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WO2015046501A1 - Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device - Google Patents

Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device Download PDF

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Publication number
WO2015046501A1
WO2015046501A1 PCT/JP2014/075854 JP2014075854W WO2015046501A1 WO 2015046501 A1 WO2015046501 A1 WO 2015046501A1 JP 2014075854 W JP2014075854 W JP 2014075854W WO 2015046501 A1 WO2015046501 A1 WO 2015046501A1
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WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
resin composition
photosensitive resin
acid
Prior art date
Application number
PCT/JP2014/075854
Other languages
French (fr)
Japanese (ja)
Inventor
享平 崎田
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2015539420A priority Critical patent/JP6082473B2/en
Priority to KR1020167007841A priority patent/KR101755423B1/en
Publication of WO2015046501A1 publication Critical patent/WO2015046501A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C08F212/24—Phenols or alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • 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
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • 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
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • 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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/124—Insulating layers formed between TFT elements and OLED elements

Definitions

  • the present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”). Moreover, it is related with the manufacturing method of the cured film using the said photosensitive resin composition, the cured film formed by hardening
  • the present invention relates to an article and a method for producing a cured film using the article.
  • Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film.
  • photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.
  • the interlayer insulating film in the display device is required to have physical properties of a cured film, such as excellent volume resistivity, solvent resistance, heat resistance, hardness, and indium tin oxide (ITO) sputtering suitability.
  • a photosensitive resin composition is disclosed in Patent Document 1, for example.
  • Patent Document 2 describes an imide sulfonate compound having a specific structure.
  • the photosensitive resin composition described in Patent Document 1 has high transmittance after curing and high sensitivity without performing post-exposure heat treatment (PEB). There is a tendency that a higher volume resistivity is required. Thus, in the photosensitive resin composition, there is no known means for achieving both higher volume resistivity while maintaining high sensitivity.
  • PEB post-exposure heat treatment
  • the present invention is intended to solve such problems, and maintains a high sensitivity, and has a higher volume resistivity, a photosensitive resin composition having a higher volume resistivity, a method for producing a cured film, a cured film, and a liquid crystal display.
  • An object is to provide a device and an organic EL display device.
  • ⁇ 1> (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2): (1) (a1) a polymer having a structural unit having an acid group protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group (2) (a1) the acid group is acid-decomposable A polymer having a structural unit having a group protected by a group, and (a2) a polymer having a structural unit having a crosslinkable group (B) a photoacid generator represented by the following general formula (I); C) solvent, Containing a photosensitive resin composition;
  • one of R 1 and R 2 represents a group represented by the following general formula (A), and the other represents a hydrogen atom;
  • R 3 represents a halogen atom, an alkylthio group, and an
  • X 1 represents an oxygen atom or a sulfur atom
  • Y 1 represents a single bond or an alkylene group having 1 to 4 carbon atoms
  • R 4 represents a hydrocarbon group having 1 to 12 carbon atoms.
  • R 5 represents an alkylene group having 1 to 4 carbon atoms
  • R 6 represents a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, or an alicyclic carbon atom having 3 to 10 carbon atoms.
  • n represents an integer of 0 to 5, and when n is 2 to 5, a plurality of R 5 may be the same or different
  • General formula (B) In the general formula (B), Y 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms, R 7 represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, carbon Represents an arylene group having 6 to 20 carbon atoms or a halogenated arylene group having 6 to 20 carbon atoms, and R 8 represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogen
  • R 3 in the general formula (I) is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, a perfluoroalkyl group having 1 to 8 carbon atoms, or a 6 to 10 carbon atoms that may be substituted with a halogen atom.
  • the photosensitive resin composition according to ⁇ 1> which represents an aryl group or an alkylaryl group having 7 to 10 carbon atoms which may be substituted with a halogen atom.
  • ⁇ 5> (B) The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the photoacid generator represented by the general formula (I) has a molecular weight of 335 to 800.
  • ⁇ 6> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 5>, further comprising a crosslinking agent.
  • ⁇ 7> (1) A step of applying the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 6> on a substrate, (2) a step of removing the solvent from the applied photosensitive resin composition; (3) a step of exposing with actinic radiation, (4) a step of developing with an aqueous developer, and (5) A method for producing a cured film comprising a post-bake step of thermosetting.
  • ⁇ 8> A cured film obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 6>.
  • ⁇ 9> The cured film according to ⁇ 8>, which is an interlayer insulating film.
  • ⁇ 10> A liquid crystal display device or an organic EL display device having the cured film according to ⁇ 8> or ⁇ 9>.
  • a photosensitive resin composition having high sensitivity and high volume resistivity, a method for producing a cured film, a cured film, a liquid crystal display device, and an organic EL display device.
  • FIG. 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device.
  • the schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film.
  • 1 shows a conceptual diagram of a configuration of an example of an organic EL display device.
  • a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
  • the description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
  • “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
  • the organic EL element in the present invention refers to an organic electroluminescence element.
  • the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent.
  • the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the acid generator represented by the general formula (I) does not include a substituent except for a group that is specified to be optionally substituted.
  • “(meth) acrylate” represents acrylate and methacrylate
  • “(meth) acryl” represents acryl and methacryl
  • “(meth) acryloyl” represents acryloyl and methacryloyl.
  • the photosensitive resin composition of the present invention comprises (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2), (1) (a1) an acid group is protected with an acid-decomposable group. (A2) a polymer having a structural unit having a crosslinkable group, (2) (a1) a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group, And (a2) a polymer having a structural unit having a crosslinkable group (B) and a photoacid generator represented by the following general formula (I).
  • R 1 and R 2 represents a group represented by the following general formula (A), and the other represents a hydrogen atom.
  • R 3 represents a halogen atom, an alkylthio group, and an alicyclic ring.
  • Formula (A) (In the general formula (A), X 1 represents an oxygen atom or a sulfur atom, Y 1 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R 4 represents a hydrocarbon having 1 to 12 carbon atoms.
  • R 5 represents an alkylene group having 1 to 4 carbon atoms
  • R 6 represents a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, or an alicyclic group having 3 to 10 carbon atoms.
  • n represents an integer of 0 to 5
  • a plurality of R 5 may be the same or different.
  • Y 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms
  • R 7 represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms
  • R 8 represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms
  • R 9 represents an alkyl group having 1 to 18 carbon atoms which may be branched, or 1 carbon atom which may be branched.
  • a halogenated alkyl group having 18 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a halogenated arylalkyl group having 7 to 20 carbon atoms A and Each independently represent 0 or 1, at least one of a and b is 1.
  • Patent Document 2 (WO2011 / 087011 pamphlet) is used as a photoresist, and volume resistivity is not a problem in the first place.
  • composition of this invention is normally used as a chemically amplified positive photosensitive resin composition.
  • the composition of the present invention comprises, as a polymer component, a polymer (1) having (a1) a structural unit having an acid group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group, And (a1) at least one of a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a2) a polymer (2) having a structural unit having a crosslinkable group. Furthermore, polymers other than these may be included.
  • the polymer component (A) in the present invention includes, in addition to the polymer (1) and / or the polymer (2), other polymers added as necessary, unless otherwise specified. means.
  • (a1) includes a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a2) a polymer having a structural unit having a crosslinkable group
  • (a1) The ratio of the polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group and the polymer having a structural unit having a crosslinkable group (a2) is preferably 95: 5 to 5:95, 80:20 to 20:80 is more preferable, and 70:30 to 30:70 is more preferable.
  • a polymer (1) is included at least from a viewpoint of volume resistivity.
  • the (A) polymer component is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof.
  • a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc.
  • the “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”.
  • the polymer component has at least a structural unit (a1) having a group in which an acid group is protected with an acid-decomposable group.
  • a polymer component has a structural unit (a1), it can be set as the highly sensitive photosensitive resin composition.
  • the “group in which the acid group is protected with an acid-decomposable group” in the present invention those known as an acid group and an acid-decomposable group can be used and are not particularly limited.
  • Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group.
  • Specific acid-decomposable groups include groups that are relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group, which will be described later), or an acid.
  • a group that is relatively difficult to decompose for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group
  • a tertiary alkyl group such as a tert-butyl ester group
  • a tertiary alkyl carbonate group such as a tert-butyl carbonate group
  • the structural unit (a1) is preferably a structural unit having a protected carboxyl group protected with an acid-decomposable group or a structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group.
  • the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order. To do.
  • the structural unit (a1-1) is a structural unit having a protected carboxyl group in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below.
  • the structural unit having a carboxyl group that can be used for the structural unit (a1-1) is not particularly limited, and a known structural unit can be used.
  • Examples thereof include a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid. It is done.
  • the structural unit (a1-1-1) used as the structural unit having a carboxyl group will be described.
  • ⁇ (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>>>>>
  • the unsaturated carboxylic acid used in the present invention include those listed below. That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, ⁇ -chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acrylic acid. And leuoxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, and the like.
  • the unsaturated dicarboxylic acid examples include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
  • the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the structural unit which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
  • the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like.
  • the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both terminals, and examples thereof include ⁇ -carboxypolycaprolactone monoacrylate and ⁇ -carboxypolycaprolactone monomethacrylate.
  • unsaturated carboxylic acid acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
  • acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acrylic acid are used. It is preferable to use leuoxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or an anhydride of an unsaturated polycarboxylic acid, and acrylic acid, methacrylic acid, 2- (meth) acrylic acid, etc. It is more preferable to use leuoxyethyl hexahydrophthalic acid.
  • the structural unit (a1-1-1) may be composed of one type alone, or may be composed of two or more types.
  • acid-decomposable group that can be used for the structural unit (a1-1) >>>>>
  • the acid-decomposable group that can be used for the structural unit (a1-1) the acid-decomposable groups described above can be used.
  • the acid-decomposable group is preferably a group having a structure protected in the form of an acetal.
  • the carboxyl group is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, the basic physical properties of the photosensitive resin composition, particularly the sensitivity and pattern shape, the formation of contact holes, the storage stability of the photosensitive resin composition
  • the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10).
  • the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10)
  • the entire protected carboxyl group is — (C ⁇ O) —O—CR 101
  • the structure is R 102 (OR 103 ).
  • R 101 and R 102 each independently represents a hydrogen atom or an alkyl group, except that R 101 and R 102 are both hydrogen atoms, and R 103 represents an alkyl group.
  • R 101 or R 102 and R 103 may be linked to form a cyclic ether.
  • R 101 to R 103 each independently represents a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic.
  • both R 101 and R 102 do not represent a hydrogen atom, and at least one of R 101 and R 102 represents an alkyl group.
  • the linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
  • R 101 to R 103 each independently represents a hydrogen atom or an alkyl group.
  • the alkyl group may be linear, branched or cyclic.
  • both R 101 and R 102 do not represent a hydrogen atom, and at least one of R 101 and R 102 represents an alkyl group.
  • the linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
  • methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
  • the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms.
  • Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.
  • the alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group.
  • R 101 , R 102 and R 103 When it has a halogen atom as a substituent, R 101 , R 102 and R 103 become a haloalkyl group, and when it has an aryl group as a substituent, R 101 , R 102 and R 103 become an aralkyl group.
  • the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an ⁇ -methylphenyl group, and a naphthyl group.
  • the alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.
  • the cyclic alkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is straight.
  • the alkyl group is a chain or branched chain, it may have a cyclic alkyl group having 3 to 12 carbon atoms as a substituent. These substituents may be further substituted with the above substituents.
  • R 101 , R 102 and R 103 represent an aryl group
  • the aryl group preferably has 6 to 12 carbon atoms, and preferably 6 to 10 carbon atoms. More preferred.
  • the aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.
  • R 101 , R 102 and R 103 can be bonded to each other to form a ring together with the carbon atom to which they are bonded.
  • Examples of the ring structure when R 101 and R 102 , R 101 and R 103, or R 102 and R 103 are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like. Note that in the general formula (a1-10), it is preferable that any one of R 101 and R 102 be a hydrogen atom or a methyl group.
  • radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the general formula (a1-10) a commercially available one may be used, or it may be synthesized by a known method. Things can also be used. For example, it can be synthesized by the synthesis method described in paragraph Nos. 0037 to 0040 of JP2011-212494A, the contents of which are incorporated herein.
  • a first preferred embodiment of the structural unit (a1-1) is a structural unit represented by the following general formula (A2 ′).
  • R 1 and R 2 each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 represents an alkyl group or an aryl group, and R 3 represents Represents an alkyl group or an aryl group, and R 1 or R 2 and R 3 may be linked to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or arylene. Represents a group.
  • R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred.
  • R 1 and R 2 are aryl groups, a phenyl group is preferred.
  • R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
  • X represents a single bond or an arylene group, and a single bond is preferred.
  • a second preferred embodiment of the structural unit (a1-1) is a structural unit represented by the following general formula (1-12).
  • Formula (1-12) (In the formula (1-12), R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 1 represents a carbonyl group or a phenylene group, and R 122 to R 128 each independently represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms.) R 121 is preferably a hydrogen atom or a methyl group. L 1 is preferably a carbonyl group. R 122 to R 128 are preferably hydrogen atoms.
  • R represents a hydrogen atom or a methyl group.
  • the structural unit (a1-2) is a structural unit (a1-2-1) having a protected phenolic hydroxyl group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below.
  • ⁇ (a1-2-1) Structural Unit Having Phenolic Hydroxyl Group examples include a hydroxystyrene structural unit and a structural unit in a novolac resin.
  • a structural unit derived from hydroxystyrene or ⁇ -methylhydroxystyrene includes: It is preferable from the viewpoint of sensitivity.
  • a structural unit represented by the following general formula (a1-20) is also preferable from the viewpoint of sensitivity.
  • R 220 represents a hydrogen atom or a methyl group
  • R 221 represents a single bond or a divalent linking group
  • R 222 represents a halogen atom or a straight chain of 1 to 5 carbon atoms or Represents a branched alkyl group
  • a represents an integer of 1 to 5
  • b represents an integer of 0 to 4
  • a + b is 5 or less
  • R 222 is 2 or more, these R 222 may be different from each other or the same.
  • R 220 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
  • R 221 represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved.
  • the divalent linking group of R 221 may be exemplified alkylene groups, specific examples R 221 is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Among these, it is preferable that R 221 is a single bond, a methylene group, or an ethylene group.
  • the divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group.
  • A represents an integer of 1 to 5, but a is preferably 1 or 2 and more preferably 1 from the viewpoint of the effects of the present invention and the ease of production.
  • the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R 221 is defined as the reference (first position).
  • R 222 is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms.
  • a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
  • B represents 0 or an integer of 1 to 4;
  • acid-decomposable group that can be used for the structural unit (a1-2) >>>>>
  • the acid-decomposable group that can be used for the structural unit (a1-2) as with the acid-decomposable group that can be used for the structural unit (a1-1), known ones can be used. It is not limited.
  • a structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability.
  • the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the above general formula (a1-10).
  • the protected phenolic hydroxyl group as a whole is —Ar—O—CR 101 R
  • the structure is 102 (OR 103 ).
  • Ar represents an arylene group.
  • Examples of the radical polymerizable monomer used for forming a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include paragraph number 0042 of JP2011-215590A. And the like.
  • a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.
  • acetal protecting group for the phenolic hydroxyl group examples include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group.
  • 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned, These can be used individually or in combination of 2 or more types.
  • the radical polymerizable monomer used for forming the structural unit (a1-2) a commercially available one may be used, or one synthesized by a known method may be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.
  • the content of the structural unit (a1) is preferably 20 to 100 mol% in the polymer, 30 -90 mol% is more preferable.
  • the content of the structural unit (a1) is preferably 3 to 70 mol% in the polymer from the viewpoint of sensitivity. More preferred is ⁇ 60 mol%.
  • the acid-decomposable group that can be used in the structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal
  • the content is preferably 20 to 50 mol%.
  • the structural unit (a1-1) is characterized by faster development than the structural unit (a1-2). Therefore, when it is desired to develop quickly, the structural unit (a1-1) is preferable. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-2).
  • the polymer component has a structural unit (a2) having a crosslinkable group.
  • the crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment.
  • Preferred embodiments of the structural unit having a crosslinkable group include an epoxy group, an oxetanyl group, a group represented by —NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and ethylene.
  • the (A) polymer component includes a structural unit including at least one of an epoxy group and an oxetanyl group.
  • the (A) polymer component preferably contains a structural unit having an epoxy group and / or an oxetanyl group (hereinafter also referred to as a structural unit (a2-1)).
  • the structural unit (a2-1) may have at least one epoxy group or oxetanyl group in one structural unit, and includes one or more epoxy groups, one or more oxetanyl groups, and two or more epoxy groups.
  • Group may have two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, and a total of epoxy groups and / or oxetanyl groups It is more preferable to have one or two, and it is more preferable to have one epoxy group or one oxetanyl group.
  • radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, and glycidyl ⁇ -n-propyl acrylate.
  • radical polymerizable monomer used for forming the structural unit having an oxetanyl group include (meth) having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A No. 2001-330953, for example. Examples thereof include acrylate esters and compounds described in paragraph No. 0027 of JP2012-088459A, the contents of which are incorporated herein.
  • radical polymerizable monomer used for forming the structural unit (a2-1) having the epoxy group and / or oxetanyl group include a monomer having a methacrylic ester structure and an acrylic ester structure. A monomer to be contained is preferable.
  • glycidyl methacrylate 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl.
  • Glycidyl ether, acrylic acid (3-ethyloxetane-3-yl) methyl, and methacrylic acid (3-ethyloxetane-3-yl) methyl are preferred from the viewpoints of copolymerization reactivity and improved properties of the cured film. .
  • These structural units can be used individually by 1 type or in combination of 2 or more types.
  • R represents a hydrogen atom or a methyl group.
  • (a2-2) Structural unit having an ethylenically unsaturated group >>>
  • the structural unit (a2) having a crosslinkable group there may be mentioned the structural unit (a2-2) having an ethylenically unsaturated group.
  • the structural unit (a2-2) is preferably a structural unit having an ethylenically unsaturated group in the side chain, and a structural unit having an ethylenically unsaturated group at the terminal and having a side chain having 3 to 16 carbon atoms. More preferred.
  • the polymer component (A) used in the present invention is a structural unit (a2-3) having a group represented by —NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Is also preferable.
  • R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
  • the structural unit (a2-3) is more preferably a structural unit having a group represented by the following general formula (a2-30).
  • Formula (a2-30) (In the general formula (a2-30), R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) R 2 is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • the alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
  • R 2 include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.
  • the content of the structural unit (a2) is preferably 5 to 90 mol% in the polymer, 20 More preferred is ⁇ 80 mol%.
  • the content of the structural unit (a2) is preferably 3 to 70 mol% from the viewpoint of chemical resistance in the polymer. 10 to 60 mol% is more preferable.
  • the content of the structural unit (a2) is preferably 3 to 70 mol% in all the structural units of the polymer component (A) regardless of any embodiment, and preferably 10 to 60 mol%. It is more preferable that By setting it within the above numerical range, a cured film having excellent characteristics can be formed.
  • the (A) polymer component may have another structural unit (a3) in addition to the structural unit (a1) and / or the structural unit (a2).
  • the structural unit (a3) may be contained in the polymer (1) and / or (2).
  • the polymer has a structural unit (a3) that does not substantially contain the structural unit (a1) and the structural unit (a2). Also good.
  • a monomer used as another structural unit (a3) For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds be able to.
  • the other structural unit (a1-3) monomers can be used alone or in combination of two or more.
  • the structural unit (a3) is styrene, methyl styrene, hydroxy styrene, ⁇ -methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, 4-hydroxy Benzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acryloylmorpholine, N-cyclohexylmale
  • styrenes and groups having an aliphatic cyclic skeleton are preferable from the viewpoint of electrical characteristics.
  • Specific examples include styrene, methylstyrene, hydroxystyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate.
  • (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion.
  • Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.
  • the other structural unit (a3) it is preferable to include a repeating unit containing an acid group.
  • the acid group in the present invention means a proton dissociable group having a pKa of less than 7.
  • the acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
  • Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Amide groups, sulfonylimide groups and the like are exemplified, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
  • the structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. .
  • (a1) the structural unit and / or (a2) the structural unit can be introduced into the same polymer, and (a1) the structural unit and (a2) the structural unit. It can also be introduced as a constituent unit of a different polymer.
  • a resin having a carboxyl group in the side chain is preferable.
  • methacrylic acid copolymer acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc.
  • side chain examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.
  • benzyl (meth) acrylate / (meth) acrylic acid copolymer 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid
  • Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein. These polymers may contain only 1 type and may contain 2 or more types.
  • SMA 1000P As these polymers, commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above, manufactured by BASF, etc.) You can also.
  • a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group it is particularly preferable from the viewpoint of sensitivity to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group.
  • a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group for example, compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein.
  • the structural unit containing an acid group is preferably 1 to 80% by mole, more preferably 1 to 50% by mole, still more preferably 5 to 40% by mole, and particularly preferably 5 to 30% by mole of the structural unit of all polymer components. 5 to 25 mol% is particularly preferred.
  • the other structural unit (a3) includes a structural unit containing at least an acid group.
  • the polymer In addition to the polymer (1) or (2), the polymer further has a polymer having another structural unit (a3) substantially free from the structural unit (a1) and the structural unit (a1-2). .
  • a form comprising a combination of two or more of the first to fifth embodiments.
  • the total amount of the polymer having (a1) and / or (a2) is preferably 99: 1 to 5:95, and 97: 3 to 30:70. Is more preferable, and 95: 5 to 50:50 is even more preferable.
  • the molecular weight of the polymer component (A) is a polystyrene-converted weight average molecular weight, and is preferably in the range of 1,000 to 200,000, more preferably 2,000 to 50,000. Various characteristics are favorable in the range of said numerical value.
  • the ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
  • the weight average molecular weight and dispersion degree of a polymer component are defined as a polystyrene conversion value by GPC measurement.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer component are, for example, HLC-8120 (manufactured by Tosoh Corporation), and TSK gel Multipore HXL-M (Tosoh ( 7.8 mm ID ⁇ 30.0 cm can be obtained by using THF (tetrahydrofuran) as an eluent.
  • (A) Production Method of Polymer Component >> also, various methods are known for the synthesis method of the polymer component (A). For example, in order to form at least the structural units represented by the above (a1) and (a3) It can be synthesized by polymerizing a radical polymerizable monomer mixture containing the radical polymerizable monomer used in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
  • the polymer preferably contains 50 mol% or more, more preferably 80 mol% or more of the structural unit derived from (meth) acrylic acid and / or its ester with respect to all the structural units. .
  • the composition of this invention contains the photo-acid generator represented by (B) general formula (I).
  • one of R 1 and R 2 represents a group represented by the following general formula (A), and the other represents a hydrogen atom.
  • R 3 represents a halogen atom, an alkylthio group, and an alicyclic ring.
  • Formula (A) (In the general formula (A), X 1 represents an oxygen atom or a sulfur atom, Y 1 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R 4 represents a hydrocarbon having 1 to 12 carbon atoms.
  • R 5 represents an alkylene group having 1 to 4 carbon atoms
  • R 6 represents a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, or an alicyclic group having 3 to 10 carbon atoms.
  • n represents an integer of 0 to 5
  • a plurality of R 5 may be the same or different.
  • Y 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms
  • R 7 represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms
  • R 8 represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms
  • R 9 represents an alkyl group having 1 to 18 carbon atoms which may be branched, or 1 carbon atom which may be branched.
  • a halogenated alkyl group having 18 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a halogenated arylalkyl group having 7 to 20 carbon atoms A and Each independently represent 0 or 1, at least one of a and b is 1.
  • R 1 and R 2 in Formula (I) >>
  • one of R 1 and R 2 represents a group represented by general formula (A), and the other represents a hydrogen atom.
  • X 1 represents an oxygen atom or a sulfur atom.
  • R 1 preferably represents a hydrogen atom
  • R 2 preferably represents a hydrogen atom.
  • R 4 represents a hydrocarbon group having 1 to 12 carbon atoms.
  • the hydrocarbon group having 1 to 12 carbon atoms is preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and still more preferably a hydrocarbon group having 1 to 3 carbon atoms.
  • the hydrocarbon group having 1 to 12 carbon atoms includes an aliphatic hydrocarbon group such as an alkylene group, an alkenyl group and an alkynylene group, an alicyclic hydrocarbon group such as a cycloalkylene group, an aliphatic hydrocarbon and an alicyclic hydrocarbon. Examples thereof include a bonded group, and an alkylene group is preferable.
  • R 4 is preferably a methylene group, an ethylene group or a propylene group, more preferably a methylene group and / or an ethylene group.
  • each R 5 independently represents an alkylene group having 1 to 4 carbon atoms.
  • the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a propylene group, and a butylene group.
  • R 5 is preferably a methylene group or an ethylene group.
  • Y 1 represents an alkylene group having 1 to 4 carbon atoms.
  • the alkylene group having 1 to 4 carbon atoms has the same meaning as described for R 5 , and the preferred range is also the same.
  • R 6 represents a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, a heterocyclic group, or a hydroxyl group.
  • alkyl group having 1 to 4 carbon atoms which may be branched include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, and an isobutyl group. .
  • Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, and bicyclo [2.1.1] hexyl. Group, bicyclo [2.2.1] heptyl group, bicyclo [3.2.1] octyl group, bicyclo [2.2.2] octyl group, adamantyl group and the like.
  • As the heterocyclic group a heterocyclic group having 3 to 10 carbon atoms is preferable.
  • heterocyclic group constituting the heterocyclic group examples include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, Isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine, isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chroman, thiochroman, isochroman, isothiochroman, indoline, isoindoline, pyrindin, Indolizine, indole, indazole, purine, quinolidine, isoquinoline, quinoline, naphthyridine, phthalazine, quinoxaline, quinazoline, cinnoline, pteridine, acri
  • R 6 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group, and even more preferably a hydrogen atom or a hydroxyl group.
  • n represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably 0 or 1.
  • n is 2 to 5
  • a plurality of R 5 may be the same or different but are preferably the same.
  • R 3 represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with any one or more of a halogen atom, an alkylthio group and an alicyclic hydrocarbon group, a halogen atom, an alkylthio group, an alkyl group and an acyl.
  • the hydrogen atom of the aliphatic hydrocarbon group having 1 to 18 carbon atoms may be substituted with any one or more of a halogen atom, an alkylthio group and an alicyclic hydrocarbon group.
  • a hydrogen atom of the alkylthio group or alicyclic hydrocarbon group which is a substituent further includes a halogen atom, an alkylthio group, and This includes the case where any one or more of the alicyclic hydrocarbon groups are substituted.
  • Other groups in the general formula (I) are also interpreted in the same manner.
  • the aliphatic hydrocarbon group having 1 to 18 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and an aliphatic hydrocarbon group having 1 to 3 carbon atoms. More preferred are group hydrocarbon groups.
  • a linear or branched alkyl group is preferable.
  • alkyl group examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, 2 -Hexyl, 3-hexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl Group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, cyclopropyl
  • halogen atom examples include fluorine, chlorine, bromine, and iodine.
  • a fluorine atom or a chlorine atom is preferable, and fluorine is more preferable.
  • the aliphatic hydrocarbon group having 1 to 18 carbon atoms substituted with a halogen atom is preferably a perfluoroalkyl group having 1 to 10 carbon atoms, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and 1 carbon atom. More preferred are 4 to 4 perfluoroalkyl groups.
  • aliphatic hydrocarbon group having 1 to 18 carbon atoms substituted with a halogen atom include, for example, trifluoromethyl, pentafluoroethyl, 2-chloroethyl, 2-bromoethyl, heptafluoropropyl, 3-bromopropyl, Nonafluorobutyl, tridecafluorohexyl, heptadecafluorooctyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,1-difluoropropyl, 1,1,2,2-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, norbornyl-1,1-difluoroethyl, norbornyltetrafluoroethyl, adamantane-1,1,2,2- Examples include halogenated alkyl
  • Examples of the aliphatic hydrocarbon having 1 to 18 carbon atoms substituted with an alkylthio group include 2-methylthioethyl, 4-methylthiobutyl, 4-butylthioethyl, etc., and include halogen atoms and carbon atoms having 1 to 18 carbon atoms.
  • Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms substituted with an alkylthio group include 1,1,2,2-tetrafluoro-3-methylthiopropyl.
  • the alkylthio group which may be present as a substituent is preferably an alkylthio group having 1 to 18 carbon atoms, more preferably an alkylthio group having 1 to 10 carbon atoms, and further preferably an alkylthio group having 1 to 6 carbon atoms.
  • alkylthio group examples include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, a sec-butylthio group, a tert-butylthio group, an isobutylthio group, an amylthio group, an isoamylthio group, and a tert-amylthio group.
  • Examples of the alicyclic hydrocarbon group which may be present as a substituent include alicyclic hydrocarbon groups having 3 to 30 carbon atoms, which may be monocyclic or condensed.
  • the aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with any one or more of a halogen atom, an alkylthio group and an alicyclic hydrocarbon group includes a halogen atom and / or an alicyclic hydrocarbon.
  • Preferred are an alkyl group having 1 to 18 carbon atoms substituted with a group, and a linear or cyclic alkyl group having 1 to 18 carbon atoms having no substituent, and a fluorine atom and / or a cyclic group having 6 to 10 carbon atoms.
  • a straight-chain alkyl group having 1 to 4 carbon atoms substituted with an alkyl group and an unsubstituted straight-chain alkyl group having 1 to 10 carbon atoms are more preferable.
  • aryl group having 6 to 20 carbon atoms which may be substituted with any one or more of a halogen atom, an alkylthio group, an alkyl group and an acyl group is any one of a halogen atom, an alkylthio group, an alkyl group and an acyl group
  • An aryl group having 6 to 14 carbon atoms which may be substituted is preferable, and an aryl group having 6 to 10 carbon atoms which may be substituted with any one or more of a halogen atom, an alkylthio group, an alkyl group and an acyl group. More preferred.
  • Examples of such an aryl group include a phenyl group, a naphthyl group, a 4-vinylphenyl group, a biphenyl group,
  • halogen atom as the substituent is described for the aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with any one or more of the above-mentioned halogen atom, alkylthio group and alicyclic hydrocarbon group. It is synonymous with the halogen atom.
  • aryl group having 6 to 20 carbon atoms substituted with a halogen atom include a pentafluorophenyl group, a chlorophenyl group, a dichlorophenyl group, a trichlorophenyl group, a 2,4-bis (trifluoromethyl) phenyl group, and a bromoethylphenyl group. Groups and the like.
  • alkylthio group as the substituent is described for the aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with any one or more of the above-mentioned halogen atom, alkylthio group and alicyclic hydrocarbon group. It is synonymous with the alkylthio group.
  • aryl group having 6 to 20 carbon atoms substituted with an alkylthio group include a 4-methylthiophenyl group, a 4-butylthiophenyl group, a 4-octylthiophenyl group, and a 4-dodecylthiophenyl group.
  • Examples of the aryl group having 6 to 20 carbon atoms substituted with a halogen atom and an alkylthio group include, for example, 1,2,3,4,5-pentafluorophenyl group, 1,2,5,6-tetrafluoro-4- Examples thereof include a methylthiophenyl group, 1,2,5,6-tetrafluoro-4-butylthiophenyl group, and 1,2,5,6-tetrafluoro-4-dodecylthiophenyl group.
  • Examples of the aryl group having 6 to 20 carbon atoms substituted with an acyl group include an acetylphenyl group, an acetylnaphthyl group, a benzoylphenyl group, a 1-anthraquinolyl group, and a 2-anthraquinolyl group.
  • the preferred range of the alkyl group as a substituent is a linear, branched or cyclic alkyl group, a linear alkyl group having 1 to 3 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or a carbon number having 6 carbon atoms. Cyclic alkyl groups are preferred. These alkyl groups may be substituted with a halogen atom (particularly a fluorine atom).
  • a preferred range of the acyl group as a substituent is that in the group represented by R—C ( ⁇ O) —, R is preferably an alkyl group or an aromatic group, and R is a methyl group, a phenyl group, a naphthyl group, an anthracenyl group. Is exemplified.
  • an alkylaryl group having 7 to 20 carbon atoms which may be substituted with a halogen atom is exemplified, and an alkylaryl group having 7 to 15 carbon atoms is preferred. More preferred are 7 to 10 alkylaryl groups.
  • Examples of such an alkylaryl group include 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-isobutyl.
  • the aryl group having 6 to 20 carbon atoms which may be substituted with any one or more of a halogen atom, an alkylthio group, an alkyl group and an acyl group is unsubstituted or substituted with a halogen atom and / or an alkyl group.
  • An aryl group having 6 to 20 carbon atoms is preferable, and a phenyl group or a naphthyl group which is unsubstituted or substituted with a fluorine atom and / or a linear alkyl group having 1 to 6 carbon atoms is more preferable.
  • Arylalkyl group having 7 to 20 carbon atoms which may be substituted with any one or more of a halogen atom and an alkylthio group
  • the arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom and / or an alkylthio group is preferably an arylalkyl group having 7 to 15 carbon atoms, and more preferably an arylalkyl group having 7 to 12 carbon atoms.
  • arylalkyl groups include benzyl group, phenethyl group, 2-phenylpropan-2-yl group, diphenylmethyl group, triphenylmethyl group, styryl group, cinnamyl group and the like.
  • the preferred range of the halogen atom as the substituent and the preferred range of the alkylthio group are each from 1 to 18 carbon atoms which may be substituted with any one or more of the halogen atom, alkylthio group and alicyclic hydrocarbon group described above. In the aliphatic hydrocarbon group, it is synonymous with the description of the halogen atom and alkylthio group as a substituent, and the preferred range is also the same.
  • Examples of the arylalkyl group having 7 to 20 carbon atoms substituted with a halogen atom include a pentafluorophenylmethyl group, a phenyldifluoromethyl group, a 2-phenyl-tetrafluoroethyl group, and a 2- (pentafluorophenyl) ethyl group. Is mentioned.
  • Examples of the arylalkyl group having 7 to 20 carbon atoms substituted with an alkylthio group include a p-methylthiobenzyl group.
  • Examples of the arylalkyl group substituted with a halogen atom and an alkylthio group include a 2,3,5,6-tetrafluoro-4-methylthiophenylethyl group.
  • the 10-camphoryl group is a group represented by the following formula (Me represents a methyl group).
  • R 3 is preferably substituted with a halogen atom from the viewpoint of sensitivity, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, a perfluoroalkyl group having 1 to 8 carbon atoms, More preferably, it is an aryl group having 6 to 10 carbon atoms that may be substituted with a halogen atom, or an alkylaryl group having 7 to 10 carbon atoms that may be substituted with a halogen atom, and a perfluoroalkyl having 1 to 4 carbon atoms More preferred are groups.
  • R 7 represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms.
  • alkylene group having 2 to 6 carbon atoms include ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butylene, butane-1,3-diyl group, butane-2,3.
  • -Diyl group butane-1,2-diyl group, pentane-1,5-diyl group, pentane-1,3-diyl group, pentane-1,4-diyl group, pentane-2,3-diyl group, hexane -1,6-diyl group, hexane-1,2-diyl group, hexane-1,3-diyl group, hexane-1,4-diyl group, hexane-2,5-diyl group, hexane-2,4- Examples thereof include a diyl group and a hexane-3,4-diyl group.
  • the halogenated alkylene group having 2 to 6 carbon atoms is obtained by substituting at least one proton in the alkylene group having 2 to 6 carbon atoms with a halogen atom.
  • halogen atom include fluorine, chlorine, bromine and iodine, and fluorine is preferred.
  • halogenated alkylene group having 2 to 6 carbon atoms examples include, for example, a tetrafluoroethylene group, 1,1-difluoroethylene group, 1-fluoroethylene group, 1,2-difluoroethylene group, hexafluoropropane 1,3-diyl Group, 1,1,2,2-tetrafluoropropane-1,3-diyl group, 1,1,2,2-tetrafluoropentane-1,5-diyl group and the like.
  • Examples of the arylene group having 6 to 20 carbon atoms include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,5-dimethyl-1,4-phenylene group, 4,4 '-Biphenylene group, diphenylmethane-4,4'-diyl group, 2,2-diphenylpropane-4,4'-diyl group, naphthalene-1,2-diyl group, naphthalene-1,3-diyl group, naphthalene- 1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-1,7-diyl group, naphthalene-1,8-diyl group, naphthalene-2,3-diyl Group, naphthalene-2,6-diyl group, naphthalene-2
  • the halogenated arylene group having 6 to 20 carbon atoms is obtained by substituting at least one proton in the arylene group having 6 to 20 carbon atoms with a halogen atom.
  • Examples of the halogenated arylene group having 6 to 20 carbon atoms include a tetrafluorophenylene group.
  • R 8 represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms.
  • Alkylene group of 2 to 6 carbon atoms R 8 represents a halogenated alkylene group having 2-6 carbon atoms, a halogenated arylene group an arylene group or a C 6 -C 20 6 to 20 carbon atoms, the carbon to which R 7 represents It is synonymous with a C 2-6 alkylene group, a C 2-6 halogenated alkylene group, a C 6-20 arylene group or a C 6-20 halogenated arylene group, and the preferred range is also the same.
  • Y 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms.
  • the alkylene group having 1 to 4 carbon atoms represented by Y 2 has the same meaning as the alkylene group having 1 to 4 carbon atoms represented by Y 1 in formula (A), and the preferred range is also the same.
  • R 9 is an optionally branched alkyl group having 1 to 18 carbon atoms, an optionally branched alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 20 carbon atoms.
  • R 9 represents an aryl group having 6 to 20 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a halogenated arylalkyl group having 7 to 20 carbon atoms.
  • a carbon number of 7 which may be substituted with an aryl group of 6 to 20 carbon atoms, a halogen atom and / or an alkylthio group which may be substituted with any of a halogen atom, an alkylthio group and an acyl group in R 3 in (I) are the same as the arylalkyl group of ⁇ 20 and the alkylaryl group of 7 to 20 carbon atoms which may be substituted with a halogen atom, and the preferred range is also the same.
  • the alkyl group having 1 to 18 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms.
  • Such alkyl groups may be branched.
  • Examples of the alkyl group having 1 to 18 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, and tert-amyl.
  • the halogenated alkyl group having 1 to 18 carbon atoms is a group in which at least one proton in the alkyl group having 1 to 18 carbon atoms is substituted with a halogen atom, and may be branched.
  • Examples of the halogenated alkyl group having 1 to 18 carbon atoms include trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, tridecafluorohexyl group, heptadecafluorooctyl group, 2,2 , 2-trifluoroethyl group, 1,1-difluoroethyl group, 1,1-difluoropropyl group, 1,1,2,2-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 2, Examples thereof include halogenated alkyl groups such as 2,3,3,3-pentafluoropropyl group and 1,1,
  • a and b each independently represents 0 or 1, at least one of a and b is 1, and a is preferably 1.
  • photoacid generator represented by the general formula (I) include the following compounds, but the present invention is not particularly limited thereto.
  • B-1 to B-17 are preferable, and B-3, B-4, B-8, B-9, B-11 to B-13, B-15, and B-16 are more preferable. .
  • the photoacid generator represented by the general formula (I) can be synthesized by a known method.
  • the description of paragraph numbers 0076 to 0080 of the pamphlet of WO2011 / 087011, can be referred to, It is incorporated herein.
  • the molecular weight of the photoacid generator represented by the general formula (I) is not particularly limited, but is preferably 335 to 800, more preferably 335 to 780, and further preferably 400 to 700.
  • the content of the photoacid generator represented by the general formula (I) is 0.1 to 10 with respect to the total solid components in the photosensitive resin composition. % By mass is preferable, 0.5 to 5% by mass is more preferable, and 1 to 3% by mass is further preferable.
  • the photoacid generator may contain only one type or two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the photosensitive resin composition of the present invention may contain a photoacid generator other than the photoacid generator represented by the general formula (I).
  • a photoacid generator a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferable, but is not limited to its chemical structure.
  • a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
  • Such a photoacid generator is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less.
  • a photoacid generator is particularly preferred.
  • the description of paragraph numbers 0070 to 0117 of JP2013-178439A can be referred to, the contents of which are incorporated herein.
  • it can also be set as the composition which does not contain photoacid generators other than the photoacid generator represented by general formula (I) substantially.
  • the phrase “substantially free” means that the amount is 5% by mass or less of the content of the photoacid generator represented by the general formula (I) in the composition of the present invention.
  • a solvent, a sensitizer, a crosslinking agent, an alkoxysilane compound, a basic compound, a surfactant, and an antioxidant are preferably added to the photosensitive resin composition of the present invention as necessary.
  • the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor.
  • Known additives such as can be added.
  • compounds described in paragraph numbers 0201 to 0224 of JP2012-8859A can be used, and the contents thereof are incorporated in the present specification.
  • the photosensitive resin composition of the present invention contains (C) a solvent.
  • the photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in a solvent.
  • a solvent used for the preparation of the composition of the present invention a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
  • known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl.
  • Ethers propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like.
  • Specific examples of the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraph numbers 0174 to 0178 of JP2011-221494A, and paragraph numbers 0167 to 0168 of JP2012-194290A. And the contents thereof are incorporated herein by reference.
  • the solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.
  • the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
  • Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
  • Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate.
  • the content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, and preferably 60 to 90 parts by mass with respect to 100 parts by mass of all components in the photosensitive resin composition. Further preferred. Only one type of solvent may be included, or two or more types of solvents may be included. When two or more types are included, the total amount is preferably within the above range.
  • the photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote the decomposition in combination with the photoacid generator.
  • the sensitizer absorbs actinic rays and enters an electronically excited state.
  • the sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur.
  • a photo-acid generator raise
  • Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.
  • Polynuclear aromatics eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene
  • xanthenes Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
  • xanthones eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone
  • cyanines eg, thiacarbocyanine, oxacarbocyanine
  • merocyanines For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, to
  • polynuclear aromatics polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable.
  • polynuclear aromatics anthracene derivatives are most preferred.
  • the addition amount of the sensitizer is 0.001 to 100 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. It is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass.
  • the sensitizer may contain only one type or two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the photosensitive resin composition of this invention contains a crosslinking agent as needed.
  • a crosslinking agent is not limited as long as a crosslinking reaction is caused by heat.
  • a compound having two or more epoxy groups and / or oxetanyl groups in the molecule is preferable.
  • the photosensitive resin composition of the present invention contains a cross-linking agent
  • the addition amount of the cross-linking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass in total of the polymer component (A).
  • the content is more preferably 0.1 to 30 parts by mass, and further preferably 0.5 to 20 parts by mass. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained.
  • Only one type of crosslinking agent may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.
  • JER152, JER157S70, JER157S65, JER806, JER828, JER1007 are commercially available products described in paragraph No. 0189 of JP2011-221494, etc.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.
  • the compound having two or more oxetanyl groups in the molecule Aron oxetane OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toagosei Co., Ltd.) can be used.
  • alkoxymethyl group-containing crosslinking agents described in paragraph numbers 0107 to 0108 of JP2012-8223A, and compounds having at least one ethylenically unsaturated double bond are also preferable. These contents can be used and are incorporated herein.
  • alkoxymethyl group-containing crosslinking agent alkoxymethylated glycoluril is preferable.
  • a blocked isocyanate compound can also be preferably employed as a crosslinking agent.
  • a block isocyanate compound It is preferable that it is a compound which has a 2 or more block isocyanate group in 1 molecule from a sclerosing
  • the blocked isocyanate group in this invention is a group which can produce
  • the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably.
  • the blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
  • the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic.
  • Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2 2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3
  • a compound and a prepolymer type skeleton compound derived from these compounds can be preferably used.
  • tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
  • Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
  • Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to.
  • a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
  • Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
  • Examples of the lactam compound include ⁇ -caprolactam and ⁇ -butyrolactam.
  • Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
  • Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
  • Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
  • Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
  • Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
  • Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.
  • the blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available.
  • Coronate AP Stable M Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above , Manufactured by Asahi Kasei Chemicals Corporation, Death Module B 1100, BL1265 MPA / X, BL
  • the photosensitive resin composition of the present invention may contain an alkoxysilane compound as an adhesion improving agent.
  • an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do.
  • the alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum.
  • the compound improves the adhesion between the insulating film and the insulating film.
  • a known silane coupling agent or the like is also effective.
  • the silane coupling agent include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltriacoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -glycid.
  • Xylpropyl dialkoxysilane ⁇ -methacryloxypropyltrialkoxysilane, ⁇ -methacryloxypropyl dialkoxysilane, ⁇ -chloropropyltrialkoxysilane, ⁇ -mercaptopropyltrialkoxysilane, ⁇ - (3,4-epoxycyclohexyl) Examples include ethyltrialkoxysilane and vinyltrialkoxysilane.
  • ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, ⁇ -glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.
  • the (alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited, and known compounds can be used.
  • the content of the alkoxysilane compound is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive composition, 0.5 to 20 parts by mass is more preferable.
  • the total amount is preferably within the above range.
  • the photosensitive resin composition of the present invention may contain a basic compound.
  • the basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include the compounds described in JP-A 2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
  • aliphatic amine examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like.
  • examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
  • aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
  • heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, pyrazole, pyridazine, purine, Pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0]
  • Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
  • Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
  • the basic compounds that can be used in the present invention may be used singly or in combination of two or more.
  • the content of the basic compound is 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid component in the photosensitive resin composition.
  • the amount is preferably 0.005 to 1 part by mass.
  • the total amount is preferably within the above range.
  • the photosensitive resin composition of the present invention may contain a surfactant.
  • a surfactant any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
  • examples of the surfactant used in the composition of the present invention include those described in paragraph Nos. 0201 to 0205 in JP2012-88459A, and paragraphs 0185 to 0188 in JP2011-215580A. Can be used and these descriptions are incorporated herein.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicon-based and fluorine-based surfactants. .
  • the following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No.
  • the surfactant is measured by gel permeation chromatography using the structural unit A and the structural unit B represented by the following general formula (I-1-1) and using tetrahydrofuran (THF) as a solvent.
  • a preferred example is a copolymer having a polystyrene-reduced weight average molecular weight (Mw) of 1,000 or more and 10,000 or less.
  • R 401 and R 403 each independently represent a hydrogen atom or a methyl group
  • R 402 represents a linear alkylene group having 1 to 4 carbon atoms
  • R 404 represents hydrogen.
  • L represents an alkylene group having 3 to 6 carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p is 10 mass% to 80 mass%.
  • the following numerical values are represented, q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.
  • L is preferably a branched alkylene group represented by the following general formula (I-1-2).
  • R 405 in formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. And an alkyl group having 2 or 3 carbon atoms is more preferred.
  • the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
  • These surfactants can be used individually by 1 type or in mixture of 2 or more types.
  • the addition amount of the surfactant is preferably 10 parts by mass or less with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. 0.001 to 10 parts by mass is more preferable, and 0.01 to 3 parts by mass is even more preferable. Only one type of surfactant may be included, or two or more types of surfactants may be included. When two or more types are included, the total amount is preferably within the above range.
  • the photosensitive resin composition of the present invention may contain an antioxidant.
  • an antioxidant a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
  • antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives.
  • phenolic antioxidants hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur oxidations are particularly preferred from the viewpoint of coloring of the cured film and reduction of the film thickness.
  • Inhibitors are preferred, and phenolic antioxidants are most preferred. These may be used individually by 1 type and may mix 2 or more types. Specific examples include the compounds described in paragraph numbers 0026 to 0031 of JP-A-2005-29515, and the compounds described in paragraph numbers 0106 to 0116 of JP-A-2011-227106. It is incorporated herein.
  • ADK STAB AO-20 ADK STAB AO-60, ADK STAB AO-80, ADK STAB LA-52, ADK STAB LA-81, ADK STAB AO-412S, ADK STAB PEP-36, IRGANOX 1035, IRGANOX 1098, and Tinuvin 144. Can be mentioned.
  • the content of the antioxidant is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. It is preferably 0.2 to 5 parts by mass, more preferably 0.5 to 4 parts by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good. Only one type of antioxidant may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.
  • an acid proliferating agent can be used for the purpose of improving sensitivity.
  • the acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
  • Specific examples of such an acid proliferating agent include acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.
  • the photosensitive resin composition of the present invention can contain a development accelerator.
  • a development accelerator those described in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
  • a development accelerator may be used individually by 1 type, and can also use 2 or more types together.
  • the addition amount of the development accelerator is from 0 to 100 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition from the viewpoint of sensitivity and residual film ratio. 30 parts by mass is preferable, 0.1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
  • the total amount is preferably within the above range.
  • thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, nitrogen-containing compounds and thermal acid generators described in WO2011-133604A1 can be used. Is incorporated herein by reference.
  • a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio.
  • the composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore diameter of 0.2 ⁇ m.
  • the method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
  • steps (1) to (5) The process of apply
  • Each step will be described below in order.
  • the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent.
  • substrate cleaning such as alkali cleaning or plasma cleaning
  • the method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
  • the substrate include inorganic substrates, resins, and resin composite materials.
  • the inorganic substrate examples include glass, quartz, silicon, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
  • the resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Substrates made of synthetic resins such as aromatic ether
  • the coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used.
  • the wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but it is usually used in the range of 0.5 to 10 ⁇ m.
  • the solvent removal step (2) the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate.
  • the heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.
  • the substrate provided with the coating film is irradiated with an actinic ray having a predetermined pattern.
  • the photoacid generator is decomposed to generate an acid.
  • the acetal group contained in the coating film component is hydrolyzed to generate a carboxyl group or a phenolic hydroxyl group.
  • a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used, and i-line (365 nm), h-line (405 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as 436 nm), can be preferably used.
  • irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
  • the exposure amount is preferably 1 to 500 mJ / cm 2 .
  • PEB Post Exposure Bake
  • the temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C.
  • the acetal group in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group or a phenolic hydroxyl group. Therefore, development is not necessarily performed without PEB. Thus, a positive image can also be formed.
  • a copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer.
  • a positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
  • the developer used in the development step preferably contains a basic compound.
  • Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and choline hydroxide; An aqueous solution of sodium silicate, sodium metasilicate, or the like can be used.
  • alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide
  • alkali metal carbonates such as sodium carbonate and potassium carbonate
  • alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates
  • ammonium hydroxides such as tetramethylammonium hydro
  • An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
  • a 0.4 to 2.5% aqueous solution of tetramethylammonium hydroxide can be mentioned.
  • the pH of the developer is preferably 10.0 to 14.0.
  • the development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
  • a rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like.
  • a known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.
  • the obtained positive image is heated to thermally decompose the acetal group to generate a carboxyl group or a phenolic hydroxyl group, and to cure by crosslinking with a crosslinking group, a crosslinking agent or the like.
  • a film can be formed.
  • This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to By proceeding the crosslinking reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like can be formed.
  • post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process).
  • middle baking it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes.
  • middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking.
  • These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
  • the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film.
  • the preferred exposure amount in the case of including a post-exposure step preferably 100 ⁇ 3,000mJ / cm 2, particularly preferably 100 ⁇ 500mJ / cm 2.
  • the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist.
  • dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.
  • the cured film of the present invention is a cured film obtained by curing the above-described composition of the present invention.
  • the cured film of the present invention can be suitably used as an interlayer insulating film.
  • the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention mentioned above.
  • the photosensitive resin composition of the present invention With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film properties, it is useful for liquid crystal display devices and organic EL display devices.
  • the liquid crystal display device of the present invention has the cured film of the present invention.
  • the liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal displays having various structures.
  • An apparatus can be mentioned.
  • specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
  • the liquid crystal driving method that can be adopted by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (Optical) method. Compensated Bend) method and the like.
  • the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device.
  • the organic insulating film (115) of JP-A-2005-284291 It can be used as an organic insulating film (212).
  • the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method.
  • the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
  • the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses.
  • a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a micro lens provided on the color filter in the solid-state image sensor Can be suitably used.
  • the color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto.
  • the elements of the TFT 16 corresponding to are arranged.
  • Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17.
  • an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
  • the light source of the backlight is not particularly limited, and a known light source can be used.
  • the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and used as the second interlayer insulating film (48) described in Japanese Patent Application Laid-Open No. 2011-145686 and the interlayer insulating film (520) described in Japanese Patent Application Laid-Open No. 2009-258758. Can do.
  • the organic EL display device of the present invention has the cured film of the present invention.
  • the organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.
  • specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
  • FIG. 2 is a conceptual diagram of an example of an organic EL display device.
  • a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
  • a bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed so as to cover the TFT 1.
  • a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3.
  • the wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
  • the flattening film 4 is formed on the insulating film 3 with the unevenness due to the wiring 2 being embedded.
  • a bottom emission type organic EL element is formed on the planarizing film 4. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
  • the first electrode 5 corresponds to the anode of the organic EL element.
  • An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do. Further, although not shown in FIG.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate.
  • An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it.
  • An EL display device is obtained.
  • a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a MEMS device can be used as a partition wall or mechanically driven. Used as part of the part.
  • MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.
  • the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010-
  • spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.
  • MATHF 2-tetrahydrofuranyl methacrylate (synthetic product)
  • MAEVE 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries)
  • StOEVE 4- (1-ethoxyethyloxy) styrene
  • OXE-30 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry)
  • GMA Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries)
  • NBMA n-butoxymethylacrylamide (manufactured by Tokyo Chemical Industry)
  • HEMA Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
  • MAA Methacrylic acid (manufactured by Wako Pure Chemical Industries)
  • MMA Methyl methacrylate (Wako Pure Chemical Industries) St: Styrene (manufactured by Wako Pure Chemical Industries)
  • the monomer components (a1) to (a3) in the table are molar ratios.
  • the numerical values of the polymerization initiator and the additive are the molar ratio of the monomer component to 100 mol.
  • the solid content concentration is shown as monomer mass / (monomer mass + solvent mass) ⁇ 100 (unit mass%).
  • Alkoxysilane compound D-1 ⁇ -Glycidoxypropyltrimethoxysilane (KBM-403: manufactured by Shin-Etsu Chemical)
  • F-1 JER828 (manufactured by Mitsubishi Chemical Holdings Corporation)
  • F-2 JER1007 (manufactured by Mitsubishi Chemical Holdings Corporation)
  • F-3 JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation)
  • G-1 ADK STAB AO-60 (manufactured by ADEKA Corporation)
  • G-2 Irganox 1035 (manufactured by BASF)
  • G-3 Irganox 1098 (manufactured by BASF)
  • the exposed photosensitive composition layer was developed with an alkali developer (0.4 wt% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
  • an alkali developer 0.4 wt% tetramethylammonium hydroxide aqueous solution
  • the optimum i-line exposure (Eopt) when resolving 10 ⁇ m line and space at 1: 1 was defined as sensitivity.
  • Examples 28 and 29 Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (Corning)), then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent, and the film thickness A photosensitive resin composition layer having a thickness of 3.0 ⁇ m was formed. Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive composition layer was developed with an alkali developer (2.38 wt% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
  • MPA 5500CF high pressure mercury lamp
  • sensitivity 40mJ / cm 2 less than 2: 40mJ / cm 2 or more 80 mJ / cm 2 less than 3: 80mJ / cm 2 or more 160 mJ / cm 2 less than 4: 160mJ / cm 2 or more
  • volume resistivity After coating the material on the aluminum substrate, it was dried at 90 ° C. for 2 minutes, exposed to 300 mJ with an ultrahigh pressure mercury lamp, and further heated in an oven at 230 ° C. for 30 minutes to form a cured film having a thickness of 3 ⁇ m. A sample obtained by depositing aluminum on the cured film was used as a sample for measuring volume resistivity. The volume resistivity measurement sample was conditioned at 23 ° C., 60% RH, and 24 h, and then volume resistivity measurement was performed using ULTRA HIGH RESISTANCE METER (manufactured by ADVANTEST). The measurement method was based on JIS K6911, and the volume resistance measurement value ( ⁇ ) was measured at an applied voltage of 10 V for 1 minute.
  • the volume resistivity ( ⁇ ⁇ cm) was calculated from the measured value, the area of the aluminum electrode, and the sample thickness.
  • the evaluation criteria are as follows, and 1 or 2 is practically preferable. 1: 1 ⁇ 10 ⁇ 16 ⁇ ⁇ cm or more 2: 5 ⁇ 10 ⁇ 15 ⁇ ⁇ cm or more and less than 1 ⁇ 10 16 ⁇ ⁇ cm 3: 1 ⁇ 10 ⁇ 15 ⁇ ⁇ cm or more and less than 5 ⁇ 10 15 ⁇ ⁇ cm 4 : Less than 1 ⁇ 10 ⁇ 15 ⁇ ⁇ cm
  • Examples 1 to 29 using the compound represented by the general formula (I) as the photoacid generator have high sensitivity and improved volume resistivity.
  • Comparative Examples 1 to 3 using a photoacid generator other than the compound represented by the general formula (I) are inferior in volume resistivity, and Comparative Example 2 is inferior in sensitivity. It can also be seen that the sensitivity and volume resistivity are further improved when a halogen atom is substituted for R 3 in the general formula (I).
  • Example 101 An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
  • a bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1.
  • a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 ⁇ m) connected to the TFT 1 through the contact hole is formed on the insulating film 3. .
  • the wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.
  • the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded.
  • the planarizing film 4 is formed on the insulating film 3 by slit-coating the photosensitive resin composition of Example 1 on the substrate, prebaking (90 ° C. ⁇ 2 minutes) on a hot plate, and then applying high pressure from above the mask. After irradiating 45 mJ / cm 2 (illuminance 20 mW / cm 2 ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C. for 60 minutes.
  • the applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.
  • a bottom emission type organic EL element was formed on the obtained planarization film 4.
  • a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7.
  • a commercially available resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials).
  • the first electrode 5 thus obtained corresponds to the anode of the organic EL element.
  • an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed.
  • the photosensitive resin composition of Example 1 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.
  • a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus.
  • a second electrode made of Al was formed on the entire surface above the substrate. The obtained board
  • substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
  • Example 102 In Example 101, an organic EL display device was produced in the same manner as in Example 101 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 2. When a drive voltage was applied to the obtained organic EL display device, it was found that the organic EL display device showed good display characteristics and had high reliability.
  • Example 103 an organic EL display device was produced in the same manner as in Example 101 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 3. When a drive voltage was applied to the obtained organic EL display device, it was found that the organic EL display device showed good display characteristics and had high reliability.
  • Example 104 an organic EL display device was produced in the same manner as in Example 101 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 4. When a drive voltage was applied to the obtained organic EL display device, it was found that the organic EL display device showed good display characteristics and had high reliability.
  • Example 105 an organic EL display device was produced in the same manner as in Example 101 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 5. When a drive voltage was applied to the obtained organic EL display device, it was found that the organic EL display device showed good display characteristics and had high reliability.
  • Example 106 In the active matrix liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 106 was obtained. That is, using the photosensitive resin composition of Example 1, the cured film 17 was formed as an interlayer insulating film by the same method as the method for forming the planarizing film 4 of the organic EL display device in Example 101. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • Example 107 a liquid crystal display device was produced in the same manner as Example 106 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 7. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • Example 108 In Example 106, a liquid crystal display device was produced in the same manner as in Example 106 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 8. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • Example 109 a liquid crystal display device was produced in the same manner as in Example 106, except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 9. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • Example 110 In Example 106, a liquid crystal display device was produced in the same manner as Example 106 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 10. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
  • TFT Thin Film Transistor
  • Wiring 3 Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT 17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter

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Abstract

Provided are: a photosensitive resin composition which has high volume resistivity, while maintaining high sensitivity; a method for producing a cured film of this photosensitive resin composition; a cured film; a liquid crystal display device; and an organic EL display device. A photosensitive resin composition which contains (A) a polymer component containing one or more polymers satisfying (1) and/or (2) described below, (B) a photoacid generator represented by general formula (I), and (C) a solvent. (1) a polymer having (a1) a constituent unit having a group wherein an acid group is protected by an acid-decomposable group and (a2) a constituent unit having a crosslinkable group (2) a polymer having (a1) a constituent unit having a group wherein an acid group is protected by an acid-decomposable group and a polymer having (a2) a constituent unit having a crosslinkable group

Description

感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置および有機ＥＬ表示装置Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, and organic EL display device
　本発明は、感光性樹脂組成物（以下、単に、「本発明の組成物」ということがある）に関する。また、上記感光性樹脂組成物を用いた硬化膜の製造方法、感光性組成物を硬化してなる硬化膜、上記硬化膜を用いた各種画像表示装置に関する。
　さらに詳しくは、液晶表示装置、有機ＥＬ（有機エレクトロルミネッセンス）表示装置、集積回路素子、固体撮像素子などの電子部品の平坦化膜、保護膜や層間絶縁膜の形成に好適な、感光性樹脂組成物およびそれを用いた硬化膜の製造方法に関する。 The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”). Moreover, it is related with the manufacturing method of the cured film using the said photosensitive resin composition, the cured film formed by hardening | curing the photosensitive composition, and various image display apparatuses using the said cured film.
More specifically, a photosensitive resin composition suitable for forming a flattening film, a protective film and an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL (organic electroluminescence) display device, an integrated circuit element, and a solid-state imaging element. The present invention relates to an article and a method for producing a cured film using the article.
　有機ＥＬ表示装置や、液晶表示装置などには、パターン形成された層間絶縁膜が設けられている。この層間絶縁膜の形成には、必要とするパターン形状を得るための工程数が少なく、しかも十分な平坦性が得られるといったことから、感光性樹脂組成物が広く使用されている。 Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.
　上記表示装置における層間絶縁膜には、体積抵抗率、耐溶剤性、耐熱性、硬度、および、酸化インジウムスズ（ＩＴＯ）スパッタ適性に優れるといった硬化膜の物性が求められている。このような感光性樹脂組成物は、例えば、特許文献１に開示されている。
　一方、特許文献２には、特定の構造を有するイミドスルホネート化合物が記載されている。 The interlayer insulating film in the display device is required to have physical properties of a cured film, such as excellent volume resistivity, solvent resistance, heat resistance, hardness, and indium tin oxide (ITO) sputtering suitability. Such a photosensitive resin composition is disclosed in Patent Document 1, for example.
On the other hand, Patent Document 2 describes an imide sulfonate compound having a specific structure.
特開２０１１－２２１４９４号公報JP 2011-212494 A ＷＯ２０１１／０８７０１１号パンフレットWO2011 / 087011 pamphlet
　本発明者が検討した結果、特許文献１に記載されている感光性樹脂組成物は、硬化後の透過率が高く、露光後加熱処理（ＰＥＢ）を行わなくても高感度であるが、近年、より高い体積抵抗率が求められる傾向にある。このように、感光性樹脂組成物において、高い感度を維持しつつ、より高い体積抵抗率を両立させる手段は知られていない。 As a result of investigation by the present inventor, the photosensitive resin composition described in Patent Document 1 has high transmittance after curing and high sensitivity without performing post-exposure heat treatment (PEB). There is a tendency that a higher volume resistivity is required. Thus, in the photosensitive resin composition, there is no known means for achieving both higher volume resistivity while maintaining high sensitivity.
　本発明は、かかる課題を解決することを目的としたものであって、高い感度を維持しつつ、より高い体積抵抗率の高い感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置および有機ＥＬ表示装置を提供することを目的とする。 The present invention is intended to solve such problems, and maintains a high sensitivity, and has a higher volume resistivity, a photosensitive resin composition having a higher volume resistivity, a method for producing a cured film, a cured film, and a liquid crystal display. An object is to provide a device and an organic EL display device.
　かかる状況のもと、本発明者が検討を行った結果、感光性樹脂組成物中に特定の構造を有するイミドスルホネート化合物を光酸発生剤として配合させることにより、上記課題を解決できることを見出し、本発明を完成させるに至った。 Under such circumstances, as a result of investigation by the present inventors, it was found that the above problem can be solved by blending an imide sulfonate compound having a specific structure in the photosensitive resin composition as a photoacid generator, The present invention has been completed.
　具体的には、以下の解決手段＜１＞により、好ましくは、＜２＞～＜１０＞により、上記課題は解決された。
＜１＞（Ａ）下記（１）および（２）の少なくとも一方を満たす重合体を含む重合体成分、
（１）（ａ１）酸基が酸分解性基で保護された基を有する構成単位、および（ａ２）架橋性基を有する構成単位を有する重合体
（２）（ａ１）酸基が酸分解性基で保護された基を有する構成単位を有する重合体、および（ａ２）架橋性基を有する構成単位を有する重合体
（Ｂ）下記一般式（Ｉ）で表される光酸発生剤、および
（Ｃ）溶剤、
を含有する、感光性樹脂組成物；
Figure JPOXMLDOC01-appb-C000004
  一般式（Ｉ）中、Ｒ1およびＲ2の一方は、下記一般式（Ａ）で表される基を表し、他方は水素原子を表す；Ｒ3は、ハロゲン原子、アルキルチオ基および脂環式炭化水素基のいずれか１つ以上で置換されてもよい炭素数１～１８の脂肪族炭化水素基、ハロゲン原子、アルキルチオ基、アルキル基およびアシル基のいずれか１つ以上で置換されてもよい炭素数６～２０のアリール基、ハロゲン原子および／またはアルキルチオ基で置換されてもよい炭素数７～２０のアリールアルキル基、１０－カンファーイル基または、下記一般式（Ｂ）で表される基を表す；
一般式（Ａ）
Figure JPOXMLDOC01-appb-C000005
  一般式（Ａ）中、Ｘ1は、酸素原子または硫黄原子を表し、Ｙ1は、単結合または炭素数１～４のアルキレン基を表し、Ｒ4は、炭素数１～１２の炭化水素基を表し、Ｒ5は、炭素数１～４のアルキレン基を表し、Ｒ6は、水素原子、分岐していてもよい炭素数１～４のアルキル基、炭素数３～１０の脂環式炭化水素基、複素環基、または水酸基を表す；ｎは、０～５の整数を表し、ｎが２～５の場合、複数存在するＲ5は同一でも異なってもよい；
一般式（Ｂ）
Figure JPOXMLDOC01-appb-C000006
  一般式（Ｂ）中、Ｙ2は、単結合または炭素数１～４のアルキレン基を表し、Ｒ7は、炭素数２～６のアルキレン基、炭素数２～６のハロゲン化アルキレン基、炭素数６～２０のアリーレン基、または炭素数６～２０のハロゲン化アリーレン基を表し、Ｒ8は、単結合、炭素数２～６のアルキレン基、炭素数２～６のハロゲン化アルキレン基、炭素数６～２０のアリーレン基または炭素数６～２０のハロゲン化アリーレン基を表し、Ｒ9は、分岐していてもよい炭素数１～１８のアルキル基、分岐していてもよい炭素数１～１８のハロゲン化アルキル基、炭素数６～２０のアリール基、炭素数６～２０のハロゲン化アリール基、炭素数７～２０のアリールアルキル基、または炭素数７～２０のハロゲン化アリールアルキル基を表す；ａおよびｂはそれぞれ独立に０または１を表し、ａおよびｂの少なくとも一方は１である。
＜２＞一般式（Ｉ）のＲ3が、炭素数１～８の脂肪族炭化水素基、炭素数１～８のパーフルオロアルキル基、ハロゲン原子で置換されてもよい炭素数６～１０のアリール基、またはハロゲン原子で置換されてもよい炭素数７～１０のアルキルアリール基を表す、＜１＞に記載の感光性樹脂組成物。
＜３＞（ａ２）構成単位における架橋性基がエポキシ基および／またはオキセタン基である、＜１＞または＜２＞に記載の感光性樹脂組成物。
＜４＞重合体成分として、少なくとも（１）を含む、＜１＞～＜３＞のいずれかに記載の感光性樹脂組成物。
＜５＞（Ｂ）一般式（Ｉ）で表される光酸発生剤の分子量が、３３５～８００である、＜１＞～＜４＞のいずれかに記載の感光性樹脂組成物。
＜６＞さらに、架橋剤を含む、＜１＞～＜５＞のいずれかに記載の感光性樹脂組成物。
＜７＞（１）＜１＞～＜６＞のいずれかに記載の感光性樹脂組成物を基板上に塗布する工程、
（２）塗布された感光性樹脂組成物から溶剤を除去する工程、
（３）活性放射線で露光する工程、
（４）水性現像液で現像する工程、および、
（５）熱硬化するポストベーク工程、を含む硬化膜の製造方法。
＜８＞＜１＞～＜６＞のいずれかに記載の感光性樹脂組成物を硬化してなる硬化膜。
＜９＞層間絶縁膜である、＜８＞に記載の硬化膜。
＜１０＞＜８＞または＜９＞に記載の硬化膜を有する、液晶表示装置または有機ＥＬ表示装置。 Specifically, the above problem has been solved by the following means <1>, preferably <2> to <10>.
<1> (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
(1) (a1) a polymer having a structural unit having an acid group protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group (2) (a1) the acid group is acid-decomposable A polymer having a structural unit having a group protected by a group, and (a2) a polymer having a structural unit having a crosslinkable group (B) a photoacid generator represented by the following general formula (I); C) solvent,
Containing a photosensitive resin composition;
Figure JPOXMLDOC01-appb-C000004
 In general formula (I), one of R 1 and R 2 represents a group represented by the following general formula (A), and the other represents a hydrogen atom; R 3 represents a halogen atom, an alkylthio group, and an alicyclic group. May be substituted with any one or more of an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a halogen atom, an alkylthio group, an alkyl group and an acyl group, which may be substituted with any one or more of the hydrocarbon groups An arylalkyl group having 7 to 20 carbon atoms, a 10-camphoryl group, or a group represented by the following general formula (B), which may be substituted with an aryl group having 6 to 20 carbon atoms, a halogen atom and / or an alkylthio group Represents;
Formula (A)
Figure JPOXMLDOC01-appb-C000005
 In general formula (A), X 1 represents an oxygen atom or a sulfur atom, Y 1 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R 4 represents a hydrocarbon group having 1 to 12 carbon atoms. R 5 represents an alkylene group having 1 to 4 carbon atoms, R 6 represents a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, or an alicyclic carbon atom having 3 to 10 carbon atoms. A hydrogen group, a heterocyclic group, or a hydroxyl group; n represents an integer of 0 to 5, and when n is 2 to 5, a plurality of R 5 may be the same or different;
General formula (B)
Figure JPOXMLDOC01-appb-C000006
 In the general formula (B), Y 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms, R 7 represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, carbon Represents an arylene group having 6 to 20 carbon atoms or a halogenated arylene group having 6 to 20 carbon atoms, and R 8 represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, carbon Represents an arylene group having 6 to 20 carbon atoms or a halogenated arylene group having 6 to 20 carbon atoms, and R 9 represents an alkyl group having 1 to 18 carbon atoms which may be branched, or 1 to 1 carbon atoms which may be branched. 18 halogenated alkyl groups, aryl groups having 6 to 20 carbon atoms, halogenated aryl groups having 6 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, or halogenated arylalkyl groups having 7 to 20 carbon atoms. A and b Each independently represent 0 or 1, at least one of a and b is 1.
<2> R 3 in the general formula (I) is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, a perfluoroalkyl group having 1 to 8 carbon atoms, or a 6 to 10 carbon atoms that may be substituted with a halogen atom. <1> The photosensitive resin composition according to <1>, which represents an aryl group or an alkylaryl group having 7 to 10 carbon atoms which may be substituted with a halogen atom.
<3> The photosensitive resin composition according to <1> or <2>, wherein the crosslinkable group in the structural unit (a2) is an epoxy group and / or an oxetane group.
<4> The photosensitive resin composition according to any one of <1> to <3>, comprising at least (1) as a polymer component.
<5> (B) The photosensitive resin composition according to any one of <1> to <4>, wherein the photoacid generator represented by the general formula (I) has a molecular weight of 335 to 800.
<6> The photosensitive resin composition according to any one of <1> to <5>, further comprising a crosslinking agent.
<7> (1) A step of applying the photosensitive resin composition according to any one of <1> to <6> on a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) a step of exposing with actinic radiation,
(4) a step of developing with an aqueous developer, and
(5) A method for producing a cured film comprising a post-bake step of thermosetting.
<8> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <6>.
<9> The cured film according to <8>, which is an interlayer insulating film.
<10> A liquid crystal display device or an organic EL display device having the cured film according to <8> or <9>.
　本発明によれば、高感度で体積抵抗率の高い感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置および有機ＥＬ表示装置を提供することが可能となった。 According to the present invention, it is possible to provide a photosensitive resin composition having high sensitivity and high volume resistivity, a method for producing a cured film, a cured film, a liquid crystal display device, and an organic EL display device.
液晶表示装置の一例の構成概念図を示す。液晶表示装置におけるアクティブマトリックス基板の模式的断面図を示し、層間絶縁膜である硬化膜１７を有している。1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film. 有機ＥＬ表示装置の一例の構成概念図を示す。ボトムエミッション型の有機ＥＬ表示装置における基板の模式的断面図を示し、平坦化膜４を有している。1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
　以下において、本発明の内容について詳細に説明する。以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。尚、本願明細書において「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。また、本発明における有機ＥＬ素子とは、有機エレクトロルミネッセンス素子のことをいう。
　本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。但し、一般式（Ｉ）で表される酸発生剤については、置換基を有していても良いことが明記されている基を除き、置換基を含まないものとする。
　なお、本明細書中において、“（メタ）アクリレート”はアクリレートおよびメタクリレートを表し、“（メタ）アクリル”はアクリルおよびメタクリルを表し、“（メタ）アクリロイル”はアクリロイルおよびメタクリロイルを表す。 Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). However, the acid generator represented by the general formula (I) does not include a substituent except for a group that is specified to be optionally substituted.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, and “(meth) acryloyl” represents acryloyl and methacryloyl.
感光性樹脂組成物：
　本発明の感光性樹脂組成物は、（Ａ）下記（１）および（２）の少なくとも一方を満たす重合体を含む重合体成分、（１）（ａ１）酸基が酸分解性基で保護された基を有する構成単位、および（ａ２）架橋性基を有する構成単位を有する重合体、（２）（ａ１）酸基が酸分解性基で保護された基を有する構成単位を有する重合体、および（ａ２）架橋性基を有する構成単位を有する重合体
（Ｂ）下記一般式（Ｉ）で表される光酸発生剤、を含有することを特徴とする。
Figure JPOXMLDOC01-appb-C000007
 （一般式（Ｉ）中、Ｒ1およびＲ2の一方は、下記一般式（Ａ）で表される基を表し、他方は水素原子を表す。Ｒ3は、ハロゲン原子、アルキルチオ基および脂環式炭化水素基のいずれか１つ以上で置換されてもよい炭素数１～１８の脂肪族炭化水素基、ハロゲン原子、アルキルチオ基、アルキル基およびアシル基のいずれか１つ以上で置換されてもよい炭素数６～２０のアリール基、ハロゲン原子および／またはアルキルチオ基で置換されてもよい炭素数７～２０のアリールアルキル基、１０－カンファーイル基または、下記一般式（Ｂ）で表される基を表す。）
一般式（Ａ）
Figure JPOXMLDOC01-appb-C000008
 （一般式（Ａ）中、Ｘ1は、酸素原子または硫黄原子を表し、Ｙ1は、単結合または炭素数１～４のアルキレン基を表し、Ｒ4は、炭素数１～１２の炭化水素基を表し、Ｒ5は、炭素数１～４のアルキレン基を表し、Ｒ6は、水素原子、分岐していてもよい炭素数１～４のアルキル基、炭素数３～１０の脂環式炭化水素基、複素環基、または水酸基を表す。ｎは、０～５の整数を表し、ｎが２～５の場合、複数存在するＲ5は同一でも異なってもよい。）
一般式（Ｂ）
Figure JPOXMLDOC01-appb-C000009
 （一般式（Ｂ）中、Ｙ2は、単結合または炭素数１～４のアルキレン基を表し、Ｒ7は、炭素数２～６のアルキレン基、炭素数２～６のハロゲン化アルキレン基、炭素数６～２０のアリーレン基、または炭素数６～２０のハロゲン化アリーレン基を表し、Ｒ8は、単結合、炭素数２～６のアルキレン基、炭素数２～６のハロゲン化アルキレン基、炭素数６～２０のアリーレン基または炭素数６～２０のハロゲン化アリーレン基を表し、Ｒ9は、分岐していてもよい炭素数１～１８のアルキル基、分岐していてもよい炭素数１～１８のハロゲン化アルキル基、炭素数６～２０のアリール基、炭素数６～２０のハロゲン化アリール基、炭素数７～２０のアリールアルキル基、または炭素数７～２０のハロゲン化アリールアルキル基を表す。ａおよびｂはそれぞれ独立に０または１を表し、ａおよびｂの少なくとも一方は１である。） Photosensitive resin composition:
The photosensitive resin composition of the present invention comprises (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2), (1) (a1) an acid group is protected with an acid-decomposable group. (A2) a polymer having a structural unit having a crosslinkable group, (2) (a1) a polymer having a structural unit having a group in which an acid group is protected with an acid-decomposable group, And (a2) a polymer having a structural unit having a crosslinkable group (B) and a photoacid generator represented by the following general formula (I).
Figure JPOXMLDOC01-appb-C000007
 (In general formula (I), one of R 1 and R 2 represents a group represented by the following general formula (A), and the other represents a hydrogen atom. R 3 represents a halogen atom, an alkylthio group, and an alicyclic ring. And may be substituted with any one or more of an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a halogen atom, an alkylthio group, an alkyl group and an acyl group, which may be substituted with any one or more of the formula hydrocarbon groups Preferred aryl group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom and / or alkylthio group, 10-camphoryl group, or the following general formula (B) Represents a group.)
Formula (A)
Figure JPOXMLDOC01-appb-C000008
 (In the general formula (A), X 1 represents an oxygen atom or a sulfur atom, Y 1 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R 4 represents a hydrocarbon having 1 to 12 carbon atoms. R 5 represents an alkylene group having 1 to 4 carbon atoms, R 6 represents a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, or an alicyclic group having 3 to 10 carbon atoms. Represents a hydrocarbon group, a heterocyclic group, or a hydroxyl group, n represents an integer of 0 to 5, and when n is 2 to 5, a plurality of R 5 may be the same or different.
General formula (B)
Figure JPOXMLDOC01-appb-C000009
 (In the general formula (B), Y 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms, R 7 represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, Represents an arylene group having 6 to 20 carbon atoms or a halogenated arylene group having 6 to 20 carbon atoms, and R 8 represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, Represents an arylene group having 6 to 20 carbon atoms or a halogenated arylene group having 6 to 20 carbon atoms, and R 9 represents an alkyl group having 1 to 18 carbon atoms which may be branched, or 1 carbon atom which may be branched. A halogenated alkyl group having 18 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a halogenated arylalkyl group having 7 to 20 carbon atoms A and Each independently represent 0 or 1, at least one of a and b is 1.)
　このような組成物を用いることにより、高い感度を維持しつつ、体積抵抗率の高い感光性樹脂組成物を提供することが可能となる。
　このような効果の詳細なメカニズムは不明であるが、以下のように推定している。
　感光性樹脂組成物に溶剤が混合している状態では、組成物中の各成分は相溶しているが、溶剤を除去する際に相溶しにくくなる。この結果、体積抵抗率にムラが発生し、硬化膜全体としての体積抵抗率が低下しやすくなる。本発明では、一般式（Ｉ）中のＲ1およびＲ2のいずれかが表す一般式（Ａ）で表される基と、架橋性基との相溶性を向上させることで、溶剤を除去する際のムラの発生を抑制し、硬化膜全体の体積抵抗率を向上できるものと推定している。
　一方、上記特許文献２（ＷＯ２０１１／０８７０１１号パンフレット）は、フォトレジストとして用いるものであり、体積抵抗率がそもそも問題にならない。 By using such a composition, it is possible to provide a photosensitive resin composition having a high volume resistivity while maintaining high sensitivity.
Although the detailed mechanism of such an effect is unknown, it is estimated as follows.
In the state where the solvent is mixed in the photosensitive resin composition, each component in the composition is compatible, but is difficult to be compatible when the solvent is removed. As a result, the volume resistivity is uneven, and the volume resistivity of the cured film as a whole tends to decrease. In the present invention, the solvent is removed by improving the compatibility of the crosslinkable group with the group represented by the general formula (A) represented by either R 1 or R 2 in the general formula (I). It is estimated that the occurrence of unevenness at the time can be suppressed and the volume resistivity of the entire cured film can be improved.
On the other hand, Patent Document 2 (WO2011 / 087011 pamphlet) is used as a photoresist, and volume resistivity is not a problem in the first place.
　以下、本発明の組成物の態様について詳細に説明する。なお、本発明の組成物は、通常、化学増幅ポジ型感光性樹脂組成物として用いられる。 Hereinafter, embodiments of the composition of the present invention will be described in detail. In addition, the composition of this invention is normally used as a chemically amplified positive photosensitive resin composition.
＜（Ａ）重合体成分＞
　本発明の組成物は、重合体成分として、（ａ１）酸基が酸分解性基で保護された基を有する構成単位および（ａ２）架橋性基を有する構成単位を有する重合体（１）、ならびに（ａ１）酸基が酸分解性基で保護された基を有する構成単位を有する重合体および（ａ２）架橋性基を有する構成単位を有する重合体（２）、の少なくとも一方を含む。さらに、これら以外の重合体を含んでいてもよい。本発明における（Ａ）重合体成分は、特に述べない限り、上記重合体（１）および／または上記重合体（２）に加え、必要に応じて添加される他の重合体を含めたものを意味する。
　（２）（ａ１）酸基が酸分解性基で保護された基を有する構成単位を有する重合体および（ａ２）架橋性基を有する構成単位を有する重合体を含む場合には、（ａ１）酸基が酸分解性基で保護された基を有する構成単位を有する重合体と（ａ２）架橋性基を有する構成単位を有する重合体との割合は、９５：５～５：９５が好ましく、８０：２０～２０：８０がより好ましく、７０：３０～３０：７０がさらに好ましい。本発明においては、体積抵抗率の観点から、重合体（１）を少なくとも含むことが好ましい。 <(A) Polymer component>
The composition of the present invention comprises, as a polymer component, a polymer (1) having (a1) a structural unit having an acid group protected with an acid-decomposable group and (a2) a structural unit having a crosslinkable group, And (a1) at least one of a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a2) a polymer (2) having a structural unit having a crosslinkable group. Furthermore, polymers other than these may be included. The polymer component (A) in the present invention includes, in addition to the polymer (1) and / or the polymer (2), other polymers added as necessary, unless otherwise specified. means.
(2) When (a1) includes a polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group and (a2) a polymer having a structural unit having a crosslinkable group, (a1) The ratio of the polymer having a structural unit having a group in which an acid group is protected by an acid-decomposable group and the polymer having a structural unit having a crosslinkable group (a2) is preferably 95: 5 to 5:95, 80:20 to 20:80 is more preferable, and 70:30 to 30:70 is more preferable. In this invention, it is preferable that a polymer (1) is included at least from a viewpoint of volume resistivity.
（Ａ）重合体成分は、付加重合型の樹脂であることが好ましく、（メタ）アクリル酸および／またはそのエステルに由来する構成単位を含む重合体であることがより好ましい。なお、（メタ）アクリル酸および／またはそのエステルに由来する構成単位以外の構成単位、例えば、スチレンに由来する構成単位や、ビニル化合物に由来する構成単位等を有していてもよい。なお、「（メタ）アクリル酸および／またはそのエステルに由来する構成単位」を「アクリル系構成単位」ともいう。 The (A) polymer component is preferably an addition polymerization type resin, and more preferably a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof. In addition, you may have structural units other than the structural unit derived from (meth) acrylic acid and / or its ester, for example, the structural unit derived from styrene, the structural unit derived from a vinyl compound, etc. The “structural unit derived from (meth) acrylic acid and / or its ester” is also referred to as “acrylic structural unit”.
＜＜（ａ１）酸基が酸分解性基で保護された基を有する構成単位＞＞
　（Ａ）重合体成分は、酸基が酸分解性基で保護された基を有する構成単位（ａ１）を少なくとも有する。（Ａ）重合体成分が構成単位（ａ１）を有することにより、極めて高感度な感光性樹脂組成物とすることができる。
　本発明における「酸基が酸分解性基で保護された基」は、酸基および酸分解性基として公知のものを使用でき、特に限定されない。
　具体的な酸基としては、カルボキシル基、および、フェノール性水酸基が好ましく挙げられる。
　また、具体的な酸分解性基としては、酸により比較的分解し易い基（例えば、後述するエステル構造、テトラヒドロピラニルエステル基、または、テトラヒドロフラニルエステル基等のアセタール系官能基）や、酸により比較的分解し難い基（例えば、ｔｅｒｔ－ブチルエステル基等の第三級アルキル基、ｔｅｒｔ－ブチルカーボネート基等の第三級アルキルカーボネート基）を用いることができる。 << (a1) Structural unit having a group in which an acid group is protected by an acid-decomposable group >>
(A) The polymer component has at least a structural unit (a1) having a group in which an acid group is protected with an acid-decomposable group. (A) When a polymer component has a structural unit (a1), it can be set as the highly sensitive photosensitive resin composition.
As the “group in which the acid group is protected with an acid-decomposable group” in the present invention, those known as an acid group and an acid-decomposable group can be used and are not particularly limited.
Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group.
Specific acid-decomposable groups include groups that are relatively easily decomposed by an acid (for example, an acetal functional group such as an ester structure, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group, which will be described later), or an acid. A group that is relatively difficult to decompose (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group) can be used.
　構成単位（ａ１）は、酸分解性基で保護された保護カルボキシル基を有する構成単位、または、酸分解性基で保護された保護フェノール性水酸基を有する構成単位であることが好ましい。
　以下、酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）と、酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）について、順にそれぞれ説明する。 The structural unit (a1) is preferably a structural unit having a protected carboxyl group protected with an acid-decomposable group or a structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group.
Hereinafter, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order. To do.
＜＜＜（ａ１－１）酸分解性基で保護された保護カルボキシル基を有する構成単位＞＞＞
　構成単位（ａ１－１）は、カルボキシル基を有する構成単位のカルボキシル基が、以下で詳細に説明する酸分解性基によって保護された保護カルボキシル基を有する構成単位である。
　上記構成単位（ａ１－１）に用いることができる上記カルボキシル基を有する構成単位としては、特に制限はなく公知の構成単位を用いることができる。例えば、不飽和モノカルボン酸、不飽和ジカルボン酸、不飽和トリカルボン酸などの、分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位（ａ１－１－１）が挙げられる。
　以下、上記カルボキシル基を有する構成単位として用いられる、構成単位（ａ１－１－１）について説明する。 <<< (a1-1) Structural Unit Having a Protected Carboxyl Group Protected with an Acid-Decomposable Group >>>
The structural unit (a1-1) is a structural unit having a protected carboxyl group in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below.
The structural unit having a carboxyl group that can be used for the structural unit (a1-1) is not particularly limited, and a known structural unit can be used. Examples thereof include a structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, such as an unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid. It is done.
Hereinafter, the structural unit (a1-1-1) used as the structural unit having a carboxyl group will be described.
＜＜＜＜（ａ１－１－１）分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位＞＞＞＞
　本発明で用いられる不飽和カルボン酸としては、以下に挙げるようなものが用いられる。
　すなわち、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、α－クロロアクリル酸、けい皮酸、２－（メタ）アクリロイロキシエチル-コハク酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチル-フタル酸、などが挙げられる。
　また、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、イタコン酸、シトラコン酸、メサコン酸などが挙げられる。
　また、カルボキシル基を有する構成単位を得るために用いられる不飽和多価カルボン酸は、その酸無水物であってもよい。具体的には、無水マレイン酸、無水イタコン酸、無水シトラコン酸などが挙げられる。また、不飽和多価カルボン酸は、多価カルボン酸のモノ（２－メタクリロイロキシアルキル）エステルであってもよく、例えば、コハク酸モノ（２－アクリロイロキシエチル）、コハク酸モノ（２－メタクリロイロキシエチル）、フタル酸モノ（２－アクリロイロキシエチル）、フタル酸モノ（２－メタクリロイロキシエチル）などが挙げられる。さらに、不飽和多価カルボン酸は、その両末端ジカルボキシポリマーのモノ（メタ）アクリレートであってもよく、例えば、ω－カルボキシポリカプロラクトンモノアクリレート、ω－カルボキシポリカプロラクトンモノメタクリレートなどが挙げられる。また、不飽和カルボン酸としては、アクリル酸－２－カルボキシエチルエステル、メタクリル酸－２－カルボキシエチルエステル、マレイン酸モノアルキルエステル、フマル酸モノアルキルエステル、４－カルボキシスチレン等も用いることができる。
　中でも、現像性の観点から、上記構成単位（ａ１－１－１）を形成するためには、アクリル酸、メタクリル酸、２－（メタ）アクリロイロキシエチル-コハク酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、２－（メタ）アクリロイロキシエチル-フタル酸、または不飽和多価カルボン酸の無水物等を用いることが好ましく、アクリル酸、メタクリル酸、２－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、を用いることがより好ましい。
　構成単位（ａ１－１－１）は、１種単独で構成されていてもよいし、２種以上で構成されていてもよい。 <<<<< (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>>
Examples of the unsaturated carboxylic acid used in the present invention include those listed below.
That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acrylic acid. And leuoxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, and the like.
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the structural unit which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both terminals, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
Among these, from the viewpoint of developability, in order to form the structural unit (a1-1-1), acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acrylic acid are used. It is preferable to use leuoxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or an anhydride of an unsaturated polycarboxylic acid, and acrylic acid, methacrylic acid, 2- (meth) acrylic acid, etc. It is more preferable to use leuoxyethyl hexahydrophthalic acid.
The structural unit (a1-1-1) may be composed of one type alone, or may be composed of two or more types.
＜＜＜＜構成単位（ａ１－１）に用いることができる酸分解性基＞＞＞＞
　構成単位（ａ１－１）に用いることができる上記酸分解性基としては、上述の酸分解性基を用いることができる。
　これらの酸分解性基の中でも、酸分解性基がアセタールの形で保護された構造を有する基であることが好ましい。例えば、カルボキシル基がアセタールの形で保護された保護カルボキシル基であることが、感光性樹脂組成物の基本物性、特に感度やパターン形状、コンタクトホールの形成性、感光性樹脂組成物の保存安定性の観点から好ましい。さらに、カルボキシル基が下記一般式（ａ１－１０）で表されるアセタールの形で保護された保護カルボキシル基であることが、感度の観点からより好ましい。なお、カルボキシル基が下記一般式（ａ１－１０）で表されるアセタールの形で保護された保護カルボキシル基である場合、保護カルボキシル基の全体としては、－（Ｃ＝Ｏ）－Ｏ－ＣＲ101Ｒ102（ＯＲ103）の構造となっている。 <<<< acid-decomposable group that can be used for the structural unit (a1-1) >>>>
As the acid-decomposable group that can be used for the structural unit (a1-1), the acid-decomposable groups described above can be used.
Among these acid-decomposable groups, the acid-decomposable group is preferably a group having a structure protected in the form of an acetal. For example, it is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, the basic physical properties of the photosensitive resin composition, particularly the sensitivity and pattern shape, the formation of contact holes, the storage stability of the photosensitive resin composition From the viewpoint of Furthermore, it is more preferable from the viewpoint of sensitivity that the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10). When the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10), the entire protected carboxyl group is — (C═O) —O—CR 101 The structure is R 102 (OR 103 ).
一般式（ａ１－１０）
Figure JPOXMLDOC01-appb-C000010
 （式（ａ１－１０）中、Ｒ101およびＲ102は、それぞれ独立に水素原子またはアルキル基を表し、但し、Ｒ101とＲ102とが共に水素原子の場合を除く。Ｒ103は、アルキル基を表す。Ｒ101またはＲ102と、Ｒ103とが連結して環状エーテルを形成してもよい。） Formula (a1-10)
Figure JPOXMLDOC01-appb-C000010
 (In formula (a1-10), R 101 and R 102 each independently represents a hydrogen atom or an alkyl group, except that R 101 and R 102 are both hydrogen atoms, and R 103 represents an alkyl group. R 101 or R 102 and R 103 may be linked to form a cyclic ether.)
　上記一般式（ａ１－１０）中、Ｒ101～Ｒ103は、それぞれ独立に水素原子またはアルキル基を表し、上記アルキル基は直鎖状、分岐鎖状、環状のいずれでもよい。ここで、Ｒ101およびＲ102の双方が水素原子を表すことはなく、Ｒ101およびＲ102の少なくとも一方はアルキル基を表す。
　上記直鎖状または分岐鎖状のアルキル基としては、炭素数１～１２であることが好ましく、炭素数１～６であることがより好ましく、炭素数１～４であることがさらに好ましい。具体的には、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、ｉ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ネオペンチル基、ｎ－ヘキシル基、テキシル基（２，３－ジメチル－２－ブチル基）、ｎ－ヘプチル基、ｎ－オクチル基、２－エチルヘキシル基、ｎ－ノニル基、ｎ－デシル基等を挙げることができる。 In the general formula (a1-10), R 101 to R 103 each independently represents a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic. Here, both R 101 and R 102 do not represent a hydrogen atom, and at least one of R 101 and R 102 represents an alkyl group.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
　上記一般式（ａ１－１０）中、Ｒ101～Ｒ103は、それぞれ独立に水素原子またはアルキル基を表す。上記アルキル基は直鎖状、分岐鎖状、環状のいずれでもよい。ここで、Ｒ101およびＲ102の双方が水素原子を表すことはなく、Ｒ101およびＲ102の少なくとも一方はアルキル基を表す。
　上記直鎖状または分岐鎖状のアルキル基としては、炭素数１～１２であることが好ましく、炭素数１～６であることがより好ましく、炭素数１～４であることがさらに好ましい。具体的には、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、ｉ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ネオペンチル基、ｎ－ヘキシル基、テキシル基（２，３－ジメチル－２－ブチル基）、ｎ－ヘプチル基、ｎ－オクチル基、２－エチルヘキシル基、ｎ－ノニル基、ｎ－デシル基等を挙げることができる。
　上記環状アルキル基としては、炭素数３～１２であることが好ましく、炭素数４～８であることがより好ましく、炭素数４～６であることがさらに好ましい。上記環状アルキル基としては、例えばシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、ノルボルニル基、イソボルニル基等を挙げることができる。 In the general formula (a1-10), R 101 to R 103 each independently represents a hydrogen atom or an alkyl group. The alkyl group may be linear, branched or cyclic. Here, both R 101 and R 102 do not represent a hydrogen atom, and at least one of R 101 and R 102 represents an alkyl group.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.
　上記アルキル基は、置換基を有していてもよく、置換基としては、ハロゲン原子、アリール基、アルコキシ基が例示できる。置換基としてハロゲン原子を有する場合、Ｒ101、Ｒ102、Ｒ103はハロアルキル基となり、置換基としてアリール基を有する場合、Ｒ101、Ｒ102、Ｒ103はアラルキル基となる。
　上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が例示され、これらの中でもフッ素原子または塩素原子が好ましい。
　また、上記アリール基としては、炭素数６～２０のアリール基が好ましく、より好ましくは炭素数６～１２であり、具体的には、フェニル基、α－メチルフェニル基、ナフチル基等が例示でき、アリール基で置換されたアルキル基全体、すなわち、アラルキル基としては、ベンジル基、α－メチルベンジル基、フェネチル基、ナフチルメチル基等が例示できる。
　上記アルコキシ基としては、炭素数１～６のアルコキシ基が好ましく、より好ましくは炭素数１～４であり、メトキシ基またはエトキシ基がより好ましい。
　また、上記アルキル基が環状アルキル基である場合、上記環状アルキル基は、置換基として炭素数１～１０の直鎖状または分岐鎖状のアルキル基を有していてもよく、アルキル基が直鎖状または分岐鎖状のアルキル基である場合には、置換基として炭素数３～１２の環状アルキル基を有していてもよい。
　これらの置換基は、上記置換基でさらに置換されていてもよい。 The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R 101 , R 102 and R 103 become a haloalkyl group, and when it has an aryl group as a substituent, R 101 , R 102 and R 103 become an aralkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an α-methylphenyl group, and a naphthyl group. Examples of the entire alkyl group substituted with an aryl group, ie, an aralkyl group, include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.
When the alkyl group is a cyclic alkyl group, the cyclic alkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group is straight. When the alkyl group is a chain or branched chain, it may have a cyclic alkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.
　上記一般式（ａ１－１０）において、Ｒ101、Ｒ102およびＲ103がアリール基を表す場合、上記アリール基は、炭素数６～１２であることが好ましく、炭素数６～１０であることがより好ましい。上記アリール基は、置換基を有していてもよく、上記置換基としては炭素数１～６のアルキル基が好ましく例示できる。アリール基としては、例えば、フェニル基、トリル基、キシリル基、クメニル基、１－ナフチル基等が例示できる。 In the general formula (a1-10), when R 101 , R 102 and R 103 represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, and preferably 6 to 10 carbon atoms. More preferred. The aryl group may have a substituent, and preferred examples of the substituent include an alkyl group having 1 to 6 carbon atoms. Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a 1-naphthyl group.
　また、Ｒ101、Ｒ102およびＲ103は、互いに結合して、それらが結合している炭素原子と一緒になって環を形成することができる。Ｒ101とＲ102、Ｒ101とＲ103またはＲ102とＲ103が結合した場合の環構造としては、例えばシクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、テトラヒドロフラニル基、アダマンチル基およびテトラヒドロピラニル基等を挙げることができる。
　なお、上記一般式（ａ１－１０）において、Ｒ101およびＲ102のいずれか一方が、水素原子またはメチル基であることが好ましい。 R 101 , R 102 and R 103 can be bonded to each other to form a ring together with the carbon atom to which they are bonded. Examples of the ring structure when R 101 and R 102 , R 101 and R 103, or R 102 and R 103 are bonded include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a tetrahydrofuranyl group, an adamantyl group, and a tetrahydropyrani group. And the like.
Note that in the general formula (a1-10), it is preferable that any one of R 101 and R 102 be a hydrogen atom or a methyl group.
　上記一般式（ａ１－１０）で表される保護カルボキシル基を有する構成単位を形成するために用いられるラジカル重合性単量体は、市販のものを用いてもよいし、公知の方法で合成したものを用いることもできる。例えば、特開２０１１－２２１４９４号公報の段落番号００３７～００４０に記載の合成方法などで合成することができ、この内容は本願明細書に組み込まれる。 As the radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the general formula (a1-10), a commercially available one may be used, or it may be synthesized by a known method. Things can also be used. For example, it can be synthesized by the synthesis method described in paragraph Nos. 0037 to 0040 of JP2011-212494A, the contents of which are incorporated herein.
　上記構成単位（ａ１－１）の第一の好ましい態様は、下記一般式（Ａ２’）で表される構成単位である。
Figure JPOXMLDOC01-appb-C000011
 （式（Ａ２’）中、Ｒ1およびＲ2は、それぞれ、水素原子、アルキル基またはアリール基を表し、少なくともＲ1およびＲ2のいずれか一方がアルキル基またはアリール基を表し、Ｒ3は、アルキル基またはアリール基を表し、Ｒ1またはＲ2と、Ｒ3とが連結して環状エーテルを形成してもよく、Ｒ4は、水素原子またはメチル基を表し、Ｘは単結合またはアリーレン基を表す。）
　Ｒ1およびＲ2がアルキル基の場合、炭素数は１～１０のアルキル基が好ましい。Ｒ1およびＲ2がアリール基の場合、フェニル基が好ましい。Ｒ1およびＲ2は、それぞれ、水素原子または炭素数１～４のアルキル基が好ましい。
　Ｒ3は、アルキル基またはアリール基を表し、炭素数１～１０のアルキル基が好ましく、１～６のアルキル基がより好ましい。
　Ｘは単結合またはアリーレン基を表し、単結合が好ましい。 A first preferred embodiment of the structural unit (a1-1) is a structural unit represented by the following general formula (A2 ′).
Figure JPOXMLDOC01-appb-C000011
 (In the formula (A2 ′), R 1 and R 2 each represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 1 and R 2 represents an alkyl group or an aryl group, and R 3 represents Represents an alkyl group or an aryl group, and R 1 or R 2 and R 3 may be linked to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents a single bond or arylene. Represents a group.)
When R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred. When R 1 and R 2 are aryl groups, a phenyl group is preferred. R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
X represents a single bond or an arylene group, and a single bond is preferred.
　上記構成単位（ａ１－１）の第二の好ましい態様は、下記一般式（１－１２）で表される構成単位である。
一般式（１－１２）
Figure JPOXMLDOC01-appb-C000012
 （式（１－１２）中、Ｒ121は水素原子または炭素数１～４のアルキル基を表し、Ｌ1はカルボニル基またはフェニレン基を表し、Ｒ122～Ｒ128はそれぞれ独立に、水素原子または炭素数１～４のアルキル基を表す。）
　Ｒ121は水素原子またはメチル基が好ましい。
　Ｌ1はカルボニル基が好ましい。
　Ｒ122～Ｒ128は、水素原子が好ましい。 A second preferred embodiment of the structural unit (a1-1) is a structural unit represented by the following general formula (1-12).
Formula (1-12)
Figure JPOXMLDOC01-appb-C000012
 (In the formula (1-12), R 121 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, L 1 represents a carbonyl group or a phenylene group, and R 122 to R 128 each independently represents a hydrogen atom or Represents an alkyl group having 1 to 4 carbon atoms.)
R 121 is preferably a hydrogen atom or a methyl group.
L 1 is preferably a carbonyl group.
R 122 to R 128 are preferably hydrogen atoms.
　上記構成単位（ａ１－１）の好ましい具体例としては、下記の構成単位が例示できる。なお、下記の構成単位中、Ｒは水素原子またはメチル基を表す。 The following structural units can be exemplified as preferred specific examples of the structural unit (a1-1). In the structural units below, R represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
＜＜＜（ａ１－２）酸分解性基で保護された保護フェノール性水酸基を有する構成単位＞＞＞
　構成単位（ａ１－２）は、フェノール性水酸基を有する構成単位が、以下で詳細に説明する酸分解性基によって保護された保護フェノール性水酸基を有する構成単位（ａ１－２－１）である。 <<< (a1-2) Structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group >>>
The structural unit (a1-2) is a structural unit (a1-2-1) having a protected phenolic hydroxyl group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below.
＜＜＜＜（ａ１－２－１）フェノール性水酸基を有する構成単位＞＞＞＞
　上記フェノール性水酸基を有する構成単位としては、ヒドロキシスチレン系構成単位やノボラック系の樹脂における構成単位が挙げられるが、これらの中では、ヒドロキシスチレン、またはα－メチルヒドロキシスチレンに由来する構成単位が、感度の観点から好ましい。またフェノール性水酸基を有する構成単位として、下記一般式（ａ１－２０）で表される構成単位も、感度の観点から好ましい。 <<<<< (a1-2-1) Structural Unit Having Phenolic Hydroxyl Group >>>>
Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene structural unit and a structural unit in a novolac resin. Among these, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene includes: It is preferable from the viewpoint of sensitivity. As the structural unit having a phenolic hydroxyl group, a structural unit represented by the following general formula (a1-20) is also preferable from the viewpoint of sensitivity.
一般式（ａ１－２０）
Figure JPOXMLDOC01-appb-C000014
 （一般式（ａ１－２０）中、Ｒ220は水素原子またはメチル基を表し、Ｒ221は単結合または二価の連結基を表し、Ｒ222はハロゲン原子または炭素数１～５の直鎖または分岐鎖状のアルキル基を表し、ａは１～５の整数を表し、ｂは０～４の整数を表し、ａ＋ｂは５以下である。なお、Ｒ222が２以上存在する場合、これらのＲ222は相互に異なっていてもよいし同じでもよい。） Formula (a1-20)
Figure JPOXMLDOC01-appb-C000014
 (In the general formula (a1-20), R 220 represents a hydrogen atom or a methyl group, R 221 represents a single bond or a divalent linking group, and R 222 represents a halogen atom or a straight chain of 1 to 5 carbon atoms or Represents a branched alkyl group, a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less, and when R 222 is 2 or more, these R 222 may be different from each other or the same.)
　上記一般式（ａ１－２０）中、Ｒ220は水素原子またはメチル基を表し、メチル基であることが好ましい。
　また、Ｒ221は単結合または二価の連結基を示す。単結合である場合には、感度を向上させることができ、さらに硬化膜の透明性を向上させることができるので好ましい。Ｒ221の二価の連結基としてはアルキレン基が例示でき、Ｒ221がアルキレン基である具体例としては、メチレン基、エチレン基、プロピレン基、イソプロピレン基、ｎ－ブチレン基、イソブチレン基、ｔｅｒｔ－ブチレン基、ペンチレン基、イソペンチレン基、ネオペンチレン基、ヘキシレン基等が挙げられる。中でも、Ｒ221が単結合、メチレン基、エチレン基であることが好ましい。また、上記二価の連結基は、置換基を有していてもよく、置換基としては、ハロゲン原子、水酸基、アルコキシ基等が挙げられる。また、ａは１～５の整数を表すが、本発明の効果の観点や、製造が容易であるという点から、ａは１または２であることが好ましく、ａが１であることがより好ましい。
　また、ベンゼン環における水酸基の結合位置は、Ｒ221と結合している炭素原子を基準（１位）としたとき、４位に結合していることが好ましい。
　Ｒ222はハロゲン原子または炭素数１～５の直鎖または分岐鎖状のアルキル基である。具体的には、フッ素原子、塩素原子、臭素原子、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。中でも製造が容易であるという点から、塩素原子、臭素原子、メチル基またはエチル基であることが好ましい。
　また、ｂは０または１～４の整数を表す。 In the general formula (a1-20), R 220 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R 221 represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be further improved. The divalent linking group of R 221 may be exemplified alkylene groups, specific examples R 221 is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Among these, it is preferable that R 221 is a single bond, a methylene group, or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. A represents an integer of 1 to 5, but a is preferably 1 or 2 and more preferably 1 from the viewpoint of the effects of the present invention and the ease of production. .
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R 221 is defined as the reference (first position).
R 222 is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
B represents 0 or an integer of 1 to 4;
＜＜＜＜構成単位（ａ１－２）に用いることができる酸分解性基＞＞＞＞
　上記構成単位（ａ１－２）に用いることができる上記酸分解性基としては、上記構成単位（ａ１－１）に用いることができる酸分解性基と同様に、公知のものを使用でき、特に限定されない。酸分解性基の中でもアセタールで保護された保護フェノール性水酸基を有する構成単位であることが、感光性樹脂組成物の基本物性、特に感度やパターン形状、感光性樹脂組成物の保存安定性、コンタクトホールの形成性の観点から好ましい。さらに、酸分解性基の中でも、フェノール性水酸基が上記一般式（ａ１－１０）で表されるアセタールの形で保護された保護フェノール性水酸基であることが、感度の観点からより好ましい。なお、フェノール性水酸基が上記一般式（ａ１－１０）で表されるアセタールの形で保護された保護フェノール性水酸基である場合、保護フェノール性水酸基の全体としては、－Ａｒ－Ｏ－ＣＲ101Ｒ102（ＯＲ103）の構造となっている。なお、Ａｒはアリーレン基を表す。
　フェノール性水酸基のアセタールエステル構造の好ましい例は、Ｒ101＝Ｒ102＝Ｒ103＝メチル基やＲ101＝Ｒ102＝メチル基でＲ103＝ベンジル基の組み合わせが例示できる。
　また、フェノール性水酸基がアセタールの形で保護された保護フェノール性水酸基を有する構成単位を形成するために用いられるラジカル重合性単量体としては、例えば、特開２０１１－２１５５９０号公報の段落番号００４２に記載のものなどが挙げられる。
　これらの中でも、４－ヒドロキシフェニルメタクリレートの１－アルコキシアルキル保護体、４－ヒドロキシフェニルメタクリレートのテトラヒドロピラニル保護体が透明性の観点から好ましい。 <<<< acid-decomposable group that can be used for the structural unit (a1-2) >>>>
As the acid-decomposable group that can be used for the structural unit (a1-2), as with the acid-decomposable group that can be used for the structural unit (a1-1), known ones can be used. It is not limited. Among the acid-decomposable groups, a structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability. Furthermore, among the acid-decomposable groups, it is more preferable from the viewpoint of sensitivity that the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the above general formula (a1-10). When the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-10), the protected phenolic hydroxyl group as a whole is —Ar—O—CR 101 R The structure is 102 (OR 103 ). Ar represents an arylene group.
Preferable examples of the acetal ester structure of the phenolic hydroxyl group include a combination of R 101 = R 102 = R 103 = methyl group, R 101 = R 102 = methyl group and R 103 = benzyl group.
Examples of the radical polymerizable monomer used for forming a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include paragraph number 0042 of JP2011-215590A. And the like.
Among these, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.
　フェノール性水酸基のアセタール保護基の具体例としては、１－アルコキシアルキル基が挙げられ、例えば、１－エトキシエチル基、１－メトキシエチル基、１－ｎ－ブトキシエチル基、１－イソブトキシエチル基、１－（２－クロロエトキシ）エチル基、１－（２－エチルヘキシルオキシ）エチル基、１－ｎ－プロポキシエチル基、１－シクロヘキシルオキシエチル基、１－（２－シクロヘキシルエトキシ）エチル基、１－ベンジルオキシエチル基などを挙げることができ、これらは単独または２種類以上を組み合わせて使用することができる。 Specific examples of the acetal protecting group for the phenolic hydroxyl group include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group. 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned, These can be used individually or in combination of 2 or more types.
　上記構成単位（ａ１－２）を形成するために用いられるラジカル重合性単量体は、市販のものを用いてもよいし、公知の方法で合成したものを用いることもできる。例えば、フェノール性水酸基を有する化合物を酸触媒の存在下でビニルエーテルと反応させることにより合成することができる。上記の合成はフェノール性水酸基を有するモノマーをその他のモノマーと予め共重合させておき、その後に酸触媒の存在下でビニルエーテルと反応させてもよい。 As the radical polymerizable monomer used for forming the structural unit (a1-2), a commercially available one may be used, or one synthesized by a known method may be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.
　上記構成単位（ａ１－２）の好ましい具体例としては、下記の構成単位が例示できるが、本発明はこれらに限定されるものではない。 As preferred specific examples of the structural unit (a1-2), the following structural units can be exemplified, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
＜＜＜構成単位（ａ１）の好ましい態様＞＞＞
　上記構成単位（ａ１）を含有する重合体が、実質的に、構成単位（ａ２）を含まない場合、構成単位（ａ１）の含有量は、重合体中、２０～１００モル％が好ましく、３０～９０モル％がより好ましい。
　上記構成単位（ａ１）を含有する重合体が、構成単位（ａ２）を含有する場合、構成単位（ａ１）の含有量は、重合体中、感度の観点から３～７０モル％が好ましく、１０～６０モル％がより好ましい。また、特に上記構成単位（ａ１）に用いることができる上記酸分解性基が、カルボキシル基がアセタールの形で保護された保護カルボキシル基を有する構成単位である場合、２０～５０モル％が好ましい。 <<< Preferred Aspect of Structural Unit (a1) >>>
When the polymer containing the structural unit (a1) does not substantially contain the structural unit (a2), the content of the structural unit (a1) is preferably 20 to 100 mol% in the polymer, 30 -90 mol% is more preferable.
When the polymer containing the structural unit (a1) contains the structural unit (a2), the content of the structural unit (a1) is preferably 3 to 70 mol% in the polymer from the viewpoint of sensitivity. More preferred is ˜60 mol%. In particular, when the acid-decomposable group that can be used in the structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, the content is preferably 20 to 50 mol%.
　上記構成単位（ａ１－１）は、上記構成単位（ａ１－２）に比べると、現像が速いという特徴がある。よって、速く現像したい場合には、構成単位（ａ１－１）が好ましい。逆に現像を遅くしたい場合には、構成単位（ａ１－２）を用いることが好ましい。 The structural unit (a1-1) is characterized by faster development than the structural unit (a1-2). Therefore, when it is desired to develop quickly, the structural unit (a1-1) is preferable. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-2).
＜＜（ａ２）架橋性基を有する構成単位＞＞
　（Ａ）重合体成分は、架橋性基を有する構成単位（ａ２）を有する。上記架橋性基は、加熱処理で硬化反応を起こす基であれば特に限定はされない。好ましい架橋性基を有する構成単位の態様としては、エポキシ基、オキセタニル基、－ＮＨ－ＣＨ2－Ｏ－Ｒ（Ｒは水素原子または炭素数１～２０のアルキル基）で表される基およびエチレン性不飽和基よりなる群から選ばれた少なくとも１つを含む構成単位が挙げられ、エポキシ基、オキセタニル基、および、－ＮＨ－ＣＨ2－Ｏ－Ｒ（Ｒは水素原子または炭素数１～２０のアルキル基）で表される基から選ばれる少なくとも１種であることが好ましい。その中でも、本発明の感光性樹脂組成物は、（Ａ）重合体成分が、エポキシ基およびオキセタニル基のうち少なくとも１つを含む構成単位を含むことが好ましい。エポキシ基およびオキセタニル基のうち少なくとも１つを含む単位とすることにより、本発明の効果がより効果的に発揮される。より詳細には、以下のものが挙げられる。 << (a2) Structural Unit Having Crosslinkable Group >>
(A) The polymer component has a structural unit (a2) having a crosslinkable group. The crosslinkable group is not particularly limited as long as it is a group that causes a curing reaction by heat treatment. Preferred embodiments of the structural unit having a crosslinkable group include an epoxy group, an oxetanyl group, a group represented by —NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) and ethylene. And a structural unit containing at least one selected from the group consisting of an unsaturated group, an epoxy group, an oxetanyl group, and —NH—CH 2 —O—R (R represents a hydrogen atom or a carbon number of 1 to 20). The alkyl group is preferably at least one selected from the group represented by Among them, in the photosensitive resin composition of the present invention, it is preferable that the (A) polymer component includes a structural unit including at least one of an epoxy group and an oxetanyl group. By using a unit containing at least one of an epoxy group and an oxetanyl group, the effects of the present invention are more effectively exhibited. In more detail, the following are mentioned.
＜＜＜（ａ２－１）エポキシ基および／またはオキセタニル基を有する構成単位＞＞＞
　上記（Ａ）重合体成分は、エポキシ基および／またはオキセタニル基を有する構成単位（以下、構成単位（ａ２－１）ともいう。）を含有することが好ましい。
　上記構成単位（ａ２－１）は、１つの構成単位中にエポキシ基またはオキセタニル基を少なくとも１つ有していればよく、１つ以上のエポキシ基および１つ以上オキセタニル基、２つ以上のエポキシ基、または、２つ以上のオキセタニル基を有していてもよく、特に限定されないが、エポキシ基および／またはオキセタニル基を合計１～３つ有することが好ましく、エポキシ基および／またはオキセタニル基を合計１または２つ有することがより好ましく、エポキシ基またはオキセタニル基を１つ有することがさらに好ましい。 <<< (a2-1) Structural Unit Having Epoxy Group and / or Oxetanyl Group >>>
The (A) polymer component preferably contains a structural unit having an epoxy group and / or an oxetanyl group (hereinafter also referred to as a structural unit (a2-1)).
The structural unit (a2-1) may have at least one epoxy group or oxetanyl group in one structural unit, and includes one or more epoxy groups, one or more oxetanyl groups, and two or more epoxy groups. Group, or may have two or more oxetanyl groups, and is not particularly limited, but preferably has a total of 1 to 3 epoxy groups and / or oxetanyl groups, and a total of epoxy groups and / or oxetanyl groups It is more preferable to have one or two, and it is more preferable to have one epoxy group or one oxetanyl group.
　エポキシ基を有する構成単位を形成するために用いられるラジカル重合性単量体の具体例としては、例えば、アクリル酸グリシジル、メタクリル酸グリシジル、α－エチルアクリル酸グリシジル、α－ｎ－プロピルアクリル酸グリシジル、α－ｎ－ブチルアクリル酸グリシジル、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－３，４－エポキシシクロヘキシルメチル、メタクリル酸－３，４－エポキシシクロヘキシルメチル、α－エチルアクリル酸－３，４－エポキシシクロヘキシルメチル、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、特許第４１６８４４３号公報の段落番号００３１～００３５に記載の脂環式エポキシ骨格を含有する化合物などが挙げられ、これらの内容は本願明細書に組み込まれる。
　オキセタニル基を有する構成単位を形成するために用いられるラジカル重合性単量体の具体例としては、例えば、特開２００１－３３０９５３号公報の段落番号００１１～００１６に記載のオキセタニル基を有する（メタ）アクリル酸エステルや、特開２０１２－０８８４５９公報の段落番号００２７に記載されている化合物などが挙げられ、これらの内容は本願明細書に組み込まれる。
　上記エポキシ基および／またはオキセタニル基を有する構成単位（ａ２－１）を形成するために用いられるラジカル重合性単量体の具体例としては、メタクリル酸エステル構造を含有するモノマー、アクリル酸エステル構造を含有するモノマーであることが好ましい。 Specific examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraph Nos. 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic And compounds containing epoxy backbone can be cited, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit having an oxetanyl group include (meth) having an oxetanyl group described in paragraph Nos. 0011 to 0016 of JP-A No. 2001-330953, for example. Examples thereof include acrylate esters and compounds described in paragraph No. 0027 of JP2012-088459A, the contents of which are incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit (a2-1) having the epoxy group and / or oxetanyl group include a monomer having a methacrylic ester structure and an acrylic ester structure. A monomer to be contained is preferable.
　これらの中でも好ましいものは、メタクリル酸グリシジル、アクリル酸－３，４－エポキシシクロヘキシルメチル、メタクリル酸３，４－エポキシシクロヘキシルメチル、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、アクリル酸（３－エチルオキセタン－３－イル）メチル、および、メタクリル酸（３－エチルオキセタン－３－イル）メチルが、共重合反応性および硬化膜の諸特性の向上の観点から好ましい。これらの構成単位は、１種単独または２種類以上を組み合わせて使用することができる。 Among these, preferred are glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl. Glycidyl ether, acrylic acid (3-ethyloxetane-3-yl) methyl, and methacrylic acid (3-ethyloxetane-3-yl) methyl are preferred from the viewpoints of copolymerization reactivity and improved properties of the cured film. . These structural units can be used individually by 1 type or in combination of 2 or more types.
　上記構成単位（ａ２－１）の好ましい具体例としては、下記の構成単位が例示できる。なお、下記の構成単位中、Ｒは、水素原子またはメチル基を表す。 As a preferred specific example of the structural unit (a2-1), the following structural units can be exemplified. In the structural units below, R represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
＜＜＜（ａ２－２）エチレン性不飽和基を有する構成単位＞＞＞
　上記架橋性基を有する構成単位（ａ２）の１つとして、エチレン性不飽和基を有する構成単位（ａ２－２）が挙げられる。上記構成単位（ａ２－２）としては、側鎖にエチレン性不飽和基を有する構成単位が好ましく、末端にエチレン性不飽和基を有し、炭素数３～１６の側鎖を有する構成単位がより好ましい。
　その他、構成単位（ａ２－２）については、特開２０１１－２１５５８０号公報の段落番号００７２～００９０の記載および特開２００８－２５６９７４の段落番号００１３～００３１に記載の化合物等が好ましいものとして挙げられ、これらの内容は本願明細書に組み込まれる。 <<< (a2-2) Structural unit having an ethylenically unsaturated group >>>
As one of the structural unit (a2) having a crosslinkable group, there may be mentioned the structural unit (a2-2) having an ethylenically unsaturated group. The structural unit (a2-2) is preferably a structural unit having an ethylenically unsaturated group in the side chain, and a structural unit having an ethylenically unsaturated group at the terminal and having a side chain having 3 to 16 carbon atoms. More preferred.
In addition, with respect to the structural unit (a2-2), compounds described in paragraph numbers 0072 to 0090 of JP2011-215580A and paragraph numbers 0013 to 0031 of JP2008-256974A are preferable. The contents of which are incorporated herein by reference.
＜＜＜（ａ２－３）－ＮＨ－ＣＨ2－Ｏ－Ｒ（Ｒは水素原子または炭素数１～２０のアルキル基）で表される基を有する構成単位＞＞＞
　本発明で用いる（Ａ）重合体成分は、－ＮＨ－ＣＨ2－Ｏ－Ｒ（Ｒは水素原子または炭素数１～２０のアルキル基）で表される基を有する構成単位（ａ２－３）も好ましい。構成単位（ａ２－３）を有することで、緩やかな加熱処理で硬化反応を起こすことができ、諸特性に優れた硬化膜を得ることができる。ここで、Ｒは炭素数１～９のアルキル基が好ましく、炭素数１～４のアルキル基がより好ましい。また、アルキル基は、直鎖、分岐または環状のアルキル基のいずれであってもよいが、好ましくは、直鎖または分岐のアルキル基である。構成単位（ａ２－３）は、より好ましくは、下記一般式（ａ２－３０）で表される基を有する構成単位である。
一般式（ａ２－３０）
Figure JPOXMLDOC01-appb-C000019
 （一般式（ａ２－３０）中、Ｒ1は水素原子またはメチル基を表し、Ｒ2は水素原子または炭素数１～２０のアルキル基を表す。）
　Ｒ2は、炭素数１～９のアルキル基が好ましく、炭素数１～４のアルキル基がさらに好ましい。また、アルキル基は、直鎖、分岐または環状のアルキル基のいずれであってもよいが、好ましくは、直鎖または分岐のアルキル基である。
　Ｒ2の具体例としては、メチル基、エチル基、ｎ－ブチル基、ｉ－ブチル基、シクロヘキシル基、およびｎ－ヘキシル基を挙げることができる。中でもｉ－ブチル基、ｎ－ブチル基、メチル基が好ましい。 <<< structural unit having a group represented by (a2-3) -NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) >>
The polymer component (A) used in the present invention is a structural unit (a2-3) having a group represented by —NH—CH 2 —O—R (R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). Is also preferable. By having the structural unit (a2-3), a curing reaction can be caused by a mild heat treatment, and a cured film having excellent characteristics can be obtained. Here, R is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group. The structural unit (a2-3) is more preferably a structural unit having a group represented by the following general formula (a2-30).
Formula (a2-30)
Figure JPOXMLDOC01-appb-C000019
 (In the general formula (a2-30), R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)
R 2 is preferably an alkyl group having 1 to 9 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. The alkyl group may be a linear, branched or cyclic alkyl group, but is preferably a linear or branched alkyl group.
Specific examples of R 2 include a methyl group, an ethyl group, an n-butyl group, an i-butyl group, a cyclohexyl group, and an n-hexyl group. Of these, i-butyl, n-butyl and methyl are preferred.
＜＜＜架橋性基を有する構成単位（ａ２）の好ましい態様＞＞＞
　上記構成単位（ａ２）を含有する重合体が、実質的に、構成単位（ａ１）を含まない場合、構成単位（ａ２）の含有量は、重合体中、５～９０モル％が好ましく、２０～８０モル％がより好ましい。
　上記構成単位（ａ２）を含有する重合体が、上記構成単位（ａ１）を含有する場合、構成単位（ａ２）の含有量は、重合体中、薬品耐性の観点から３～７０モル％が好ましく、１０～６０モル％がより好ましい。
　本発明では、さらに、いずれの態様にかかわらず、（Ａ）重合体成分の全構成単位中、構成単位（ａ２）の含有量が３～７０モル％であることが好ましく、１０～６０モル％であることがより好ましい。
　上記の数値の範囲内とすることで、諸特性に優れる硬化膜を形成できる。 <<< Preferred Aspect of Structural Unit (a2) Having Crosslinkable Group >>>
When the polymer containing the structural unit (a2) does not substantially contain the structural unit (a1), the content of the structural unit (a2) is preferably 5 to 90 mol% in the polymer, 20 More preferred is ˜80 mol%.
When the polymer containing the structural unit (a2) contains the structural unit (a1), the content of the structural unit (a2) is preferably 3 to 70 mol% from the viewpoint of chemical resistance in the polymer. 10 to 60 mol% is more preferable.
In the present invention, the content of the structural unit (a2) is preferably 3 to 70 mol% in all the structural units of the polymer component (A) regardless of any embodiment, and preferably 10 to 60 mol%. It is more preferable that
By setting it within the above numerical range, a cured film having excellent characteristics can be formed.
＜＜（ａ３）その他の構成単位＞＞
　本発明において、（Ａ）重合体成分は、上記構成単位（ａ１）および／または構成単位（ａ２）に加えて、これら以外の他の構成単位（ａ３）を有していてもよい。構成単位（ａ３）は、上記重合体（１）および／または（２）が含んでいてもよい。また、上記重合体（１）または（２）とは別に、実質的に構成単位（ａ１）および構成単位（ａ２）を含まずに他の構成単位（ａ３）を有する重合体を有していてもよい。 << (a3) Other structural units >>
In the present invention, the (A) polymer component may have another structural unit (a3) in addition to the structural unit (a1) and / or the structural unit (a2). The structural unit (a3) may be contained in the polymer (1) and / or (2). In addition to the polymer (1) or (2), the polymer has a structural unit (a3) that does not substantially contain the structural unit (a1) and the structural unit (a2). Also good.
　その他の構成単位（ａ３）となるモノマーとしては、特に制限はなく、例えば、スチレン類、（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸環状アルキルエステル、（メタ）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、ビシクロ不飽和化合物類、マレイミド化合物類、不飽和芳香族化合物、共役ジエン系化合物、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無水物、その他の不飽和化合物を挙げることができる。また、後述するとおり、酸基を有する構成単位を有していてもよい。その他の構成単位（ａ１－３）となるモノマーは、単独または２種類以上を組み合わせて使用することができる。 There is no restriction | limiting in particular as a monomer used as another structural unit (a3), For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds be able to. Moreover, you may have the structural unit which has an acid group so that it may mention later. The other structural unit (a1-3) monomers can be used alone or in combination of two or more.
　構成単位（ａ３）は、具体的には、スチレン、メチルスチレン、ヒドロキシスチレン、α－メチルスチレン、アセトキシスチレン、メトキシスチレン、エトキシスチレン、クロロスチレン、ビニル安息香酸メチル、ビニル安息香酸エチル、４－ヒドロキシ安息香酸（３－メタクリロイルオキシプロピル）エステル、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸イソボルニル、（メタ）アクリロイルモルホリン、Ｎ－シクロヘキシルマレイミド、アクリロニトリル、エチレングリコールモノアセトアセテートモノ（メタ）アクリレートなどによる構成単位を挙げることができる。この他、特開２００４－２６４６２３号公報の段落番号００２１～００２４に記載の化合物を挙げることができる。 Specifically, the structural unit (a3) is styrene, methyl styrene, hydroxy styrene, α-methyl styrene, acetoxy styrene, methoxy styrene, ethoxy styrene, chlorostyrene, methyl vinyl benzoate, ethyl vinyl benzoate, 4-hydroxy Benzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acryloylmorpholine, N-cyclohexylmaleimide, acrylonitrile, ethylene glycol monoa It can be mentioned a structural unit due preparative acetate mono (meth) acrylate. In addition, compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.
　また、その他の構成単位（ａ３）としてスチレン類、脂肪族環式骨格を有する基が、電気特性の観点で好ましい。具体的にはスチレン、メチルスチレン、ヒドロキシスチレン、α－メチルスチレン、ジシクロペンタニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート等が挙げられる。 Further, as other structural unit (a3), styrenes and groups having an aliphatic cyclic skeleton are preferable from the viewpoint of electrical characteristics. Specific examples include styrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and benzyl (meth) acrylate.
　さらにまた、その他の構成単位（ａ３）として（メタ）アクリル酸アルキルエステルが、密着性の観点で好ましい。具体的には（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ｎ－ブチル等が挙げられ、（メタ）アクリル酸メチルがより好ましい。 Furthermore, as other structural unit (a3), (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable.
　その他の構成単位（ａ３）として、酸基を含む繰り返し単位を含むことが好ましい。酸基を含むことにより、アルカリ性の現像液に溶けやすくなり、本発明の効果がより効果的に発揮される。本発明における酸基とは、ｐＫａが７より小さいプロトン解離性基を意味する。酸基は、通常、酸基を形成しうるモノマーを用いて、酸基を含む構成単位として、重合体に組み込まれる。このような酸基を含む構成単位を重合体中に含めることにより、アルカリ性の現像液に対して溶けやすくなる傾向にある。
　本発明で用いられる酸基としては、カルボン酸基由来のもの、スルホンアミド基に由来のもの、ホスホン酸基に由来のもの、スルホン酸基に由来のもの、フェノール性水酸基に由来するもの、スルホンアミド基、スルホニルイミド基等が例示され、カルボン酸基由来のものおよび／またはフェノール性水酸基に由来のものが好ましい。
　本発明で用いられる酸基を含む構成単位は、スチレンに由来する構成単位や、ビニル化合物に由来する構成単位、（メタ）アクリル酸および／またはそのエステルに由来する構成単位であることがより好ましい。例えば、特開２０１２－８８４５９号公報の段落番号００２１～００２３および段落番号００２９～００４４記載の化合物を用いることができ、この内容は本願明細書に組み込まれる。なかでも、ｐ－ヒドロキシスチレン、（メタ）アクリル酸、マレイン酸、無水マレイン酸に由来する構成単位が好ましい。 As the other structural unit (a3), it is preferable to include a repeating unit containing an acid group. By containing an acid group, it becomes easy to dissolve in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group in the present invention means a proton dissociable group having a pKa of less than 7. The acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Amide groups, sulfonylimide groups and the like are exemplified, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. . For example, compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein. Of these, structural units derived from p-hydroxystyrene, (meth) acrylic acid, maleic acid, and maleic anhydride are preferred.
　酸基を含む繰り返し単位の導入方法としては、（ａ１）構成単位および／または（ａ２）構成単位と同じ重合体に導入することもできるし、（ａ１）構成単位および（ａ２）構成単位とは異なる重合体の構成単位として導入することもできる。
　このような重合体としては、側鎖にカルボキシル基を有する樹脂が好ましい。例えば、特開昭５９－４４６１５号、特公昭５４－３４３２７号、特公昭５８－１２５７７号、特公昭５４－２５９５７号、特開昭５９－５３８３６号、特開昭５９－７１０４８号の各公報に記載されているような、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体等、並びに側鎖にカルボキシル基を有する酸性セルロース誘導体、水酸基を有するポリマーに酸無水物を付加させたもの等が挙げられ、さらに側鎖に（メタ）アクリロイル基を有する高分子重合体も好ましいものとして挙げられる。 As a method for introducing a repeating unit containing an acid group, (a1) the structural unit and / or (a2) the structural unit can be introduced into the same polymer, and (a1) the structural unit and (a2) the structural unit. It can also be introduced as a constituent unit of a different polymer.
As such a polymer, a resin having a carboxyl group in the side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.
　例えば、ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、２－ヒドロキシエチル（メタ）アクリレート／ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、特開平７－１４０６５４号公報に記載の、２－ヒドロキシプロピル（メタ）アクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシ－３－フェノキシプロピルアクリレート／ポリメチルメタクリレートマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／メチルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体などが挙げられる。
　その他にも、特開平７－２０７２１１号公報、特開平８－２５９８７６号公報、特開平１０－３００９２２号公報、特開平１１－１４０１４４号公報、特開平１１－１７４２２４号公報、特開２０００－５６１１８号公報、特開２００３－２３３１７９号公報、特開２００９－５２０２０号公報等に記載の公知の高分子化合物を使用することができ、これらの内容は本願明細書に組み込まれる。
　これらの重合体は、１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。 For example, benzyl (meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid Copolymer and the like.
In addition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118 Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein.
These polymers may contain only 1 type and may contain 2 or more types.
　これらの重合体として、市販されている、ＳＭＡ　１０００Ｐ、ＳＭＡ　２０００Ｐ、ＳＭＡ　３０００Ｐ、ＳＭＡ　１４４０Ｆ、ＳＭＡ　１７３５２Ｐ、ＳＭＡ　２６２５Ｐ、ＳＭＡ　３８４０Ｆ（以上、サートマー社製）、ＡＲＵＦＯＮ　ＵＣ－３０００、ＡＲＵＦＯＮ　ＵＣ－３５１０、ＡＲＵＦＯＮ　ＵＣ－３９００、ＡＲＵＦＯＮ　ＵＣ－３９１０、ＡＲＵＦＯＮ　ＵＣ－３９２０、ＡＲＵＦＯＮ　ＵＣ－３０８０（以上、東亞合成（株）製）、Ｊｏｎｃｒｙｌ　６９０、Ｊｏｎｃｒｙｌ　６７８、Ｊｏｎｃｒｙｌ　６７、Ｊｏｎｃｒｙｌ　５８６（以上、ＢＡＳＦ製）等を用いることもできる。 As these polymers, commercially available SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, SMA 3840F (above, manufactured by Sartomer), ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncryl 690, Joncryl 678, Joncryl 67, Joncryl 586 (above, manufactured by BASF, etc.) You can also.
　本発明では、特に、カルボキシル基を有する構成単位、または、フェノール性水酸基を有する構成単位を含有することが、感度の観点で好ましい。例えば、特開２０１２－８８４５９号公報の段落番号００２１～００２３および段落番号００２９～００４４記載の化合物を用いることができ、この内容は本願明細書に組み込まれる。 In the present invention, it is particularly preferable from the viewpoint of sensitivity to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group. For example, compounds described in JP 2012-88459 A, paragraph numbers 0021 to 0023 and paragraph numbers 0029 to 0044 can be used, the contents of which are incorporated herein.
　酸基を含む構成単位は、全重合体成分の構成単位の１～８０モル％が好ましく、１～５０モル％がより好ましく、５～４０モル％がさらに好ましく、５～３０モル％が特に好ましく、５～２５モル％が特に好ましい。 The structural unit containing an acid group is preferably 1 to 80% by mole, more preferably 1 to 50% by mole, still more preferably 5 to 40% by mole, and particularly preferably 5 to 30% by mole of the structural unit of all polymer components. 5 to 25 mol% is particularly preferred.
　以下に、本発明の重合体成分の好ましい実施形態を挙げるが、本発明はこれらに限定されるものではない。
（第１の実施形態）
　重合体（１）が、さらに、１種または２種以上のその他の構成単位（ａ３）を有する態様。
（第２の実施形態）
　重合体（２）における、（ａ１）酸基が酸分解性基で保護された基を有する構成単位を有する重合体が、さらに、１種または２種以上のその他の構成単位（ａ３）を有する態様。
（第３の実施形態）
　重合体（２）における、（ａ２）架橋性基を有する構成単位を有する重合体が、さらに、１種または２種以上のその他の構成単位（ａ３）を有する態様。
（第４の実施形態）
　上記第１～第３の実施形態のいずれかにおいて、その他の構成単位（ａ３）として、少なくとも酸基を含む構成単位を含む態様。
（第５の実施形態）
　上記重合体（１）または（２）とは別に、さらに、実質的に構成単位（ａ１）および構成単位（ａ１－２）を含まずに他の構成単位（ａ３）を有する重合体を有する態様。
（第６の実施形態）
　上記第１～第５の実施形態の２以上の組み合わせからなる形態。 Although preferable embodiment of the polymer component of this invention is given to the following, this invention is not limited to these.
(First embodiment)
The aspect in which the polymer (1) further has one or more other structural units (a3).
(Second Embodiment)
In the polymer (2), the polymer (a1) having a structural unit having a group in which an acid group is protected by an acid-decomposable group further has one or more other structural units (a3). Aspect.
(Third embodiment)
The aspect in which the polymer (a2) having a structural unit having a crosslinkable group in the polymer (2) further has one or more other structural units (a3).
(Fourth embodiment)
In any one of the first to third embodiments, the other structural unit (a3) includes a structural unit containing at least an acid group.
(Fifth embodiment)
In addition to the polymer (1) or (2), the polymer further has a polymer having another structural unit (a3) substantially free from the structural unit (a1) and the structural unit (a1-2). .
(Sixth embodiment)
A form comprising a combination of two or more of the first to fifth embodiments.
　実質的に（ａ１）および（ａ２）を含まずに他の構成単位（ａ３）を有する重合体を有する態様においては、（ａ１）および／または（ａ２）を有する重合体の合計量と、実質的に（ａ１）および（ａ２）を含まずに他の構成単位（ａ３）を有する重合体の合計量との重量割合は、９９：１～５：９５が好ましく、９７：３～３０：７０がより好ましく、９５：５～５０：５０がさらに好ましい。 In an embodiment having a polymer having another structural unit (a3) substantially free of (a1) and (a2), the total amount of the polymer having (a1) and / or (a2) Specifically, the weight ratio with respect to the total amount of the polymer having other structural units (a3) not including (a1) and (a2) is preferably 99: 1 to 5:95, and 97: 3 to 30:70. Is more preferable, and 95: 5 to 50:50 is even more preferable.
＜＜（Ａ）重合体成分の分子量＞＞
　（Ａ）重合体成分の分子量は、ポリスチレン換算重量平均分子量で、好ましくは１，０００～２００，０００、より好ましくは２，０００～５０，０００の範囲である。上記の数値の範囲内であると、諸特性が良好である。数平均分子量と重量平均分子量の比（分散度）は１．０～５．０が好ましく１．５～３．５がより好ましい。
　（Ａ）重合体成分の重量平均分子量及び分散度は、ＧＰＣ測定によるポリスチレン換算値として定義される。本明細書において、重合体成分の重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８１２０（東ソー（株）製）を用い、カラムとしてＴＳＫ ｇｅｌ Ｍｕｌｔｉｐｏｒｅ ＨＸＬ－Ｍ（東ソー（株）製、７．８ｍｍＩＤ×３０．０ｃｍを、溶離液としてＴＨＦ(テトラヒドロフラン)を用いることによって求めることができる。 << (A) Molecular Weight of Polymer Component >>
The molecular weight of the polymer component (A) is a polystyrene-converted weight average molecular weight, and is preferably in the range of 1,000 to 200,000, more preferably 2,000 to 50,000. Various characteristics are favorable in the range of said numerical value. The ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
(A) The weight average molecular weight and dispersion degree of a polymer component are defined as a polystyrene conversion value by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer component are, for example, HLC-8120 (manufactured by Tosoh Corporation), and TSK gel Multipore HXL-M (Tosoh ( 7.8 mm ID × 30.0 cm can be obtained by using THF (tetrahydrofuran) as an eluent.
＜＜（Ａ）重合体成分の製造方法＞＞
　また、（Ａ）重合体成分の合成法についても、様々な方法が知られているが、一例を挙げると、少なくとも上記（ａ１）および上記（ａ３）で表される構成単位を形成するために用いられるラジカル重合性単量体を含むラジカル重合性単量体混合物を有機溶剤中、ラジカル重合開始剤を用いて重合することにより合成することができる。また、いわゆる高分子反応で合成することもできる。
　（Ａ）重合体は、（メタ）アクリル酸および／またはそのエステルに由来する構成単位を、全構成単位に対し、５０モル％以上含有することが好ましく、８０モル％以上含有することがより好ましい。 << (A) Production Method of Polymer Component >>
Also, various methods are known for the synthesis method of the polymer component (A). For example, in order to form at least the structural units represented by the above (a1) and (a3) It can be synthesized by polymerizing a radical polymerizable monomer mixture containing the radical polymerizable monomer used in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
(A) The polymer preferably contains 50 mol% or more, more preferably 80 mol% or more of the structural unit derived from (meth) acrylic acid and / or its ester with respect to all the structural units. .
＜（Ｂ）一般式（Ｉ）で表される光酸発生剤＞
　本発明の組成物は、（Ｂ）一般式（Ｉ）で表される光酸発生剤を含む。
Figure JPOXMLDOC01-appb-C000020
 （一般式（Ｉ）中、Ｒ1およびＲ2の一方は、下記一般式（Ａ）で表される基を表し、他方は水素原子を表す。Ｒ3は、ハロゲン原子、アルキルチオ基および脂環式炭化水素基のいずれか１つ以上で置換されてもよい炭素数１～１８の脂肪族炭化水素基、ハロゲン原子、アルキルチオ基、アルキル基およびアシル基のいずれか１つ以上で置換されてもよい炭素数６～２０のアリール基、ハロゲン原子および／またはアルキルチオ基で置換されてもよい炭素数７～２０のアリールアルキル基、１０－カンファーイル基または、下記一般式（Ｂ）で表される基を表す。）
一般式（Ａ）
Figure JPOXMLDOC01-appb-C000021
 （一般式（Ａ）中、Ｘ1は、酸素原子または硫黄原子を表し、Ｙ1は、単結合または炭素数１～４のアルキレン基を表し、Ｒ4は、炭素数１～１２の炭化水素基を表し、Ｒ5は、炭素数１～４のアルキレン基を表し、Ｒ6は、水素原子、分岐していてもよい炭素数１～４のアルキル基、炭素数３～１０の脂環式炭化水素基、複素環基、または水酸基を表す。ｎは、０～５の整数を表し、ｎが２～５の場合、複数存在するＲ5は同一でも異なってもよい。）
一般式（Ｂ）
Figure JPOXMLDOC01-appb-C000022
 （一般式（Ｂ）中、Ｙ2は、単結合または炭素数１～４のアルキレン基を表し、Ｒ7は、炭素数２～６のアルキレン基、炭素数２～６のハロゲン化アルキレン基、炭素数６～２０のアリーレン基、または炭素数６～２０のハロゲン化アリーレン基を表し、Ｒ8は、単結合、炭素数２～６のアルキレン基、炭素数２～６のハロゲン化アルキレン基、炭素数６～２０のアリーレン基または炭素数６～２０のハロゲン化アリーレン基を表し、Ｒ9は、分岐していてもよい炭素数１～１８のアルキル基、分岐していてもよい炭素数１～１８のハロゲン化アルキル基、炭素数６～２０のアリール基、炭素数６～２０のハロゲン化アリール基、炭素数７～２０のアリールアルキル基、または炭素数７～２０のハロゲン化アリールアルキル基を表す。ａおよびｂはそれぞれ独立に０または１を表し、ａおよびｂの少なくとも一方は１である。） <(B) Photoacid generator represented by general formula (I)>
The composition of this invention contains the photo-acid generator represented by (B) general formula (I).
Figure JPOXMLDOC01-appb-C000020
 (In general formula (I), one of R 1 and R 2 represents a group represented by the following general formula (A), and the other represents a hydrogen atom. R 3 represents a halogen atom, an alkylthio group, and an alicyclic ring. And may be substituted with any one or more of an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a halogen atom, an alkylthio group, an alkyl group and an acyl group, which may be substituted with any one or more of the formula hydrocarbon groups Preferred aryl group having 6 to 20 carbon atoms, arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom and / or alkylthio group, 10-camphoryl group, or the following general formula (B) Represents a group.)
Formula (A)
Figure JPOXMLDOC01-appb-C000021
 (In the general formula (A), X 1 represents an oxygen atom or a sulfur atom, Y 1 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R 4 represents a hydrocarbon having 1 to 12 carbon atoms. R 5 represents an alkylene group having 1 to 4 carbon atoms, R 6 represents a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, or an alicyclic group having 3 to 10 carbon atoms. Represents a hydrocarbon group, a heterocyclic group, or a hydroxyl group, n represents an integer of 0 to 5, and when n is 2 to 5, a plurality of R 5 may be the same or different.
General formula (B)
Figure JPOXMLDOC01-appb-C000022
 (In the general formula (B), Y 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms, R 7 represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, Represents an arylene group having 6 to 20 carbon atoms or a halogenated arylene group having 6 to 20 carbon atoms, and R 8 represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, Represents an arylene group having 6 to 20 carbon atoms or a halogenated arylene group having 6 to 20 carbon atoms, and R 9 represents an alkyl group having 1 to 18 carbon atoms which may be branched, or 1 carbon atom which may be branched. A halogenated alkyl group having 18 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a halogenated arylalkyl group having 7 to 20 carbon atoms A and Each independently represent 0 or 1, at least one of a and b is 1.)
＜＜一般式（Ｉ）のＲ1およびＲ2＞＞
　一般式（Ｉ）中、Ｒ1およびＲ2の一方は、一般式（Ａ）で表される基を表し、他方は水素原子を表す。 << R 1 and R 2 in Formula (I) >>
In general formula (I), one of R 1 and R 2 represents a group represented by general formula (A), and the other represents a hydrogen atom.
＜＜＜一般式（Ａ）で表される基＞＞＞
　一般式（Ａ）中、Ｘ1は、酸素原子または硫黄原子を表す。
　Ｘ1が硫黄原子を表す場合、Ｒ1が水素原子を表すことが好ましく、Ｘ1が酸素原子を表す場合、Ｒ2が水素原子を表すことが好ましい。 <<< Group Represented by General Formula (A) >>>
In general formula (A), X 1 represents an oxygen atom or a sulfur atom.
When X 1 represents a sulfur atom, R 1 preferably represents a hydrogen atom, and when X 1 represents an oxygen atom, R 2 preferably represents a hydrogen atom.
　一般式（Ａ）中、Ｒ4は、炭素数１～１２の炭化水素基を表す。
　炭素数１～１２の炭化水素基としては、炭素数１～１０の炭化水素基が好ましく、炭素数１～６の炭化水素基がより好ましく、炭素数１～３の炭化水素基がさらに好ましい。
　炭素数１～１２の炭化水素基は、アルキレン基、アルケニル基、アルキニレン基などの脂肪族炭化水素基、シクロアルキレン基などの脂環式炭化水素基、脂肪族炭化水素と脂環式炭化水素が結合した基などが挙げられ、アルキレン基が好ましい。
　具体的には、例えば、メチレン基、エチレン基、プロパン－１，３－ジイル基、プロパン－１，２－ジイル基、ブチレン基、ブタン－１，３－ジイル基、ブタン－２，３－ジイル基、ブタン－１，２－ジイル基、ペンチレン基、へキシレン基、シクロヘキシレン基、シクロヘキシレンメチル基、ヘプチレン基、オクチレン基、シクロヘキシレンエチル基、メチレンシクロヘキシレンメチル基、ノニレン基、デシレン基、アダマンチレン基、ノルボルニレン基、イソノルボルニレン基、ドデシレン基、ウンデシレン基などが挙げられる。
　これらの中でも、Ｒ4は、メチレン基、エチレン基、プロピレン基が好ましく、メチレン基および／またはエチレン基が好ましい。 In the general formula (A), R 4 represents a hydrocarbon group having 1 to 12 carbon atoms.
The hydrocarbon group having 1 to 12 carbon atoms is preferably a hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms, and still more preferably a hydrocarbon group having 1 to 3 carbon atoms.
The hydrocarbon group having 1 to 12 carbon atoms includes an aliphatic hydrocarbon group such as an alkylene group, an alkenyl group and an alkynylene group, an alicyclic hydrocarbon group such as a cycloalkylene group, an aliphatic hydrocarbon and an alicyclic hydrocarbon. Examples thereof include a bonded group, and an alkylene group is preferable.
Specifically, for example, methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butylene group, butane-1,3-diyl group, butane-2,3-diyl Group, butane-1,2-diyl group, pentylene group, hexylene group, cyclohexylene group, cyclohexylenemethyl group, heptylene group, octylene group, cyclohexyleneethyl group, methylenecyclohexylenemethyl group, nonylene group, decylene group, Examples thereof include an adamantylene group, norbornylene group, isonorbornylene group, dodecylene group, and undecylene group.
Among these, R 4 is preferably a methylene group, an ethylene group or a propylene group, more preferably a methylene group and / or an ethylene group.
　一般式（Ａ）中、Ｒ5は、それぞれ独立に炭素数１～４のアルキレン基を表す。炭素数１～４のアルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基などが挙げられる。これらの中でも、Ｒ5は、メチレン基、エチレン基が好ましい。 In general formula (A), each R 5 independently represents an alkylene group having 1 to 4 carbon atoms. Examples of the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a propylene group, and a butylene group. Among these, R 5 is preferably a methylene group or an ethylene group.
　一般式（Ａ）中、Ｙ1は、炭素数１～４のアルキレン基を表す。炭素数１～４のアルキレン基としては、Ｒ5で述べたものと同義であり、好ましい範囲も同様である。 In general formula (A), Y 1 represents an alkylene group having 1 to 4 carbon atoms. The alkylene group having 1 to 4 carbon atoms has the same meaning as described for R 5 , and the preferred range is also the same.
　一般式（Ａ）中、Ｒ6は、水素原子、分岐していてもよい炭素数１～４のアルキル基、炭素数３～１０の脂環式炭化水素基、複素環基、または水酸基を表す。
　分岐していてもよい炭素数１～４のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、イソブチル基などが挙げられる。
　炭素数３～１０の脂環式炭化水素基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基、ビシクロ［２．１．１］ヘキシル基、ビシクロ［２．２．１］ヘプチル基、ビシクロ［３．２．１］オクチル基、ビシクロ［２．２．２］オクチル基、アダマンチル基などが挙げられる。
　複素環基としては、炭素数３～１０の複素環基が好ましく、これを構成する複素環名で例示すると、ピロール、チオフェン、フラン、ピラン、チオピラン、イミダゾール、ピラゾール、チアゾール、イソチアゾール、オキサゾール、イソオキサゾール、ピリジン、ピラジン、ピリミジン、ピリダジン、ピロリジン、ピラゾリジン、イミダゾリジン、イソオキサゾリジン、イソチアゾリジン、ピペリジン、ピペラジン、モルホリン、チオモルホリン、クロマン、チオクロマン、イソクロマン、イソチオクロマン、インドリン、イソインドリン、ピリンジン、インドリジン、インドール、インダゾール、プリン、キノリジン、イソキノリン、キノリン、ナフチリジン、フタラジン、キノキサリン、キナゾリン、シンノリン、プテリジン、アクリジン、ペリミジン、フェナントロリン、カルバゾール、カルボリン、フェナジン、アンチリジン、チアジアゾール、オキサジアゾール、トリアジン、トリアゾール、テトラゾール、ベンゾイミダゾール、ベンゾオキサゾール、ベンゾチアゾール、ベンゾチアジアゾール、ベンゾフロキサン、ナフトイミダゾール、ベンゾトリアゾール、テトラアザインデン及び上記の複素環中に存在する不飽和結合または共役結合に水素添加された飽和複素環（テトラヒドロフラン環等）などが挙げられる。 In general formula (A), R 6 represents a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, a heterocyclic group, or a hydroxyl group. .
Examples of the alkyl group having 1 to 4 carbon atoms which may be branched include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, and an isobutyl group. .
Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, and bicyclo [2.1.1] hexyl. Group, bicyclo [2.2.1] heptyl group, bicyclo [3.2.1] octyl group, bicyclo [2.2.2] octyl group, adamantyl group and the like.
As the heterocyclic group, a heterocyclic group having 3 to 10 carbon atoms is preferable. Examples of the heterocyclic group constituting the heterocyclic group include pyrrole, thiophene, furan, pyran, thiopyran, imidazole, pyrazole, thiazole, isothiazole, oxazole, Isoxazole, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidine, pyrazolidine, imidazolidine, isoxazolidine, isothiazolidine, piperidine, piperazine, morpholine, thiomorpholine, chroman, thiochroman, isochroman, isothiochroman, indoline, isoindoline, pyrindin, Indolizine, indole, indazole, purine, quinolidine, isoquinoline, quinoline, naphthyridine, phthalazine, quinoxaline, quinazoline, cinnoline, pteridine, acrizi , Perimidine, phenanthroline, carbazole, carboline, phenazine, anti-lysine, thiadiazole, oxadiazole, triazine, triazole, tetrazole, benzimidazole, benzoxazole, benzothiazole, benzothiadiazole, benzofuroxan, naphthimidazole, benzotriazole, tetraaza Examples thereof include indene and saturated heterocycles (tetrahydrofuran rings and the like) obtained by hydrogenating unsaturated bonds or conjugated bonds present in the above heterocycles.
　これらの中でも、Ｒ6は、水素原子、炭素数１～４のアルキル基、水酸基が好ましく、水素原子、メチル基、エチル基、水酸基がより好ましく、水素原子または水酸基がさらに好ましい。 Among these, R 6 is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyl group, more preferably a hydrogen atom, a methyl group, an ethyl group, or a hydroxyl group, and even more preferably a hydrogen atom or a hydroxyl group.
　一般式（Ａ）中、ｎは、０～５の整数を表し、０～３の整数が好ましく、０～２の整数がより好ましく、０または１がさらに好ましい。ｎが２～５の場合、複数存在するＲ5は同一でも異なってもよいが、同一である方が好ましい。 In general formula (A), n represents an integer of 0 to 5, preferably an integer of 0 to 3, more preferably an integer of 0 to 2, and still more preferably 0 or 1. When n is 2 to 5, a plurality of R 5 may be the same or different but are preferably the same.
＜＜一般式（Ｉ）のＲ3＞＞
　Ｒ3は、ハロゲン原子、アルキルチオ基および脂環式炭化水素基のいずれか１つ以上で置換されてもよい炭素数１～１８の脂肪族炭化水素基、ハロゲン原子、アルキルチオ基、アルキル基およびアシル基のいずれか１つ以上で置換されてもよい炭素数６～２０のアリール基、ハロゲン原子およびアルキルチオ基のいずれか１つ以上で置換されてもよい炭素数７～２０のアリールアルキル基、１０－カンファーイル基または、下記一般式（Ｂ）で表される基を表す。
　ここで、ハロゲン原子、アルキルチオ基および脂環式炭化水素基のいずれか１つ以上で置換されてもよいとは、炭素数１～１８の脂肪族炭化水素基の水素原子が、ハロゲン原子、アルキルチオ基および脂環式炭化水素基のいずれか１つ以上で置換されている場合のほか、置換基である、アルキルチオ基や脂環式炭化水素基の水素原子が、さらに、ハロゲン原子、アルキルチオ基および脂環式炭化水素基のいずれか１つ以上で置換されている場合も含む趣旨である。一般式（Ｉ）における他の基についても同様に解釈する。 << R 3 in Formula (I) >>
R 3 represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with any one or more of a halogen atom, an alkylthio group and an alicyclic hydrocarbon group, a halogen atom, an alkylthio group, an alkyl group and an acyl. An arylalkyl group having 7 to 20 carbon atoms which may be substituted with any one or more of an aryl group having 6 to 20 carbon atoms, a halogen atom and an alkylthio group which may be substituted with any one or more groups; 10 -Represents a camphoryl group or a group represented by the following general formula (B).
Here, the hydrogen atom of the aliphatic hydrocarbon group having 1 to 18 carbon atoms may be substituted with any one or more of a halogen atom, an alkylthio group and an alicyclic hydrocarbon group. In addition to the case where it is substituted with any one or more of a group and an alicyclic hydrocarbon group, a hydrogen atom of the alkylthio group or alicyclic hydrocarbon group which is a substituent further includes a halogen atom, an alkylthio group, and This includes the case where any one or more of the alicyclic hydrocarbon groups are substituted. Other groups in the general formula (I) are also interpreted in the same manner.
＜＜＜ハロゲン原子、アルキルチオ基および脂環式炭化水素基のいずれか１つ以上で置換されてもよい炭素数１～１８の脂肪族炭化水素基＞＞＞
　炭素数１～１８の脂肪族炭化水素基としては、炭素数１～８の脂肪族炭化水素基が好ましく、炭素数１～６の脂肪族炭化水素基がより好ましく、炭素数１～３の脂肪族炭化水素基がさらに好ましい。脂肪族炭化水素基としては、直鎖または分岐のアルキル基が好ましい。
　アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、イソブチル基、アミル基、イソアミル基、ｔｅｒｔ－アミル基、ヘキシル基、２－ヘキシル基、３－ヘキシル基、ヘプチル基、２－ヘプチル基、３－ヘプチル基、イソヘプチル基、ｔｅｒｔ－ヘプチル基、オクチル基、イソオクチル基、ｔｅｒｔ－オクチル基、２－エチルヘキシル基、ノニル基、イソノニル基、デシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、へプタデシル基、オクタデシル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基、ビシクロ［２．１．１］ヘキシル基、ビシクロ［２．２．１］ヘプチル基、ビシクロ［３．２．１］オクチル基、ビシクロ［２．２．２］オクチル基、アダマンチル基などが挙げられる。 <<<< C1-C18 aliphatic hydrocarbon group which may be substituted with any one or more of a halogen atom, an alkylthio group and an alicyclic hydrocarbon group >>
The aliphatic hydrocarbon group having 1 to 18 carbon atoms is preferably an aliphatic hydrocarbon group having 1 to 8 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and an aliphatic hydrocarbon group having 1 to 3 carbon atoms. More preferred are group hydrocarbon groups. As the aliphatic hydrocarbon group, a linear or branched alkyl group is preferable.
Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, 2 -Hexyl, 3-hexyl, heptyl, 2-heptyl, 3-heptyl, isoheptyl, tert-heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl Group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group , Bicyclo [2.1.1] Sill group, bicyclo [2.2.1] heptyl, bicyclo [3.2.1] octyl, bicyclo [2.2.2] octyl group and an adamantyl group.
　置換基として有していても良い、ハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられ、フッ素原子または塩素原子が好ましく、フッ素がより好ましい。
　ハロゲン原子で置換された炭素数１～１８の脂肪族炭化水素基としては、炭素数１～１０のパーフルオロアルキル基が好ましく、炭素数１～６のパーフルオロアルキル基がより好ましく、炭素数１～４のパーフルオロアルキル基がさらに好ましい。ハロゲン原子で置換された炭素数１～１８の脂肪族炭化水素基の具体例としては、例えば、トリフルオロメチル、ペンタフルオロエチル、２－クロロエチル、２－ブロモエチル、ヘプタフルオロプロピル、３－ブロモプロピル、ノナフルオロブチル、トリデカフルオロヘキシル、ヘプタデカフルオロオクチル、２，２，２－トリフルオロエチル、１，１－ジフルオロエチル、１，１－ジフルオロプロピル、１，１，２，２－テトラフルオロプロピル、３，３，３－トリフルオロプロピル、２，２，３，３，３－ペンタフルオロプロピル、ノルボルニル－１，１－ジフルオロエチル、ノルボルニルテトラフルオロエチル、アダマンタン－１，１，２，２－テトラフルオロプロピル等のハロゲン化アルキル基などが挙げられる。アルキルチオ基で置換された炭素数１～１８の脂肪族炭化水素としては、例えば、２－メチルチオエチル、４－メチルチオブチル、４－ブチルチオエチル等が挙げられ、ハロゲン原子及び炭素数１～１８のアルキルチオ基で置換された炭素数１～１８の脂肪族炭化水素基としては、１，１，２，２－テトラフルオロ－３－メチルチオプロピル等が挙げられる。 Examples of the halogen atom that may be present as a substituent include fluorine, chlorine, bromine, and iodine. A fluorine atom or a chlorine atom is preferable, and fluorine is more preferable.
The aliphatic hydrocarbon group having 1 to 18 carbon atoms substituted with a halogen atom is preferably a perfluoroalkyl group having 1 to 10 carbon atoms, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and 1 carbon atom. More preferred are 4 to 4 perfluoroalkyl groups. Specific examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms substituted with a halogen atom include, for example, trifluoromethyl, pentafluoroethyl, 2-chloroethyl, 2-bromoethyl, heptafluoropropyl, 3-bromopropyl, Nonafluorobutyl, tridecafluorohexyl, heptadecafluorooctyl, 2,2,2-trifluoroethyl, 1,1-difluoroethyl, 1,1-difluoropropyl, 1,1,2,2-tetrafluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, norbornyl-1,1-difluoroethyl, norbornyltetrafluoroethyl, adamantane-1,1,2,2- Examples include halogenated alkyl groups such as tetrafluoropropyl. Examples of the aliphatic hydrocarbon having 1 to 18 carbon atoms substituted with an alkylthio group include 2-methylthioethyl, 4-methylthiobutyl, 4-butylthioethyl, etc., and include halogen atoms and carbon atoms having 1 to 18 carbon atoms. Examples of the aliphatic hydrocarbon group having 1 to 18 carbon atoms substituted with an alkylthio group include 1,1,2,2-tetrafluoro-3-methylthiopropyl.
　置換基として有していても良い、アルキルチオ基としては、炭素数１～１８のアルキルチオ基が好ましく、炭素数１～１０のアルキルチオ基がより好ましく、炭素数１～６のアルキルチオ基がさらに好ましい。アルキルチオ基としては、具体的には、メチルチオ基、エチルチオ基、プロピルチオ基、イソプロピルチオ基、ブチルチオ基、ｓｅｃ－ブチルチオ基、ｔｅｒｔ－ブチルチオ基、イソブチルチオ基、アミルチオ基、イソアミルチオ基、ｔｅｒｔ－アミルチオ基、ヘキシルチオ基、ヘプチルチオ基、イソヘプチルチオ基、ｔｅｒｔ－ヘプチルチオ基、オクチルチオ基、イソオクチルチオ基、ｔｅｒｔ－オクチルチオ基、２－エチルヘキシルチオ基、ノニルチオ基、デシルチオ基、ウンデシルチオ基、ドデシルチオ基、トリデシルチオ基、テトラデシルチオ基、ペンタデシルチオ基、ヘキサデシルチオ基、へプタデシルチオ基、オクタデシルチオ基などが挙げられる。 The alkylthio group which may be present as a substituent is preferably an alkylthio group having 1 to 18 carbon atoms, more preferably an alkylthio group having 1 to 10 carbon atoms, and further preferably an alkylthio group having 1 to 6 carbon atoms. Specific examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, a sec-butylthio group, a tert-butylthio group, an isobutylthio group, an amylthio group, an isoamylthio group, and a tert-amylthio group. Group, hexylthio group, heptylthio group, isoheptylthio group, tert-heptylthio group, octylthio group, isooctylthio group, tert-octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, undecylthio group, dodecylthio group, tridecylthio group, Examples include a tetradecylthio group, a pentadecylthio group, a hexadecylthio group, a heptadecylthio group, and an octadecylthio group.
　置換基として有していても良い、脂環式炭化水素基は、炭素数３～３０の脂環式炭化水素基が例示され、単環であっても縮合環であってもよい。 Examples of the alicyclic hydrocarbon group which may be present as a substituent include alicyclic hydrocarbon groups having 3 to 30 carbon atoms, which may be monocyclic or condensed.
　特に、ハロゲン原子、アルキルチオ基および脂環式炭化水素基のいずれか１つ以上で置換されてもよい炭素数１～１８の脂肪族炭化水素基としては、ハロゲン原子および／または脂環式炭化水素基で置換されている炭素数１～１８のアルキル基、ならびに、置換基を有さない炭素数１～１８の直鎖または環状アルキル基が好ましく、フッ素原子および／または炭素数６～１０の環状アルキル基で置換された、炭素数１～４の直鎖アルキル基、ならびに、無置換の、炭素数１～１０の直鎖アルキル基がより好ましい。 In particular, the aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with any one or more of a halogen atom, an alkylthio group and an alicyclic hydrocarbon group includes a halogen atom and / or an alicyclic hydrocarbon. Preferred are an alkyl group having 1 to 18 carbon atoms substituted with a group, and a linear or cyclic alkyl group having 1 to 18 carbon atoms having no substituent, and a fluorine atom and / or a cyclic group having 6 to 10 carbon atoms. A straight-chain alkyl group having 1 to 4 carbon atoms substituted with an alkyl group and an unsubstituted straight-chain alkyl group having 1 to 10 carbon atoms are more preferable.
＜＜＜ハロゲン原子、アルキルチオ基、アルキル基およびアシル基のいずれか１つ以上で置換されてもよい炭素数６～２０のアリール基＞＞＞
　ハロゲン原子、アルキルチオ基、アルキル基およびアシル基のいずれか１つ以上で置換されてもよい炭素数６～２０のアリール基としては、ハロゲン原子、アルキルチオ基、アルキル基およびアシル基のいずれか１つ以上で置換されてもよい炭素数６～１４のアリール基が好ましく、ハロゲン原子、アルキルチオ基、アルキル基およびアシル基のいずれか１つ以上で置換されてもよい炭素数６～１０のアリール基がより好ましい。このようなアリール基としては、フェニル基、ナフチル基、４－ビニルフェニル基、ビフェニル基、アントラセニル基などが挙げられる。 <<< C6-C20 aryl group optionally substituted with any one or more of a halogen atom, an alkylthio group, an alkyl group and an acyl group >>>
The aryl group having 6 to 20 carbon atoms which may be substituted with any one or more of a halogen atom, an alkylthio group, an alkyl group and an acyl group is any one of a halogen atom, an alkylthio group, an alkyl group and an acyl group An aryl group having 6 to 14 carbon atoms which may be substituted is preferable, and an aryl group having 6 to 10 carbon atoms which may be substituted with any one or more of a halogen atom, an alkylthio group, an alkyl group and an acyl group. More preferred. Examples of such an aryl group include a phenyl group, a naphthyl group, a 4-vinylphenyl group, a biphenyl group, and an anthracenyl group.
　置換基としてのハロゲン原子の好ましい範囲は、上述のハロゲン原子、アルキルチオ基および脂環式炭化水素基のいずれか１つ以上で置換されてもよい炭素数１～１８の脂肪族炭化水素基で述べたハロゲン原子と同義である。
　ハロゲン原子で置換された炭素数６～２０のアリール基としては、例えば、ペンタフルオロフェニル基、クロロフェニル基、ジクロロフェニル基、トリクロロフェニル基、２，４－ビス（トリフルオロメチル）フェニル基、ブロモエチルフェニル基等が挙げられる。 The preferred range of the halogen atom as the substituent is described for the aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with any one or more of the above-mentioned halogen atom, alkylthio group and alicyclic hydrocarbon group. It is synonymous with the halogen atom.
Examples of the aryl group having 6 to 20 carbon atoms substituted with a halogen atom include a pentafluorophenyl group, a chlorophenyl group, a dichlorophenyl group, a trichlorophenyl group, a 2,4-bis (trifluoromethyl) phenyl group, and a bromoethylphenyl group. Groups and the like.
　置換基としてのアルキルチオ基の好ましい範囲は、上述のハロゲン原子、アルキルチオ基および脂環式炭化水素基のいずれか１つ以上で置換されてもよい炭素数１～１８の脂肪族炭化水素基で述べたアルキルチオ基と同義である。
　アルキルチオ基で置換された炭素数６～２０のアリール基としては、例えば、４－メチルチオフェニル基、４－ブチルチオフェニル基、４－オクチルチオフェニル基、４－ドデシルチオフェニル基などが挙げられる。 The preferred range of the alkylthio group as the substituent is described for the aliphatic hydrocarbon group having 1 to 18 carbon atoms which may be substituted with any one or more of the above-mentioned halogen atom, alkylthio group and alicyclic hydrocarbon group. It is synonymous with the alkylthio group.
Examples of the aryl group having 6 to 20 carbon atoms substituted with an alkylthio group include a 4-methylthiophenyl group, a 4-butylthiophenyl group, a 4-octylthiophenyl group, and a 4-dodecylthiophenyl group.
　ハロゲン原子およびアルキルチオ基で置換された炭素数６～２０のアリール基としては、例えば、１，２，３，４，５－ペンタフルオロフェニル基、１，２，５，６－テトラフルオロ－４－メチルチオフェニル基、１，２，５，６－テトラフルオロ－４－ブチルチオフェニル基、１，２，５，６－テトラフルオロ－４－ドデシルチオフェニル基等が挙げられる。
　また、アシル基で置換された炭素数６～２０のアリール基としては、例えば、アセチルフェニル基、アセチルナフチル基、ベンゾイルフェニル基、１－アントラキノリル基、２－アントラキノリル基などが挙げられる。 Examples of the aryl group having 6 to 20 carbon atoms substituted with a halogen atom and an alkylthio group include, for example, 1,2,3,4,5-pentafluorophenyl group, 1,2,5,6-tetrafluoro-4- Examples thereof include a methylthiophenyl group, 1,2,5,6-tetrafluoro-4-butylthiophenyl group, and 1,2,5,6-tetrafluoro-4-dodecylthiophenyl group.
Examples of the aryl group having 6 to 20 carbon atoms substituted with an acyl group include an acetylphenyl group, an acetylnaphthyl group, a benzoylphenyl group, a 1-anthraquinolyl group, and a 2-anthraquinolyl group.
　置換基としてのアルキル基の好ましい範囲は、直鎖、分岐、環状のアルキル基であり、炭素数１～３の直鎖のアルキル基、炭素数３～５の分岐のアルキル基、炭素数６の環状アルキル基が好ましい。これらのアルキル基は、ハロゲン原子（特に、フッ素原子）で置換されていてもよい。
　置換基としてのアシル基の好ましい範囲は、Ｒ－Ｃ（＝Ｏ）－で表される基において、Ｒがアルキル基または芳香族基が好ましく、Ｒはメチル基、フェニル基、ナフチル基、アントラセニル基が例示される。 The preferred range of the alkyl group as a substituent is a linear, branched or cyclic alkyl group, a linear alkyl group having 1 to 3 carbon atoms, a branched alkyl group having 3 to 5 carbon atoms, or a carbon number having 6 carbon atoms. Cyclic alkyl groups are preferred. These alkyl groups may be substituted with a halogen atom (particularly a fluorine atom).
A preferred range of the acyl group as a substituent is that in the group represented by R—C (═O) —, R is preferably an alkyl group or an aromatic group, and R is a methyl group, a phenyl group, a naphthyl group, an anthracenyl group. Is exemplified.
　ハロゲン原子で置換されてもよいアリール基の好ましい一態様として、ハロゲン原子で置換されてもよい炭素数７～２０のアルキルアリール基が例示され、炭素数７～１５のアルキルアリール基が好ましく炭素数７～１０のアルキルアリール基がより好ましい。このようなアルキルアリール基としては、例えば、２－メチルフェニル基、３－メチルフェニル基、４－メチルフェニル基、３－イソプロピルフェニル基、４－イソプロピルフェニル基、４－ブチルフェニル基、４－イソブチルフェニル基、４－ｔｅｒｔ－ブチルフェニル基、４－ヘキシルフェニル基、４－シクロヘキシルフェニル基、４－オクチルフェニル基、４－（２－エチルヘキシル）フェニル基、２，３－ジメチルフェニル基、２，４－ジメチルフェニル基、２，５－ジメチルフェニル基、２，６－ジメチルフェニル基、３，４－ジメチルフェニル基、３，５－ジメチルフェニル基、２，４－ジｔｅｒｔ－ブチルフェニル基、２，５－ジｔｅｒｔ－ブチルフェニル基、２，６－ジ－ｔｅｒｔ－ブチルフェニル基、２，４－ジｔｅｒｔ－ペンチルフェニル基、２，５－ジｔｅｒｔ－アミルフェニル基、２，５－ジｔｅｒｔ－オクチルフェニル基、シクロヘキシルフェニル基、２，４，５－トリメチルフェニル基、２，４，６－トリメチルフェニル基、２，４，６－トリイソプロピルフェニル基等が挙げられる。 As a preferred embodiment of the aryl group which may be substituted with a halogen atom, an alkylaryl group having 7 to 20 carbon atoms which may be substituted with a halogen atom is exemplified, and an alkylaryl group having 7 to 15 carbon atoms is preferred. More preferred are 7 to 10 alkylaryl groups. Examples of such an alkylaryl group include 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 3-isopropylphenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-isobutyl. Phenyl group, 4-tert-butylphenyl group, 4-hexylphenyl group, 4-cyclohexylphenyl group, 4-octylphenyl group, 4- (2-ethylhexyl) phenyl group, 2,3-dimethylphenyl group, 2,4 -Dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-ditert-butylphenyl group, 2, 5-di-tert-butylphenyl group, 2,6-di-tert-butylphenyl group, 2,4-ditert Pentylphenyl group, 2,5-ditert-amylphenyl group, 2,5-ditert-octylphenyl group, cyclohexylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, Examples include 2,4,6-triisopropylphenyl group.
　特に、ハロゲン原子、アルキルチオ基、アルキル基およびアシル基のいずれか１つ以上で置換されてもよい炭素数６～２０のアリール基としては、無置換または、ハロゲン原子および／もしくはアルキル基で置換された、炭素数６～２０のアリール基が好ましく、無置換または、フッ素原子および／もしくは直鎖の炭素数１～６のアルキル基で置換された、フェニル基またはナフチル基がより好ましい。 In particular, the aryl group having 6 to 20 carbon atoms which may be substituted with any one or more of a halogen atom, an alkylthio group, an alkyl group and an acyl group is unsubstituted or substituted with a halogen atom and / or an alkyl group. An aryl group having 6 to 20 carbon atoms is preferable, and a phenyl group or a naphthyl group which is unsubstituted or substituted with a fluorine atom and / or a linear alkyl group having 1 to 6 carbon atoms is more preferable.
＜＜＜ハロゲン原子およびアルキルチオ基のいずれか１つ以上で置換されてもよい炭素数７～２０のアリールアルキル基＞＞＞
　ハロゲン原子および／またはアルキルチオ基で置換されてもよい炭素数７～２０のアリールアルキル基としては、炭素数７～１５のアリールアルキル基が好ましく炭素数７～１２のアリールアルキル基がより好ましい。このようなアリールアルキル基としては、例えば、ベンジル基、フェネチル基、２－フェニルプロパン－２－イル基、ジフェニルメチル基、トリフェニルメチル基、スチリル基、シンナミル基等が挙げられる。
　置換基としてのハロゲン原子の好ましい範囲およびアルキルチオ基の好ましい範囲は、それぞれ、上述したハロゲン原子、アルキルチオ基および脂環式炭化水素基のいずれか１つ以上で置換されてもよい炭素数１～１８の脂肪族炭化水素基における、置換基としてのハロゲン原子およびアルキルチオ基の記載と同義であり、好ましい範囲も同様である。 <<<< Arylalkyl group having 7 to 20 carbon atoms which may be substituted with any one or more of a halogen atom and an alkylthio group >>
The arylalkyl group having 7 to 20 carbon atoms which may be substituted with a halogen atom and / or an alkylthio group is preferably an arylalkyl group having 7 to 15 carbon atoms, and more preferably an arylalkyl group having 7 to 12 carbon atoms. Examples of such arylalkyl groups include benzyl group, phenethyl group, 2-phenylpropan-2-yl group, diphenylmethyl group, triphenylmethyl group, styryl group, cinnamyl group and the like.
The preferred range of the halogen atom as the substituent and the preferred range of the alkylthio group are each from 1 to 18 carbon atoms which may be substituted with any one or more of the halogen atom, alkylthio group and alicyclic hydrocarbon group described above. In the aliphatic hydrocarbon group, it is synonymous with the description of the halogen atom and alkylthio group as a substituent, and the preferred range is also the same.
　ハロゲン原子で置換された炭素数７～２０のアリールアルキル基としては、例えば、ペンタフルオロフェニルメチル基、フェニルジフルオロメチル基、２－フェニル－テトラフルオロエチル基、２－（ペンタフルオロフェニル）エチル基等が挙げられる。
　アルキルチオ基で置換された炭素数７～２０のアリールアルキル基としては、例えば、ｐ－メチルチオベンジル基等が挙げられる。
　ハロゲン原子およびアルキルチオ基で置換されたアリールアルキル基としては、例えば、２，３，５，６－テトラフルオロ－４－メチルチオフェニルエチル基等が挙げられる。 Examples of the arylalkyl group having 7 to 20 carbon atoms substituted with a halogen atom include a pentafluorophenylmethyl group, a phenyldifluoromethyl group, a 2-phenyl-tetrafluoroethyl group, and a 2- (pentafluorophenyl) ethyl group. Is mentioned.
Examples of the arylalkyl group having 7 to 20 carbon atoms substituted with an alkylthio group include a p-methylthiobenzyl group.
Examples of the arylalkyl group substituted with a halogen atom and an alkylthio group include a 2,3,5,6-tetrafluoro-4-methylthiophenylethyl group.
＜＜＜１０－カンファーイル基＞＞＞
　１０－カンファーイル基は、下記式で表される基である（Ｍｅはメチル基を表す）。
Figure JPOXMLDOC01-appb-C000023
 <<< 10-camphoryl group >>>
The 10-camphoryl group is a group represented by the following formula (Me represents a methyl group).
Figure JPOXMLDOC01-appb-C000023
　一般式（Ｉ）中、Ｒ3は、感度の観点から、ハロゲン原子で置換されていることが好ましく、炭素数１～８の脂肪族炭化水素基、炭素数１～８のパーフルオロアルキル基、ハロゲン原子で置換されてもよい炭素数６～１０のアリール基、ハロゲン原子で置換されてもよい炭素数７～１０のアルキルアリール基であることがより好ましく、炭素数１～４のパーフルオロアルキル基がさらに好ましい。 In general formula (I), R 3 is preferably substituted with a halogen atom from the viewpoint of sensitivity, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, a perfluoroalkyl group having 1 to 8 carbon atoms, More preferably, it is an aryl group having 6 to 10 carbon atoms that may be substituted with a halogen atom, or an alkylaryl group having 7 to 10 carbon atoms that may be substituted with a halogen atom, and a perfluoroalkyl having 1 to 4 carbon atoms More preferred are groups.
＜＜＜一般式（Ｂ）で表される基＞＞＞
　Ｒ7は、炭素数２～６のアルキレン基、炭素数２～６のハロゲン化アルキレン基、炭素数６～２０のアリーレン基、または炭素数６～２０のハロゲン化アリーレン基を表す。
　炭素数２～６のアルキレン基としては、例えば、エチレン基、プロパン－１，３－ジイル基、プロパン－１，２－ジイル基、ブチレン、ブタン－１，３－ジイル基、ブタン－２，３－ジイル基、ブタン－１，２－ジイル基、ペンタン－１，５－ジイル基、ペンタン－１，３－ジイル基、ペンタン－１，４－ジイル基、ペンタン－２，３－ジイル基、ヘキサン－１，６－ジイル基、ヘキサン－１，２－ジイル基、ヘキサン－１，３－ジイル基、ヘキサン－１，４－ジイル基、ヘキサン－２，５－ジイル基、ヘキサン－２，４－ジイル基、ヘキサン－３，４－ジイル基等が挙げられる。
　炭素数２～６のハロゲン化アルキレン基は、炭素数２～６のアルキレン基中の少なくとも１つのプロトンがハロゲン原子で置換されたものである。ハロゲン原子としては、フッ素、塩素、臭素、ヨウ素が挙げられ、フッ素が好ましい。炭素数２～６のハロゲン化アルキレン基としては、例えば、テトラフルオロエチレン基、１，１－ジフルオロエチレン基、１－フルオロエチレン基、１，２－ジフルオロエチレン基、ヘキサフルオロプロパン１，３－ジイル基、１，１，２，２－テトラフルオロプロパン－１，３－ジイル基、１，１，２，２－テトラフルオロペンタン－１，５－ジイル基等が挙げられる。
　炭素数６～２０のアリーレン基としては、例えば、１，２－フェニレン基、１，３－フェニレン基、１，４－フェニレン基、２，５－ジメチル－１，４－フェニレン基、４，４'－ビフェニレン基、ジフェニルメタン－４，４’－ジイル基、２，２－ジフェニルプロパン－４，４’－ジイル基、ナフタレン－１，２－ジイル基、ナフタレン－１，３－ジイル基、ナフタレン－１，４－ジイル基、ナフタレン－１，５－ジイル基、ナフタレン－１，６－ジイル基、ナフタレン－１，７－ジイル基、ナフタレン－１，８－ジイル基、ナフタレン－２，３－ジイル基、ナフタレン－２，６－ジイル基、ナフタレン－２，７－ジイル基等が挙げられる。
　炭素数６～２０のハロゲン化アリーレン基は、炭素数６～２０のアリーレン基中の少なくとも１つのプロトンがハロゲン原子で置換されたものである。炭素数６～２０のハロゲン化アリーレン基としては、例えばテトラフルオロフェニレン基などが挙げられる。 <<< Group Represented by Formula (B) >>>
R 7 represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms.
Examples of the alkylene group having 2 to 6 carbon atoms include ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butylene, butane-1,3-diyl group, butane-2,3. -Diyl group, butane-1,2-diyl group, pentane-1,5-diyl group, pentane-1,3-diyl group, pentane-1,4-diyl group, pentane-2,3-diyl group, hexane -1,6-diyl group, hexane-1,2-diyl group, hexane-1,3-diyl group, hexane-1,4-diyl group, hexane-2,5-diyl group, hexane-2,4- Examples thereof include a diyl group and a hexane-3,4-diyl group.
The halogenated alkylene group having 2 to 6 carbon atoms is obtained by substituting at least one proton in the alkylene group having 2 to 6 carbon atoms with a halogen atom. Examples of the halogen atom include fluorine, chlorine, bromine and iodine, and fluorine is preferred. Examples of the halogenated alkylene group having 2 to 6 carbon atoms include, for example, a tetrafluoroethylene group, 1,1-difluoroethylene group, 1-fluoroethylene group, 1,2-difluoroethylene group, hexafluoropropane 1,3-diyl Group, 1,1,2,2-tetrafluoropropane-1,3-diyl group, 1,1,2,2-tetrafluoropentane-1,5-diyl group and the like.
Examples of the arylene group having 6 to 20 carbon atoms include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,5-dimethyl-1,4-phenylene group, 4,4 '-Biphenylene group, diphenylmethane-4,4'-diyl group, 2,2-diphenylpropane-4,4'-diyl group, naphthalene-1,2-diyl group, naphthalene-1,3-diyl group, naphthalene- 1,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, naphthalene-1,7-diyl group, naphthalene-1,8-diyl group, naphthalene-2,3-diyl Group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group and the like.
The halogenated arylene group having 6 to 20 carbon atoms is obtained by substituting at least one proton in the arylene group having 6 to 20 carbon atoms with a halogen atom. Examples of the halogenated arylene group having 6 to 20 carbon atoms include a tetrafluorophenylene group.
　Ｒ8は、単結合、炭素数２～６のアルキレン基、炭素数２～６のハロゲン化アルキレン基、炭素数６～２０のアリーレン基または炭素数６～２０のハロゲン化アリーレン基を表す。Ｒ8が表わす炭素数２～６のアルキレン基、炭素数２～６のハロゲン化アルキレン基、炭素数６～２０のアリーレン基または炭素数６～２０のハロゲン化アリーレン基は、Ｒ7が表わす炭素数２～６のアルキレン基、炭素数２～６のハロゲン化アルキレン基、炭素数６～２０のアリーレン基または炭素数６～２０のハロゲン化アリーレン基と同義であり、好ましい範囲も同様である。 R 8 represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a halogenated arylene group having 6 to 20 carbon atoms. Alkylene group of 2 to 6 carbon atoms R 8 represents a halogenated alkylene group having 2-6 carbon atoms, a halogenated arylene group an arylene group or a C 6 -C 20 6 to 20 carbon atoms, the carbon to which R 7 represents It is synonymous with a C 2-6 alkylene group, a C 2-6 halogenated alkylene group, a C 6-20 arylene group or a C 6-20 halogenated arylene group, and the preferred range is also the same.
　Ｙ2は、単結合または炭素数１～４のアルキレン基を表す。Ｙ2が表わす炭素数１～４のアルキレン基は、一般式（Ａ）中のＹ1が表わす炭素数１～４のアルキレン基と同義であり、好ましい範囲も同様である。 Y 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms. The alkylene group having 1 to 4 carbon atoms represented by Y 2 has the same meaning as the alkylene group having 1 to 4 carbon atoms represented by Y 1 in formula (A), and the preferred range is also the same.
　Ｒ9は、分枝を有していてもよい炭素数１～１８のアルキル基、分枝を有していてもよい炭素数１～１８のハロゲン化アルキル基、炭素数６～２０のアリール基、炭素数６～２０のハロゲン化アリール基、炭素数７～２０のアリールアルキル基、または炭素数７～２０のハロゲン化アリールアルキル基を表す。
　Ｒ9が表わす炭素数６～２０のアリール基、炭素数６～２０のハロゲン化アリール基、炭素数７～２０のアリールアルキル基、または炭素数７～２０のハロゲン化アリールアルキル基は、一般式（Ｉ）におけるＲ3におけるハロゲン原子、アルキルチオ基、およびアシル基のいずれかで置換されてもよい炭素数６～２０のアリール基、ハロゲン原子および／またはアルキルチオ基で置換されてもよい炭素数７～２０のアリールアルキル基、ハロゲン原子で置換されてもよい炭素数７～２０のアルキルアリール基とそれぞれ同義であり、好ましい範囲も同様である。
　炭素数１～１８のアルキル基としては、炭素数１～１０のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましく、炭素数１～３のアルキル基がさらに好ましい。このようなアルキル基は、分枝であってもよい。炭素数１～１８のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、イソブチル基、アミル基、イソアミル基、ｔｅｒｔ－アミル基、ヘキシル基、２－ヘキシル基、３－ヘキシル基、ヘプチル基、２－ヘプチル基、３－ヘプチル基、イソヘプチル基、ｔｅｒｔ－ヘプチル基、オクチル基、イソオクチル基、ｔｅｒｔ－オクチル基、２－エチルヘキシル基、ノニル基、イソノニル基、デシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、へプタデシル基、オクタデシル基、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロデシル基、ビシクロ［２．１．１］ヘキシル基、ビシクロ［２．２．１］ヘプチル基、ビシクロ［３．２．１］オクチル基、ビシクロ［２．２．２］オクチル基、アダマンチル基などが挙げられる。
　炭素数１～１８のハロゲン化アルキル基は、炭素数１～１８のアルキル基中の少なくとも１つのプロトンがハロゲン原子で置換されたものであり、分枝していてもよい。炭素数１～１８のハロゲン化アルキル基としては、例えば、トリフルオロメチル基、ペンタフルオロエチル基、ヘプタフルオロプロピル基、ノナフルオロブチル基、トリデカフルオロヘキシル基、ヘプタデカフルオロオクチル基、２，２，２－トリフルオロエチル基、１，１－ジフルオロエチル基、１，１－ジフルオロプロピル基、１，１，２，２－テトラフルオロプロピル基、３，３，３－トリフルオロプロピル基、２，２，３，３，３－ペンタフルオロプロピル基、１，１，２，２－テトラフルオロテトラデシル基等のハロゲン化アルキル基が挙げられる。 R 9 is an optionally branched alkyl group having 1 to 18 carbon atoms, an optionally branched alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 20 carbon atoms. Represents a halogenated aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a halogenated arylalkyl group having 7 to 20 carbon atoms.
R 9 represents an aryl group having 6 to 20 carbon atoms, a halogenated aryl group having 6 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, or a halogenated arylalkyl group having 7 to 20 carbon atoms. A carbon number of 7 which may be substituted with an aryl group of 6 to 20 carbon atoms, a halogen atom and / or an alkylthio group which may be substituted with any of a halogen atom, an alkylthio group and an acyl group in R 3 in (I) Are the same as the arylalkyl group of ˜20 and the alkylaryl group of 7 to 20 carbon atoms which may be substituted with a halogen atom, and the preferred range is also the same.
The alkyl group having 1 to 18 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms. Such alkyl groups may be branched. Examples of the alkyl group having 1 to 18 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, amyl, isoamyl, and tert-amyl. Group, hexyl group, 2-hexyl group, 3-hexyl group, heptyl group, 2-heptyl group, 3-heptyl group, isoheptyl group, tert-heptyl group, octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl Group, nonyl group, isononyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, Cyclooctyl group, cyclodecyl group, bicyclo 2.1.1] hexyl, bicyclo [2.2.1] heptyl, bicyclo [3.2.1] octyl, bicyclo [2.2.2] octyl group and an adamantyl group.
The halogenated alkyl group having 1 to 18 carbon atoms is a group in which at least one proton in the alkyl group having 1 to 18 carbon atoms is substituted with a halogen atom, and may be branched. Examples of the halogenated alkyl group having 1 to 18 carbon atoms include trifluoromethyl group, pentafluoroethyl group, heptafluoropropyl group, nonafluorobutyl group, tridecafluorohexyl group, heptadecafluorooctyl group, 2,2 , 2-trifluoroethyl group, 1,1-difluoroethyl group, 1,1-difluoropropyl group, 1,1,2,2-tetrafluoropropyl group, 3,3,3-trifluoropropyl group, 2, Examples thereof include halogenated alkyl groups such as 2,3,3,3-pentafluoropropyl group and 1,1,2,2-tetrafluorotetradecyl group.
　ａおよびｂはそれぞれ独立に０または１を表し、ａおよびｂの少なくとも一方は１であり、ａが１であることが好ましい。 A and b each independently represents 0 or 1, at least one of a and b is 1, and a is preferably 1.
　一般式（Ｉ）で表される光酸発生剤の具体例としては、以下のような化合物が挙げられるが、本発明では特にこれに限定されない。 Specific examples of the photoacid generator represented by the general formula (I) include the following compounds, but the present invention is not particularly limited thereto.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　上記例示化合物の中でも、Ｂ－１～Ｂ－１７が好ましく、Ｂ－３、Ｂ－４、Ｂ－８、Ｂ－９、Ｂ－１１～Ｂ－１３、Ｂ－１５、Ｂ－１６がより好ましい。 Among the above exemplified compounds, B-1 to B-17 are preferable, and B-3, B-4, B-8, B-9, B-11 to B-13, B-15, and B-16 are more preferable. .
　一般式（Ｉ）で表される光酸発生剤は、公知の方法で合成することができ、例えば、ＷＯ２０１１／０８７０１１号パンフレットの段落番号００７６～００８０の記載を参酌することができ、この内容は本願明細書に組み込まれる。 The photoacid generator represented by the general formula (I) can be synthesized by a known method. For example, the description of paragraph numbers 0076 to 0080 of the pamphlet of WO2011 / 087011, can be referred to, It is incorporated herein.
　一般式（Ｉ）で表される光酸発生剤の分子量としては、特に制限はないが、３３５～８００が好ましく、３３５～７８０がより好ましく、４００～７００がさらに好ましい。 The molecular weight of the photoacid generator represented by the general formula (I) is not particularly limited, but is preferably 335 to 800, more preferably 335 to 780, and further preferably 400 to 700.
　本発明の感光性樹脂組成物において、（Ｂ）一般式（Ｉ）で表される光酸発生剤の含有量は、感光性樹脂組成物中の全固形成分に対して、０．１～１０質量％が好ましく、０．５～５質量％がより好ましく、１～３質量％がさらに好ましい。光酸発生剤は、１種類のみ含んでいても良いし、２種類以上含んでいても良い。２種類以上含む場合は、合計量が上記範囲となることが好ましい。 In the photosensitive resin composition of the present invention, (B) the content of the photoacid generator represented by the general formula (I) is 0.1 to 10 with respect to the total solid components in the photosensitive resin composition. % By mass is preferable, 0.5 to 5% by mass is more preferable, and 1 to 3% by mass is further preferable. The photoacid generator may contain only one type or two or more types. When two or more types are included, the total amount is preferably within the above range.
　また、本発明の感光性樹脂組成物は、一般式（Ｉ）で表される光酸発生剤以外の光酸発生剤を含有していてもよい。このような光酸発生剤としては、波長３００ｎｍ以上、好ましくは波長３００～４５０ｎｍの活性光線に感応し、酸を発生する化合物が好ましいが、その化学構造に制限されるものではない。また、波長３００ｎｍ以上の活性光線に直接感応しない光酸発生剤についても、増感剤と併用することによって波長３００ｎｍ以上の活性光線に感応し、酸を発生する化合物であれば、増感剤と組み合わせて好ましく用いることができる。このような光酸発生剤としては、ｐＫａが４以下の酸を発生する光酸発生剤が好ましく、ｐＫａが３以下の酸を発生する光酸発生剤がより好ましく、２以下の酸を発生する光酸発生剤が特に好ましい。
　このような光酸発生剤の具体例としては、特開２０１３－１７８４３９号公報の段落番号００７０～０１１７の記載を参酌することができ、この内容は本願明細書に組み込まれる。
　一方、本発明では、一般式（Ｉ）で表される光酸発生剤以外の光酸発生剤を実質的に含まない組成物とすることもできる。実質的に含まないとは、本発明の組成物中における、一般式（Ｉ）で表される光酸発生剤の含有量の５質量％以下の量であることをいう。 The photosensitive resin composition of the present invention may contain a photoacid generator other than the photoacid generator represented by the general formula (I). As such a photoacid generator, a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid is preferable, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. Such a photoacid generator is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and an acid of 2 or less. A photoacid generator is particularly preferred.
As specific examples of such a photoacid generator, the description of paragraph numbers 0070 to 0117 of JP2013-178439A can be referred to, the contents of which are incorporated herein.
On the other hand, in this invention, it can also be set as the composition which does not contain photoacid generators other than the photoacid generator represented by general formula (I) substantially. The phrase “substantially free” means that the amount is 5% by mass or less of the content of the photoacid generator represented by the general formula (I) in the composition of the present invention.
＜その他の成分＞
　本発明の感光性樹脂組成物には、上記成分に加えて、必要に応じて、溶剤、増感剤、架橋剤、アルコキシシラン化合物、塩基性化合物、界面活性剤、酸化防止剤を好ましく加えることができる。さらに本発明の感光性樹脂組成物には、酸増殖剤、現像促進剤、可塑剤、熱ラジカル発生剤、熱酸発生剤、紫外線吸収剤、増粘剤、および、有機または無機の沈殿防止剤などの公知の添加剤を加えることができる。また、これらの化合物としては、例えば特開２０１２－８８４５９号公報の段落番号０２０１～０２２４の記載の化合物を使用することができ、これらの内容は本願明細書に組み込まれる。 <Other ingredients>
In addition to the components described above, a solvent, a sensitizer, a crosslinking agent, an alkoxysilane compound, a basic compound, a surfactant, and an antioxidant are preferably added to the photosensitive resin composition of the present invention as necessary. Can do. Furthermore, the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives such as can be added. Further, as these compounds, for example, compounds described in paragraph numbers 0201 to 0224 of JP2012-8859A can be used, and the contents thereof are incorporated in the present specification.
＜＜（Ｃ）溶剤＞＞
　本発明の感光性樹脂組成物は、（Ｃ）溶剤を含有する。本発明の感光性樹脂組成物は、本発明の必須成分と、さらに後述の任意の成分を溶剤に溶解した溶液として調製されることが好ましい。本発明の組成物の調製に用いられる溶剤としては、必須成分および任意成分を均一に溶解し、各成分と反応しないものが用いられる。
　本発明の感光性樹脂組成物に使用される溶剤としては、公知の溶剤を用いることができ、エチレングリコールモノアルキルエーテル類、エチレングリコールジアルキルエーテル類、エチレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類、プロピレングリコールジアルキルエーテル類、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類、ジエチレングリコールジアルキルエーテル類、ジエチレングリコールモノアルキルエーテルアセテート類、ジプロピレングリコールモノアルキルエーテル類、ジプロピレングリコールジアルキルエーテル類、ジ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類、エステル類、ケトン類、アミド類、ラクトン類等が例示できる。また、本発明の感光性樹脂組成物に使用される溶剤の具体例としては特開２０１１－２２１４９４号公報の段落番号０１７４～０１７８に記載の溶剤、特開２０１２－１９４２９０公報の段落番号０１６７～０１６８に記載の溶剤も挙げられ、これらの内容は本願明細書に組み込まれる。 << (C) Solvent >>
The photosensitive resin composition of the present invention contains (C) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in a solvent. As a solvent used for the preparation of the composition of the present invention, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
As the solvent used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl. Ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether Examples include acetates, esters, ketones, amides, lactones and the like. Specific examples of the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraph numbers 0174 to 0178 of JP2011-221494A, and paragraph numbers 0167 to 0168 of JP2012-194290A. And the contents thereof are incorporated herein by reference.
　また、これらの溶剤にさらに必要に応じて、ベンジルエチルエーテル、ジヘキシルエーテル、エチレングリコールモノフェニルエーテルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、イソホロン、カプロン酸、カプリル酸、１－オクタノール、１－ノナール、ベンジルアルコール、アニソール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジエチル、炭酸エチレン、炭酸プロピレン等の溶剤を添加することもできる。これら溶剤は、１種単独でまたは２種以上を混合して使用することができる。本発明に用いることができる溶剤は、１種単独、または、２種を併用することが好ましく、２種を併用することがより好ましく、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類またはジアルキルエーテル類、ジアセテート類とジエチレングリコールジアルキルエーテル類、あるいは、エステル類とブチレングリコールアルキルエーテルアセテート類とを併用することがさらに好ましい。 In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.
　また、溶剤としては、沸点１３０℃以上１６０℃未満の溶剤、沸点１６０℃以上の溶剤、または、これらの混合物であることが好ましい。
　沸点１３０℃以上１６０℃未満の溶剤としては、プロピレングリコールモノメチルエーテルアセテート（沸点１４６℃）、プロピレングリコールモノエチルエーテルアセテート(沸点１５８℃)、プロピレングリコールメチル－ｎ－ブチルエーテル（沸点１５５℃）、プロピレングリコールメチル－ｎ－プロピルエーテル（沸点１３１℃）が例示できる。
　沸点１６０℃以上の溶剤としては、３－エトキシプロピオン酸エチル（沸点１７０℃）、ジエチレングリコールメチルエチルエーテル（沸点１７６℃）、プロピレングリコールモノメチルエーテルプロピオネート（沸点１６０℃）、ジプロピレングリコールメチルエーテルアセテート（沸点２１３℃）、３－メトキシブチルエーテルアセテート（沸点１７１℃）、ジエチレングリコールジエチエルエーテル（沸点１８９℃）、ジエチレングリコールジメチルエーテル（沸点１６２℃）、プロピレングリコールジアセテート（沸点１９０℃）、ジエチレングリコールモノエチルエーテルアセテート（沸点２２０℃）、ジプロピレングリコールジメチルエーテル（沸点１７５℃）、１，３－ブチレングリコールジアセテート（沸点２３２℃）が例示できる。 Further, the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.
　本発明の感光性樹脂組成物における、溶剤の含有量は、感光性樹脂組成物中の全成分１００質量部当たり、５０～９５質量部であることが好ましく、６０～９０質量部であることがさらに好ましい。溶剤は１種類のみ含んでいても良いし、２種類以上含んでいても良い。２種類以上含む場合は、合計量が上記範囲となることが好ましい。 The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, and preferably 60 to 90 parts by mass with respect to 100 parts by mass of all components in the photosensitive resin composition. Further preferred. Only one type of solvent may be included, or two or more types of solvents may be included. When two or more types are included, the total amount is preferably within the above range.
＜＜増感剤＞＞
　本発明の感光性樹脂組成物は、光酸発生剤との組み合わせにおいて、その分解を促進させるために、増感剤を含有することが好ましい。増感剤は、活性光線を吸収して電子励起状態となる。電子励起状態となった増感剤は、光酸発生剤と接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより光酸発生剤は化学変化を起こして分解し、酸を生成する。好ましい増感剤の例としては、以下の化合物類に属しており、かつ３５０ｎｍから４５０ｎｍの波長域のいずれかに吸収波長を有する化合物を挙げることができる。 << Sensitizer >>
The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote the decomposition in combination with the photoacid generator. The sensitizer absorbs actinic rays and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.
　多核芳香族類（例えば、ピレン、ペリレン、トリフェニレン、アントラセン、９，１０－ジブトキシアントラセン、９，１０－ジエトキシアントラセン，３，７－ジメトキシアントラセン、９，１０－ジプロピルオキシアントラセン）、キサンテン類（例えば、フルオレッセイン、エオシン、エリスロシン、ローダミンＢ、ローズベンガル）、キサントン類（例えば、キサントン、チオキサントン、ジメチルチオキサントン、ジエチルチオキサントン）、シアニン類（例えばチアカルボシアニン、オキサカルボシアニン）、メロシアニン類（例えば、メロシアニン、カルボメロシアニン）、ローダシアニン類、オキソノール類、チアジン類（例えば、チオニン、メチレンブルー、トルイジンブルー）、アクリジン類（例えば、アクリジンオレンジ、クロロフラビン、アクリフラビン）、アクリドン類（例えば、アクリドン、１０－ブチル－２－クロロアクリドン）、アントラキノン類（例えば、アントラキノン）、スクアリリウム類（例えば、スクアリリウム）、スチリル類、ベーススチリル類（例えば、２－［２－［４－（ジメチルアミノ）フェニル］エテニル］ベンゾオキサゾール）、クマリン類（例えば、７－ジエチルアミノ４－メチルクマリン、７－ヒドロキシ４－メチルクマリン、２，３，６，７－テトラヒドロ－９－メチル－１Ｈ，５Ｈ，１１Ｈ［１］ベンゾピラノ［６，７，８－ｉｊ］キノリジン－１１－ノン）。
　これら増感剤の中でも、多核芳香族類、アクリドン類、スチリル類、ベーススチリル類、クマリン類が好ましく、多核芳香族類がより好ましい。多核芳香族類の中でもアントラセン誘導体が最も好ましい。 Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squaryliums (eg, squarylium), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.
　本発明の感光性樹脂組成物が増感剤を含有する場合、増感剤の添加量は、感光性樹脂組成物中の全固形成分１００質量部に対し、０.００１～１００質量部であることが好ましく、０．１～５０質量部であることがより好ましく、０．５～２０質量部であることがさらに好ましい。増感剤は、１種類のみ含んでいても良いし、２種類以上含んでいても良い。２種類以上含む場合は、合計量が上記範囲となることが好ましい。 When the photosensitive resin composition of the present invention contains a sensitizer, the addition amount of the sensitizer is 0.001 to 100 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. It is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass. The sensitizer may contain only one type or two or more types. When two or more types are included, the total amount is preferably within the above range.
＜＜架橋剤＞＞
　本発明の感光性樹脂組成物は、必要に応じ、架橋剤を含有することが好ましい。架橋剤を添加することにより、本発明の感光性樹脂組成物により得られる硬化膜をより強固な膜とすることができる。
　架橋剤としては、熱によって架橋反応が起こるものであれば制限は無い。例えば、以下に述べる分子内に２個以上のエポキシ基および／またはオキセタニル基を有する化合物、アルコキシメチル基含有架橋剤、または、少なくとも１個のエチレン性不飽和二重結合を有する化合物、ブロックイソシアネート化合物等を添加することができ、分子内に２個以上のエポキシ基および／またはオキセタニル基を有する化合物が好ましい。分子内に２個以上のエポキシ基および／またはオキセタニル基を有する化合物を配合すると硬化膜の表面荒れ抑制や露光現像後のパターンの矩形性向上という効果がより効果的に発揮される。
　本発明の感光性樹脂組成物が架橋剤を含有する場合、架橋剤の添加量は、上記（Ａ）重合体成分の合計１００質量部に対し、０．０１～５０質量部であることが好ましく、０．１～３０質量部であることがより好ましく、０．５～２０質量部であることがさらに好ましい。この範囲で添加することにより、機械的強度および耐溶剤性に優れた硬化膜が得られる。架橋剤は１種類のみ含んでいても良いし、２種類以上含んでいても良い。２種類以上含む場合は、合計量が上記範囲となることが好ましい。 << Crosslinking agent >>
It is preferable that the photosensitive resin composition of this invention contains a crosslinking agent as needed. By adding a crosslinking agent, the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
The crosslinking agent is not limited as long as a crosslinking reaction is caused by heat. For example, a compound having two or more epoxy groups and / or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, or a blocked isocyanate compound A compound having two or more epoxy groups and / or oxetanyl groups in the molecule is preferable. When a compound having two or more epoxy groups and / or oxetanyl groups in the molecule is blended, the effects of suppressing the surface roughness of the cured film and improving the rectangularity of the pattern after exposure and development are more effectively exhibited.
When the photosensitive resin composition of the present invention contains a cross-linking agent, the addition amount of the cross-linking agent is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass in total of the polymer component (A). The content is more preferably 0.1 to 30 parts by mass, and further preferably 0.5 to 20 parts by mass. By adding in this range, a cured film having excellent mechanical strength and solvent resistance can be obtained. Only one type of crosslinking agent may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.
＜＜＜分子内に２個以上のエポキシ基および／またはオキセタニル基を有する化合物＞＞＞
　分子内に２個以上のエポキシ基を有する化合物の具体例としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂肪族エポキシ樹脂等を挙げることができる。 <<< Compound having two or more epoxy groups and / or oxetanyl groups in the molecule >>>
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do.
　これらは市販品として入手できる。例えば、ＪＥＲ１５２、ＪＥＲ１５７Ｓ７０、ＪＥＲ１５７Ｓ６５、ＪＥＲ８０６、ＪＥＲ８２８、ＪＥＲ１００７（（株）三菱ケミカルホールディングス製）など、特開２０１１－２２１４９４号公報の段落番号０１８９に記載の市販品などが挙げられ、その他にも、デナコールＥＸ－６１１、ＥＸ－６１２、ＥＸ－６１４、ＥＸ－６１４Ｂ、ＥＸ－６２２、ＥＸ－５１２、ＥＸ－５２１、ＥＸ－４１１、ＥＸ－４２１、ＥＸ－３１３、ＥＸ－３１４、ＥＸ－３２１、ＥＸ－２１１、ＥＸ－２１２、ＥＸ－８１０、ＥＸ－８１１、ＥＸ－８５０、ＥＸ－８５１、ＥＸ－８２１、ＥＸ－８３０、ＥＸ－８３２、ＥＸ－８４１、ＥＸ－９１１、ＥＸ－９４１、ＥＸ－９２０、ＥＸ－９３１、ＥＸ－２１２Ｌ、ＥＸ－２１４Ｌ、ＥＸ－２１６Ｌ、ＥＸ－３２１Ｌ、ＥＸ－８５０Ｌ、ＤＬＣ－２０１、ＤＬＣ－２０３、ＤＬＣ－２０４、ＤＬＣ－２０５、ＤＬＣ－２０６、ＤＬＣ－３０１、ＤＬＣ－４０２（以上ナガセケムテック製）、ＹＨ－３００、ＹＨ－３０１、ＹＨ－３０２、ＹＨ－３１５、ＹＨ－３２４、ＹＨ－３２５（以上新日鐵化学製）などが挙げられる。これらは１種単独または２種以上を組み合わせて使用することができる。
　これらの中でも、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂および脂肪族エポキシ樹脂がより好ましく挙げられ、ビスフェノールＡ型エポキシ樹脂が特に好ましく挙げられる。
　分子内に２個以上のオキセタニル基を有する化合物の具体例としては、アロンオキセタンＯＸＴ－１２１、ＯＸＴ－２２１、ＯＸ－ＳＱ、ＰＮＯＸ（以上、東亞合成（株）製）を用いることができる。
　また、オキセタニル基を含む化合物は、単独でまたはエポキシ基を含む化合物と混合して使用することが好ましい。 These are available as commercial products. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like are commercially available products described in paragraph No. 0189 of JP2011-221494, etc. EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX- 211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, EX-216L, X-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (manufactured by Nagase Chemtech), YH-300, YH-301 YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel Chemical Co., Ltd.) and the like. These can be used alone or in combination of two or more.
Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.
As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron oxetane OXT-121, OXT-221, OX-SQ, and PNOX (manufactured by Toagosei Co., Ltd.) can be used.
Moreover, it is preferable to use the compound containing an oxetanyl group individually or in mixture with the compound containing an epoxy group.
　また、その他の架橋剤としては、特開２０１２－８２２３号公報の段落番号０１０７～０１０８に記載のアルコキシメチル基含有架橋剤、および少なくとも１個のエチレン性不飽和二重結合を有する化合物なども好ましく用いることができ、これらの内容は本願明細書に組み込まれる。アルコキシメチル基含有架橋剤としては、アルコキシメチル化グリコールウリルが好ましい。 Further, as other crosslinking agents, alkoxymethyl group-containing crosslinking agents described in paragraph numbers 0107 to 0108 of JP2012-8223A, and compounds having at least one ethylenically unsaturated double bond are also preferable. These contents can be used and are incorporated herein. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.
＜＜＜ブロックイソシアネート化合物＞＞＞
　本発明の感光性樹脂組成物では、架橋剤として、ブロックイソシアネート系化合物も好ましく採用できる。ブロックイソシアネート化合物は、特に制限はないが、硬化性の観点から、１分子内に２以上のブロックイソシアネート基を有する化合物であることが好ましい。
　なお、本発明におけるブロックイソシアネート基とは、熱によりイソシアネート基を生成することが可能な基であり、例えば、ブロック剤とイソシアネート基とを反応させイソシアネート基を保護した基が好ましく例示できる。また、上記ブロックイソシアネート基は、９０℃～２５０℃の熱によりイソシアネート基を生成することが可能な基であることが好ましい。
　また、ブロックイソシアネート化合物としては、その骨格は特に限定されるものではなく、１分子中にイソシアネート基を２個有するものであればどのようなものでもよく、脂肪族、脂環族または芳香族のポリイソシアネートであってよいが、例えば２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、イソホロンジイソシアネート、１，６－ヘキサメチレンジイソシアネート、１，３－トリメチレンジイソシアネート、１，４－テトラメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、１，９－ノナメチレンジイソシアネート、１，１０－デカメチレンジイソシアネート、１，４－シクロヘキサンジイソシアネート、２，２'－ジエチルエーテルジイソシアネート、ジフェニルメタン－４，４'－ジイソシアネート、ｏ－キシレンジイソシアネート、ｍ－キシレンジイソシアネート、ｐ－キシレンジイソシアネート、メチレンビス（シクロヘキシルイソシアネート）、シクロヘキサン－１，３－ジメチレンジイソシアネート、シクロヘキサン－１，４－ジメチレレンジイソシアネート、１，５－ナフタレンジイソシアネート、ｐ－フェニレンジイソシアネート、３，３'－メチレンジトリレン－４，４'－ジイソシアネート、４，４'－ジフェニルエーテルジイソシアネート、テトラクロロフェニレンジイソシアネート、ノルボルナンジイソシアネート、水素化１，３－キシリレンジイソシアネート、水素化１，４－キシリレンジイソシアネート等のイソシアネート化合物およびこれらの化合物から派生するプレポリマー型の骨格の化合物を好適に用いることができる。これらの中でも、トリレンジイソシアネート（ＴＤＩ）やジフェニルメタンジイソシアネート（ＭＤＩ）、ヘキサメチレンジイソシアネート（ＨＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）が特に好ましい。
　本発明の感光性樹脂組成物におけるブロックイソシアネート化合物の母構造としては、ビウレット型、イソシアヌレート型、アダクト型、２官能プレポリマー型等を挙げることができる。
　上記ブロックイソシアネート化合物のブロック構造を形成するブロック剤としては、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物、メルカプタン化合物、イミダゾール系化合物、イミド系化合物等を挙げることができる。これらの中でも、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物から選ばれるブロック剤が特に好ましい。 <<< Blocked isocyanate compound >>>
In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably employed as a crosslinking agent. Although there is no restriction | limiting in particular in a block isocyanate compound, It is preferable that it is a compound which has a 2 or more block isocyanate group in 1 molecule from a sclerosing | hardenable viewpoint.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. The blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
Further, the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic. Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2 2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1 , 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene ditolylene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate , Isocyanation of hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate, etc. A compound and a prepolymer type skeleton compound derived from these compounds can be preferably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
　上記オキシム化合物としては、オキシム、および、ケトオキシムが挙げられ、具体的には、アセトキシム、ホルムアルドキシム、シクロヘキサンオキシム、メチルエチルケトンオキシム、シクロヘキサノンオキシム、ベンゾフェノンオキシム、アセトキシム等が例示できる。
　上記ラクタム化合物としてはε－カプロラクタム、γ－ブチロラクタム等が例示できる。
　上記フェノール化合物としては、フェノール、ナフトール、クレゾール、キシレノール、ハロゲン置換フェノール等が例示できる。
　上記アルコール化合物としては、メタノール、エタノール、プロパノール、ブタノール、シクロヘキサノール、エチ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、乳酸アルキル等が例示できる。
　上記アミン化合物としては、１級アミンおよび２級アミンが上げられ、芳香族アミン、脂肪族アミン、脂環族アミンいずれでもよく、アニリン、ジフェニルアミン、エチレンイミン、ポリエチレンイミン等が例示できる。
　上記活性メチレン化合物としては、マロン酸ジエチル、マロン酸ジメチル、アセト酢酸エチル、アセト酢酸メチル等が例示できる。
　上記ピラゾール化合物としては、ピラゾール、メチルピラゾール、ジメチルピラゾール等が例示できる。
　上記メルカプタン化合物としては、アルキルメルカプタン、アリールメルカプタン等が例示できる。 Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.
　本発明の感光性樹脂組成物に使用できるブロックイソシアネート化合物は、市販品として入手可能であり、例えば、コロネートＡＰステーブルＭ、コロネート２５０３、２５１５、２５０７、２５１３、２５５５、ミリオネートＭＳ－５０（以上、日本ポリウレタン工業（株）製）、タケネートＢ－８３０、Ｂ－８１５Ｎ、Ｂ－８２０ＮＳＵ、Ｂ－８４２Ｎ、Ｂ－８４６Ｎ、Ｂ－８７０Ｎ、Ｂ－８７４Ｎ、Ｂ－８８２Ｎ（以上、三井化学（株）製）、デュラネート１７Ｂ－６０ＰＸ、１７Ｂ－６０Ｐ、ＴＰＡ－Ｂ８０Ｘ、ＴＰＡ－Ｂ８０Ｅ、ＭＦ－Ｂ６０Ｘ、ＭＦ－Ｂ６０Ｂ、ＭＦ－Ｋ６０Ｘ、ＭＦ－Ｋ６０Ｂ、Ｅ４０２－Ｂ８０Ｂ、ＳＢＮ－７０Ｄ、ＳＢＢ－７０Ｐ、Ｋ６０００（以上、旭化成ケミカルズ（株）製）、デスモジュールＢＬ１１００、ＢＬ１２６５　ＭＰＡ／Ｘ、ＢＬ３５７５／１、ＢＬ３２７２ＭＰＡ、ＢＬ３３７０ＭＰＡ、ＢＬ３４７５ＢＡ／ＳＮ、ＢＬ５３７５ＭＰＡ、ＶＰＬＳ２０７８／２、ＢＬ４２６５ＳＮ、ＰＬ３４０、ＰＬ３５０、スミジュールＢＬ３１７５（以上、住化バイエルウレタン（株）製）等を好ましく使用することができる。 The blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above , Manufactured by Asahi Kasei Chemicals Corporation, Death Module B 1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) etc. are preferably used can do.
＜＜アルコキシシラン化合物＞＞
　本発明の感光性樹脂組成物は、密着改良剤としてアルコキシシラン化合物を含有してもよい。アルコキシシラン化合物を用いると、本発明の感光性樹脂組成物により形成された膜と基板との密着性を向上できたり、本発明の感光性樹脂組成物により形成された膜の性質を調整することができる。本発明の感光性樹脂組成物に用いることができるアルコキシシラン化合物は、基材となる無機物、例えば、シリコン、酸化シリコン、窒化シリコン等のシリコン化合物、金、銅、モリブデン、チタン、アルミニウム等の金属と絶縁膜との密着性を向上させる化合物であることが好ましい。具体的には、公知のシランカップリング剤等も有効である。
　シランカップリング剤としては、例えば、γ－アミノプロピルトリメトキシシラン、γ－アミノ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アコキシシラン、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ジアルコキシシラン、γ－メタクリロキシプロピルトリアルコキシシラン、γ－メタクリロキシプロピ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）エチルトリアルコキシシラン、ビニルトリアルコキシシランが挙げられる。これらのうち、γ－グリシドキシプロピルトリアルコキシシランやγ－メタクリロキシプロピルトリアルコキシシランがより好ましく、γ－グリシドキシプロピルトリアルコキシシランがさらに好ましく、３－グリシドキシプロピルトリメトキシシランがよりさらに好ましい。これらは１種単独または２種以上を組み合わせて使用することができる。 << alkoxysilane compound >>
The photosensitive resin composition of the present invention may contain an alkoxysilane compound as an adhesion improving agent. When an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do. The alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. Preferably, the compound improves the adhesion between the insulating film and the insulating film. Specifically, a known silane coupling agent or the like is also effective.
Examples of the silane coupling agent include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycid. Xylpropyl dialkoxysilane, γ-methacryloxypropyltrialkoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) Examples include ethyltrialkoxysilane and vinyltrialkoxysilane. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.
　本発明の感光性樹脂組成物における（アルコキシシラン化合物は、特にこれらに限定することなく、公知のものを使用することができる。
　本発明の感光性樹脂組成物がアルコキシシランを含有する場合、アルコキシシラン化合物の含有量は、感光性組成物中の全固形分１００質量部に対して、０．１～３０質量部が好ましく、０．５～２０質量部がより好ましい。２種類以上含む場合は、合計量が上記範囲となることが好ましい。 The (alkoxysilane compound in the photosensitive resin composition of the present invention is not particularly limited, and known compounds can be used.
When the photosensitive resin composition of the present invention contains an alkoxysilane, the content of the alkoxysilane compound is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive composition, 0.5 to 20 parts by mass is more preferable. When two or more types are included, the total amount is preferably within the above range.
＜＜塩基性化合物＞＞
　本発明の感光性樹脂組成物は、塩基性化合物を含有してもよい。塩基性化合物としては、化学増幅レジストで用いられるものの中から任意に選択して使用することができる。例えば、脂肪族アミン、芳香族アミン、複素環式アミン、第四級アンモニウムヒドロキシド、カルボン酸の第四級アンモニウム塩等が挙げられる。これらの具体例としては、特開２０１１－２２１４９４号公報の段落番号０２０４～０２０７に記載の化合物が挙げられ、これらの内容は本願明細書に組み込まれる。 << basic compound >>
The photosensitive resin composition of the present invention may contain a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include the compounds described in JP-A 2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.
　具体的には、脂肪族アミンとしては、例えば、トリメチルアミン、ジエチルアミン、トリエチルアミン、ジ－ｎ－プロピルアミン、トリ－ｎ－プロピルアミン、ジ－ｎ－ペンチルアミン、トリ－ｎ－ペンチルアミン、ジエタノールアミン、トリエタノールアミン、ジシクロヘキシルアミン、ジシクロヘキシルメチルアミンなどが挙げられる。
　芳香族アミンとしては、例えば、アニリン、ベンジルアミン、Ｎ，Ｎ－ジメチルアニリン、ジフェニルアミンなどが挙げられる。
　複素環式アミンとしては、例えば、ピリジン、２－メチルピリジン、４－メチルピリジン、２－エチルピリジン、４－エチルピリジン、２－フェニルピリジン、４－フェニルピリジン、Ｎ－メチル－４－フェニルピリジン、４－ジメチルアミノピリジン、イミダゾール、ベンズイミダゾール、４－メチルイミダゾール、２－フェニルベンズイミダゾール、トリフェニルイミダゾール、ニコチン、ニコチン酸、ニコチン酸アミド、キノリン、８－オキシキノリン、ピラジン、ピラゾール、ピリダジン、プリン、ピロリジン、ピペリジン、ピペラジン、モルホリン、４－メチルモルホリン、Ｎ－シクロヘキシル－Ｎ’－［２－（４－モルホリニル）エチル］チオ尿素、１，５－ジアザビシクロ［４．３．０］－５－ノネン、１，８－ジアザビシクロ［５．３．０］－７－ウンデセン、１，８－ジアザビシクロ［５．４．０］－７－ウンデセンなどが挙げられる。
　第四級アンモニウムヒドロキシドとしては、例えば、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラ－ｎ－ブチルアンモニウムヒドロキシド、テトラ－ｎ－ヘキシルアンモニウムヒドロキシドなどが挙げられる。
　カルボン酸の第四級アンモニウム塩としては、例えば、テトラメチルアンモニウムアセテート、テトラメチルアンモニウムベンゾエート、テトラ－ｎ－ブチルアンモニウムアセテート、テトラ－ｎ－ブチルアンモニウムベンゾエートなどが挙げられる。
　本発明に用いることができる塩基性化合物は、１種単独で使用しても、２種以上を併用してもよい。 Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, pyrazole, pyridazine, purine, Pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea, 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.3.0] -7-undecene, 1,8-diazabicyclo [5.4.0] -7-undecene and the like.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
The basic compounds that can be used in the present invention may be used singly or in combination of two or more.
　本発明の感光性樹脂組成物が塩基性化合物を含有する場合、塩基性化合物の含有量は、感光性樹脂組成物中の全固形成分１００質量部に対し、０．００１～３質量部であることが好ましく、０．００５～１質量部であることがより好ましい。２種類以上含む場合は、合計量が上記範囲となることが好ましい。 When the photosensitive resin composition of the present invention contains a basic compound, the content of the basic compound is 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid component in the photosensitive resin composition. The amount is preferably 0.005 to 1 part by mass. When two or more types are included, the total amount is preferably within the above range.
＜＜界面活性剤＞＞
　本発明の感光性樹脂組成物は、界面活性剤を含有してもよい。界面活性剤としては、アニオン系、カチオン系、ノニオン系、または、両性のいずれでも使用することができるが、好ましい界面活性剤はノニオン界面活性剤である。本発明の組成物に用いられる界面活性剤としては、例えば、特開２０１２－８８４５９号公報の段落番号０２０１～０２０５に記載のものや、特開２０１１－２１５５８０号公報の段落番号０１８５～０１８８に記載のものを用いることができ、これらの記載は本願明細書に組み込まれる。
　ノニオン系界面活性剤の例としては、ポリオキシエチレン高級アルキルエーテル類、ポリオキシエチレン高級アルキルフェニルエーテル類、ポリオキシエチレングリコールの高級脂肪酸ジエステル類、シリコン系、フッ素系界面活性剤を挙げることができる。また、以下商品名で、ＫＰ－３４１、Ｘ－２２－８２２（信越化学工業（株）製）、ポリフローＮｏ．９９Ｃ（共栄社化学（株）製）、エフトップ（三菱マテリアル化成社製）、メガファック（ＤＩＣ（株）製）、フロラードノベックＦＣ－４４３０（住友スリーエム（株）製）、サーフロンＳ－２４２（ＡＧＣセイミケミカル社製）、ＰｏｌｙＦｏｘＰＦ－６３２０（ＯＭＮＯＶＡ社製）、ＳＨ－８４００（東レ・ダウコーニングシリコン）、フタージェントＦＴＸ－２１８Ｇ（ネオス社製）等を挙げることができる。
　また、界面活性剤として、下記一般式（Ｉ－１－１）で表される構成単位Ａおよび構成単位Ｂを含み、テトラヒドロフラン（ＴＨＦ）を溶媒とした場合のゲルパーミエーションクロマトグラフィーで測定されるポリスチレン換算の重量平均分子量（Ｍｗ）が１，０００以上１０，０００以下である共重合体を好ましい例として挙げることができる。 << Surfactant >>
The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. Examples of the surfactant used in the composition of the present invention include those described in paragraph Nos. 0201 to 0205 in JP2012-88459A, and paragraphs 0185 to 0188 in JP2011-215580A. Can be used and these descriptions are incorporated herein.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicon-based and fluorine-based surfactants. . The following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by Mitsubishi Materials Kasei Co., Ltd.), MegaFac (manufactured by DIC Corporation), Florard Novec FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-242 (Manufactured by AGC Seimi Chemical Co., Ltd.), PolyFox PF-6320 (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicon), and Fantent FTX-218G (manufactured by Neos).
Further, the surfactant is measured by gel permeation chromatography using the structural unit A and the structural unit B represented by the following general formula (I-1-1) and using tetrahydrofuran (THF) as a solvent. A preferred example is a copolymer having a polystyrene-reduced weight average molecular weight (Mw) of 1,000 or more and 10,000 or less.
一般式（Ｉ－１－１）
Figure JPOXMLDOC01-appb-C000035
 （式（Ｉ－１－１）中、Ｒ401およびＲ403はそれぞれ独立に、水素原子またはメチル基を表し、Ｒ402は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ404は水素原子または炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐおよびｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｓは１以上１０以下の整数を表す。） Formula (I-1-1)
Figure JPOXMLDOC01-appb-C000035
 (In the formula (I-1-1), R 401 and R 403 each independently represent a hydrogen atom or a methyl group, R 402 represents a linear alkylene group having 1 to 4 carbon atoms, and R 404 represents hydrogen. Represents an atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is 10 mass% to 80 mass%. The following numerical values are represented, q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.
　上記Ｌは、下記一般式（Ｉ－１－２）で表される分岐アルキレン基であることが好ましい。一般式（Ｉ－１－２）におけるＲ405は、炭素数１以上４以下のアルキル基を表し、相溶性と被塗布面に対する濡れ性の点で、炭素数１以上３以下のアルキル基が好ましく、炭素数２または３のアルキル基がより好ましい。ｐとｑとの和（ｐ＋ｑ）は、ｐ＋ｑ＝１００、すなわち、１００質量％であることが好ましい。 L is preferably a branched alkylene group represented by the following general formula (I-1-2). R 405 in formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. And an alkyl group having 2 or 3 carbon atoms is more preferred. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.
一般式（Ｉ－１－２）
Figure JPOXMLDOC01-appb-C000036
 Formula (I-1-2)
Figure JPOXMLDOC01-appb-C000036
　上記共重合体の重量平均分子量（Ｍｗ）は、１，５００以上５，０００以下がより好ましい。
　これらの界面活性剤は、１種単独でまたは２種以上を混合して使用することができる。 The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
These surfactants can be used individually by 1 type or in mixture of 2 or more types.
　本発明の感光性樹脂組成物が界面活性剤を含有する場合、界面活性剤の添加量は、感光性樹脂組成物中の全固形成分１００質量部に対し、１０質量部以下であることが好ましく、０．００１～１０質量部であることがより好ましく、０．０１～３質量部であることがさらに好ましい。界面活性剤は１種類のみ含んでいても良いし、２種類以上含んでいても良い。２種類以上含む場合は、合計量が上記範囲となることが好ましい。 When the photosensitive resin composition of the present invention contains a surfactant, the addition amount of the surfactant is preferably 10 parts by mass or less with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. 0.001 to 10 parts by mass is more preferable, and 0.01 to 3 parts by mass is even more preferable. Only one type of surfactant may be included, or two or more types of surfactants may be included. When two or more types are included, the total amount is preferably within the above range.
＜＜酸化防止剤＞＞
　本発明の感光性樹脂組成物は、酸化防止剤を含有してもよい。酸化防止剤としては、公知の酸化防止剤を含有することができる。酸化防止剤を添加することにより、硬化膜の着色を防止できる、または、分解による膜厚減少を低減でき、また、耐熱透明性に優れるという利点がある。
　このような酸化防止剤としては、例えば、リン系酸化防止剤、アミド類、ヒドラジド類、ヒンダードアミン系酸化防止剤、イオウ系酸化防止剤、フェノール系酸化防止剤、アスコルビン酸類、硫酸亜鉛、糖類、亜硝酸塩、亜硫酸塩、チオ硫酸塩、ヒドロキシルアミン誘導体などを挙げることができる。これらの中では、硬化膜の着色、膜厚減少の観点から特にフェノール系酸化防止剤、ヒンダードアミン系酸化防止剤、リン系酸化防止剤、アミド系酸化防止剤、ヒドラジド系酸化防止剤、イオウ系酸化防止剤が好ましく、フェノール系酸化防止剤が最も好ましい。これらは１種単独で用いてもよいし、２種以上を混合してもよい。
　具体例としては、特開２００５－２９５１５号公報の段落番号００２６～００３１に記載の化合物、特開２０１１-２２７１０６号公報の段落番号０１０６～０１１６に記載の化合物を挙げる事ができ、これらの内容は本願明細書に組み込まれる。
　好ましい市販品として、アデカスタブＡＯ－２０、アデカスタブＡＯ－６０、アデカスタブＡＯ－８０、アデカスタブＬＡ－５２、アデカスタブＬＡ－８１、アデカスタブＡＯ－４１２Ｓ、アデカスタブＰＥＰ－３６、イルガノックス１０３５、イルガノックス１０９８、チヌビン１４４を挙げる事ができる。 << Antioxidant >>
The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Among them, phenolic antioxidants, hindered amine antioxidants, phosphorus antioxidants, amide antioxidants, hydrazide antioxidants, sulfur oxidations are particularly preferred from the viewpoint of coloring of the cured film and reduction of the film thickness. Inhibitors are preferred, and phenolic antioxidants are most preferred. These may be used individually by 1 type and may mix 2 or more types.
Specific examples include the compounds described in paragraph numbers 0026 to 0031 of JP-A-2005-29515, and the compounds described in paragraph numbers 0106 to 0116 of JP-A-2011-227106. It is incorporated herein.
Preferred commercially available products are ADK STAB AO-20, ADK STAB AO-60, ADK STAB AO-80, ADK STAB LA-52, ADK STAB LA-81, ADK STAB AO-412S, ADK STAB PEP-36, IRGANOX 1035, IRGANOX 1098, and Tinuvin 144. Can be mentioned.
　本発明の感光性樹脂組成物が酸化防止剤を含有する場合、酸化防止剤の含有量は、感光性樹脂組成物中の全固形成分１００質量部に対し、０．１～１０質量部であることが好ましく、０．２～５質量部であることがより好ましく、０．５～４質量部であることが特に好ましい。この範囲にすることで、形成された膜の十分な透明性が得られ、且つ、パターン形成時の感度も良好となる。酸化防止剤は１種類のみ含んでいても良いし、２種類以上含んでいても良い。２種類以上含む場合は、合計量が上記範囲となることが好ましい。 When the photosensitive resin composition of the present invention contains an antioxidant, the content of the antioxidant is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. It is preferably 0.2 to 5 parts by mass, more preferably 0.5 to 4 parts by mass. By setting it within this range, sufficient transparency of the formed film can be obtained, and the sensitivity at the time of pattern formation becomes good. Only one type of antioxidant may be included, or two or more types may be included. When two or more types are included, the total amount is preferably within the above range.
＜＜酸増殖剤＞＞
　本発明の感光性樹脂組成物は、感度向上を目的に、酸増殖剤を用いることができる。
　本発明に用いることができる酸増殖剤は、酸触媒反応によってさらに酸を発生して反応系内の酸濃度を上昇させることができる化合物であり、酸が存在しない状態では安定に存在する化合物である。
　このような酸増殖剤の具体例としては、特開２０１１－２２１４９４の段落番号０２２６～０２２８に記載の酸増殖剤が挙げられ、この内容は本願明細書に組み込まれる。 << Acid Proliferator >>
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
Specific examples of such an acid proliferating agent include acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.
＜＜現像促進剤＞＞
　本発明の感光性樹脂組成物は、現像促進剤を含有することができる。
　現像促進剤としては、特開２０１２－０４２８３７号公報の段落番号０１７１～０１７２に記載されているものを参酌でき、この内容は本願明細書に組み込まれる。
　現像促進剤は、１種を単独で用いてもよいし、２種以上を併用することも可能である。
　本発明の感光性樹脂組成物が現像促進剤を含有する場合、現像促進剤の添加量は、感度と残膜率の観点から、感光性組成物の全固形分１００質量部に対し、０～３０質量部が好ましく、０．１～２０質量部がより好ましく、０．５～１０質量部であることが最も好ましい。２種類以上含む場合は、合計量が上記範囲となることが好ましい。
　また、その他の添加剤としては特開２０１２－８２２３号公報の段落番号０１２０～０１２１に記載の熱ラジカル発生剤、ＷＯ２０１１／１３６０７４Ａ１に記載の窒素含有化合物および熱酸発生剤も用いることができ、これらの内容は本願明細書に組み込まれる。 << Development accelerator >>
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, those described in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
When the photosensitive resin composition of the present invention contains a development accelerator, the addition amount of the development accelerator is from 0 to 100 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive composition from the viewpoint of sensitivity and residual film ratio. 30 parts by mass is preferable, 0.1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable. When two or more types are included, the total amount is preferably within the above range.
In addition, as other additives, thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, nitrogen-containing compounds and thermal acid generators described in WO2011-133604A1, can be used. Is incorporated herein by reference.
＜感光性樹脂組成物の調製方法＞
　各成分を所定の割合でかつ任意の方法で混合し、攪拌溶解して感光性樹脂組成物を調製する。例えば、成分を、それぞれ予め溶剤に溶解させた溶液とした後、これらを所定の割合で混合して樹脂組成物を調製することもできる。以上のように調製した組成物溶液は、例えば孔径０．２μｍのフィルター等を用いてろ過した後に、使用することもできる。 <Method for preparing photosensitive resin composition>
Each component is mixed at a predetermined ratio by an arbitrary method, and dissolved by stirring to prepare a photosensitive resin composition. For example, a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio. The composition solution prepared as described above can be used after being filtered using, for example, a filter having a pore diameter of 0.2 μm.
硬化膜の製造方法：
　本発明の硬化膜の製造方法は、以下の（１）～（５）の工程を含むことが好ましい。
　（１）本発明の感光性樹脂組成物を基板上に塗布する工程；
　（２）塗布された感光性樹脂組成物から溶剤を除去する工程；
　（３）溶剤が除去された感光性樹脂組成物を活性光線により露光する工程；
　（４）露光された感光性樹脂組成物を水性現像液により現像する工程；
　（５）現像された感光性樹脂組成物を熱硬化するポストベーク工程。
　以下に各工程を順に説明する。 Method for producing cured film:
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) The process of apply | coating the photosensitive resin composition of this invention on a board | substrate;
(2) A step of removing the solvent from the applied photosensitive resin composition;
(3) The process of exposing the photosensitive resin composition from which the solvent was removed with actinic rays;
(4) A step of developing the exposed photosensitive resin composition with an aqueous developer;
(5) A post-baking step of thermosetting the developed photosensitive resin composition.
Each step will be described below in order.
　（１）の塗布工程では、本発明の感光性樹脂組成物を基板上に塗布して溶剤を含む湿潤膜とすることが好ましい。感光性樹脂組成物を基板へ塗布する前にアルカリ洗浄やプラズマ洗浄といった基板の洗浄を行うことが好ましく、さらに基板洗浄後にヘキサメチルジシラザンで基板表面を処理することがより好ましい。この処理を行うことにより、感光性樹脂組成物の基板への密着性が向上する傾向にある。ヘキサメチルジシラザンで基板表面を処理する方法としては、特に限定されないが、例えば、ヘキサメチルジシラザン蒸気に中に基板を晒しておく方法等が挙げられる。
　上記の基板としては、無機基板、樹脂、樹脂複合材料などが挙げられる。
　無機基板としては、例えばガラス、石英、シリコン、シリコンナイトライド、および、それらのような基板上にモリブデン、チタン、アルミ、銅などを蒸着した複合基板が挙げられる。
　樹脂としては、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリスチレン、ポリカーボネート、ポリスルホン、ポリエーテルスルホン、ポリアリレート、アリルジグリコールカーボネート、ポリアミド、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリベンズアゾール、ポリフェニレンサルファイド、ポリシクロオレフィン、ノルボルネン樹脂、ポリクロロトリフルオロエチレン等のフッ素樹脂、液晶ポリマー、アクリル樹脂、エポキシ樹脂、シリコン樹脂、アイオノマー樹脂、シアネート樹脂、架橋フマル酸ジエステル、環状ポリオレフィン、芳香族エーテル、マレイミドーオレフィン、セルロース、エピスルフィド化合物等の合成樹脂からなる基板が挙げられる。
　これらの基板は、上記の形態のまま用いられる場合は少なく、通常、最終製品の形態によって、例えばＴＦＴ素子のような多層積層構造が形成されている。
　基板への塗布方法は特に限定されず、例えば、スリットコート法、スプレー法、ロールコート法、回転塗布法、流延塗布法、スリットアンドスピン法等の方法を用いることができる。
　塗布したときの湿潤膜厚は特に限定されるものではなく、用途に応じた膜厚で塗布することができるが、通常は０．５～１０μｍの範囲で使用される。
　さらに、基板に本発明で用いられる組成物を塗布する前に、特開２００９－１４５３９５号公報に記載されているような、所謂プリウェット法を適用することも可能である。 In the application step (1), the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the photosensitive resin composition to the substrate, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicon, silicon nitride, and a composite substrate in which molybdenum, titanium, aluminum, copper, or the like is vapor-deposited on such a substrate.
The resins include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyethersulfone, polyarylate, allyl diglycol carbonate, polyamide, polyimide, polyamideimide, polyetherimide, poly Fluorine resins such as benzazole, polyphenylene sulfide, polycycloolefin, norbornene resin, polychlorotrifluoroethylene, liquid crystal polymer, acrylic resin, epoxy resin, silicone resin, ionomer resin, cyanate resin, crosslinked fumaric acid diester, cyclic polyolefin, aromatic Substrates made of synthetic resins such as aromatic ethers, maleimide-olefins, cellulose, episulfide compounds, etc. It is below.
These substrates are rarely used in the above-described form, and usually a multilayer laminated structure such as a TFT element is formed depending on the form of the final product.
The coating method on the substrate is not particularly limited, and for example, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, a slit and spin method, or the like can be used.
The wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but it is usually used in the range of 0.5 to 10 μm.
Furthermore, before applying the composition used in the present invention to the substrate, it is possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
　（２）の溶剤除去工程では、塗布された上記の膜から、減圧（バキューム）および／または加熱等により、溶剤を除去して基板上に乾燥塗膜を形成させる。溶剤除去工程の加熱条件は、好ましくは７０～１３０℃で３０～３００秒間程度である。温度と時間が上記範囲である場合、パターンの密着性がより良好で、且つ残渣もより低減できる傾向にある。 (2) In the solvent removal step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.
　（３）の露光工程では、塗膜を設けた基板に所定のパターンの活性光線を照射する。この工程では、光酸発生剤が分解し酸が発生する。発生した酸の触媒作用により、塗膜成分中に含まれるアセタール基が加水分解されて、カルボキシル基またはフェノール性水酸基が生成する。
　活性光線による露光光源としては、低圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ＬＥＤ光源、エキシマレーザー発生装置などを用いることができ、ｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）、ｇ線（４３６ｎｍ）などの波長３００ｎｍ以上４５０ｎｍ以下の波長を有する活性光線が好ましく使用できる。また、必要に応じて長波長カットフィルター、短波長カットフィルター、バンドパスフィルターのような分光フィルターを通して照射光を調整することもできる。露光量は好ましくは１～５００ｍＪ／ｃｍ2である。
　露光装置としては、ミラープロジェクションアライナー、ステッパー、スキャナー、プロキシミティ、コンタクト、マイクロレンズアレイ、レンズスキャナ、レーザー露光、など各種方式の露光機を用いることができる。
　酸触媒の生成した領域において、上記の加水分解反応を加速させるために、露光後加熱処理：Ｐｏｓｔ　Ｅｘｐｏｓｕｒｅ　Ｂａｋｅ（以下、「ＰＥＢ」ともいう。）を行うことができる。ＰＥＢにより、アセタール基からのカルボキシル基またはフェノール性水酸基の生成を促進させることができる。ＰＥＢを行う場合の温度は、３０℃以上１３０℃以下であることが好ましく、４０℃以上１１０℃以下がより好ましく、５０℃以上１００℃以下が特に好ましい。
　ただし、本発明におけるアセタール基は、酸分解の活性化エネルギーが低く、露光による酸発生剤由来の酸により容易に分解し、カルボキシル基またはフェノール性水酸基を生じるため、必ずしもＰＥＢを行うことなく、現像によりポジ画像を形成することもできる。 In the exposure step (3), the substrate provided with the coating film is irradiated with an actinic ray having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acetal group contained in the coating film component is hydrolyzed to generate a carboxyl group or a phenolic hydroxyl group.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used, and i-line (365 nm), h-line (405 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as 436 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mJ / cm 2 .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, and a laser exposure can be used.
In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acetal group. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
However, the acetal group in the present invention has a low activation energy for acid decomposition and is easily decomposed by an acid derived from an acid generator by exposure to generate a carboxyl group or a phenolic hydroxyl group. Therefore, development is not necessarily performed without PEB. Thus, a positive image can also be formed.
　（４）の現像工程では、遊離したカルボキシル基またはフェノール性水酸基を有する共重合体を、アルカリ性現像液を用いて現像する。アルカリ性現像液に溶解しやすいカルボキシル基またはフェノール性水酸基を有する樹脂組成物を含む露光部領域を除去することにより、ポジ画像が形成する。
　現像工程で使用する現像液には、塩基性化合物が含まれることが好ましい。塩基性化合物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物類；炭酸ナトリウム、炭酸カリウムなどのアルカリ金属炭酸塩類；重炭酸ナトリウム、重炭酸カリウムなどのアルカリ金属重炭酸塩類；テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド、コリンヒドロキシド等のアンモニウムヒドロキシド類等のアンモニウムヒドロキシド類；ケイ酸ナトリウム、メタケイ酸ナトリウムなどの水溶液を使用することができる。また、上記アルカリ類の水溶液にメタノールやエタノールなどの水溶性有機溶剤や界面活性剤を適当量添加した水溶液を現像液として使用することもできる。
　好ましい現像液として、テトラメチルアンモニウムヒドロキシドの０．４～２．５％水溶液を挙げる事ができる。
　現像液のｐＨは、好ましくは１０．０～１４．０である。
　現像時間は、好ましくは３０～５００秒間であり、また、現像の手法は液盛り法（パドル法）、シャワー法、ディップ法等の何れでもよい。
　現像の後に、リンス工程を行うこともできる。リンス工程では、現像後の基板を純水などで洗うことで、付着している現像液除去、現像残渣除去を行う。リンス方法は公知の方法を用いることができる。例えばシャワーリンスやディップリンスなどを挙げる事ができる。 In the developing step (4), a copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
The developer used in the development step preferably contains a basic compound. Examples of the basic compound include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkalis such as sodium bicarbonate and potassium bicarbonate Metal bicarbonates; ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, and choline hydroxide; An aqueous solution of sodium silicate, sodium metasilicate, or the like can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
As a preferred developing solution, a 0.4 to 2.5% aqueous solution of tetramethylammonium hydroxide can be mentioned.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.
　（５）のポストベーク工程では、得られたポジ画像を加熱することにより、アセタール基を熱分解しカルボキシル基またはフェノール性水酸基を生成させ、架橋性基、架橋剤等と架橋させることにより、硬化膜を形成することができる。この加熱は、ホットプレートやオーブン等の加熱装置を用いて、所定の温度、例えば１８０～２５０℃で所定の時間、例えばホットプレート上なら５～９０分間、オーブンならば３０～１２０分間、加熱処理をすることが好ましい。このように架橋反応を進行させることにより、耐熱性、硬度等により優れた保護膜や層間絶縁膜を形成することができる。また、加熱処理を行う際は窒素雰囲気下で行うことにより、透明性をより向上させることもできる。
　ポストベークの前に、比較的低温でベークを行った後にポストベークすることもできる（ミドルベーク工程の追加）。ミドルベークを行う場合は、９０～１５０℃で１～６０分加熱した後に、２００℃以上の高温でポストベークすることが好ましい。また、ミドルベーク、ポストベークを３段階以上の多段階に分けて加熱する事もできる。このようなミドルベーク、ポストベークの工夫により、パターンのテーパー角を調整することができる。これらの加熱は、ホットプレート、オーブン、赤外線ヒーターなど、公知の加熱方法を使用することができる。
　なお、ポストベークに先立ち、パターンを形成した基板に活性光線により全面再露光（ポスト露光）した後、ポストベークすることにより未露光部分に存在する光酸発生剤から酸を発生させ、架橋工程を促進する触媒として機能させることができ、膜の硬化反応を促進することができる。ポスト露光工程を含む場合の好ましい露光量としては、１００～３，０００ｍＪ／ｃｍ2が好ましく、１００～５００ｍＪ／ｃｍ2が特に好ましい。 In the post-baking step of (5), the obtained positive image is heated to thermally decompose the acetal group to generate a carboxyl group or a phenolic hydroxyl group, and to cure by crosslinking with a crosslinking group, a crosslinking agent or the like. A film can be formed. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 250 ° C. for a predetermined time, for example, 5 to 90 minutes on the hot plate, 30 to 120 minutes for the oven. It is preferable to By proceeding the crosslinking reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like can be formed. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When middle baking is performed, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. The preferred exposure amount in the case of including a post-exposure step, preferably 100 ~ 3,000mJ / cm 2, particularly preferably 100 ~ 500mJ / cm 2.
　さらに、本発明の感光性樹脂組成物より得られた硬化膜は、ドライエッチングレジストとして使用することもできる。ポストベーク工程により熱硬化して得られた硬化膜をドライエッチングレジストとして使用する場合、エッチング処理としてはアッシング、プラズマエッチング、オゾンエッチングなどのドライエッチング処理を行うことができる。 Furthermore, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. In the case where a cured film obtained by thermal curing in a post-baking process is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.
硬化膜：
　本発明の硬化膜は、上述した本発明の組成物を硬化して得られた硬化膜である。
　本発明の硬化膜は、層間絶縁膜として好適に用いることができる。また、本発明の硬化膜は、上述した本発明の硬化膜の形成方法により得られた硬化膜であることが好ましい。
　本発明の感光性樹脂組成物により、絶縁性に優れ、高温でベークされた場合においても高い透明性を有する層間絶縁膜が得られる。本発明の感光性樹脂組成物を用いてなる層間絶縁膜は、高い透明性を有し、硬化膜物性に優れるため、液晶表示装置や有機ＥＬ表示装置の用途に有用である。 Cured film:
The cured film of the present invention is a cured film obtained by curing the above-described composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention mentioned above.
With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film properties, it is useful for liquid crystal display devices and organic EL display devices.
液晶表示装置：
　本発明の液晶表示装置は、本発明の硬化膜を有することを特徴とする。
　本発明の液晶表示装置としては、上記本発明の感光性樹脂組成物を用いて形成される平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の液晶表示装置を挙げることができる。
　例えば、本発明の液晶表示装置が具備するＴＦＴ（Ｔｈｉｎ－Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ）の具体例としては、アモルファスシリコン－ＴＦＴ、低温ポリシリコンーＴＦＴ、酸化物半導体ＴＦＴ等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのＴＦＴに組み合わせて好ましく用いることができる。
　また、本発明の液晶表示装置が取りうる液晶駆動方式としてはＴＮ（ＴｗｉｓｔｅｄＮｅｍａｔｉｃ）方式、ＶＡ（Ｖｉｒｔｉｃａｌ　Ａｌｉｇｎｍｅｎｔ）方式、ＩＰＳ（Ｉｎ－Ｐｌａｃｅ－Ｓｗｉｔｃｈｉｎｇ）方式、ＦＦＳ（Ｆｒｉｎｇｓ　Ｆｉｅｌｄ　Ｓｗｉｔｃｈｉｎｇ）方式、ＯＣＢ（Ｏｐｔｉｃａｌ　Ｃｏｍｐｅｎｓａｔｅｄ　Ｂｅｎｄ）方式などが挙げられる。
　パネル構成においては、ＣＯＡ（Ｃｏｌｏｒ　Ｆｉｌｔｅｒ　ｏｎ　Ａｌｌａｙ）方式の液晶表示装置でも本発明の硬化膜を用いることができ、例えば、特開２００５－２８４２９１の有機絶縁膜（１１５）や、特開２００５－３４６０５４の有機絶縁膜（２１２）として用いることができる。また、本発明の液晶表示装置が取りうる液晶配向膜の具体的な配向方式としてはラビング配向法、光配向方などが挙げられる。また、特開２００３－１４９６４７号公報や特開２０１１－２５７７３４号公報に記載のＰＳＡ（Ｐｏｌｙｍｅｒ　Ｓｕｓｔａｉｎｅｄ　Ａｌｉｇｎｍｅｎｔ）技術によってポリマー配向支持されていてもよい。
　また、本発明の感光性樹脂組成物および本発明の硬化膜は、上記用途に限定されず種々の用途に使用することができる。例えば、平坦化膜や層間絶縁膜以外にも、カラーフィルターの保護膜や、液晶表示装置における液晶層の厚みを一定に保持するためのスペーサーや固体撮像素子においてカラーフィルター上に設けられるマイクロレンズ等に好適に用いることができる。
　図１は、アクティブマトリックス方式の液晶表示装置１０の一例を示す概念的断面図である。このカラー液晶表示装置１０は、背面にバックライトユニット１２を有する液晶パネルであって、液晶パネルは、偏光フィルムが貼り付けられた２枚のガラス基板１４，１５の間に配置されたすべての画素に対応するＴＦＴ１６の素子が配置されている。ガラス基板上に形成された各素子には、硬化膜１７中に形成されたコンタクトホール１８を通して、画素電極を形成するＩＴＯ透明電極１９が配線されている。ＩＴＯ透明電極１９の上には、液晶２０の層とブラックマトリックスを配置したＲＧＢカラーフィルター２２が設けられている。
　バックライトの光源としては、特に限定されず公知の光源を用いることができる。例えば白色ＬＥＤ、青色・赤色・緑色などの多色ＬＥＤ、蛍光灯（冷陰極管）、有機ＥＬなどを挙げる事ができる。
　また、液晶表示装置は、３Ｄ（立体視）型のものとしたり、タッチパネル型のものとしたりすることも可能である。さらにフレキシブル型にすることも可能であり、特開２０１１－１４５６８６号公報に記載の第２層間絶縁膜（４８）や、特開２００９－２５８７５８号公報に記載の層間絶縁膜（５２０）として用いることができる。 Liquid crystal display:
The liquid crystal display device of the present invention has the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal displays having various structures. An apparatus can be mentioned.
For example, specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
In addition, as a liquid crystal driving method that can be adopted by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (Optical) method. Compensated Bend) method and the like.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of JP-A-2005-284291, It can be used as an organic insulating film (212). Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a micro lens provided on the color filter in the solid-state image sensor Can be suitably used.
FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and used as the second interlayer insulating film (48) described in Japanese Patent Application Laid-Open No. 2011-145686 and the interlayer insulating film (520) described in Japanese Patent Application Laid-Open No. 2009-258758. Can do.
有機ＥＬ表示装置：
　本発明の有機ＥＬ表示装置は、本発明の硬化膜を有することを特徴とする。
　本発明の有機ＥＬ表示装置としては、上記本発明の感光性樹脂組成物を用いて形成される平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の各種有機ＥＬ表示装置や液晶表示装置を挙げることができる。
　例えば、本発明の有機ＥＬ表示装置が具備するＴＦＴ（Ｔｈｉｎ－Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ）の具体例としては、アモルファスシリコン－ＴＦＴ、低温ポリシリコンーＴＦＴ、酸化物半導体ＴＦＴ等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのＴＦＴに組み合わせて好ましく用いることができる。
　図２は、有機ＥＬ表示装置の一例の構成概念図である。ボトムエミッション型の有機ＥＬ表示装置における基板の模式的断面図を示し、平坦化膜４を有している。
　ガラス基板６上にボトムゲート型のＴＦＴ１を形成し、このＴＦＴ１を覆う状態でＳｉ3Ｎ4から成る絶縁膜３が形成されている。絶縁膜３に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してＴＦＴ１に接続される配線２（高さ１．０μｍ）が絶縁膜３上に形成されている。配線２は、ＴＦＴ１間または、後の工程で形成される有機ＥＬ素子とＴＦＴ１とを接続するためのものである。
　さらに、配線２の形成による凹凸を平坦化するために、配線２による凹凸を埋め込む状態で絶縁膜３上に平坦化膜４が形成されている。
　平坦化膜４上には、ボトムエミッション型の有機ＥＬ素子が形成されている。すなわち、平坦化膜４上に、ＩＴＯからなる第一電極５が、コンタクトホール７を介して配線２に接続させて形成されている。また、第一電極５は、有機ＥＬ素子の陽極に相当する。
　第一電極５の周縁を覆う形状の絶縁膜８が形成されており、この絶縁膜８を設けることによって、第一電極５とこの後の工程で形成する第二電極との間のショートを防止することができる。
　さらに、図２には図示していないが、所望のパターンマスクを介して、正孔輸送層、有機発光層、電子輸送層を順次蒸着して設け、次いで、基板上方の全面にＡｌから成る第二電極を形成し、封止用ガラス板と紫外線硬化型エポキシ樹脂を用いて貼り合わせることで封止し、各有機ＥＬ素子にこれを駆動するためのＴＦＴ１が接続されてなるアクティブマトリックス型の有機ＥＬ表示装置が得られる。 Organic EL display:
The organic EL display device of the present invention has the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 2 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening film 4 is formed on the insulating film 3 with the unevenness due to the wiring 2 being embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.
　本発明の感光性樹脂組成物は、硬化性および硬化膜特性に優れるため、ＭＥＭＳデバイスの構造部材として、本発明の感光性樹脂組成物を用いて形成されたレジストパターンを隔壁としたり、機械駆動部品の一部として組み込んで使用される。このようなＭＥＭＳ用デバイスとしては、例えばＳＡＷフィルター、ＢＡＷフィルター、ジャイロセンサー、ディスプレイ用マイクロシャッター、イメージセンサー、電子ペーパー、インクジェットヘッド、バイオチップ、封止剤等の部品が挙げられる。より具体的な例は、特表２００７－５２２５３１、特開２００８－２５０２００、特開２００９－２６３５４４等に例示されている。 Since the photosensitive resin composition of the present invention is excellent in curability and cured film characteristics, a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a MEMS device can be used as a partition wall or mechanically driven. Used as part of the part. Examples of such MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.
　本発明の感光性樹脂組成物は、平坦性や透明性に優れるため、例えば特開２０１１－１０７４７６号公報の図２に記載のバンク層（１６）および平坦化膜（５７）、特開２０１０－９７９３号公報の図４（ａ）に記載の隔壁（１２）および平坦化膜（１０２）、特開２０１０－２７５９１号公報の図１０に記載のバンク層（２２１）および第３層間絶縁膜（２１６ｂ）、特開２００９－１２８５７７号公報の図４（ａ）に記載の第２層間絶縁膜（１２５）および第３層間絶縁膜（１２６）、特開２０１０－１８２６３８号公報の図３に記載の平坦化膜（１２）および画素分離絶縁膜（１４）などの形成に用いることもできる。この他、液晶表示装置における液晶層の厚みを一定に保持するためのスペーサーや、ファクシミリ、電子複写機、固体撮像素子等のオンチップカラーフィルターの結像光学系あるいは光ファイバコネクタのマイクロレンズにも好適に用いることができる。 Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010- The partition wall (12) and the planarization film (102) described in FIG. 4 (a) of Japanese Patent No. 9793, the bank layer (221) and the third interlayer insulating film (216b) described in FIG. 10 of Japanese Patent Application Laid-Open No. 2010-27591. ), The second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and the flatness described in FIG. 3 of JP-A-2010-182638. It can also be used to form a chemical film (12) and a pixel isolation insulating film (14). In addition, spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices, imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。 The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.
　以下の合成例において、以下の符号はそれぞれ以下の化合物を表す。
ＭＡＴＨＦ：２－テトラヒドロフラニルメタクリレート（合成品）
ＭＡＥＶＥ：１－エトキシエチルメタクリレート（和光純薬工業製）
ＳｔＯＥＶＥ:４－（１－エトキシエチルオキシ）スチレン
ＯＸＥ－３０：３－エチル－３－オキセタニルメチルメタクリレート（大阪有機化学工業製）
ＧＭＡ：グリシジルメタクリレート（和光純薬工業製）
ＮＢＭＡ：ｎ－ブトキシメチルアクリルアミド（東京化成製）
ＨＥＭＡ：ヒドロキシエチルメタクリレート（和光純薬社製）
ＭＡＡ：メタクリル酸（和光純薬工業製）
ＭＭＡ：メチルメタクリレート（和光純薬工業製）
Ｓｔ：スチレン（和光純薬工業製）
ＤＣＰＭ：ジシクロペンタニルメタクリレート
ＳｔＯＨ:４－ヒドロキシスチレン
Ｖ－６０１：ジメチル－２，２’－アゾビス（２－メチルプロピオネート）（和光純薬工業製）
Ｖ－６５：２，２‘－アゾビス（２，４－ジメチルバレロニトリル）（和光純薬工業製）
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセタート
ＭＥＤＧ：メチルエチルジグリコール In the following synthesis examples, the following symbols represent the following compounds, respectively.
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries)
StOEVE: 4- (1-ethoxyethyloxy) styrene OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry)
GMA: Glycidyl methacrylate (manufactured by Wako Pure Chemical Industries)
NBMA: n-butoxymethylacrylamide (manufactured by Tokyo Chemical Industry)
HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries)
MMA: Methyl methacrylate (Wako Pure Chemical Industries)
St: Styrene (manufactured by Wako Pure Chemical Industries)
DCPM: Dicyclopentanyl methacrylate StOH: 4-hydroxystyrene V-601: Dimethyl-2,2′-azobis (2-methylpropionate) (manufactured by Wako Pure Chemical Industries)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate MEDG: Methyl ethyl diglycol
＜ＭＡＴＨＦの合成＞
　メタクリル酸（８６ｇ、１ｍｏｌ）を１５℃に冷却しておき、カンファースルホン酸（４．６ｇ、０．０２ｍｏｌ）添加した。その溶液に、２－ジヒドロフラン（７１ｇ、１ｍｏｌ、１．０当量）を滴下した。１時間攪拌した後に、飽和炭酸水素ナトリウム（５００ｍＬ）を加え、酢酸エチル（５００ｍＬ）で抽出し、硫酸マグネシウムで乾燥後、不溶物を濾過後４０℃以下で減圧濃縮し、残渣の黄色油状物を減圧蒸留して沸点（ｂｐ．）５４～５６℃／３．５ｍｍＨｇ留分のメタクリル酸テトラヒドロ－２Ｈ－フラン－２－イル（ＭＡＴＨＦ）１２５ｇを無色油状物として得た（収率８０％）。 <Synthesis of MATHF>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium hydrogen carbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, filtered, and the insoluble material was filtered and concentrated under reduced pressure at 40 ° C. or lower. Distillation under reduced pressure afforded 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.
＜重合体Ｐ－１の合成例＞
　３つ口フラスコにＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）（８９ｇ）を入れ、窒素雰囲気下において９０℃に昇温した。その溶液にＭＡＡ（全単量体成分中の９．５ｍｏｌ％となる量）、ＭＡＴＨＦ（全単量体成分中の４３ｍｏｌ％となる量）、ＧＭＡ（全単量体成分中の４７．５ｍｏｌ％に相当）、Ｖ－６５（全単量体成分の合計１００ｍｏｌ％に対して４ｍｏｌ％に相当）を溶解させ、２時間かけて滴下した。滴下終了後２時間攪拌し、反応を終了させた。それにより重合体Ｐ－１を得た。なお、溶剤以外の成分（固形分と称する。）の濃度が４０質量％になるよう調整した。
　モノマー種類等を下記表に示す通りに変更し、他の重合体を合成した。 <Synthesis Example of Polymer P-1>
PGMEA (propylene glycol monomethyl ether acetate) (89 g) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. MAA (amount to be 9.5 mol% in all monomer components), MATH (amount to be 43 mol% in all monomer components), GMA (47.5 mol% in all monomer components) V-65 (corresponding to 4 mol% with respect to the total of 100 mol% of all monomer components) was dissolved and added dropwise over 2 hours. After completion of the dropwise addition, the reaction was terminated by stirring for 2 hours. Thereby, a polymer P-1 was obtained. In addition, it adjusted so that the density | concentration of components (referred to as solid content) other than a solvent might be 40 mass%.
Monomers and the like were changed as shown in the following table, and other polymers were synthesized.
Figure JPOXMLDOC01-appb-T000037
Figure JPOXMLDOC01-appb-T000037
　上記表において、表中の（ａ１）～（ａ３）の単量体成分は、モル比である。重合開始剤および添加剤の数値は、単量体成分を１００ｍｏｌに対するｍｏｌ比である。固形分濃度は、モノマー質量／（モノマー質量＋溶剤質量）×１００（単位質量％）として示している。重合開始剤としてＶ－６０１を用いた場合は、反応温度は９０℃、Ｖ－６５を用いた場合は７０℃を反応温度とした。 In the above table, the monomer components (a1) to (a3) in the table are molar ratios. The numerical values of the polymerization initiator and the additive are the molar ratio of the monomer component to 100 mol. The solid content concentration is shown as monomer mass / (monomer mass + solvent mass) × 100 (unit mass%). When V-601 was used as the polymerization initiator, the reaction temperature was 90 ° C., and when V-65 was used, the reaction temperature was 70 ° C.
＜Ｂ－１の合成＞
　窒素雰囲気下、３口フラスコに、４－ブロモナフタル酸無水物９．２９ｇ、ジメチルスルホキシド３４ｇ、１，４－ジアザビシクロ[２．２．２]オクタン４．１４ｇを添加し、オクタンチオール５．１４ｇを３０℃以下で滴下し、４０℃で５時間攪拌した。反応液にメタノール７０ｍＬを入れて氷冷し、３０分攪拌後、析出した結晶をろ取、乾燥して、中間体Ｂ－１Ａを８．６５ｇ得た。
　続いて、窒素雰囲気下、３口フラスコに、Ｂ－１Ａを８．２１ｇ、ジメチルホルムアミド２７．５ｇ、塩酸ヒドロキシルアミン２．００ｇを添加して、４８重量％水酸化ナトリウム水溶液２．４０ｇを３０℃以下で滴下し、室温で２時間攪拌した。反応液に蒸留水３０ｍLを添加して氷冷し、３０分攪拌後、濃塩酸１．００ｇを添加してさらに１時間攪拌した。析出した結晶をろ取、乾燥して、中間体Ｂ－１Ｂを８．３５ｇ得た。
　３口フラスコに、Ｂ－１Ｂを３．５７ｇ、ジクロロメタン２５ｇ、ピリジン１．０３ｇを添加して攪拌後、トリフルオロメタンスルホン酸無水物２．９６ｇを１５～２０℃で滴下し、２５℃で３時間攪拌した。反応液に蒸留水２０ｍLとジクロロメタン２０ｇを添加して攪拌し、分液後、ジクロロメタン層を０．２５重量％水酸化ナトリウム水溶液３０ｍLで２回、５重量％塩酸水溶液３０ｍLで１回、蒸留水４０ｍLで３回水洗した。有機層を濃縮後、ｎ－ヘプタン２５ｇを添加して攪拌し、析出した結晶をろ取、乾燥してＢ－１を３．８３ｇ得た。 <Synthesis of B-1>
Under a nitrogen atmosphere, 9.29 g of 4-bromonaphthalic anhydride, 34 g of dimethyl sulfoxide, and 4.14 g of 1,4-diazabicyclo [2.2.2] octane were added to a three-necked flask, and 5.14 g of octanethiol was added to 30 g. The solution was added dropwise at a temperature of not higher than ° C. and stirred at 40 ° C. for 5 hours. 70 mL of methanol was added to the reaction solution and the mixture was ice-cooled and stirred for 30 minutes. The precipitated crystals were collected by filtration and dried to obtain 8.65 g of Intermediate B-1A.
Subsequently, 8.21 g of B-1A, 27.5 g of dimethylformamide, and 2.00 g of hydroxylamine hydrochloride were added to a three-necked flask in a nitrogen atmosphere, and 2.40 g of a 48 wt% aqueous sodium hydroxide solution was added to 30 ° C. The solution was added dropwise below and stirred at room temperature for 2 hours. Distilled water (30 mL) was added to the reaction solution, and the mixture was ice-cooled. After stirring for 30 minutes, 1.00 g of concentrated hydrochloric acid was added and the mixture was further stirred for 1 hour. The precipitated crystals were collected by filtration and dried to obtain 8.35 g of intermediate B-1B.
To a three-necked flask, 3.51 g of B-1B, 25 g of dichloromethane and 1.03 g of pyridine were added and stirred, and 2.96 g of trifluoromethanesulfonic anhydride was added dropwise at 15 to 20 ° C. Stir. Distilled water (20 mL) and dichloromethane (20 g) were added to the reaction mixture and stirred. After separation, the dichloromethane layer was twice with 0.25 wt% aqueous sodium hydroxide solution (30 mL), 5 wt% aqueous hydrochloric acid solution (30 mL) once, and distilled water (40 mL). And washed three times with water. After the organic layer was concentrated, 25 g of n-heptane was added and stirred, and the precipitated crystals were collected by filtration and dried to obtain 3.83 g of B-1.
＜Ｂ－２～Ｂ－１８の合成＞
　Ｂ－１と同様に、対応する酸無水物中間体を合成し、塩酸ヒドロキシルアミンでイミド体へと誘導後、スルホン酸エステル化することで、Ｂ－２～Ｂ－１８を合成した。 <Synthesis of B-2 to B-18>
Similarly to B-1, the corresponding acid anhydride intermediate was synthesized, derivatized with hydroxylamine hydrochloride to an imide, and then sulfonated to synthesize B-2 to B-18.
＜感光性樹脂組成物の調製＞
　下記表に記載の固形分比となるように各成分を秤量し、溶剤（ＰＧＭＥＡ：ＭＥＤＧ＝１：１）に固形分濃度１５％になるまで溶解混合し、口径０．２μｍのポリテトラフルオロエチレン製フィルターで濾過して、各種実施例および比較例の感光性樹脂組成物を得た。 <Preparation of photosensitive resin composition>
Each component is weighed so as to have the solid content ratio shown in the following table, dissolved and mixed in a solvent (PGMEA: MEDG = 1: 1) until the solid content concentration becomes 15%, and polytetrafluoroethylene having a diameter of 0.2 μm. It filtered with the filter made from, and obtained the photosensitive resin composition of various Examples and a comparative example.
　実施例および比較例に用いた各化合物を示す略号の詳細は、以下の通りである。
（一般式（Ｉ）で表される光酸発生剤）
Ｂ－１～Ｂ－１７：下記構造の化合物
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
 The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.
(Photoacid generator represented by general formula (I))
B-1 to B-17: Compounds having the following structures
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Ｂ－１’～Ｂ－３’：下記構造の化合物
Figure JPOXMLDOC01-appb-C000041
 B-1 ′ to B-3 ′: Compounds having the following structures
Figure JPOXMLDOC01-appb-C000041
（塩基性化合物）
Ｃ－１：下記構造の化合物
Figure JPOXMLDOC01-appb-C000042
 Ｃ－２：１,８－ジアザビシクロ[５.４.０]-７-ウンデセン
Ｃ－３：トリフェニルイミダゾール (Basic compound)
C-1: Compound having the following structure
Figure JPOXMLDOC01-appb-C000042
 C-2: 1,8-diazabicyclo [5.4.0] -7-undecene C-3: triphenylimidazole
（アルコキシシラン化合物）
Ｄ－１：γ－グリシドキシプロピルトリメトキシシラン（ＫＢＭ－４０３:信越化学製） (Alkoxysilane compound)
D-1: γ-Glycidoxypropyltrimethoxysilane (KBM-403: manufactured by Shin-Etsu Chemical)
（界面活性剤）
Ｅ－１：下記構造式で示されるパーフルオロアルキル基含有ノニオン界面活性剤（Ｆ－５５４，ＤＩＣ製）
Figure JPOXMLDOC01-appb-C000043
 (Surfactant)
E-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC)
Figure JPOXMLDOC01-appb-C000043
（その他の添加剤）
Ｆ－１：ＪＥＲ８２８（（株）三菱ケミカルホールディングス製）
Ｆ－２：ＪＥＲ１００７（（株）三菱ケミカルホールディングス製）
Ｆ－３：ＪＥＲ１５７Ｓ６５（（株）三菱ケミカルホールディングス製）
Ｇ－１：アデカスタブＡＯ－６０（（株）ＡＤＥＫＡ製）
Ｇ－２：イルガノックス１０３５（ＢＡＳＦ製）
Ｇ－３：イルガノックス１０９８（ＢＡＳＦ製） (Other additives)
F-1: JER828 (manufactured by Mitsubishi Chemical Holdings Corporation)
F-2: JER1007 (manufactured by Mitsubishi Chemical Holdings Corporation)
F-3: JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation)
G-1: ADK STAB AO-60 (manufactured by ADEKA Corporation)
G-2: Irganox 1035 (manufactured by BASF)
G-3: Irganox 1098 (manufactured by BASF)
＜評価項目＞
（感度）実施例１～２７および比較例１～３
　ガラス基板（コーニング１７３７、０．７ｍｍ厚（コーニング社製））上に、各感光性樹脂組成物をスリット塗布した後、９０℃／１２０秒ホットプレート上でプリベークして溶剤を揮発させ、膜厚３．０μｍの感光性樹脂組成物層を形成した。
　次に、得られた感光性樹脂組成物層を、キヤノン（株）製　ＭＰＡ　５５００ＣＦ（高圧水銀灯）を用いて、所定のマスクを介して露光した。そして、露光後の感光性組成物層を、アルカリ現像液（０．４重量％のテトラメチルアンモニウムヒドロキシド水溶液）で２３℃／６０秒間現像した後、超純水で２０秒リンスした。
　これらの操作により１０μｍのラインアンドスペースを１：１で解像する時の最適ｉ線露光量（Ｅｏｐｔ）を感度とした。
　１：４０ｍＪ／ｃｍ2未満
　２：４０ｍＪ／ｃｍ2以上８０ｍＪ／ｃｍ2未満
　３：８０ｍＪ／ｃｍ2以上１６０ｍＪ／ｃｍ2未満
　４：１６０ｍＪ／ｃｍ2以上 <Evaluation items>
(Sensitivity) Examples 1-27 and Comparative Examples 1-3
Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (Corning)), then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent, and the film thickness A photosensitive resin composition layer having a thickness of 3.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive composition layer was developed with an alkali developer (0.4 wt% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
By these operations, the optimum i-line exposure (Eopt) when resolving 10 μm line and space at 1: 1 was defined as sensitivity.
1: 40mJ / cm 2 less than 2: 40mJ / cm 2 or more 80 mJ / cm 2 less than 3: 80mJ / cm 2 or more 160 mJ / cm 2 less than 4: 160mJ / cm 2 or more
（感度）実施例２８および２９
 ガラス基板（コーニング１７３７、０．７ｍｍ厚（コーニング社製））上に、各感光性樹脂組成物をスリット塗布した後、９０℃／１２０秒ホットプレート上でプリベークして溶剤を揮発させ、膜厚３．０μｍの感光性樹脂組成物層を形成した。
　次に、得られた感光性樹脂組成物層を、キヤノン（株）製　ＭＰＡ　５５００ＣＦ（高圧水銀灯）を用いて、所定のマスクを介して露光した。そして、露光後の感光性組成物層を、アルカリ現像液（２．３８重量％のテトラメチルアンモニウムヒドロキシド水溶液）で２３℃／６０秒間現像した後、超純水で２０秒リンスした。
　これらの操作により１０μｍのラインアンドスペースを１：１で解像する時の最適ｉ線露光量（Ｅｏｐｔ）を感度とした。
　１：４０ｍＪ／ｃｍ2未満
　２：４０ｍＪ／ｃｍ2以上８０ｍＪ／ｃｍ2未満
　３：８０ｍＪ／ｃｍ2以上１６０ｍＪ／ｃｍ2未満
　４：１６０ｍＪ／ｃｍ2以上 (Sensitivity) Examples 28 and 29
Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (Corning)), then pre-baked on a hot plate at 90 ° C. for 120 seconds to volatilize the solvent, and the film thickness A photosensitive resin composition layer having a thickness of 3.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive composition layer was developed with an alkali developer (2.38 wt% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
By these operations, the optimum i-line exposure (Eopt) when resolving 10 μm line and space at 1: 1 was defined as sensitivity.
1: 40mJ / cm 2 less than 2: 40mJ / cm 2 or more 80 mJ / cm 2 less than 3: 80mJ / cm 2 or more 160 mJ / cm 2 less than 4: 160mJ / cm 2 or more
（体積抵抗率）
　アルミ基板上に材料を塗布したのち、９０℃で２分乾燥後、超高圧水銀灯で３００ｍJ露光し、更に、２３０℃で３０分オーブンで加熱し、膜厚３μｍの硬化膜を形成した。この硬化膜上にアルミ蒸着を行ったものを体積抵抗率測定用サンプルとした。
　上記体積抵抗率測定用サンプルを２３℃、６０％ＲＨ、２４ｈ調湿した後、ＵＬＴＲＡ ＨＩＧＨ ＲＥＳＩＳＴＡＮＣＥ ＭＥＴＥＲ（ＡＤＶＡＮＴＥＳＴ製）にて体積抵抗率測定を行った。測定方法はＪＩＳ Ｋ６９１１に準拠し、印加電圧１０Ｖ、１分で体積抵抗測定値（Ω）を測定した。本測定値と、アルミ電極の面積及び試料厚みより、体積抵抗率（Ω・ｃｍ）を算出した。
　評価基準は以下の通りであり、１または２が実用上好ましい。
　１：１×１０×16Ω・ｃｍ以上
　２：５×１０×15Ω・ｃｍ以上１×１０16Ω・ｃｍ未満
　３：１×１０×15Ω・ｃｍ以上５×１０15Ω・ｃｍ未満
　４：１×１０×15Ω・ｃｍ未満 (Volume resistivity)
After coating the material on the aluminum substrate, it was dried at 90 ° C. for 2 minutes, exposed to 300 mJ with an ultrahigh pressure mercury lamp, and further heated in an oven at 230 ° C. for 30 minutes to form a cured film having a thickness of 3 μm. A sample obtained by depositing aluminum on the cured film was used as a sample for measuring volume resistivity.
The volume resistivity measurement sample was conditioned at 23 ° C., 60% RH, and 24 h, and then volume resistivity measurement was performed using ULTRA HIGH RESISTANCE METER (manufactured by ADVANTEST). The measurement method was based on JIS K6911, and the volume resistance measurement value (Ω) was measured at an applied voltage of 10 V for 1 minute. The volume resistivity (Ω · cm) was calculated from the measured value, the area of the aluminum electrode, and the sample thickness.
The evaluation criteria are as follows, and 1 or 2 is practically preferable.
1: 1 × 10 × 16 Ω · cm or more 2: 5 × 10 × 15 Ω · cm or more and less than 1 × 10 16 Ω · cm 3: 1 × 10 × 15 Ω · cm or more and less than 5 × 10 15 Ω · cm 4 : Less than 1 × 10 × 15 Ω · cm
Figure JPOXMLDOC01-appb-T000044
Figure JPOXMLDOC01-appb-T000044
　上記表から、光酸発生剤として一般式（Ｉ）で表される化合物を用いた実施例１～２９は、高感度であり、体積抵抗率も向上していることが分かる。一方、一般式（Ｉ）で表される化合物でない光酸発生剤を用いた比較例１～３は、いずれも体積抵抗率が劣っており、比較例２は感度も劣っていることが分かる。
　また、一般式（Ｉ）中のＲ3にハロゲン原子が置換していると、感度と体積抵抗率がより向上することが分かる。 From the above table, it can be seen that Examples 1 to 29 using the compound represented by the general formula (I) as the photoacid generator have high sensitivity and improved volume resistivity. On the other hand, it can be seen that Comparative Examples 1 to 3 using a photoacid generator other than the compound represented by the general formula (I) are inferior in volume resistivity, and Comparative Example 2 is inferior in sensitivity.
It can also be seen that the sensitivity and volume resistivity are further improved when a halogen atom is substituted for R 3 in the general formula (I).
＜表示装置の作製＞
（実施例１０１）
　薄膜トランジスター（ＴＦＴ）を用いた有機ＥＬ表示装置を以下の方法で作製した（図２参照）。
　ガラス基板６上にボトムゲート型のＴＦＴ１を形成し、このＴＦＴ１を覆う状態でＳｉ3Ｎ4から成る絶縁膜３を形成した。次に、この絶縁膜３に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してＴＦＴ１に接続される配線２（高さ１．０μｍ）を絶縁膜３上に形成した。この配線２は、ＴＦＴ１間または、後の工程で形成される有機ＥＬ素子とＴＦＴ１とを接続するためのものである。
　さらに、配線２の形成による凹凸を平坦化するために、配線２による凹凸を埋め込む状態で絶縁膜３上へ平坦化膜４を形成した。絶縁膜３上への平坦化膜４の形成は、実施例１の感光性樹脂組成物を基板上にスリット塗布し、ホットプレート上でプリベーク（９０℃×２分）した後、マスク上から高圧水銀灯を用いてｉ線（３６５ｎｍ）を４５ｍＪ／ｃｍ2（照度２０ｍＷ／ｃｍ2）照射した後、アルカリ水溶液にて現像してパターンを形成し、２３０℃で６０分間の加熱処理を行った。
　感光性樹脂組成物を塗布する際の塗布性は良好で、露光、現像、焼成の後に得られた硬化膜には、しわやクラックの発生は認められなかった。さらに、配線２の平均段差は５００ｎｍ、作製した平坦化膜４の膜厚は２，０００ｎｍであった。
　次に、得られた平坦化膜４上に、ボトムエミッション型の有機ＥＬ素子を形成した。まず、平坦化膜４上に、ＩＴＯからなる第一電極５を、コンタクトホール７を介して配線２に接続させて形成した。その後、市販のレジストを塗布、プリベークし、所望のパターンのマスクを介して露光し、現像した。このレジストパターンをマスクとして、ＩＴＯエッチャント用いたウエットエッチングによりパターン加工を行った。その後、レジスト剥離液（リムーバ１００、ＡＺエレクトロニックマテリアルズ社製）を用いてレジストパターンを５０℃で剥離した。こうして得られた第一電極５は、有機ＥＬ素子の陽極に相当する。 <Production of display device>
(Example 101)
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by slit-coating the photosensitive resin composition of Example 1 on the substrate, prebaking (90 ° C. × 2 minutes) on a hot plate, and then applying high pressure from above the mask. After irradiating 45 mJ / cm 2 (illuminance 20 mW / cm 2 ) with i-line (365 nm) using a mercury lamp, a pattern was formed by developing with an alkaline aqueous solution, and heat treatment was performed at 230 ° C. for 60 minutes.
The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average step of the wiring 2 was 500 nm, and the thickness of the prepared planarizing film 4 was 2,000 nm.
Next, a bottom emission type organic EL element was formed on the obtained planarization film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a commercially available resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.
　次に、第一電極５の周縁を覆う形状の絶縁膜８を形成した。絶縁膜８には、実施例１の感光性樹脂組成物を用い、上述した方法と同様の方法で絶縁膜８を形成した。この絶縁膜８を設けることによって、第一電極５とこの後の工程で形成する第二電極との間のショートを防止することができる。
　さらに、真空蒸着装置内で所望のパターンマスクを介して、正孔輸送層、有機発光層、電子輸送層を順次蒸着して設けた。次いで、基板上方の全面にＡｌから成る第二電極を形成した。得られた上記基板を蒸着機から取り出し、封止用ガラス板と紫外線硬化型エポキシ樹脂を用いて貼り合わせることで封止した。
　以上のようにして、各有機ＥＬ素子にこれを駆動するためのＴＦＴ１が接続してなるアクティブマトリックス型の有機ＥＬ表示装置が得られた。駆動回路を介して電圧を印加したところ、良好な表示特性を示し、信頼性の高い有機ＥＬ表示装置であることが分かった。 Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the photosensitive resin composition of Example 1 was used, and the insulating film 8 was formed by the same method as described above. By providing this insulating film 8, it is possible to prevent a short circuit between the first electrode 5 and the second electrode formed in the subsequent process.
Furthermore, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving the organic EL element was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.
（実施例１０２）
　実施例１０１において、実施例１の感光性樹脂組成物を実施例２の感光性樹脂組成物に換えたこと以外は、実施例１０１と同様に有機ＥＬ表示装置を作製した。得られた有機ＥＬ表示装置に対して、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い有機ＥＬ表示装置であることが分かった。 (Example 102)
In Example 101, an organic EL display device was produced in the same manner as in Example 101 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 2. When a drive voltage was applied to the obtained organic EL display device, it was found that the organic EL display device showed good display characteristics and had high reliability.
（実施例１０３）
　実施例１０１において、実施例１の感光性樹脂組成物を実施例３の感光性樹脂組成物に換えたこと以外は、実施例１０１と同様に有機ＥＬ表示装置を作製した。得られた有機ＥＬ表示装置に対して、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い有機ＥＬ表示装置であることが分かった。 (Example 103)
In Example 101, an organic EL display device was produced in the same manner as in Example 101 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 3. When a drive voltage was applied to the obtained organic EL display device, it was found that the organic EL display device showed good display characteristics and had high reliability.
（実施例１０４）
　実施例１０１において、実施例１の感光性樹脂組成物を実施例４の感光性樹脂組成物に換えたこと以外は、実施例１０１と同様に有機ＥＬ表示装置を作製した。得られた有機ＥＬ表示装置に対して、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い有機ＥＬ表示装置であることが分かった。 (Example 104)
In Example 101, an organic EL display device was produced in the same manner as in Example 101 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 4. When a drive voltage was applied to the obtained organic EL display device, it was found that the organic EL display device showed good display characteristics and had high reliability.
（実施例１０５）
　実施例１０１において、実施例１の感光性樹脂組成物を実施例５の感光性樹脂組成物に換えたこと以外は、実施例１０１と同様に有機ＥＬ表示装置を作製した。得られた有機ＥＬ表示装置に対して、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い有機ＥＬ表示装置であることが分かった。 (Example 105)
In Example 101, an organic EL display device was produced in the same manner as in Example 101 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 5. When a drive voltage was applied to the obtained organic EL display device, it was found that the organic EL display device showed good display characteristics and had high reliability.
（実施例１０６）
　特許第３３２１００３号公報の図１に記載のアクティブマトリクス型液晶表示装置において、層間絶縁膜として硬化膜１７を以下のようにして形成し、実施例１０６の液晶表示装置を得た。すなわち、実施例１の感光性樹脂組成物を用い、上記実施例１０１における有機ＥＬ表示装置の平坦化膜４の形成方法と同様の方法で、層間絶縁膜として硬化膜１７を形成した。
　得られた液晶表示装置に対して、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 (Example 106)
In the active matrix liquid crystal display device described in FIG. 1 of Japanese Patent No. 3321003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 106 was obtained. That is, using the photosensitive resin composition of Example 1, the cured film 17 was formed as an interlayer insulating film by the same method as the method for forming the planarizing film 4 of the organic EL display device in Example 101.
When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
（実施例１０７）
　実施例１０６において、実施例１の感光性樹脂組成物を実施例７の感光性樹脂組成物に換えたこと以外は、実施例１０６と同様に液晶表示装置を作製した。得られた液晶表示装置に対して、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 (Example 107)
In Example 106, a liquid crystal display device was produced in the same manner as Example 106 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 7. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
（実施例１０８）
　実施例１０６において、実施例１の感光性樹脂組成物を実施例８の感光性樹脂組成物に換えたこと以外は、実施例１０６と同様に液晶表示装置を作製した。得られた液晶表示装置に対して、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 (Example 108)
In Example 106, a liquid crystal display device was produced in the same manner as in Example 106 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 8. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
（実施例１０９）
　実施例１０６において、実施例１の感光性樹脂組成物を実施例９の感光性樹脂組成物に換えたこと以外は、実施例１０６と同様に液晶表示装置を作製した。得られた液晶表示装置に対して、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 (Example 109)
In Example 106, a liquid crystal display device was produced in the same manner as in Example 106, except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 9. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
（実施例１１０）
　実施例１０６において、実施例１の感光性樹脂組成物を実施例１０の感光性樹脂組成物に換えたこと以外は、実施例１０６と同様に液晶表示装置を作製した。得られた液晶表示装置に対して、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 (Example 110)
In Example 106, a liquid crystal display device was produced in the same manner as Example 106 except that the photosensitive resin composition of Example 1 was replaced with the photosensitive resin composition of Example 10. When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
　１：ＴＦＴ（薄膜トランジスター）
　２：配線
　３：絶縁膜
　４：平坦化膜
　５：第一電極
　６：ガラス基板
　７：コンタクトホール
　８：絶縁膜
　１０：液晶表示装置
　１２：バックライトユニット
　１４，１５：ガラス基板
　１６：ＴＦＴ
　１７：硬化膜
　１８：コンタクトホール
　１９：ＩＴＯ透明電極
　２０：液晶
　２２：カラーフィルター 1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter

Claims (10)

  1. （Ａ）下記（１）および（２）の少なくとも一方を満たす重合体を含む重合体成分、
    （１）（ａ１）酸基が酸分解性基で保護された基を有する構成単位、および（ａ２）架橋性基を有する構成単位を有する重合体
    （２）（ａ１）酸基が酸分解性基で保護された基を有する構成単位を有する重合体、および（ａ２）架橋性基を有する構成単位を有する重合体
    （Ｂ）下記一般式（Ｉ）で表される光酸発生剤、および
    （Ｃ）溶剤、
    を含有する、感光性樹脂組成物；
    Figure JPOXMLDOC01-appb-C000001
      一般式（Ｉ）中、Ｒ1およびＲ2の一方は、下記一般式（Ａ）で表される基を表し、他方は水素原子を表す；Ｒ3は、ハロゲン原子、アルキルチオ基および脂環式炭化水素基のいずれか１つ以上で置換されてもよい炭素数１～１８の脂肪族炭化水素基、ハロゲン原子、アルキルチオ基、アルキル基およびアシル基のいずれか１つ以上で置換されてもよい炭素数６～２０のアリール基、ハロゲン原子および／またはアルキルチオ基で置換されてもよい炭素数７～２０のアリールアルキル基、１０－カンファーイル基または、下記一般式（Ｂ）で表される基を表す；
    一般式（Ａ）
    Figure JPOXMLDOC01-appb-C000002
      一般式（Ａ）中、Ｘ1は、酸素原子または硫黄原子を表し、Ｙ1は、単結合または炭素数１～４のアルキレン基を表し、Ｒ4は、炭素数１～１２の炭化水素基を表し、Ｒ5は、炭素数１～４のアルキレン基を表し、Ｒ6は、水素原子、分岐していてもよい炭素数１～４のアルキル基、炭素数３～１０の脂環式炭化水素基、複素環基、または水酸基を表す；ｎは、０～５の整数を表し、ｎが２～５の場合、複数存在するＲ5は同一でも異なってもよい；
    一般式（Ｂ）
    Figure JPOXMLDOC01-appb-C000003
      一般式（Ｂ）中、Ｙ2は、単結合または炭素数１～４のアルキレン基を表し、Ｒ7は、炭素数２～６のアルキレン基、炭素数２～６のハロゲン化アルキレン基、炭素数６～２０のアリーレン基、または炭素数６～２０のハロゲン化アリーレン基を表し、Ｒ8は、単結合、炭素数２～６のアルキレン基、炭素数２～６のハロゲン化アルキレン基、炭素数６～２０のアリーレン基または炭素数６～２０のハロゲン化アリーレン基を表し、Ｒ9は、分岐していてもよい炭素数１～１８のアルキル基、分岐していてもよい炭素数１～１８のハロゲン化アルキル基、炭素数６～２０のアリール基、炭素数６～２０のハロゲン化アリール基、炭素数７～２０のアリールアルキル基、または炭素数７～２０のハロゲン化アリールアルキル基を表す；ａおよびｂはそれぞれ独立に０または１を表し、ａおよびｂの少なくとも一方は１である。     (A) a polymer component containing a polymer that satisfies at least one of the following (1) and (2):
    (1) (a1) a polymer having a structural unit having an acid group protected with an acid-decomposable group, and (a2) a polymer having a structural unit having a crosslinkable group (2) (a1) the acid group is acid-decomposable A polymer having a structural unit having a group protected by a group, and (a2) a polymer having a structural unit having a crosslinkable group (B) a photoacid generator represented by the following general formula (I); C) solvent,
    Containing a photosensitive resin composition;
    Figure JPOXMLDOC01-appb-C000001
     In general formula (I), one of R 1 and R 2 represents a group represented by the following general formula (A), and the other represents a hydrogen atom; R 3 represents a halogen atom, an alkylthio group, and an alicyclic group. May be substituted with any one or more of an aliphatic hydrocarbon group having 1 to 18 carbon atoms, a halogen atom, an alkylthio group, an alkyl group and an acyl group, which may be substituted with any one or more of the hydrocarbon groups An arylalkyl group having 7 to 20 carbon atoms, a 10-camphoryl group, or a group represented by the following general formula (B), which may be substituted with an aryl group having 6 to 20 carbon atoms, a halogen atom and / or an alkylthio group Represents;
    Formula (A)
    Figure JPOXMLDOC01-appb-C000002
     In general formula (A), X 1 represents an oxygen atom or a sulfur atom, Y 1 represents a single bond or an alkylene group having 1 to 4 carbon atoms, and R 4 represents a hydrocarbon group having 1 to 12 carbon atoms. R 5 represents an alkylene group having 1 to 4 carbon atoms, R 6 represents a hydrogen atom, an optionally branched alkyl group having 1 to 4 carbon atoms, or an alicyclic carbon atom having 3 to 10 carbon atoms. A hydrogen group, a heterocyclic group, or a hydroxyl group; n represents an integer of 0 to 5, and when n is 2 to 5, a plurality of R 5 may be the same or different;
    General formula (B)
    Figure JPOXMLDOC01-appb-C000003
     In the general formula (B), Y 2 represents a single bond or an alkylene group having 1 to 4 carbon atoms, R 7 represents an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, carbon Represents an arylene group having 6 to 20 carbon atoms or a halogenated arylene group having 6 to 20 carbon atoms, and R 8 represents a single bond, an alkylene group having 2 to 6 carbon atoms, a halogenated alkylene group having 2 to 6 carbon atoms, carbon Represents an arylene group having 6 to 20 carbon atoms or a halogenated arylene group having 6 to 20 carbon atoms, and R 9 represents an alkyl group having 1 to 18 carbon atoms which may be branched, or 1 to 1 carbon atoms which may be branched. 18 halogenated alkyl groups, aryl groups having 6 to 20 carbon atoms, halogenated aryl groups having 6 to 20 carbon atoms, arylalkyl groups having 7 to 20 carbon atoms, or halogenated arylalkyl groups having 7 to 20 carbon atoms. A and b Each independently represent 0 or 1, at least one of a and b is 1.
  2. 一般式（Ｉ）のＲ3が、炭素数１～８の脂肪族炭化水素基、炭素数１～８のパーフルオロアルキル基、ハロゲン原子で置換されてもよい炭素数６～１０のアリール基、またはハロゲン原子で置換されてもよい炭素数７～１０のアルキルアリール基を表す、請求項１に記載の感光性樹脂組成物。 R 3 in the general formula (I) is an aliphatic hydrocarbon group having 1 to 8 carbon atoms, a perfluoroalkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms that may be substituted with a halogen atom, 2. The photosensitive resin composition according to claim 1, which represents an alkylaryl group having 7 to 10 carbon atoms which may be substituted with a halogen atom.
  3. （ａ２）構成単位における架橋性基がエポキシ基および／またはオキセタン基である、請求項１または２に記載の感光性樹脂組成物。 (A2) The photosensitive resin composition of Claim 1 or 2 whose crosslinkable group in a structural unit is an epoxy group and / or an oxetane group.
  4. 前記重合体成分として、少なくとも（１）を含む、請求項１～３のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 3, comprising at least (1) as the polymer component.
  5. （Ｂ）一般式（Ｉ）で表される光酸発生剤の分子量が、３３５～８００である、請求項１～４のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 4, wherein the molecular weight of the photoacid generator represented by (B) the general formula (I) is 335 to 800.
  6. さらに、架橋剤を含む、請求項１～５のいずれか１項に記載の感光性樹脂組成物。 6. The photosensitive resin composition according to claim 1, further comprising a crosslinking agent.
  7. （１）請求項１～６のいずれか１項に記載の感光性樹脂組成物を基板上に塗布する工程、
    （２）塗布された感光性樹脂組成物から溶剤を除去する工程、
    （３）活性放射線で露光する工程、
    （４）水性現像液で現像する工程、および、
    （５）熱硬化するポストベーク工程、を含む硬化膜の製造方法。     (1) a step of applying the photosensitive resin composition according to any one of claims 1 to 6 on a substrate;
    (2) a step of removing the solvent from the applied photosensitive resin composition;
    (3) a step of exposing with actinic radiation,
    (4) a step of developing with an aqueous developer, and
    (5) A method for producing a cured film comprising a post-bake step of thermosetting.
  8. 請求項１～６のいずれか１項に記載の感光性樹脂組成物を硬化してなる硬化膜。 A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 6.
  9. 層間絶縁膜である、請求項８に記載の硬化膜。 The cured film according to claim 8, which is an interlayer insulating film.
  10. 請求項８または９に記載の硬化膜を有する、液晶表示装置または有機ＥＬ表示装置。 A liquid crystal display device or an organic EL display device having the cured film according to claim 8.
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