., Ltd., product name "i-Miller CFS-4EP-LL”
  • a radiation-sensitive film (thickness: 3.0 ⁇ m). Formed.
  • an i-line stepper (manufactured by Nikon Corporation, product name "NSR2005i9C") is set with a reticle capable of forming a 1.0 ⁇ m line and space pattern, and the exposure is changed from 100 to 2000 mJ / cm 2. The process was performed. The obtained exposure film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. Then, after rinsing with ultrapure water and shaking off and drying, a laminate composed of a developing film having a line and space pattern and a silicon wafer was obtained.
  • top loss (film thickness of unexposed portion-film thickness of line portion) / (film thickness of unexposed portion) ⁇ 100, and evaluated according to the following criteria.
  • Top loss is less than 25%
  • B Top loss is 25% or more and less than 40%
  • C Top loss is 40% or more ⁇ Heat flow resistance>
  • the prepared resin composition is applied onto a silicon wafer by a spin coating method, and then heat-dried (prebaked) at 120 ° C. for 2 minutes using a hot plate to form a radiation-sensitive film (thickness: 3.0 ⁇ m). Formed.
  • an exposure step was performed by changing the exposure amount from 100 to 2000 mJ / cm 2 using a mask capable of forming a 2.0 ⁇ m via pattern.
  • the obtained exposure film was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds.
  • a laminate composed of a developing film having a via hole of 2.0 ⁇ m and a silicon wafer was obtained.
  • the obtained 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 at 230 ° C.
  • the developing film was cured by holding for 1 hour to obtain a resin film.
  • Via diameter reduction rate (%) (Beer diameter before curing-after curing). Via diameter) / (Beer diameter before curing) ⁇ 100 was used to calculate the reduction rate of the via diameter due to curing, and evaluated according to the following criteria.
  • the prepared resin composition was applied onto a silicon wafer by a spin coating method, and heat-dried (prebaked) at 120 ° C.
  • film thickness change rate (%)
  • the rate of change in film thickness is 20% or more , And / or at least one of cracks and peeling
  • Example 1 ⁇ Preparation of cyclic olefin polymer (A-1)> N-Phenyl-bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide (NBPI) 40 mol% and 4-hydroxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] 100 parts by mass of a monomer mixture consisting of 60 mol% of dodeca-9-ene (TCDC), 2.0 parts by mass of 1,5-hexadien, (1,3-dimesityl imidazoline-2-ylidene).
  • TCDC dodeca-9-ene
  • the obtained cyclic olefin polymer (A-1) has a polymerization conversion rate of 99.7% by mass, a weight average molecular weight (in terms of polystyrene) of 7200, a number average molecular weight of 4700, a molecular weight distribution of 1.53, and a hydrogenation rate. It was 99.7%.
  • the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-1) was 34.4% by mass.
  • the amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 ⁇ m to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 1.
  • Example 2 In preparing the resin composition, the amount of the cyclic olefin polymer (A-1) was changed from 75 parts to 55 parts (corresponding to the solid content), the amount of the cresol novolak resin (B-1) was changed from 25 parts to 45 parts, and , The cyclic olefin polymer (A-1) and the resin composition were prepared in the same manner as in Example 1 except that the amount of the cross-linking agent (D-1) was changed from 30 parts to 35 parts, and various evaluations were performed. went. The results are shown in Table 1.
  • Example 3 In preparing the resin composition, the amount of the cyclic olefin polymer (A-1) was changed from 75 parts to 30 parts (corresponding to the solid content), and the amount of the cresol novolak resin (B-1) was changed from 25 parts to 70 parts.
  • a cyclic olefin polymer (A-1) and a resin composition were prepared in the same manner as in Example 1 except for the above, and various evaluations were performed. The results are 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 the cyclic olefin polymer (A-1) except that the NBPI was 31.5 mol% and the TCDC was 68.5 mol%. did.
  • the obtained cyclic olefin polymer (A-2) has a polymerization conversion rate of 99.8% by mass, a weight average molecular weight (in terms of polystyrene) of 7300, a number average molecular weight of 4800, a molecular weight distribution of 1.52, and a hydrogenation rate. , 99.9%.
  • the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-2) was 34.3% by mass.
  • ⁇ Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)> 50 parts (equivalent to solid content) of polymer solution of cyclic olefin polymer (A-2), cresol novolac resin (B-2) (manufactured by Asahi Organic Materials Co., Ltd., product name "TMR30B25G", weight average molecular weight: 9000, softened 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 30 parts of (C-1), 37 parts of cross-linking agent (D-1), cross-linking agent (D-5) (manufactured by Honshu Chemical Industry Co., Ltd., product name "HMOM
  • the amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 ⁇ m to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 1.
  • Example 5 ⁇ Preparation of cyclic olefin polymers (A-1) and (A-2)> A cyclic olefin polymer (A-1) was prepared in the same manner as in Example 1, and a cyclic olefin polymer (A-2) was prepared in the same manner as in Example 4.
  • the amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 ⁇ m to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 1.
  • Example 7 ⁇ Preparation of cyclic olefin polymer (A-3)> N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide (NEHI) was 40 mol% and TCDC was 60 mol% without using NBPI.
  • a cyclic olefin polymer (A-3) having a protonic polar group was prepared in the same manner as the cyclic olefin polymer (A-1) except for the above.
  • the obtained cyclic olefin polymer (A-3) has a polymerization conversion rate of 99.8% by mass, a weight average molecular weight (in terms of polystyrene) of 8500, a number average molecular weight of 5800, a molecular weight distribution of 1.47, and a hydrogenation rate. , 99.9%. Moreover, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-3) was 34.3% by mass.
  • 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 part by mass of 1-hexene, (1,3-dimesityl imidazoline-2-iriden) (tricyclohexylphosphine). 0.06 parts by mass of benzylidene ruthenium dichloride and 300 parts by mass of diethylene glycol methyl ethyl ether were charged into a nitrogen-substituted glass pressure-resistant reactor and reacted at 80 ° C. for 4 hours with stirring to obtain a polymerization reaction solution.
  • 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 carry out a hydrogenation reaction, and contains a cyclic olefin polymer (A-4) having a protonic polar group.
  • a polymer solution was obtained.
  • the obtained cyclic olefin polymer (A-4) has a polymerization conversion rate of 99.3% by mass, a weight average molecular weight (in terms of polystyrene) of 20600, a number average molecular weight of 11500, a molecular weight distribution of 1.79, and a hydrogenation rate. , 99.8%.
  • the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-4) was 25.3% by mass.
  • the amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 ⁇ m to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 1.
  • Example 8 ⁇ Preparation of cyclic olefin polymers (A-2) and (A-4)> A cyclic olefin polymer (A-2) was prepared in the same manner as in Example 4, and a cyclic olefin polymer (A-4) was prepared in the same manner as in Example 7.
  • ⁇ Preparation of radiation-sensitive resin composition > 30 parts (equivalent to solid content) of the polymer solution of the cyclic olefin polymer (A-2), 30 parts (equivalent to solid content) of the polymer solution of the cyclic olefin polymer (A-4), cresol novolac resin (B-) 1) 40 parts, acid generator (C-1) 30 parts, cross-linking agent (D-1) 15 parts, cross-linking agent (D-3) (manufactured by Daicel, product name "EHPE3150", 2, 2 15 parts of 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of -bis (hydroxymethyl) -1-butanol), 10 parts of cross-linking agent (D-6), and diethylene glycol methyl ethyl as a solvent.
  • the ether was mixed and dissolved.
  • the amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass.
  • the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 ⁇ m to prepare a resin composition.
  • Various evaluations were carried out using the obtained resin composition. The results are shown in Table 1.
  • Example 9 In preparing the resin composition, the amount of the cyclic olefin polymer (A-1) was changed from 75 parts to 15 parts (corresponding to the solid content), and the amount of the cresol novolak resin (B-1) was changed from 25 parts to 85 parts. A cyclic olefin polymer (A-1) and a resin composition were prepared in the same manner as in Example 1 except for the above, and various evaluations were performed. The results are shown in Table 2.
  • Example 10 When preparing the resin composition, the amount of the cyclic olefin polymer (A-2) was changed from 50 parts to 85 parts (corresponding to the solid content), and the amount of the cresol novolak resin (B-2) was changed from 50 parts to 15 parts. Then, the cyclic olefin polymer (A-2) and the resin composition were prepared in the same manner as in Example 4 except that the amount of the cross-linking agent (D-1) was changed from 37 parts to 35 parts. Evaluation was performed. The results are shown in Table 2.
  • the amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 ⁇ m to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 2.
  • the amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 ⁇ m to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 2.
  • MC / pC / mX indicates m-cresol / p-cresol / m-xylenol (molar ratio).
  • MC / pC indicates m-cresol / p-cresol (molar ratio).
  • Epoxy refers to a polyfunctional epoxy compound
  • Metal refers to a polyfunctional methoxymethyl (alkoxymethyl) compound.
  • Comparative Example 1 using the resin composition containing no cresol novolak resin (B), it can be seen that the top loss of the line pattern in the resin film cannot be suppressed.
  • Comparative Example 2 using the resin composition containing no cyclic olefin polymer (A), it can be seen that the relative permittivity of the resin film increases and the heat flow resistance decreases.
  • Comparative Example 3 using a resin composition containing a cresol novolak resin but having a softening point of less than 140 ° C., the heat flow resistance of the resin film is lowered.
  • Comparative Example 4 using the resin composition containing no cross-linking agent (D), it can be seen that the chemical resistance and heat flow resistance of the resin film are lowered.
  • Comparative Example 5 using the resin composition containing the phenol novolac resin but not the cresol novolak resin (B), the top loss of the line pattern in the resin film could not be suppressed, and the heat flow resistance of the resin film was lowered. You can see that it does. It can be seen that in Comparative Example 6 using the resin composition containing the polyvinylphenol resin but not the cyclic olefin polymer (A), the heat flow resistance of the resin film is lowered.
  • the present invention it is possible to provide a radiation-sensitive resin composition capable of forming a resin film having excellent heat flow resistance while suppressing the top loss of the line pattern.

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Abstract

The purpose of the present invention is to provide a radiation-sensitive resin composition capable of forming a resin film in which top loss of a line pattern is suppressed and which exhibits excellent heat flow resistance. This radiation-sensitive resin composition contains (A) a cyclic olefin polymer having a protonic polar group; (B) a cresol novolac resin having a softening point of 140ºC or higher; (C) an acid generator; and (D) a crosslinking agent.

Description

感放射線性樹脂組成物Radiation-sensitive resin composition
　本発明は、感放射線性樹脂組成物に関するものである。 The present invention relates to a radiation-sensitive resin composition.
　集積回路素子、固体撮像素子、カラーフィルター、各種表示素子（例えば、有機ＥＬ素子、液晶表示素子）、およびブラックマトリックス等の電子部品には、その劣化や損傷を防止するための表面保護膜、素子表面や配線を平坦化するための平坦化膜、層状に配置される配線の間を絶縁するための層間絶縁膜といった種々の樹脂膜が設けられている。 Electronic components such as integrated circuit elements, solid-state imaging elements, color filters, various display elements (for example, organic EL elements and liquid crystal display elements), and black matrices have surface protective films and elements to prevent deterioration and damage. Various resin films such as a flattening film for flattening the surface and wiring and an interlayer insulating film for insulating between the wiring arranged in layers are provided.
　このような樹脂膜の形成には、例えば、樹脂成分と、活性放射線（紫外線（ｇ線やｉ線等の単一波長の紫外線を含む）、ＫｒＦエキシマレーザー光、およびＡｒＦエキシマレーザー光に例示される光線；電子線に例示される粒子線など）の照射によって酸を発生する酸発生剤とを含有する感放射線性樹脂組成物（以下、「樹脂組成物」と略記する場合がある。）が従来から用いている。具体的には、樹脂組成物を用いて得られる感放射線性膜に対して、活性放射線を照射し、得られた露光膜の露光部を現像液により除去（現像）する等して、用途に応じた所望のパターン形状を有する樹脂膜を得ることができる。
　そして従来、このような樹脂組成物の樹脂成分として、プロトン性極性基を有する環状オレフィン重合体が使用されている（例えば、特許文献１～２を参照）。 Examples of the formation of such a resin film include a resin component, active radiation (ultraviolet rays (including ultraviolet rays having a single wavelength such as g-ray and i-ray), KrF excimer laser light, and ArF excimer laser light). A radiation-sensitive resin composition (hereinafter, may be abbreviated as "resin composition") containing an acid generator that generates an acid by irradiation with an ultraviolet ray (such as a particle beam exemplified for an electron beam). It has been used conventionally. Specifically, the radiation-sensitive film obtained by using the resin composition is irradiated with active radiation, and the exposed portion of the obtained exposure film is removed (developed) with a developing solution, etc. A resin film having a desired pattern shape can be obtained.
Conventionally, a cyclic olefin polymer having a protonic polar group has been used as a resin component of such a resin composition (see, for example, Patent Documents 1 and 2).
特開２０１６－５０８７５９号公報Japanese Unexamined Patent Publication No. 2016-508759 国際公開第２０１５／１４１７１９号International Publication No. 2015/141719
　しかしながら、プロトン性極性基を有する環状オレフィン重合体を含んでなる従来の樹脂組成物を用いて、微細なラインアンドスペースパターン形状を有する樹脂膜を形成すると、未露光部からなるラインパターンの高さがパターンを有さない未露光部の高さよりも減じてしまう（即ち、ラインパターンのトップロスが生じる）場合があった。
　また一般に、樹脂組成物を用いて樹脂膜を形成するに際しては、露光および現像後に熱硬化などを目的として加熱処理を行う場合があるが、このような加熱処理の際に、露光および現像により形成された所期のパターン形状が損なわれる場合がある。そのため、樹脂組成物を用いて形成される樹脂膜には、加熱処理を経て形成される場合でも、所期のパターン形状を維持する性質（熱フロー耐性）を高めることが求められていた。 However, when a resin film having a fine line-and-space pattern shape is formed by using a conventional resin composition containing a cyclic olefin polymer having a protonic polar group, the height of the line pattern including the unexposed portion is high. In some cases, the height is less than the height of the unexposed portion having no pattern (that is, a top loss of the line pattern occurs).
In general, when a resin film is formed using a resin composition, heat treatment may be performed for the purpose of heat curing after exposure and development. However, during such heat treatment, the resin film is formed by exposure and development. The desired pattern shape may be impaired. Therefore, the resin film formed by using the resin composition is required to enhance the property (heat flow resistance) of maintaining the desired pattern shape even when it is formed through heat treatment.
　そこで、本発明は、ラインパターンのトップロスが抑制されていると共に、熱フロー耐性に優れる樹脂膜を形成しうる感放射線性樹脂組成物の提供を目的とする。 Therefore, an object of the present invention is to provide a radiation-sensitive resin composition capable of forming a resin film having excellent heat flow resistance while suppressing the top loss of the line pattern.
　本発明者は、上記課題を解決することを目的として鋭意検討を行った。そして、本発明者は、樹脂成分として、プロトン性極性基を有する環状オレフィン重合体に加えて軟化点が所定の値以上であるクレゾールノボラック樹脂を含有し、そして更に酸発生剤および架橋剤を含有する樹脂組成物を用いて樹脂膜を形成すれば、ラインパターンのトップロスを抑制しつつ、熱フロー耐性を高めうることを見出し、本発明を完成させた。 The present inventor conducted a diligent study for the purpose of solving the above problems. Then, the present inventor contains, as a resin component, a cresol novolac resin having a softening point of a predetermined value or more in addition to a cyclic olefin polymer having a protonic polar group, and further contains an acid generator and a cross-linking agent. We have found that if a resin film is formed using the resin composition to be used, the heat flow resistance can be enhanced while suppressing the top loss of the line pattern, and the present invention has been completed.
　即ち、この発明は、上記課題を有利に解決することを目的とするものであり、本発明の感放射線性樹脂組成物は、プロトン性極性基を有する環状オレフィン重合体（Ａ）、軟化点が１４０℃以上のクレゾールノボラック樹脂（Ｂ）、酸発生剤（Ｃ）、および架橋剤（Ｄ）を含むことを特徴とする。上述した（Ａ）～（Ｄ）の成分を含有する樹脂組成物を用いれば、ラインパターンのトップロスが抑制されていると共に、熱フロー耐性に優れる樹脂膜を形成することができる。
　なお、本発明において、「軟化点」は、ＪＩＳ　Ｋ６９１０：２００７に記載の環球法により測定することができる。 That is, the present invention aims to advantageously solve the above problems, and the radiation-sensitive resin composition of the present invention has a cyclic olefin polymer (A) having a protonic polar group and a softening point. It is characterized by containing a cresol novolak resin (B) at 140 ° C. or higher, an acid generator (C), and a cross-linking agent (D). By using the resin composition containing the above-mentioned components (A) to (D), the top loss of the line pattern can be suppressed and a resin film having excellent heat flow resistance can be formed.
In the present invention, the "softening point" can be measured by the ring-and-ball method described in JIS K6910: 2007.
　ここで、本発明の感放射線性樹脂組成物は、前記クレゾールノボラック樹脂（Ｂ）が、クレゾール骨格とキシレノール骨格とを含むことが好ましい。クレゾールに由来する骨格と、キシレノールに由来する骨格とを含むクレゾールノボラック樹脂（Ｂ）を用いれば、樹脂膜の熱フロー耐性を更に向上させることができる。 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. By using the cresol novolak resin (B) containing a skeleton derived from cresol and a skeleton derived from xylenol, the heat flow resistance of the resin film can be further improved.
　また、本発明の感放射線性樹脂組成物は、前記酸発生剤（Ｃ）がキノンジアジド化合物であることが好ましい。酸発生剤（Ｃ）としてキノンジアジド化合物を用いれば、樹脂膜に形成されたラインアンドスペースパターンの解像度を向上させることができる。 Further, in the radiation-sensitive resin composition of the present invention, it is preferable that the acid generator (C) is a quinonediazide compound. When a quinone diazide compound is used as the acid generator (C), the resolution of the line and space pattern formed on the resin film can be improved.
　そして、本発明の感放射線性樹脂組成物は、前記架橋剤（Ｄ）が、多官能エポキシ化合物、多官能アルコキシメチル化合物、および多官能メチロール化合物からなる群から選択される少なくとも１つであることが好ましい。架橋剤（Ｄ）として、多官能エポキシ化合物、多官能アルコキシメチル化合物、および／または多官能メチロール化合物を用いれば、樹脂膜の耐薬品性を高めつつ、熱フロー耐性を更に向上させることができる。 In the radiation-sensitive resin composition of the present invention, the cross-linking 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. Is preferable. When a polyfunctional epoxy compound, a polyfunctional alkoxymethyl compound, and / or a polyfunctional methylol compound is used as the cross-linking agent (D), the chemical resistance of the resin film can be enhanced and the heat flow resistance can be further improved.
　加えて、本発明の感放射線性樹脂組成物は、前記環状オレフィン重合体（Ａ）と前記クレゾールノボラック樹脂（Ｂ）の合計中に占める前記環状オレフィン重合体（Ａ）の割合が、１０質量％以上９０質量％以下であることが好ましい。環状オレフィン重合体（Ａ）とクレゾールノボラック樹脂（Ｂ）を上述した量比で用いれば、樹脂膜の比誘電率を低下させつつ、当該樹脂膜に形成されたラインパターンのトップロスを一層抑制することができる。 In addition, in the radiation-sensitive resin composition of the present invention, the ratio of the cyclic olefin polymer (A) to the total of the cyclic olefin polymer (A) and the cresol novolak resin (B) is 10% by mass. It is preferably 90% by mass or more. When the cyclic olefin polymer (A) and the cresol novolak resin (B) are used in the above-mentioned quantitative ratio, the relative permittivity of the resin film is lowered, and the top loss of the line pattern formed on the resin film is further suppressed. be able to.
　また、本発明の感放射線樹脂組成物は、前記クレゾールノボラック樹脂（Ｂ）に含まれるクレゾール類に由来する骨格中において、パラ体骨格の含有量に対するメタ体骨格の含有量のモル比（即ち、ｍ／ｐ比）が５．０以下であることが好ましい。クレゾール類に由来する骨格中において、パラ体に由来する骨格の含有量に対するメタ体に由来する含有量の比が、モル基準で５．０以下であるクレゾールノボラック樹脂（Ｂ）を用いれば、樹脂膜におけるラインパターンのトップロスを一層抑制しつつ、熱フロー耐性を更に向上させることができる。
　なお、本発明において、「ｍ／ｐ比」は、核磁気共鳴法（例えば、13Ｃ－ＮＭＲ）などの既知の方法で測定することができる。 Further, the radiation-sensitive resin composition of the present invention has a molar ratio of the content of the meta-skeleton to the content of the para-skeleton in the skeleton derived from the cresols contained in the cresol novolak resin (B) (that is, The m / p ratio) is preferably 5.0 or less. If the cresol novolac resin (B) in which the ratio of the content derived from the meta form to the content of the skeleton derived from the para form in the skeleton derived from cresols is 5.0 or less on a molar basis, the resin is used. The heat flow resistance can be further improved while further suppressing the top loss of the line pattern in the film.
In the present invention, the "m / p ratio" can be measured by a known method such as nuclear magnetic resonance (for example, 13 C-NMR).
　本発明によれば、ラインパターンのトップロスが抑制されていると共に、熱フロー耐性に優れる樹脂膜を形成しうる感放射線性樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a radiation-sensitive resin composition capable of forming a resin film having excellent heat flow resistance while suppressing the top loss of the line pattern.
　以下、本発明の実施形態について詳細に説明する。
　本発明の感放射線性樹脂組成物は、樹脂膜の形成に用いることができ、当該樹脂膜は、例えば、ウェハレベルパッケージ技術によって製造される電子部品において、表面保護膜、平坦化膜、層間絶縁膜等として用いることができる。 Hereinafter, embodiments of the present invention will be described in detail.
The radiation-sensitive resin composition of the present invention can be used for forming a resin film, and the resin film can be used, for example, in electronic components manufactured by wafer level packaging technology, as a surface protective film, a flattening film, and interlayer insulation. It can be used as a film or the like.
　本発明の感放射線性樹脂組成物は、プロトン性極性基を有する環状オレフィン重合体（Ａ）、軟化点が１４０℃以上のクレゾールノボラック樹脂（Ｂ）、酸発生剤（Ｃ）、および架橋剤（Ｄ）を含有し、任意に、溶剤や、その他の配合剤を含有する。
　そして、本発明の感放射線性樹脂組成物は、樹脂成分として、上述した環状オレフィン重合体（Ａ）およびクレゾールノボラック樹脂（Ｂ）含みつつ、酸発生剤（Ｃ）および架橋剤（Ｄ）を含有しているので、当該樹脂組成物を用いれば、ラインパターンのトップロスが抑制されていると共に、熱フロー耐性に優れる樹脂膜を形成することができる。 The radiation-sensitive resin composition of the present invention comprises 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 cross-linking agent ( D) is contained, and optionally, a solvent and other compounding agents are contained.
The radiation-sensitive resin composition of the present invention contains the above-mentioned cyclic olefin polymer (A) and cresol novolac resin (B) as resin components, and also contains an acid generator (C) and a cross-linking agent (D). Therefore, if the resin composition is used, the top loss of the line pattern can be suppressed and a resin film having excellent heat flow resistance can be formed.
＜環状オレフィン重合体（Ａ）＞
　環状オレフィン重合体（Ａ）は、プロトン性極性基を有すると共に、環状オレフィン骨格を有する重合体である。 <Cyclic olefin polymer (A)>
The cyclic olefin polymer (A) is a polymer having a protonic polar group and a cyclic olefin skeleton.
＜＜プロトン性極性基＞＞
　環状オレフィン重合体（Ａ）は、プロトン性極性基を備えることにより、現像液（特には、後述するアルカリ現像液）に対する溶解性を有する。また、熱硬化に際してプロトン性極性基が架橋剤（Ｄ）と反応し、環状オレフィン重合体（Ａ）等の樹脂成分が強固な架橋構造をとることができるため、樹脂膜に優れた熱フロー耐性および耐薬品性を付与することができる。 << Protic polar group >>
The cyclic olefin polymer (A) has a solubility in a developing solution (particularly, an alkaline developing solution described later) by having a protonic polar group. Further, since the protonic polar group reacts with the cross-linking agent (D) during thermosetting and the resin component such as the cyclic olefin polymer (A) can have a strong cross-linked structure, the resin film has excellent heat flow resistance. And chemical resistance can be imparted.
　ここで、プロトン性極性基とは、水素原子が直接結合している周期表第１５族または第１６族に属する原子を含む基をいう。周期表第１５族または第１６族に属する原子としては、周期表第１５族または第１６族の第２または第３周期に属する原子が好ましく、より好ましくは酸素原子、窒素原子または硫黄原子であり、特に好ましくは酸素原子である。 Here, the protic 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. As the atom belonging to the 15th group or the 16th group of the periodic table, the atom belonging to the 2nd or 3rd period of the 15th group or the 16th period of the periodic table is preferable, and an oxygen atom, a nitrogen atom or a sulfur atom is more preferable. , Particularly preferably an oxygen atom.
　このようなプロトン性極性基の具体例としては、水酸基、カルボキシル基（ヒドロキシカルボニル基）、スルホン酸基、リン酸基等の酸素原子を有する極性基；第一級アミノ基、第二級アミノ基、第一級アミド基、第二級アミド基（イミド基）等の窒素原子を有する極性基；チオール基等の硫黄原子を有する極性基；が挙げられる。これらの中でも、酸素原子を有する極性基が好ましく、カルボキシル基、水酸基がより好ましく、カルボキシル基が更に好ましい。
　なお、環状オレフィン重合体（Ａ）は、プロトン性極性基を１種のみ有していてもよく、２種以上有していてもよい。 Specific examples of such a 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; a primary amino group and a secondary amino group. , A polar group having a nitrogen atom such as a primary amide group and a secondary amide group (imide group); a polar group having a sulfur atom such as a thiol group; Among these, a polar group having an oxygen atom is preferable, a carboxyl group and a hydroxyl group are more preferable, and a carboxyl group is further preferable.
The cyclic olefin polymer (A) may have only one type of protonic polar group, or may have two or more types.
＜＜組成＞＞
　そして、環状オレフィン重合体（Ａ）に上述したプロトン性極性基を導入する方法は特に限定されない。すなわち、環状オレフィン重合体（Ａ）は、例えば、プロトン性極性基を有する環状オレフィン単量体（ａ）に由来する繰り返し単位を含み、任意に、その他の単量体（ｂ）に由来する繰り返し単位を含む重合体であってもよいし、プロトン性極性基を有しない環状オレフィン重合体に変性剤を用いてプロトン性極性基が導入されてなる重合体であってもよいが、前者が好ましい。 << Composition >>
The method for introducing the above-mentioned protonic polar group into the cyclic olefin polymer (A) is not particularly limited. That is, the cyclic olefin polymer (A) contains, for example, a repeating unit derived from the cyclic olefin monomer (a) having a protic polar group, and optionally, a repeating unit derived from another monomer (b). It may be a polymer containing a unit, or it may be a polymer in which a protonic polar group is introduced into a cyclic olefin polymer having no protonal polar group by using a modifier, but the former is preferable. ..
［プロトン性極性基を有する環状オレフィン単量体（ａ）］
　プロトン性極性基を有する環状オレフィン単量体（ａ）としては、上述したプロトン性極性基、および環状オレフィン構造を有する単量体であれば特に限定されないが、例えば、カルボキシル基を有する環状オレフィン単量体、水酸基を有する環状オレフィン単量体が好適に挙げられる。 [Cyclic olefin monomer (a) having a protonic 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-mentioned protonic polar group and a cyclic olefin structure, but for example, a cyclic olefin simple having a carboxyl group. A cyclic olefin monomer having a metric or a hydroxyl group is preferably used.
―カルボキシル基を有する環状オレフィン単量体―
　カルボキシル基を有する環状オレフィン単量体としては、例えば、２－ヒドロキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－メチル－２－ヒドロキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－カルボキシメチル－２－ヒドロキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－２－メトキシカルボニルメチルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－２－エトキシカルボニルメチルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－２－プロポキシカルボニルメチルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－２－ブトキシカルボニルメチルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－２－ペンチルオキシカルボニルメチルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－２－ヘキシルオキシカルボニルメチルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－２－シクロヘキシルオキシカルボニルメチルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－２－フェノキシカルボニルメチルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－２－ナフチルオキシカルボニルメチルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－２－ビフェニルオキシカルボニルメチルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－２－ベンジルオキシカルボニルメチルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－２－ヒドロキシエトキシカルボニルメチルビシクロ［２．２．１］ヘプト－５－エン、２，３－ジヒドロキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－３－メトキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－３－エトキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－３－プロポキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－３－ブトキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－３－ペンチルオキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－３－ヘキシルオキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－３－シクロヘキシルオキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－３－フェノキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－３－ナフチルオキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－３－ビフェニルオキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－３－ベンジルオキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－３－ヒドロキシエトキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニル－３－ヒドロキシカルボニルメチルビシクロ［２．２．１］ヘプト－５－エン、３－メチル－２－ヒドロキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、３－ヒドロキシメチル－２－ヒドロキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシカルボニルトリシクロ［５．２．１．０2,6］デカ－３，８－ジエン、４－ヒドロキシカルボニルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－メチル－４－ヒドロキシカルボニルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４，５－ジヒドロキシカルボニルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－カルボキシメチル－４－ヒドロキシカルボニルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、Ｎ－（ヒドロキシカルボニルメチル）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（ヒドロキシカルボニルエチル）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（ヒドロキシカルボニルペンチル）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（ジヒドロキシカルボニルエチル）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（ジヒドロキシカルボニルプロピル）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（ヒドロキシカルボニルフェネチル）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－（４－ヒドロキシフェニル）－１－（ヒドロキシカルボニル）エチル）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（ヒドロキシカルボニルフェニル）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミドが挙げられる。 -Cyclic olefin monomer having a carboxyl group-
Examples of the cyclic olefin monomer having a carboxyl group include 2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene and 2-methyl-2-hydroxycarbonylbicyclo [2.2.1] hept-. 5-ene, 2-carboxymethyl-2-hydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-methoxycarbonylmethylbicyclo [2.2.1] hept-5-ene , 2-Hydroxycarbonyl-2-ethoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-propoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2 -Hydroxycarbonyl-2-butoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-pentyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2- Hydroxycarbonyl-2-hexyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-cyclohexyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2- Hydroxycarbonyl-2-phenoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-naphthyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxy Carbonyl-2-biphenyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-2-benzyloxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2-hydroxy Carbonyl-2-hydroxyethoxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 2,3-dihydroxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-methoxy Carbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-ethoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-propoxycarbonylbicyclo [2] .2.1] Hept-5-ene, 2-hydroxycarbonyl-3-butoxycarbonylbicyclo [2.2.1] Hept-5-ene, 2-hydroxycarbonyl-3-pentyloxycarbonylbicyclo [2.2. 1] Hept-5-ene, 2-hydro Xycarbonyl-3-hexyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-cyclohexyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl -3-phenoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-naphthyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3- Biphenyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-benzyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-hydroxyethoxy Carbonylbicyclo [2.2.1] hept-5-ene, 2-hydroxycarbonyl-3-hydroxycarbonylmethylbicyclo [2.2.1] hept-5-ene, 3-methyl-2-hydroxycarbonylbicyclo [2] .2.1] Hept-5-ene, 3-hydroxymethyl-2-hydroxycarbonylbicyclo [2.2.1] Hept-5-ene, 2-hydroxycarbonyltricyclo [5.2.1.0 2, 6 ] 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- (hydroxycarbonylmethyl) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (hydroxycarbonylethyl) bicyclo [2] .2.1] Hept-5-en-2,3-dicarboxyimide, N- (hydroxycarbonylpentyl) bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N- (Dihydroxycarbonylethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (dihydroxycarbonylpropyl) bicyclo [2.2.1] hept-5-en-2, 3-Dicarboxyimide, N- (hydroxycarbonylphenethyl) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (2- (4-hydroxyphenyl) -1-( Hydroxycarbonyl) ethyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (hydroxycarbonylphenyl) bicyclo [2.2.1] hept-5-en-2, Examples include 3-dicarboxyimide.
―水酸基を有する環状オレフィン単量体―
　水酸基を有する環状オレフィン単量体としては、例えば、２－（４－ヒドロキシフェニル）ビシクロ［２．２．１］ヘプト－５－エン、２－メチル－２－（４－ヒドロキシフェニル）ビシクロ［２．２．１］ヘプト－５－エン、４－（４－ヒドロキシフェニル）テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－メチル－４－（４－ヒドロキシフェニル）テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、２－ヒドロキシビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシメチルビシクロ［２．２．１］ヘプト－５－エン、２－ヒドロキシエチルビシクロ［２．２．１］ヘプト－５－エン、２－メチル－２－ヒドロキシメチルビシクロ［２．２．１］ヘプト－５－エン、２，３－ジヒドロキシメチルビシクロ［２．２．１］ヘプト－５－エン、２－（ヒドロキシエトキシカルボニル）ビシクロ［２．２．１］ヘプト－５－エン、２－メチル－２－（ヒドロキシエトキシカルボニル）ビシクロ［２．２．１］ヘプト－５－エン、２－（１－ヒドロキシ－１－トリフルオロメチル－２，２，２－トリフルオロエチル）ビシクロ［２．２．１］ヘプト－５－エン、２－（２－ヒドロキシ－２－トリフルオロメチル－３，３，３－トリフルオロプロピル）ビシクロ［２．２．１］ヘプト－５－エン、３－ヒドロキシトリシクロ［５．２．１．０2,6］デカ－４，８－ジエン、３－ヒドロキシメチルトリシクロ［５．２．１．０2,6］デカ－４，８－ジエン、４－ヒドロキシテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－ヒドロキシメチルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４，５－ジヒドロキシメチルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－（ヒドロキシエトキシカルボニル）テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－メチル－４－（ヒドロキシエトキシカルボニル）テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、Ｎ－（ヒドロキシエチル）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（ヒドロキシフェニル）ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミドが挙げられる。 -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] hept-5-ene and 2-methyl-2- (4-hydroxyphenyl) bicyclo [2]. .2.1] Hept-5-ene, 4- (4-hydroxyphenyl) tetracyclo [6.2.1.1 3,6 . 0 2,7 ] 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] hept-5-ene, 2-hydroxymethylbicyclo [2.2.1] hept-5-ene, 2-hydroxyethyl Bicyclo [2.2.1] hept-5-ene, 2-methyl-2-hydroxymethylbicyclo [2.2.1] hept-5-ene, 2,3-dihydroxymethylbicyclo [2.2.1] Hept-5-ene, 2- (hydroxyethoxycarbonyl) bicyclo [2.2.1] hept-5-ene, 2-methyl-2- (hydroxyethoxycarbonyl) bicyclo [2.2.1] hept-5- En, 2- (1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) bicyclo [2.2.1] hept-5-ene, 2- (2-hydroxy-2-trifluoro) Methyl-3,3,3-trifluoropropyl) bicyclo [2.2.1] hept-5-ene, 3-hydroxytricyclo [5.2.1.0 2,6 ] deca-4,8-diene , 3-Hydroxymethyltricyclo [5.2.1.0 2,6 ] Deca-4,8-diene, 4-Hydroxytetracyclo [6.2.1.1 3,6 . 0 2,7 ] 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] Hept-5-ene-2,3-dicarboxyimide, N- (hydroxyphenyl) bicyclo [2.2] .1] Hept-5-ene-2,3-dicarboxyimide.
　これらの中でも、現像液（特には後述するアルカリ現像液）に対する溶解性を高めると共に、樹脂膜の金属に対する密着性を向上させる観点から、カルボキシル基を有する環状オレフィン単量体が好ましく、４－ヒドロキシカルボニルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エンがより好ましい。なお、環状オレフィン単量体（ａ）は、１種を単独で使用しても、２種以上を組み合わせて使用してもよい。 Among these, a cyclic olefin monomer having a carboxyl group is preferable, and 4-hydroxy is preferable from the viewpoint of improving the solubility in a developing solution (particularly an alkaline developing solution described later) and improving the adhesion of the resin film to a metal. Carbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-ene is more preferable. The cyclic olefin monomer (a) may be used alone or in combination of two or more.
―含有割合―
　そして、環状オレフィン重合体（Ａ）中における環状オレフィン単量体（ａ）に由来する繰り返し単位の含有割合は、全繰り返し単位を１００モル％として、１０モル％以上であることが好ましく、２０モル％以上であることがより好ましく、３０モル％以上であることが更に好ましく、９０モル％以下であることが好ましく、８０モル％以下であることがより好ましく、７０モル％以下であることが更に好ましい。環状オレフィン単量体（ａ）に由来する繰り返し単位の割合が１０モル％以上であれば樹脂膜の熱フロー耐性を更に向上させることができ、９０モル％以下であれば樹脂膜の比誘電率を低下させることができる。 -Content ratio-
The content ratio of the repeating unit derived from the cyclic olefin monomer (a) in the cyclic olefin polymer (A) is preferably 10 mol% or more, preferably 20 mol, with the total repeating unit as 100 mol%. % Or more, more preferably 30 mol% or more, more preferably 90 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less. preferable. If the proportion 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 if it is 90 mol% or less, the relative permittivity of the resin film. Can be reduced.
［その他の単量体（ｂ）］
　その他の単量体（ｂ）としては、上述した環状オレフィン単量体（ａ）と共重合可能な単量体であれば特に限定されない。環状オレフィン単量体（ａ）と共重合可能な単量体としては、プロトン性極性基以外の極性基を有する環状オレフィン単量体（ｂ１）、極性基を有さない環状オレフィン単量体（ｂ２）、および環状オレフィン以外の単量体（ｂ３）が挙げられる。 [Other monomer (b)]
The other monomer (b) is not particularly limited as long as it is a monomer copolymerizable with the above-mentioned cyclic olefin monomer (a). Examples of the monomer copolymerizable with the cyclic olefin monomer (a) include a cyclic olefin monomer (b1) having a polar group other than the protonic polar group and a cyclic olefin monomer having no polar group (b1). Examples thereof include b2) and a monomer (b3) other than the cyclic olefin.
―単量体（ｂ１）－
　プロトン性極性基以外の極性基を有する環状オレフィン単量体（ｂ１）としては、例えば、Ｎ－置換イミド基、エステル基、シアノ基、酸無水物基、またはハロゲン原子を有する環状オレフィン単量体が挙げられる。 -Polymer (b1)-
Examples of the cyclic olefin monomer (b1) having a polar group other than the protonic polar group include an N-substituted imide group, an ester group, a cyano group, an acid anhydride group, or a cyclic olefin monomer having a halogen atom. Can be mentioned.
　Ｎ－置換イミド基を有する環状オレフィン単量体としては、例えば、下記式（１）で表される単量体、下記式（２）で表される単量体が挙げられる。
Figure JPOXMLDOC01-appb-C000001
 　〔式（１）中、Ｒ2は炭素原子数１以上１６以下のアルキル基、またはアリール基を表し、ｎは１または２を表す。〕
Figure JPOXMLDOC01-appb-C000002
 　〔式（２）中、Ｒ3は炭素原子数１以上３以下の２価のアルキレン基、Ｒ4は、炭素原子数１以上１０以下の１価のアルキル基または炭素原子数１以上１０以下の１価のハロゲン化アルキル基を表す。なお、２つのＲ4は同一でも異なっていてもよい。〕 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).
Figure JPOXMLDOC01-appb-C000001
 [In the formula (1), R 2 represents an alkyl group or an aryl group having 1 to 16 carbon atoms, and n represents 1 or 2. ]
Figure JPOXMLDOC01-appb-C000002
 [In the formula (2), R 3 is a divalent alkylene group having 1 or more and 3 or less carbon atoms, and R 4 is a monovalent alkyl group having 1 or more and 10 or less carbon atoms or 1 or more and 10 or less carbon atoms. Represents a monovalent alkyl halide group. The two R 4s may be the same or different. ]
　式（１）中、Ｒ2の炭素原子数１以上１６以下のアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ウンデシル基、ｎ－ドデシル基、ｎ－トリデシル基、ｎ－テトラデシル基、ｎ－ペンタデシル基、ｎ－ヘキサデシル基等の直鎖状アルキル基；シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロノニル基、シクロデシル基、シクロウンデシル基、シクロドデシル基、ノルボルニル基、ボルニル基、イソボルニル基、デカヒドロナフチル基、トリシクロデカニル基、アダマンチル基等の環状アルキル基；２－プロピル基、２－ブチル基、２－メチル－１－プロピル基、２－メチル－２－プロピル基、１－メチルブチル基、２－メチルブチル基、１－メチルペンチル基、１－エチルブチル基、２－メチルヘキシル基、２－エチルヘキシル基、４－メチルヘプチル基、１－メチルノニル基、１－メチルトリデシル基、１－メチルテトラデシル基などの分岐状アルキル基；が挙げられる。
　式（１）中、Ｒ2のアリール基としては、例えば、ベンジル基が挙げられる。
　これらの中でも、環状オレフィン重合体（Ａ）の溶剤への溶解性を向上させると共に、樹脂膜の熱フロー耐性を更に向上させる観点から、炭素原子数４以上１４以下のアルキル基およびアリール基が好ましく、炭素原子数６以上１０以下のアルキル基およびアリール基がより好ましい。 In the formula (1) , examples of the alkyl group having 1 or more and 16 or less carbon atoms of R 2 include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group and an 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-hexadecyl group, etc. Linear alkyl 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 Cyclic alkyl groups such as groups, decahydronaphthyl groups, tricyclodecanyl groups, adamantyl groups; 2-propyl groups, 2-butyl groups, 2-methyl-1-propyl groups, 2-methyl-2-propyl groups, 1 -Methylbutyl group, 2-methylbutyl group, 1-methylpentyl group, 1-ethylbutyl group, 2-methylhexyl group, 2-ethylhexyl group, 4-methylheptyl group, 1-methylnonyl group, 1-methyltridecyl group, 1 -A branched alkyl group such as a methyltetradecyl group;
In the formula (1), examples of the aryl group of R 2 include a benzyl group.
Among these, alkyl groups and aryl groups having 4 to 14 carbon atoms are preferable 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. , Alkyl groups and aryl groups having 6 or more and 10 or less carbon atoms are more preferable.
　そして、式（１）で表される単量体の具体例としては、ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－フェニル－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－メチルビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－エチルビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－プロピルビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－ブチルビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－シクロヘキシルビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－アダマンチルビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－メチルブチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－メチルブチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－メチルペンチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－メチルペンチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－エチルブチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－エチルブチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－メチルヘキシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－メチルヘキシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（３－メチルヘキシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－ブチルペンチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－ブチルペンチル）－ビシクロ［２．２．１］ヘプト－５－エン－２,３－ジカルボキシイミド、Ｎ－（１－メチルヘプチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－メチルヘプチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（３－メチルヘプチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（４－メチルヘプチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－エチルヘキシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－エチルヘキシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（３－エチルヘキシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－プロピルペンチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－プロピルペンチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－メチルオクチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－メチルオクチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（３－メチルオクチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（４－メチルオクチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－エチルヘプチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－エチルヘプチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（３－エチルヘプチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（４－エチルヘプチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－プロピルヘキシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－プロピルヘキシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（３－プロピルヘキシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－メチルノニル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－メチルノニル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（３－メチルノニル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（４－メチルノニル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（５－メチルノニル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－エチルオクチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（２－エチルオクチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（３－エチルオクチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（４－エチルオクチル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－メチルデシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－メチルドデシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－メチルウンデシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－メチルトリデシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－メチルテトラデシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－（１－メチルペンタデシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド、Ｎ－フェニル－テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン－４，５－ジカルボキシイミド、Ｎ－（２，４－ジメトキシフェニル）－テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン－４，５－ジカルボキシイミドが挙げられる。 Specific examples of the monomer represented by the formula (1) include bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide and N-phenyl-bicyclo [2.2]. .1] Hept-5-en-2,3-dicarboxyimide, N-methylbicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N-ethylbicyclo [2.2] .1] Hept-5-en-2,3-dicarboxyimide, N-propylbicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N-butylbicyclo [2.2] .1] Hept-5-en-2,3-dicarboxyimide, N-cyclohexylbicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N-adamantylbicyclo [2.2] .1] Hept-5-en-2,3-dicarboxyimide, N- (1-methylbutyl) -bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N-( 2-Methylbutyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-methylpentyl) -bicyclo [2.2.1] hept-5-ene- 2,3-Dicarboxyimide, N- (2-methylpentyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (1-ethylbutyl) -bicyclo [2 .2.1] Hept-5-en-2,3-dicarboxyimide, N- (2-ethylbutyl) -bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N -(1-Methylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-methylhexyl) -bicyclo [2.2.1] hept-5 -En-2,3-dicarboxyimide, N- (3-methylhexyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (1-butylpentyl) -Vicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-butylpentyl) -bicyclo [2.2.1] hept-5-ene-2,3- Dicarboxyimide, N- (1-methylheptyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (2-methylheptyl) -bicyclo [2.2. 1] Hept-5-en-2,3-dicarboxyimide, N- (3-methylheptyl) -bicyclo [2.2.1] Hept-5-en-2,3- Dicarboxyimide, N- (4-methylheptyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (1-ethylhexyl) -bicyclo [2.2.1] ] Hept-5-en-2,3-dicarboxyimide, N- (2-ethylhexyl) -bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N- (3-) Ethylhexyl) -bicyclo [2.2.1] hept-5-en-2,3-dicarboxyimide, N- (1-propylpentyl) -bicyclo [2.2.1] hept-5-en-2, 3-Dicarboxyimide, N- (2-propylpentyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (1-methyloctyl) -bicyclo [2. 2.1] Hept-5-en-2,3-dicarboxyimide, N- (2-methyloctyl) -bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N -(3-Methyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-methyloctyl) -bicyclo [2.2.1] hept-5 -En-2,3-dicarboxyimide, N- (1-ethylheptyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (2-ethylheptyl) -Vicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (3-ethylheptyl) -bicyclo [2.2.1] hept-5-ene-2,3- Dicarboxyimide, N- (4-ethylheptyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (1-propylhexyl) -bicyclo [2.2. 1] Hept-5-en-2,3-dicarboxyimide, N- (2-propylhexyl) -bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N-( 3-propylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-methylnonyl) -bicyclo [2.2.1] hept-5-ene- 2,3-Dicarboxyimide, N- (2-methylnonyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (3-methylnonyl) -bicyclo [2. 2.1] Hept-5-en-2,3-dicarboxyimide, N- (4-methylnonyl) -bicyclo [2.2.1] Hept- 5-en-2,3-dicarboxyimide, N- (5-methylnonyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (1-ethyloctyl) -Vicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-ethyloctyl) -bicyclo [2.2.1] hept-5-ene-2,3- Dicarboxyimide, N- (3-ethyloctyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (4-ethyloctyl) -bicyclo [2.2. 1] Hept-5-en-2,3-dicarboxyimide, N- (1-methyldecyl) -bicyclo [2.2.1] Hept-5-en-2,3-dicarboxyimide, N- (1) -Methyldodecyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-methylundecyl) -bicyclo [2.2.1] hept-5-ene -2,3-dicarboxyimide, N- (1-methyltridecyl) -bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide, N- (1-methyltetradecyl) -Vicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (1-methylpentadecyl) -bicyclo [2.2.1] hept-5-en-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-en-4,5-dicarboxyimide can be mentioned.
　式（２）中、Ｒ3の炭素原子数１以上３以下の２価のアルキレン基としては、メチレン基、エチレン基、プロピレン基およびイソプロピレン基が挙げられる。これらの中でも、重合活性が良好であるため、メチレン基およびエチレン基が好ましい。 In the formula (2), examples of the divalent alkylene group having 1 or more and 3 or less carbon atoms of R 3 include a methylene group, an ethylene group, a propylene group and an isopropylene group. Among these, a methylene group and an ethylene group are preferable because the polymerization activity is good.
　式（２）中、Ｒ4の炭素原子数１以上１０以下の１価のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ヘキシル基およびシクロヘキシル基が挙げられる。
　式（２）中、Ｒ4の炭素原子数１以上１０以下の１価のハロゲン化アルキル基としては、例えば、フルオロメチル基、クロロメチル基、ブロモメチル基、ジフルオロメチル基、ジクロロメチル基、トリフルオロメチル基、トリクロロメチル基、２，２，２－トリフルオロエチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、パーフルオロブチル基およびパーフルオロペンチル基が挙げられる。
　これら中でも、環状オレフィン重合体（Ａ）の溶剤への溶解性を向上させる観点から、Ｒ4としては、メチル基およびエチル基が好ましい。 In the formula (2) , examples of the monovalent alkyl group having 1 or more and 10 or less carbon atoms of R 4 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group and tert-butyl. Groups include groups, hexyl groups and cyclohexyl groups.
In the formula (2) , examples of the monovalent alkyl halide group having 1 to 10 carbon atoms of R 4 include fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group and trifluoro. Examples thereof include a methyl group, a trichloromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, a heptafluoropropyl group, a perfluorobutyl group and a perfluoropentyl group.
Among these, a methyl group and an ethyl group are preferable as R 4 from the viewpoint of improving the solubility of the cyclic olefin polymer (A) in a solvent.
　なお、式（１）、（２）で表される単量体は、例えば、対応するアミンと、５－ノルボルネン－２，３－ジカルボン酸無水物とのイミド化反応により得ることができる。また、得られた単量体は、イミド化反応の反応液を既知の方法で分離・精製することにより効率よく単離できる。 The monomers represented by the formulas (1) and (2) can be obtained, for example, by an imidization reaction between the corresponding amine and 5-norbornene-2,3-dicarboxylic acid anhydride. Further, the obtained monomer can be efficiently isolated by separating and purifying the reaction solution of the imidization reaction by a known method.
　エステル基を有する環状オレフィン単量体としては、例えば、２－アセトキシビシクロ［２．２．１］ヘプト－５－エン、２－アセトキシメチルビシクロ［２．２．１］ヘプト－５－エン、２－メトキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－エトキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－プロポキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－ブトキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－シクロヘキシルオキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－メチル－２－メトキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－メチル－２－エトキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－メチル－２－プロポキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－メチル－２－ブトキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－メチル－２－シクロヘキシルオキシカルボニルビシクロ［２．２．１］ヘプト－５－エン、２－（２，２，２－トリフルオロエトキシカルボニル）ビシクロ［２．２．１］ヘプト－５－エン、２－メチル－２－（２，２，２－トリフルオロエトキシカルボニル）ビシクロ［２．２．１］ヘプト－５－エン、２－メトキシカルボニルトリシクロ［５．２．１．０2,6］デカ－８－エン、２－エトキシカルボニルトリシクロ［５．２．１．０2,6］デカ－８－エン、２－プロポキシカルボニルトリシクロ［５．２．１．０2,6］デカ－８－エン、４－アセトキシテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－メトキシカルボニルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－エトキシカルボニルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－プロポキシカルボニルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－ブトキシカルボニルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－メチル－４－メトキシカルボニルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－メチル－４－エトキシカルボニルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－メチル－４－プロポキシカルボニルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－メチル－４－ブトキシカルボニルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－（２，２，２－トリフルオロエトキシカルボニル）テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－メチル－４－（２，２，２－トリフルオロエトキシカルボニル）テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エンが挙げられる。 Examples of the cyclic olefin monomer having an ester group include 2-acetoxybicyclo [2.2.1] hept-5-ene and 2-acetoxymethylbicyclo [2.2.1] hept-5-ene, 2 -Methoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-ethoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-propoxycarbonylbicyclo [2.2.1] hept-5 -En, 2-butoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-cyclohexyloxycarbonylbicyclo [2.2.1] hept-5-ene, 2-methyl-2-methoxycarbonylbicyclo [ 2.2.1] Hept-5-ene, 2-methyl-2-ethoxycarbonylbicyclo [2.2.1] Hept-5-ene, 2-methyl-2-propoxycarbonylbicyclo [2.2.1] Hept-5-ene, 2-methyl-2-butoxycarbonylbicyclo [2.2.1] hept-5-ene, 2-methyl-2-cyclohexyloxycarbonylbicyclo [2.2.1] hept-5-ene , 2- (2,2,2-trifluoroethoxycarbonyl) bicyclo [2.2.1] hept-5-ene, 2-methyl-2- (2,2,2-trifluoroethoxycarbonyl) bicyclo [2 .2.1] hept-5-ene, 2-methoxycarbonyl tricyclo [5.2.1.0 2, 6] dec-8-ene, 2-ethoxycarbonyl tricyclo [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-ethoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-ene, 4-propoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-ene, 4-butoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-ene, 4-methyl-4-methoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-ene, 4-methyl-4-ethoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-ene, 4-methyl-4-propoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-ene, 4-methyl-4-butoxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-ene, 4- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-ene, 4-methyl-4- (2,2,2-trifluoroethoxycarbonyl) tetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-en can be mentioned.
　シアノ基を有する環状オレフィン単量体としては、例えば、４－シアノテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－メチル－４－シアノテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４，５－ジシアノテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、２－シアノビシクロ［２．２．１］ヘプト－５－エン、２－メチル－２－シアノビシクロ［２．２．１］ヘプト－５－エン、２，３－ジシアノビシクロ［２．２．１］ヘプト－５－エンが挙げられる。 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-cyanotetracyclo [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] hept-5-ene, 2-methyl-2-cyanobicyclo [2.2.1] hept-5-ene, 2 , 3-Dicyanobicyclo [2.2.1] Hept-5-ene.
　酸無水物基を有する環状オレフィン単量体としては、例えば、テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン－４，５－ジカルボン酸無水物、ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボン酸無水物、２－カルボキシメチル－２－ヒドロキシカルボニルビシクロ［２．２．１］ヘプト－５－エン無水物が挙げられる。 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] Hept-5-ene-2,3-dicarboxylic acid anhydride, 2-carboxymethyl-2- Hydroxycarbonylbicyclo [2.2.1] hept-5-ene anhydride can be mentioned.
　ハロゲン原子を有する環状オレフィン単量体としては、例えば、２－クロロビシクロ［２．２．１］ヘプト－５－エン、２－クロロメチルビシクロ［２．２．１］ヘプト－５－エン、２－（クロロフェニル）ビシクロ［２．２．１］ヘプト－５－エン、４－クロロテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン、４－メチル－４－クロロテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エンが挙げられる。 Examples of the cyclic olefin monomer having a halogen atom include 2-chlorobicyclo [2.2.1] hept-5-ene and 2-chloromethylbicyclo [2.2.1] hept-5-ene, 2 -(Chlorophenyl) bicyclo [2.2.1] hept-5-ene, 4-chlorotetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-ene, 4-methyl-4-chlorotetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-9-en can be mentioned.
―単量体（ｂ２）―
　極性基を有さない環状オレフィン単量体（ｂ２）としては、例えば、ビシクロ［２．２．１］ヘプト－２－エン（「ノルボルネン」ともいう。）、５－エチル－ビシクロ［２．２．１］ヘプト－２－エン、５－ブチル－ビシクロ［２．２．１］ヘプト－２－エン、５－エチリデン－ビシクロ［２．２．１］ヘプト－２－エン、５－メチリデン－ビシクロ［２．２．１］ヘプト－２－エン、５－ビニル－ビシクロ［２．２．１］ヘプト－２－エン、トリシクロ［５．２．１．０2,6］デカ－３，８－ジエン（慣用名：ジシクロペンタジエン）、テトラシクロ［１０．２．１．０2,11．０4,9］ペンタデカ－４，６，８，１３－テトラエン、テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－４－エン（「テトラシクロドデセン」ともいう。）、９－メチル－テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－４－エン、９－エチル－テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－４－エン、９－メチリデン－テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－４－エン、９－エチリデン－テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－４－エン、９－ビニル－テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－４－エン、９－プロペニル－テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－４－エン、ペンタシクロ［９．２．１．１3,9．０2,10．０4,8］ペンタデカ－５，１２－ジエン、シクロブテン、シクロペンテン、シクロペンタジエン、シクロヘキセン、シクロヘプテン、シクロオクテン、シクロオクタジエン、インデン、３ａ，５，６，７ａ－テトラヒドロ－４，７－メタノ－１Ｈ－インデン、９－フェニル－テトラシクロ［６．２．１．１3,6．０2,7］ドデカ－４－エン、テトラシクロ［９．２．１．０2,10．０3,8］テトラデカ－３，５，７，１２－テトラエン、ペンタシクロ［９．２．１．１3,9．０2,10．０4,8］ペンタデカ－１２－エンが挙げられる。 ― Monomer (b2) ―
Examples of the cyclic olefin monomer (b2) having no polar group include bicyclo [2.2.1] hept-2-ene (also referred to as “norbornene”) and 5-ethyl-bicyclo [2.2]. .1] Hept-2-ene, 5-butyl-bicyclo [2.2.1] hept-2-ene, 5-ethylidene-bicyclo [2.2.1] hept-2-ene, 5-methylidene-bicyclo [2.2.1] Hept-2-ene, 5-vinyl-bicyclo [2.2.1] Hept-2-ene, tricyclo [5.2.1.0 2,6 ] Deca-3,8- diene (common name: dicyclopentadiene), tetracyclo [10.2.1.0 2,11. 0 4,9 ] Pentadeca-4,6,8,13-tetraene, tetracyclo [6.2.1.1 3,6 . 0 2,7 ] Dodeca-4-ene (also referred to as "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-tetracyclo [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-propenyl-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-en can be mentioned.
―単量体（ｂ３）―
　環状オレフィン以外の単量体（ｂ３）としては、例えば、エチレン；プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、３－メチル－１－ブテン、３－メチル－１－ペンテン、３－エチル－１－ペンテン、４－メチル－１－ペンテン、４－メチル－１－ヘキセン、４，４－ジメチル－１－ヘキセン、４，４－ジメチル－１－ペンテン、４－エチル－１－ヘキセン、３－エチル－１－ヘキセン、１－オクテン、１－デセン、１－ドデセン、１－テトラデセン、１－ヘキサデセン、１－オクタデセン、１－エイコセン等の炭素原子数３以上２０以下のα－オレフィン；１，４－ヘキサジエン、１，５－ヘキサジエン、４－メチル－１，４－ヘキサジエン、５－メチル－１，４－ヘキサジエン、１，７－オクタジエン等の非共役ジエン、およびこれらの誘導体；が挙げられる。 ― Monomer (b3) ―
Examples of the monomer (b3) other than the cyclic olefin include ethylene; propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl. -1-Pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3 -Ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and other α-olefins with 3 to 20 carbon atoms; 1, Non-conjugated diene such as 4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadene, and derivatives thereof;
　上述した単量体（ｂ１）～（ｂ３）等のその他の単量体（ｂ）は、１種を単独で使用しても、２種以上を組み合わせて使用してもよい。そしてこれらの中でも、樹脂膜の熱フロー耐性を更に向上させる観点から、プロトン性極性基以外の極性基を有する環状オレフィン単量体（ｂ１）が好ましく、Ｎ－置換イミド基を有する環状オレフィン単量体がより好ましい。 As the other monomers (b) such as the above-mentioned monomers (b1) to (b3), one kind may be used alone or two or more kinds may be used in combination. 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 single amount having an N-substituted imide group is preferable. The body is more preferred.
―含有割合―
　そして、環状オレフィン重合体（Ａ）中におけるその他の単量体（ｂ）に由来する繰り返し単位の含有割合は、全繰り返し単位を１００モル％として、１０モル％以上であることが好ましく、２０モル％以上であることがより好ましく、３０モル％以上であることが更に好ましく、９０モル％以下であることが好ましく、８０モル％以下であることがより好ましく、７０モル％以下であることが更に好ましい。その他の単量体（ｂ）に由来する繰り返し単位の割合が１０モル％以上であれば樹脂膜の比誘電率を低下させることができ、９０モル％以下であれば樹脂膜の熱フロー耐性を更に向上させることができる。 -Content ratio-
The content ratio of the repeating unit derived from the other monomer (b) in the cyclic olefin polymer (A) is preferably 10 mol% or more, preferably 20 mol, with the total repeating unit as 100 mol%. % Or more, more preferably 30 mol% or more, more preferably 90 mol% or less, more preferably 80 mol% or less, further preferably 70 mol% or less. preferable. If the proportion of the repeating unit derived from the other monomer (b) is 10 mol% or more, the relative permittivity of the resin film can be lowered, and if it is 90 mol% or less, the heat flow resistance of the resin film is increased. It can be further improved.
＜＜調製方法＞＞
　プロトン性極性基を有する環状オレフィン重合体（Ａ）を調製する方法は特に限定されず、例えば、以下の（ｉ）および（ｉｉ）の方法：
（ｉ）プロトン性極性基を有する環状オレフィン単量体（ａ）と、任意に使用されるその他の単量体（ｂ）を含む単量体組成物を重合し、任意に、水素添加反応を行う方法、または
（ｉｉ）プロトン性極性基を有しない環状オレフィン重合体を、プロトン性極性基を有する変性剤を用いて変性する方法、
　挙げられる。これらの中でも（ｉ）の方法が好ましい。 << Preparation method >>
The method for preparing the cyclic olefin polymer (A) having a protonic polar group is not particularly limited, and for example, the following methods (i) and (ii):
(I) A monomer composition containing a cyclic olefin monomer (a) having a protic polar group and another monomer (b) used arbitrarily is polymerized, and an optional hydrogenation reaction is carried out. The method to be carried out, or (ii) a method of modifying a cyclic olefin polymer having no protonic polar group with a modifier having a protonic polar group.
Can be mentioned. Among these, the method (i) is preferable.
［調製方法（ｉ）］
　環状オレフィン単量体（ａ）と、任意にその他の単量体（ｂ）を含む単量体組成物を重合する方法は特に限定されず、既知の方法を用いることができる。具体的な重合方法としては、例えば、開環重合、付加重合が挙げられるが、開環重合が好ましい。すなわち、環状オレフィン重合体（Ａ）は、開環重合体または付加重合体であることが好ましく、開環重合体であることがより好ましい。 [Preparation method (i)]
The method for polymerizing the cyclic olefin monomer (a) and the monomer composition optionally containing the other monomer (b) is not particularly limited, and a known method can be used. Specific examples of the polymerization method include ring-opening polymerization and addition polymerization, and ring-opening polymerization is preferable. That is, the cyclic olefin polymer (A) is preferably a ring-opening polymer or an addition polymer, and more preferably a ring-opening polymer.
　なお、開環重合の方法としては、例えば、メタセシス反応触媒の存在下で、プロトン性極性基を有する環状オレフィン単量体（ａ）および必要に応じて用いられるその他の単量体（ｂ）を重合する開環メタセシス重合が挙げられる。開環メタセシス重合の方法としては、例えば、国際公開第２０１０／１１０３２３号に記載されている方法を採用することができる。 As a method of ring-opening polymerization, for example, a cyclic olefin monomer (a) having a protonic polar group and another monomer (b) used as needed in the presence of a metathesis reaction catalyst are used. Ring-opening metathesis polymerization that polymerizes can be mentioned. As a method for ring-opening metathesis polymerization, for example, the method described in International Publication No. 2010/10123 can be adopted.
　また、環状オレフィン重合体（Ａ）の調製に開環重合を用いる場合、得られた開環重合体に、更に水素添加反応を行い、主鎖に含まれる炭素－炭素二重結合が水素添加された水素添加物とすることが好ましい。環状オレフィン重合体（Ａ）が水素添加物である場合、水素化された炭素－炭素二重結合の割合（水素添加率）は、樹脂膜の耐熱性を更に向上させる観点から、５０％以上であることが好ましく、７０％以上であることがより好ましく、９０％以上であることが更に好ましく、９５％以上であることが特に好ましい。
　なお、本発明において、「水素添加率」は、1Ｈ－ＮＭＲスペクトルを用いて測定することができる。 When ring-opening polymerization is used to prepare the cyclic olefin polymer (A), the obtained ring-opening polymer is further hydrogenated to hydrogenate the carbon-carbon double bond contained in the main chain. It is preferable to use a hydrogenated additive. When the cyclic olefin polymer (A) is a hydrogenated product, the ratio of hydrogenated carbon-carbon double bonds (hydrogenation rate) is 50% or more from the viewpoint of further improving the heat resistance of the resin film. It is preferably 70% or more, more preferably 90% or more, and particularly preferably 95% or more.
In the present invention, the "hydrogenation rate" can be measured using a 1 H-NMR spectrum.
［調製方法（ｉｉ）］
　プロトン性極性基を有しない環状オレフィン重合体を調製する方法は特に限定されない。プロトン性極性基を有しない環状オレフィン重合体は、例えば、上述した単量体（ｂ１）および（ｂ２）のうち少なくとも１種と、必要に応じて単量体（ｂ３）とを任意に組み合わせて、既知の方法で重合することによって得ることができる。そして、得られた重合体を、プロトン性極性基を有する変性剤を用いて変性する方法は、常法に従えばよく、通常、ラジカル発生剤の存在下で行われる。
　なお、プロトン性極性基を有する変性剤としては、プロトン性極性基と反応性の炭素－炭素不飽和結合の双方を有する化合物を用いることができ、具体的には、国際公開第２０１５／１４１７１７号に記載されたものを用いることができる。 [Preparation method (ii)]
The method for preparing a cyclic olefin polymer having no protonic polar group is not particularly limited. The cyclic olefin polymer having no protic polar group is, for example, an optional combination of at least one of the above-mentioned monomers (b1) and (b2) and, if necessary, the monomer (b3). , Can be obtained by polymerization by known methods. Then, the method of modifying the obtained polymer with a modifier having a protonic polar group may follow a conventional method, and is usually carried out in the presence of a radical generator.
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, International Publication No. 2015/141717. Can be used as described in.
＜＜重量平均分子量＞＞
　環状オレフィン重合体（Ａ）の重量平均分子量は、１０００以上であることが好ましく、３０００以上であることがより好ましく、５０００以上であることが更に好ましく、１０００００以下であることが好ましく、５００００以下であることがより好ましく、３００００以下であることが更に好ましい。環状オレフィン重合体（Ａ）の重量平均分子量が１０００以上であれば、樹脂膜におけるラインパターンのトップロスを一層抑制しつつ、当該樹脂膜の熱フロー耐性を更に向上させることができる。また、樹脂膜の耐薬品性を高めることができる。一方、環状オレフィン重合体（Ａ）の重量平均分子量が１０００００以下であれば、環状オレフィン重合体（Ａ）の溶剤への溶解性を十分に確保することができる。
　なお、本発明において、環状オレフィン重合体（Ａ）の「重量平均分子量」および「数平均分子量」は、テトラヒドロフラン等の溶媒を溶離液としたゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）により、ポリスチレン換算値として求められる値である。
　また、環状オレフィン重合体（Ａ）の重量平均分子量および数平均分子量は、合成条件（例えば、分子量調節剤の量）を調整することにより制御することができる。 << 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, further preferably 5000 or more, preferably 100,000 or less, and preferably 50,000 or less. It is more preferably present, and further preferably 30,000 or less. When the weight average molecular weight of the cyclic olefin polymer (A) is 1000 or more, the top loss of the line pattern in the resin film can be further suppressed, and the heat flow resistance of the resin film can be further improved. In addition, the chemical resistance of the resin film can be improved. On the other hand, when the weight average molecular weight of the cyclic olefin polymer (A) is 100,000 or less, the solubility of the cyclic olefin polymer (A) in a solvent can be sufficiently ensured.
In the present invention, the "weight average molecular weight" and "number average molecular weight" of the cyclic olefin polymer (A) are converted into polystyrene by gel permeation chromatography (GPC) using a solvent such as tetrahydrofuran as an eluent. It is a value obtained as a value.
Further, the weight average molecular weight and the number average molecular weight of the cyclic olefin polymer (A) can be controlled by adjusting the synthesis conditions (for example, the amount of the molecular weight modifier).
＜＜分子量分布＞＞
　また、環状オレフィン重合体（Ａ）の分子量分布（重量平均分子量／数平均分子量）は、４以下であることが好ましく、３以下であることがより好ましく、２．５以下であることが更に好ましい。環状オレフィン重合体（Ａ）の分子量分布が４以下であれば、樹脂膜におけるラインパターンのトップロスを一層抑制しつつ、熱フロー耐性を更に向上させることができる。また、樹脂膜の耐薬品性を高めることができる。
　なお、環状オレフィン重合体（Ａ）の分子量分布は、例えば、特開２００６－３０７１５５号公報に記載された方法により、低下させることができる。 << Molecular weight distribution >>
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 even more preferably 2.5 or less. .. When the molecular weight distribution of the cyclic olefin polymer (A) is 4 or less, the heat flow resistance can be further improved while further suppressing the top loss of the line pattern in the resin film. In addition, the chemical resistance of the resin film can be improved.
The molecular weight distribution of the cyclic olefin polymer (A) can be reduced by, for example, the method described in JP-A-2006-307155.
＜クレゾールノボラック樹脂（Ｂ）＞
　本発明の樹脂組成物は、樹脂成分として、上述した環状オレフィン重合体（Ａ）に加えて、軟化点が１４０℃以上のクレゾールノボラック樹脂（Ｂ）を含有する。樹脂組成物が、クレゾールノボラック樹脂（Ｂ）を含有することで、トップロスが抑制されたラインパターンを有する樹脂膜を形成することができる。 <Cresol novolac resin (B)>
The resin composition of the present invention contains, as a resin component, a cresol novolac resin (B) having a softening point of 140 ° C. or higher, in addition to the cyclic olefin polymer (A) described above. When the resin composition contains the cresol novolak resin (B), it is possible to form a resin film having a line pattern in which top loss is suppressed.
　ここで、クレゾールノボラック樹脂（Ｂ）は、クレゾール類を含むフェノール類と、アルデヒド類とを縮合することにより得られる樹脂である。 Here, the cresol novolak resin (B) is a resin obtained by condensing phenols including cresols with aldehydes.
＜＜クレゾール類を含むフェノール類＞＞
　クレゾールノボラック樹脂（Ｂ）の調製に用いられるフェノール類は、クレゾール類が含まれていれば特に限定されず、クレゾール類のみであってもよく、クレゾール類とクレゾール類以外のフェノール類（以下、「その他のフェノール類」と称する。）を併用してもよい。 << Phenols including cresols >>
The phenols used for the preparation of the cresol novolak resin (B) are not particularly limited as long as they contain cresols, and may be only cresols, and phenols other than cresols and cresols (hereinafter, "" Other phenols ”) may be used in combination.
―クレゾール類―
　クレゾール類とは、フェノール（Ｃ6Ｈ5ＯＨ）のベンゼン環上の５個の水素原子のうち、少なくとも１個がメチル基で置換され、残りの水素原子は置換されていない化合物の群を意味する。クレゾール類としては、例えば、クレゾール（ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール）、キシレノール（２，５－キシレノール（２，５－ジメチルフェノール）、３，５－キシレノール（３，５－ジメチルフェノール）等）、トリメチルフェノール（２，３，５－トリメチルフェノール等）が挙げられる。これらは、１種を単独で使用しても、２種以上を組み合わせて使用してもよい。そしてこれらの中でも、樹脂膜の熱フロー耐性を更に向上させる観点から、クレゾールとキシレノールを併用することが好ましく、ｍ－クレゾールと、ｐ－クレゾールと、３，５－キシレノールとを併用することがより好ましい。換言すると、クレゾールノボラック樹脂（Ｂ）は、クレゾール類に由来する骨格として、クレゾール骨格とキシレノール骨格とを含むことが好ましく、ｍ－クレゾール骨格と、ｐ－クレゾール骨格と、３，５－キシレノール骨格とを含むことがより好ましい。 -Cresols-
Cresols mean 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. To do. Examples of cresols include cresol (o-cresol, m-cresol, p-cresol), xylenol (2,5-xylenol (2,5-dimethylphenol)), and 3,5-xylenol (3,5-dimethylphenol). ) Etc.), trimethylphenol (2,3,5-trimethylphenol, etc.). These may be used individually by 1 type, or may be used in combination of 2 or more type. Among these, from the viewpoint of further improving the heat flow resistance of the resin film, it is preferable to use cresol and xylenol in combination, and it is more preferable to use m-cresol, p-cresol, and 3,5-xylenol in combination. preferable. In other words, the cresol novolak resin (B) preferably contains a cresol skeleton and a xylenol skeleton as cresol-derived skeletons, and includes an m-cresol skeleton, a p-cresol skeleton, and a 3,5-xylenol skeleton. It is more preferable to include.
　また、クレゾール類として、メタ体（ｍ－クレゾール、３，５－キシレノール（ｍ－キシレノール））と、パラ体（ｐ－クレゾール）とを併用する場合、クレゾールノボラック樹脂（Ｂ）に含まれるクレゾール類に由来する骨格中の、パラ体骨格（ｐ－クレゾール骨格）の含有量に対するメタ体骨格（ｍ－クレゾール骨格、３，５－キシレノール骨格）の含有量のモル比（ｍ／ｐ比）は、０．５以上であることが好ましく、１．０以上であることがより好ましく、２．０以上であることが更に好ましく、２．２以上であることが特に好ましく、５．０以下であることが好ましく、４．０以下であることがより好ましく、３．０以下であることが更に好ましく、２．５以下であることが特に好ましい。ｍ／ｐ比が上述した範囲内であれば、樹脂膜におけるラインパターンのトップロスを一層抑制しつつ、熱フロー耐性を更に向上させることができる。 Further, when the meta form (m-cresol, 3,5-xylenol (m-xylenol)) and the para form (p-cresol) are used in combination as cresols, the cresols contained in the cresol novolak resin (B). The molar ratio (m / p ratio) of the content of meta-body skeleton (m-cresol skeleton, 3,5-xylenol skeleton) to the content of para-body skeleton (p-cresol skeleton) in the skeleton derived from It is preferably 0.5 or more, more preferably 1.0 or more, further preferably 2.0 or more, particularly preferably 2.2 or more, and 5.0 or less. Is more preferable, 4.0 or less is more preferable, 3.0 or less is further preferable, and 2.5 or less is particularly preferable. When the m / p ratio is within the above range, the heat flow resistance can be further improved while further suppressing the top loss of the line pattern in the resin film.
　なお、クレゾールノボラック樹脂（Ｂ）の調製に用いるフェノール類中のクレゾール類の割合は、フェノール類全体の量を１００質量％として、５０質量％以上であることが好ましく、９５質量％以上であることがより好ましく、９７質量％以上であることが更に好ましく、１００質量％であること（即ち、フェノール類としてはクレゾール類のみを使用すること）が特に好ましい。 The proportion of cresols in the phenols used for the preparation of the cresol novolak resin (B) is preferably 50% by mass or more, preferably 95% by mass or more, assuming that the total amount of the phenols is 100% by mass. Is more preferable, 97% by mass or more is further preferable, and 100% by mass (that is, only cresols are used as phenols) is particularly preferable.
―その他のフェノール類―
　クレゾールノボラック樹脂（Ｂ）の調製に用いることができる、上述したクレゾール類以外のフェノール類としては、一価のフェノール化合物、二価以上のフェノール化合物（多価フェノール化合物）が挙げられる。なお、その他のフェノール類は、１種を単独で使用しても、２種以上を組み合わせて使用してもよい。 -Other phenols-
Examples of phenols other than the above-mentioned cresols that can be used for the preparation of the cresol novolak resin (B) include monovalent phenol compounds and divalent or higher phenol compounds (polyphenol compounds). As for other phenols, one type may be used alone, or two or more types may be used in combination.
　一価のフェノール化合物としては、例えば、フェノール；２－エチルフェノール、３－エチルフェノール、４－エチルフェノール、２－プロピルフェノール、３－プロピルフェノール、４－プロピルフェノール、２－ｔ－ブチルフェノール、３－ｔ－ブチルフェノール、４－ｔ－ブチルフェノール、２，５－ジエチルフェノール、３，５－ジエチルフェノール、２－ｔ－ブチル－４？メチルフェノール、２－ｔ－ブチル－５－メチルフェノール、２－ｔ－ブチル－３－メチルフェノール、２，３，５－トリエチルフェノールなどのアルキルフェノール；２－メトキシフェノール、３－メトキシフェノール、４－メトキシフェノール、２－エトキシフェノール、３－エトキシフェノール、４－エトキシフェノール、２，３－ジメトキシフェノール、２，５－ジメトキシフェノールなどのアルコキシフェノール；２－フェニルフェノール、３－フェニルフェノール、４－フェニルフェノールなどのアリールフェノール；２－イソプロペニルフェノール、４－イソプロペニルフェノール、２－メチル－４－イソプロペニルフェノール、２－エチル－４－イソプロペニルフェノールなどのアルケニルフェノール；などを挙げることができる。 Examples of the monovalent phenol compound include 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? Alkylphenols such as methylphenol, 2-t-butyl-5-methylphenol, 2-t-butyl-3-methylphenol, 2,3,5-triethylphenol; 2-methoxyphenol, 3-methoxyphenol, 4-methoxy Alkoxyphenols such as phenol, 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, 2,3-dimethoxyphenol, 2,5-dimethoxyphenol; 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, etc. Arylphenols; alkenylphenols such as 2-isopropenylphenol, 4-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4-isopropenylphenol; and the like.
　二価以上のフェノール化合物としては、例えば、レゾルシノール、２－メチルレゾルシノール、４－メチルレゾルシノール、５－メチルレゾルシノール、２－メトキシレゾルシノール、４－メトキシレゾルシノール；ヒドロキノン；カテコール、４－ｔ－ブチルカテコール、３－メトキシカテコール；４，４’ －ジヒドロキシビフェニル、２，２－ビス（４－ヒドロキシフェニル）プロパン；ピロガロール；フロログルシノール；などを挙げることができる。 Examples of the divalent or higher phenol compound include resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-methoxyresorcinol, 4-methoxyresorcinol; hydroquinone; catechol, 4-t-butylcatechol, 3 -Methoxycatechol; 4,4'-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane; pyrogallol; fluororesorcinol; and the like.
＜＜アルデヒド類＞＞
　上述したクレゾール類を含むフェノール類との縮合反応に供するアルデヒド類としては、脂肪族アルデヒド、脂環式アルデヒドおよび芳香族アルデヒドが挙げられる。 << Aldehydes >>
Examples of the aldehydes to be subjected to the condensation reaction with the phenols including the above-mentioned cresols include aliphatic aldehydes, alicyclic aldehydes and aromatic aldehydes.
―脂肪族アルデヒド―
　脂肪族アルデヒドとしては、例えば、ホルムアルデヒド、トリオキサン（メタホルムアルデヒド）、パラホルムアルデヒド、アセトアルデヒド、プロピオンアルデヒド、ｎ－ブチルアルデヒド、イソブチルアルデヒド、トリメチルアセトアルデヒド、ｎ－ヘキシルアルデヒド、アクロレイン、クロトンアルデヒドなどを挙げることができる。 -Aliphatic aldehyde-
Examples of the aliphatic aldehyde include formaldehyde, trioxane (metaformaldehyde), paraformaldehyde, acetaldehyde, propionaldehyde, n-butylaldehyde, isobutylaldehyde, trimethylacetaldehyde, n-hexylaldehyde, achlorine, and crotonaldehyde. ..
―脂環式アルデヒド―
　脂環式アルデヒドとしては、例えば、シクロペンタンアルデヒド、シクロヘキサンアルデヒド、フルフラール、フリルアクロレインなどを挙げることができる。 -Alicyclic aldehyde-
Examples of the alicyclic aldehyde include cyclopentane aldehyde, cyclohexane aldehyde, furfural, and frill acrolein.
―芳香族アルデヒド―
　芳香族アルデヒドとしては、例えば、ベンズアルデヒド、ｏ－トルアルデヒド、ｍ－トルアルデヒド、ｐ－トルアルデヒド、ｐ－エチルベンズアルデヒド、２，４－ジメチルベンズアルデヒド、２，５－ジメチルベンズアルデヒド、３，４－ジメチルベンズアルデヒド、３，５－ジメチルベンズアルデヒド、ｏ－クロロベンズアルデヒド、ｍ－クロロベンズアルデヒド、ｐ－クロロベンズアルデヒド、ｏ－ヒドロキシベンズアルデヒド、ｍ－ヒドロキシベンズアルデヒド、ｐ－ヒドロキシベンズアルデヒド、ｏ－アニスアルデヒド、ｍ－アニスアルデヒド、ｐ－アニスアルデヒド、テレフタルアルデヒド、フェニルアセトアルデヒド、α－フェニルプロピオンアルデヒド、β－フェニルプロピオンアルデヒド、桂皮アルデヒドなどを挙げることができる。 -Aromatic aldehyde-
Examples of aromatic aldehydes include benzaldehyde, o-tolaldehyde, m-tolualdehyde, p-tolualdehyde, p-ethylbenzaldehyde, 2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde, and 3,4-dimethylbenzaldehyde. , 3,5-Dimethylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-anisaldehyde, m-anisaldehyde, p- Examples thereof include annisaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropionaldehyde, β-phenylpropionaldehyde, and katsura aldehyde.
　上述したアルデヒド類は、１種を単独で使用しても、２種以上を組み合わせて使用してもよい。そしてこれらの中でも、脂肪族アルデヒドが好ましく、ホルムアルデヒドがより好ましい。 The above-mentioned aldehydes may be used alone or in combination of two or more. Among these, aliphatic aldehydes are preferable, and formaldehyde is more preferable.
＜＜調製方法＞＞
　クレゾールノボラック樹脂（Ｂ）は、上述したクレゾール類を含むフェノール類と、アルデヒド類とを縮合反応に供することにより調製することができる。この縮合反応は、例えば、酸性触媒を用いた既知の方法により行うことができる。用いる酸性触媒としては、例えば、塩酸、硫酸、ギ酸、酢酸、シュウ酸、ｐ－トルエンスルホン酸などを挙げることができる。 << Preparation method >>
The cresol novolak resin (B) can be prepared by subjecting the above-mentioned phenols containing cresols and aldehydes to a condensation reaction. This condensation reaction can be carried out, for example, by a known method using an acidic catalyst. Examples of the acidic catalyst used include hydrochloric acid, sulfuric acid, formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid and the like.
＜＜軟化点＞＞
　クレゾールノボラック樹脂（Ｂ）の軟化点は、１４０℃以上であることが必要であり、１５０℃以上であることが好ましく、１６０℃以上であることがより好ましい。軟化点が１４０℃未満であると、樹脂膜の熱フロー耐性を確保することができない。
　なお、クレゾールノボラック樹脂（Ｂ）の軟化点の上限は、特に限定されないが、取り扱い性の観点から、３００℃以下であることが好ましい。
　また、クレゾールノボラック樹脂（Ｂ）の軟化点は、縮合反応に用いるフェノール類およびアルデヒド類の種類や、縮合反応の条件を調整することにより制御することができる。 << Softening point >>
The softening point of the cresol novolak resin (B) needs to be 140 ° C. or higher, preferably 150 ° C. or higher, and more preferably 160 ° C. or higher. If the softening point is less than 140 ° C., the heat flow resistance of the resin film cannot be ensured.
The upper limit of the softening point of the cresol novolak resin (B) is not particularly limited, but is preferably 300 ° C. or lower from the viewpoint of handleability.
Further, the softening point of the cresol novolak resin (B) can be controlled by adjusting the types of phenols and aldehydes used in the condensation reaction and the conditions of the condensation reaction.
＜＜重量平均分子量＞＞
　クレゾールノボラック樹脂（Ｂ）の重量平均分子量は、１０００以上であることが好ましく、３０００以上であることがより好ましく、６０００以上であることが更に好ましく、２００００以下であることが好ましく、１５０００以下であることがより好ましく、１００００以下であることが更に好ましい。重量平均分子量が１０００以上であれば、軟化点が高まり樹脂膜の熱フロー耐性を更に向上させることができる。また、樹脂膜におけるラインパターンのトップロスを一層抑制することができる。一方、重量平均分子量が２００００以下であれば、クレゾールノボラック樹脂（Ｂ）の溶剤への溶解性を十分に確保することができる。
　なお、本発明において、クレゾールノボラック樹脂（Ｂ）の「重量平均分子量」は、テトラヒドロフラン等の溶媒を溶離液としたゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）により、ポリスチレン換算値として求められる値である。
　また、クレゾールノボラック樹脂（Ｂ）の重量平均分子量は、縮合反応に用いるフェノール類およびアルデヒド類の種類や、縮合反応の条件を調整することにより制御することができる。 << 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, further preferably 6000 or more, preferably 20000 or less, and preferably 15000 or less. More preferably, it is more preferably 10,000 or less. When the weight average molecular weight is 1000 or more, the softening point is increased and the heat flow resistance of the resin film can be further improved. In addition, the top loss of the line pattern in the resin film can be further suppressed. On the other hand, when the weight average molecular weight is 20000 or less, the solubility of the cresol novolak resin (B) in the solvent can be sufficiently ensured.
In the present invention, the "weight average molecular weight" of the cresol novolak resin (B) is a value obtained as a polystyrene-equivalent value by gel permeation chromatography (GPC) using a solvent such as tetrahydrofuran as an eluent. ..
Further, the weight average molecular weight of the cresol novolak resin (B) can be controlled by adjusting the types of phenols and aldehydes used in the condensation reaction and the conditions of the condensation reaction.
＜環状オレフィン重合体（Ａ）とクレゾールノボラック樹脂（Ｂ）の含有量比＞
　ここで、上述した環状オレフィン重合体（Ａ）と、上述したクレゾールノボラック樹脂（Ｂ）の合計中に占める環状オレフィン重合体（Ａ）の割合は、環状オレフィン重合体（Ａ）とクレゾールノボラック樹脂（Ｂ）の合計量を１００質量％として、１０質量％以上であることが好ましく、２０質量％以上であることがより好ましく、３０質量％以上であることが更に好ましく、９０質量％以下であることが好ましく、８０質量％以下であることがより好ましく、７５質量％以下であることが更に好ましい。環状オレフィン重合体（Ａ）とクレゾールノボラック樹脂（Ｂ）の合計中に占める環状オレフィン重合体（Ａ）の割合が１０質量％以上であれば、樹脂膜の比誘電率を十分に低下させることができ、９０質量％以下であれば、樹脂膜におけるラインパターンのトップロスを一層抑制することができる。 <Content ratio of cyclic olefin polymer (A) to cresol novolac resin (B)>
Here, the ratio of the cyclic olefin polymer (A) to the total of the above-mentioned cyclic olefin polymer (A) and the above-mentioned cresol novolac resin (B) is the cyclic olefin polymer (A) and the cresol novolac resin (B). When the total amount of B) is 100% by mass, it is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and 90% by mass or less. Is more preferable, 80% by mass or less is more preferable, and 75% by mass or less is further preferable. If the ratio of the cyclic olefin polymer (A) to the total of the cyclic olefin polymer (A) and the cresol novolak resin (B) is 10% by mass or more, the relative permittivity of the resin film can be sufficiently reduced. If it is 90% by mass or less, the top loss of the line pattern in the resin film can be further suppressed.
＜酸発生剤（Ｃ）＞
　酸発生剤（Ｃ）は、活性放射線の照射により分解して、カルボン酸などの酸成分を発生する化合物である。そして、酸発生剤（Ｃ）を含む本発明の樹脂組成物を用いて形成した感放射線性膜は、活性放射線を照射されると、露光部のアルカリ溶解性が増加する。 <Acid generator (C)>
The acid generator (C) is a compound that decomposes by irradiation with active radiation to generate an acid component such as a carboxylic acid. When the radiation-sensitive film formed by using the resin composition of the present invention containing the acid generator (C) is irradiated with active radiation, the alkali solubility of the exposed portion increases.
　ここで、酸発生剤（Ｃ）としては、例えば、アジド化合物、オニウム塩化合物、ハロゲン化有機化合物、α，α’－ビス（スルホニル）ジアゾメタン系化合物、α－カルボニル－α’－スルホニルジアゾメタン系化合物、スルホン化合物、有機酸エステル化合物、有機酸アミド化合物、有機酸イミド化合物、アセトフェノン化合物、トリアリールスルホニウム塩が挙げられるが、得られるラインアンドスペースパターンの解像度に優れるという観点から、アジド化合物が好ましく、キノンジアジド化合物がより好ましい。 Here, examples of the acid generator (C) include azide compounds, onium salt compounds, halogenated organic compounds, α, α'-bis (sulfonyl) diazomethane compounds, and α-carbonyl-α'-sulfonyl diazomethane compounds. , Sulphonic acid ester compound, organic acid amide compound, organic acid imide compound, acetophenone compound, triarylsulfonium salt, and azide compound is preferable from the viewpoint of excellent resolution of the obtained line and space pattern. A quinone diazide compound is more preferred.
　酸発生剤（Ｃ）として好適に用いられるキノンジアジド化合物としては、例えば、キノンジアジドスルホン酸ハライドとフェノール性水酸基を有する化合物とのエステル化合物を用いることができる。ここで、キノンジアジドスルホン酸ハライドの具体例としては、１，２－ナフトキノンジアジド－５－スルホン酸クロライド、１，２－ナフトキノンジアジド－４－スルホン酸クロライド、１，２－ベンゾキノンジアジド－５－スルホン酸クロライド等が挙げられる。また、フェノール性水酸基を有する化合物の具体例としては、１，１，３－トリス（２，５－ジメチル－４－ヒドロキシフェニル）－３－フェニルプロパン、４，４’－［１－［４－［１－［４－ヒドロキシフェニル］－１－メチルエチル］フェニル］エチリデン］ビスフェノール、２，３，４－トリヒドロキシベンゾフェノン、２，３，４，４’－テトラヒドロキシベンゾフェノン、２－ビス（４－ヒドロキシフェニル）プロパン、トリス（４－ヒドロキシフェニル）メタン、１，１，１－トリス（４－ヒドロキシ－３－メチルフェニル）エタン、１，１，２，２－テトラキス（４－ヒドロキシフェニル）エタン、ノボラック樹脂のオリゴマー、フェノール性水酸基を１つ以上有する化合物とジシクロペンタジエンとを共重合して得られるオリゴマー等が挙げられる。
　中でも、酸発生剤（Ｃ）としては、１，２－ナフトキノンジアジド－５－スルホン酸クロライドと４，４’－［１－［４－［１－［４－ヒドロキシフェニル］－１－メチルエチル］フェニル］エチリデン］ビスフェノールとのエステル化合物（縮合物）が好ましい。
　なお、酸発生剤（Ｃ）は、１種を単独で使用しても、２種以上を組み合わせて使用してもよい。 As the quinone diazide compound preferably used as the acid generator (C), for example, an ester compound of quinone diazido sulfonic acid halide and a compound having a phenolic hydroxyl group can be used. Here, specific examples of quinonediazide sulfonic acid halide include 1,2-naphthoquinonediazide-5-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride, and 1,2-benzoquinonediazide-5-sulfonic acid. Chloride and the like can be mentioned. Specific examples of the compound having a phenolic hydroxyl group include 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane and 4,4'-[1- [4- [4-]. [1- [4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, 2,3,4-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2-bis (4-bis) Hydroxyphenyl) propane, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy-3-methylphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, Examples thereof include 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, the acid generator (C) includes 1,2-naphthoquinonediazide-5-sulfonic acid chloride and 4,4'-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl]. An ester compound (condensate) with phenyl] ethylidene] bisphenol is preferable.
The acid generator (C) may be used alone or in combination of two or more.
＜＜含有量＞＞
　本発明の樹脂組成物中における酸発生剤（Ｃ）の含有量は、環状オレフィン重合体（Ａ）とクレゾールノボラック樹脂（Ｂ）の合計１００質量部当たり、１０質量部以上であることが好ましく、１５質量部以上であることがより好ましく、２５質量部以上であることが更に好ましく、３０質量部以上であることが特に好ましく、１００質量部以下であることが好ましく、７０質量部以下であることがより好ましく、５０質量部以下であることが更に好ましい。酸発生剤（Ｃ）の含有量が環状オレフィン重合体（Ａ）とクレゾールノボラック樹脂（Ｂ）の合計１００質量部当たり１０質量部以上であれば、露光部のアルカリ現像液に対する溶解性を十分に高めることができる。また、樹脂組成物を用いて微細なラインアンドスペースパターンを形成するに際し、未露光部にも僅かながら活性照射線があたりラインパターンのトップロスが生じる場合がある。しかしながら、酸発生剤（Ｃ）の含有量が環状オレフィン重合体（Ａ）とクレゾールノボラック樹脂（Ｂ）の合計１００質量部当たり１００質量部以下であれば、意に反して未露光部のアルカリ現像液に対する溶解性が高まることもなく、未露光部からなるラインパターンのトップロスを一層抑制することができる。 << Content >>
The content of the acid generator (C) in the resin composition of the present invention is preferably 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). It is more preferably 15 parts by mass or more, further preferably 25 parts by mass or more, particularly preferably 30 parts by mass or more, preferably 100 parts by mass or less, and 70 parts by mass or less. Is more preferable, and 50 parts by mass or less is further preferable. When the content of the acid generator (C) is 10 parts by mass or more per 100 parts by mass of the total of the cyclic olefin polymer (A) and the cresol novolak resin (B), the solubility of the exposed part in the alkaline developer is sufficient. Can be enhanced. Further, when forming a fine line-and-space pattern using the resin composition, the active irradiation line may slightly hit the unexposed portion and a top loss of the line pattern may occur. 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 novolak resin (B), the unexposed portion is alkaline-developed. The top loss of the line pattern composed of the unexposed portion can be further suppressed without increasing the solubility in the liquid.
＜架橋剤（Ｄ）＞
　架橋剤（Ｄ）は、環状オレフィン重合体（Ａ）が有するプロトン性極性基、クレゾールノボラック樹脂（Ｂ）が有する水酸基、および／またはクレゾールノボラック樹脂（Ｂ）が有する芳香環と架橋反応しうる化合物である。樹脂組成物が架橋剤（Ｄ）を含有することで、得られる樹脂膜の熱フロー耐性および耐薬品性を向上させることができる。 <Crosslinking agent (D)>
The cross-linking agent (D) is a compound capable of cross-linking 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. When the resin composition contains the cross-linking agent (D), the heat flow resistance and chemical resistance of the obtained resin film can be improved.
　ここで、架橋剤（Ｄ）としては、環状オレフィン重合体（Ａ）のプロトン性極性基および／またはクレゾールノボラック樹脂（Ｂ）の水酸基と反応しうる官能基を、１分子内に２つ以上有する化合物であれば特に限定されないが、多官能エポキシ化合物（エポキシ基を２つ以上有する化合物）、多官能アルコキシメチル化合物（アルコキシメチル基を２つ以上有する化合物）、および多官能メチロール化合物（メチロール基を２つ以上有する化合物）を挙げることができる。
　なお、架橋剤（Ｄ）は、１種を単独で使用しても、２種以上を組み合わせて使用してもよい。 Here, the cross-linking agent (D) has 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. The compound is not particularly limited as long as it is a compound, but a polyfunctional epoxy compound (a compound having two or more epoxy groups), a polyfunctional alkoxymethyl compound (a compound having two or more alkoxymethyl groups), and a polyfunctional methylol compound (a methylol group). Compounds having two or more) can be mentioned.
The cross-linking agent (D) may be used alone or in combination of two or more.
＜＜多官能エポキシ化合物＞＞
　多官能エポキシ化合物としては、例えば、トリス（２，３－エポキシプロピル）イソシアヌレート、１，４－ブタンジオールジグリシジルエーテル、１，２－エポキシ－４－（エポキシエチル）シクロヘキサン、グリセロールトリグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、２，６－ジグリシジルフェニルグリシジルエーテル、１，１，３－トリス［ｐ－（２，３－エポキシプロポキシ）フェニル］プロパン、１，２－シクロヘキサンジカルボン酸ジグリシジルエステル、４，４’－メチレンビス（Ｎ，Ｎ－ジグリシジルアニリン）、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、トリメチロールエタントリグリシジルエーテル、ビスフェノールＡジグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、エポキシ化ブタンテトラカルボン酸テトラキス（３－シクロヘキセニルメチル）修飾ε－カプロラクトン、および２，２－ビス(ヒドロキシメチル)－１－ブタノールの１，２－エポキシ－４－(２－オキシラニル)シクロヘキサン付加物等が挙げられる。 << Polyfunctional Epoxy Compound >>
Examples of the polyfunctional epoxy compound include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, and 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, trimethylol ethanetriglycidyl ether, bisphenol A diglycidyl ether, pentaerythritol polyglycidyl ether, Tepoxy butane tetracarboxylic acid tetrakis (3-cyclohexenylmethyl) -modified ε-caprolactone and 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol And so on.
　また、多官能エポキシ化合物の市販品としては、例えば、エポリード（登録商標）ＧＴ４０１、エポリードＰＢ３６００、エポリードＰＢ４７００、セロキサイド（登録商標）２０２１、セロキサイド３０００、ＥＨＰＥ３１５０（以上、ダイセル社製）；ｊＥＲ１００１、ｊＥＲ１００２、ｊＥＲ１００３、ｊＥＲ１００４、ｊＥＲ１００７、ｊＥＲ１００９、ｊＥＲ１０１０、ｊＥＲ８２８、ｊＥＲ８７１、ｊＥＲ８７２、ｊＥＲ１８０Ｓ７５、ｊＥＲ８０７、ｊＥＲ１５２、ｊＥＲ１５４（以上、三菱化学社製）；ＥＰＰＮ２０１、ＥＰＰＮ２０２、ＥＯＣＮ－１０２、ＥＯＣＮ－１０３Ｓ、ＥＯＣＮ－１０４Ｓ、ＥＯＣＮ－１０２０、ＥＯＣＮ－１０２５、ＥＯＣＮ－１０２７（以上、日本化薬社製）；エピクロン（登録商標）２００、エピクロン４００（以上、ＤＩＣ社製）；デナコール（登録商標）ＥＸ－６１１、デナコールＥＸ－６１２、デナコールＥＸ－６１４、デナコールＥＸ－６２２、デナコールＥＸ－４１１、デナコールＥＸ－５１２、デナコールＥＸ－５２２、デナコールＥＸ－４２１、デナコールＥＸ－３１３、デナコールＥＸ－３１４、デナコールＥＸ－３２１（以上、ナガセケムテックス社製）；ＴＥＰＩＣ－Ｓ（日産化学工業社製）などが挙げられる。 Commercially available products of the polyfunctional epoxy compound include, for example, Epolide (registered trademark) GT401, Epolide PB3600, Epolide PB4700, Celoxide (registered trademark) 2021, Celoxide 3000, EHPE3150 (all manufactured by DIC CORPORATION); jER1001, jER1002, jER1003, jER1004, jER1007, jER1009, jER1010, jER828, jER871, jER872, jER180S75, jER807, jER152, jER154 (all manufactured by Mitsubishi Chemical Industries, Ltd.); EPPN201, EPPN202, EOCN-102, EOCN-103S, EOCN-104S 1020, EOCN-1025, EOCN-1027 (above, manufactured by Nippon Kayaku); Epicron (registered trademark) 200, Epicron 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, Denacol EX-321 (above, Nagase Chemtex) (Manufactured by Nissan Chemical Industries, Ltd.); TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.) and the like.
＜＜多官能アルコキシメチル化合物＞＞
　多官能アルコキシメチル化合物としては、例えば、２つ以上のアルコキシメチル基が芳香環に直接結合してなるフェノール化合物、アミノ基が２つ以上のアルコキシメチル基で置換されてなるメラミン化合物、２つ以上のアルコキシメチル基で置換されてなるウレア化合物が挙げられる。 << Polyfunctional Alkoxy Methyl Compound >>
Examples of the polyfunctional alkoxymethyl compound include a phenol compound in which two or more alkoxymethyl groups are directly bonded to an aromatic ring, a melamine compound in which an amino group is substituted with two or more alkoxymethyl groups, and two or more. Examples of the urea compound are substituted with the alkoxymethyl group of the above.
　２つ以上のアルコキシメチル基が芳香環に直接結合してなるフェノール化合物としては、例えば、ジメトキシメチル置換フェノール化合物、テトラメトキシメチル置換ビフェニル化合物、ヘキサメトキシメチル置換トリフェニル化合物が挙げられる。
　より具体的には、２，６－ジメトキシメチル－４－ｔ－ブチルフェノール、２，６－ジメトキシメチル－ｐ－クレゾール、３，３’，５，５’－テトラメトキシメチル－４，４’－ジヒドロキシビフェニル（例えば、製品名「ＴＭＯＭ－ＢＰ」、本州化学工業社製）、１，１－ビス［３，５－ジ（メトキシメチル）－４－ヒドロキシフェニル］－１－フェニルエタン、４，４’，４’’－（エチリデン）トリス［２，６－ビス（メトキシメチル）フェノール］（例えば、製品名「ＨＭＯＭ－ＴＰＨＡＰ」、本州化学工業社製）、４，４’－［１－［４－［１－［４－ヒドロキシ－３，５－ビス（メトキシメチル）フェニル］－１－メチルエチル]フェニル]エチリデン]ビス［２，６－ビス(メトキシメチル)フェノール］（例えば、製品名「ＨＭＸ－ＰＡ」旭有機材社製）などが挙げられる。 Examples of the phenol compound in which two or more alkoxymethyl groups are directly bonded to the 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'-dihydroxy Biphenyl (for example, product name "TMOM-BP", manufactured by Honshu Kagaku Kogyo Co., Ltd.), 1,1-bis [3,5-di (methoxymethyl) -4-hydroxyphenyl] -1-phenylethane, 4,4' , 4''- (Echiliden) tris [2,6-bis (methoxymethyl) phenol] (for example, product name "HMOM-TPHAP", manufactured by Honshu Chemical Industry Co., Ltd.), 4,4'-[1- [4- [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 Materials Co., Ltd.) and the like.
　アミノ基が２つ以上のアルコキシメチル基で置換されてなるメラミン化合物としては、例えば、Ｎ，Ｎ’－ジメトキシメチルメラミン、Ｎ，Ｎ’，Ｎ’’－トリメトキシメチルメラミン、Ｎ，Ｎ，Ｎ’，Ｎ’’－テトラメトキシメチルメラミン、Ｎ，Ｎ，Ｎ’，Ｎ’，Ｎ’’－ペンタメトキシメチルメラミン、Ｎ，Ｎ，Ｎ’，Ｎ’，Ｎ’’，Ｎ’’－ヘキサメトキシメチルメラミン（例えば、製品名「ニカラック（登録商標）ＭＷ－３９０ＬＭ」、製品名「ニカラックＭＷ－１００ＬＭ」、何れも三和ケミカル社製）、あるいはこれらの重合体などが挙げられる。 Examples of the melamine compound in which the 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''-Hexamethoxy Examples thereof include methyl melamine (for example, product name "Nikalac (registered trademark) MW-390LM", product name "Nikalac MW-100LM", all manufactured by Sanwa Chemical Co., Ltd.), or polymers thereof.
　２つ以上のアルコキシメチル基で置換されてなるウレア化合物としては、例えば、製品名「ニカラックＭＸ２７０」、製品名「ニカラックＭＸ２８０」、製品名「ニカラックＭＸ２９０」（何れも三和ケミカル社製）が挙げられる。 Examples of the urea compound substituted with two or more alkoxymethyl groups include the product name "Nikalac MX270", the product name "Nikalac MX280", and the product name "Nikalac MX290" (all manufactured by Sanwa Chemical Co., Ltd.). Be done.
＜＜多官能メチロール化合物＞＞
　多官能メチロール化合物としては、例えば、２つ以上のメチロール基が芳香環に直接結合してなるフェノール化合物が挙げられる。
　そして、２つ以上のメチロール基が芳香環に直接結合してなるフェノール化合物としては、２，４－２，４－ジヒドロキシメチル－６－メチルフェノール、２，６－ビス(ヒドロキシメチル)－ｐ－クレゾール、４－ターシャリー－２,６－ビス（ヒドロキシメチル）フェノール、ビス（２－ヒドロキシ－３－ヒドロキシメチル－５－メチルフェニル）メタン（製品名「ＤＭ－ＢＩＰＣ－Ｆ」、旭有機材社製）、ビス（４－ヒドロキシ－３－ヒドロキシメチル－５－メチルフェニル）メタン（製品名「ＤＭ－ＢＩＯＣ－Ｆ」、旭有機材社製）、２，２－ビス（４－ヒドロキシ－３,５－ジヒドロキシメチルフェニル）プロパン（製品名「ＴＭ－ＢＩＰ－Ａ」、旭有機材社製）などが挙げられる。 << Polyfunctional methylol compound >>
Examples of the polyfunctional methylol compound include a phenol compound in which two or more methylol groups are directly bonded to an aromatic ring.
Phenol compounds in which two or more methylol groups are directly bonded to the aromatic ring include 2,4-2,4-dihydroxymethyl-6-methylphenol and 2,6-bis (hydroxymethyl) -p-. Cresol, 4-territory-2,6-bis (hydroxymethyl) phenol, bis (2-hydroxy-3-hydroxymethyl-5-methylphenyl) methane (product name "DM-BIPC-F", Asahi Organic Materials Co., Ltd. , Bis (4-hydroxy-3-hydroxymethyl-5-methylphenyl) methane (product name "DM-BIOC-F", manufactured by Asahi Organic Materials Co., Ltd.), 2,2-bis (4-hydroxy-3, 5-dihydroxymethylphenyl) propane (product name "TM-BIP-A", manufactured by Asahi Organic Materials Co., Ltd.) and the like can be mentioned.
　上述した架橋剤（Ｄ）の中でも、樹脂膜の熱フロー耐性を一層高めつつ、耐薬品性を向上させる観点から、多官能エポキシ化合物と多官能アルコキシメチル化合物の少なくとも一方を用いることが好ましく、多官能エポキシ化合物と多官能アルコキシメチル化合物の双方を用いることがより好ましい。
　また、多官能エポキシ化合物としては、樹脂膜の耐薬品性を良好に向上させる観点から、エポリードＧＴ４０１（物質名：エポキシ化ブタンテトラカルボン酸テトラキス（３－シクロヘキセニルメチル）修飾ε－カプロラクトン）などの脂環式構造を有する多官能エポキシ化合物、および、エポリードＰＢ４７００などの末端Ｈのエポキシ化ポリブタジエンからなる群より選択される少なくとも１種を含むことが好ましく、エポリードＧＴ４０１などの脂環式構造を有する多官能エポキシ化合物、および、エポリードＰＢ４７００などの主鎖中にグリシジルエーテル構造を有する末端Ｈのエポキシ化ポリブタジエンからなる群より選択される少なくとも１種を含むことがより好ましく、少なくともエポキシ化ブタンテトラカルボン酸テトラキス（３－シクロヘキセニルメチル）修飾ε－カプロラクトンを含むことが更に好ましい。 Among the above-mentioned cross-linking agents (D), it is preferable to use at least one of a polyfunctional epoxy compound and a polyfunctional alkoxymethyl compound from the viewpoint of further improving the heat flow resistance of the resin film and improving the chemical resistance. It is more preferable to use both a functional epoxy compound and a polyfunctional alkoxymethyl compound.
Further, as the polyfunctional epoxy compound, from the viewpoint of improving the chemical resistance of the resin film satisfactorily, Eporide GT401 (substance name: epoxidized butane tetracarboxylic acid tetrakis (3-cyclohexenylmethyl) modified ε-caprolactone) and the like are used. It is preferable to contain at least one selected from the group consisting of a polyfunctional epoxy compound having an alicyclic structure and an epoxidized polybutadiene having a terminal H such as Epolide PB4700, and a polydide having an alicyclic structure such as Epolide GT401. It is more preferable to contain at least one selected from the group consisting of a functional epoxy compound and an epoxidized polybutadiene having a glycidyl ether structure at the terminal H in the main chain such as Epolide PB4700, and at least tetrakis epoxidized butanetetracarboxylic acid. It is more preferred to include a (3-cyclohexenylmethyl) modified ε-caprolactone.
［含有量］
　本発明の樹脂組成物中における架橋剤（Ｄ）の含有量は、環状オレフィン重合体（Ａ）とクレゾールノボラック樹脂（Ｂ）の合計１００質量部当たり、１５質量部以上であることが好ましく、２０質量部以上であることがより好ましく、３０質量部以上であることが更に好ましく、４０質量部以上であることが特に好ましく、１２０質量部以下であることが好ましく、８０質量部以下であることがより好ましく、６０質量部以下であることが更に好ましく、５０質量部以下であることが特に好ましい。架橋剤（Ｄ）の含有量が環状オレフィン重合体（Ａ）とクレゾールノボラック樹脂（Ｂ）の合計１００質量部当たり１５質量部以上であれば、樹脂膜の熱フロー耐性および耐薬品性を更に向上させることができ、１２０質量部以下であれば、解像度に優れるラインアンドスペースパターンを形成することができる。
　また、多官能エポキシ化合物と、多官能アルコキシメチル化合物および多官能メチロール化合物の少なくとも一方（多官能アルコキシメチル化合物および／または多官能メチロール化合物）とを併用する場合、多官能エポキシ化合物と、多官能アルコキシメチル化合物および／または多官能メチロール化合物との質量比（多官能エポキシ化合物：多官能アルコキシメチル化合物および／または多官能メチロール化合物）は、１：１～１：０．１の範囲内であることが好ましく、１：０．５～１：０．２５の範囲内であることがより好ましい。多官能エポキシ化合物：多官能アルコキシメチル化合物および／または多官能メチロール化合物が上述の範囲内であれば、ラインアンドスペースパターンの解像度、熱フロー耐性および耐薬品性のバランスに優れた樹脂膜を形成することができる。 [Content]
The content of the cross-linking agent (D) in the resin composition of the present invention is preferably 15 parts by mass or more per 100 parts by mass in total of the cyclic olefin polymer (A) and the cresol novolac resin (B). It is more preferably parts by mass or more, more preferably 30 parts by mass or more, particularly preferably 40 parts by mass or more, preferably 120 parts by mass or less, and preferably 80 parts by mass or less. It is more preferably 60 parts by mass or less, and particularly preferably 50 parts by mass or less. When the content of the cross-linking 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 novolak resin (B), the heat flow resistance and chemical resistance of the resin film are further improved. If it is 120 parts by mass or less, a line-and-space pattern having excellent resolution can be formed.
Further, when the polyfunctional epoxy compound is used in combination with at least one of the polyfunctional alkoxymethyl compound and the polyfunctional methylol compound (polyfunctional alkoxymethyl compound and / or the polyfunctional methylol compound), the polyfunctional epoxy compound and the polyfunctional alkoxy The mass ratio to the methyl compound and / or the polyfunctional methylol compound (polyfunctional epoxy compound: polyfunctional alkoxymethyl compound and / or polyfunctional methylol compound) may be in the range of 1: 1 to 1: 0.1. It is preferably in the range of 1: 0.5 to 1: 0.25, more preferably. Polyfunctional epoxy compound: When the polyfunctional alkoxymethyl compound and / or the polyfunctional methylol compound is within the above range, a resin film having an excellent balance of line-and-space pattern resolution, heat flow resistance and chemical resistance is formed. be able to.
＜溶剤＞
　本発明の樹脂組成物は、溶剤を含有していてもよい。即ち、本発明の樹脂組成物は、溶剤中に、プロトン性極性基を有する環状オレフィン重合体（Ａ）、軟化点が１４０℃以上のクレゾールノボラック樹脂（Ｂ）、酸発生剤（Ｃ）、架橋剤（Ｄ）、および任意に添加されるその他の配合剤が、溶解および／または分散してなる、感放射線性樹脂液であってもよい。
　溶剤としては、特に限定されず、樹脂組成物の溶剤として既知のもの、例えば、アセトン、メチルエチルケトン、シクロペンタノン、２－ヘキサノン、３－ヘキサノン、２－ヘプタノン、３－ヘプタノン、４－ヘプタノン、２－オクタノン、３－オクタノン、４－オクタノンなどの直鎖のケトン類；ｎ－プロピルアルコール、イソプロピルアルコール、ｎ－ブチルアルコール、シクロヘキサノールなどのアルコール類；エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジオキサンなどのエーテル類；エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテルなどのアルコールエーテル類；ギ酸プロピル、ギ酸ブチル、酢酸プロピル、酢酸ブチル、プロピオン酸メチル、プロピオン酸エチル、酪酸メチル、酪酸エチル、乳酸メチル、乳酸エチルなどのエステル類；セロソルブアセテート、メチルセロソルブアセテート、エチルセロソルブアセテート、プロピルセロソルブアセテート、ブチルセロソルブアセテートなどのセロソルブエステル類；プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノブチルエーテルなどのプロピレングリコール類；ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテルなどのジエチレングリコール類；γ－ブチロラクトン、γ－バレロラクトン、γ－カプロラクトン、γ－カプリロラクトンなどの飽和γ－ラクトン類；トリクロロエチレンなどのハロゲン化炭化水素類；トルエン、キシレンなどの芳香族炭化水素類；ジメチルアセトアミド、ジメチルホルムアミド、Ｎ－メチルアセトアミドなどのその他の極性溶媒；が挙げられる。
　溶剤は、１種を単独で使用しても、２種以上を組み合わせて使用してもよい。 <Solvent>
The resin composition of the present invention may contain a solvent. That is, the resin composition of the present invention contains 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 crosslink in a solvent. The agent (D) and other compounding agents to be optionally added may be a radiation-sensitive resin solution in which the agent (D) and other compounding agents added optionally are dissolved and / or dispersed.
The solvent is not particularly limited, and known as a solvent for the resin composition, for example, acetone, methyl ethyl ketone, cyclopentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2 -Straight chain ketones such as octanone, 3-octanone and 4-octanone; alcohols such as n-propyl alcohol, isopropyl alcohol, n-butyl alcohol and cyclohexanol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dioxane and the like. Ethers; alcohol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl lactate, ethyl lactate Esters such as: Cellosolve esters such as cellosolve acetate, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, butyl cellosolve acetate; propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene. Propropylene glycols such as 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; γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-capri Saturated γ-lactones such as lolactone; halogenated hydrocarbons such as trichloroethylene; aromatic hydrocarbons such as toluene and xylene; other polar solvents such as dimethylacetamide, dimethylformamide and N-methylacetamide; ..
As the solvent, one type may be used alone, or two or more types may be used in combination.
＜その他の配合剤＞
　本発明の樹脂組成物は、上述した成分以外の配合剤を含有していてもよい。その他の配合剤としては、例えば、環状オレフィン重合体（Ａ）およびクレゾールノボラック樹脂（Ｂ）以外の樹脂成分、シランカップリング剤、酸性基または熱潜在性酸性基を有する化合物、溶解促進剤、界面活性剤、酸化防止剤、増感剤、光安定剤、消泡剤、顔料、染料、フィラーが挙げられる。なお、その他の配合剤は、１種を単独で使用しても、２種以上を組み合わせて使用してもよい。 <Other compounding agents>
The resin composition of the present invention may contain a compounding agent other than the above-mentioned components. Other compounding agents include, for example, resin components other than the cyclic olefin polymer (A) and the cresol novolak resin (B), a silane coupling agent, a compound having an acidic group or a thermopotential acidic group, a dissolution accelerator, and a surfactant. Examples include activators, antioxidants, sensitizers, light stabilizers, defoamers, pigments, dyes and fillers. As for other compounding agents, one type may be used alone, or two or more types may be used in combination.
＜感放射線性樹脂組成物の調製方法＞
　本発明の樹脂組成物を調製する方法は、特に限定されず、樹脂組成物を構成する各成分を混合すればよい。
　具体的には、本発明の樹脂組成物は、環状オレフィン重合体（Ａ）と、クレゾールノボラック樹脂（Ｂ）と、酸発生剤（Ｃ）と、架橋剤（Ｄ）と、任意に用いられるその他の配合剤とを、上述した溶剤中で混合することで、溶剤に溶解または分散して得ることが好ましい。この操作により、樹脂組成物は、溶液または分散液の形態で（即ち、感放射線性樹脂液として）得られる。
　上記混合は、特に限定されず、既知の混合機を用いて行う。また、混合後に既知の方法でろ過をおこなってもよい。
　そして、本発明の樹脂組成物である感放射線性樹脂液の固形分濃度は、通常、１質量％以上７０質量％以下、好ましくは５質量％以上６０質量％以下、より好ましくは１０質量％以上５０質量％以下である。固形分濃度が上述した範囲内であれば、感放射線性樹脂液の溶解安定性および塗布性、並びに形成される樹脂膜の膜厚均一性および平坦性等が高度にバランスされ得る。 <Method of preparing radiation-sensitive resin composition>
The method for preparing the resin composition of the present invention is not particularly limited, and each component constituting the resin composition may be mixed.
Specifically, the resin composition of the present invention includes a cyclic olefin polymer (A), a cresol novolac resin (B), an acid generator (C), a cross-linking agent (D), and others arbitrarily used. It is preferable to obtain by dissolving or dispersing in the solvent by mixing the compounding agent of the above in the above-mentioned solvent. By this operation, the resin composition is obtained in the form of a solution or a dispersion (that is, as a radiation-sensitive resin solution).
The above mixing is not particularly limited, and is carried out using a known mixer. Further, after mixing, filtration may be performed by a known method.
The solid content concentration of the radiation-sensitive resin liquid, which is the resin composition of the present invention, is usually 1% by mass or more and 70% by mass or less, preferably 5% by mass or more and 60% by mass or less, and more preferably 10% by mass or more. It is 50% by mass or less. When the solid content concentration is within the above range, the dissolution stability and coatability of the radiation-sensitive resin liquid, the film thickness uniformity and flatness of the formed resin film, and the like can be highly balanced.
＜樹脂膜の形成方法＞
　本発明の感放射線性樹脂組成物を用いて、半導体素子が実装されたシリコンウェハ等の基板上に樹脂膜を形成することができる。
　そして、基板上に樹脂膜を形成する方法は、特に限定されない。樹脂膜は、例えば、溶剤を含む感放射線性樹脂組成物（即ち、感放射線性樹脂液）を用いて、基板上に感放射線性膜を形成する工程（感放射線性膜形成工程）と、感放射線性膜に活性放射線を照射して露光膜を得る工程（露光工程）と、露光膜を現像して現像膜を得る工程（現像工程）と、現像膜を硬化して樹脂膜を得る工程（硬化工程）とを経て製造することができる。 <Method of forming resin film>
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.
The method of forming the resin film on the substrate is not particularly limited. For the resin film, for example, a step of forming a radiation-sensitive film on a substrate (that is, a radiation-sensitive film forming step) using a radiation-sensitive resin composition containing a solvent (that is, a radiation-sensitive resin solution) and a feeling. A step of irradiating a radioactive film with active radiation to obtain an exposure film (exposure step), a step of developing the exposure film to obtain a development film (development step), and a step of curing the development film to obtain a resin film (exposure step). It can be manufactured through a curing step).
＜＜感放射線性膜形成工程＞＞
　感放射線性樹脂液を用いて基板上に感放射線性膜を形成する方法は、特に限定されず、例えば、塗布法やフィルム積層法等の方法を用いることができる。 << Radiation-sensitive film forming process >>
The method for forming the radiation-sensitive film on the substrate using the radiation-sensitive resin liquid is not particularly limited, and for example, a coating method, a film lamination method, or the like can be used.
［塗布法］
　塗布法は、感放射線性樹脂液を基板上に塗布した後、加熱乾燥により溶剤を除去して感放射線性膜を形成する方法である。感放射線性樹脂液を塗布する方法としては、例えば、スプレー法、スピンコート法、ロールコート法、ダイコート法、ドクターブレード法、回転塗布法、スリットコート法、バー塗布法、スクリーン印刷法、インクジェット法等の各種の方法を採用することができる。加熱乾燥条件は、各成分の種類や配合割合に応じて異なるが、加熱温度は、通常、３０～１５０℃、好ましくは６０～１３０℃であり、加熱時間は、通常、０．５～９０分間、好ましくは１～６０分間、より好ましくは１～３０分間である。 [Painting method]
The coating method is a method in which a radiation-sensitive resin solution is applied onto a substrate and then the solvent is removed by heating and drying to form a radiation-sensitive film. Examples of the method for applying the radiation-sensitive resin liquid include a spray method, a spin coating method, a roll coating method, a die coating method, a doctor blade method, a rotary coating method, a slit coating method, a bar coating method, a screen printing method, and an inkjet method. Various methods such as, etc. can be adopted. The heating and drying conditions differ depending on the type and blending ratio of each component, but the heating temperature is usually 30 to 150 ° C., preferably 60 to 130 ° C., and the heating time is usually 0.5 to 90 minutes. , Preferably 1 to 60 minutes, more preferably 1 to 30 minutes.
［フィルム積層法］
　フィルム積層法は、感放射線性樹脂液を感放射線性膜形成用基材（樹脂フィルムや金属フィルム等）上に塗布した後、加熱乾燥により溶剤を除去して感放射線性膜を得、次いで、得られた感放射線性膜を基板上に積層する方法である。加熱乾燥条件は、各成分の種類や配合割合に応じて適宜選択することができるが、加熱温度は、通常、３０～１５０℃であり、加熱時間は、通常、０．５～９０分間である。感放射線性膜の基板上への積層は、加圧ラミネータ、プレス、真空ラミネータ、真空プレス、ロールラミネータ等の圧着機を用いて行なうことができる。 [Film Deposition Modeling]
In the film laminating method, a radiation-sensitive resin solution is applied on a base material for forming a radiation-sensitive film (resin film, metal film, etc.), and then the solvent is removed by heat drying to obtain a radiation-sensitive film, and then a radiation-sensitive film is obtained. This is a method of laminating the obtained radiation-sensitive film on a substrate. The heating and drying conditions can be appropriately selected according to the type and blending ratio of each component, but the heating temperature is usually 30 to 150 ° C., and the heating time is usually 0.5 to 90 minutes. .. The radiation-sensitive film can be laminated on the substrate by using a crimping machine such as a pressure laminator, a press, a vacuum laminator, a vacuum press, or a roll laminator.
　上述の何れかの手法で基板上に形成される感放射線性膜の厚さとしては、特に限定されず、用途に応じて適宜設定すればよいが、好ましくは０．１～１００μｍ、より好ましくは０．５～５０μｍ、更に好ましくは０．５～３０μｍである。 The thickness of the radiation-sensitive film formed on the substrate by any of the above-mentioned methods is not particularly limited and may be appropriately set according to the intended use, but is preferably 0.1 to 100 μm, more preferably 0.1 to 100 μm. It is 0.5 to 50 μm, more preferably 0.5 to 30 μm.
＜＜露光工程＞＞
　次いで、上述の感放射線性膜形成工程で形成した感放射線性膜に活性放射線を照射して、潜像パターンを有する露光膜を得る。 << Exposure process >>
Next, the radiation-sensitive film formed in the above-mentioned radiation-sensitive film forming step is irradiated with active radiation to obtain an exposed film having a latent image pattern.
［活性放射線］
　活性放射線としては、感放射線性膜に含有される酸発生剤（Ｃ）を活性化させて、露光部における樹脂成分の現像液に対する溶解性（特には、アルカリ現像液に対する溶解性）を向上させうるものであれば特に限定されない。具体的には、紫外線（ｇ線やｉ線等の単一波長の紫外線を含む）、ＫｒＦエキシマレーザー光、およびＡｒＦエキシマレーザー光に例示される光線；電子線に例示される粒子線；等を用いることができる。
　なお、活性放射線として光線を用いる場合は、単一波長光であっても、混合波長光であってもよい。 [Active radiation]
As the active radiation, the acid generator (C) contained in the radiation-sensitive film is activated to improve the solubility of the resin component in the developing solution (particularly, the solubility in the alkaline developing solution) in the exposed portion. There is no particular limitation as long as it is possible. Specifically, ultraviolet rays (including ultraviolet rays having a single wavelength such as g-rays and i-rays), KrF excimer laser light, and light rays exemplified by ArF excimer laser light; particle beams exemplified by electron beams; and the like. Can be used.
When light rays are used as the active radiation, it may be single wavelength light or mixed wavelength light.
［露光条件］
　上述した活性放射線を、選択的にパターン状に照射して潜像パターンを形成する方法としては、常法に従えばよく、例えば、縮小投影露光装置等により、紫外線、ＫｒＦエキシマレーザー光、およびＡｒＦエキシマレーザー光等の光線を所望のマスクパターンを介して照射する方法、または、電子線等の粒子線により描画する方法を用いることができる。
　照射条件は、使用する活性放射線に応じて適宜選択されるが、例えば、波長２００～４５０ｎｍの光線を使用する場合、照射量は、通常１０～５，０００ｍＪ／ｃｍ2、好ましくは５０～１，５００ｍＪ／ｃｍ2の範囲であり、照射時間と照度に応じて決まる。
　なお、活性放射線を照射した後、得られた露光膜に対して、必要に応じて、６０～１５０℃程度の温度で１～１０分間程度、加熱処理を施してもよい。 [Exposure conditions]
As a method of selectively irradiating the above-mentioned active radiation in a pattern to form a latent image pattern, a conventional method may be followed. For example, an ultraviolet ray, KrF excimer laser light, and ArF may be used by a reduced projection exposure device or the like. A method of irradiating a light beam such as excimer laser light through a desired mask pattern, or a method of drawing with a particle beam such as an electron beam can be used.
The irradiation conditions are appropriately selected according to the active radiation to be used. For example, when light rays having a wavelength of 200 to 450 nm are used, the irradiation amount is usually 10 to 5,000 mJ / cm 2 , preferably 50 to 1, The range is 500 mJ / cm 2 , and it depends on the irradiation time and illuminance.
After irradiating the active radiation, the obtained exposure film may be heat-treated at a temperature of about 60 to 150 ° C. for about 1 to 10 minutes, if necessary.
＜＜現像工程＞＞
　次に、上述の露光工程において露光膜に形成された潜像パターンを、現像液により現像して顕在化し、現像膜を得る。 << Development process >>
Next, the latent image pattern formed on the exposure film in the above-mentioned exposure step is developed with a developing solution to make it manifest, and a developing film is obtained.
［現像液］
　現像液としては、アルカリ現像液を用いることができる。アルカリ現像液は、アルカリ性化合物を水性媒体に溶解させて得ることができる。 [Developer]
An alkaline developer can be used as the developer. The alkaline developer can be obtained by dissolving an alkaline compound in an aqueous medium.
　アルカリ性化合物としては、例えば、アルカリ金属塩、アミン、アンモニウム塩を使用することができる。アルカリ性化合物は、無機化合物であっても有機化合物であってもよい。アルカリ性化合物の具体例としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム等のアルカリ金属塩；アンモニア；エチルアミン、ｎ－プロピルアミン等の第一級アミン；ジエチルアミン、ジ－ｎ－プロピルアミン等の第二級アミン；トリエチルアミン、メチルジエチルアミン等の第三級アミン；テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、コリン等の第四級アンモニウム塩；ジメチルエタノールアミン、トリエタノールアミン等のアルコールアミン；ピロール、ピペリジン、１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン、１，５－ジアザビシクロ［４．３．０］ノナ－５－エン、Ｎ－メチルピロリドン等の環状アミン類；が挙げられる。これらアルカリ性化合物は、１種を単独で使用しても、２種以上を組み合わせて使用してもよい。
　アルカリ現像液の水性媒体としては、水；メタノール、エタノール等の水溶性有機溶剤を使用することができる。
　またアルカリ現像液は、界面活性剤等を適当量添加したものであってもよい。 As the alkaline compound, for example, an alkali metal salt, an amine, or an ammonium salt can be used. The alkaline compound may be an inorganic compound or an organic compound. Specific examples of alkaline compounds 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; diethylamine and di. Secondary amines such as -n-propylamine; Tertiary amines such as triethylamine and methyldiethylamine; Tertiary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide and choline; dimethyl Alcohol amines such as ethanolamine and triethanolamine; pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] nona-5-ene , N-Methylpyrrolidone and other cyclic amines; These alkaline compounds may be used alone or in combination of two or more.
As the aqueous medium of the alkaline developer, water; a water-soluble organic solvent such as methanol or ethanol can be used.
Further, the alkaline developer may be one to which an appropriate amount of a surfactant or the like is added.
［現像方法］
　潜像パターンを有する露光膜に現像液を接触させる方法としては、例えば、パドル法、スプレー法、ディッピング法等の方法が用いられる。また、現像温度は、通常、０～１００℃、好ましくは５～５５℃、より好ましくは１０～３０℃の範囲で適宜選択され、現像時間は、通常、３０～１８０秒間の範囲で適宜選択される。 [Development method]
As a method of bringing the developer into contact with the exposure film having a latent image pattern, for example, a paddle method, a spray method, a dipping method and the like are used. The developing temperature is usually appropriately selected in the range of 0 to 100 ° C., preferably 5 to 55 ° C., more preferably 10 to 30 ° C., and the developing time is usually appropriately selected in the range of 30 to 180 seconds. To.
　このようにして目的とするパターンが形成された現像膜は、必要に応じて、現像残渣を除去するために、リンス液でリンスすることができる。リンス処理の後、残存しているリンス液を圧縮空気や圧縮窒素により除去することが好ましい。
　更に、必要に応じて、現像膜中に残存する酸発生剤（Ｃ）を失活させるために、現像膜に活性放射線を照射することもできる。活性放射線の照射には、「露光工程」で上述した方法を使用することができる。なお、活性放射線の照射と同時に、または活性放射線の照射後に現像膜を加熱してもよい。加熱方法としては、例えば、電子部品をホットプレートやオーブン内で加熱する方法が挙げられる。加熱温度は、通常、８０～３００℃、好ましくは１００～２００℃の範囲である。 The developing film on which the desired pattern is formed in this way can be rinsed with a rinsing solution, if necessary, in order to remove the developing residue. After the rinsing treatment, it is preferable to remove the remaining rinsing liquid with compressed air or compressed nitrogen.
Further, if necessary, the developing film can be irradiated with active radiation in order to inactivate the acid generator (C) remaining in the developing film. For the irradiation of active radiation, the method described above in the "exposure step" can be used. The developing film may be heated at the same time as the irradiation of the active radiation or after the irradiation of the active radiation. Examples of the heating method include a method of heating an electronic component in a hot plate or an oven. The heating temperature is usually in the range of 80 to 300 ° C, preferably 100 to 200 ° C.
＜＜硬化工程＞＞
　そして、上述の現像工程でパターン化された現像膜を硬化して、パターン化された樹脂膜を得る。
　硬化の方法は、感放射線性樹脂液に含有させた架橋剤（Ｄ）の種類に応じて適宜方法を選択すればよいが、通常、加熱により行なう。
　加熱方法は、例えば、ホットプレート、オーブン等を用いて行なうことができる。加熱温度は、通常、１５０～２５０℃であり、加熱時間は、現像膜の面積や厚さ、使用機器等により適宜選択され、例えばホットプレートを用いる場合は、通常、５～１２０分間、オーブンを用いる場合は、通常、３０～１５０分間の範囲である。また、加熱は、必要に応じて不活性ガス雰囲気下で行ってもよい。不活性ガスとしては、酸素を含まず、かつ、現像膜を酸化させないものであればよく、例えば、窒素、アルゴン、ヘリウム、ネオン、キセノン、クリプトン等が挙げられる。これらの中でも窒素とアルゴンが好ましく、特に窒素が好ましい。特に、酸素含有量が０．１体積％以下、好ましくは０．０１体積％以下の不活性ガス、特に窒素が好適である。これらの不活性ガスは、１種を単独で使用しても、２種以上を組み合わせて使用してもよい。 << Curing process >>
Then, the patterned developing film is cured in the above-mentioned developing step to obtain a patterned resin film.
The curing method may be appropriately selected depending on the type of the cross-linking agent (D) contained in the radiation-sensitive resin liquid, but is usually carried out by heating.
The heating method can be performed using, for example, a hot plate, an oven, or the like. The heating temperature is usually 150 to 250 ° C., and the heating time is appropriately selected depending on the area and thickness of the developing film, the equipment used, etc. For example, when using a hot plate, the oven is usually operated for 5 to 120 minutes. When used, it is usually in the range of 30-150 minutes. Further, heating may be performed in an inert gas atmosphere, if necessary. The inert gas may be any gas that does not contain oxygen and does not oxidize the developing film, and examples thereof include nitrogen, argon, helium, neon, xenon, and krypton. Among these, nitrogen and argon are preferable, and nitrogen is particularly 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 preferable. These inert gases may be used alone or in combination of two or more.
　以下、本発明について実施例に基づき具体的に説明するが、本発明はこれら実施例に限定されるものではない。
　実施例および比較例において、比誘電率、トップロス、熱フロー耐性、および耐薬品性は、以下のようにして評価した。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples.
In Examples and Comparative Examples, the relative permittivity, top loss, heat flow resistance, and chemical resistance were evaluated as follows.
＜比誘電率＞
　スパッタリング装置（芝浦エレテック社製、製品名「ｉ－Ｍｉｌｌｅｒ　ＣＦＳ－４ＥＰ－ＬＬ」）を用いて５０ｎｍ膜厚のアルミ膜を形成した４インチシリコンウェハ上に、調製した樹脂組成物をスピンコート法により塗布し、次いで、ホットプレートを用いて１２０℃で２分間加熱乾燥（プリベーク）して、感放射線性膜を形成した。当該膜を、窒素中において２３０℃で１時間加熱することにより硬化させ、１０μｍ厚の硬化膜付きシリコンウェハを得た。これを０．１モル%の塩酸水溶液に１２時間浸漬してアルミのエッチングを行うことで、シリコンウェハから硬化膜を剥離させた。この硬化膜を幅２ｍｍ、長さ５０ｍｍの短冊状に切り出して試験片とし、この試験片について空洞共振器法により１０ＧＨｚにおける比誘電率の測定を行い、下記の基準で評価した。
　Ａ：比誘電率が２．８５未満
　Ｂ：比誘電率が２．８５以上３．００未満
　Ｃ：比誘電率が３．００以上
＜トップロス＞
　シリコンウェハ上に、調製した樹脂組成物をスピンコート法により塗布し、次いで、ホットプレートを用いて１２０℃で２分間加熱乾燥（プリベーク）して、感放射線性膜（膜厚３．０μｍ）を形成した。次いで、i線ステッパー（ニコン社製、製品名「ＮＳＲ２００５ｉ９Ｃ」）に１．０μｍのラインアンドスペースパターンを形成可能なレチクルをセットし、１００から２０００ｍＪ／ｃｍ2まで露光量を変化させることにより、露光工程を行った。得られた露光膜に対して、２．３８質量％テトラメチルアンモニウムヒドロキシド水溶液を用いて、６０秒間現像処理を行った。その後、超純水でのリンスおよび振り切り乾燥を経て、ラインアンドスペースパターンを有する現像膜と、シリコンウェハとからなる積層体を得た。そして、走査電子顕微鏡（ＳＥＭ）を用いて、得られた積層体のラインアンドスペースパターン部分の断面を観察し、ラインとスペースが１：１となる露光量におけるライン部の膜厚を測長した。また、ラインアンドスペースパターンを形成していない未露光部の膜厚も、ＳＥＭにより測長した。そして式：トップロス（％）＝（未露光部の膜厚－ライン部の膜厚）／（未露光部の膜厚）×１００を用いてトップロスを算出し、下記基準で評価した。
　Ａ：トップロスが２５％未満
　Ｂ：トップロスが２５％以上４０％未満
　Ｃ：トップロスが４０％以上
＜熱フロー耐性＞
　シリコンウェハ上に、調製した樹脂組成物をスピンコート法により塗布し、次いで、ホットプレートを用いて１２０℃で２分間加熱乾燥（プリベーク）して、感放射線性膜（膜厚３．０μｍ）を形成した。次いで、２．０μｍのビアパターンを形成可能なマスクを用い、１００から２０００ｍＪ／ｃｍ2まで露光量を変化させることにより、露光工程を行った。得られた露光膜に対して、２．３８重量％テトラメチルアンモニウムヒドロキシド水溶液を用いて、６０秒間現像処理を行った。その後、超純水でのリンスおよび振り切り乾燥を経て、２．０μｍのビアホールを有する現像膜と、シリコンウェハとからなる積層体を得た。なお、光学顕微鏡で観察、測長し、２．０μｍのビアパターンが開口していることを確認した。得られた積層体を、窒素中で５０℃から１１０℃まで２℃／分で昇温し、１１０℃で３０分間保持した後、２３０℃まで３℃／分で昇温し、更に２３０℃で1時間保持することで現像膜を硬化させて樹脂膜を得た。そして、硬化前に２．０μｍのビアパターンが開口していた露光量におけるビア径を、光学顕微鏡で測長し、式：ビア径の減少割合（％）＝（硬化前のビア径－硬化後のビア径）／（硬化前のビア径）×１００を用いて、硬化によるビア径の減少割合を算出し、下記基準で評価した。
　Ａ：ビア径の減少割合が５％未満
　Ｂ：ビア径の減少割合が５％以上１０％未満
　Ｃ：ビア径の減少割合が１０％以上
＜耐薬品性＞
　シリコンウェハ上に、調製した樹脂組成物をスピンコート法により塗布し、ホットプレートを用いて１２０℃で２分間加熱乾燥（プリベーク）して、感放射線性膜を形成した。次いで、窒素中で５０℃から１１０℃まで２℃／分で昇温し、１１０℃で３０分間保持した後、２３０℃まで３℃／分で昇温し、更に２３０℃で１時間保持することで感放射線性膜を硬化させて硬化膜を得た。これを２３℃においてモノエタノールアミン／ジメチルスルホキシド＝７／３（質量比）に１５分間浸漬し、式：膜厚の変化割合（％）＝｜浸漬前の膜厚－浸漬後の膜厚｜／（浸漬前の膜厚）×１００を用いて、浸漬による膜厚の変化割合を算出し、硬化膜の目視観察の結果（クラック、剥がれ有無）とあわせて下記基準で評価した。
　Ａ：膜厚の変化割合が１０％未満、並びに、クラックおよび剥がれ無し
　Ｂ：膜厚の変化割合が１０％以上２０％未満、並びに、クラックおよび剥がれ無し
　Ｃ：膜厚の変化割合が２０％以上、および／または、クラックと剥がれの少なくとも何れか有り <Relative permittivity>
The prepared resin composition was spin-coated on a 4-inch silicon wafer on which an aluminum film having a film thickness of 50 nm was formed using a sputtering device (manufactured by Shibaura Eletech Co., Ltd., product name "i-Miller CFS-4EP-LL"). It was applied and then heat-dried (prebaked) at 120 ° C. for 2 minutes using a hot plate to form a radiation-sensitive film. The film was cured by heating in nitrogen at 230 ° C. for 1 hour to obtain a silicon wafer with a cured film having a thickness of 10 μm. This was immersed in a 0.1 mol% hydrochloric acid aqueous solution for 12 hours to etch aluminum, thereby peeling the cured film from the silicon wafer. This cured film was cut into strips having a width of 2 mm and a length of 50 mm to form test pieces, and the relative permittivity of this test piece was measured at 10 GHz by the cavity resonator method and evaluated according to the following criteria.
A: Relative permittivity is less than 2.85 B: Relative permittivity is 2.85 or more and less than 3.00 C: Relative permittivity is 3.00 or more <Top loss>
The prepared resin composition is applied onto a silicon wafer by a spin coating method, and then heat-dried (prebaked) at 120 ° C. for 2 minutes using a hot plate to form a radiation-sensitive film (thickness: 3.0 μm). Formed. Next, an i-line stepper (manufactured by Nikon Corporation, product name "NSR2005i9C") is set with a reticle capable of forming a 1.0 μm line and space pattern, and the exposure is changed from 100 to 2000 mJ / cm 2. The process was performed. The obtained exposure film was developed with a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 60 seconds. Then, after rinsing with ultrapure water and shaking off and drying, a laminate composed of a developing film having a line and space pattern and a silicon wafer was obtained. Then, using a scanning electron microscope (SEM), the cross section of the line-and-space pattern portion of the obtained laminate was observed, and the film thickness of the line portion was measured at an exposure amount in which the line and space were 1: 1. .. The film thickness of the unexposed portion that did not form the line-and-space pattern was also measured by SEM. Then, the top loss was calculated using the formula: top loss (%) = (film thickness of unexposed portion-film thickness of line portion) / (film thickness of unexposed portion) × 100, and evaluated according to the following criteria.
A: Top loss is less than 25% B: Top loss is 25% or more and less than 40% C: Top loss is 40% or more <Heat flow resistance>
The prepared resin composition is applied onto a silicon wafer by a spin coating method, and then heat-dried (prebaked) at 120 ° C. for 2 minutes using a hot plate to form a radiation-sensitive film (thickness: 3.0 μm). Formed. Next, an exposure step was performed by changing the exposure amount from 100 to 2000 mJ / cm 2 using a mask capable of forming a 2.0 μm via pattern. The obtained exposure film was developed with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds. Then, after rinsing with ultrapure water and shaking off and drying, a laminate composed of a developing film having a via hole of 2.0 μm and a silicon wafer was obtained. By observing and measuring the length with an optical microscope, it was confirmed that a 2.0 μm via pattern was open. The obtained 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 at 230 ° C. The developing film was cured by holding for 1 hour to obtain a resin film. Then, the via diameter at the exposure amount at which the 2.0 μm via pattern was opened before curing was measured with an optical microscope, and the formula: Via diameter reduction rate (%) = (Beer diameter before curing-after curing). Via diameter) / (Beer diameter before curing) × 100 was used to calculate the reduction rate of the via diameter due to curing, and evaluated according to the following criteria.
A: Via diameter reduction rate is less than 5% B: Via diameter reduction rate is 5% or more and less than 10% C: Via diameter reduction rate is 10% or more <Chemical resistance>
The prepared resin composition was applied onto a silicon wafer by a spin coating method, and heat-dried (prebaked) at 120 ° C. for 2 minutes using a hot plate to form a radiation-sensitive film. Then, the temperature is raised in nitrogen from 50 ° C. to 110 ° C. at 2 ° C./min, held at 110 ° C. for 30 minutes, then raised to 230 ° C. at 3 ° C./min, and further held at 230 ° C. for 1 hour. The radiation-sensitive film was cured in 1 to obtain a cured film. This was immersed in monoethanolamine / dimethylsulfoxide = 7/3 (mass ratio) at 23 ° C. for 15 minutes, and the formula: film thickness change rate (%) = | film thickness before immersion-film thickness after immersion | / Using (film thickness before immersion) × 100, the rate of change in film thickness due to immersion was calculated, and evaluated according to the following criteria together with the results of visual observation of the cured film (presence or absence of cracks and peeling).
A: The rate of change in film thickness is less than 10% and no cracks and peeling B: The rate of change in film thickness is 10% or more and less than 20%, and no cracks and peeling C: The rate of change in film thickness is 20% or more , And / or at least one of cracks and peeling
（実施例１）
＜環状オレフィン重合体（Ａ－１）の調製＞
　Ｎ－フェニル－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド（ＮＢＰＩ）４０モル％および４－ヒドロキシカルボニルテトラシクロ［６．２．１．１3,6．０2,7］ドデカ－９－エン（ＴＣＤＣ）６０モル％からなる単量体混合物１００質量部、１，５－ヘキサジエン２．０質量部、（１，３－ジメシチルイミダゾリン－２－イリデン）（トリシクロヘキシルホスフィン）ベンジリデンルテニウムジクロリド（「Ｏｒｇ．Ｌｅｔｔ．，第１巻，９５３頁，１９９９年」に記載された方法で合成した）０．０２質量部、並びにジエチレングリコールメチルエチルエーテル２００質量部を、窒素置換したガラス製耐圧反応器に仕込み、攪拌しつつ８０℃にて４時間反応させて重合反応液を得た。
　そして、得られた重合反応液をオートクレーブに入れて、１５０℃、水素圧４ＭＰａで、５時間攪拌して水素化反応を行い、プロトン性極性基を有する環状オレフィン重合体（Ａ－１）を含む重合体溶液を得た。得られた環状オレフィン重合体（Ａ－１）の重合転化率は９９．７質量％、重量平均分子量（ポリスチレン換算）は７２００、数平均分子量は４７００、分子量分布は１．５３、水素添加率は９９．７％であった。また、得られた環状オレフィン重合体（Ａ－１）の重合体溶液の固形分濃度は３４．４質量％であった。
＜感放射線性樹脂組成物（感放射線性樹脂液）の調製＞
　環状オレフィン重合体（Ａ－１）の重合体溶液を７５部（固形分相当）、クレゾールノボラック樹脂（Ｂ－１）（旭有機材社製、製品名「ＴＭＲ３０Ｂ３５Ｇ」、重量平均分子量：７０００、軟化点：１６３℃、ｍ－クレゾール／ｐ－クレゾール／ｍ－キシレノール＝６０／３０／１０（モル比）とホルムアルデヒドの縮合重合体、ｍ／ｐ比：約２．３）を２５部、酸発生剤（Ｃ－１）（東洋合成社製、製品名「ＴＳ２５０」、キノンジアジド化合物（４，４’－［１－［４－［１－［４－ヒドロキシフェニル］－１－メチルエチル］フェニル］エチリデン］ビスフェノール（１．０モル部）と１，２－ナフトキノンジアジド－５－スルホン酸クロライド（２．５モル部）との縮合物））を３０部、架橋剤（Ｄ－１）（ダイセル社製、製品名「エポリードＧＴ４０１」、脂環式構造を有する多官能エポキシ化合物）を３０部、架橋剤（Ｄ－４）（三和ケミカル社製、製品名「ニカラックＭＷ－１００ＬＭ」、Ｎ，Ｎ，Ｎ’，Ｎ’，Ｎ’’，Ｎ’’－ヘキサメトキシメチルメラミン）を１０部、および、溶剤としてジエチレングリコールメチルエチルエーテルを混合し、溶解させた。なお、ジエチレングリコールメチルエチルエーテルの使用量は、固形分濃度が４０質量％となる量とした。次いで、得られた溶液を孔径０．４５μｍのポリテトラフルオロエチレン製フィルターでろ過して樹脂組成物を調製した。得られた樹脂組成物を用いて各種評価を行った。結果を表１に示す。 (Example 1)
<Preparation of cyclic olefin polymer (A-1)>
N-Phenyl-bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxyimide (NBPI) 40 mol% and 4-hydroxycarbonyltetracyclo [6.2.1.1 3,6 . 0 2,7 ] 100 parts by mass of a monomer mixture consisting of 60 mol% of dodeca-9-ene (TCDC), 2.0 parts by mass of 1,5-hexadien, (1,3-dimesityl imidazoline-2-ylidene). ) (Tricyclohexylphosphine) 0.02 parts by mass of benzylidene ruthenium dichloride (synthesized by the method described in "Org. Lett., Vol. 1, p. 953, 1999"), and 200 parts by mass of diethylene glycol methyl ethyl ether. The mixture was charged in a glass pressure-resistant reactor substituted with nitrogen and reacted at 80 ° C. for 4 hours with stirring to obtain a polymerization reaction solution.
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 carry out a hydrogenation reaction, and contains a cyclic olefin polymer (A-1) having a protonic polar group. A polymer solution was obtained. The obtained cyclic olefin polymer (A-1) has a polymerization conversion rate of 99.7% by mass, a weight average molecular weight (in terms of polystyrene) of 7200, a number average molecular weight of 4700, a molecular weight distribution of 1.53, and a hydrogenation rate. It was 99.7%. Moreover, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-1) was 34.4% by 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 novolak resin (B-1) (manufactured by Asahi Organic Materials Co., Ltd., product name "TMR30B35G", weight average molecular weight: 7000, softened 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) (manufactured by Toyo Synthetic Co., Ltd., product name "TS250", quinonediazide compound (4,5'-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] 30 parts of bisphenol (1.0 mol part) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (2.5 mol part)), cross-linking agent (D-1) (manufactured by Daicel Co., Ltd., Product name "Epolide GT401", 30 parts of polyfunctional epoxy compound having an alicyclic structure), cross-linking agent (D-4) (manufactured by Sanwa Chemical Co., Ltd., product name "Nicolac MW-100LM", N, N, N 10 parts of', N', N'', N''-hexamethoxymethylmelamine) and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. The amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 1.
（実施例２）
　樹脂組成物の調製に際し、環状オレフィン重合体（Ａ－１）の量を７５部から５５部（固形分相当）に、クレゾールノボラック樹脂（Ｂ－１）の量を２５部から４５部に、そして、架橋剤（Ｄ－１）の量を３０部から３５部に変更した以外は、実施例１と同様にして、環状オレフィン重合体（Ａ－１）および樹脂組成物を調製し、各種評価を行った。結果を表１に示す。 (Example 2)
In preparing the resin composition, the amount of the cyclic olefin polymer (A-1) was changed from 75 parts to 55 parts (corresponding to the solid content), the amount of the cresol novolak resin (B-1) was changed from 25 parts to 45 parts, and , The cyclic olefin polymer (A-1) and the resin composition were prepared in the same manner as in Example 1 except that the amount of the cross-linking agent (D-1) was changed from 30 parts to 35 parts, and various evaluations were performed. went. The results are shown in Table 1.
（実施例３）
　樹脂組成物の調製に際し、環状オレフィン重合体（Ａ－１）の量を７５部から３０部（固形分相当）に、クレゾールノボラック樹脂（Ｂ－１）の量を２５部から７０部に変更した以外は、実施例１と同様にして、環状オレフィン重合体（Ａ－１）および樹脂組成物を調製し、各種評価を行った。結果を表１に示す。 (Example 3)
In preparing the resin composition, the amount of the cyclic olefin polymer (A-1) was changed from 75 parts to 30 parts (corresponding to the solid content), and the amount of the cresol novolak resin (B-1) was changed from 25 parts to 70 parts. A cyclic olefin polymer (A-1) and a resin composition were prepared in the same manner as in Example 1 except for the above, and various evaluations were performed. The results are shown in Table 1.
（実施例４）
＜環状オレフィン重合体（Ａ－２）の調製＞
　ＮＢＰＩを３１．５モル％、ＴＣＤＣを６８．５モル％とした以外は環状オレフィン重合体（Ａ－１）と同様にして、プロトン性極性基を有する環状オレフィン重合体（Ａ－２）を調製した。得られた環状オレフィン重合体（Ａ－２）の重合転化率は９９．８質量％、重量平均分子量（ポリスチレン換算）は７３００、数平均分子量は４８００、分子量分布は１．５２、水素添加率は、９９．９％であった。また、得られた環状オレフィン重合体（Ａ－２）の重合体溶液の固形分濃度は３４．３質量％であった。
＜感放射線性樹脂組成物（感放射線性樹脂液）の調製＞
　環状オレフィン重合体（Ａ－２）の重合体溶液を５０部（固形分相当）、クレゾールノボラック樹脂（Ｂ－２）（旭有機材社製、製品名「ＴＭＲ３０Ｂ２５Ｇ」、重量平均分子量：９０００、軟化点：１６７℃、ｍ－クレゾール／ｐ－クレゾール／ｍ－キシレノール＝６０／３０／１０（モル比）とホルムアルデヒドの縮合重合体、ｍ／ｐ比：約２．３）を５０部、酸発生剤（Ｃ－１）を３０部、架橋剤（Ｄ－１）を３７部、架橋剤（Ｄ－５）（本州化学工業社製、製品名「ＨＭＯＭ－ＴＰＨＡＰ」、４，４’，４’’－（エチリデン）トリス［２，６－ビス（メトキシメチル）フェノール］）を１０部、および、溶剤としてジエチレングリコールメチルエチルエーテルを混合し、溶解させた。なお、ジエチレングリコールメチルエチルエーテルの使用量は、固形分濃度が４０質量％となる量とした。次いで、得られた溶液を孔径０．４５μｍのポリテトラフルオロエチレン製フィルターでろ過して樹脂組成物を調製した。得られた樹脂組成物を用いて各種評価を行った。結果を表１に示す。 (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 the cyclic olefin polymer (A-1) except that the NBPI was 31.5 mol% and the TCDC was 68.5 mol%. did. The obtained cyclic olefin polymer (A-2) has a polymerization conversion rate of 99.8% by mass, a weight average molecular weight (in terms of polystyrene) of 7300, a number average molecular weight of 4800, a molecular weight distribution of 1.52, and a hydrogenation rate. , 99.9%. Moreover, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-2) was 34.3% by mass.
<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>
50 parts (equivalent to solid content) of polymer solution of cyclic olefin polymer (A-2), cresol novolac resin (B-2) (manufactured by Asahi Organic Materials Co., Ltd., product name "TMR30B25G", weight average molecular weight: 9000, softened 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 30 parts of (C-1), 37 parts of cross-linking agent (D-1), cross-linking agent (D-5) (manufactured by Honshu Chemical Industry Co., Ltd., product name "HMOM-TPHAP", 4, 4', 4'' -(Echiliden) tris [2,6-bis (methoxymethyl) phenol]) was mixed with 10 parts and diethylene glycol methyl ethyl ether as a solvent to dissolve them. The amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 1.
（実施例５）
＜環状オレフィン重合体（Ａ－１）および（Ａ－２）の調製＞
　実施例１と同様にして環状オレフィン重合体（Ａ－１）を、実施例４と同様にして環状オレフィン重合体（Ａ－２）をそれぞれ調製した。
＜感放射線性樹脂組成物（感放射線性樹脂液）の調製＞
　環状オレフィン重合体（Ａ－１）の重合体溶液を２５部（固形分相当）、環状オレフィン重合体（Ａ－２）の重合体溶液を３０部（固形分相当）、クレゾールノボラック樹脂（Ｂ－２）を４５部、酸発生剤（Ｃ－１）を３０部、架橋剤（Ｄ－１）を３５部、架橋剤（Ｄ－４）を１０部、および、溶剤としてジエチレングリコールメチルエチルエーテルを混合し、溶解させた。なお、ジエチレングリコールメチルエチルエーテルの使用量は、固形分濃度が４０質量％となる量とした。次いで、得られた溶液を孔径０．４５μｍのポリテトラフルオロエチレン製フィルターでろ過して樹脂組成物を調製した。得られた樹脂組成物を用いて各種評価を行った。結果を表１に示す。 (Example 5)
<Preparation of cyclic olefin polymers (A-1) and (A-2)>
A cyclic olefin polymer (A-1) was prepared in the same manner as in Example 1, and a cyclic olefin polymer (A-2) was prepared in the same manner as in Example 4.
<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>
25 parts (equivalent to solid content) of the polymer solution of the cyclic olefin polymer (A-1), 30 parts (equivalent to solid content) of the polymer solution of the cyclic olefin polymer (A-2), cresol novolac resin (B-). 2) is 45 parts, acid generator (C-1) is 30 parts, cross-linking agent (D-1) is 35 parts, cross-linking agent (D-4) is 10 parts, and diethylene glycol methyl ethyl ether is mixed as a solvent. And dissolved. The amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 1.
（実施例６）
＜環状オレフィン重合体（Ａ－１）の調製＞
　実施例１と同様にして環状オレフィン重合体（Ａ－１）を調製した。
＜感放射線性樹脂組成物（感放射線性樹脂液）の調製＞
　環状オレフィン重合体（Ａ－１）の重合体溶液を６０部（固形分相当）、クレゾールノボラック樹脂（Ｂ－２）を２０部、クレゾールノボラック樹脂（Ｂ－３）（旭有機材社製、製品名「ＳＥ３０１０」、重量平均分子量：５０００、軟化点：１５５℃、ｍ－クレゾール／ｐ－クレゾール＝７０／３０（モル比）とホルムアルデヒドの縮合重合体、ｍ／ｐ比：約２．３）を２０部、酸発生剤（Ｃ－１）を３０部、架橋剤（Ｄ－１）を３０部、架橋剤（Ｄ－６）（旭有機材社製、製品名「ＨＭＸ－ＰＡ」、４，４’－［１－［４－［１－［４－ヒドロキシ－３，５－ビス（メトキシメチル）フェニル］－１－メチルエチル]フェニル]エチリデン]ビス［２，６－ビス(メトキシメチル)フェノール］）を１５部、および、溶剤としてジエチレングリコールメチルエチルエーテルを混合し、溶解させた。なお、ジエチレングリコールメチルエチルエーテルの使用量は、固形分濃度が４０質量％となる量とした。次いで、得られた溶液を孔径０．４５μｍのポリテトラフルオロエチレン製フィルターでろ過して樹脂組成物を調製した。得られた樹脂組成物を用いて各種評価を行った。結果を表１に示す。 (Example 6)
<Preparation of cyclic olefin polymer (A-1)>
A cyclic olefin polymer (A-1) was prepared in the same manner as in Example 1.
<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>
60 parts (equivalent to solid content) of polymer solution of cyclic olefin polymer (A-1), 20 parts of cresol novolac resin (B-2), cresol novolac resin (B-3) (manufactured by Asahi Organic Materials Co., Ltd.) 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, cross-linking agent (D-1) 30 parts, cross-linking agent (D-6) (manufactured by Asahi Organic Materials Co., Ltd., product name "HMX-PA", 4, 4'-[1- [4- [1- [4-hydroxy-3,5-bis (methoxymethyl) phenyl] -1-methylethyl] phenyl] ethylidene] bis [2,6-bis (methoxymethyl) phenol ]) Was mixed with 15 parts and diethylene glycol methyl ethyl ether as a solvent to dissolve them. The amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 1.
（実施例７）
＜環状オレフィン重合体（Ａ－３）の調製＞
　ＮＢＰＩを使用せず、Ｎ－（２－エチルヘキシル）－ビシクロ［２．２．１］ヘプト－５－エン－２，３－ジカルボキシイミド（ＮＥＨＩ）を４０モル％、ＴＣＤＣを６０モル％とした以外は環状オレフィン重合体（Ａ－１）と同様にして、プロトン性極性基を有する環状オレフィン重合体（Ａ－３）を調製した。得られた環状オレフィン重合体（Ａ－３）の重合転化率は９９．８質量％、重量平均分子量（ポリスチレン換算）は８５００、数平均分子量は５８００、分子量分布は１．４７、水素添加率は、９９．９％であった。また、得られた環状オレフィン重合体（Ａ－３）の重合体溶液の固形分濃度は３４．３質量％であった。
＜環状オレフィン重合体（Ａ－４）の調製＞
　ＮＢＰＩ１６モル％、ＮＥＨＩ１６モル％、およびＴＣＤＣ６８モル％からなる単量体混合物１００質量部、１－ヘキセン１．０質量部、（１，３－ジメシチルイミダゾリン－２－イリデン）（トリシクロヘキシルホスフィン）ベンジリデンルテニウムジクロリド０．０６質量部、並びにジエチレングリコールメチルエチルエーテル３００質量部を、窒素置換したガラス製耐圧反応器に仕込み、攪拌しつつ８０℃にて４時間反応させて重合反応液を得た。
　そして、得られた重合反応液をオートクレーブに入れて、１５０℃、水素圧４ＭＰａで、５時間攪拌して水素化反応を行い、プロトン性極性基を有する環状オレフィン重合体（Ａ－４）を含む重合体溶液を得た。得られた環状オレフィン重合体（Ａ－４）の重合転化率は９９．３質量％、重量平均分子量（ポリスチレン換算）は２０６００、数平均分子量は１１５００、分子量分布は１．７９、水素添加率は、９９．８％であった。また、得られた環状オレフィン重合体（Ａ－４）の重合体溶液の固形分濃度は２５．３質量％であった。
＜感放射線性樹脂組成物（感放射線性樹脂液）の調製＞
　環状オレフィン重合体（Ａ－３）の重合体溶液を２０部（固形分相当）、環状オレフィン重合体（Ａ－４）の重合体溶液を３０部（固形分相当）、クレゾールノボラック樹脂（Ｂ－４）（旭有機材社製、製品名「ＥＰ４０５０Ｇ」、重量平均分子量：７６００、軟化点：１５６℃、ｍ－クレゾール／ｐ－クレゾール＝６０／４０（モル比）とホルムアルデヒドの縮合重合体、ｍ／ｐ比：１．５）を５０部、酸発生剤（Ｃ－１）を３０部、架橋剤（Ｄ－１）を１５部、架橋剤（Ｄ－２）（日産化学工業社製、製品名「ＴＥＰＩＣ－Ｓ」、トリス（２，３－エポキシプロピル）イソシアヌレート（イソシアヌル酸トリグリシジル））を１５部、架橋剤（Ｄ－７）（本州化学工業社製、製品名「ＴＭＯＭ－ＢＰ」、３，３’，５，５’－テトラメトキシメチル－４，４’－ジヒドロキシビフェニル）を１０部、並びに、溶剤としてジエチレングリコールメチルエチルエーテルを混合し、溶解させた。なお、ジエチレングリコールメチルエチルエーテルの使用量は、固形分濃度が４０質量％となる量とした。次いで、得られた溶液を孔径０．４５μｍのポリテトラフルオロエチレン製フィルターでろ過して樹脂組成物を調製した。得られた樹脂組成物を用いて各種評価を行った。結果を表１に示す。 (Example 7)
<Preparation of cyclic olefin polymer (A-3)>
N- (2-ethylhexyl) -bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide (NEHI) was 40 mol% and TCDC was 60 mol% without using NBPI. A cyclic olefin polymer (A-3) having a protonic polar group was prepared in the same manner as the cyclic olefin polymer (A-1) except for the above. The obtained cyclic olefin polymer (A-3) has a polymerization conversion rate of 99.8% by mass, a weight average molecular weight (in terms of polystyrene) of 8500, a number average molecular weight of 5800, a molecular weight distribution of 1.47, and a hydrogenation rate. , 99.9%. Moreover, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-3) was 34.3% by 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 part by mass of 1-hexene, (1,3-dimesityl imidazoline-2-iriden) (tricyclohexylphosphine). 0.06 parts by mass of benzylidene ruthenium dichloride and 300 parts by mass of diethylene glycol methyl ethyl ether were charged into a nitrogen-substituted glass pressure-resistant reactor and reacted at 80 ° C. for 4 hours with stirring to obtain a polymerization reaction solution.
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 carry out a hydrogenation reaction, and contains a cyclic olefin polymer (A-4) having a protonic polar group. A polymer solution was obtained. The obtained cyclic olefin polymer (A-4) has a polymerization conversion rate of 99.3% by mass, a weight average molecular weight (in terms of polystyrene) of 20600, a number average molecular weight of 11500, a molecular weight distribution of 1.79, and a hydrogenation rate. , 99.8%. Moreover, the solid content concentration of the polymer solution of the obtained cyclic olefin polymer (A-4) was 25.3% by mass.
<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>
20 parts (equivalent to solid content) of the polymer solution of the cyclic olefin polymer (A-3), 30 parts (equivalent to solid content) of the polymer solution of the cyclic olefin polymer (A-4), cresol novolac resin (B-). 4) (Manufactured by Asahi Organic Materials Co., Ltd., product name "EP4050G", weight average molecular weight: 7600, softening point: 156 ° C., m-cresol / p-cresol = 60/40 (molar ratio) and formaldehyde condensation polymer, m / P ratio: 1.5) 50 parts, acid generator (C-1) 30 parts, cross-linking agent (D-1) 15 parts, cross-linking agent (D-2) (manufactured by Nissan Chemical Industries, Ltd.) Name "TEPIC-S", Tris (2,3-epoxypropyl) isocyanurate (triglycidyl isocyanurate)) 15 parts, cross-linking agent (D-7) (manufactured by Honshu Chemical Industry Co., Ltd., product name "TMOM-BP" , 3,3', 5,5'-tetramethoxymethyl-4,4'-dihydroxybiphenyl) and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. The amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 1.
（実施例８）
＜環状オレフィン重合体（Ａ－２）、（Ａ－４）の調製＞
　実施例４と同様にして環状オレフィン重合体（Ａ－２）を、実施例７と同様にして環状オレフィン重合体（Ａ－４）をそれぞれ調製した。
＜感放射線性樹脂組成物（感放射線性樹脂液）の調製＞
　環状オレフィン重合体（Ａ－２）の重合体溶液を３０部（固形分相当）、環状オレフィン重合体（Ａ－４）の重合体溶液を３０部（固形分相当）、クレゾールノボラック樹脂（Ｂ－１）を４０部、酸発生剤（Ｃ－１）を３０部、架橋剤（Ｄ－１）を１５部、架橋剤（Ｄ－３）（ダイセル社製、製品名「ＥＨＰＥ３１５０」、２，２－ビス(ヒドロキシメチル)－１－ブタノールの１，２－エポキシ－４－(２－オキシラニル)シクロヘキサン付加物）を１５部、架橋剤（Ｄ－６）を１０部、および、溶剤としてジエチレングリコールメチルエチルエーテルを混合し、溶解させた。なお、ジエチレングリコールメチルエチルエーテルの使用量は、固形分濃度が４０質量％となる量とした。次いで、得られた溶液を孔径０．４５μｍのポリテトラフルオロエチレン製フィルターでろ過して樹脂組成物を調製した。得られた樹脂組成物を用いて各種評価を行った。結果を表１に示す。 (Example 8)
<Preparation of cyclic olefin polymers (A-2) and (A-4)>
A cyclic olefin polymer (A-2) was prepared in the same manner as in Example 4, and a cyclic olefin polymer (A-4) was prepared in the same manner as in Example 7.
<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>
30 parts (equivalent to solid content) of the polymer solution of the cyclic olefin polymer (A-2), 30 parts (equivalent to solid content) of the polymer solution of the cyclic olefin polymer (A-4), cresol novolac resin (B-) 1) 40 parts, acid generator (C-1) 30 parts, cross-linking agent (D-1) 15 parts, cross-linking agent (D-3) (manufactured by Daicel, product name "EHPE3150", 2, 2 15 parts of 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of -bis (hydroxymethyl) -1-butanol), 10 parts of cross-linking agent (D-6), and diethylene glycol methyl ethyl as a solvent. The ether was mixed and dissolved. The amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 1.
（実施例９）
　樹脂組成物の調製に際し、環状オレフィン重合体（Ａ－１）の量を７５部から１５部（固形分相当）に、クレゾールノボラック樹脂（Ｂ－１）の量を２５部から８５部に変更した以外は、実施例１と同様にして、環状オレフィン重合体（Ａ－１）および樹脂組成物を調製し、各種評価を行った。結果を表２に示す。 (Example 9)
In preparing the resin composition, the amount of the cyclic olefin polymer (A-1) was changed from 75 parts to 15 parts (corresponding to the solid content), and the amount of the cresol novolak resin (B-1) was changed from 25 parts to 85 parts. A cyclic olefin polymer (A-1) and a resin composition were prepared in the same manner as in Example 1 except for the above, and various evaluations were performed. The results are shown in Table 2.
（実施例１０）
　樹脂組成物の調製に際し、環状オレフィン重合体（Ａ－２）の量を５０部から８５部（固形分相当）に、クレゾールノボラック樹脂（Ｂ－２）の量を５０部から１５部に変更し、そして、架橋剤（Ｄ－１）の量を３７部から３５部に変更した以外は、実施例４と同様にして、環状オレフィン重合体（Ａ－２）および樹脂組成物を調製し、各種評価を行った。結果を表２に示す。 (Example 10)
When preparing the resin composition, the amount of the cyclic olefin polymer (A-2) was changed from 50 parts to 85 parts (corresponding to the solid content), and the amount of the cresol novolak resin (B-2) was changed from 50 parts to 15 parts. Then, the cyclic olefin polymer (A-2) and the resin composition were prepared in the same manner as in Example 4 except that the amount of the cross-linking agent (D-1) was changed from 37 parts to 35 parts. Evaluation was performed. The results are shown in Table 2.
（比較例１）
＜環状オレフィン重合体（Ａ－１）の調製＞
　実施例１と同様にして環状オレフィン重合体（Ａ－１）を調製した。
＜感放射線性樹脂組成物（感放射線性樹脂液）の調製＞
　環状オレフィン重合体（Ａ－１）の重合体溶液を１００部（固形分相当）、酸発生剤（Ｃ－１）を２８部、架橋剤（Ｄ－１）を３５部、架橋剤（Ｄ－４）を１５部、および、溶剤としてジエチレングリコールメチルエチルエーテルを混合し、溶解させた。なお、ジエチレングリコールメチルエチルエーテルの使用量は、固形分濃度が４０質量％となる量とした。次いで、得られた溶液を孔径０．４５μｍのポリテトラフルオロエチレン製フィルターでろ過して樹脂組成物を調製した。得られた樹脂組成物を用いて各種評価を行った。結果を表２に示す。 (Comparative Example 1)
<Preparation of cyclic olefin polymer (A-1)>
A cyclic olefin polymer (A-1) was prepared in the same manner as in Example 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 the acid generator (C-1), 35 parts of the cross-linking agent (D-1), and the cross-linking agent (D-). 15 parts of 4) and diethylene glycol methyl ethyl ether as a solvent were mixed and dissolved. The amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 2.
（比較例２）
　クレゾールノボラック樹脂（Ｂ－４）を１００部、酸発生剤（Ｃ－１）を２５部、架橋剤（Ｄ－１）を３０部、架橋剤（Ｄ－７）を１０部、および、溶剤としてジエチレングリコールメチルエチルエーテルを混合し、溶解させた。なお、ジエチレングリコールメチルエチルエーテルの使用量は、固形分濃度が４０質量％となる量とした。次いで、得られた溶液を孔径０．４５μｍのポリテトラフルオロエチレン製フィルターでろ過して樹脂組成物を調製した。得られた樹脂組成物を用いて各種評価を行った。結果を表２に示す。 (Comparative Example 2)
100 parts of cresol novolak resin (B-4), 25 parts of acid generator (C-1), 30 parts of cross-linking agent (D-1), 10 parts of cross-linking agent (D-7), and as a solvent Diethylene glycol methyl ethyl ether was mixed and dissolved. The amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 2.
（比較例３）
＜環状オレフィン重合体（Ａ－３）の調製＞
　実施例７と同様にして環状オレフィン重合体（Ａ－３）を調製した。
＜感放射線性樹脂組成物（感放射線性樹脂液）の調製＞
　環状オレフィン重合体（Ａ－３）の重合体溶液を５０部（固形分相当）、クレゾールノボラック樹脂（Ｂ－５）（旭有機材社製、製品名「ＥＰ６０４０Ａ」、重量平均分子量：２６００、軟化点：１３０℃、ｍ－クレゾール／ｐ－クレゾール＝４０／６０（モル比）とホルムアルデヒドの縮合重合体、ｍ／ｐ比：約０．６７）を５０部、酸発生剤（Ｃ－１）を２８部、架橋剤（Ｄ－１）を３５部、架橋剤（Ｄ－３）を１０部、架橋剤（Ｄ－６）を１０部、および、溶剤としてジエチレングリコールメチルエチルエーテルを混合し、溶解させた。なお、ジエチレングリコールメチルエチルエーテルの使用量は、固形分濃度が４０質量％となる量とした。次いで、得られた溶液を孔径０．４５μｍのポリテトラフルオロエチレン製フィルターでろ過して樹脂組成物を調製した。得られた樹脂組成物を用いて各種評価を行った。結果を表２に示す。 (Comparative Example 3)
<Preparation of cyclic olefin polymer (A-3)>
A cyclic olefin polymer (A-3) was prepared in the same manner as in Example 7.
<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>
50 parts (equivalent to solid content) of polymer solution of cyclic olefin polymer (A-3), cresol novolak resin (B-5) (manufactured by Asahi Organic Materials Co., Ltd., product name "EP6040A", weight average molecular weight: 2600, softened 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, 35 parts of the cross-linking agent (D-1), 10 parts of the cross-linking agent (D-3), 10 parts of the cross-linking agent (D-6), and diethylene glycol methyl ethyl ether as a solvent are mixed and dissolved. It was. The amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 2.
（比較例４）
＜環状オレフィン重合体（Ａ－１）の調製＞
　実施例１と同様にして環状オレフィン重合体（Ａ－１）を調製した。
＜感放射線性樹脂組成物（感放射線性樹脂液）の調製＞
　環状オレフィン重合体（Ａ－１）の重合体溶液を５０部（固形分相当）、クレゾールノボラック樹脂（Ｂ－１）を５０部、酸発生剤（Ｃ－１）を３０部、および、溶剤としてジエチレングリコールメチルエチルエーテルを混合し、溶解させた。なお、ジエチレングリコールメチルエチルエーテルの使用量は、固形分濃度が４０質量％となる量とした。次いで、得られた溶液を孔径０．４５μｍのポリテトラフルオロエチレン製フィルターでろ過して樹脂組成物を調製した。得られた樹脂組成物を用いて各種評価を行った。結果を表２に示す。 (Comparative Example 4)
<Preparation of cyclic olefin polymer (A-1)>
A cyclic olefin polymer (A-1) was prepared in the same manner as in Example 1.
<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>
50 parts (equivalent to solid content) of the polymer solution of the cyclic olefin polymer (A-1), 50 parts of the cresol novolac resin (B-1), 30 parts of the acid generator (C-1), and as a solvent. Diethylene glycol methyl ethyl ether was mixed and dissolved. The amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 2.
（比較例５）
＜環状オレフィン重合体（Ａ－１）の調製＞
　実施例１と同様にして環状オレフィン重合体（Ａ－１）を調製した。
＜感放射線性樹脂組成物（感放射線性樹脂液）の調製＞
　環状オレフィン重合体（Ａ－１）の重合体溶液を６０部（固形分相当）、フェノールノボラック樹脂（旭有機材社製、製品名「ＰＡＰＳ－ＰＮ４」、Ｍｗ：１３００、軟化点：１１０℃）を４０部、酸発生剤（Ｃ－１）を３０部、架橋剤（Ｄ－２）を３０部、架橋剤（Ｄ－７）を１０部、および、溶剤としてジエチレングリコールメチルエチルエーテルを混合し、溶解させた。なお、ジエチレングリコールメチルエチルエーテルの使用量は、固形分濃度が４０質量％となる量とした。次いで、得られた溶液を孔径０．４５μｍのポリテトラフルオロエチレン製フィルターでろ過して樹脂組成物を調製した。得られた樹脂組成物を用いて各種評価を行った。結果を表２に示す。 (Comparative Example 5)
<Preparation of cyclic olefin polymer (A-1)>
A cyclic olefin polymer (A-1) was prepared in the same manner as in Example 1.
<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>
60 parts (equivalent to solid content) of a polymer solution of the cyclic olefin polymer (A-1), phenol novolac resin (manufactured by Asahi Organic Materials Co., Ltd., product name "PAPS-PN4", Mw: 1300, softening point: 110 ° C.) 40 parts, an acid generator (C-1) 30 parts, a cross-linking agent (D-2) 30 parts, a cross-linking agent (D-7) 10 parts, and diethylene glycol methyl ethyl ether as a solvent. It was dissolved. The amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 2.
（比較例６）
＜感放射線性樹脂組成物（感放射線性樹脂液）の調製＞
　クレゾールノボラック樹脂（Ｂ―１）を５０部、ポリビニルフェノール樹脂（丸善石油化学社製、製品名「Ｓ－２Ｐ」）を５０部、酸発生剤（Ｃ－１）を２８部、架橋剤（Ｄ－１）を３０部、架橋剤（Ｄ－５）を１０部、および、溶剤としてジエチレングリコールメチルエチルエーテルを混合し、溶解させた。なお、ジエチレングリコールメチルエチルエーテルの使用量は、固形分濃度が４０質量％となる量とした。次いで、得られた溶液を孔径０．４５μｍのポリテトラフルオロエチレン製フィルターでろ過して樹脂組成物を調製した。得られた樹脂組成物を用いて各種評価を行った。結果を表２に示す。 (Comparative Example 6)
<Preparation of radiation-sensitive resin composition (radiation-sensitive resin solution)>
50 parts of cresol novolak resin (B-1), 50 parts of polyvinylphenol resin (manufactured by Maruzen Petrochemical Co., Ltd., product name "S-2P"), 28 parts of acid generator (C-1), cross-linking agent (D) -1) was mixed with 30 parts, a cross-linking agent (D-5) with 10 parts, and diethylene glycol methyl ethyl ether as a solvent to dissolve them. The amount of diethylene glycol methyl ethyl ether used was such that the solid content concentration was 40% by mass. Then, the obtained solution was filtered through a filter made of polytetrafluoroethylene having a pore size of 0.45 μm to prepare a resin composition. Various evaluations were carried out using the obtained resin composition. The results are shown in Table 2.
　なお、以下に示す表１～２中、
「ｍＣ／ｐＣ／ｍＸ」は、ｍ－クレゾール／ｐ－クレゾール／ｍ－キシレノール（モル比）を示し、
「ｍＣ／ｐＣ」は、ｍ－クレゾール／ｐ－クレゾール（モル比）を示し、
「エポキシ」は、多官能エポキシ化合物を示し、
「メトキシメチル」は、多官能メトキシメチル（アルコキシメチル）化合物を示す。 In addition, in Tables 1 and 2 shown below,
"MC / pC / mX" indicates m-cresol / p-cresol / m-xylenol (molar ratio).
"MC / pC" indicates m-cresol / p-cresol (molar ratio).
"Epoxy" refers to a polyfunctional epoxy compound,
"Methoxymethyl" refers to a polyfunctional methoxymethyl (alkoxymethyl) compound.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表１～２より、プロトン性極性基を有する環状オレフィン重合体（Ａ）、軟化点が１４０℃以上のクレゾールノボラック樹脂（Ｂ）、酸発生剤（Ｃ）、および架橋剤（Ｄ）を含む実施例１～１０の樹脂組成物を用いれば、ラインパターンのトップロスが抑制されていると共に、熱フロー耐性に優れる樹脂膜を形成可能であることが分かる。また、実施例１～１０では、比誘電率が低く、且つ耐薬品性に優れる樹脂膜を形成可能であることも分かる。
　一方、表２の比較例１～６より、以下のことが分かる。
　クレゾールノボラック樹脂（Ｂ）を含まない樹脂組成物を用いた比較例１では、樹脂膜におけるラインパターンのトップロスを抑制できないことが分かる。
　環状オレフィン重合体（Ａ）を含まない樹脂組成物を用いた比較例２では、樹脂膜の比誘電率が上昇してしまい、また、熱フロー耐性が低下することが分かる。
　クレゾールノボラック樹脂を含むが、その軟化点が１４０℃未満である樹脂組成物を用いた比較例３では、樹脂膜の熱フロー耐性が低下することが分かる。
　架橋剤（Ｄ）を含まない樹脂組成物を用いた比較例４では、樹脂膜の耐薬品性および熱フロー耐性が低下することが分かる。
　フェノールノボラック樹脂を含む一方で、クレゾールノボラック樹脂（Ｂ）を含まない樹脂組成物を用いた比較例５では、樹脂膜におけるラインパターンのトップロスを抑制できず、また樹脂膜の熱フロー耐性が低下することが分かる。
　ポリビニルフェノール樹脂を含む一方で、環状オレフィン重合体（Ａ）を含まない樹脂組成物を用いた比較例６では、樹脂膜の熱フロー耐性が低下することが分かる。 From Tables 1 and 2, the cyclic olefin polymer (A) having a protonic polar group, the cresol novolac resin (B) having a softening point of 140 ° C. or higher, the acid generator (C), and the cross-linking agent (D) were included. It can be seen that when the resin compositions of Examples 1 to 10 are used, the top loss of the line pattern is suppressed and a resin film having excellent heat flow resistance can be formed. It can also be seen that in Examples 1 to 10, it is possible to form a resin film having a low relative permittivity and excellent chemical resistance.
On the other hand, the following can be seen from Comparative Examples 1 to 6 in Table 2.
In Comparative Example 1 using the resin composition containing no cresol novolak resin (B), it can be seen that the top loss of the line pattern in the resin film cannot be suppressed.
In Comparative Example 2 using the resin composition containing no cyclic olefin polymer (A), it can be seen that the relative permittivity of the resin film increases and the heat flow resistance decreases.
It can be seen that in Comparative Example 3 using a resin composition containing a cresol novolak resin but having a softening point of less than 140 ° C., the heat flow resistance of the resin film is lowered.
In Comparative Example 4 using the resin composition containing no cross-linking agent (D), it can be seen that the chemical resistance and heat flow resistance of the resin film are lowered.
In Comparative Example 5 using the resin composition containing the phenol novolac resin but not the cresol novolak resin (B), the top loss of the line pattern in the resin film could not be suppressed, and the heat flow resistance of the resin film was lowered. You can see that it does.
It can be seen that in Comparative Example 6 using the resin composition containing the polyvinylphenol resin but not the cyclic olefin polymer (A), the heat flow resistance of the resin film is lowered.
　本発明によれば、ラインパターンのトップロスが抑制されていると共に、熱フロー耐性に優れる樹脂膜を形成しうる感放射線性樹脂組成物を提供することができる。 According to the present invention, it is possible to provide a radiation-sensitive resin composition capable of forming a resin film having excellent heat flow resistance while suppressing the top loss of the line pattern.

Claims (6)

  1. 　プロトン性極性基を有する環状オレフィン重合体（Ａ）、軟化点が１４０℃以上のクレゾールノボラック樹脂（Ｂ）、酸発生剤（Ｃ）、および架橋剤（Ｄ）を含む、感放射線性樹脂組成物。 A radiation-sensitive resin composition containing a cyclic olefin polymer (A) having a protonic polar group, a cresol novolak resin (B) having a softening point of 140 ° C. or higher, an acid generator (C), and a cross-linking agent (D). ..
  2. 　前記クレゾールノボラック樹脂（Ｂ）が、クレゾール骨格とキシレノール骨格とを含む、請求項１に記載の感放射線性樹脂組成物。 The radiation-sensitive resin composition according to claim 1, wherein the cresol novolak resin (B) contains a cresol skeleton and a xylenol skeleton.
  3. 　前記酸発生剤（Ｃ）がキノンジアジド化合物である、請求項１または２に記載の感放射線性樹脂組成物。 The radiation-sensitive resin composition according to claim 1 or 2, wherein the acid generator (C) is a quinonediazide compound.
  4. 　前記架橋剤（Ｄ）が、多官能エポキシ化合物、多官能アルコキシメチル化合物、および多官能メチロール化合物からなる群から選択される少なくとも１つである、請求項１～３の何れかに記載の感放射線性樹脂組成物。 The radiation-sensitive radiation according to any one of claims 1 to 3, wherein the cross-linking 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. Sex resin composition.
  5. 　前記環状オレフィン重合体（Ａ）と前記クレゾールノボラック樹脂（Ｂ）の合計中に占める前記環状オレフィン重合体（Ａ）の割合が、１０質量％以上９０質量％以下である、請求項１～４の何れかに記載の感放射線性樹脂組成物。 Claims 1 to 4, wherein the ratio of the cyclic olefin polymer (A) to the total of the cyclic olefin polymer (A) and the cresol novolak resin (B) is 10% by mass or more and 90% by mass or less. The radiation-sensitive resin composition according to any one.
  6. 　前記クレゾールノボラック樹脂（Ｂ）に含まれるクレゾール類に由来する骨格中において、パラ体骨格の含有量に対するメタ体骨格の含有量のモル比が５．０以下である、請求項１～５の何れかに記載の感放射線性樹脂組成物。 Any of claims 1 to 5, wherein the molar ratio of the content of the meta-body skeleton to the content of the para-body skeleton is 5.0 or less in the skeleton derived from the cresols contained in the cresol novolak resin (B). The radiation-sensitive resin composition described in the skeleton.
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