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WO2015046501A1 - Composition de résine photosensible, procédé de production de film durci, film durci, dispositif d'affichage à cristaux liquides et dispositif d'affichage el organique - Google Patents

Composition de résine photosensible, procédé de production de film durci, film durci, dispositif d'affichage à cristaux liquides et dispositif d'affichage el organique 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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Prior art keywords
group
carbon atoms
resin composition
photosensitive resin
acid
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Ceased
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PCT/JP2014/075854
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English (en)
Japanese (ja)
Inventor
享平 崎田
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Fujifilm Corp
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Fujifilm Corp
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Priority to JP2015539420A priority Critical patent/JP6082473B2/ja
Priority to KR1020167007841A priority patent/KR101755423B1/ko
Publication of WO2015046501A1 publication Critical patent/WO2015046501A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Emergency Medicine (AREA)
  • Optics & Photonics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Materials For Photolithography (AREA)
  • Electroluminescent Light Sources (AREA)
  • Liquid Crystal (AREA)

Abstract

L'invention concerne : une composition de résine photosensible qui présente une grande résistivité transversale, tout en conservant une sensibilité élevée; un procédé de production d'un film durci de cette composition de résine photosensible; un film durci; un dispositif d'affichage à cristaux liquides; et un dispositif d'affichage EL organique. L'invention concerne une composition de résine photosensible qui contient (A) un composant polymère renfermant un ou plusieurs polymères qui satisfont (1) et/ou (2) décrits ci-dessous, (B) un générateur photoacide représenté par la formule générale (I), et (C) un solvant. (1) un polymère ayant (a1) une unité constitutive présentant un groupe dans lequel un groupe acide est protégé par un groupe décomposable en milieu acide et (a2) une unité constitutive présentant un groupe réticulable (2) un polymère ayant (a1) une unité constitutive présentant un groupe dans lequel un groupe acide est protégé par un groupe décomposable en milieu acide et un polymère ayant (a2) une unité constitutive présentant un groupe réticulable
PCT/JP2014/075854 2013-09-30 2014-09-29 Composition de résine photosensible, procédé de production de film durci, film durci, dispositif d'affichage à cristaux liquides et dispositif d'affichage el organique Ceased WO2015046501A1 (fr)

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KR1020167007841A KR101755423B1 (ko) 2013-09-30 2014-09-29 감광성 수지 조성물, 경화막의 제조 방법, 경화막, 액정 표시 장치 및 유기 el 표시 장치

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WO2016043941A1 (fr) * 2014-09-18 2016-03-24 Heraeus Precious Metals North America Daychem LLC Composés dérivés sulfoniques utilisés en tant que photogénérateurs d'acides dans des applications de photorésine
US9477150B2 (en) 2015-03-13 2016-10-25 Heraeus Precious Metals North America Daychem LLC Sulfonic acid derivative compounds as photoacid generators in resist applications
EP3182203A1 (fr) 2015-12-18 2017-06-21 Heraeus Precious Metals North America Daychem LLC Combinaison de dérivés de nit avec sensibilisateurs
WO2018101353A1 (fr) * 2016-11-30 2018-06-07 株式会社Adeka Composition photosensible de type négatif, et produit durci associé ainsi que procédé de fabrication de celui-ci
WO2018101352A1 (fr) * 2016-11-30 2018-06-07 株式会社Adeka Composition photosensible de type positif, motif mettant en œuvre celle-ci, et procédé de fabrication de motif
WO2018110399A1 (fr) * 2016-12-12 2018-06-21 サンアプロ株式会社 Générateur de photoacide et composition de résine pour une photolithographie
JP2024501319A (ja) * 2020-12-28 2024-01-11 サムヤン コーポレイション 新規なナフタルイミドのスルホン酸誘導体、並びにそれを含む光酸発生剤及びフォトレジスト組成物
WO2024041660A1 (fr) * 2022-08-26 2024-02-29 常州强力先端电子材料有限公司 Générateur de photoacide à base de sulfonate, son procédé de préparation, procédé de formation de motifs au moyen de celui-ci, composition de réserve de celui-ci et utilisation associée

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KR102130135B1 (ko) * 2017-09-04 2020-07-03 주식회사 엘지화학 다기능성 광산발생제 및 이를 포함하는 후막용 포토레지스트 조성물
KR102129049B1 (ko) 2017-09-11 2020-07-01 주식회사 엘지화학 광산 발생제 및 이를 포함하는 후막용 화학 증폭형 포지티브 타입 포토레지스트 조성물
KR102868165B1 (ko) * 2019-07-19 2025-10-01 주식회사 동진쎄미켐 포지티브형 감광성 수지 조성물, 감광성 수지 필름 및 이를 이용한 디스플레이 장치
KR102729062B1 (ko) * 2022-12-06 2024-11-13 한인정밀화학(주) 광산발생제 및 이를 포함하는 포토레지스트 조성물

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WO2011087011A1 (fr) * 2010-01-13 2011-07-21 株式会社Adeka Nouveau composé dérivé d'acide sulfonique et nouveau composé dérivé d'acide naphtalique
JP2013083937A (ja) * 2011-09-29 2013-05-09 Fujifilm Corp 感光性樹脂組成物、硬化膜並びにその製造方法
JP2014186309A (ja) * 2013-02-19 2014-10-02 Jsr Corp ネガ型感放射線性樹脂組成物、表示素子用硬化膜、表示素子用硬化膜の形成方法及び表示素子

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016043941A1 (fr) * 2014-09-18 2016-03-24 Heraeus Precious Metals North America Daychem LLC Composés dérivés sulfoniques utilisés en tant que photogénérateurs d'acides dans des applications de photorésine
US9383644B2 (en) 2014-09-18 2016-07-05 Heraeus Precious Metals North America Daychem LLC Sulfonic acid derivative compounds as photoacid generators in resist applications
US9477150B2 (en) 2015-03-13 2016-10-25 Heraeus Precious Metals North America Daychem LLC Sulfonic acid derivative compounds as photoacid generators in resist applications
US9709886B2 (en) 2015-03-13 2017-07-18 Heraeus Precious Metals North America Daychem LLC Sulfonic acid derivative compounds as photoacid generators in resist applications
EP3182203A1 (fr) 2015-12-18 2017-06-21 Heraeus Precious Metals North America Daychem LLC Combinaison de dérivés de nit avec sensibilisateurs
WO2018101353A1 (fr) * 2016-11-30 2018-06-07 株式会社Adeka Composition photosensible de type négatif, et produit durci associé ainsi que procédé de fabrication de celui-ci
WO2018101352A1 (fr) * 2016-11-30 2018-06-07 株式会社Adeka Composition photosensible de type positif, motif mettant en œuvre celle-ci, et procédé de fabrication de motif
WO2018110399A1 (fr) * 2016-12-12 2018-06-21 サンアプロ株式会社 Générateur de photoacide et composition de résine pour une photolithographie
JP2024501319A (ja) * 2020-12-28 2024-01-11 サムヤン コーポレイション 新規なナフタルイミドのスルホン酸誘導体、並びにそれを含む光酸発生剤及びフォトレジスト組成物
JP7673204B2 (ja) 2020-12-28 2025-05-08 サムヤン コーポレイション 新規なナフタルイミドのスルホン酸誘導体、並びにそれを含む光酸発生剤及びフォトレジスト組成物
WO2024041660A1 (fr) * 2022-08-26 2024-02-29 常州强力先端电子材料有限公司 Générateur de photoacide à base de sulfonate, son procédé de préparation, procédé de formation de motifs au moyen de celui-ci, composition de réserve de celui-ci et utilisation associée

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