WO2016076205A1 - Radiation sensitive resin composition, cured film for display elements, method for forming cured film for display elements, and display element - Google Patents

Radiation sensitive resin composition, cured film for display elements, method for forming cured film for display elements, and display element Download PDF

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Publication number
WO2016076205A1
WO2016076205A1 PCT/JP2015/081227 JP2015081227W WO2016076205A1 WO 2016076205 A1 WO2016076205 A1 WO 2016076205A1 JP 2015081227 W JP2015081227 W JP 2015081227W WO 2016076205 A1 WO2016076205 A1 WO 2016076205A1
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group
carbon atoms
groups
acid
radiation
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PCT/JP2015/081227
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French (fr)
Japanese (ja)
Inventor
洋助 今野
徹 石部
濱田　謙一
高英 浅岡
晃幸 松本
大佑 石川
仁成 松本
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Jsr株式会社
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Publication of WO2016076205A1 publication Critical patent/WO2016076205A1/en

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/10—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds
    • C09B69/103—Polymeric dyes; Reaction products of dyes with monomers or with macromolecular compounds containing a diaryl- or triarylmethane dye
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

Definitions

  • the present invention relates to a radiation-sensitive resin composition, a cured film for display element, a method for forming a cured film for display element, and a display element.
  • the display element is provided with a cured film such as an interlayer insulating film, a spacer, or a protective film that insulates wirings arranged in layers.
  • a cured film such as an interlayer insulating film is required to have insulating properties (low dielectric properties), corrosion resistance (can suppress corrosion of wiring provided on a coated substrate), and the like.
  • a radiation sensitive resin composition is widely used as a material for forming an interlayer insulating film or the like. The radiation-sensitive resin composition is required to have good sensitivity to radiation.
  • a protective group is dissociated by an acid, a composition containing a resin that becomes soluble in an alkaline aqueous solution, a crosslinking agent and an acid generator, an acetal structure or a ketal structure and an epoxy group And a composition containing an acid generator have been proposed (see Japanese Patent Application Laid-Open Nos. 2004-4669 and 2004-264623).
  • the present invention has been made on the basis of the circumstances as described above, and its purpose is a curing having a good radiation sensitivity, a small amount of change in the thickness of a non-exposed portion, and excellent insulation and corrosion resistance.
  • a radiation-sensitive resin composition capable of obtaining a film, a cured film for a display element formed from the composition, a method for forming the cured film for a display element, and a display element having the cured film for a display element That is.
  • the invention made to solve the above problems is a polymer (hereinafter also referred to as “[A] polymer”), a radiation-sensitive acid generator (hereinafter also referred to as “[B] acid generator”). And at least one compound having an acid dissociable group and represented by any one of formulas (1-1) to (1-6) below (hereinafter also referred to as “[C] compound”).
  • one or more Xs are each independently an organic group having an acid dissociable group.
  • a plurality of R 1 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent.
  • n 1 is an integer of 1 to 3.
  • n 2 is an integer of 0-2.
  • a plurality of R 2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent.
  • A represents a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, a phenylene group, an oxygen atom, a sulfur atom, or at least a part of hydrogen atoms of a methylene group, an alkylene group having 2 to 12 carbon atoms, or a phenylene group.
  • n 3 is an integer of 1 to 3.
  • n 4 is an integer of 1 to 3.
  • a plurality of R 3 and a plurality of R 4 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon.
  • a plurality of R 5 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent.
  • m is an integer of 0 to 10.
  • a plurality of R 6 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent.
  • p is an integer of 0 to 10.
  • R 7 represents at least one of an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or a hydrogen atom included in these groups. A part of the group is substituted with a substituent.
  • n 5 is an integer of 1 to 3.
  • n 6 is an integer of 1 to 5.
  • n 7 is an integer of 0 to 5.
  • X represents an organic group having an acid dissociable group.
  • the plurality of R 8 are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or a part or all of hydrogen atoms possessed by these groups Is a group substituted with a substituent. * Indicates a binding site.
  • Another invention made to solve the above problems is a cured film for a display element formed from the radiation-sensitive resin composition. Furthermore, a step of forming a coating film on the substrate, a step of irradiating at least a part of the coating film, a step of developing the coating film irradiated with the radiation, and a step of heating the developed coating film And a display element comprising the cured film for display element, and a method for forming the cured film for display element using the radiation-sensitive resin composition for forming the coating film.
  • the radiation-sensitive resin composition and the method for forming a cured film for a display element according to the present invention have good radiation sensitivity, a small amount of change in the thickness of the non-exposed area, and the resulting cured film has excellent insulation and corrosion. Preventive properties can be exhibited. Moreover, the cured film for display elements of this invention can exhibit the outstanding insulation and corrosion prevention property, and can be used suitably for a display element.
  • the radiation-sensitive resin composition contains a [A] polymer, a [B] acid generator, and a [C] compound.
  • the radiation-sensitive composition preferably further contains [D] antioxidant as a suitable component, and may contain other optional components.
  • the radiation sensitive resin composition is used for forming a cured film for a display element. Moreover, the said radiation sensitive resin composition is normally used for positive type pattern formation using an alkali developing solution.
  • an acid is generated from the [B] acid generator in the exposed area by exposure during pattern formation, and the acid dissociable group of the [C] compound is dissociated by this acid. Thereby, the difference in the solubility with respect to the developing solution between an exposed part and a non-exposed part increases, and favorable radiation sensitivity is exhibited.
  • the low molecular weight [C] compound has an acid-dissociable group as compared with the polymer, and compared with the radiation-sensitive composition using the polymer having an acid-dissociable group, The change in solubility in the developer becomes significant.
  • the [A] polymer hardens
  • each component will be described.
  • a polymer is a component which becomes a main material of the cured film obtained.
  • the well-known polymer normally contained in a radiation sensitive resin composition can be used 1 type or in mixture of 2 or more types.
  • a polymer having suitable solubility in an alkali developer and curability by heating is preferably used.
  • polymer (A-1) acrylic resin having carboxy group, (A-2) polyimide or polyimide precursor, (A-3) polysiloxane, and (A-4) aromatic It is preferable to include at least one selected from the group consisting of polyethers.
  • the radiation-sensitive resin composition suitably functions as a positive-type radiation-sensitive resin composition using an alkali developer.
  • the acrylic resin having a carboxy group has alkali solubility due to the carboxy group.
  • the acrylic resin having a carboxy group preferably has a structural unit having a carboxy group and a structural unit having a polymerizable group. In this case, it is possible to satisfactorily exhibit the solubility (alkali developability) and curability in an alkali developer.
  • the structural unit having a polymerizable group is preferably at least one structural unit selected from the group consisting of a structural unit having an epoxy group and a structural unit having a (meth) acryloyloxy group.
  • a structural unit having an epoxy group preferably at least one structural unit selected from the group consisting of a structural unit having an epoxy group and a structural unit having a (meth) acryloyloxy group.
  • the acrylic resin having a carboxy group contains the specific structural unit, a stronger cured film can be formed.
  • the structural unit having a (meth) acryloyloxy group is, for example, a method in which (meth) acrylic acid is reacted with an epoxy group in a polymer, or a (meth) acrylic acid ester having an epoxy group is reacted with a carboxy group in the polymer. It may be formed by a method, a method of reacting a hydroxy group in a polymer with a (meth) acrylic acid ester having an isocyanate group, a method of reacting an acid anhydride site in a polymer with a (meth) acrylic acid hydroxy ester, or the like. it can. Among these, the method of reacting the (meth) acrylic acid ester which has an epoxy group with the carboxy group in a polymer is preferable.
  • the acrylic resin containing a structural unit having a carboxy group and a structural unit having an epoxy group as a polymerizable group is a group comprising (a1) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride in the presence of a polymerization initiator in a solvent. At least one selected from the above (hereinafter also referred to as “(a1) compound”) and (a2) an epoxy group-containing unsaturated compound (hereinafter also referred to as “(a2) compound”). Can be synthesized. (A3) A hydroxy group-containing unsaturated compound that gives a hydroxy group-containing structural unit (hereinafter also referred to as “(a3) compound”) may be further added to form a copolymer.
  • an acrylic resin having a carboxy group a structural unit other than the structural unit derived from the compound (a4) other than the above-described compounds (a1) to (a3) (the structural unit derived from the above-described compounds (a1) to (a3)).
  • An unsaturated compound to be added) can be further added to form a copolymer.
  • Examples of the compound (a1) include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated dicarboxylic acid anhydrides.
  • Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.
  • Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like.
  • anhydride of unsaturated dicarboxylic acid examples include anhydrides of the compounds exemplified as the dicarboxylic acid.
  • acrylic acid, methacrylic acid and maleic anhydride are more preferred from the viewpoints of copolymerization reactivity, solubility in an alkaline aqueous solution, and availability.
  • These (a1) compounds may be used alone or in admixture of two or more.
  • the lower limit of the use ratio of the compound is preferably (A-1) 5% by mass, more preferably 10% by mass, based on the total of all monomers forming the carboxy group-containing acrylic resin. On the other hand, as this upper limit, 30 mass% is preferable and 25 mass% is more preferable. (A1) By making the use ratio of a compound into such a range, while being able to optimize the solubility with respect to the alkaline aqueous solution of the acrylic resin which has a carboxy group, the film
  • the compound (a2) is an epoxy group-containing unsaturated compound having radical polymerizability.
  • the epoxy group include an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3-epoxy structure), a 3,4-epoxytricyclo [5.2.1.0 2.6 ] decyl group, and the like. Can be mentioned.
  • unsaturated compounds having an oxiranyl group examples include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, and 6,7-acrylic acid.
  • glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylate 4-epoxycyclohexyl, 3,4-epoxycyclohexyl acrylate, and 3,4-epoxytricyclo [5.2.1.0 2.6 ] decyl acrylate are copolymerization reactivity and solvent resistance such as insulating film From the viewpoint of improving the above.
  • Examples of unsaturated compounds having an oxetanyl group include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, and 3- (acryloyl).
  • (a2) compounds glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable.
  • These (a2) compounds may be used alone or in combination of two or more.
  • the lower limit of the use ratio of the compound is preferably (A-1) 5% by mass, more preferably 10% by mass, based on the total of all monomers forming the acrylic resin having a carboxy group. On the other hand, as this upper limit, 60 mass% is preferable and 50 mass% is more preferable. (A2) By making the usage-amount of a compound into such a range, the cured film which has the outstanding sclerosis
  • ((A3) Compound) examples include (meth) acrylic acid ester having a hydroxy group, (meth) acrylic acid ester having a phenolic hydroxyl group, and hydroxystyrene.
  • acrylic acid ester having a hydroxy group examples include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate.
  • methacrylic acid ester having a hydroxy group examples include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, and 6-hydroxyhexyl methacrylate.
  • Examples of the acrylate ester having a phenolic hydroxyl group include 2-hydroxyphenyl acrylate and 4-hydroxyphenyl acrylate.
  • Examples of the methacrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl methacrylate and 4-hydroxyphenyl methacrylate.
  • hydroxystyrene examples include o-hydroxystyrene, p-hydroxystyrene, ⁇ -methyl-p-hydroxystyrene and the like. These (a3) compounds may be used alone or in admixture of two or more.
  • the lower limit of the use ratio of the compound is preferably (A-1) 1% by mass, more preferably 5% by mass, based on the total of all monomers forming the carboxy group-containing acrylic resin. On the other hand, as this upper limit, 30 mass% is preferable and 25 mass% is more preferable. (A3) By making the use ratio of a compound into such a range, the solubility with respect to alkaline aqueous solution etc. can be optimized.
  • the compound (a4) is not particularly limited as long as it is an unsaturated compound other than the compounds (a1) to (a3).
  • Examples of the compound (a4) include methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid chain alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, Examples include maleimide compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, and other unsaturated compounds.
  • chain alkyl esters of methacrylic acid include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, and n-methacrylate.
  • Examples include lauryl, tridecyl methacrylate, and n-stearyl methacrylate.
  • cyclic alkyl esters of methacrylic acid examples include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 2,6 ] decane-8-yl methacrylate, and tricyclomethacrylate [5.2.1]. .0 2,6 ] decan-8-yloxyethyl, isobornyl methacrylate, and the like.
  • acrylic acid chain alkyl esters examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-acrylate.
  • acrylic acid chain alkyl esters examples include lauryl, tridecyl acrylate, and n-stearyl acrylate.
  • cyclic alkyl ester of acrylic acid examples include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl acrylate, and tricyclo [5.2. 1.0 2,6 ] decan-8-yloxyethyl, isobornyl acrylate, and the like.
  • methacrylic acid aryl ester examples include phenyl methacrylate and benzyl methacrylate.
  • acrylic acid aryl ester examples include phenyl acrylate and benzyl acrylate.
  • Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.
  • maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.
  • unsaturated aromatic compound examples include styrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene and the like.
  • conjugated diene examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.
  • Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, and 3- (meth) acryloyloxytetrahydrofuran-2-one.
  • Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.
  • methacrylic acid chain alkyl ester methacrylic acid cyclic alkyl ester, methacrylic acid aryl ester, maleimide compound, tetrahydrofuran skeleton, unsaturated aromatic compound, and acrylic acid cyclic alkyl ester are preferable.
  • styrene methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate, p -Methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide and tetrahydrofurfuryl methacrylate are preferred from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.
  • These (a4) compounds may be used alone or in admixture of two or more.
  • the use ratio of the compound is preferably (A-1) 10% by mass or more and 80% by mass or less based on the total of all monomers forming the acrylic resin having a carboxy group.
  • the lower limit of the polystyrene-equivalent weight average molecular weight (Mw) by GPC of the acrylic resin having a carboxy group is preferably 1,000, and more preferably 3,000.
  • the upper limit is preferably 15,000 and more preferably 10,000.
  • the polyimide or polyimide precursor is not particularly limited, but polyamic acid (polyimidic acid) and polyamic acid ester which are polyimide precursors are preferable.
  • the polyimide precursor include a polymer having a structural unit represented by the following formula (M-1) as a main structure.
  • the polymer having the structural unit represented by the formula (M-1) as the main structure can be a polymer having an imide ring, an oxazole ring, other cyclic structures, etc. by heating or an appropriate catalyst. Due to the annular structure, the heat resistance and solvent resistance are dramatically improved.
  • the main structure means that the structural unit occupies 50 mol% or more of all the structural units.
  • the content of the structural unit represented by the formula (M-1) is preferably 70 mol% or more, and more preferably 90 mol% or more.
  • R 1c represents a (2 + p + m 1 ) -valent organic group having 2 or more carbon atoms.
  • examples of the organic group include a substituted or unsubstituted hydrocarbon group.
  • R 1c is a structure derived from a polyvalent carboxylic acid.
  • Polyvalent carboxylic acids include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, bis (carboxyphenyl) propane and other aromatic dicarboxylic acids; cyclohexanedicarboxylic acid, adipic acid and other aliphatic dicarboxylic acids; trimellitic acid , Tricarboxylic acids such as trimesic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid Aromatic tetracarboxylic acids such as acid-1,4-phenylene ester; aliphatic tetracarboxylic acids such as butanete
  • the acid which has hydroxy groups such as hydroxyphthalic acid and hydroxy trimellitic acid, can also be mentioned. Two or more of these acids can also be used.
  • the structural unit preferably contains 50 mol% or more of an acid residue having a hydroxy group.
  • R 1c preferably has an aromatic ring from the viewpoint of heat resistance, and is preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms.
  • R 2c represents a (2 + q + r) -valent organic group having 2 or more carbon atoms.
  • the organic group include a substituted or unsubstituted hydrocarbon group and a group (ether group) in which a substituted or unsubstituted hydrocarbon group is linked by an oxygen atom.
  • R 2c is a structure derived from diamine.
  • R 2c preferably has an aromatic ring from the viewpoint of heat resistance.
  • diamines examples include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone, and bis (amino-hydroxy).
  • R 3c and R 4c are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • the organic group include a substituted or unsubstituted aliphatic or aromatic hydrocarbon group.
  • 10 mol% or more and 90 mol% or less of R 3c and R 4c are hydrogen atoms.
  • R 3 and R 4 each contain at least one monovalent hydrocarbon group having 1 to 16 carbon atoms, and the others are hydrogen atoms.
  • n 8 is 10 to 100,000. If n8 is less than 10, the solubility of the polymer in an alkaline developer becomes too high, and the contrast between the exposed area and the unexposed area cannot be obtained, and a desired pattern may not be formed. On the other hand, the n 8 is greater than 100,000, too small solubility in an alkaline developer of the polymer, exposed portions not dissolved, a desired pattern can not be formed.
  • the upper limit of n 8 is preferably 1,000, and more preferably 100. Further, in view of solubility and elongation enhancer, 20 is preferably a lower limit of n 8.
  • the polysiloxane is not particularly limited as long as it is a polymer having a siloxane bond, but is preferably a hydrolyzed condensate of a hydrolyzable silane compound.
  • the “hydrolyzable silane compound” is usually a silanol group or siloxane that is hydrolyzed by heating in the temperature range of room temperature (about 25 ° C.) to 100 ° C. in the presence of non-catalyst and excess water. A compound having a hydrolyzable group that forms a condensate. In the radiation-sensitive resin composition, some of the hydrolyzable silane compounds have a part or all of the hydrolyzable groups in the molecule in an unhydrolyzed state and other hydrolyzable silanes. It may remain in a monomer state without condensing with the compound.
  • Hydrolysis condensate means a hydrolysis condensate obtained by condensing some silanol groups of a hydrolyzed silane compound.
  • hydrolyzable silane compound examples include a compound represented by the following formula (S-1) (hereinafter also referred to as “(S1) compound”).
  • R 1d is an alkyl group having 1 to 6 carbon atoms.
  • R 2d is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, an epoxy group, a 3,4-cycloepoxy group, an oxetanyl group, An amino group or an isocyanate group.
  • q 1 is an integer of 0-20.
  • n 9 is an integer of 0 to 3. However, if the R 1d and R 2d is more, the plurality of R 1d and R 2d each independently satisfy the above definition.
  • Examples of the alkyl group having 1 to 6 carbon atoms represented by R 1d include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a butyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of easy hydrolysis.
  • Examples of the alkyl group having 1 to 20 carbon atoms represented by R 2d include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, n-pentyl group, 3-methylbutyl group, 2-methylbutyl group, 1-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group Etc.
  • the carbon number of the alkyl group having 1 to 20 carbon atoms is preferably 1 to 10 and more preferably 1 to 3.
  • Examples of the fluorinated alkyl group having 1 to 6 carbon atoms include a trifluoromethyl group, a tetrafluoroethyl group, and a heptafluoropropyl group.
  • the (S-1) compound having n 9 of 1 is a silane compound having one non-hydrolyzable group and three hydrolyzable groups.
  • the silane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, and ethyltributoxysilane.
  • the (S-1) compound having n 9 of 2 is a silane compound having two non-hydrolyzable groups and two hydrolyzable groups.
  • Examples of the silane compound include 3-methacryloxypropylmethyldimethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, and ⁇ -isocyanatopropylmethyldimethoxysilane.
  • the (S-1) compound having n 9 of 3 is a silane compound having three non-hydrolyzable groups and one hydrolyzable group.
  • the silane compound include 3-methacryloxypropyldimethylmethoxysilane, ⁇ -glycidoxypropyldimethylmethoxysilane, ⁇ -aminopropyldimethylmethoxysilane, ⁇ -isocyanatopropyldimethylmethoxysilane, and the like.
  • the (S-1) compound in which n 9 is 0 is a silane compound having four hydrolyzable groups.
  • the silane compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane and the like.
  • Polysiloxane (hydrolysis condensation)
  • Polysiloxane is usually heated in the temperature range of room temperature (about 25 ° C.) to 100 ° C. in the presence of excess water and optionally in the presence of a solvent or catalyst to hydrolyze the hydrolyzable silane compound. It can synthesize
  • Examples of the solvent for the hydrolysis condensation reaction include alcohols, ethers, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether Pionate, aromatic hydrocarbons, ketones, other esters and the like can be mentioned. These solvents may be used alone or in combination of two or more.
  • a catalyst for hydrolysis condensation reaction an acid catalyst, a base catalyst, and an alkoxide are preferable.
  • Mw polystyrene-equivalent weight average molecular weight
  • the upper limit is preferably 15,000 and more preferably 10,000.
  • aromatic polyether refers to a polymer having a structure in which aromatic rings are connected by an ether bond (oxygen atom).
  • aromatic polyether those having a structural unit represented by the following formula (T-1), a structural unit represented by the following formula (T-2), or a combination thereof are preferable.
  • R 1e to R 4e are each independently a monovalent organic group having 1 to 12 carbon atoms.
  • a to d are each independently an integer of 0 to 4.
  • R 1e to R 4e and a to d are the same as those in the above formula (T-1).
  • Y is a single bond, —SO 2 — or —C ( ⁇ O) —.
  • R 5e and R 6e are each independently a halogen atom, a monovalent organic group having 1 to 12 carbon atoms, or a nitro group.
  • e and f are each independently an integer of 0 to 4.
  • m 2 is 0 or 1. However, when m 2 is 0, R 6e is not a cyano group.
  • Examples of the monovalent organic group having 1 to 12 carbon atoms represented by R 1e to R 4e in the formulas (T-1) and (T-2) include an aliphatic or aromatic hydrocarbon group, an alkoxy group, A carboxy group etc. can be mentioned.
  • the aromatic polyether preferably has a structural unit represented by the following formula (T-3), a structural unit represented by the following formula (T-4), or a combination thereof.
  • R 7e and R 8e are each independently a monovalent organic group having 1 to 12 carbon atoms.
  • Z is a single bond, —O—, —S—, —SO 2 —,> C ⁇ O, —CONH—, —COO—, a divalent hydrocarbon group having 1 to 12 carbon atoms, or 1 to 12 is a group in which at least part of hydrogen atoms of 12 divalent hydrocarbon groups is substituted with at least one selected from the group consisting of a carboxy group, a hydroxy group, a sulfo group and a fluorine atom.
  • g and h are each independently an integer of 0 to 4.
  • n is 0 or 1.
  • Examples of the monovalent organic group having 1 to 12 carbon atoms represented by R 7e and R 8e include an aliphatic or aromatic hydrocarbon group, an alkoxy group, and a carboxy group.
  • Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms represented by Z include methanediyl group, ethane-1,1-diyl group, propane-2,2-diyl group, and n-pentane-2,2-diyl. Groups, alkanediyl groups such as n-hexane-2,2-diyl group, alkenediyl groups, and arenediyl groups.
  • R 5e , R 6e , Y, m 2 , e and f are each independently R 5e , R 6e , Y, m 2 , in the above formula (T-2). It is synonymous with e and f.
  • R 7e, R 8e, Z, n, g and h are each independently, R 7e in the formula (T-3), the same meanings as R 8e, Z, n, g and h.
  • the lower limit of the weight average molecular weight (Mw) in terms of polystyrene by GPC of the aromatic polyether is preferably 3,000, and more preferably 5,000.
  • the upper limit is preferably 20,000, and more preferably 15,000.
  • the acid generator is a compound that generates an acid upon irradiation with radiation.
  • the radiation for example, visible light, ultraviolet light, far ultraviolet light, electron beam (charged particle beam), X-ray or the like can be used.
  • the acid generator is not particularly limited as long as it generates an acid (for example, carboxylic acid, sulfonic acid, etc.) by irradiation with radiation.
  • the form of the acid generator may be the form of an acid generator that is a compound as described later, the form of a photoacid generator incorporated as part of a polymer, or both of these forms. Good.
  • Radiation sensitive acid generators include oxime sulfonate compounds, onium salts, N-sulfonyloxyimides (sulfonimide compounds), halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, quinone diazide compounds, etc. Is mentioned. Among these, an oxime sulfonate compound and N-sulfonyloxyimide are preferable, and an oxime sulfonate compound is more preferable.
  • oxime sulfonate compound As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by following formula (3) is preferable.
  • R b is an alkyl group, an alicyclic hydrocarbon group, an aryl group, or a group in which at least a part of hydrogen atoms of these groups is substituted with a substituent.
  • the alkyl group represented by R b has 1 to 10 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-hexyl group, and n-octyl group. And a linear or branched alkyl group.
  • the alicyclic hydrocarbon group represented by Rb include monocyclic or polycyclic alicyclic hydrocarbon groups having 3 to 20 carbon atoms such as a cyclopropyl group and a cyclohexyl group.
  • Examples of the aryl group represented by Rb include aryl groups having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.
  • Examples of the substituent that these alkyl groups, alicyclic hydrocarbon groups, and aryl groups may have include a halogen atom, an alkoxy group having 1 to 10 carbon atoms, and an alicyclic group (7,7-dimethyl-2).
  • -A bridged alicyclic group such as an oxonorbornyl group, preferably a bicycloalkyl group).
  • Examples of the compound containing an oxime sulfonate group represented by the above formula (3) include compounds represented by the following formulas (3-i) to (3-v).
  • N-sulfonyloxyimide (sulfonimide compound)
  • N-sulfonyloxyimide (sulfonimide compound)
  • Examples of the N-sulfonyloxyimide (sulfonimide compound) include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- ( 2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoro) Methylphenylsulfonyloxy) phthalimide, N- (2-fluorophenyl
  • a radiation sensitive acid generator may be used individually by 1 type, and 2 or more types may be mixed and used for it.
  • a lower limit of content of the radiation sensitive acid generator in the said radiation sensitive resin composition 0.1 mass part is preferable with respect to 100 mass parts of [A] polymers, and 1 mass part is more preferable.
  • this upper limit 10 mass parts is preferable and 5 mass parts is more preferable.
  • the compound [C] is a compound represented by the following formulas (1-1) to (1-6). These compounds can be used alone or in combination with each other.
  • one or more Xs are each independently an organic group having an acid dissociable group.
  • a plurality of R 1 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent.
  • n 1 is an integer of 1 to 3.
  • n 2 is an integer of 0-2.
  • a plurality of R 2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent.
  • A represents a single bond, a methylene group (ethanediyl group), an alkylene group having 2 to 12 carbon atoms (alkanediyl group), a phenylene group (benzenediyl group), an oxygen atom, a sulfur atom, or a methylene group, and 2 to 12 carbon atoms.
  • At least a part of the hydrogen atoms of the alkylene group or phenylene group is a group represented by the following formula (1-7), a group substituted with a fluorine atom or a carboxy group.
  • n 3 is an integer of 1 to 3.
  • n 4 is an integer of 1 to 3.
  • a plurality of R 3 and a plurality of R 4 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon.
  • a plurality of R 5 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent.
  • m is an integer of 0 to 10.
  • a plurality of R 6 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent.
  • p is an integer of 0 to 10.
  • R 7 represents at least one of an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or a hydrogen atom included in these groups. A part of the group is substituted with a substituent.
  • n 5 is an integer of 1 to 3.
  • n 6 is an integer of 1 to 5.
  • n 7 is an integer of 0 to 5.
  • the plurality of R 7 may be the same or different from each other.
  • X represents an organic group having an acid dissociable group.
  • the plurality of R 8 are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or a part or all of hydrogen atoms possessed by these groups Is a group substituted with a substituent. * Indicates a binding site.
  • the acid dissociable group in the organic group having an acid dissociable group represented by X refers to a group that can be dissociated by the action of an acid by replacing a hydrogen atom such as a carboxy group or a phenolic hydroxyl group.
  • An organic group refers to a group containing at least one carbon atom.
  • the dissociation of the acid dissociable group generates a carboxy group or a phenolic hydroxyl group.
  • Examples of the organic group having an acid-dissociable group represented by X include groups represented by the following formula (2-1) or formula (2-2).
  • the organic group represented by X includes an acid dissociable group having such a structure, the acid dissociable group can be dissociated even by heating. Accordingly, the [C] compound containing such a group becomes an acid in the heating step after development, and can accelerate the curing reaction of the [A] polymer.
  • R 1a and R 2a each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or at least a part of the hydrogen atoms of the hydrocarbon group is a hydroxy group, A group substituted by a halogen atom or a cyano group.
  • R 3a is a hydrocarbon group having 1 to 30 carbon atoms, a group containing an oxygen atom at the carbon-carbon boundary or bond-side terminal of the carbon hydrogen group, or at least a part of the hydrogen atoms of these groups is a hydroxy group , A group substituted with a halogen atom or a cyano group.
  • Y 1 is a single bond, a carbonyl group or a group represented by —Z 1 —C ( ⁇ O) —.
  • Z 1 is a divalent linking group having 1 to 20 carbon atoms.
  • R 4a to R 10a are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. r is 1 or 2. When r is 2, the plurality of R 7a and R 8a may be the same or different.
  • Y 2 is a single bond, a carbonyl group or a group represented by —Z 2 —C ( ⁇ O) —.
  • Z 2 is a divalent linking group having 1 to 10 carbon atoms.
  • Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 1a to R 3a include linear and branched alkyl groups having 1 to 30 carbon atoms, alicyclic hydrocarbon groups having 3 to 30 carbon atoms, Examples thereof include aromatic hydrocarbon groups having 6 to 30 carbon atoms.
  • linear and branched alkyl groups examples include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n- Linear alkyl groups such as tetradecyl group, n-octadecyl group, branched alkyl groups such as i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group, 3-hexyl group, etc. Can be mentioned.
  • the alicyclic hydrocarbon group may be monocyclic or polycyclic, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a bornyl group, a norbornyl group, and an adamantyl group.
  • the aromatic hydrocarbon group may be a single ring, a structure in which a single ring is linked, a condensed ring, or a structure in which an aromatic ring and an aliphatic hydrocarbon group are linked.
  • Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a tolyl group, and a benzyl group.
  • R 1a is preferably a hydrogen atom.
  • R 2a is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group.
  • R 3a is preferably a hydrocarbon group having 1 to 30 carbon atoms (an alkoxy group having 1 to 30 carbon atoms) containing an oxygen atom at the terminal end on the bond side, and a linear or branched alkoxy group having 1 to 20 carbon atoms.
  • a cycloalkoxy group having 3 to 20 carbon atoms more preferably a linear or branched alkoxy group having 1 to 8 carbon atoms and a cycloalkoxy group having 3 to 8 carbon atoms.
  • Examples of the divalent linking group having 1 to 20 carbon atoms represented by Z 1 include a divalent chain hydrocarbon group having 1 to 20 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms.
  • a divalent hydrocarbon group such as a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or —O—, —SO—, —SO at the end of the bond site of these divalent hydrocarbon groups.
  • 2 -, - OSO 2 -, - CO -, - CONH- divalent heteroatom-containing group is a linking group such as may be exemplified.
  • Examples of the divalent chain hydrocarbon group include alkanediyl groups such as methanediyl group and ethanediyl group, and alkenediyl groups such as ethenediyl group.
  • Examples of the divalent alicyclic hydrocarbon group include cycloalkanediyl groups such as cyclohexanediyl group.
  • Examples of the divalent aromatic hydrocarbon group include benzenediyl group, toluenediyl group, indenediyl group and other monocycles, polycycles, structures in which an aromatic ring and an aliphatic hydrocarbon group are linked, and aromatic rings and alicyclic rings. A condensed ring etc. can be mentioned.
  • Z 1 is preferably —O—CH 2 — and a linking group represented by the following formula.
  • hydrocarbon group having 1 to 12 carbon atoms represented by the above R 4a to R 10a examples include linear and branched alkyl groups having 1 to 12 carbon atoms, alicyclic hydrocarbon groups having 3 to 12 carbon atoms, Mention may be made of aromatic hydrocarbon groups having 6 to 12 carbon atoms. Specific examples thereof include a part of those exemplified as the hydrocarbon group represented by R 1a to R 3a .
  • R 4a to R 10a are preferably hydrogen atoms.
  • Divalent particular groups and preferred groups of the linking group of the Z 2 at 1 to 20 carbon atoms represented is of 1 to 20 carbon atoms represented by Z 1 in the formula (2-1) described above The same as the linking group.
  • Examples of the alkyl group having 1 to 12 carbon atoms represented by R 1 to R 8 in the formulas (1-1) to (1-7) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, Examples thereof include n-butyl group.
  • Examples of the alkoxy group having 1 to 12 carbon atoms represented by R 1 to R 8 include a methoxy group, an ethoxy group, and a cyclohexyloxy group.
  • Examples of the alicyclic hydrocarbon group represented by R 1 to R 8 include a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 12 carbon atoms such as a cyclopropyl group, a cyclohexyl group, and a cyclopropenyl group. Is mentioned.
  • Examples of the aryl group represented by R 1 to R 8 include monocyclic or polycyclic aryl groups having 6 to 12 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.
  • substituents include halogen atoms such as chlorine atoms, alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups, hydroxy groups, carboxy groups, and cyano groups.
  • R 1 in formula (1-1) is preferably a hydrogen atom.
  • the number of R 1 other than a hydrogen atom is preferably 0 to 2, more preferably 0 and 1.
  • n 1 is preferably 2 or 3.
  • n 2 is preferably 0 or 1.
  • R 2 in formula (1-2) is preferably a hydrogen atom or an alkyl group (such as a methoxymethyl group) in which one hydrogen atom may be substituted with an alkoxy group.
  • the number of R 2 other than a hydrogen atom is preferably 0 to 2 per benzene ring.
  • alkylene group having 2 to 12 carbon atoms examples include ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1 , 1-diyl group, propane-2,2-diyl group, propane-1,3-diyl group, n-butane-2,2-diyl group, n-pentane-2,2-diyl group, n-hexane- 2,2-diyl group and the like can be mentioned.
  • A is preferably a single bond, a methylene group, a hexafluoropropane-2,2-diyl group or a group in which one of the hydrogen atoms of the methylene group is substituted with a group represented by the formula (1-7).
  • n 3 and n 4 are each preferably 1.
  • R 3 in formula (1-3) is preferably a hydrogen atom.
  • the number of R 3 other than a hydrogen atom is preferably 0 to 2, more preferably 0 and 1, per benzene ring.
  • R 4 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms and a group represented by the formula (1-7), more preferably a methyl group or a group represented by the formula (1-7).
  • R 5 in formula (1-4) is preferably a hydrogen atom and an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom and a methyl group.
  • the number of R 5 other than a hydrogen atom is preferably 0 to 2, more preferably 0 and 1, per benzene ring.
  • m is preferably 0 to 2, and more preferably 1.
  • M is preferably 1 or more.
  • R 6 in the formula (1-5) is preferably a hydrogen atom and an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom and a methyl group.
  • the number of R 6 other than a hydrogen atom is preferably 0 to 2, more preferably 0 or 1, per benzene ring.
  • p is preferably 0 to 2, and more preferably 1. Further, p is preferably 1 or more.
  • n 5 is preferably 2.
  • n 6 is preferably 3 to 5, and more preferably 4.
  • n 7 is preferably 0.
  • R 8 in formula (1-7) is preferably a hydrogen atom.
  • the number of R 8 other than a hydrogen atom is preferably 0 to 2, more preferably 0 and 1.
  • [C] compound examples include compounds (C-1) to (C-25) as shown below.
  • the [C] compound is not a polymer but a low molecular compound having a molecular weight of 3,000 or less, for example.
  • the lower limit of the molecular weight of the compound is preferably 100, and more preferably 150.
  • the upper limit is preferably 2,500.
  • the [C] compound can be synthesized by substituting a hydrogen atom of a phenolic hydroxyl group or carboxy group such as an aromatic compound having a phenolic hydroxyl group or carboxy group with an acid dissociable group.
  • the synthesis reaction can be performed according to a conventional method.
  • As the synthesis method for example, the Chemical Society of Japan, New Experimental Chemistry Course “Synthesis and Reaction of Organic Compounds”, published by Maruzen Co., Ltd. (1988), J. Chem. F. W. McOmie, Protective Groups in Organic Chemistry, Plenum Press (1973), T.M. W. Examples include the methods described in Greene, Protective Groups in Organic Synthesis, John Wiley & Sons (1981).
  • aromatic compound having a phenolic hydroxyl group or carboxy group examples include phenol, cresol, thymol, 4,4 ′, 4 ′′ -methylidynetrisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl).
  • An aromatic compound having a phenolic hydroxyl group such as 4,4′-diol; Benzoic acid, phthalic acid, trimesic acid, trimellitic acid, 4,4'-biphenyldicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 1,3 ,
  • Aromatic compounds having a carboxy group such as 5-tris (4-carboxyphenyl) benzene; Examples thereof include aromatic compounds having a phenolic hydroxyl group and a carboxy group such as salicylic acid and 3,4,5-trihydroxybenzoic acid.
  • the compound represented by the formula (1-6) can be synthesized by substituting the hydrogen atom of the carboxy group of the cyclic ether having a carboxy group with an acid dissociable group.
  • the cyclic ether having a carboxy group include tetrahydrofuran-2,3,4,5-tetracarboxylic acid, tetrahydrofuran-2-carboxylic acid, 3-methyl-3-oxetanecarboxylic acid, tetrahydropyran-4-carboxylic acid and the like. be able to.
  • the content of the [C] compound in the said radiation sensitive resin composition As a lower limit of content of the [C] compound in the said radiation sensitive resin composition, 5 mass parts is preferable with respect to 100 mass parts of [A] polymers, 10 mass parts is more preferable, 15 mass parts is Further preferred. On the other hand, as this upper limit, 200 mass parts is preferable, 100 mass parts is more preferable, and 40 mass parts is further more preferable.
  • the undesirable oxidation reaction in a composition can be suppressed.
  • the antioxidant include phenolic antioxidants, sulfur antioxidants, amine antioxidants, and the like, and phenolic antioxidants are preferable.
  • Phenol antioxidants include styrenated phenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-p-ethylphenol, 2,4,6-tri- t-butylphenol, butylhydroxyanisole, 1-hydroxy-3-methyl-4-isopropylbenzene, mono-t-butyl-p-cresol, mono-t-butyl-m-cresol, 2,4-dimethyl-6-t -Butylphenol, butylated bisphenol A, 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'methylene-bis- (4-ethyl-6-t-butylphenol), 2 , 2'-methylene-bis (4-methyl-6-t-nonylphenol), 2,2'-isobutylidene-bis- (4,6-dimethylphenol) ), 4,4′-butylidene-bis- (3-methyl-6-tert-butyl
  • the lower limit of the content of the antioxidant is preferably 0.1 parts by mass and more preferably 0.2 parts by mass with respect to 100 parts by mass of the [A] polymer.
  • this upper limit 10 mass parts is preferable, 5 mass parts is more preferable, and 2 mass parts is further more preferable.
  • the radiation-sensitive resin composition contains, as optional components, [E] adhesion assistant, [F] polyfunctional monomer, [G] inorganic oxide particles, [H] solvent, [I] surfactant, and the like. be able to.
  • [E] Adhesion aid> In the said radiation sensitive resin composition, in order to improve the adhesiveness of a board
  • a functional silane coupling agent is preferably used.
  • functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, epoxy groups (preferably oxiranyl groups), thiol groups, and the like.
  • functional silane coupling agents include trimethoxysilylbenzoic acid, ⁇ -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -glycidoxy Propyltrimethoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, ⁇ -chloropropyltrialkoxysilane, ⁇ -mercaptopropyltrialkoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyl Examples include oxypropyltrimethoxysilane.
  • 3-glycidyloxypropyltrimethoxysilane ⁇ -glycidoxypropylalkyldialkoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane and ⁇ -methacryloxypropyltrimethoxysilane are preferred.
  • the lower limit of the content of the adhesion assistant is preferably 0.5 parts by mass and more preferably 1 part by mass with respect to 100 parts by mass of the polymer [A].
  • the upper limit is preferably 20 parts by mass, and more preferably 10 parts by mass.
  • Polyfunctional monomers include allylated cyclohexyl di (meth) acrylate, 2,5-hexanedi (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) Acrylate, 1,3-butylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) ) Acrylate, 1,10-decanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, neo Emissions
  • the content of the polyfunctional monomer is, for example, in the range of 10% by mass to 150% by mass with respect to 100 parts by mass of the polymer [A] from the viewpoint of sensitivity to exposure light.
  • the inorganic oxide particles can maintain the electrical insulation of the resulting cured product and can control the dielectric constant, which is a dielectric property.
  • the inorganic oxide particles are also used for the purpose of controlling the refractive index of the cured film, controlling the transparency of the cured film, suppressing cracks by relaxing the curing shrinkage, and improving the surface hardness of the cured film. .
  • the inorganic oxide particle is an oxide containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium and hafnium. There may be mentioned physical particles.
  • oxide particles of silicon, zirconium, titanium or zinc are preferable, and silica particles which are oxide particles of silicon, oxide particles of zirconium or titanium, and barium titanate (BaTiO 3 ) are particularly preferable. These can be used alone or in combination of two or more.
  • the inorganic oxide particles may be composite oxide particles of the above elements. Examples of the composite oxide particles include barium titanate and strontium titanate.
  • ATO antimony-tin oxide
  • these inorganic oxide particles commercially available ones such as Nanotech (registered trademark) manufactured by CI Kasei Co., Ltd. can be used.
  • the shape of the inorganic oxide particles is not particularly limited, and may be spherical or amorphous, and may be hollow particles, porous particles, core-shell particles, or the like. Moreover, the volume average particle diameter of the [F] inorganic oxide particles determined by a dynamic light scattering method is preferably 5 nm or more and 200 nm or less.
  • the content of the inorganic oxide particles is not particularly limited, but may be 1 part by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the [A] polymer.
  • the said radiation sensitive resin composition contains [G] inorganic oxide particle, it can further contain a dispersing agent. With the dispersant, [G] inorganic oxide particles can be uniformly dispersed in the radiation-sensitive resin composition, and coatability and the like can be improved.
  • Solvents include alcohols such as methanol, ethanol, isopropyl alcohol, butanol and octanol; ethyl acetate, butyl acetate, ethyl lactate, ⁇ -butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3- Esters such as methyl methoxypropionate and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol ethyl methyl ether; dimethylformamide, N, N-dimethylacetamide, Amides such as N-methylpyrrolidone; acetone, methyl ethyl
  • Surfactant can be added in order to improve the applicability of the radiation-sensitive resin composition, reduce coating unevenness, and improve the developability of the radiation irradiated part.
  • preferable surfactants include fluorine-based surfactants and silicone-based surfactants.
  • content of surfactant it is 0.01 mass part or more and 10 mass parts or less with respect to 100 mass parts of [A] polymers.
  • the said radiation sensitive resin composition is prepared by mixing each component mentioned above in a predetermined ratio.
  • solid content concentration of the said radiation sensitive resin composition it is 10 to 50 mass%, for example.
  • the said display element cured film is formed from the said radiation sensitive resin composition. Since the said cured film is formed from the said radiation sensitive resin composition, it is excellent in insulation and corrosion prevention property.
  • the cured film having such characteristics is, for example, a bank (partition) defining a region for forming an interlayer insulating film, a planarizing film, and a light emitting layer of an electronic device of a display element, a spacer, a protective film, and a color filter. It can be used for coloring patterns.
  • a bank partition
  • the method for forming the cured film for display element includes a step of forming a coating film on a substrate using the radiation-sensitive resin composition (hereinafter, also referred to as “coating layer forming step”), at least a part of the coating film.
  • a step of irradiating the film with radiation hereinafter also referred to as “irradiation step”
  • a step of developing the coating film irradiated with the radiation hereinafter also referred to as “development step”
  • heating the developed coating film A process hereinafter also referred to as a “heating process”.
  • a cured film having excellent radiation sensitivity, a small amount of change in film thickness at the non-exposed portion, and excellent insulation and corrosion resistance can be obtained.
  • the radiation-sensitive resin composition is used and applied onto a substrate to form a coating film.
  • the said radiation sensitive resin composition contains a solvent, it is preferable to remove a solvent by prebaking an application surface.
  • Examples of the substrate include glass, quartz, silicone, and resin.
  • Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of a cyclic olefin, and a hydrogenated product thereof.
  • the pre-baking conditions are usually 70 ° C. or higher and 120 ° C. or lower and 1 minute or longer and 10 minutes or shorter, although they vary depending on the type of each component, the blending ratio, and the like.
  • the coating film is irradiated with radiation and exposed.
  • exposing it exposes normally through the photomask which has a predetermined pattern.
  • the radiation used for the exposure include visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, electromagnetic waves such as X-rays and gamma rays, electron beam, and charged particle beams such as ⁇ rays.
  • the radiation radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable.
  • the upper limit of the exposure dose is preferably 20,000J / m 2, 10,000J / m 2 is more preferable.
  • the lower limit of the exposure amount for example, be a 1 J / m 2, preferably 500J / m 2, 1,500J / m 2 is more preferable.
  • This exposure amount is a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (“OAI model 356” manufactured by OAI Optical Associates).
  • an alkaline aqueous solution is preferable.
  • the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.
  • an organic solvent such as a ketone organic solvent or an alcohol organic solvent can be used.
  • a water-soluble organic solvent such as methanol or ethanol or a surfactant
  • concentration of the alkali in aqueous alkali solution from a viewpoint of obtaining suitable developability, 0.1 to 5 mass% is preferable.
  • Examples of the developing method include a liquid piling method, a dipping method, a rocking dipping method, a shower method and the like.
  • the development time varies depending on the composition of the radiation sensitive resin composition, but is usually from 10 seconds to 180 seconds.
  • washing with running water is performed for 30 seconds or more and 90 seconds or less, and then a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.
  • Heating process In this step, the developed coating film is heated.
  • a heating device such as a hot plate or an oven to heat the patterned thin film
  • the curing reaction of the [A] polymer can be promoted to form a cured film.
  • heating temperature it is 120 to 250 degreeC, for example.
  • the heating time varies depending on the type of heating equipment, but for example, it is 5 minutes to 30 minutes for a hot plate and 30 minutes to 90 minutes for an oven.
  • the step baking method etc. which perform a heating process 2 times or more can also be used. In this way, a patterned thin film corresponding to the desired cured film can be formed on the surface of the substrate.
  • the display element includes a cured film for the display element.
  • Examples of the display element include a liquid crystal display element and an organic EL display element.
  • the liquid crystal display element is composed of, for example, a liquid crystal cell, a polarizing plate, and the like. Since this liquid crystal display element is provided with the cured film having excellent insulating properties and corrosion prevention properties, it has excellent long-term reliability and the like.
  • liquid crystal display device manufacturing methods are given below.
  • a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared.
  • an interlayer insulating film as a cured film, a spacer, a protective film, etc.
  • an alignment film having liquid crystal alignment ability is formed on the substrate on which these cured films are formed.
  • These substrates are arranged facing each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed on the inside. .
  • liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to form a liquid crystal cell.
  • a liquid crystal display element is obtained by bonding a polarizing plate on both outer surfaces of a liquid crystal cell.
  • the cured film formed from the radiation-sensitive resin composition can be used as a planarization film formed on the TFT element, a partition defining a light emitting site, or the like.
  • TCA tricarboxycyclopentylacetic acid dianhydride
  • TMHQ 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester
  • TCA tricarboxycyclopentylacetic acid dianhydride
  • TMHQ 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester
  • This polymer (A-3) had Mw of 6,000 and a molecular weight distribution (Mw / Mn) of 2.3.
  • the polymer (A-4) had an Mw of 12,000 and a molecular weight distribution (Mw / Mn) of 2.5.
  • the temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-5).
  • the solid content concentration of this polymer solution was 31.8% by weight, the polymer (A-5) had a weight average molecular weight (Mw) of 9,000, and a molecular weight distribution (Mw / Mn) of 2.3. It was.
  • the obtained reaction solution was dropped into a 0.1N aqueous hydrochloric acid solution to precipitate a reaction product represented by the formula (a).
  • the obtained reaction product was washed with water until neutral, and the unreacted product was distilled off at 80 ° C. under reduced pressure.
  • the molecular weight of the reaction product was 850.86 and the yield was 80%.
  • the procedure was the same as in Synthesis Example 1 except that 5 parts by mass of the obtained reaction product, 3 parts by mass of 3,4-dihydro-2H-pyran, and 0.8 parts by mass of pyridinium p-toluenesulfonate were used.
  • a compound (C-24) having an acid dissociable group was obtained.
  • reaction was performed at 140 ° C. for 3 hours. After completion of the reaction, the solvent and water were distilled off under reduced pressure to obtain a reaction product represented by the formula (b).
  • the molecular weight of the reaction product was 1671.76, and the yield was 9.6 g (99% yield).
  • the same procedure as in Synthesis Example 1 except that 5 parts by mass of the obtained reaction product, 1.5 parts by mass of 3,4-dihydro-2H-pyran, and 0.4 parts by mass of pyridinium p-toluenesulfonate were used. To obtain a compound (C-25) having an acid dissociable group.
  • ⁇ Preparation of radiation-sensitive resin composition [Example 1] 3 parts by mass of the radiation sensitive acid generator (B-1) and the compound (C-1) 20 having an acid dissociable group with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer (A-1) 3 parts by mass and 3 parts by mass of 3-glycidyloxypropyltrimethoxysilane as an adhesion assistant are mixed and dissolved in diethylene glycol ethyl methyl ether so that the solid content concentration is 30% by mass, and then a membrane having a pore size of 0.2 ⁇ m. It filtered with the filter and the radiation sensitive resin composition was prepared.
  • Examples 2 to 25 and Comparative Examples 1 and 2 The same operation as in Example 1 except that [A] polymer, [B] acid generator, [C] compound and [D] antioxidant of the types and blending amounts shown in Tables 2 to 3 below were used. Then, radiation sensitive resin compositions of Examples 2 to 25 and Comparative Examples 1 and 2 were prepared. In any radiation sensitive resin composition, 3 parts by mass of 3-glycidyloxypropyltrimethoxysilane was mixed as an adhesion assistant, as in Example 1. In Tables 2 and 3, “-” indicates that the corresponding component was not blended.
  • a cured film was formed from the radiation-sensitive resin compositions of Examples 1 to 25 and Comparative Examples 1 and 2, and radiation sensitivity, residual film ratio, relative dielectric constant (insulating property), and wiring corrosion (by the method described below) Corrosion prevention) was evaluated.
  • the evaluation results of Examples 1 to 25 and Comparative Examples 1 and 2 are shown in Tables 2 to 3.
  • a coating film was formed on a silicon substrate in the same manner as in “Evaluation of radiation sensitivity of radiation-sensitive composition”. Then, after irradiating the coating film with a predetermined amount of ultraviolet rays through a mask having a 100 ⁇ m line-and-space (one-to-one) pattern, a 2.38 mass% tetramethylammonium hydroxide aqueous solution was used. Development processing was performed at 25 ° C. for 80 seconds. Next, washing with running ultrapure water for 1 minute was performed, followed by drying to form a pattern. The post-development pattern height (T1) was measured with a stylus type film thickness measuring apparatus (“ ⁇ -step” manufactured by KLA Tencor).
  • the patterned silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to obtain a thermally cured pattern.
  • the pattern height (t1) after thermosetting was measured. From these measured values, the remaining film ratio ⁇ (T1-t1) / T1 ⁇ ⁇ 100 [%] was calculated. At this time, it is good when the remaining film ratio is 80% or more, and it can be evaluated as poor when it is less than 80%.
  • the relative dielectric constant is measured by the CV method at a frequency of 10 kHz using an electrode (“HP16451B” from Yokogawa-Hewlett-Packard) and a precision LCR meter (“HP4284A” from Yokogawa-Hewlett-Packard).
  • the dielectric constant is 3.7 or less, if the insulation is good, it can be evaluated that the insulation is poor when it exceeds 3.7.
  • the radiation-sensitive resin compositions and cured films of Examples 1 to 25 were excellent in radiation sensitivity, residual film rate, insulation and corrosion prevention.
  • the radiation-sensitive resin compositions and cured films of Comparative Examples 1 and 2 were inferior in any of radiation sensitivity, residual film ratio, insulation and corrosion prevention properties.
  • the radiation-sensitive resin composition of the present invention can be suitably used as a cured film such as an interlayer insulating film, a spacer, or a protective film of a display element.

Abstract

Provided are: a radiation sensitive resin composition which has good radiation sensitivity and undergoes a small film thickness change in a non-exposure part, and which is capable of providing a cured film that exhibits excellent insulating properties and corrosion prevention properties; a cured film for display elements, which is formed from this composition; a method for forming this cured film for display elements; and a display element which comprises this cured film for display elements. The present invention is a radiation sensitive resin composition for forming a cured film for display elements, which contains a polymer, a radiation sensitive acid generator and a compound having an acid-cleavable group. The polymer is preferably an acrylic resin having a carboxy group, a polyimide, a polyimide precursor, a polysiloxane, an aromatic polyether or a combination thereof.

Description

感放射線性樹脂組成物、表示素子用硬化膜、表示素子用硬化膜の形成方法及び表示素子Radiation-sensitive resin composition, cured film for display element, method for forming cured film for display element, and display element
　本発明は、感放射線性樹脂組成物、表示素子用硬化膜、表示素子用硬化膜の形成方法及び表示素子に関する。 The present invention relates to a radiation-sensitive resin composition, a cured film for display element, a method for forming a cured film for display element, and a display element.
　表示素子には、層状に配置される配線間を絶縁する層間絶縁膜、スペーサー、保護膜等の硬化膜が設けられている。層間絶縁膜等の硬化膜には、絶縁性（低誘電性）や、腐食防止性（被覆した基板に設けられている配線の腐食を抑制できること）などが要求される。一方、層間絶縁膜等の形成材料としては、感放射線性樹脂組成物が広く使用されている。感放射線性樹脂組成物には、放射線に対する感度が良好であること等が求められる。 The display element is provided with a cured film such as an interlayer insulating film, a spacer, or a protective film that insulates wirings arranged in layers. A cured film such as an interlayer insulating film is required to have insulating properties (low dielectric properties), corrosion resistance (can suppress corrosion of wiring provided on a coated substrate), and the like. On the other hand, a radiation sensitive resin composition is widely used as a material for forming an interlayer insulating film or the like. The radiation-sensitive resin composition is required to have good sensitivity to radiation.
　このような感放射線性樹脂組成物としては、保護基が酸により解離し、アルカリ水溶液に可溶となる樹脂、架橋剤及び酸発生剤を含有する組成物や、アセタール構造又はケタール構造とエポキシ基とを有する樹脂及び酸発生剤を含有する組成物が提案されている（特開２００４－４６６９号公報、特開２００４－２６４６２３号公報参照）。 As such a radiation sensitive resin composition, a protective group is dissociated by an acid, a composition containing a resin that becomes soluble in an alkaline aqueous solution, a crosslinking agent and an acid generator, an acetal structure or a ketal structure and an epoxy group And a composition containing an acid generator have been proposed (see Japanese Patent Application Laid-Open Nos. 2004-4669 and 2004-264623).
　上記従来の感放射線性樹脂組成物を用いて表示素子の硬化膜の形成を試みた場合、現像後の加熱工程における非露光部の膜厚減少量が大きく、硬化膜の平坦性が損なわれ、あるいは設計膜厚からのずれが生じる不都合がある。また、放射線感度等についても、改善の余地がある。 When trying to form a cured film of a display element using the conventional radiation-sensitive resin composition, the film thickness reduction amount of the non-exposed part in the heating process after development is large, and the flatness of the cured film is impaired, Alternatively, there is a disadvantage that deviation from the design film thickness occurs. There is also room for improvement in radiation sensitivity and the like.
特開２００４－４６６９号公報JP 2004-4669 A 特開２００４－２６４６２３号公報JP 2004-264623 A
　本発明は、以上のような事情に基づいてなされたものであり、その目的は、良好な放射線感度を有し、非露光部の膜厚変化量が小さく、絶縁性及び腐食防止性に優れる硬化膜を得ることができる感放射線性樹脂組成物、この組成物から形成される表示素子用硬化膜、この表示素子用硬化膜の形成方法、及びこの表示素子用硬化膜を有する表示素子を提供することである。 The present invention has been made on the basis of the circumstances as described above, and its purpose is a curing having a good radiation sensitivity, a small amount of change in the thickness of a non-exposed portion, and excellent insulation and corrosion resistance. A radiation-sensitive resin composition capable of obtaining a film, a cured film for a display element formed from the composition, a method for forming the cured film for a display element, and a display element having the cured film for a display element That is.
　上記課題を解決するためになされた発明は、重合体（以下、「［Ａ］重合体」ともいう。）、感放射線性酸発生体（以下、「［Ｂ］酸発生体」ともいう。）、及び酸解離性基を有し、下記式（１－１）～（１－６）のいずれかの式で表される少なくとも１種の化合物（以下、「［Ｃ］化合物」ともいう。）を含む表示素子用硬化膜形成用の感放射線性樹脂組成物である。
Figure JPOXMLDOC01-appb-C000005
 　式（１－１）～（１－６）中、１又は複数のＸは、それぞれ独立して、酸解離性基を有する有機基である。
　式（１－１）中、複数のＲ１は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。ｎ１は、１～３の整数である。ｎ２は、０～２の整数である。
　式（１－２）中、複数のＲ２は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。Ａは、単結合、メチレン基、炭素数２～１２のアルキレン基、フェニレン基、酸素原子、硫黄原子、又はメチレン基、炭素数２～１２のアルキレン基若しくはフェニレン基が有する水素原子の少なくとも一部が下記式（１－７）で表される基、フッ素原子若しくはカルボキシ基で置換された基である。ｎ３は、１～３の整数である。ｎ４は、１～３の整数である。
　式（１－３）中、複数のＲ３及び複数のＲ４は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、これらの基が有する水素原子の少なくとも一部が置換基で置換された基、又は下記式（１－７）で表される基である。
　式（１－４）中、複数のＲ５は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。ｍは、０～１０の整数である。
　式（１－５）中、複数のＲ６は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。ｐは、０～１０の整数である。
　式（１－６）中、Ｒ７は、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。ｎ５は、１～３の整数である。ｎ６は、１～５の整数である。ｎ７は、０～５の整数である。ｎ７が２以上である場合、複数のＲ７は、それぞれ同一でも異なっていてもよい。
Figure JPOXMLDOC01-appb-C000006
 　式（１－７）中、Ｘは、酸解離性基を有する有機基である。複数のＲ８は、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の一部又は全部が置換基で置換された基である。＊は、結合する部位を示す。 The invention made to solve the above problems is a polymer (hereinafter also referred to as “[A] polymer”), a radiation-sensitive acid generator (hereinafter also referred to as “[B] acid generator”). And at least one compound having an acid dissociable group and represented by any one of formulas (1-1) to (1-6) below (hereinafter also referred to as “[C] compound”). A radiation-sensitive resin composition for forming a cured film for a display element.
Figure JPOXMLDOC01-appb-C000005
 In formulas (1-1) to (1-6), one or more Xs are each independently an organic group having an acid dissociable group.
In the formula (1-1), a plurality of R 1 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent. n 1 is an integer of 1 to 3. n 2 is an integer of 0-2.
In formula (1-2), a plurality of R 2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent. A represents a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, a phenylene group, an oxygen atom, a sulfur atom, or at least a part of hydrogen atoms of a methylene group, an alkylene group having 2 to 12 carbon atoms, or a phenylene group. Is a group represented by the following formula (1-7), a group substituted with a fluorine atom or a carboxy group. n 3 is an integer of 1 to 3. n 4 is an integer of 1 to 3.
In formula (1-3), a plurality of R 3 and a plurality of R 4 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon. A group, an aryl group, a group in which at least part of hydrogen atoms of these groups are substituted with a substituent, or a group represented by the following formula (1-7).
In formula (1-4), a plurality of R 5 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent. m is an integer of 0 to 10.
In formula (1-5), a plurality of R 6 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent. p is an integer of 0 to 10.
In formula (1-6), R 7 represents at least one of an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or a hydrogen atom included in these groups. A part of the group is substituted with a substituent. n 5 is an integer of 1 to 3. n 6 is an integer of 1 to 5. n 7 is an integer of 0 to 5. When n 7 is 2 or more, the plurality of R 7 may be the same or different from each other.
Figure JPOXMLDOC01-appb-C000006
 In formula (1-7), X represents an organic group having an acid dissociable group. The plurality of R 8 are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or a part or all of hydrogen atoms possessed by these groups Is a group substituted with a substituent. * Indicates a binding site.
　上記課題を解決するためになされた別の発明は、当該感放射線性樹脂組成物から形成される表示素子用硬化膜である。さらに、基板上に塗膜を形成する工程、この塗膜の少なくとも一部に放射線を照射する工程、上記放射線が照射された塗膜を現像する工程、及び上記現像された塗膜を加熱する工程を備え、上記塗膜の形成に当該感放射線性樹脂組成物を用いる表示素子用硬化膜の形成方法、並びに当該表示素子用硬化膜を備える表示素子も本発明に含まれる。 Another invention made to solve the above problems is a cured film for a display element formed from the radiation-sensitive resin composition. Furthermore, a step of forming a coating film on the substrate, a step of irradiating at least a part of the coating film, a step of developing the coating film irradiated with the radiation, and a step of heating the developed coating film And a display element comprising the cured film for display element, and a method for forming the cured film for display element using the radiation-sensitive resin composition for forming the coating film.
　本発明の感放射線性樹脂組成物及び表示素子用硬化膜の形成方法は、良好な放射線感度を有し、非露光部の膜厚変化量が小さく、得られる硬化膜が優れた絶縁性及び腐食防止性を発揮することができる。また、本発明の表示素子用硬化膜は、優れた絶縁性及び腐食防止性を発揮することができ、表示素子に好適に用いることができる。 The radiation-sensitive resin composition and the method for forming a cured film for a display element according to the present invention have good radiation sensitivity, a small amount of change in the thickness of the non-exposed area, and the resulting cured film has excellent insulation and corrosion. Preventive properties can be exhibited. Moreover, the cured film for display elements of this invention can exhibit the outstanding insulation and corrosion prevention property, and can be used suitably for a display element.
＜感放射線性樹脂組成物＞
　当該感放射線性樹脂組成物は、［Ａ］重合体、［Ｂ］酸発生体、及び［Ｃ］化合物を含有する。当該感放射線性組成物は、好適な成分として、［Ｄ］酸化防止剤をさらに含有することが好ましく、その他の任意成分を含有してもよい。 <Radiation sensitive resin composition>
The radiation-sensitive resin composition contains a [A] polymer, a [B] acid generator, and a [C] compound. The radiation-sensitive composition preferably further contains [D] antioxidant as a suitable component, and may contain other optional components.
　当該感放射線性樹脂組成物は、表示素子用の硬化膜の形成に用いられる。また、当該感放射線性樹脂組成物は、通常、アルカリ現像液を用いたポジ型のパターン形成に用いられる。当該感放射線性樹脂組成物においては、パターン形成の際の露光により、露光部において［Ｂ］酸発生体から酸が発生し、この酸により［Ｃ］化合物の酸解離性基が解離する。これにより、露光部と非露光部との間の現像液に対する溶解性の差異が高まり、良好な放射線感度が発揮される。なお、このように、重合体と比較して低分子量の［Ｃ］化合物が酸解離性基を有することで、酸解離性基を有する重合体を用いた感放射線性組成物と比較して、現像液に対する溶解性の変化が顕著になる。また、露光後の加熱により［Ａ］重合体が硬化し、膜厚変化量が小さく、誘電率が低く、優れた腐食防止性を有する硬化膜を得ることができる。以下、各成分について説明する。 The radiation sensitive resin composition is used for forming a cured film for a display element. Moreover, the said radiation sensitive resin composition is normally used for positive type pattern formation using an alkali developing solution. In the radiation sensitive resin composition, an acid is generated from the [B] acid generator in the exposed area by exposure during pattern formation, and the acid dissociable group of the [C] compound is dissociated by this acid. Thereby, the difference in the solubility with respect to the developing solution between an exposed part and a non-exposed part increases, and favorable radiation sensitivity is exhibited. In addition, in this way, the low molecular weight [C] compound has an acid-dissociable group as compared with the polymer, and compared with the radiation-sensitive composition using the polymer having an acid-dissociable group, The change in solubility in the developer becomes significant. Moreover, the [A] polymer hardens | cures by the heating after exposure, the film thickness change amount is small, a dielectric constant is low, and the cured film which has the outstanding corrosion prevention property can be obtained. Hereinafter, each component will be described.
＜［Ａ］重合体＞
　［Ａ］重合体は得られる硬化膜の主材となる成分である。［Ａ］重合体としては、通常、感放射線性樹脂組成物に含有される公知の重合体を一種又は二種以上混合して用いることができる。なお、［Ａ］重合体としては、酸解離性基を有していない重合体を用いることが好ましい。酸解離性基を有していない重合体を用いることで、膜厚変化量をより小さくすることなどができる。 <[A] polymer>
[A] A polymer is a component which becomes a main material of the cured film obtained. [A] As a polymer, the well-known polymer normally contained in a radiation sensitive resin composition can be used 1 type or in mixture of 2 or more types. In addition, it is preferable to use the polymer which does not have an acid dissociable group as [A] polymer. By using a polymer that does not have an acid dissociable group, the amount of change in film thickness can be further reduced.
　［Ａ］重合体は、通常、アルカリ現像液に対する適度な溶解性及び加熱による硬化性を有するものが好適に用いられる。このような［Ａ］重合体としては、（Ａ－１）カルボキシ基を有するアクリル樹脂、（Ａ－２）ポリイミド又はポリイミド前駆体、（Ａ－３）ポリシロキサン、及び（Ａ－４）芳香族ポリエーテルからなる群より選ばれる少なくとも１種を含むことが好ましい。これらの重合体を用いることにより、膜厚変化量をより小さくし、絶縁性や腐食防止性をより高めることができる。また、［Ａ］重合体がこれらの重合体であることにより、当該感放射線性樹脂組成物は、アルカリ現像液を用いるポジ型の感放射線性樹脂組成物として好適に機能する。 [A] A polymer having suitable solubility in an alkali developer and curability by heating is preferably used. As such [A] polymer, (A-1) acrylic resin having carboxy group, (A-2) polyimide or polyimide precursor, (A-3) polysiloxane, and (A-4) aromatic It is preferable to include at least one selected from the group consisting of polyethers. By using these polymers, the amount of change in film thickness can be further reduced, and the insulation and corrosion resistance can be further increased. Moreover, when the [A] polymer is such a polymer, the radiation-sensitive resin composition suitably functions as a positive-type radiation-sensitive resin composition using an alkali developer.
（（Ａ－１）カルボキシ基を有するアクリル樹脂）
　（Ａ－１）カルボキシ基を有するアクリル樹脂は、カルボキシ基によりアルカリ溶解性を有する。（Ａ－１）カルボキシ基を有するアクリル樹脂は、カルボキシ基を有する構造単位と重合性基を有する構造単位とを有することが好ましい。この場合、アルカリ現像液に対する可溶性（アルカリ現像性）と硬化性とを良好に発揮することができる。 ((A-1) Acrylic resin having carboxy group)
(A-1) The acrylic resin having a carboxy group has alkali solubility due to the carboxy group. (A-1) The acrylic resin having a carboxy group preferably has a structural unit having a carboxy group and a structural unit having a polymerizable group. In this case, it is possible to satisfactorily exhibit the solubility (alkali developability) and curability in an alkali developer.
　重合性基を有する構造単位は、エポキシ基を有する構造単位及び（メタ）アクリロイルオキシ基を有する構造単位からなる群より選ばれる少なくとも１種の構造単位であることが好ましい。カルボキシ基を有するアクリル樹脂が、上記特定の構造単位を含むことで、より強固な硬化膜を形成することができる。 The structural unit having a polymerizable group is preferably at least one structural unit selected from the group consisting of a structural unit having an epoxy group and a structural unit having a (meth) acryloyloxy group. When the acrylic resin having a carboxy group contains the specific structural unit, a stronger cured film can be formed.
　（メタ）アクリロイルオキシ基を有する構造単位は、例えば重合体中のエポキシ基に（メタ）アクリル酸を反応させる方法、重合体中のカルボキシ基にエポキシ基を有する（メタ）アクリル酸エステルを反応させる方法、重合体中のヒドロキシ基にイソシアネート基を有する（メタ）アクリル酸エステルを反応させる方法、重合体中の酸無水物部位に（メタ）アクリル酸ヒドロキシエステルを反応させる方法等により形成することができる。これらの中でも、重合体中のカルボキシ基にエポキシ基を有する（メタ）アクリル酸エステルを反応させる方法が好ましい。 The structural unit having a (meth) acryloyloxy group is, for example, a method in which (meth) acrylic acid is reacted with an epoxy group in a polymer, or a (meth) acrylic acid ester having an epoxy group is reacted with a carboxy group in the polymer. It may be formed by a method, a method of reacting a hydroxy group in a polymer with a (meth) acrylic acid ester having an isocyanate group, a method of reacting an acid anhydride site in a polymer with a (meth) acrylic acid hydroxy ester, or the like. it can. Among these, the method of reacting the (meth) acrylic acid ester which has an epoxy group with the carboxy group in a polymer is preferable.
　カルボキシ基を有する構造単位と重合性基としてエポキシ基を有する構造単位を含むアクリル樹脂は、溶媒中で重合開始剤の存在下、（ａ１）不飽和カルボン酸及び不飽和カルボン酸無水物からなる群より選択される少なくとも１種（以下、「（ａ１）化合物」ともいう。）と、（ａ２）エポキシ基含有不飽和化合物（以下、「（ａ２）化合物」ともいう。）とを共重合して合成することができる。（ａ３）ヒドロキシ基含有構造単位を与えるヒドロキシ基含有不飽和化合物（以下、「（ａ３）化合物」ともいう。）をさらに加えて、共重合体とすることもできる。さらに、カルボキシ基を有するアクリル樹脂の製造においては、上述の（ａ１）～（ａ３）化合物以外の（ａ４）化合物（上述の（ａ１）～（ａ３）化合物に由来する構造単位以外の構造単位を与える不飽和化合物）をさらに加えて、共重合体とすることもできる。次に、（ａ１）～（ａ４）の各化合物を詳述する。 The acrylic resin containing a structural unit having a carboxy group and a structural unit having an epoxy group as a polymerizable group is a group comprising (a1) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride in the presence of a polymerization initiator in a solvent. At least one selected from the above (hereinafter also referred to as “(a1) compound”) and (a2) an epoxy group-containing unsaturated compound (hereinafter also referred to as “(a2) compound”). Can be synthesized. (A3) A hydroxy group-containing unsaturated compound that gives a hydroxy group-containing structural unit (hereinafter also referred to as “(a3) compound”) may be further added to form a copolymer. Further, in the production of an acrylic resin having a carboxy group, a structural unit other than the structural unit derived from the compound (a4) other than the above-described compounds (a1) to (a3) (the structural unit derived from the above-described compounds (a1) to (a3)). An unsaturated compound to be added) can be further added to form a copolymer. Next, the compounds (a1) to (a4) will be described in detail.
（（ａ１）化合物）
　（ａ１）化合物としては、不飽和モノカルボン酸、不飽和ジカルボン酸、不飽和ジカルボン酸の無水物等が挙げられる。 ((A1) Compound)
Examples of the compound (a1) include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated dicarboxylic acid anhydrides.
　不飽和モノカルボン酸としては、例えばアクリル酸、メタクリル酸、クロトン酸等が挙げられる。 Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.
　不飽和ジカルボン酸としては、例えばマレイン酸、フマル酸、シトラコン酸、メサコン酸、イタコン酸等が挙げられる。 Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like.
　不飽和ジカルボン酸の無水物としては、例えば上記ジカルボン酸として例示した化合物の無水物等が挙げられる。 Examples of the anhydride of unsaturated dicarboxylic acid include anhydrides of the compounds exemplified as the dicarboxylic acid.
　これらの（ａ１）化合物のうち、アクリル酸、メタクリル酸及び無水マレイン酸が、共重合反応性、アルカリ水溶液に対する溶解性及び入手の容易性などからより好ましい。これらの（ａ１）化合物は、単独で用いてもよいし、２種以上を混合して用いてもよい。 Among these (a1) compounds, acrylic acid, methacrylic acid and maleic anhydride are more preferred from the viewpoints of copolymerization reactivity, solubility in an alkaline aqueous solution, and availability. These (a1) compounds may be used alone or in admixture of two or more.
　（ａ１）化合物の使用割合の下限値としては、（Ａ－１）カルボキシ基を有するアクリル樹脂を形成する全モノマーの合計に基づいて、５質量％が好ましく、１０質量％がより好ましい。一方、この上限値としては、３０質量％が好ましく、２５質量％がより好ましい。（ａ１）化合物の使用割合をこのような範囲とすることによって、カルボキシ基を有するアクリル樹脂のアルカリ水溶液に対する溶解性を最適化するとともに、放射線性感度に優れる膜を形成することができる。 (A1) The lower limit of the use ratio of the compound is preferably (A-1) 5% by mass, more preferably 10% by mass, based on the total of all monomers forming the carboxy group-containing acrylic resin. On the other hand, as this upper limit, 30 mass% is preferable and 25 mass% is more preferable. (A1) By making the use ratio of a compound into such a range, while being able to optimize the solubility with respect to the alkaline aqueous solution of the acrylic resin which has a carboxy group, the film | membrane excellent in a radiation sensitivity can be formed.
（（ａ２）化合物）
　（ａ２）化合物は、ラジカル重合性を有するエポキシ基含有不飽和化合物である。エポキシ基としては、オキシラニル基（１，２－エポキシ構造）、オキセタニル基（１，３－エポキシ構造）、３，４－エポキシトリシクロ［５．２．１．０２．６］デシル基等が挙げられる。 ((A2) Compound)
The compound (a2) is an epoxy group-containing unsaturated compound having radical polymerizability. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure), an oxetanyl group (1,3-epoxy structure), a 3,4-epoxytricyclo [5.2.1.0 2.6 ] decyl group, and the like. Can be mentioned.
　オキシラニル基を有する不飽和化合物としては、例えばアクリル酸グリシジル、メタクリル酸グリシジル、メタクリル酸２－メチルグリシジル、アクリル酸３，４－エポキシブチル、メタクリル酸３，４－エポキシブチル、アクリル酸６，７－エポキシヘプチル、メタクリル酸６，７－エポキシヘプチル、α－エチルアクリル酸－６，７－エポキシヘプチル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、メタクリル酸３，４－エポキシシクロへキシルメチル等が挙げられる。これらのうち、メタクリル酸グリシジル、メタクリル酸２－メチルグリシジル、メタクリル酸－６，７－エポキシヘプチル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、メタクリル酸３，４－エポキシシクロヘキシル、アクリル酸３，４－エポキシシクロヘキシル、及び３，４－エポキシトリシクロ［５．２．１．０２．６］デシルアクリレートが、共重合反応性及び絶縁膜等の耐溶媒性等の向上の観点から好ましい。 Examples of unsaturated compounds having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, and 6,7-acrylic acid. Epoxyheptyl, 6,7-epoxyheptyl methacrylate, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylate 4-epoxycyclohexylmethyl and the like. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3, methacrylate 4-epoxycyclohexyl, 3,4-epoxycyclohexyl acrylate, and 3,4-epoxytricyclo [5.2.1.0 2.6 ] decyl acrylate are copolymerization reactivity and solvent resistance such as insulating film From the viewpoint of improving the above.
　オキセタニル基を有する不飽和化合物としては、例えば
　３－（アクリロイルオキシメチル）オキセタン、３－（アクリロイルオキシメチル）－２－メチルオキセタン、３－（アクリロイルオキシメチル）－３－エチルオキセタン、３－（アクリロイルオキシメチル）－２－フェニルオキセタン、３－（２－アクリロイルオキシエチル）オキセタン、３－（２－アクリロイルオキシエチル）－２－エチルオキセタン、３－（２－アクリロイルオキシエチル）－３－エチルオキセタン、３－（２－アクリロイルオキシエチル）－２－フェニルオキセタン等のアクリル酸エステル；
　３－（メタクリロイルオキシメチル）オキセタン、３－（メタクリロイルオキシメチル）－２－メチルオキセタン、３－（メタクリロイルオキシメチル）－３－エチルオキセタン、３－（メタクリロイルオキシメチル）－２－フェニルオキセタン、３－（２－メタクリロイルオキシエチル）オキセタン、３－（２－メタクリロイルオキシエチル）－２－エチルオキセタン、３－（２－メタクリロイルオキシエチル）－３－エチルオキセタン、３－（２－メタクリロイルオキシエチル）－２－フェニルオキセタン、３－（２－メタクリロイルオキシエチル）－２，２－ジフルオロオキセタン等のメタクリル酸エステル等が挙げられる。 Examples of unsaturated compounds having an oxetanyl group include 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, and 3- (acryloyl). Oxymethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, Acrylic acid esters such as 3- (2-acryloyloxyethyl) -2-phenyloxetane;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2 -Methacrylic acid esters such as phenyl oxetane and 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane.
　これらの（ａ２）化合物のうち、メタクリル酸グリシジル、メタクリル酸３，４－エポキシシクロヘキシル、及び３－（メタクリロイルオキシメチル）－３－エチルオキセタンが好ましい。これらの（ａ２）化合物は、単独で用いてもよいし、２種以上を混合して用いてもよい。 Of these (a2) compounds, glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable. These (a2) compounds may be used alone or in combination of two or more.
　（ａ２）化合物の使用割合の下限値としては、（Ａ－１）カルボキシ基を有するアクリル樹脂を形成する全モノマー合計に基づいて、５質量％が好ましく、１０質量％がより好ましい。一方、この上限値としては、６０質量％が好ましく、５０質量％がより好ましい。（ａ２）化合物の使用割合をこのような範囲とすることによって、優れた硬化性等を有する硬化膜を形成することができる。 (A2) The lower limit of the use ratio of the compound is preferably (A-1) 5% by mass, more preferably 10% by mass, based on the total of all monomers forming the acrylic resin having a carboxy group. On the other hand, as this upper limit, 60 mass% is preferable and 50 mass% is more preferable. (A2) By making the usage-amount of a compound into such a range, the cured film which has the outstanding sclerosis | hardenability etc. can be formed.
（（ａ３）化合物）
　（ａ３）化合物としては、例えばヒドロキシ基を有する（メタ）アクリル酸エステル、フェノール性水酸基を有する（メタ）アクリル酸エステル、ヒドロキシスチレン等が挙げられる。 ((A3) Compound)
Examples of the (a3) compound include (meth) acrylic acid ester having a hydroxy group, (meth) acrylic acid ester having a phenolic hydroxyl group, and hydroxystyrene.
　ヒドロキシ基を有するアクリル酸エステルとしては、アクリル酸２－ヒドロキシエチル、アクリル酸３－ヒドロキシプロピル、アクリル酸４－ヒドロキシブチル、アクリル酸５－ヒドロキシペンチル、アクリル酸６－ヒドロキシヘキシル等が挙げられる。 Examples of the acrylic acid ester having a hydroxy group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate.
　ヒドロキシ基を有するメタクリル酸エステルとしては、メタクリル酸２－ヒドロキシエチル、メタクリル酸３－ヒドロキシプロピル、メタクリル酸４－ヒドロキシブチル、メタクリル酸５－ヒドロキシペンチル、メタクリル酸６－ヒドロキシヘキシル等が挙げられる。 Examples of the methacrylic acid ester having a hydroxy group include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, and 6-hydroxyhexyl methacrylate.
　フェノール性水酸基を有するアクリル酸エステルとしては、アクリル酸２－ヒドロキシフェニル、アクリル酸４－ヒドロキシフェニル等が挙げられる。フェノール性水酸基を有するメタクリル酸エステルとしては、メタクリル酸２－ヒドロキシフェニル、メタクリル酸４－ヒドロキシフェニル等が挙げられる。 Examples of the acrylate ester having a phenolic hydroxyl group include 2-hydroxyphenyl acrylate and 4-hydroxyphenyl acrylate. Examples of the methacrylic acid ester having a phenolic hydroxyl group include 2-hydroxyphenyl methacrylate and 4-hydroxyphenyl methacrylate.
　ヒドロキシスチレンとしては、ｏ－ヒドロキシスチレン、ｐ－ヒドロキシスチレン、α－メチル－ｐ－ヒドロキシスチレン等が挙げられる。これらの（ａ３）化合物は、単独で用いてもよいし２種以上を混合して用いてもよい。 Examples of hydroxystyrene include o-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxystyrene and the like. These (a3) compounds may be used alone or in admixture of two or more.
　（ａ３）化合物の使用割合の下限値としては、（Ａ－１）カルボキシ基を有するアクリル樹脂を形成する全モノマーの合計に基づいて、１質量％が好ましく、５質量％がより好ましい。一方、この上限値としては、３０質量％が好ましく、２５質量％がより好ましい。（ａ３）化合物の使用割合をこのような範囲とすることで、アルカリ水溶液に対する溶解性を最適化することなどができる。 (A3) The lower limit of the use ratio of the compound is preferably (A-1) 1% by mass, more preferably 5% by mass, based on the total of all monomers forming the carboxy group-containing acrylic resin. On the other hand, as this upper limit, 30 mass% is preferable and 25 mass% is more preferable. (A3) By making the use ratio of a compound into such a range, the solubility with respect to alkaline aqueous solution etc. can be optimized.
（（ａ４）化合物）
　（ａ４）化合物は、（ａ１）～（ａ３）化合物以外の不飽和化合物であれば、特に制限されるものではない。（ａ４）化合物としては、例えばメタクリル酸鎖状アルキルエステル、メタクリル酸環状アルキルエステル、アクリル酸鎖状アルキルエステル、アクリル酸環状アルキルエステル、メタクリル酸アリールエステル、アクリル酸アリールエステル、不飽和ジカルボン酸ジエステル、マレイミド化合物、不飽和芳香族化合物、共役ジエン、テトラヒドロフラン骨格等をもつ不飽和化合物、及びその他の不飽和化合物等が挙げられる。 ((A4) compound)
The compound (a4) is not particularly limited as long as it is an unsaturated compound other than the compounds (a1) to (a3). Examples of the compound (a4) include methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid chain alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, Examples include maleimide compounds, unsaturated aromatic compounds, conjugated dienes, unsaturated compounds having a tetrahydrofuran skeleton, and other unsaturated compounds.
　メタクリル酸鎖状アルキルエステルとしては、例えばメタクリル酸メチル、メタクリル酸エチル、メタクリル酸ｎ－ブチル、メタクリル酸ｓｅｃ－ブチル、メタクリル酸ｔ－ブチル、メタクリル酸２－エチルヘキシル、メタクリル酸イソデシル、メタクリル酸ｎ－ラウリル、メタクリル酸トリデシル、メタクリル酸ｎ－ステアリル等が挙げられる。 Examples of chain alkyl esters of methacrylic acid include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, and n-methacrylate. Examples include lauryl, tridecyl methacrylate, and n-stearyl methacrylate.
　メタクリル酸環状アルキルエステルとしては、例えばメタクリル酸シクロヘキシル、メタクリル酸２－メチルシクロヘキシル、メタクリル酸トリシクロ［５．２．１．０２，６］デカン－８－イル、メタクリル酸トリシクロ［５．２．１．０２，６］デカン－８－イルオキシエチル、メタクリル酸イソボルニル等が挙げられる。 Examples of cyclic alkyl esters of methacrylic acid include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 2,6 ] decane-8-yl methacrylate, and tricyclomethacrylate [5.2.1]. .0 2,6 ] decan-8-yloxyethyl, isobornyl methacrylate, and the like.
　アクリル酸鎖状アルキルエステルとしては、例えばアクリル酸メチル、アクリル酸エチル、アクリル酸ｎ－ブチル、アクリル酸ｓｅｃ－ブチル、アクリル酸ｔ－ブチル、アクリル酸２－エチルヘキシル、アクリル酸イソデシル、アクリル酸ｎ－ラウリル、アクリル酸トリデシル、アクリル酸ｎ－ステアリル等が挙げられる。 Examples of acrylic acid chain alkyl esters include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, and n-acrylate. Examples include lauryl, tridecyl acrylate, and n-stearyl acrylate.
　アクリル酸環状アルキルエステルとしては、例えばアクリル酸シクロヘキシル、アクリル酸－２－メチルシクロヘキシル、アクリル酸トリシクロ［５．２．１．０２，６］デカン－８－イル、アクリル酸トリシクロ［５．２．１．０２，６］デカン－８－イルオキシエチル、アクリル酸イソボルニル等が挙げられる。 Examples of the cyclic alkyl ester of acrylic acid include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl acrylate, and tricyclo [5.2. 1.0 2,6 ] decan-8-yloxyethyl, isobornyl acrylate, and the like.
　メタクリル酸アリールエステルとしては、例えばメタクリル酸フェニル、メタクリル酸ベンジル等が挙げられる。 Examples of the methacrylic acid aryl ester include phenyl methacrylate and benzyl methacrylate.
　アクリル酸アリールエステルとしては、例えばアクリル酸フェニル、アクリル酸ベンジル等が挙げられる。 Examples of the acrylic acid aryl ester include phenyl acrylate and benzyl acrylate.
　不飽和ジカルボン酸ジエステルとしては、例えばマレイン酸ジエチル、フマル酸ジエチル、イタコン酸ジエチル等が挙げられる。 Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.
　マレイミド化合物としては、例えばＮ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド、Ｎ－ベンジルマレイミド、Ｎ－（４－ヒドロキシフェニル）マレイミド、Ｎ－（４－ヒドロキシベンジル）マレイミド、Ｎ－スクシンイミジル－３－マレイミドベンゾエート、Ｎ－スクシンイミジル－４－マレイミドブチレート、Ｎ－スクシンイミジル－６－マレイミドカプロエート、Ｎ－スクシンイミジル－３－マレイミドプロピオネート、Ｎ－（９－アクリジニル）マレイミド等が挙げられる。 Examples of maleimide compounds include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) maleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.
　不飽和芳香族化合物としては、例えばスチレン、α－メチルスチレン、ｍ－メチルスチレン、ｐ－メチルスチレン、ビニルトルエン、ｐ－メトキシスチレン等が挙げられる。 Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene and the like.
　共役ジエンとしては、例えば１，３－ブタジエン、イソプレン、２，３－ジメチル－１，３－ブタジエン等が挙げられる。 Examples of the conjugated diene include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.
　テトラヒドロフラン骨格を含有する不飽和化合物としては、例えばメタクリル酸テトラヒドロフルフリル、２－メタクリロイルオキシ－プロピオン酸テトラヒドロフルフリルエステル、３－（メタ）アクリロイルオキシテトラヒドロフラン－２－オンなどが挙げられる。 Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl methacrylate, 2-methacryloyloxy-propionic acid tetrahydrofurfuryl ester, and 3- (meth) acryloyloxytetrahydrofuran-2-one.
　その他の不飽和化合物としては、例えばアクリロニトリル、メタクリロニトリル、塩化ビニル、塩化ビニリデン、アクリルアミド、メタクリルアミド、酢酸ビニル等が挙げられる。 Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.
　これらの（ａ４）化合物のうち、メタクリル酸鎖状アルキルエステル、メタクリル酸環状アルキルエステル、メタクリル酸アリールエステル、マレイミド化合物、テトラヒドロフラン骨格、不飽和芳香族化合物、アクリル酸環状アルキルエステルが好ましい。これらのうち、特に、スチレン、メタクリル酸メチル、メタクリル酸ｔ－ブチル、メタクリル酸ｎ－ラウリル、メタクリル酸ベンジル、メタクリル酸トリシクロ［５．２．１．０２，６］デカン－８－イル、ｐ－メトキシスチレン、アクリル酸２－メチルシクロヘキシル、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド及びメタクリル酸テトラヒドロフルフリルが、共重合反応性及びアルカリ水溶液に対する溶解性の点から好ましい。これらの（ａ４）化合物は、単独で用いてもよいし、２種以上を混合して用いてもよい。 Among these (a4) compounds, methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid aryl ester, maleimide compound, tetrahydrofuran skeleton, unsaturated aromatic compound, and acrylic acid cyclic alkyl ester are preferable. Of these, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl methacrylate, p -Methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide and tetrahydrofurfuryl methacrylate are preferred from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution. These (a4) compounds may be used alone or in admixture of two or more.
　（ａ４）化合物の使用割合としては、（Ａ－１）カルボキシ基を有するアクリル樹脂を形成する全モノマーの合計に基づいて、１０質量％以上８０質量以下％が好ましい。 (A4) The use ratio of the compound is preferably (A-1) 10% by mass or more and 80% by mass or less based on the total of all monomers forming the acrylic resin having a carboxy group.
　カルボキシ基を有するアクリル樹脂のＧＰＣによるポリスチレン換算重量平均分子量（Ｍｗ）の下限値としては１，０００が好ましく、３，０００がより好ましい。一方、この上限値としては、１５，０００が好ましく、１０，０００がより好ましい。Ｍｗを上記下限値以上とすることで、当該感放射線性樹脂組成物の成膜性を改善できる。一方、Ｍｗを上記上限値以下とすることによって、当該感放射線性樹脂組成物の現像性の低下を防止できる。 The lower limit of the polystyrene-equivalent weight average molecular weight (Mw) by GPC of the acrylic resin having a carboxy group is preferably 1,000, and more preferably 3,000. On the other hand, the upper limit is preferably 15,000 and more preferably 10,000. By setting Mw to be equal to or higher than the lower limit, the film formability of the radiation sensitive resin composition can be improved. On the other hand, by making Mw equal to or less than the above upper limit value, it is possible to prevent the developability of the radiation sensitive resin composition from being lowered.
（（Ａ－２）ポリイミド又はポリイミド前駆体）
　（Ａ－２）ポリイミド又はポリイミド前駆体としては、特に限定されないが、好ましくはポリイミド前駆体であるポリアミド酸（ポリイミック酸）及びポリアミド酸エステルである。ポリイミド前駆体としては、下記式（Ｍ－１）で表される構造単位を主構造とするポリマーを挙げることができる。式（Ｍ－１）で表される構造単位を主構造とするポリマーは、加熱あるいは適当な触媒により、イミド環、オキサゾール環、その他の環状構造等を有するポリマーとなり得るものである。環状構造となることで、耐熱性、耐溶剤性が飛躍的に向上する。ここで、主構造とは、その構造単位が全構造単位の５０モル％以上を占めることを意味する。式（Ｍ－１）で表される構造単位の含有割合は、７０モル％以上が好ましく、９０モル％以上がより好ましい。 ((A-2) Polyimide or polyimide precursor)
(A-2) The polyimide or polyimide precursor is not particularly limited, but polyamic acid (polyimidic acid) and polyamic acid ester which are polyimide precursors are preferable. Examples of the polyimide precursor include a polymer having a structural unit represented by the following formula (M-1) as a main structure. The polymer having the structural unit represented by the formula (M-1) as the main structure can be a polymer having an imide ring, an oxazole ring, other cyclic structures, etc. by heating or an appropriate catalyst. Due to the annular structure, the heat resistance and solvent resistance are dramatically improved. Here, the main structure means that the structural unit occupies 50 mol% or more of all the structural units. The content of the structural unit represented by the formula (M-1) is preferably 70 mol% or more, and more preferably 90 mol% or more.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式（Ｍ－１）中、Ｒ１ｃは炭素数２以上の（２＋ｐ＋ｍ１）価の有機基を示す。この有機基としては、置換又は非置換の炭化水素基等を挙げることができる。Ｒ１ｃは、多価カルボン酸に由来する構造である。多価カルボン酸としては、テレフタル酸、イソフタル酸、ジフェニルエーテルジカルボン酸、ナフタレンジカルボン酸、ビス（カルボキシフェニル）プロパン等の芳香族ジカルボン酸；シクロヘキサンジカルボン酸、アジピン酸等の脂肪族ジカルボン酸；トリメリット酸、トリメシン酸等のトリカルボン酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸、ビフェニルテトラカルボン酸、ジフェニルエーテルテトラカルボン酸、ジフェニルスルホンテトラカルボン酸、１，３－ジヒドロ－１，３－ジオキソ－５－イソベンゾフランカルボン酸－１，４－フェニレンエステル等の芳香族テトラカルボン酸；ブタンテトラカルボン酸、シクロペンタンテトラカルボン酸（２，３，５－トリカルボキシシクロペンチル酢酸等）等の脂肪族テトラカルボン酸；これらのカルボキシ基の水素原子をメチル基やエチル基に置換したエステル化合物や酸無水物等を挙げることができる。また、ヒドロキシフタル酸、ヒドロキシトリメリット酸等のヒドロキシ基を有する酸も挙げることができる。これらの酸を２種以上用いることもできる。アルカリ現像液に対する溶解性や感光性の点から、上記構造単位はヒドロキシ基を有する酸の残基を５０モル％以上含むことが好ましい。Ｒ１ｃは、耐熱性の点から芳香族環を有することが好ましく、炭素数６～３０の３価又は４価の有機基が好ましい。 In the formula (M-1), R 1c represents a (2 + p + m 1 ) -valent organic group having 2 or more carbon atoms. Examples of the organic group include a substituted or unsubstituted hydrocarbon group. R 1c is a structure derived from a polyvalent carboxylic acid. Polyvalent carboxylic acids include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, bis (carboxyphenyl) propane and other aromatic dicarboxylic acids; cyclohexanedicarboxylic acid, adipic acid and other aliphatic dicarboxylic acids; trimellitic acid , Tricarboxylic acids such as trimesic acid, pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid Aromatic tetracarboxylic acids such as acid-1,4-phenylene ester; aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid (such as 2,3,5-tricarboxycyclopentylacetic acid) Carboxylic acid; can be exemplified an ester compound or an acid anhydride a hydrogen atom is replaced with a methyl group or an ethyl group of carboxy group. Moreover, the acid which has hydroxy groups, such as hydroxyphthalic acid and hydroxy trimellitic acid, can also be mentioned. Two or more of these acids can also be used. From the viewpoint of solubility in alkali developer and photosensitivity, the structural unit preferably contains 50 mol% or more of an acid residue having a hydroxy group. R 1c preferably has an aromatic ring from the viewpoint of heat resistance, and is preferably a trivalent or tetravalent organic group having 6 to 30 carbon atoms.
　式（Ｍ－１）中、Ｒ２ｃは炭素数２以上の（２＋ｑ＋ｒ）価の有機基を示す。この有機基としては、置換又は非置換の炭化水素基や、置換又は非置換の炭化水素基が酸素原子で連結された基（エーテル基）等を挙げることができる。Ｒ２ｃは、ジアミンに由来する構造である。Ｒ２ｃは、耐熱性の点から芳香族環を有することが好ましい。ジアミンとしては、フェニレンジアミン、ジアミノジフェニルエーテル、アミノフェノキシベンゼン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ビス（トリフルオロメチル）ベンチジン、ビス（アミノフェノキシフェニル）プロパン、ビス（アミノフェノキシフェニル）スルホン、ビス（アミノ－ヒドロキシ－フェニル）ヘキサフルオロプロパン、ジアミノジヒドロキシピリミジン、ジアミノジヒドロキシピリジン、ヒドロキシ－ジアミノ－ピリミジン、ジアミノフェノール、ジヒドロキシベンチジン、ジアミノ安息香酸、ジアミノテレフタル酸、２，２’－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、これらの芳香族環の水素をアルキル基やハロゲン原子で置換した化合物や、脂肪族のシクロヘキシルジアミン、メチレンビスシクロヘキシルアミン、ヘキサメチレンジアミン等を挙げることができる。 In Formula (M-1), R 2c represents a (2 + q + r) -valent organic group having 2 or more carbon atoms. Examples of the organic group include a substituted or unsubstituted hydrocarbon group and a group (ether group) in which a substituted or unsubstituted hydrocarbon group is linked by an oxygen atom. R 2c is a structure derived from diamine. R 2c preferably has an aromatic ring from the viewpoint of heat resistance. Examples of diamines include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone, and bis (amino-hydroxy). -Phenyl) hexafluoropropane, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybenzidine, diaminobenzoic acid, diaminoterephthalic acid, 2,2'-bis (3-amino-4-hydroxy) Phenyl) hexafluoropropane, compounds in which the hydrogens of these aromatic rings are substituted with alkyl groups or halogen atoms, and aliphatic cyclohexanes. Examples include xyldiamine, methylenebiscyclohexylamine, and hexamethylenediamine.
　式（Ｍ－１）中、Ｒ３ｃ及びＲ４ｃは、それぞれ独立して、水素原子又は炭素数１～２０の１価の有機基である。この有機基としては、置換又は非置換の脂肪族又は芳香族炭化水素基等を挙げることができる。アルカリ現像液に対する溶解性と、得られる感放射線性樹脂組成物の溶液安定性の点から、Ｒ３ｃ及びＲ４ｃのそれぞれ１０モル％以上９０モル％以下が水素原子であることが好ましい。さらには、Ｒ３及びＲ４が、それぞれ炭素数１～１６の１価の炭化水素基を少なくとも１つ以上含有し、その他は水素原子であることがより好ましい。 In formula (M-1), R 3c and R 4c are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Examples of the organic group include a substituted or unsubstituted aliphatic or aromatic hydrocarbon group. From the viewpoint of solubility in an alkali developer and solution stability of the resulting radiation-sensitive resin composition, it is preferable that 10 mol% or more and 90 mol% or less of R 3c and R 4c are hydrogen atoms. Furthermore, it is more preferable that R 3 and R 4 each contain at least one monovalent hydrocarbon group having 1 to 16 carbon atoms, and the others are hydrogen atoms.
　式（Ｍ－１）中、ｐ及びｑは、それぞれ独立して、０～４の整数であり、ｐ＋ｑ＞０が好ましい。また、ｍ１及びｒは、それぞれ独立して、０～２の整数であり、１及び２が好ましい。ｎ８は、１０以上１００，０００以下である。ｎ８が１０未満であると、ポリマーのアルカリ現像液への溶解性が大きくなり過ぎ、露光部と非露光部のコントラストが得られず所望のパターンが形成できない場合がある。一方、ｎ８が１００，０００より大きいと、ポリマーのアルカリ現像液への溶解性が小さくなり過ぎ、露光部が溶解せず、所望のパターンが形成できない場合がある。ポリマーのアルカリ現像液への溶解性などの点から、ｎ８の上限としては１，０００が好ましく、１００がより好ましい。また、溶解性や伸度向上などの点から、ｎ８の下限としては２０が好ましい。 In the formula (M-1), p and q are each independently an integer of 0 to 4, and p + q> 0 is preferable. M 1 and r are each independently an integer of 0 to 2, with 1 and 2 being preferred. n 8 is 10 to 100,000. If n8 is less than 10, the solubility of the polymer in an alkaline developer becomes too high, and the contrast between the exposed area and the unexposed area cannot be obtained, and a desired pattern may not be formed. On the other hand, the n 8 is greater than 100,000, too small solubility in an alkaline developer of the polymer, exposed portions not dissolved, a desired pattern can not be formed. From the viewpoint of solubility of the polymer in an alkaline developer, the upper limit of n 8 is preferably 1,000, and more preferably 100. Further, in view of solubility and elongation enhancer, 20 is preferably a lower limit of n 8.
（（Ａ－３）ポリシロキサン）
　（Ａ－３）ポリシロキサンは、シロキサン結合を有する重合体であれば特に制限されないが、加水分解性シラン化合物の加水分解縮合物が好ましい。 ((A-3) Polysiloxane)
(A-3) The polysiloxane is not particularly limited as long as it is a polymer having a siloxane bond, but is preferably a hydrolyzed condensate of a hydrolyzable silane compound.
　「加水分解性シラン化合物」とは、通常、無触媒かつ過剰の水の共存下、室温（約２５℃）以上１００℃以下の温度範囲内で加熱することにより、加水分解してシラノール基又はシロキサン縮合物を生成する加水分解基を有する化合物をいう。なお、当該感放射線性樹脂組成物中において、一部の加水分解性シラン化合物は、その分子中の一部又は全部の加水分解性基が未加水分解の状態で、かつ他の加水分解性シラン化合物と縮合せずに単量体の状態で残っていてもよい。 The “hydrolyzable silane compound” is usually a silanol group or siloxane that is hydrolyzed by heating in the temperature range of room temperature (about 25 ° C.) to 100 ° C. in the presence of non-catalyst and excess water. A compound having a hydrolyzable group that forms a condensate. In the radiation-sensitive resin composition, some of the hydrolyzable silane compounds have a part or all of the hydrolyzable groups in the molecule in an unhydrolyzed state and other hydrolyzable silanes. It may remain in a monomer state without condensing with the compound.
　「加水分解縮合物」は、加水分解されたシラン化合物の一部のシラノール基同士が縮合した加水分解縮合物を意味する。 "Hydrolysis condensate" means a hydrolysis condensate obtained by condensing some silanol groups of a hydrolyzed silane compound.
　加水分解性シラン化合物としては、下記式（Ｓ－１）で表される化合物（以下、「（Ｓ１）化合物」とも言う。）を挙げることができる。 Examples of the hydrolyzable silane compound include a compound represented by the following formula (S-1) (hereinafter also referred to as “(S1) compound”).
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　式（Ｓ－１）中、Ｒ１ｄは、炭素数１～６のアルキル基である。Ｒ２ｄは、水素原子、炭素数１～２０のアルキル基、炭素数１～２０のフッ化アルキル基、フェニル基、トリル基、ナフチル基、エポキシ基、３，４－シクロエポキシ基、オキセタニル基、アミノ基又はイソシアネート基である。ｑ１は０～２０の整数である。ｎ９は０～３の整数である。但し、Ｒ１ｄ及びＲ２ｄが複数となる場合、複数のＲ１ｄ及びＲ２ｄはそれぞれ独立して上記定義を満たす。 In formula (S-1), R 1d is an alkyl group having 1 to 6 carbon atoms. R 2d is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a fluorinated alkyl group having 1 to 20 carbon atoms, a phenyl group, a tolyl group, a naphthyl group, an epoxy group, a 3,4-cycloepoxy group, an oxetanyl group, An amino group or an isocyanate group. q 1 is an integer of 0-20. n 9 is an integer of 0 to 3. However, if the R 1d and R 2d is more, the plurality of R 1d and R 2d each independently satisfy the above definition.
　上記Ｒ１ｄで表される炭素数１～６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、ｉ－プロピル基、ブチル基等が挙げられる。これらのうち、加水分解の容易性の観点から、メチル基及びエチル基が好ましい。 Examples of the alkyl group having 1 to 6 carbon atoms represented by R 1d include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and a butyl group. Among these, a methyl group and an ethyl group are preferable from the viewpoint of easy hydrolysis.
　上記Ｒ２ｄで表される炭素数１～２０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、ｉ－プロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、３－メチルブチル基、２－メチルブチル基、１－メチルブチル基、２，２－ジメチルプロピル基、ｎ－ヘキシル基、４－メチルペンチル基、３－メチルペンチル基、２－メチルペンチル基等が挙げられる。炭素数１～２０のアルキル基の炭素数としては、１～１０が好ましく、１～３がより好ましい。 Examples of the alkyl group having 1 to 20 carbon atoms represented by R 2d include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, n-pentyl group, 3-methylbutyl group, 2-methylbutyl group, 1-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group Etc. The carbon number of the alkyl group having 1 to 20 carbon atoms is preferably 1 to 10 and more preferably 1 to 3.
　炭素数１～６のフッ化アルキル基としては、トリフルオロメチル基、テトラフルオロエチル基、ヘプタフルオロプロピル基等が挙げられる。 Examples of the fluorinated alkyl group having 1 to 6 carbon atoms include a trifluoromethyl group, a tetrafluoroethyl group, and a heptafluoropropyl group.
　ｎ９が１の（Ｓ－１）化合物は、１個の非加水分解性基と３個の加水分解性基とを有するシラン化合物である。このシラン化合物としては、例えばメチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリ－ｉ－プロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリ－ｉ－プロポキシシラン、エチルトリブトキシシラン、ブチルトリメトキシシラン、フェニルトリメトキシシラン、トリルトリメトキシシラン、ナフチルトリメトキシシラン、フェニルトリエトキシシラン、ナフチルトリエトキシシラン、アミノトリメトキシシラン、アミノトリエトキシシラン、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシ、γ－グリシドキシプロピルトリメトキシシラン、３－イソシアノプロピルトリメトキシシラン、３－イソシアノプロピルトリエトキシシランｏ－トリルトリメトキシシラン、ｍ－トリルトリメトキシシランｐ－トリルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、２－メタクリロキシエチルトリメトキシシラン、２－メタクリロキシエチルトリエトキシシラン、２－メタクリロキシエチルトリプロポキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－メタクリロキシプロピルトリプロポキシシラン、２－アクリロキシエチルトリメトキシシラン、２－アクリロキシエチルトリエトキシシラン、２－アクリロキシエチルトリプロポキシシラン、３－アクリロキシプロピルトリメトキシシラン、３－アクリロキシプロピルトリエトキシシラン、３－アクリロキシプロピルトリプロポキシシラン、３－メタクリロキシプロピルトリメトキシシラン、３－メタクリロキシプロピルトリエトキシシラン、３－メタクリロキシプロピルトリプロポキシシラン、トリフルオロプロピルトリメトキシシラン、トリフルオロプロピルトリエトキシシラン、トリフルオロブチルトリメトキシシラン、３－（トリメトキシシリル）プロピル無水コハク酸等のトリアルコキシシラン化合物等が挙げられる。 The (S-1) compound having n 9 of 1 is a silane compound having one non-hydrolyzable group and three hydrolyzable groups. Examples of the silane compound include methyltrimethoxysilane, methyltriethoxysilane, methyltri-i-propoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-i-propoxysilane, and ethyltributoxysilane. , Butyltrimethoxysilane, phenyltrimethoxysilane, tolyltrimethoxysilane, naphthyltrimethoxysilane, phenyltriethoxysilane, naphthyltriethoxysilane, aminotrimethoxysilane, aminotriethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxy, γ-glycidoxypropyltrimethoxysilane, 3-isocyanopropyltrimethoxysilane, 3-isocyanopropyltriethoxysilane o-tolyl Limethoxysilane, m-tolyltrimethoxysilane, p-tolyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 2-methacryloxyethyltrimethoxysilane, 2-methacryloxyethyltriethoxysilane, 2-methacryloxyethyltripropoxy Silane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, 2-acryloxyethyltrimethoxysilane, 2-acryloxyethyltriethoxysilane, 2-acrylic Loxyethyltripropoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyltripropoxysilane, 3-methacryl Roxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltripropoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, trifluorobutyltrimethoxysilane, 3- (trimethoxy And trialkoxysilane compounds such as silyl) propyl succinic anhydride.
　ｎ９が２の（Ｓ－１）化合物は、２個の非加水分解性基と２個の加水分解性基とを有するシラン化合物である。このシラン化合物としては、例えば３－メタクリロキシプロピルメチルジメトキシシラン、γ－グリシドキシプロピルメチルジメトキシシラン、γ－アミノプロピルメチルジメトキシシラン、γ－イソシアネートプロピルメチルジメトキシシラン等が挙げられる。 The (S-1) compound having n 9 of 2 is a silane compound having two non-hydrolyzable groups and two hydrolyzable groups. Examples of the silane compound include 3-methacryloxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-isocyanatopropylmethyldimethoxysilane.
　ｎ９が３の（Ｓ－１）化合物は、３個の非加水分解性基と１個の加水分解性基とを有するシラン化合物である。このシラン化合物としては、例えば３－メタクリロキシプロピルジメチルメトキシシラン、γ－グリシドキシプロピルジメチルメトキシシラン、γ－アミノプロピルジメチルメトキシシラン、γ－イソシアネートプロピルジメチルメトキシシラン等が挙げられる。 The (S-1) compound having n 9 of 3 is a silane compound having three non-hydrolyzable groups and one hydrolyzable group. Examples of the silane compound include 3-methacryloxypropyldimethylmethoxysilane, γ-glycidoxypropyldimethylmethoxysilane, γ-aminopropyldimethylmethoxysilane, γ-isocyanatopropyldimethylmethoxysilane, and the like.
　ｎ９が０の（Ｓ－１）化合物は、４個の加水分解性基を有するシラン化合物である。このシラン化合物としては、例えばテトラメトキシシラン、テトラエトキシシラン、テトラブトキシシラン、テトラ－ｎ－プロポキシシラン、テトラ－ｉ－プロポキシシラン等が挙げられる。 The (S-1) compound in which n 9 is 0 is a silane compound having four hydrolyzable groups. Examples of the silane compound include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane and the like.
（ポリシロキサンの合成（加水分解縮合））
　ポリシロキサンは、通常、過剰の水の共存下、必要に応じて溶媒や触媒の共存下、室温（約２５℃）以上１００℃以下の温度範囲内で加熱し、加水分解性シラン化合物の加水分解により得られるシラノール基を縮合することで合成できる。 (Synthesis of polysiloxane (hydrolysis condensation))
Polysiloxane is usually heated in the temperature range of room temperature (about 25 ° C.) to 100 ° C. in the presence of excess water and optionally in the presence of a solvent or catalyst to hydrolyze the hydrolyzable silane compound. It can synthesize | combine by condensing the silanol group obtained by this.
　加水分解縮合反応のための溶媒としては、例えばアルコール類、エーテル類、グリコールエーテル、エチレングリコールアルキルエーテルアセテート、ジエチレングリコールアルキルエーテル、プロピレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテルアセテート、プロピレングリコールモノアルキルエーテルプロピオネート、芳香族炭化水素類、ケトン類、他のエステル類等が挙げられる。これらの溶媒は、単独で使用してもよく２種以上を併用してもよい。加水分解縮合反応のための触媒としては、酸触媒、塩基触媒、アルコキシドが好ましい。 Examples of the solvent for the hydrolysis condensation reaction include alcohols, ethers, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether Pionate, aromatic hydrocarbons, ketones, other esters and the like can be mentioned. These solvents may be used alone or in combination of two or more. As a catalyst for hydrolysis condensation reaction, an acid catalyst, a base catalyst, and an alkoxide are preferable.
　加水分解縮合物等のポリシロキサンのＧＰＣによるポリスチレン換算重量平均分子量（Ｍｗ）の下限値としては、５００が好ましく、１，０００がより好ましい。一方、この上限値としては、１５，０００が好ましく、１０，０００がより好ましい。ポリシロキサンのＭｗを上記下限値以上とすることで、当該感放射線性樹脂組成物の成膜性を改善できる。一方、ポリシロキサンのＭｗを上記上限値以下とすることによって、当該感放射線性樹脂組成物の現像性の低下を防止できる。 As a lower limit of polystyrene-equivalent weight average molecular weight (Mw) by GPC of polysiloxane such as hydrolysis condensate, 500 is preferable, and 1,000 is more preferable. On the other hand, the upper limit is preferably 15,000 and more preferably 10,000. By making Mw of polysiloxane more than the said lower limit, the film formability of the said radiation sensitive resin composition can be improved. On the other hand, by making Mw of the polysiloxane not more than the above upper limit value, it is possible to prevent the developability of the radiation-sensitive resin composition from being lowered.
（（Ａ－４）芳香族ポリエーテル）
　（Ａ－４）芳香族ポリエーテルは、芳香環がエーテル結合（酸素原子）で連結された構造を有するポリマーをいう。芳香族ポリエーテルとしては、下記式（Ｔ－１）で表される構造単位、下記式（Ｔ－２）で表される構造単位又はこれらの組み合わせを有するものが好ましい。 ((A-4) aromatic polyether)
(A-4) An aromatic polyether refers to a polymer having a structure in which aromatic rings are connected by an ether bond (oxygen atom). As the aromatic polyether, those having a structural unit represented by the following formula (T-1), a structural unit represented by the following formula (T-2), or a combination thereof are preferable.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式（Ｔ－１）中、Ｒ１ｅ～Ｒ４ｅは、それぞれ独立して、炭素数１～１２の１価の有機基である。ａ～ｄは、それぞれ独立して、０～４の整数である。 In formula (T-1), R 1e to R 4e are each independently a monovalent organic group having 1 to 12 carbon atoms. a to d are each independently an integer of 0 to 4.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　式（Ｔ－２）中、Ｒ１ｅ～Ｒ４ｅ及びａ～ｄの定義は、上記式（Ｔ－１）のものと同じである。Ｙは、単結合、－ＳＯ２－又は－Ｃ（＝Ｏ）－である。Ｒ５ｅ及びＲ６ｅは、それぞれ独立して、ハロゲン原子、炭素数１～１２の１価の有機基又はニトロ基である。ｅ及びｆは、それぞれ独立して、０～４の整数である。ｍ２は、０又は１である。但し、ｍ２が０のとき、Ｒ６ｅはシアノ基ではない。 In the formula (T-2), the definitions of R 1e to R 4e and a to d are the same as those in the above formula (T-1). Y is a single bond, —SO 2 — or —C (═O) —. R 5e and R 6e are each independently a halogen atom, a monovalent organic group having 1 to 12 carbon atoms, or a nitro group. e and f are each independently an integer of 0 to 4. m 2 is 0 or 1. However, when m 2 is 0, R 6e is not a cyano group.
　式（Ｔ－１）及び（Ｔ－２）中のＲ１ｅ～Ｒ４ｅで表される炭素数１～１２の１価の有機基としては、脂肪族又は芳香族の炭化水素基、アルコキシ基、カルボキシ基等を挙げることができる。 Examples of the monovalent organic group having 1 to 12 carbon atoms represented by R 1e to R 4e in the formulas (T-1) and (T-2) include an aliphatic or aromatic hydrocarbon group, an alkoxy group, A carboxy group etc. can be mentioned.
　（Ａ－４）芳香族ポリエーテルとしては、下記式（Ｔ－３）で表される構造単位、下記式（Ｔ－４）で表される構造単位又はこれらの組み合わせを有することも好ましい。 (A-4) The aromatic polyether preferably has a structural unit represented by the following formula (T-3), a structural unit represented by the following formula (T-4), or a combination thereof.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　上記式（Ｔ－３）中、Ｒ７ｅ及びＲ８ｅは、それぞれ独立して、炭素数１～１２の１価の有機基である。Ｚは、単結合、－Ｏ－、－Ｓ－、－ＳＯ２－、＞Ｃ＝Ｏ、－ＣＯＮＨ－、－ＣＯＯ－、炭素数１～１２の２価の炭化水素基、又は炭素数１～１２の２価の炭化水素基の水素原子の少なくとも一部がカルボキシ基、ヒドロキシ基、スルホ基及びフッ素原子からなる群より選ばれる少なくとも１種で置換された基である。ｇ及びｈは、それぞれ独立して、０～４の整数である。ｎは、０又は１である。 In the above formula (T-3), R 7e and R 8e are each independently a monovalent organic group having 1 to 12 carbon atoms. Z is a single bond, —O—, —S—, —SO 2 —,> C═O, —CONH—, —COO—, a divalent hydrocarbon group having 1 to 12 carbon atoms, or 1 to 12 is a group in which at least part of hydrogen atoms of 12 divalent hydrocarbon groups is substituted with at least one selected from the group consisting of a carboxy group, a hydroxy group, a sulfo group and a fluorine atom. g and h are each independently an integer of 0 to 4. n is 0 or 1.
　Ｒ７ｅ及びＲ８ｅで表される炭素数１～１２の１価の有機基としては、脂肪族又は芳香族の炭化水素基、アルコキシ基、カルボキシ基等を挙げることができる。 Examples of the monovalent organic group having 1 to 12 carbon atoms represented by R 7e and R 8e include an aliphatic or aromatic hydrocarbon group, an alkoxy group, and a carboxy group.
　Ｚで表される炭素数１～１２の２価の炭化水素基としては、メタンジイル基、エタン－１，１－ジイル基、プロパン－２，２－ジイル基、ｎ－ペンタン－２，２－ジイル基、ｎ－ヘキサン－２，２－ジイル基等のアルカンジイル基、アルケンジイル基、アレーンジイル基などを挙げることができる。 Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms represented by Z include methanediyl group, ethane-1,1-diyl group, propane-2,2-diyl group, and n-pentane-2,2-diyl. Groups, alkanediyl groups such as n-hexane-2,2-diyl group, alkenediyl groups, and arenediyl groups.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　上記式（Ｔ－４）中、Ｒ５ｅ、Ｒ６ｅ、Ｙ、ｍ２、ｅ及びｆは、それぞれ独立して、上記式（Ｔ－２）中のＲ５ｅ、Ｒ６ｅ、Ｙ、ｍ２、ｅ及びｆと同義である。Ｒ７ｅ、Ｒ８ｅ、Ｚ、ｎ、ｇ及びｈは、それぞれ独立して、上記式（Ｔ－３）中のＲ７ｅ、Ｒ８ｅ、Ｚ、ｎ、ｇ及びｈと同義である。 In the above formula (T-4), R 5e , R 6e , Y, m 2 , e and f are each independently R 5e , R 6e , Y, m 2 , in the above formula (T-2). It is synonymous with e and f. R 7e, R 8e, Z, n, g and h are each independently, R 7e in the formula (T-3), the same meanings as R 8e, Z, n, g and h.
　芳香族ポリエーテルのＧＰＣによるポリスチレン換算重量平均分子量（Ｍｗ）の下限値としては、３，０００が好ましく、５，０００がより好ましい。一方、この上限値としては、２０，０００が好ましく、１５，０００がより好ましい。Ｍｗを上記下限値以上とすることで、当該感放射線性樹脂組成物の成膜性を改善できる。一方、Ｍｗを上記上限値以下とすることによって、当該感放射線性樹脂組成物の現像性の低下を防止できる。 The lower limit of the weight average molecular weight (Mw) in terms of polystyrene by GPC of the aromatic polyether is preferably 3,000, and more preferably 5,000. On the other hand, the upper limit is preferably 20,000, and more preferably 15,000. By setting Mw to be equal to or higher than the lower limit, the film formability of the radiation sensitive resin composition can be improved. On the other hand, by making Mw equal to or less than the above upper limit value, it is possible to prevent the developability of the radiation sensitive resin composition from being lowered.
＜［Ｂ］酸発生体＞
　［Ｂ］酸発生体は、放射線の照射によって酸を発生する化合物である。ここで、放射線としては、例えば可視光線、紫外線、遠紫外線、電子線（荷電粒子線）、Ｘ線等を使用することができる。［Ｂ］酸発生体としては、放射線の照射によって酸（例えばカルボン酸、スルホン酸等）を発生させるものである限り、特に限定されない。［Ｂ］酸発生体の形態としては、後述するような化合物である酸発生剤の形態でもよく、重合体の一部として組み込まれた光酸発生基の形態でもよく、これらの両方の形態でもよい。 <[B] Acid generator>
[B] The acid generator is a compound that generates an acid upon irradiation with radiation. Here, as the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam (charged particle beam), X-ray or the like can be used. [B] The acid generator is not particularly limited as long as it generates an acid (for example, carboxylic acid, sulfonic acid, etc.) by irradiation with radiation. [B] The form of the acid generator may be the form of an acid generator that is a compound as described later, the form of a photoacid generator incorporated as part of a polymer, or both of these forms. Good.
　感放射線性酸発生剤としては、オキシムスルホネート化合物、オニウム塩、Ｎ－スルホニルオキシイミド（スルホンイミド化合物）、ハロゲン含有化合物、ジアゾメタン化合物、スルホン化合物、スルホン酸エステル化合物、カルボン酸エステル化合物、キノンジアジド化合物等が挙げられる。これらの中でも、オキシムスルホネート化合物及びＮ－スルホニルオキシイミドが好ましく、オキシムスルホネート化合物がさらにが好ましい。 Radiation sensitive acid generators include oxime sulfonate compounds, onium salts, N-sulfonyloxyimides (sulfonimide compounds), halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, quinone diazide compounds, etc. Is mentioned. Among these, an oxime sulfonate compound and N-sulfonyloxyimide are preferable, and an oxime sulfonate compound is more preferable.
（オキシムスルホネート化合物）
　上記オキシムスルホネート化合物としては、下記式（３）で表されるオキシムスルホネート基を含有する化合物が好ましい。 (Oxime sulfonate compound)
As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by following formula (3) is preferable.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　式（３）中、Ｒｂは、アルキル基、脂環式炭化水素基、アリール基又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。 In Formula (3), R b is an alkyl group, an alicyclic hydrocarbon group, an aryl group, or a group in which at least a part of hydrogen atoms of these groups is substituted with a substituent.
　上記式（３）において、Ｒｂで表されるアルキル基としては、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ヘキシル基、ｎ－オクチル基等の炭素数１～１０の直鎖状又は分岐状アルキル基を挙げることができる。Ｒｂで表される脂環式炭化水素基としては、シクロプロピル基、シクロヘキシル基等の単環又は多環の炭素数３～２０の脂環式炭化水素基を挙げることができる。Ｒｂで表されるアリール基としては、フェニル基、トリル基、ナフチル基等の炭素数６～２０のアリール基を挙げることができる。これらのアルキル基、脂環式炭化水素基、アリール基が有していてもよい置換基としては、ハロゲン原子、炭素数１～１０のアルコキシ基、脂環式基（７，７－ジメチル－２－オキソノルボルニル基等の有橋式脂環式基を含む、好ましくはビシクロアルキル基等）等を挙げることができる。 In the above formula (3), the alkyl group represented by R b has 1 to 10 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-hexyl group, and n-octyl group. And a linear or branched alkyl group. Examples of the alicyclic hydrocarbon group represented by Rb include monocyclic or polycyclic alicyclic hydrocarbon groups having 3 to 20 carbon atoms such as a cyclopropyl group and a cyclohexyl group. Examples of the aryl group represented by Rb include aryl groups having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group. Examples of the substituent that these alkyl groups, alicyclic hydrocarbon groups, and aryl groups may have include a halogen atom, an alkoxy group having 1 to 10 carbon atoms, and an alicyclic group (7,7-dimethyl-2). -A bridged alicyclic group such as an oxonorbornyl group, preferably a bicycloalkyl group).
　上記式（３）で表されるオキシムスルホネート基を含有する化合物としては、例えば下記式（３－ｉ）～（３－ｖ）でそれぞれ表される化合物等が挙げられる。 Examples of the compound containing an oxime sulfonate group represented by the above formula (3) include compounds represented by the following formulas (3-i) to (3-v).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　上記化合物（３－ｉ）［（５－プロピルスルフォニルオキシイミノ－５Ｈ－チオフェン－２－イリデン）－（２－メチルフェニル）アセトニトリル］、化合物（３－ｉｉ）［（５Ｈ－オクチルスルフォニルオキシイミノ－５Ｈ－チオフェン－２－イリデン）－（２－メチルフェニル）アセトニトリル］、化合物（３－ｉｉｉ）［（カンファースルフォニルオキシイミノ－５Ｈ－チオフェン－２－イリデン）－（２－メチルフェニル）アセトニトリル］、化合物（３－ｉｖ）［（５－ｐ－トルエンスルフォニルオキシイミノ－５Ｈ－チオフェン－２－イリデン）－（２－メチルフェニル）アセトニトリル］、及び化合物（３－ｖ）２－（オクチルスルホニルオキシイミノ）－２－（４－メトキシフェニル）アセトニトリルは、市販品として入手できる。 Compound (3-i) [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], compound (3-ii) [(5H-octylsulfonyloxyimino-5H -Thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], compound (3-iii) [(camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], compound ( 3-iv) [(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], and compound (3-v) 2- (octylsulfonyloxyimino) -2 -(4-Methoxyphenyl) acetonitrile is available as a commercial product It can be.
（Ｎ－スルホニルオキシイミド（スルホンイミド化合物））
　上記Ｎ－スルホニルオキシイミド（スルホンイミド化合物）としては、例えばＮ－（トリフルオロメチルスルホニルオキシ）スクシンイミド、Ｎ－（カンファスルホニルオキシ）スクシンイミド、Ｎ－（４－メチルフェニルスルホニルオキシ）スクシンイミド、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）スクシンイミド、Ｎ－（４－フルオロフェニルスルホニルオキシ）スクシンイミド、Ｎ－（トリフルオロメチルスルホニルオキシ）フタルイミド、Ｎ－（カンファスルホニルオキシ）フタルイミド、Ｎ－（２－トリフルオロメチルフェニルスルホニルオキシ）フタルイミド、Ｎ－（２－フルオロフェニルスルホニルオキシ）フタルイミド、Ｎ－（トリフルオロメチルスルホニルオキシ）ジフェニルマレイミド、Ｎ－（カンファスルホニルオキシ）ジフェニルマレイミド、トリフルオロメタンスルホン酸－１，８－ナフタルイミド等が挙げられる。 (N-sulfonyloxyimide (sulfonimide compound))
Examples of the N-sulfonyloxyimide (sulfonimide compound) include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- ( 2-trifluoromethylphenylsulfonyloxy) succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoro) Methylphenylsulfonyloxy) phthalimide, N- (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (can § sulfonyloxy) diphenyl maleimide, trifluoromethanesulfonic acid 1,8-naphthalimide and the like.
　感放射線性酸発生剤は、１種を単独で使用してもよいし、２種以上を混合して使用してもよい。当該感放射線性樹脂組成物における感放射線性酸発生剤の含有量の下限値としては、［Ａ］重合体１００質量部に対して、０．１質量部が好ましく、１質量部がより好ましい。一方、この上限値としては、１０質量部が好ましく、５質量部がより好ましい。感放射線性酸発生剤の含有量が上記範囲にあると、放射線感度を最適化することができ、また、得られる硬化膜の透明性等も好適なものとなる。 A radiation sensitive acid generator may be used individually by 1 type, and 2 or more types may be mixed and used for it. As a lower limit of content of the radiation sensitive acid generator in the said radiation sensitive resin composition, 0.1 mass part is preferable with respect to 100 mass parts of [A] polymers, and 1 mass part is more preferable. On the other hand, as this upper limit, 10 mass parts is preferable and 5 mass parts is more preferable. When the content of the radiation-sensitive acid generator is within the above range, the radiation sensitivity can be optimized, and the transparency of the resulting cured film is also suitable.
＜［Ｃ］化合物＞
　［Ｃ］化合物は、下記式（１－１）～（１－６）で表される化合物である。これらの化合物はそれぞれ単独で、又は互いに組み合わせて使用することができる。 <[C] Compound>
The compound [C] is a compound represented by the following formulas (1-1) to (1-6). These compounds can be used alone or in combination with each other.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　式（１－１）～（１－６）中、１又は複数のＸは、それぞれ独立して、酸解離性基を有する有機基である。
　式（１－１）中、複数のＲ１は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。ｎ１は、１～３の整数である。ｎ２は、０～２の整数である。
　式（１－２）中、複数のＲ２は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。Ａは、単結合、メチレン基（エタンジイル基）、炭素数２～１２のアルキレン基（アルカンジイル基）、フェニレン基（ベンゼンジイル基）、酸素原子、硫黄原子、又はメチレン基、炭素数２～１２のアルキレン基若しくはフェニレン基が有する水素原子の少なくとも一部が下記式（１－７）で表される基、フッ素原子若しくはカルボキシ基で置換された基である。ｎ３は、１～３の整数である。ｎ４は、１～３の整数である。
　式（１－３）中、複数のＲ３及び複数のＲ４は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、これらの基が有する水素原子の少なくとも一部が置換基で置換された基、又は下記式（１－７）で表される基である。
　式（１－４）中、複数のＲ５は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。ｍは、０～１０の整数である。
　式（１－５）中、複数のＲ６は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。ｐは、０～１０の整数である。
　式（１－６）中、Ｒ７は、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。ｎ５は、１～３の整数である。ｎ６は、１～５の整数である。ｎ７は、０～５の整数である。ｎ７が２以上である場合、複数のＲ７は、それぞれ同一でも異なっていてもよい。 In formulas (1-1) to (1-6), one or more Xs are each independently an organic group having an acid dissociable group.
In the formula (1-1), a plurality of R 1 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent. n 1 is an integer of 1 to 3. n 2 is an integer of 0-2.
In formula (1-2), a plurality of R 2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent. A represents a single bond, a methylene group (ethanediyl group), an alkylene group having 2 to 12 carbon atoms (alkanediyl group), a phenylene group (benzenediyl group), an oxygen atom, a sulfur atom, or a methylene group, and 2 to 12 carbon atoms. At least a part of the hydrogen atoms of the alkylene group or phenylene group is a group represented by the following formula (1-7), a group substituted with a fluorine atom or a carboxy group. n 3 is an integer of 1 to 3. n 4 is an integer of 1 to 3.
In formula (1-3), a plurality of R 3 and a plurality of R 4 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon. A group, an aryl group, a group in which at least part of hydrogen atoms of these groups are substituted with a substituent, or a group represented by the following formula (1-7).
In formula (1-4), a plurality of R 5 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent. m is an integer of 0 to 10.
In formula (1-5), a plurality of R 6 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent. p is an integer of 0 to 10.
In formula (1-6), R 7 represents at least one of an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or a hydrogen atom included in these groups. A part of the group is substituted with a substituent. n 5 is an integer of 1 to 3. n 6 is an integer of 1 to 5. n 7 is an integer of 0 to 5. When n 7 is 2 or more, the plurality of R 7 may be the same or different from each other.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　式（１－７）中、Ｘは、酸解離性基を有する有機基である。複数のＲ８は、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の一部又は全部が置換基で置換された基である。＊は、結合する部位を示す。 In formula (1-7), X represents an organic group having an acid dissociable group. The plurality of R 8 are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or a part or all of hydrogen atoms possessed by these groups Is a group substituted with a substituent. * Indicates a binding site.
　Ｘで表される酸解離性基を有する有機基における酸解離性基とは、カルボキシ基やフェノール性水酸基等の水素原子を置換し、酸の作用により解離し得る基をいう。有機基とは、少なくとも１個の炭素原子を含む基をいう。Ｘで表される酸解離性基においては、酸解離性基の解離により、カルボキシ基やフェノール性水酸基等が生じる。 The acid dissociable group in the organic group having an acid dissociable group represented by X refers to a group that can be dissociated by the action of an acid by replacing a hydrogen atom such as a carboxy group or a phenolic hydroxyl group. An organic group refers to a group containing at least one carbon atom. In the acid dissociable group represented by X, the dissociation of the acid dissociable group generates a carboxy group or a phenolic hydroxyl group.
　Ｘで表される酸解離性基を有する有機基としては、下記式（２－１）又は式（２－２）で表される基を挙げることができる。Ｘで表される有機基がこのような構造の酸解離性基を含む場合、加熱によってもこの酸解離性基が解離することができる。従って、このような基を含む［Ｃ］化合物は、現像後の加熱工程において酸となり、［Ａ］重合体の硬化反応を促進させることなどもできる。 Examples of the organic group having an acid-dissociable group represented by X include groups represented by the following formula (2-1) or formula (2-2). When the organic group represented by X includes an acid dissociable group having such a structure, the acid dissociable group can be dissociated even by heating. Accordingly, the [C] compound containing such a group becomes an acid in the heating step after development, and can accelerate the curing reaction of the [A] polymer.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　式（２－１）中、Ｒ１ａ及びＲ２ａは、それぞれ独立して、水素原子、炭素数１～３０の炭化水素基、又はこの炭化水素基が有する水素原子の少なくとも一部がヒドロキシ基、ハロゲン原子若しくはシアノ基で置換された基である。但し、Ｒ１ａ及びＲ２ａが共に水素原子である場合はない。Ｒ３ａは、炭素数１～３０の炭化水素基、この炭素水素基の炭素－炭素間若しくは結合手側末端に酸素原子を含む基、又はこれらの基が有する水素原子の少なくとも一部がヒドロキシ基、ハロゲン原子若しくはシアノ基で置換された基である。Ｙ１は、単結合、カルボニル基又は－Ｚ１－Ｃ（＝Ｏ）－で表される基である。Ｚ１は、炭素数１～２０の２価の連結基である。 In formula (2-1), R 1a and R 2a each independently represent a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or at least a part of the hydrogen atoms of the hydrocarbon group is a hydroxy group, A group substituted by a halogen atom or a cyano group. However, there is no case where R 1a and R 2a are both hydrogen atoms. R 3a is a hydrocarbon group having 1 to 30 carbon atoms, a group containing an oxygen atom at the carbon-carbon boundary or bond-side terminal of the carbon hydrogen group, or at least a part of the hydrogen atoms of these groups is a hydroxy group , A group substituted with a halogen atom or a cyano group. Y 1 is a single bond, a carbonyl group or a group represented by —Z 1 —C (═O) —. Z 1 is a divalent linking group having 1 to 20 carbon atoms.
　式（２－２）中、Ｒ４ａ～Ｒ１０ａは、それぞれ独立して、水素原子又は炭素数１～１２の炭化水素基である。ｒは、１又は２である。ｒが２の場合、複数のＲ７ａ及びＲ８ａは、それぞれ同一でも異なっていてもよい。Ｙ２は、単結合、カルボニル基又は－Ｚ２－Ｃ（＝Ｏ）－で表される基である。Ｚ２は、炭素数１～１０の２価の連結基である。 In formula (2-2), R 4a to R 10a are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. r is 1 or 2. When r is 2, the plurality of R 7a and R 8a may be the same or different. Y 2 is a single bond, a carbonyl group or a group represented by —Z 2 —C (═O) —. Z 2 is a divalent linking group having 1 to 10 carbon atoms.
　上記Ｒ１ａ～Ｒ３ａで表される炭素数１～３０の炭化水素基としては、炭素数１～３０の直鎖状及び分岐状アルキル基、炭素数３～３０の脂環式炭化水素基、炭素数６～３０の芳香族炭化水素基等を挙げることができる。 Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R 1a to R 3a include linear and branched alkyl groups having 1 to 30 carbon atoms, alicyclic hydrocarbon groups having 3 to 30 carbon atoms, Examples thereof include aromatic hydrocarbon groups having 6 to 30 carbon atoms.
　直鎖状及び分岐状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－オクチル基、ｎ－ドデシル基、ｎ－テトラデシル基、ｎ－オクタデシル基等の直鎖状アルキル基、ｉ－プロピル基、ｉ－ブチル基、ｔ－ブチル基、ネオペンチル基、２－ヘキシル基、３－ヘキシル基等の分岐状アルキル基等が挙げられる。 Examples of the linear and branched alkyl groups include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n- Linear alkyl groups such as tetradecyl group, n-octadecyl group, branched alkyl groups such as i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group, 3-hexyl group, etc. Can be mentioned.
　脂環式炭化水素基は、単環でも多環でもよく、例えばシクロプロピル基、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、ボルニル基、ノルボルニル基、アダマンチル基等が挙げられる。 The alicyclic hydrocarbon group may be monocyclic or polycyclic, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a bornyl group, a norbornyl group, and an adamantyl group.
　芳香族炭化水素基は、単環、単環が連結した構造、縮合環でもよく、芳香環と脂肪族炭化水素基とが連結した構造であってもよい。芳香族炭化水素基しては、例えばフェニル基、ナフチル基、トリル基、ベンジル基等が挙げられる。 The aromatic hydrocarbon group may be a single ring, a structure in which a single ring is linked, a condensed ring, or a structure in which an aromatic ring and an aliphatic hydrocarbon group are linked. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, a tolyl group, and a benzyl group.
　上記Ｒ１ａとしては、水素原子が好ましい。
　上記Ｒ２ａとしては、炭素数１～６の直鎖状及び分岐状アルキル基が好ましく、メチル基がより好ましい。
　上記Ｒ３ａとしては、結合手側末端に酸素原子を含む炭素数１～３０の炭化水素基（炭素数１～３０のアルコキシ基）が好ましく、炭素数１～２０の直鎖状及び分岐状アルコキシ基並びに炭素数３～２０のシクロアルコキシ基がより好ましく、炭素数１～８の直鎖状及び分岐状アルコキシ基並びに炭素数３～８のシクロアルコキシ基がさらに好ましい。 R 1a is preferably a hydrogen atom.
R 2a is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group.
R 3a is preferably a hydrocarbon group having 1 to 30 carbon atoms (an alkoxy group having 1 to 30 carbon atoms) containing an oxygen atom at the terminal end on the bond side, and a linear or branched alkoxy group having 1 to 20 carbon atoms. And a cycloalkoxy group having 3 to 20 carbon atoms, more preferably a linear or branched alkoxy group having 1 to 8 carbon atoms and a cycloalkoxy group having 3 to 8 carbon atoms.
　上記Ｚ１で表される炭素数１～２０の２価の連結基としては、炭素数１～２０の２価の鎖状炭化水素基、炭素数３～２０の２価の脂環式炭化水素基、炭素数６～２０の２価の芳香族炭化水素基等の２価の炭化水素基や、これらの２価の炭化水素基の結合部位側末端に－Ｏ－、－ＳＯ－、－ＳＯ２－、－ＯＳＯ２－、－ＣＯ－、－ＣＯＮＨ－等の２価のヘテロ原子含有基が連結した基を例示することができる。 Examples of the divalent linking group having 1 to 20 carbon atoms represented by Z 1 include a divalent chain hydrocarbon group having 1 to 20 carbon atoms and a divalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. A divalent hydrocarbon group such as a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or —O—, —SO—, —SO at the end of the bond site of these divalent hydrocarbon groups. 2 -, - OSO 2 -, - CO -, - CONH- divalent heteroatom-containing group is a linking group such as may be exemplified.
　２価の鎖状炭化水素基としては、メタンジイル基、エタンジイル基等のアルカンジイル基、エテンジイル基等のアルケンジイル基等を挙げることができる。２価の脂環式炭化水素基としては、シクロヘキサンジイル基等のシクロアルカンジイル基等を挙げることができる。２価の芳香族炭化水素基としては、ベンゼンジイル基、トルエンジイル基、インデンジイル基等の単環、多環、芳香環と脂肪族炭化水素基とが連結した構造、芳香環と脂環との縮合環等を挙げることができる。 Examples of the divalent chain hydrocarbon group include alkanediyl groups such as methanediyl group and ethanediyl group, and alkenediyl groups such as ethenediyl group. Examples of the divalent alicyclic hydrocarbon group include cycloalkanediyl groups such as cyclohexanediyl group. Examples of the divalent aromatic hydrocarbon group include benzenediyl group, toluenediyl group, indenediyl group and other monocycles, polycycles, structures in which an aromatic ring and an aliphatic hydrocarbon group are linked, and aromatic rings and alicyclic rings. A condensed ring etc. can be mentioned.
　上記Ｚ１としては、－Ｏ－ＣＨ２－及び下記式で表される連結基が好ましい。 Z 1 is preferably —O—CH 2 — and a linking group represented by the following formula.
Figure JPOXMLDOC01-appb-C000018
 　上記式中の２つの＊は、それぞれ結合する部位を示す。
Figure JPOXMLDOC01-appb-C000018
 Two * s in the above formulas indicate the sites to be bonded to.
　上記Ｒ４ａ～Ｒ１０ａで表される炭素数１～１２の炭化水素基としては、炭素数１～１２の直鎖状及び分岐状アルキル基、炭素数３～１２の脂環式炭化水素基、炭素数６～１２の芳香族炭化水素基を挙げることができる。これらの具体的例は、Ｒ１ａ～Ｒ３ａで表される炭化水素基として例示したものの一部等を挙げることができる。Ｒ４ａ～Ｒ１０ａとしては、水素原子が好ましい。 Examples of the hydrocarbon group having 1 to 12 carbon atoms represented by the above R 4a to R 10a include linear and branched alkyl groups having 1 to 12 carbon atoms, alicyclic hydrocarbon groups having 3 to 12 carbon atoms, Mention may be made of aromatic hydrocarbon groups having 6 to 12 carbon atoms. Specific examples thereof include a part of those exemplified as the hydrocarbon group represented by R 1a to R 3a . R 4a to R 10a are preferably hydrogen atoms.
　上記Ｚ２で表される炭素数１～２０の２価の連結基の具体的な基及び好ましい基は、上述した式（２－１）中のＺ１で表される炭素数１～２０の連結基と同様である。 Divalent particular groups and preferred groups of the linking group of the Z 2 at 1 to 20 carbon atoms represented is of 1 to 20 carbon atoms represented by Z 1 in the formula (2-1) described above The same as the linking group.
　式（１－１）～（１－７）中のＲ１～Ｒ８で表される炭素数１～１２のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基等が挙げられる。 Examples of the alkyl group having 1 to 12 carbon atoms represented by R 1 to R 8 in the formulas (1-1) to (1-7) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, Examples thereof include n-butyl group.
　上記Ｒ１～Ｒ８で表される炭素数１～１２のアルコキシ基としては、メトキシ基、エトキシ基、シクロヘキシルオキシ基等が挙げられる。 Examples of the alkoxy group having 1 to 12 carbon atoms represented by R 1 to R 8 include a methoxy group, an ethoxy group, and a cyclohexyloxy group.
　上記Ｒ１～Ｒ８で表される脂環式炭化水素基としては、シクロプロピル基、シクロヘキシル基、シクロプロペニル基等の炭素数３～１２の単環又は多環の脂環式炭化水素基等が挙げられる。 Examples of the alicyclic hydrocarbon group represented by R 1 to R 8 include a monocyclic or polycyclic alicyclic hydrocarbon group having 3 to 12 carbon atoms such as a cyclopropyl group, a cyclohexyl group, and a cyclopropenyl group. Is mentioned.
　上記Ｒ１～Ｒ８で表されるアリール基としては、フェニル基、トリル基、ナフチル基等の炭素数６～１２の単環又は多環のアリール基が挙げられる。 Examples of the aryl group represented by R 1 to R 8 include monocyclic or polycyclic aryl groups having 6 to 12 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.
　上記Ｒ１～Ｒ８で表される炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基及びアリール基が有する水素原子の一部又は全部を置換することができる置換基としては、塩素原子等のハロゲン原子、メトキシ基、エトキシ基等の炭素数１～６のアルコキシ基、ヒドロキシ基、カルボキシ基、シアノ基等が挙げられる。 Substituting part or all of the hydrogen atoms of the alkyl group having 1 to 12 carbon atoms, the alkoxy group having 1 to 12 carbon atoms, the alicyclic hydrocarbon group and the aryl group represented by R 1 to R 8. Examples of substituents that can be used include halogen atoms such as chlorine atoms, alkoxy groups having 1 to 6 carbon atoms such as methoxy groups and ethoxy groups, hydroxy groups, carboxy groups, and cyano groups.
　式（１－１）中のＲ１としては、水素原子が好ましい。水素原子以外のＲ１の数としては、０～２個が好ましく、０及び１個が好ましい。ｎ１としては、２及び３が好ましい。ｎ２としては、０及び１が好ましい。 R 1 in formula (1-1) is preferably a hydrogen atom. The number of R 1 other than a hydrogen atom is preferably 0 to 2, more preferably 0 and 1. n 1 is preferably 2 or 3. n 2 is preferably 0 or 1.
　式（１－２）中のＲ２としては、水素原子及び１個の水素原子がアルコキシ基で置換されていてもよいアルキル基（メトキシメチル基等）が好ましい。水素原子以外のＲ２の数としては、１つのベンゼン環あたり０～２個が好ましい。 R 2 in formula (1-2) is preferably a hydrogen atom or an alkyl group (such as a methoxymethyl group) in which one hydrogen atom may be substituted with an alkoxy group. The number of R 2 other than a hydrogen atom is preferably 0 to 2 per benzene ring.
　式（１－２）中のＡで表される炭素数２～１２のアルキレン基（アルカンジイル基）としては、エタン－１，１－ジイル基、エタン－１，２－ジイル基、プロパン－１，１－ジイル基、プロパン－２，２－ジイル基、プロパン－１，３－ジイル基、ｎ－ブタン－２，２－ジイル基、ｎ－ペンタン－２，２－ジイル基、ｎ－ヘキサン－２，２－ジイル基等を挙げることができる。Ａとしては、単結合、メチレン基、ヘキサフルオロプロパン－２，２－ジイル基及びメチレン基の水素原子の一つが式（１－７）で表される基で置換された基が好ましい。ｎ３及びｎ４としては、それぞれ１が好ましい。 Examples of the alkylene group having 2 to 12 carbon atoms (alkanediyl group) represented by A in the formula (1-2) include ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1 , 1-diyl group, propane-2,2-diyl group, propane-1,3-diyl group, n-butane-2,2-diyl group, n-pentane-2,2-diyl group, n-hexane- 2,2-diyl group and the like can be mentioned. A is preferably a single bond, a methylene group, a hexafluoropropane-2,2-diyl group or a group in which one of the hydrogen atoms of the methylene group is substituted with a group represented by the formula (1-7). n 3 and n 4 are each preferably 1.
　式（１－３）中のＲ３としては、水素原子が好ましい。水素原子以外のＲ３の数としては、１つのベンゼン環あたり０～２個が好ましく、０及び１個が好ましい。Ｒ４としては、水素原子、炭素数１～１２のアルキル基及び式（１－７）で表される基が好ましく、メチル基及び式（１－７）で表される基がより好ましい。 R 3 in formula (1-3) is preferably a hydrogen atom. The number of R 3 other than a hydrogen atom is preferably 0 to 2, more preferably 0 and 1, per benzene ring. R 4 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms and a group represented by the formula (1-7), more preferably a methyl group or a group represented by the formula (1-7).
　式（１－４）中のＲ５としては、水素原子及び炭素数１～１２のアルキル基が好ましく、水素原子及びメチル基がより好ましい。水素原子以外のＲ５の数としては、１つのベンゼン環あたり０～２個が好ましく、０及び１個が好ましい。ｍは０～２が好ましく、１がより好ましい。また、ｍは１以上であることも好ましい。 R 5 in formula (1-4) is preferably a hydrogen atom and an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom and a methyl group. The number of R 5 other than a hydrogen atom is preferably 0 to 2, more preferably 0 and 1, per benzene ring. m is preferably 0 to 2, and more preferably 1. M is preferably 1 or more.
　式（１－５）中のＲ６としては、水素原子及び炭素数１～１２のアルキル基が好ましく、水素原子及びメチル基がより好ましい。水素原子以外のＲ６の数としては、１つのベンゼン環あたり０～２個が好ましく、０及び１個が好ましい。ｐは０～２が好ましく、１がより好ましい。また、ｐは１以上であることも好ましい。 R 6 in the formula (1-5) is preferably a hydrogen atom and an alkyl group having 1 to 12 carbon atoms, more preferably a hydrogen atom and a methyl group. The number of R 6 other than a hydrogen atom is preferably 0 to 2, more preferably 0 or 1, per benzene ring. p is preferably 0 to 2, and more preferably 1. Further, p is preferably 1 or more.
　式（１－６）中のｎ５は、２が好ましい。ｎ６は、３～５が好ましく、４がより好ましい。ｎ７は、０が好ましい。 In formula (1-6), n 5 is preferably 2. n 6 is preferably 3 to 5, and more preferably 4. n 7 is preferably 0.
　式（１－７）中のＲ８としては、水素原子が好ましい。水素原子以外のＲ８の数としては、０～２個が好ましく、０及び１個が好ましい。 R 8 in formula (1-7) is preferably a hydrogen atom. The number of R 8 other than a hydrogen atom is preferably 0 to 2, more preferably 0 and 1.
　［Ｃ］化合物の具体例としては、例えば以下に示すような化合物（Ｃ－１）～（Ｃ－２５）を例示することができる。 Specific examples of the [C] compound include compounds (C-1) to (C-25) as shown below.
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　［Ｃ］化合物は、重合体では無く、例えば分子量３，０００以下の低分子化合物である。［Ｃ］化合物の分子量の下限値としては１００が好ましく、１５０がより好ましい。一方、この上限値としては、２，５００が好ましい。 The [C] compound is not a polymer but a low molecular compound having a molecular weight of 3,000 or less, for example. [C] The lower limit of the molecular weight of the compound is preferably 100, and more preferably 150. On the other hand, the upper limit is preferably 2,500.
　［Ｃ］化合物は、フェノール性水酸基又はカルボキシ基を有する芳香族化合物等のフェノール性水酸基又はカルボキシ基の水素原子を酸解離性基で置換することにより合成することが可能である。合成反応は、常法に従って反応させることができる。合成方法としては、例えば日本化学会編、新実験化学講座「有機化合物の合成と反応」（株）丸善発行（１９８８）、Ｊ．Ｆ．Ｗ．ＭｃＯｍｉｅ，Ｐｒｏｔｅｃｔｉｖｅ　Ｇｒｏｕｐｓ　ｉｎ　Ｏｒｇａｎｉｃ　Ｃｈｅｍｉｓｔｒｙ，Ｐｌｅｎｕｍ　Ｐｒｅｓｓ（１９７３）、Ｔ．Ｗ．Ｇｒｅｅｎｅ，Ｐｒｏｔｅｃｔｉｖｅ　Ｇｒｏｕｐｓ　ｉｎ　Ｏｒｇａｎｉｃ　Ｓｙｎｔｈｅｓｉｓ，Ｊｏｈｎ　Ｗｉｌｅｙ　＆　Ｓｏｎｓ（１９８１）に記載されている方法を挙げることができる。 The [C] compound can be synthesized by substituting a hydrogen atom of a phenolic hydroxyl group or carboxy group such as an aromatic compound having a phenolic hydroxyl group or carboxy group with an acid dissociable group. The synthesis reaction can be performed according to a conventional method. As the synthesis method, for example, the Chemical Society of Japan, New Experimental Chemistry Course “Synthesis and Reaction of Organic Compounds”, published by Maruzen Co., Ltd. (1988), J. Chem. F. W. McOmie, Protective Groups in Organic Chemistry, Plenum Press (1973), T.M. W. Examples include the methods described in Greene, Protective Groups in Organic Synthesis, John Wiley & Sons (1981).
　フェノール性水酸基又はカルボキシ基を有する芳香族化合物としては、例えば
　フェノール、クレゾール、チモール、４，４’，４’’－メチリジントリスフェノール、２，６－ビス［（２－ヒドロキシ－５－メチルフェニル）メチル］－４－メチルフェノール、α，α，α’－トリス（４－ヒドロキシフェニル）－１－エチル－４－イソプロピルベンゼン、３，３’，５，５’－テトラキス（メトキシメチル）ビフェニル－４，４’－ジオール等のフェノール性水酸基を有する芳香族化合物；
　安息香酸、フタル酸、トリメシン酸、トリメリット酸、４，４’－ビフェニルジカルボン酸、ジフェニルメタン－４，４’－ジカルボン酸、２，２－ビス（４－カルボキシフェニル）ヘキサフルオロプロパン、１，３，５－トリス（４－カルボキシフェニル）ベンゼン等のカルボキシ基を有する芳香族化合物；
　サリチル酸、３，４，５－トリヒドロキシ安息香酸等のフェノール性水酸基及びカルボキシ基を有する芳香族化合物等を挙げることができる。 Examples of the aromatic compound having a phenolic hydroxyl group or carboxy group include phenol, cresol, thymol, 4,4 ′, 4 ″ -methylidynetrisphenol, 2,6-bis [(2-hydroxy-5-methylphenyl). ) Methyl] -4-methylphenol, α, α, α′-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene, 3,3 ′, 5,5′-tetrakis (methoxymethyl) biphenyl- An aromatic compound having a phenolic hydroxyl group such as 4,4′-diol;
Benzoic acid, phthalic acid, trimesic acid, trimellitic acid, 4,4'-biphenyldicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 1,3 , Aromatic compounds having a carboxy group such as 5-tris (4-carboxyphenyl) benzene;
Examples thereof include aromatic compounds having a phenolic hydroxyl group and a carboxy group such as salicylic acid and 3,4,5-trihydroxybenzoic acid.
　［Ｃ］化合物のうち、式（１－６）で表される化合物は、カルボキシ基を有する環状エーテルのカルボキシ基の水素原子を酸解離性基で置換することにより合成することが可能である。カルボキシ基を有する環状エーテルとしては、テトラヒドロフラン－２，３，４，５－テトラカルボン酸、テトラヒドロフラン－２－カルボン酸、３－メチル－３－オキセタンカルボン酸、テトラヒドロピラン－４－カルボン酸等を挙げることができる。 Among the [C] compounds, the compound represented by the formula (1-6) can be synthesized by substituting the hydrogen atom of the carboxy group of the cyclic ether having a carboxy group with an acid dissociable group. Examples of the cyclic ether having a carboxy group include tetrahydrofuran-2,3,4,5-tetracarboxylic acid, tetrahydrofuran-2-carboxylic acid, 3-methyl-3-oxetanecarboxylic acid, tetrahydropyran-4-carboxylic acid and the like. be able to.
　当該感放射線性樹脂組成物における［Ｃ］化合物の含有量の下限値としては、［Ａ］重合体１００質量部に対して、５質量部が好ましく、１０質量部がより好ましく、１５質量部がさらに好ましい。一方、この上限値としては、２００質量部が好ましく、１００質量部がより好ましく、４０質量部がさらに好ましい。［Ｃ］化合物の含有量をこのような範囲とすることで、例えば現像液となるアルカリ水溶液に対する放射線の照射部分と非照射部分との溶解度の差を大きくして、パターニング性能を向上させることなどができる。 As a lower limit of content of the [C] compound in the said radiation sensitive resin composition, 5 mass parts is preferable with respect to 100 mass parts of [A] polymers, 10 mass parts is more preferable, 15 mass parts is Further preferred. On the other hand, as this upper limit, 200 mass parts is preferable, 100 mass parts is more preferable, and 40 mass parts is further more preferable. By setting the content of the [C] compound in such a range, for example, the difference in solubility between the irradiated portion and the non-irradiated portion with respect to the alkaline aqueous solution serving as the developer is increased, and the patterning performance is improved. Can do.
＜［Ｄ］酸化防止剤＞
　当該感放射線性樹脂組成物が［Ｄ］酸化防止剤を含有することにより、組成物中の好ましくない酸化反応を抑えることができる。［Ｄ］酸化防止剤としては、フェノール系酸化防止剤、硫黄系酸化防止剤、アミン系酸化防止剤等が挙げられるが、フェノール系酸化防止剤が好ましい。 <[D] Antioxidant>
When the said radiation sensitive resin composition contains [D] antioxidant, the undesirable oxidation reaction in a composition can be suppressed. [D] Examples of the antioxidant include phenolic antioxidants, sulfur antioxidants, amine antioxidants, and the like, and phenolic antioxidants are preferable.
　フェノール系酸化防止剤としては、スチレン化フェノール、２，６－ジ－ｔ－ブチル－４－メチルフェノール、２，６－ジ－ｔ－ブチル－ｐ－エチルフェノール、２，４，６－トリ－ｔ－ブチルフェノール、ブチルヒドロキシアニソール、１－ヒドロキシ－３－メチル－４－イソプロピルベンゼン、モノ－ｔ－ブチル－ｐ－クレゾール、モノ－ｔ－ブチル－ｍ－クレゾール、２，４－ジメチル－６－ｔ－ブチルフェノール、ブチル化ビスフェノールＡ、２，２’－メチレン－ビス－（４－メチル－６－ｔ－ブチルフェノール）、２，２’メチレン－ビス－（４－エチル－６－ｔ－ブチルフェノール）、２，２’－メチレン－ビス（４－メチル－６－ｔ－ノニルフェノール）、２，２’－イソブチリデン－ビス－（４，６－ジメチルフェノール）、４，４’－ブチリデン－ビス－（３－メチル－６－ｔ－ブチルフェノール）、４，４’－メチレン－ビス－（２，６－ジ－ｔ－ブチルフェノール）、２，２－チオ－ビス－（４－メチル－６－ｔ－ブチルフェノール）、４，４’－チオ－ビス－（３－メチル－６－ｔ－ブチルフェノール）、４，４’－チオ－ビス－（２－メチル－６－ブチルフェノール）、４，４’－チオ－ビス－（６－ｔ－ブチル－３－メチルフェノール）、ビス（３－メチル－４－ヒドロキシ－５－ｔ－ブチルベンゼン）スルフィド、２，２－チオ［ジエチル－ビス－３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェノール）プロピオネート］、ビス［３，３－ビス（４’－ヒドロキシ－３’－ｔ－ブチルフェノール）ブチリックアシッド］グリコールエステル、ビス［２－（２－ヒドロキシ－５－メチル－３－ｔ－ブチルベンゼン）－４－メチル－６－ｔ－ブチルフェニル］テレフタレート、１，３，５－トリス（３’，５’－ジ－ｔ－ブチル－４’－ヒドロキシベンジル）イソシアヌレート、Ｎ，Ｎ’－ヘキサメチレン－ビス（３，５－ジ－ｔ－ブチル－４－ヒドロキシ－ヒドロキシアミド）、Ｎ－オクタデシル－３－（４’－ヒドロキシ－３’，５’－ジ－ｔ－ブチルフェノール）プロピオネート、テトラキス［メチレン－（３’，５’－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］メタン、１，１’－ビス（４－ヒドロキシフェニル）シクロヘキサン、モノ（α－メチルベンゼン）フェノール、ジ（α－メチルベンジル）フェノール、トリ（α－メチルベンジル）フェノール、ビス（２’－ヒドロキシ－３’－ｔ－ブチル－５’－メチルベンジル）４－メチル－フェノール、２，５－ジ－ｔ－アミルハイドロキノン、２，６－ジ－ブチル－α－ジメチルアミノ－ｐ－クレゾール、２，５－ジ－ｔ－ブチルハイドロキノン、３，５－ジ－ｔ－ブチル－４－ヒドロキシベンジルリン酸のジエチルエステル、トリス－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）－イソシアヌレイト、ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］等が挙げられる。［Ｄ］酸化防止剤は、単独で又は２種以上組み合わせて用いることができる。 Phenol antioxidants include styrenated phenol, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-p-ethylphenol, 2,4,6-tri- t-butylphenol, butylhydroxyanisole, 1-hydroxy-3-methyl-4-isopropylbenzene, mono-t-butyl-p-cresol, mono-t-butyl-m-cresol, 2,4-dimethyl-6-t -Butylphenol, butylated bisphenol A, 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'methylene-bis- (4-ethyl-6-t-butylphenol), 2 , 2'-methylene-bis (4-methyl-6-t-nonylphenol), 2,2'-isobutylidene-bis- (4,6-dimethylphenol) ), 4,4′-butylidene-bis- (3-methyl-6-tert-butylphenol), 4,4′-methylene-bis- (2,6-di-tert-butylphenol), 2,2-thio- Bis- (4-methyl-6-tert-butylphenol), 4,4′-thio-bis- (3-methyl-6-tert-butylphenol), 4,4′-thio-bis- (2-methyl-6) -Butylphenol), 4,4′-thio-bis- (6-tert-butyl-3-methylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzene) sulfide, 2,2-thio [Diethyl-bis-3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate], bis [3,3-bis (4′-hydroxy-3′-tert-butylphenol) butyric acid] Glycol Este Bis [2- (2-hydroxy-5-methyl-3-t-butylbenzene) -4-methyl-6-t-butylphenyl] terephthalate, 1,3,5-tris (3 ′, 5′-di) -T-butyl-4'-hydroxybenzyl) isocyanurate, N, N'-hexamethylene-bis (3,5-di-t-butyl-4-hydroxy-hydroxyamide), N-octadecyl-3- (4 '-Hydroxy-3', 5'-di-t-butylphenol) propionate, tetrakis [methylene- (3 ', 5'-di-t-butyl-4-hydroxyphenyl) propionate] methane, 1,1'-bis (4-hydroxyphenyl) cyclohexane, mono (α-methylbenzene) phenol, di (α-methylbenzyl) phenol, tri (α-methylbenzyl) phenol, Bis (2′-hydroxy-3′-t-butyl-5′-methylbenzyl) 4-methyl-phenol, 2,5-di-t-amylhydroquinone, 2,6-di-butyl-α-dimethylamino- p-cresol, 2,5-di-t-butylhydroquinone, diethyl ester of 3,5-di-t-butyl-4-hydroxybenzyl phosphate, tris- (3,5-di-tert-butyl-4- Hydroxybenzyl) -isocyanurate, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and the like. [D] Antioxidants can be used alone or in combination of two or more.
　［Ｄ］酸化防止剤の含有量の下限値としては、［Ａ］重合体１００質量部に対し、０．１質量部が好ましく、０．２質量部がより好ましい。一方、この上限値としては、１０質量部が好ましく、５質量部がより好ましく、２質量部がさらに好ましい。 [D] The lower limit of the content of the antioxidant is preferably 0.1 parts by mass and more preferably 0.2 parts by mass with respect to 100 parts by mass of the [A] polymer. On the other hand, as this upper limit, 10 mass parts is preferable, 5 mass parts is more preferable, and 2 mass parts is further more preferable.
＜その他の任意成分＞
　当該感放射線性樹脂組成物は、任意成分として、［Ｅ］密着助剤、［Ｆ］多官能モノマー、［Ｇ］無機酸化物粒子、［Ｈ］溶剤、［Ｉ］界面活性剤等を含有することができる。 <Other optional components>
The radiation-sensitive resin composition contains, as optional components, [E] adhesion assistant, [F] polyfunctional monomer, [G] inorganic oxide particles, [H] solvent, [I] surfactant, and the like. be able to.
＜［Ｅ］密着助剤＞
　当該感放射線性樹脂組成物においては、基板と得られる硬化膜との接着性を向上させるために［Ｅ］密着助剤使用することができる。このような密着助剤としては、官能性シランカップリング剤が好ましく使用される。官能性シランカップリング剤の例としては、カルボキシル基、メタクリロイル基、イソシアネート基、エポキシ基（好ましくはオキシラニル基）、チオール基等の反応性置換基を有するシランカップリング剤等が挙げられる。 <[E] Adhesion aid>
In the said radiation sensitive resin composition, in order to improve the adhesiveness of a board | substrate and the cured film obtained, [E] adhesion | attachment adjuvant can be used. As such an adhesion assistant, a functional silane coupling agent is preferably used. Examples of functional silane coupling agents include silane coupling agents having reactive substituents such as carboxyl groups, methacryloyl groups, isocyanate groups, epoxy groups (preferably oxiranyl groups), thiol groups, and the like.
　官能性シランカップリング剤の具体例としては、トリメトキシシリル安息香酸、γ－メタクリロキシプロピルトリメトキシシラン、ビニルトリアセトキシシラン、ビニルトリメトキシシラン、γ－イソシアネートプロピルトリエトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルアルキルジアルコキシシラン、γ－クロロプロピルトリアルコキシシラン、γ－メルカプトプロピルトリアルコキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシジルオキシプロピルトリメトキシシラン等が挙げられる。これらの中でも、３－グリシジルオキシプロピルトリメトキシシラン、γ－グリシドキシプロピルアルキルジアルコキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン及びγ－メタクリロキシプロピルトリメトキシシランが好ましい。 Specific examples of functional silane coupling agents include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxy Propyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyl Examples include oxypropyltrimethoxysilane. Of these, 3-glycidyloxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane are preferred.
　［Ｅ］密着助剤の含有量の下限値としては、重合体［Ａ］１００質量部に対して、０．５質量部が好ましく、１質量部がより好ましい。一方、この上限値としては２０質量部が好ましく、１０質量部がより好ましい。［Ｅ］密着助剤の含有量を上記範囲とすることによって、形成される硬化膜と基板との密着性が改善される。 [E] The lower limit of the content of the adhesion assistant is preferably 0.5 parts by mass and more preferably 1 part by mass with respect to 100 parts by mass of the polymer [A]. On the other hand, the upper limit is preferably 20 parts by mass, and more preferably 10 parts by mass. [E] By setting the content of the adhesion assistant in the above range, the adhesion between the formed cured film and the substrate is improved.
＜［Ｆ］多官能モノマー＞
　当該感放射線性樹脂組成物が［Ｆ］多官能モノマーを含有することにより、得られる硬化膜の耐熱性、耐溶剤性等を向上させることができる。 <[F] polyfunctional monomer>
When the said radiation sensitive resin composition contains a [F] polyfunctional monomer, the heat resistance of the obtained cured film, solvent resistance, etc. can be improved.
　［Ｆ］多官能モノマーとしては、アリル化シクロヘキシルジ（メタ）アクリレート、２，５－ヘキサンジ（メタ）アクリレート、１，３－ブタンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，３－ブチレングリコールジ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、グリセロールジ（メタ）アクリレート、メトキシ化シクロヘキシルジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、トリグリセロールジ（メタ）アクリレート等のジ（メタ）タクリレート類；
ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパンＰＯ変性トリ（メタ）アクリレート、トリメチロールプロパンＥＯ変性トリ（メタ）アクリレート、ベンジルメルカプタン（メタ）トリアクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールモノヒドロキシペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート等の３官能以上の（メタ）アクリレート類；等の多官能（メタ）アクリレート等を挙げることができる。 [F] Polyfunctional monomers include allylated cyclohexyl di (meth) acrylate, 2,5-hexanedi (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) Acrylate, 1,3-butylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) ) Acrylate, 1,10-decanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, glycerol di (meth) acrylate, methoxylated cyclohexyl di (meth) acrylate, neo Emissions chill glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, di (meth) methacrylate such as triglycerol di (meth) acrylate;
Pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane PO modified tri (meth) acrylate, trimethylolpropane EO modified tri (meth) acrylate, benzyl mercaptan (meth) triacrylate, ditrimethylolpropane Polyfunctional (meth) acrylates such as tetra (meth) acrylates, dipentaerythritol monohydroxypenta (meth) acrylates, trifunctional or higher functional (meth) acrylates such as dipentaerythritol hexa (meth) acrylate; it can.
　［Ｆ］多官能モノマーの含有量としては、露光光に対する感度の点などから、［Ａ］重合体１００質量部に対して、例えば１０質量％以上１５０質量％以下の範囲である。 [F] The content of the polyfunctional monomer is, for example, in the range of 10% by mass to 150% by mass with respect to 100 parts by mass of the polymer [A] from the viewpoint of sensitivity to exposure light.
＜［Ｇ］無機酸化物粒子＞
　［Ｇ］無機酸化物粒子は、得られる硬化物の電気絶縁性を維持するとともに、誘電特性である比誘電率を制御することができる。また、［Ｇ］無機酸化物粒子は、硬化膜の屈折率の制御、硬化膜の透明性の制御、硬化収縮を緩和することによるクラックの抑制、硬化膜の表面硬度向上という目的等でも用いられる。 <[G] Inorganic oxide particles>
[G] The inorganic oxide particles can maintain the electrical insulation of the resulting cured product and can control the dielectric constant, which is a dielectric property. [G] The inorganic oxide particles are also used for the purpose of controlling the refractive index of the cured film, controlling the transparency of the cured film, suppressing cracks by relaxing the curing shrinkage, and improving the surface hardness of the cured film. .
　［Ｇ］無機酸化物粒子は、ケイ素、アルミニウム、ジルコニウム、チタン、亜鉛、インジウム、スズ、アンチモン、ストロンチウム、バリウム、セリウム及びハフニウムからなる群より選ばれる少なくとも一つの元素を含む酸化物である無機酸化物粒子を挙げることができる。 [G] The inorganic oxide particle is an oxide containing at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony, strontium, barium, cerium and hafnium. There may be mentioned physical particles.
　そして、この群の中でもケイ素、ジルコニウム、チタン又は亜鉛の酸化物粒子が好ましく、ケイ素の酸化物粒子であるシリカ粒子、ジルコニウム又はチタンの酸化物粒子やチタン酸バリウム（ＢａＴｉＯ３）が特に好ましい。これらは１種単独で又は２種以上を組み合わせて用いることができる。また、無機酸化物粒子は、上記元素の複合酸化物粒子であってもよい。この複合酸化物粒子としては例えばチタン酸バリウム、チタン酸ストロンチウム等が挙げられる。また硬化物の電気絶縁性を損なわない範囲でＡＴＯ（ａｎｔｉｍｏｎｙ－ｔｉｎ　ｏｘｉｄｅ）、ＩＴＯ（ｉｎｄｉｕｍ－ｔｉｎ　ｏｘｉｄｅ）、ＩＺＯ（ｉｎｄｉｕｍ－ｚｉｎｃ　ｏｘｉｄｅ）等を用いることもできる。これらの無機酸化物粒子としては、市販のもの、例えばシーアイ化成社のナノテック（登録商標）等を使用することができる。 Among these groups, oxide particles of silicon, zirconium, titanium or zinc are preferable, and silica particles which are oxide particles of silicon, oxide particles of zirconium or titanium, and barium titanate (BaTiO 3 ) are particularly preferable. These can be used alone or in combination of two or more. The inorganic oxide particles may be composite oxide particles of the above elements. Examples of the composite oxide particles include barium titanate and strontium titanate. Moreover, ATO (antimony-tin oxide), ITO (indium-tin oxide), IZO (indium-zinc oxide), etc. can also be used in the range which does not impair the electrical insulation of hardened | cured material. As these inorganic oxide particles, commercially available ones such as Nanotech (registered trademark) manufactured by CI Kasei Co., Ltd. can be used.
　［Ｇ］無機酸化物粒子の形状は、特に限定されず、球状でも不定形のものでもよく、中空粒子、多孔質粒子、コア・シェル型粒子等であっても構わない。また、動的光散乱法で求めた［Ｆ］無機酸化物粒子の体積平均粒子径は５ｎｍ以上２００ｎｍ以下が好ましい。 [G] The shape of the inorganic oxide particles is not particularly limited, and may be spherical or amorphous, and may be hollow particles, porous particles, core-shell particles, or the like. Moreover, the volume average particle diameter of the [F] inorganic oxide particles determined by a dynamic light scattering method is preferably 5 nm or more and 200 nm or less.
　［Ｇ］無機酸化物粒子の含有量としては、特に限定されないが、［Ａ］重合体１００質量部に対して、１質量部以上５００質量部以下とすることができる。なお、当該感放射線性樹脂組成物が［Ｇ］無機酸化物粒子を含有する場合、分散剤をさらに含有することができる。分散剤により、感放射線性樹脂組成物中に均一に［Ｇ］無機酸化物粒子を分散させることができ、塗布性等を高めることができる。 [G] The content of the inorganic oxide particles is not particularly limited, but may be 1 part by mass or more and 500 parts by mass or less with respect to 100 parts by mass of the [A] polymer. In addition, when the said radiation sensitive resin composition contains [G] inorganic oxide particle, it can further contain a dispersing agent. With the dispersant, [G] inorganic oxide particles can be uniformly dispersed in the radiation-sensitive resin composition, and coatability and the like can be improved.
＜［Ｈ］溶剤＞
　［Ｈ］溶剤は、当該感放射線性樹脂組成物を所望の固形分濃度に調整するほか、各成分を均一かつ安定に溶解させることができる。［Ｈ］溶剤としては、メタノール、エタノール、イソプロピルアルコール、ブタノール、オクタノール等のアルコール類；酢酸エチル、酢酸ブチル、乳酸エチル、γ－ブチロラクトン、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、３－メトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等のエステル類；エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、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エチルメチルエーテル等のエーテル類；ジメチルフォルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン等のアミド類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類を用いることができる。［Ｈ］溶剤は、１種又は２種以上を混合して用いることができる。 <[H] solvent>
[H] The solvent can adjust the radiation-sensitive resin composition to a desired solid content concentration and can dissolve each component uniformly and stably. [H] Solvents include alcohols such as methanol, ethanol, isopropyl alcohol, butanol and octanol; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3- Esters such as methyl methoxypropionate and ethyl 3-ethoxypropionate; ethers such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol ethyl methyl ether; dimethylformamide, N, N-dimethylacetamide, Amides such as N-methylpyrrolidone; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclo Ketones such as cyclohexanone; benzene, toluene, xylene, aromatic hydrocarbons such as ethylbenzene. [H] The solvent may be used alone or in combination of two or more.
＜［Ｉ］界面活性剤＞
　［Ｉ］界面活性剤は、当該感放射線性樹脂組成物の塗布性の改善、塗布ムラの低減及び放射線照射部の現像性を改良するために添加することができる。好ましい界面活性剤の例としては、フッ素系界面活性剤及びシリコーン系界面活性剤が挙げられる。［Ｉ］界面活性剤の含有量としては、［Ａ］重合体１００質量部に対して、例えば０．０１質量部以上１０質量部以下とすることができる。 <[I] Surfactant>
[I] Surfactant can be added in order to improve the applicability of the radiation-sensitive resin composition, reduce coating unevenness, and improve the developability of the radiation irradiated part. Examples of preferable surfactants include fluorine-based surfactants and silicone-based surfactants. [I] As content of surfactant, it is 0.01 mass part or more and 10 mass parts or less with respect to 100 mass parts of [A] polymers.
＜感放射線性樹脂組成物の調製＞
　当該感放射線性樹脂組成物は、上述した各成分を所定の割合で混合することで調製される。当該感放射線性樹脂組成物の固形分濃度としては、例えば１０質量％以上５０質量％以下である。 <Preparation of radiation-sensitive resin composition>
The said radiation sensitive resin composition is prepared by mixing each component mentioned above in a predetermined ratio. As solid content concentration of the said radiation sensitive resin composition, it is 10 to 50 mass%, for example.
＜表示素子用硬化膜＞
　当該表示素子用硬化膜は、当該感放射線性樹脂組成物から形成される。当該硬化膜は、当該感放射線性樹脂組成物から形成されているため、絶縁性や腐食防止性に優れる。このような特性を有する当該硬化膜は、例えば表示素子の電子デバイスの層間絶縁膜、平坦化膜、発光層を形成するための領域を規定するバンク（隔壁）、スペーサー、保護膜、カラーフィルタ用着色パターン等に使用できる。なお、当該硬化膜の形成方法としては特に限定されないが、次に説明する硬化膜の形成方法を適用することが好ましい。 <Curing film for display element>
The said display element cured film is formed from the said radiation sensitive resin composition. Since the said cured film is formed from the said radiation sensitive resin composition, it is excellent in insulation and corrosion prevention property. The cured film having such characteristics is, for example, a bank (partition) defining a region for forming an interlayer insulating film, a planarizing film, and a light emitting layer of an electronic device of a display element, a spacer, a protective film, and a color filter. It can be used for coloring patterns. In addition, although it does not specifically limit as a formation method of the said cured film, It is preferable to apply the formation method of the cured film demonstrated below.
＜表示素子用硬化膜の形成方法＞
　当該表示素子用硬化膜の形成方法は、当該感放射線性樹脂組成物を用い、基板上に塗膜を形成する工程（以下、「塗膜形成工程」ともいう）、上記塗膜の少なくとも一部に放射線を照射する工程（以下、「照射工程」ともいう）、上記放射線が照射された塗膜を現像する工程（以下、「現像工程」ともいう）、及び上記現像された塗膜を加熱する工程（以下、「加熱工程」ともいう）を有する。 <Method for forming cured film for display element>
The method for forming the cured film for display element includes a step of forming a coating film on a substrate using the radiation-sensitive resin composition (hereinafter, also referred to as “coating layer forming step”), at least a part of the coating film. A step of irradiating the film with radiation (hereinafter also referred to as “irradiation step”), a step of developing the coating film irradiated with the radiation (hereinafter also referred to as “development step”), and heating the developed coating film A process (hereinafter also referred to as a “heating process”).
　当該形成方法によれば、放射線感度に優れ、非露光部の膜厚変化量が小さく、絶縁性及び腐食防止性に優れる硬化膜を得ることができる。 According to the formation method, a cured film having excellent radiation sensitivity, a small amount of change in film thickness at the non-exposed portion, and excellent insulation and corrosion resistance can be obtained.
（塗膜形成工程）
　本工程では、当該感放射線性樹脂組成物を用い、基板上に塗布して塗膜を形成する。当該感放射線性樹脂組成物が溶剤を含む場合には、塗布面をプレベークすることによって溶媒を除去することが好ましい。 (Coating film formation process)
In this step, the radiation-sensitive resin composition is used and applied onto a substrate to form a coating film. When the said radiation sensitive resin composition contains a solvent, it is preferable to remove a solvent by prebaking an application surface.
　上記基板としては、例えばガラス、石英、シリコーン、樹脂等が挙げられる。上記樹脂としては、例えばポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエーテルスルホン、ポリカーボネート、ポリイミド、環状オレフィンの開環重合体及びその水素添加物等が挙げられる。プレベークの条件としては、各成分の種類、配合割合等によっても異なるが、通常７０℃以上１２０℃以下、１分以上１０分以下である。 Examples of the substrate include glass, quartz, silicone, and resin. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of a cyclic olefin, and a hydrogenated product thereof. The pre-baking conditions are usually 70 ° C. or higher and 120 ° C. or lower and 1 minute or longer and 10 minutes or shorter, although they vary depending on the type of each component, the blending ratio, and the like.
（照射工程）
　本工程では、塗膜の少なくとも一部に放射線を照射し露光する。露光する際には、通常所定のパターンを有するフォトマスクを介して露光する。露光に使用される放射線としては、可視光線、紫外線、遠紫外線、極端紫外線、Ｘ線、ガンマ線等の電磁波、電子線、α線等の荷電子粒子線等が挙げられる。放射線としては、波長が１９０ｎｍ以上４５０ｎｍ以下の範囲にある放射線が好ましく、３６５ｎｍの紫外線を含む放射線がより好ましい。露光量の上限としては、２０，０００Ｊ／ｍ２が好ましく、１０，０００Ｊ／ｍ２がより好ましい。一方、露光量の下限としては、例えば１Ｊ／ｍ２とすることができ、５００Ｊ／ｍ２が好ましく、１，５００Ｊ／ｍ２がより好ましい。この露光量は、放射線の波長３６５ｎｍにおける強度を照度計（ＯＡＩ　Ｏｐｔｉｃａｌ　Ａｓｓｏｃｉａｔｅｓ社の「ＯＡＩ　ｍｏｄｅｌ３５６」）により測定した値である。 (Irradiation process)
In this step, at least a part of the coating film is irradiated with radiation and exposed. When exposing, it exposes normally through the photomask which has a predetermined pattern. Examples of the radiation used for the exposure include visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, electromagnetic waves such as X-rays and gamma rays, electron beam, and charged particle beams such as α rays. As the radiation, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation including ultraviolet light of 365 nm is more preferable. The upper limit of the exposure dose is preferably 20,000J / m 2, 10,000J / m 2 is more preferable. On the other hand, the lower limit of the exposure amount, for example, be a 1 J / m 2, preferably 500J / m 2, 1,500J / m 2 is more preferable. This exposure amount is a value obtained by measuring the intensity of radiation at a wavelength of 365 nm with an illuminometer (“OAI model 356” manufactured by OAI Optical Associates).
（現像工程）
　本工程では、放射線が照射された塗膜を現像する。露光後の塗膜を現像することにより、不要な部分（放射線の照射部分）を除去して所定のパターンを形成する。 (Development process)
In this step, the coating film irradiated with radiation is developed. By developing the coated film after exposure, unnecessary portions (radiation irradiated portions) are removed to form a predetermined pattern.
　この工程で使用される現像液としては、アルカリ性の水溶液が好ましい。アルカリとしては、例えば水酸化ナトリウム、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、アンモニア等の無機アルカリ；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等の４級アンモニウム塩などが挙げられる。現像液としては、ケトン系有機溶媒、アルコール系有機溶媒等の有機溶媒を使用することもできる。 As the developer used in this step, an alkaline aqueous solution is preferable. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. . As the developer, an organic solvent such as a ketone organic solvent or an alcohol organic solvent can be used.
　アルカリ水溶液には、メタノール、エタノール等の水溶性有機溶媒や界面活性剤を適当量添加して使用することもできる。アルカリ水溶液におけるアルカリの濃度としては、好適な現像性を得る観点から、０．１質量％以上５質量％以下が好ましい。 An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline aqueous solution. As a density | concentration of the alkali in aqueous alkali solution, from a viewpoint of obtaining suitable developability, 0.1 to 5 mass% is preferable.
　現像方法としては、例えば液盛り法、ディッピング法、揺動浸漬法、シャワー法等が挙げられる。現像時間としては、当該感放射線性樹脂組成物の組成によって異なるが、通常１０秒以上１８０秒以下である。 Examples of the developing method include a liquid piling method, a dipping method, a rocking dipping method, a shower method and the like. The development time varies depending on the composition of the radiation sensitive resin composition, but is usually from 10 seconds to 180 seconds.
　このような現像処理に続いて、例えば流水洗浄を３０秒以上９０秒以下行った後、例えば圧縮空気や圧縮窒素で風乾させることによって、所望のパターンを形成できる。 Following such development processing, for example, washing with running water is performed for 30 seconds or more and 90 seconds or less, and then a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.
（加熱工程）
　本工程では、現像された塗膜を加熱する。加熱には、ホットプレート、オーブン等の加熱装置を用い、パターニングされた薄膜を加熱することで、［Ａ］重合体の硬化反応を促進して、硬化膜を形成することができる。加熱温度としては、例えば１２０℃以上２５０℃以下である。加熱時間としては、加熱機器の種類により異なるが、例えばホットプレートでは５分以上３０分以下、オーブンでは３０分以上９０分以下である。また、２回以上の加熱工程を行うステップベーク法等を用いることもできる。このようにして、目的とする硬化膜に対応するパターン状薄膜を基板の表面上に形成できる。 (Heating process)
In this step, the developed coating film is heated. For the heating, by using a heating device such as a hot plate or an oven to heat the patterned thin film, the curing reaction of the [A] polymer can be promoted to form a cured film. As heating temperature, it is 120 to 250 degreeC, for example. The heating time varies depending on the type of heating equipment, but for example, it is 5 minutes to 30 minutes for a hot plate and 30 minutes to 90 minutes for an oven. Moreover, the step baking method etc. which perform a heating process 2 times or more can also be used. In this way, a patterned thin film corresponding to the desired cured film can be formed on the surface of the substrate.
＜表示素子＞
　当該表示素子は、当該表示素子用硬化膜を備えている。当該表示素子としては、例えば液晶表示素子、有機ＥＬ表示素子等が挙げられる。 <Display element>
The display element includes a cured film for the display element. Examples of the display element include a liquid crystal display element and an organic EL display element.
　液晶表示素子は、例えば液晶セル、偏光板等により構成されている。この液晶表示素子は、絶縁性や腐食防止性等に優れる当該硬化膜を備えているため、長期間の信頼性等に優れる。 The liquid crystal display element is composed of, for example, a liquid crystal cell, a polarizing plate, and the like. Since this liquid crystal display element is provided with the cured film having excellent insulating properties and corrosion prevention properties, it has excellent long-term reliability and the like.
　液晶表示素子の製造方法を以下に例示する。まず、片面に透明導電膜（電極）を有する透明基板を一対（２枚）準備する。この基板の透明導電膜上に、当該感放射線性樹脂組成物を用い、上記＜表示素子用硬化膜の形成方法＞に記載の方法に従い、硬化膜としての層間絶縁膜、スペーサー、保護膜等を形成する。次いで、これらの硬化膜が形成された基板上に液晶配向能を有する配向膜を形成する。これらの基板を、その配向膜が形成された側の面を内側にして、それぞれの配向膜の液晶配向方向が直交又は逆平行となるように一定の間隙（セルギャップ）を介して対向配置する。次いで、基板の表面（配向膜）及びスペーサーにより区画されたセルギャップ内に液晶を充填し、充填孔を封止して液晶セルを構成する。そして、液晶セルの両外表面に、偏光板を貼り合わせることにより、液晶表示素子が得られる。 Examples of liquid crystal display device manufacturing methods are given below. First, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared. Using the radiation sensitive resin composition on the transparent conductive film of this substrate, according to the method described in <Method for forming cured film for display element>, an interlayer insulating film as a cured film, a spacer, a protective film, etc. Form. Next, an alignment film having liquid crystal alignment ability is formed on the substrate on which these cured films are formed. These substrates are arranged facing each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed on the inside. . Next, liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to form a liquid crystal cell. And a liquid crystal display element is obtained by bonding a polarizing plate on both outer surfaces of a liquid crystal cell.
　一方、有機エレクトロルミネッセンス素子においては、当該感放射線性樹脂組成物から形成される硬化膜は、ＴＦＴ素子上に形成される平坦化膜、発光部位を規定する隔壁等として使用できる。 On the other hand, in the organic electroluminescence element, the cured film formed from the radiation-sensitive resin composition can be used as a planarization film formed on the TFT element, a partition defining a light emitting site, or the like.
　以下、本発明を実施例に基づいて具体的に説明するが、本発明は、これらの実施例に限定されるものではない。なお、［Ａ］重合体の重量平均分子量（Ｍｗ）は、以下の方法により測定した。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In addition, the weight average molecular weight (Mw) of [A] polymer was measured with the following method.
［重量平均分子量（Ｍｗ）］
　下記条件下、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定した。
　　装置：昭和電工社の「ＧＰＣ－１０１」
　　カラム：ＧＰＣ－ＫＦ－８０１、ＧＰＣ－ＫＦ－８０２、ＧＰＣ－ＫＦ－８０３及びＧＰＣ－ＫＦ－８０４を結合
　　移動相：テトラヒドロフラン
　　カラム温度：４０℃
　　流速：１．０ｍＬ／分
　　試料濃度：１．０質量％
　　試料注入量：１００μＬ
　　検出器：示差屈折計
　　標準物質：単分散ポリスチレン [Weight average molecular weight (Mw)]
It measured by gel permeation chromatography (GPC) under the following conditions.
Equipment: “GPC-101” from Showa Denko
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran Column temperature: 40 ° C
Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene
＜［Ａ］重合体の合成例＞
［合成例１］重合体（Ａ－１）の合成
　冷却管及び撹拌機を備えたフラスコに、２，２’－アゾビス（２，４－ジメチルバレロニトリル）８質量部及びジエチレングリコールメチルエチルエーテル２２０質量部を仕込んだ。引き続き、メタクリル酸１３質量部、メタクリル酸グリシジル４０質量部、α－メチル－ｐ－ヒドロキシスチレン１０質量部、スチレン１０質量部、テトラヒドロフルフリルメタクリレート１２質量部、Ｎ－シクロヘキシルマレイミド１５質量部及びｎ－ラウリルメタクリレート１０質量部を仕込み、窒素置換した後、緩やかに攪拌しつつ、溶液の温度を７０℃に上昇させ、この温度を５時間保持して重合した。これによりアルカリ可溶性樹脂である（Ａ－１）カルボキシ基を有するアクリル樹脂としての重合体（Ａ－１）を含有する重合体溶液を得た。この重合体溶液の固形分濃度は、３１．９質量％であり、重合体（Ａ－１）のＭｗは８，０００、分子量分布（Ｍｗ／Ｍｎ）は２．３であった。 <[A] Polymer Synthesis Example>
[Synthesis Example 1] Synthesis of polymer (A-1) In a flask equipped with a condenser and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methyl ethyl ether Prepared the department. Subsequently, 13 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of α-methyl-p-hydroxystyrene, 10 parts by weight of styrene, 12 parts by weight of tetrahydrofurfuryl methacrylate, 15 parts by weight of N-cyclohexylmaleimide and n- After charging 10 parts by mass of lauryl methacrylate and purging with nitrogen, the temperature of the solution was raised to 70 ° C. while gently stirring, and this temperature was maintained for 5 hours for polymerization. As a result, a polymer solution containing the polymer (A-1) as an acrylic resin having a carboxyl group (A-1) which is an alkali-soluble resin was obtained. The solid content concentration of this polymer solution was 31.9% by mass, the Mw of the polymer (A-1) was 8,000, and the molecular weight distribution (Mw / Mn) was 2.3.
［合成例２］重合体（Ａ－２）の合成
　反応容器に重合溶剤としてプロピレングリコールモノエチルエーテルアセテート８０質量部を加えた後、重合溶剤の合計８０ｇに対し固形分濃度２０質量％となるように、ジアミン化合物及びテトラカルボン酸誘導体であるテトラカルボン酸二無水物を重合溶剤中に加えた。ジアミン化合物としては、２，２’－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン（ＢＡＨＦ）を用い、これを溶解させた後、テトラカルボン酸二無水物として２，３，５－トリカルボキシシクロペンチル酢酸二無水物（ＴＣＡ）と１，３－ジヒドロ－１，３－ジオキソ－５－イソベンゾフランカルボン酸－１，４－フェニレンエステル（ＴＭＨＱ）とを、テトラカルボン酸二無水物の組成がＴＣＡ：ＴＭＨＱ＝９５：５（モル比）となるように投入した。そして、ジアミン化合物の全体量１００モル部に対し、テトラカルボン酸二無水物は９０モル部を加えた。その後、この混合物を６０℃で３時間反応させた。これにより、固形分濃度２０％での溶液粘度１００ｍＰａ・ｓの（Ａ－２）ポリイミド又はポリイミド前駆体としてのポリアミック酸である重合体（Ａ－２）を含有する溶液を約１００ｇ得た。 [Synthesis Example 2] Synthesis of polymer (A-2) After adding 80 parts by mass of propylene glycol monoethyl ether acetate as a polymerization solvent to the reaction vessel, the solid content concentration becomes 20% by mass with respect to a total of 80 g of the polymerization solvent. In addition, a diamine compound and tetracarboxylic dianhydride which is a tetracarboxylic acid derivative were added to the polymerization solvent. As the diamine compound, 2,2′-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) was used, dissolved, and then converted into 2,3,5-tetracarboxylic dianhydride. Composition of tricarboxycyclopentylacetic acid dianhydride (TCA) and 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester (TMHQ) Was added so that TCA: TMHQ = 95: 5 (molar ratio). And 90 mol part added tetracarboxylic dianhydride with respect to 100 mol part of whole quantity of a diamine compound. Thereafter, the mixture was reacted at 60 ° C. for 3 hours. As a result, about 100 g of a solution containing (A-2) polyimide having a solution viscosity of 100 mPa · s at a solid content concentration of 20% or a polymer (A-2) which is a polyamic acid as a polyimide precursor was obtained.
［合成例３］重合体（Ａ－３）の合成
　撹拌機付の容器内に、プロピレングリコールモノメチルエーテル２０質量部を仕込み、引き続き、メチルトリメトキシシラン７０質量部、及びトリルトリメトキシシラン３０質量部を仕込み、溶液温度が６０℃になるまで加熱した。溶液温度が６０℃に到達後、リン酸０．１５質量部、イオン交換水１９質量部を仕込み、７５℃になるまで加熱し、４時間保持した。さらに、溶液温度を４０℃にし、この温度を保ちながらエバポレーションすることで、イオン交換水及び加水分解縮合で発生したメタノールを除去した。これによりアルカリ可溶性樹脂である（Ａ－３）ポリシロキサンとしての重合体（Ａ－３）を得た。この重合体（Ａ－３）のＭｗは６，０００、分子量分布（Ｍｗ／Ｍｎ）は２．３であった。 [Synthesis Example 3] Synthesis of polymer (A-3) In a vessel equipped with a stirrer, 20 parts by mass of propylene glycol monomethyl ether was charged, followed by 70 parts by mass of methyltrimethoxysilane and 30 parts by mass of tolyltrimethoxysilane. And heated until the solution temperature reached 60 ° C. After the solution temperature reached 60 ° C., 0.15 parts by mass of phosphoric acid and 19 parts by mass of ion-exchanged water were charged, heated to 75 ° C. and held for 4 hours. Furthermore, the solution temperature was set to 40 ° C., and evaporation was performed while maintaining this temperature, thereby removing ion-exchanged water and methanol generated by hydrolysis and condensation. As a result, polymer (A-3) as polysiloxane (A-3), which is an alkali-soluble resin, was obtained. This polymer (A-3) had Mw of 6,000 and a molecular weight distribution (Mw / Mn) of 2.3.
［合成例４］重合体（Ａ－４）の合成
　冷却管、ディーンスターク及び撹拌機を備えたフラスコに、モノマーとして２，６－ジフルオロベンゾニトリルを１．７質量部、２，２－ビス（４－ヒドロキシフェニル）プロパンを０．５質量部、５，５－ビス（４－ヒドロキフェニル）ヘキサン酸を０．５質量部、塩基として炭酸カリウム２．２質量部を仕込み、溶媒としてＮ，Ｎ－ジメチルアセトアミド１００質量部、トルエン２５質量部を加えた。真空引きと窒素置換を繰り返し、系中の水を除去した。その後、反応系中を窒素加圧下にし、緩やかに攪拌しつつ、溶液の温度を１３０℃に上昇させ、この温度を４時間保持して重合した。これにより、アルカリ可溶性樹脂である（Ａ－４）芳香族ポリエーテルとしての重合体（Ａ－４）を含有する溶液を得た。得られた重合体溶液にイオン交換樹脂を加え、４時間撹拌して濾過した。重合体溶液を濾過し、Ｎ，Ｎ－ジメチルアセトアミドで固形分を洗浄した後、溶液を回収し、得られた溶液を水で再沈することで目的の樹脂を得た。重合体（Ａ－４）のＭｗは１２，０００、分子量分布（Ｍｗ／Ｍｎ）は２．５であった。 [Synthesis Example 4] Synthesis of Polymer (A-4) In a flask equipped with a condenser, a Dean Stark and a stirrer, 1.7 parts by mass of 2,6-difluorobenzonitrile as a monomer, 2,2-bis ( 4-hydroxyphenyl) propane (0.5 parts by mass), 5,5-bis (4-hydroxyphenyl) hexanoic acid (0.5 parts by mass), potassium carbonate (2.2 parts by mass) as a base, N, N -100 parts by weight of dimethylacetamide and 25 parts by weight of toluene were added. Vacuuming and nitrogen substitution were repeated to remove water in the system. Thereafter, the reaction system was under nitrogen pressure, the temperature of the solution was raised to 130 ° C. while gently stirring, and this temperature was maintained for 4 hours for polymerization. As a result, a solution containing the polymer (A-4) as the aromatic polyether (A-4) as an aromatic polyether was obtained. An ion exchange resin was added to the resulting polymer solution, and the mixture was stirred for 4 hours and filtered. The polymer solution was filtered, the solid content was washed with N, N-dimethylacetamide, the solution was recovered, and the resulting solution was reprecipitated with water to obtain the desired resin. The polymer (A-4) had an Mw of 12,000 and a molecular weight distribution (Mw / Mn) of 2.5.
［合成例５］［Ａ］重合体（Ａ－５）の合成
　冷却管及び攪拌機を備えたフラスコに、２，２’－アゾビス（２，４－ジメチルバレロニトリル）７質量部、ジエチレングリコールエチルメチルエーテル２００質量部を仕込んだ。引き続き、１－エトキシエチルメタクリレート４０質量部、スチレン１０質量部、メタクリル酸グリシジル４０質量部、２－ヒドロキシエチルメタクリレート１０質量部、及びα－メチルスチレンダイマー３質量部を仕込み窒素置換した後、ゆるやかに撹拌を始めた。溶液の温度を７０℃に上昇させ、この温度を５時間保持し重合体（Ａ－５）を含む重合体溶液を得た。この重合体溶液の固形分濃度は、３１．８重量％であり、重合体（Ａ－５）の重量平均分子量（Ｍｗ）は９，０００、分子量分布（Ｍｗ／Ｍｎ）は２．３であった。 Synthesis Example 5 Synthesis of [A] Polymer (A-5) In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile), diethylene glycol ethyl methyl ether 200 parts by weight were charged. Subsequently, after 40 parts by mass of 1-ethoxyethyl methacrylate, 10 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, and 3 parts by mass of α-methylstyrene dimer were charged with nitrogen, gently Stirring started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the polymer (A-5). The solid content concentration of this polymer solution was 31.8% by weight, the polymer (A-5) had a weight average molecular weight (Mw) of 9,000, and a molecular weight distribution (Mw / Mn) of 2.3. It was.
＜［Ｃ］酸解離性基を有する化合物の合成＞
［合成例６］酸解離性基を有する化合物（Ｃ－１）の合成
　撹拌機を備えた反応容器に、トリメシン酸を５質量部（シグマアルドリッチ社）、３，４－ジヒドロ－２Ｈ－ピラン（シグマアルドリッチ社）を７．２質量部、触媒としてｐ－トルエンスルホン酸ピリジニウム（ＰＰＴＳ：シグマアルドリッチ社）を１．８質量部、テトラヒドロフラン５０質量部を入れた後、室温で２時間撹拌した。得られた反応生成物を水洗した後、未反応物を減圧留去することにより目的の酸解離性基を有する化合物（Ｃ－１）を収率８０％で得た。化合物（Ｃ－１）の１Ｈ－ＮＭＲ（３００ＭＨｚ，ＣＤＣＬ３）は、δ１．６０－２．１８（１８Ｈ，ｍ），δ３．５４（６Ｈ，ｍ），δ６．４７（３Ｈ，ｔ），δ８．８２（３Ｈ，ｓ）であった。 <Synthesis of compound having [C] acid dissociable group>
[Synthesis Example 6] Synthesis of Compound (C-1) Having Acid Dissociable Group In a reaction vessel equipped with a stirrer, 5 parts by mass of trimesic acid (Sigma Aldrich), 3,4-dihydro-2H-pyran ( After adding 7.2 parts by mass of Sigma Aldrich), 1.8 parts by mass of pyridinium p-toluenesulfonate (PPTS: Sigma Aldrich) and 50 parts by mass of tetrahydrofuran as a catalyst, the mixture was stirred at room temperature for 2 hours. The obtained reaction product was washed with water, and the unreacted product was distilled off under reduced pressure to obtain the target compound (C-1) having an acid dissociable group in a yield of 80%. 1 H-NMR (300 MHz, CDCL3) of Compound (C-1) is δ1.60-2.18 (18H, m), δ3.54 (6H, m), δ6.47 (3H, t), δ8 .82 (3H, s).
［合成例７～２８］酸解離性基を有する化合物（Ｃ－２）～（Ｃ－２３）の合成
　下記表１に示す種類及び配合量の各成分を用いた以外は合成例１と同様の手法にて酸解離性基を有する化合物（Ｃ－２）～（Ｃ－２３）を得た。 [Synthesis Examples 7 to 28] Synthesis of Compounds (C-2) to (C-23) Having Acid-Dissociable Groups The same as Synthesis Example 1 except that the components of the types and blending amounts shown in Table 1 below were used. Compounds (C-2) to (C-23) having acid dissociable groups were obtained by the method.
［合成例２９］酸解離性基を有する化合物（Ｃ－２４）の合成
　下記スキームに従って、化合物（Ｃ－２４）を合成した。すなわち、攪拌機を備えた反応容器に４，４’，４’’，４’’’－（（２－ヒドロキシ－５－メチル－１，３－フェニレン）ビス（メタントリイル））テトラキス（２－メチルフェノール）を１０質量部、クロロ酢酸ｔｅｒｔ－ブチルを４０質量部、１，８－ジアザビシクロ［５．４．０］－７－ウンデセンを１６質量部及びＮ－メチルピロリドンを５０質量部入れた後、８０℃で６時間反応を行った。得られた反応溶液を０．１Ｎの塩酸水溶液に滴下し、式（ａ）で表される反応生成物を析出させた。得られた反応生成物は中性になるまで水洗し、未反応物を８０℃で減圧留去した。反応生成物の分子量は８５０．８６で収率８０％であった。得られた反応生成物を５質量部、３，４－ジヒドロ－２Ｈ－ピランを３質量部、ｐ－トルエンスルホン酸ピリジニウムを０．８質量部用いた以外は合成例１と同様の手法にて酸解離性基を有する化合物（Ｃ－２４）を得た。 [Synthesis Example 29] Synthesis of Compound (C-24) Having Acid-Dissociable Group Compound (C-24) was synthesized according to the following scheme. That is, 4,4 ′, 4 ″, 4 ′ ″-((2-hydroxy-5-methyl-1,3-phenylene) bis (methanetriyl)) tetrakis (2-methylphenol) was added to a reaction vessel equipped with a stirrer. ) 10 parts by mass, tert-butyl chloroacetate 40 parts by mass, 1,8-diazabicyclo [5.4.0] -7-undecene 16 parts by mass and N-methylpyrrolidone 50 parts by mass, The reaction was carried out at 6 ° C. for 6 hours. The obtained reaction solution was dropped into a 0.1N aqueous hydrochloric acid solution to precipitate a reaction product represented by the formula (a). The obtained reaction product was washed with water until neutral, and the unreacted product was distilled off at 80 ° C. under reduced pressure. The molecular weight of the reaction product was 850.86 and the yield was 80%. The procedure was the same as in Synthesis Example 1 except that 5 parts by mass of the obtained reaction product, 3 parts by mass of 3,4-dihydro-2H-pyran, and 0.8 parts by mass of pyridinium p-toluenesulfonate were used. A compound (C-24) having an acid dissociable group was obtained.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
［合成例３０］酸解離性基を有する化合物（Ｃ－２５）の合成
　下記スキームに従って、化合物（Ｃ－２５）を合成した。すなわち、攪拌機を備えた反応容器に４，４’，４’’，４’’’－（（２－ヒドロキシ－５－メチル－１，３－フェニレン）ビス（メタントリイル））テトラキス（２－メチルフェノール）（１．０モル）と１，２－ナフトキノンジアジド－５－スルホン酸クロリド（５．０モル）との縮合物を１０質量部、水を５質量部、ジエチレングリコールエチルメチルエーテルを５０質量部を入れた後、１４０℃で３時間反応を行った。反応終了後、溶剤と水を減圧留去し、式（ｂ）で表される反応生成物を得た。反応生成物の分子量は１６７１．７６で収量は９．６ｇ（収率９９％）であった。得られた反応生成物を５質量部、３，４－ジヒドロ－２Ｈ－ピランを１．５質量部、ｐ－トルエンスルホン酸ピリジニウムを０．４質量部用いた以外は合成例１と同様の手法にて酸解離性基を有する化合物（Ｃ－２５）を得た。 [Synthesis Example 30] Synthesis of Compound (C-25) Having Acid-Dissociable Group Compound (C-25) was synthesized according to the following scheme. That is, 4,4 ′, 4 ″, 4 ′ ″-((2-hydroxy-5-methyl-1,3-phenylene) bis (methanetriyl)) tetrakis (2-methylphenol) was added to a reaction vessel equipped with a stirrer. ) (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (5.0 mol) in 10 parts by mass, water in 5 parts by mass, and diethylene glycol ethyl methyl ether in 50 parts by mass. After the addition, the reaction was performed at 140 ° C. for 3 hours. After completion of the reaction, the solvent and water were distilled off under reduced pressure to obtain a reaction product represented by the formula (b). The molecular weight of the reaction product was 1671.76, and the yield was 9.6 g (99% yield). The same procedure as in Synthesis Example 1 except that 5 parts by mass of the obtained reaction product, 1.5 parts by mass of 3,4-dihydro-2H-pyran, and 0.4 parts by mass of pyridinium p-toluenesulfonate were used. To obtain a compound (C-25) having an acid dissociable group.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　なお、合成例６～３０で得られた化合物（Ｃ－１）～（Ｃ－２５）は、［発明を実施するための形態］に例示した式（Ｃ－１）～（Ｃ－２５）で表される化合物である。 The compounds (C-1) to (C-25) obtained in Synthesis Examples 6 to 30 are represented by the formulas (C-1) to (C-25) exemplified in [Mode for Carrying Out the Invention]. It is a compound represented.
Figure JPOXMLDOC01-appb-T000025
Figure JPOXMLDOC01-appb-T000025
＜感放射線性樹脂組成物の調製＞
　実施例及び比較例の感放射線性樹脂組成物の調製に用いた［Ｂ］感放射線性酸発生体及び［Ｄ］酸化防止剤を以下に示す。
［Ｂ］感放射線性酸発生体
　Ｂ－１：［（５－プロピルスルフォニルオキシイミノ－５Ｈ－チオフェン－２－イリデン）－（２－メチルフェニル）アセトニトリル］　　（ＢＡＳＦ社の「ＩＲＧＡＣＵＲＥ　ＰＡＧ　１０３」）
　Ｂ－２：［（５－ｐ－トルエンスルフォニルオキシイミノ－５Ｈ－チオフェン－２－イリデン）－（２－メチルフェニル）アセトニトリル］　　（ＢＡＳＦ社の「ＩＲＧＡＣＵＲＥ　ＰＡＧ　１２１」）
　Ｂ－３：トリフルオロメタンスルホン酸－１，８－ナフタルイミド
　Ｂ－４：１，１，１－トリ（ｐ－ヒドロキシフェニル）エタン（１．０モル）と１，２－ナフトキノンジアジド－５－スルホン酸クロリド（２．０モル）との縮合物
［Ｄ］酸化防止剤
　Ｄ－１：トリス－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシベンジル）－イソシアヌレイト（ＡＤＥＫＡ社の「アデカスタブＡＯ－２０」）
　Ｄ－２：ペンタエリスリトールテトラキス［３－（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］（ＡＤＥＫＡ社の「アデカスタブＡＯ－６０」） <Preparation of radiation-sensitive resin composition>
[B] The radiation sensitive acid generator and [D] antioxidant used for the preparation of the radiation sensitive resin compositions of Examples and Comparative Examples are shown below.
[B] Radiation-sensitive acid generator B-1: [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile] (“IRGACURE PAG 103” from BASF)
B-2: [(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile] (“IRGACURE PAG 121” from BASF)
B-3: trifluoromethanesulfonic acid-1,8-naphthalimide B-4: 1,1,1-tri (p-hydroxyphenyl) ethane (1.0 mol) and 1,2-naphthoquinonediazide-5-sulfone Condensate with acid chloride (2.0 mol) [D] Antioxidant D-1: Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate (“ADEKA STAB” from ADEKA) AO-20 ")
D-2: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (“ADEKA STAB AO-60” from ADEKA)
＜感放射線性樹脂組成物の調製＞
［実施例１］
　重合体（Ａ－１）１００質量部（固形分）に相当する量に対して、感放射線性酸発生体（Ｂ－１）３質量部、酸解離性基を有する化合物（Ｃ－１）２０質量部、及び密着助剤として３－グリシジルオキシプロピルトリメトキシシラン３質量部を混合し、固形分濃度が３０質量％となるようにジエチレングリコールエチルメチルエーテルに溶解させた後、孔径０．２μｍのメンブランフィルタで濾過して、感放射線性樹脂組成物を調製した。 <Preparation of radiation-sensitive resin composition>
[Example 1]
3 parts by mass of the radiation sensitive acid generator (B-1) and the compound (C-1) 20 having an acid dissociable group with respect to an amount corresponding to 100 parts by mass (solid content) of the polymer (A-1) 3 parts by mass and 3 parts by mass of 3-glycidyloxypropyltrimethoxysilane as an adhesion assistant are mixed and dissolved in diethylene glycol ethyl methyl ether so that the solid content concentration is 30% by mass, and then a membrane having a pore size of 0.2 μm. It filtered with the filter and the radiation sensitive resin composition was prepared.
［実施例２～２５及び比較例１～２］
　下記表２～３に示す種類及び配合量の［Ａ］重合体、［Ｂ］酸発生体、［Ｃ］化合物及び［Ｄ］酸化防止剤をそれぞれ用いたこと以外は実施例１と同様に操作し、実施例２～２５及び比較例１～２の感放射線性樹脂組成物を調製した。なお、いずれの感放射線性樹脂組成物においても、実施例１と同様に、密着助剤として３－グリシジルオキシプロピルトリメトキシシラン３質量部を混合している。表２～３において、「－」は該当する成分を配合しなかったことを示す。 [Examples 2 to 25 and Comparative Examples 1 and 2]
The same operation as in Example 1 except that [A] polymer, [B] acid generator, [C] compound and [D] antioxidant of the types and blending amounts shown in Tables 2 to 3 below were used. Then, radiation sensitive resin compositions of Examples 2 to 25 and Comparative Examples 1 and 2 were prepared. In any radiation sensitive resin composition, 3 parts by mass of 3-glycidyloxypropyltrimethoxysilane was mixed as an adhesion assistant, as in Example 1. In Tables 2 and 3, “-” indicates that the corresponding component was not blended.
＜評価＞
　実施例１～２５及び比較例１～２の感放射線性樹脂組成物から硬化膜を形成し、以下に説明する手法により、放射線感度、残膜率、比誘電率（絶縁性）及び配線腐食（腐食防止性）を評価した。実施例１～２５及び比較例１～２の評価結果を表２～３に示す。 <Evaluation>
A cured film was formed from the radiation-sensitive resin compositions of Examples 1 to 25 and Comparative Examples 1 and 2, and radiation sensitivity, residual film ratio, relative dielectric constant (insulating property), and wiring corrosion (by the method described below) Corrosion prevention) was evaluated. The evaluation results of Examples 1 to 25 and Comparative Examples 1 and 2 are shown in Tables 2 to 3.
［感放射線性組成物の放射線感度の評価］
　スピンナーを用い、６０℃で６０秒間ＨＭＤＳ処理したシリコン基板上に感放射線性樹脂組成物を塗布した後、９０℃にて２分間ホットプレート上でプレベークして膜厚３．０μｍの塗膜を形成した。この塗膜にキヤノン社のＭＰＡ－６００ＦＡ露光機を用い、幅１０μｍのライン・アンド・スペースパターンを有するパターンマスクを介して、水銀ランプによって所定量の紫外線を照射した。次いで、テトラメチルアンモニウムヒドロキシド２．３８質量％水溶液よりなる現像液を用い、２５℃で６０秒現像処理を行った後、超純水で１分間流水洗浄を行った。このとき、幅１０μｍのライン・アンド・スペースパターンを形成可能な最小露光量を測定した。この測定値が１５０ｍＪ／ｍ２未満の場合に感度は良好であり、１５０ｍＪ／ｍ２以上の場合に不良と評価できる。 [Evaluation of radiation sensitivity of radiation-sensitive composition]
Using a spinner, a radiation sensitive resin composition was applied on a silicon substrate that had been HMDS treated at 60 ° C. for 60 seconds, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. did. The coating film was irradiated with a predetermined amount of ultraviolet rays by a mercury lamp through a pattern mask having a line and space pattern having a width of 10 μm using a Canon MPA-600FA exposure machine. Next, using a developer composed of a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, development processing was carried out at 25 ° C. for 60 seconds, and then washed with running ultrapure water for 1 minute. At this time, the minimum exposure amount capable of forming a line and space pattern having a width of 10 μm was measured. Sensitivity if the measurement value is less than 150 mJ / m 2 is good, can be evaluated as defective in the case of 150 mJ / m 2 or more.
［残膜率の評価］
　上記「感放射線性組成物の放射線感度の評価」と同様に、シリコン基板上に塗膜を形成した。次いで、１００μｍのライン・アンド・スペース（１対１）のパターンを有するマスクを介して、塗膜に対し所定量の紫外線を照射した後、２．３８質量％のテトラメチルアンモニウムヒドロキシド水溶液にて２５℃で８０秒間現像処理を行った。次いで、超純水で１分間流水洗浄を行い、乾燥することにより、パターンを形成した。
　現像後パターン高さ（Ｔ１）を触針式膜厚測定装置（ＫＬＡテンコール社の「α―ステップ」）により測定した。その後、パターン形成されたシリコン基板をクリーンオーブン内にて２２０℃で１時間加熱して、熱硬化後のパターンを得た。同様にして、熱硬化後のパターン高さ（ｔ１）を測定した。これらの測定値から、残膜率｛（Ｔ１－ｔ１）／Ｔ１｝×１００〔％〕を算出した。このとき、残膜率が８０％以上の場合に良好であり、８０％未満の場合に不良と評価できる。 [Evaluation of remaining film ratio]
A coating film was formed on a silicon substrate in the same manner as in “Evaluation of radiation sensitivity of radiation-sensitive composition”. Then, after irradiating the coating film with a predetermined amount of ultraviolet rays through a mask having a 100 μm line-and-space (one-to-one) pattern, a 2.38 mass% tetramethylammonium hydroxide aqueous solution was used. Development processing was performed at 25 ° C. for 80 seconds. Next, washing with running ultrapure water for 1 minute was performed, followed by drying to form a pattern.
The post-development pattern height (T1) was measured with a stylus type film thickness measuring apparatus (“α-step” manufactured by KLA Tencor). Thereafter, the patterned silicon substrate was heated in a clean oven at 220 ° C. for 1 hour to obtain a thermally cured pattern. Similarly, the pattern height (t1) after thermosetting was measured. From these measured values, the remaining film ratio {(T1-t1) / T1} × 100 [%] was calculated. At this time, it is good when the remaining film ratio is 80% or more, and it can be evaluated as poor when it is less than 80%.
［絶縁性（比誘電率）の評価］
　スピンナーを用い、ＳＵＳ基板上に感放射線性樹脂組成物を塗布した後、９０℃にて２分間ホットプレート上でプレベークして膜厚３．０μｍの塗膜を形成した。露光機（キャノン社の「ＭＰＡ－６００ＦＡ」）を用い、積算照射量が９，０００Ｊ／ｍ２となるように上記塗膜を露光し、露光した基板をクリーンオーブン内にて２００℃で３０分加熱することにより、ＳＵＳ基板上に絶縁膜を形成した。次いで、蒸着法により、上記絶縁膜上にＰｔ／Ｐｄ電極パターンを形成して誘電率測定用サンプルを作製した。この電極パターンを有する基板について、電極（横河・ヒューレットパッカード社の「ＨＰ１６４５１Ｂ、」）及びプレシジョンＬＣＲメーター（横河・ヒューレットパッカード社の「ＨＰ４２８４Ａ」）を用い、周波数１０ｋＨｚでＣＶ法により比誘電率の測定を行った。比誘電率が３．７以下の場合に絶縁性が良好であると、３．７を超える場合に絶縁性が不良であると評価できる。 [Evaluation of insulation (dielectric constant)]
After applying the radiation sensitive resin composition on the SUS substrate using a spinner, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. Using an exposure machine (Canon's “MPA-600FA”), the coating film was exposed so that the integrated dose was 9,000 J / m 2, and the exposed substrate was placed in a clean oven at 200 ° C. for 30 minutes. An insulating film was formed on the SUS substrate by heating. Next, a Pt / Pd electrode pattern was formed on the insulating film by vapor deposition to produce a dielectric constant measurement sample. For the substrate having this electrode pattern, the relative dielectric constant is measured by the CV method at a frequency of 10 kHz using an electrode (“HP16451B” from Yokogawa-Hewlett-Packard) and a precision LCR meter (“HP4284A” from Yokogawa-Hewlett-Packard). Was measured. When the dielectric constant is 3.7 or less, if the insulation is good, it can be evaluated that the insulation is poor when it exceeds 3.7.
［配線腐食の評価］
　スピンナーを用い、アルミで形成された櫛形の配線基板上に感放射線性樹脂組成物を塗布した後、９０℃にて２分間ホットプレート上でプレベークして膜厚３．０μｍの塗膜を形成した。露光機（キャノン社の「ＭＰＡ－６００ＦＡ」）を用い、積算照射量が９，０００Ｊ／ｍ２となるように上記塗膜を露光し、露光した基板をクリーンオーブン内にて２００℃で３０分加熱することにより、配線基板上に絶縁膜を形成した。この配線基板について、６５℃／９０％の湿熱条件下にて、５００時間放置し、配線腐食試験を実施した。試験後の基板について、配線腐食の有無を顕微鏡で観察して配線腐食性を以下の基準で評価した。
　　Ａ：配線腐食なし
　　Ｂ：配線腐食あり [Evaluation of wiring corrosion]
Using a spinner, a radiation-sensitive resin composition was applied on a comb-shaped wiring board formed of aluminum, and then pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. . Using an exposure machine (Canon's “MPA-600FA”), the coating film was exposed so that the integrated dose was 9,000 J / m 2, and the exposed substrate was placed in a clean oven at 200 ° C. for 30 minutes. By heating, an insulating film was formed on the wiring board. The wiring board was left for 500 hours under a moist heat condition of 65 ° C./90%, and a wiring corrosion test was performed. About the board | substrate after a test, the presence or absence of wiring corrosion was observed with the microscope and wiring corrosivity was evaluated on the following references | standards.
A: No wiring corrosion B: Wiring corrosion
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000026
Figure JPOXMLDOC01-appb-T000027
Figure JPOXMLDOC01-appb-T000027
　表２～３の結果から明らかなように、実施例１～２５の感放射線性樹脂組成物及び硬化膜は、放射線感度、残膜率、絶縁性及び腐食防止性に優れるものであった。これに対し、比較例１～２の感放射線性樹脂組成物及び硬化膜は、放射線感度、残膜率、絶縁性及び腐食防止性のいずれかが劣っていた。 As is clear from the results in Tables 2 to 3, the radiation-sensitive resin compositions and cured films of Examples 1 to 25 were excellent in radiation sensitivity, residual film rate, insulation and corrosion prevention. In contrast, the radiation-sensitive resin compositions and cured films of Comparative Examples 1 and 2 were inferior in any of radiation sensitivity, residual film ratio, insulation and corrosion prevention properties.
　本発明の感放射線性樹脂組成物は、表示素子の層間絶縁膜、スペーサー、保護膜等の硬化膜として好適に用いることができる。
  The radiation-sensitive resin composition of the present invention can be suitably used as a cured film such as an interlayer insulating film, a spacer, or a protective film of a display element.

Claims (8)

  1. 　重合体、
    　感放射線性酸発生体、及び
    　酸解離性基を有し、下記式（１－１）～（１－６）のいずれかの式で表される少なくとも１種の化合物
    を含む表示素子用硬化膜形成用の感放射線性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式（１－１）～（１－６）中、１又は複数のＸは、それぞれ独立して、酸解離性基を有する有機基である。
    　式（１－１）中、複数のＲ１は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。ｎ１は、１～３の整数である。ｎ２は、０～２の整数である。
    　式（１－２）中、複数のＲ２は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。Ａは、単結合、メチレン基、炭素数２～１２のアルキレン基、フェニレン基、酸素原子、硫黄原子、又はメチレン基、炭素数２～１２のアルキレン基若しくはフェニレン基が有する水素原子の少なくとも一部が下記式（１－７）で表される基、フッ素原子若しくはカルボキシ基で置換された基である。ｎ３は、１～３の整数である。ｎ４は、１～３の整数である。
    　式（１－３）中、複数のＲ３及び複数のＲ４は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、これらの基が有する水素原子の少なくとも一部が置換基で置換された基、又は下記式（１－７）で表される基である。
    　式（１－４）中、複数のＲ５は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。ｍは、０～１０の整数である。
    　式（１－５）中、複数のＲ６は、それぞれ独立して、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。ｐは、０～１０の整数である。
    　式（１－６）中、Ｒ７は、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。ｎ５は、１～３の整数である。ｎ６は、１～５の整数である。ｎ７は、０～５の整数である。ｎ７が２以上である場合、複数のＲ７は、それぞれ同一でも異なっていてもよい。）
    Figure JPOXMLDOC01-appb-C000002
     （式（１－７）中、Ｘは、酸解離性基を有する有機基である。複数のＲ８は、水素原子、炭素数１～１２のアルキル基、炭素数１～１２のアルコキシ基、脂環式炭化水素基、アリール基、又はこれらの基が有する水素原子の一部又は全部が置換基で置換された基である。＊は、結合する部位を示す。）     Polymer,
    Radiation-sensitive acid generator, and cured film for display element having an acid-dissociable group and containing at least one compound represented by any one of formulas (1-1) to (1-6) below Radiation sensitive resin composition for forming.
    Figure JPOXMLDOC01-appb-C000001
     (In the formulas (1-1) to (1-6), one or more Xs are each independently an organic group having an acid dissociable group.
    In the formula (1-1), a plurality of R 1 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent. n 1 is an integer of 1 to 3. n 2 is an integer of 0-2.
    In formula (1-2), a plurality of R 2 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent. A represents a single bond, a methylene group, an alkylene group having 2 to 12 carbon atoms, a phenylene group, an oxygen atom, a sulfur atom, or at least a part of hydrogen atoms of a methylene group, an alkylene group having 2 to 12 carbon atoms, or a phenylene group. Is a group represented by the following formula (1-7), a group substituted with a fluorine atom or a carboxy group. n 3 is an integer of 1 to 3. n 4 is an integer of 1 to 3.
    In formula (1-3), a plurality of R 3 and a plurality of R 4 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alicyclic hydrocarbon. A group, an aryl group, a group in which at least part of hydrogen atoms of these groups are substituted with a substituent, or a group represented by the following formula (1-7).
    In formula (1-4), a plurality of R 5 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent. m is an integer of 0 to 10.
    In formula (1-5), a plurality of R 6 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, Alternatively, these groups are groups in which at least a part of the hydrogen atoms are substituted with a substituent. p is an integer of 0 to 10.
    In formula (1-6), R 7 represents at least one of an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group, an aryl group, or a hydrogen atom included in these groups. A part of the group is substituted with a substituent. n 5 is an integer of 1 to 3. n 6 is an integer of 1 to 5. n 7 is an integer of 0 to 5. When n 7 is 2 or more, the plurality of R 7 may be the same or different from each other. )
    Figure JPOXMLDOC01-appb-C000002
     (In the formula (1-7), X is an organic group having an acid-dissociable group. The plurality of R 8 are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, An alicyclic hydrocarbon group, an aryl group, or a group in which some or all of the hydrogen atoms of these groups are substituted with a substituent.
  2. 　上記Ｘで表される有機基が、下記式（２－１）で表される基、及び下記式（２－２）で表される基の少なくとも一方である請求項１に記載の感放射線性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000003
     （式（２－１）中、Ｒ１ａ及びＲ２ａは、それぞれ独立して、水素原子、炭素数１～３０の炭化水素基、又はこの炭化水素基が有する水素原子の少なくとも一部がヒドロキシ基、ハロゲン原子若しくはシアノ基で置換された基である。但し、Ｒ１ａ及びＲ２ａが共に水素原子である場合はない。Ｒ３ａは、炭素数１～３０の炭化水素基、この炭素水素基の炭素－炭素間若しくは結合手側末端に酸素原子を含む基、又はこれらの基が有する水素原子の少なくとも一部がヒドロキシ基、ハロゲン原子若しくはシアノ基で置換された基である。Ｙ１は、単結合、カルボニル基又は－Ｚ１－Ｃ（＝Ｏ）－で表される基である。Ｚ１は、炭素数１～２０の２価の連結基である。
    　式（２－２）中、Ｒ４ａ～Ｒ１０ａは、それぞれ独立して、水素原子又は炭素数１～１２の炭化水素基である。ｒは、１又は２である。ｒが２の場合、複数のＲ７ａ及びＲ８ａは、それぞれ同一でも異なっていてもよい。Ｙ２は、単結合、カルボニル基又は－Ｚ２－Ｃ（＝Ｏ）－で表される基である。Ｚ２は、炭素数１～１０の２価の連結基である。）     The radiation-sensitive property according to claim 1, wherein the organic group represented by X is at least one of a group represented by the following formula (2-1) and a group represented by the following formula (2-2). Resin composition.
    Figure JPOXMLDOC01-appb-C000003
     (In the formula (2-1), R 1a and R 2a are each independently a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or at least a part of the hydrogen atoms of the hydrocarbon group is a hydroxy group. , A group substituted with a halogen atom or a cyano group, provided that R 1a and R 2a are not both hydrogen atoms, R 3a is a hydrocarbon group having 1 to 30 carbon atoms, A group containing an oxygen atom between carbon-carbon or at the bond-side end, or a group in which at least a part of hydrogen atoms of these groups are substituted with a hydroxy group, a halogen atom or a cyano group Y 1 is a single group. A bond, a carbonyl group, or a group represented by —Z 1 —C (═O) —, wherein Z 1 is a divalent linking group having 1 to 20 carbon atoms;
    In formula (2-2), R 4a to R 10a are each independently a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms. r is 1 or 2. When r is 2, the plurality of R 7a and R 8a may be the same or different. Y 2 is a single bond, a carbonyl group or a group represented by —Z 2 —C (═O) —. Z 2 is a divalent linking group having 1 to 10 carbon atoms. )
  3. 　上記重合体が、カルボキシ基を有するアクリル樹脂、ポリイミド若しくはポリイミド前駆体、ポリシロキサン、芳香族ポリエーテル又はこれらの組み合わせである請求項１又は請求項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 polymer is an acrylic resin having a carboxy group, polyimide or a polyimide precursor, polysiloxane, aromatic polyether, or a combination thereof.
  4. 　上記感放射線性酸発生体が、下記式（３）で表されるオキシムスルホネート基を含む化合物である請求項１、請求項２又は請求項３に記載の感放射線性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000004
     （式（３）中、Ｒｂは、アルキル基、脂環式炭化水素基、アリール基又はこれらの基が有する水素原子の少なくとも一部が置換基で置換された基である。）     The radiation sensitive resin composition according to claim 1, wherein the radiation sensitive acid generator is a compound containing an oxime sulfonate group represented by the following formula (3).
    Figure JPOXMLDOC01-appb-C000004
     (In Formula (3), Rb is an alkyl group, an alicyclic hydrocarbon group, an aryl group, or a group in which at least a part of hydrogen atoms of these groups is substituted with a substituent.)
  5. 　酸化防止剤をさらに含有する請求項１から請求項４のいずれか１項に記載の感放射線性樹脂組成物。 The radiation sensitive resin composition according to any one of claims 1 to 4, further comprising an antioxidant.
  6. 　請求項１から請求項５のいずれか１項に記載の感放射線性樹脂組成物から形成される表示素子用硬化膜。 A cured film for a display element formed from the radiation-sensitive resin composition according to any one of claims 1 to 5.
  7. 　基板上に塗膜を形成する工程、
    　この塗膜の少なくとも一部に放射線を照射する工程、
    　上記放射線が照射された塗膜を現像する工程、及び
    　上記現像された塗膜を加熱する工程を備え、
    　上記塗膜の形成に請求項１から請求項５のいずれか１項に記載の感放射線性樹脂組成物を用いる表示素子用硬化膜の形成方法。     Forming a coating film on the substrate;
    Irradiating at least a part of the coating film with radiation,
    A step of developing the coating film irradiated with the radiation, and a step of heating the developed coating film,
    The formation method of the cured film for display elements which uses the radiation sensitive resin composition of any one of Claims 1-5 for formation of the said coating film.
  8. 　請求項６に記載の表示素子用硬化膜を備える表示素子。
          A display element provided with the cured film for display elements of Claim 6.
PCT/JP2015/081227 2014-11-14 2015-11-05 Radiation sensitive resin composition, cured film for display elements, method for forming cured film for display elements, and display element WO2016076205A1 (en)

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