Classifications

• • 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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