WO2014002861A1 - Photosensitive resin composition, method for producing cured film, cured film, organic el display device, and liquid crystal display device - Google Patents

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

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Publication number
WO2014002861A1
WO2014002861A1 PCT/JP2013/066914 JP2013066914W WO2014002861A1 WO 2014002861 A1 WO2014002861 A1 WO 2014002861A1 JP 2013066914 W JP2013066914 W JP 2013066914W WO 2014002861 A1 WO2014002861 A1 WO 2014002861A1
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group
resin composition
photosensitive resin
acid
carbon atoms
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PCT/JP2013/066914
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French (fr)
Japanese (ja)
Inventor
大助 柏木
山田　悟
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富士フイルム株式会社
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Priority to KR1020147035129A priority Critical patent/KR101791024B1/en
Priority to CN201380033024.0A priority patent/CN104395826B/en
Priority to JP2014522574A priority patent/JP5941543B2/en
Publication of WO2014002861A1 publication Critical patent/WO2014002861A1/en

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • 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
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • 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
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/106—Binder containing

Definitions

  • the present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”).
  • the present invention also relates to a method for producing a cured film using the photosensitive resin composition, a cured film obtained by curing the photosensitive composition, and various image display apparatuses using the cured film. More specifically, a photosensitive resin composition suitable for forming a planarizing film, a protective film, and an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, an integrated circuit element, and a solid-state image sensor, and the use thereof
  • the present invention relates to a method for producing a cured film.
  • 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 above display device is desired to have high transparency. Yes. For this reason, it has been attempted to use an acrylic resin having excellent transparency as a film-forming component. For example, those described in Patent Document 1 are known.
  • the present invention aims to solve such problems, and an object thereof is to provide a photosensitive resin composition capable of forming a uniform contact hole while maintaining high sensitivity and transparency after heat resistance.
  • an alicyclic ring having a molecular weight of less than 1000 is used as a crosslinking agent using a structural unit having an epoxy group as a structural unit of a crosslinkable group contained in a polymer component. It has been found that a uniform contact hole can be formed by blending the formula epoxy compound while maintaining high sensitivity and transparency after heating. Although this mechanism is not clear, it is considered that the alicyclic epoxy compound quickly traps the acid generated by the acid generator, so that a uniform contact hole can be formed.
  • ⁇ 1> 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 a residue in which an acid group is protected with an acid-decomposable group, and (a2) a structural unit having an epoxy group, (2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having an epoxy group, (B) Photoacid generator (C) A photosensitive resin composition containing an alicyclic epoxy compound having a molecular weight of less than 1000, and (D) a solvent.
  • Formula (2) (In the formula (2), R 2 represents an organic group having 1 to 15 carbon atoms.) ⁇ 5>
  • Formula (3) (In the formula (3), R 3 represents an organic group having 1 to 15 carbon atoms.)
  • ⁇ 7> The photosensitive resin composition according to ⁇ 1> or ⁇ 2>, wherein the (C) alicyclic epoxy compound is represented by the following formula (X-1).
  • Formula (X-1) (In the formula (X-1), R 4 represents an organic group having 1 to 27 carbon atoms. R 5 represents a substituent having 1 to 27 carbon atoms, respectively, except for one alicyclic epoxy group. (The number of carbon atoms is 3 to 30.) ⁇ 8> The photosensitive resin composition according to any one of ⁇ 1>, ⁇ 2>, and ⁇ 7>, wherein the (C) alicyclic epoxy compound is represented by the following formula (X-2): .
  • Formula (X-1) (In the formula (X-2), R 4 represents an organic group having 1 to 27 carbon atoms, and R 5 represents a substituent having 1 to 27 carbon atoms, except for one alicyclic epoxy group.
  • ⁇ 13> (1) A step of applying the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 12> on a substrate, (2) a step of removing the solvent from the applied photosensitive resin composition; (3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic radiation, (4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and (5) A method for producing a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition.
  • the method for forming a cured film according to ⁇ 13> including a step of exposing the entire surface of the developed photosensitive resin composition after the developing step and before the post-baking step.
  • ⁇ 15> A cured film formed by the method according to ⁇ 13> or ⁇ 14>.
  • ⁇ 16> The cured film according to ⁇ 15>, which is an interlayer insulating film.
  • ⁇ 17> An organic EL display device or a liquid crystal display device having the cured film according to ⁇ 15> or ⁇ 16>.
  • the photosensitive resin composition according to any one of the above, wherein (A) the polymer component is 50 to 99.9 parts by mass and (B) the photoacid generator is 100 parts by mass of the total solid content.
  • a composition comprising 0.1 to 10 parts by mass of (C) 0.1 to 10 parts by mass of an alicyclic epoxy compound having a molecular weight of less than 1000.
  • the present invention makes it possible to provide a photosensitive resin composition capable of forming a uniform contact hole while maintaining high sensitivity and transparency after heat resistance.
  • 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 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 photosensitive resin composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) is (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 a residue in which an acid group is protected with an acid-decomposable group, and (a2) a structural unit having an epoxy group, (2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having an epoxy group, (B) A photoacid generator (C) includes an alicyclic epoxy compound having a molecular weight of less than 1,000, and (D) a solvent.
  • the photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition.
  • the composition of the present invention will be described in detail.
  • the composition of the present invention comprises (1) (a1) 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 an epoxy group, as a polymer component, and (2) At least one of (a1) 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 an epoxy group are included. Furthermore, polymers other than these may be included.
  • the polymer component (A) in the present invention (hereinafter referred to as “component (A)”) is added in addition to the above (1) and / or (2) unless otherwise stated. Including those polymers.
  • Component A has (a1) at least a structural unit having a group in which an acid group is protected with an acid-decomposable group.
  • component (A) has the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
  • group in which the acid group is protected with an acid-decomposable group 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.
  • the acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal group such as an ester structure of a group represented by the formula (A1), a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group) A functional group) or a group that is relatively difficult to decompose with an acid (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).
  • an acid for example, an acetal group such as an ester structure of a group represented by the formula (A1), a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group
  • a functional group for example, a tertiary alkyl group such as a tert-butyl ester group or a
  • the structural unit having a group in which the acid group is protected with an acid-decomposable group is a structural unit having a protected carboxyl group protected with an acid-decomposable group, or a protected phenolic group protected with an acid-decomposable group.
  • a structural unit having a hydroxyl group is preferred.
  • 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) having a protected carboxyl group protected with an acid-decomposable group is a protected carboxyl in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below.
  • a structural unit having a group is not particularly limited, and a known structural unit can be used.
  • 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, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid
  • a structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride.
  • the structural units having both the unsaturated group and the structure derived from the acid anhydride will be described in order.
  • ⁇ (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 as the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule 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, and 2- (meth) acrylic acid.
  • Examples include leuoxyethyl hexahydrophthalic acid and 2- (meth) acryloyloxyethyl-phthalic acid.
  • Examples of the unsaturated dicarboxylic acid 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 ends, 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.
  • the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or unsaturated polyhydric carboxylic acid anhydride It is preferable to use acrylic acid, methacrylic acid, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid.
  • the structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may be composed of one kind alone or two or more kinds. May be.
  • (a1-1-2) Structural unit having both an ethylenically unsaturated group and a structure derived from an acid anhydride >>>>
  • the structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride is obtained by reacting a hydroxyl group present in the structural unit having an ethylenically unsaturated group with an acid anhydride.
  • a unit derived from the obtained monomer is preferred.
  • the acid anhydride known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc.
  • phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
  • the reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol% from the viewpoint of developability.
  • 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) having a protected carboxyl group protected by the acid-decomposable group the above-mentioned acid-decomposable groups can be used.
  • these acid-decomposable groups it is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal. It is preferable from the viewpoint of the storage stability of the composition.
  • the carboxyl group is more preferably a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10) from the viewpoint of sensitivity.
  • 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.
  • R 101 , R 102 and R 103 represent an alkyl group
  • the alkyl group may be linear, branched or cyclic.
  • 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 In the case of a linear or branched alkyl group, 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, more preferably 6 to 10 carbon atoms. preferable.
  • 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 silyl group, a cumenyl group, and a 1-naphthyl group.
  • R 101 , R 102 and R 103 can be bonded together 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.
  • 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 numbers 0037 to 0040 of JP2011-212494A.
  • a first preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit represented by the following general formula.
  • 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 is an alkyl group or an aryl group, and R 3 is an alkyl group or Represents an aryl group, 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 an arylene 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) having a protected carboxyl group protected with an acid-decomposable group is a structural unit of the following general formula.
  • 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
  • R 122 to R 128 each independently represents a hydrogen atom or 1 to 4 carbon atoms.
  • Represents an alkyl group of 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) having a protected phenolic hydroxyl group protected with an acid-decomposable group is a protected phenolic 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 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.
  • 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. Specifically, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
  • B represents 0 or an integer of 1 to 4;
  • the acid-decomposable group that can be used in the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group includes a structure having a protected carboxyl group protected by the acid-decomposable group Similar to the acid-decomposable group that can be used for the unit (a1-1), known ones can be used and are not particularly 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 more preferably a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-10) from the viewpoint of sensitivity.
  • 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) having a protected phenolic hydroxyl group protected by the acid-decomposable group a commercially available one may be used, or a known method may be used. What was synthesize
  • combined by can also 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 structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group the following structural units can be exemplified, but the present invention is not limited thereto.
  • the structural unit (a1) is 20 to 100 in the polymer containing the structural unit (a1).
  • the mol% is preferable, and 30 to 90 mol% is more preferable.
  • the structural unit (a1) is a polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of sensitivity, it is preferably 3 to 70 mol%, more preferably 10 to 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) having a protected carboxyl group protected with an acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, when it is desired to develop quickly, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-2) 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 is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, when it is desired to develop quickly, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.
  • the component (A) has a structural unit (a2) having an epoxy group.
  • the structural unit (a2) having an epoxy group may have at least one epoxy group in one structural unit, and preferably has 1 to 3 epoxy groups in total, and 1 or 2 epoxy groups in total. It is more preferable to have one, and it is still more preferable to have one epoxy 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 (a2) having the epoxy group include a monomer containing a methacrylic ester structure and a monomer containing an acrylic ester structure. preferable.
  • glycidyl methacrylate 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetane-3-yl) methacrylate, and methacrylic acid ( 3-ethyloxetane-3-yl) methyl.
  • These structural units can be used individually by 1 type or in combination of 2 or more types.
  • Preferred examples of the structural unit (a2) having an epoxy group include the following structural units.
  • R represents a hydrogen atom or a methyl group.
  • the structural unit (a2) is 5 to 90% in the polymer containing the structural unit (a2).
  • the mol% is preferable, and 20 to 80 mol% is more preferable.
  • the structural unit (a2) is a polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of chemical resistance, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.
  • the structural unit (a2) is preferably contained in an amount of 3 to 70 mol%, more preferably 10 to 60 mol% in all the structural units of the component (A), regardless of any embodiment.
  • the content is preferably 20 to 60 mol%, and most preferably.
  • the epoxy group which the structural unit (a2) has is not an alicyclic epoxy group.
  • the transparency and chemical resistance of the cured film obtained from the photosensitive resin composition are improved.
  • the component (A) may have another structural unit (a3) in addition to the structural units (a1) and / or (a2). These structural units may be contained in the polymer component (1) and / or (2). Further, apart from the polymer component (1) or (2), it may have a polymer component having other structural unit (a3) substantially not containing (a1) and (a2). . Apart from the polymer component (1) or (2), in the case of containing a polymer component having other structural unit (a3) substantially not containing (a1) and (a2), The blending amount is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less in all polymer components.
  • 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 monomer which becomes another structural unit (a3) can be used individually or in combination of 2 or more types.
  • the other structural unit (a3) includes a structural unit containing at least an acid group.
  • the structural unit (a3) specifically includes styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, ⁇ -methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinylbenzoic acid.
  • styrenes and groups having an aliphatic cyclic skeleton are preferable from the viewpoint of electrical characteristics. Specifically, styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, ⁇ -methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned.
  • (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 content of the structural unit (a3) is preferably 60 mol% or less, more preferably 50 mol% or less, and further preferably 40 mol% or less.
  • 0 mol% may be sufficient, it can be set as 1 mol% or more, for example, Furthermore, it can be set as 5 mol% or more. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.
  • the other structural unit (a3) preferably contains 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. .
  • 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 20 mol% is particularly preferable.
  • a polymer having other structural unit (a3) without substantially containing (a1) and (a2) may be included. .
  • Such a polymer is preferably a resin having a carboxyl group in the side chain.
  • a resin having a carboxyl group in the side chain For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048
  • methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc. and side chain
  • acidic cellulose derivatives having a carboxyl group those obtained by adding an acid anhydride to a polymer having a hydroxyl group
  • high molecular polymers having a (meth) acryloyl group in the side chain examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a
  • 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
  • JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118 Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein.
  • ARUFON UC-3000, ARUFON UC-3510, ARUFON are commercially available as these polymers.
  • UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncryl 680, Joncryl 682, Joncryl 690, Joncryl 678, JoncrJr 67 Etc.) can also be used.
  • These other polymers may contain only 1 type, and may contain 2 or more types.
  • the molecular weight of the polymer (A) is a polystyrene-equivalent weight average molecular weight, preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and still more preferably 10,000 to 50,000. 000 range. 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 component (A) is used to form at least the structural units represented by (a1) and (a3). It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
  • the photosensitive resin composition of the present invention preferably contains the component (A) in a proportion of 50 to 99.9 parts by mass, and in a proportion of 70 to 98 parts by mass with respect to 100 parts by mass of the total solid content. More preferred.
  • the photosensitive resin composition of the present invention contains (B) a photoacid generator.
  • a photoacid generator also referred to as “component (B)”
  • 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.
  • the chemical structure is not limited.
  • 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.
  • the photoacid generator used in the present invention 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. Most preferred are photoacid generators that generate.
  • photoacid generator examples include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation.
  • photoacid generators can be used singly or in combination of two or more.
  • trichloromethyl-s-triazines diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-212494A. It can be illustrated.
  • Preferred examples of the oxime sulfonate compound that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1).
  • the alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
  • the alkyl group of R 21 is a bridged type such as an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cyclic alkyl group (7,7-dimethyl-2-oxonorbornyl group). It may be substituted with an alicyclic group, preferably a bicycloalkyl group.
  • aryl group for R 21 an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable.
  • the aryl group of R 21 may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.
  • the above compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B2).
  • R 42 represents an alkyl group or an aryl group
  • X represents an alkyl group, an alkoxy group, or a halogen atom
  • m4 represents an integer of 0 to 3
  • m4 represents 2 or When X is 3, the plurality of X may be the same or different.
  • the alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
  • the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
  • the halogen atom as X is preferably a chlorine atom or a fluorine atom.
  • m4 is preferably 0 or 1. In the above general formula (B2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R 42 is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.
  • the compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B3).
  • R 43 has the same meaning as R 42 in the formula (B2), and X 1 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and n4 represents an integer of 0 to 5.
  • R 43 in the above general formula (B3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group.
  • Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferred, and n-octyl group is particularly preferred.
  • X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
  • n4 is preferably from 0 to 2, particularly preferably from 0 to 1.
  • Specific examples of the compound represented by the general formula (B3) include ⁇ - (methylsulfonyloxyimino) benzyl cyanide, ⁇ - (ethylsulfonyloxyimino) benzyl cyanide, ⁇ - (n-propylsulfonyloxyimino).
  • Benzyl cyanide ⁇ - (n-butylsulfonyloxyimino) benzyl cyanide, ⁇ - (4-toluenesulfonyloxyimino) benzyl cyanide, ⁇ -[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, ⁇ -[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, ⁇ -[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, ⁇ -[(n-butylsulfonyloxyimino) -4- Methoxyphenyl] acetonitrile, ⁇ -[(4 It can be given toluenesulfonyl) -4-methoxyphenyl] acetonitrile.
  • preferable oxime sulfonate compounds include the following compounds (i) to (viii), and the like can be used singly or in combination of two or more. Compounds (i) to (viii) can be obtained as commercial products. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.
  • the compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably a compound represented by the following general formula (OS-1).
  • R 101 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group.
  • R102 represents an alkyl group or an aryl group.
  • X 101 represents —O—, —S—, —NH—, —NR 105 —, —CH 2 —, —CR 106 H—, or —CR 105 R 107 —, wherein R 105 to R 107 are alkyl groups.
  • R 121 to R 124 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R 121 to R 124 may be bonded to each other to form a ring.
  • R 121 to R 124 are preferably a hydrogen atom, a halogen atom and an alkyl group, and an embodiment in which at least two of R 121 to R 124 are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R 121 to R 124 are all hydrogen atoms is preferable from the viewpoint of sensitivity. Any of the aforementioned functional groups may further have a substituent.
  • the compound represented by the general formula (OS-1) is more preferably a compound represented by the following general formula (OS-2).
  • R 101 , R 102 and R 121 to R 124 have the same meanings as in the formula (OS-1), and preferred examples thereof are also the same.
  • R 101 in the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, and is represented by the general formula (OS-2).
  • R 101 is most preferably a cyano group, a phenyl group, or a naphthyl group.
  • the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.
  • the compound containing the oxime sulfonate structure represented by the above general formula (B1) includes the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS-5). It is preferable that it is an oxime sulfonate compound represented by these.
  • R 22 , R 25 and R 28 each independently represents an alkyl group, an aryl group or a heteroaryl group
  • R 23 , R 26 and R 29 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom
  • R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group.
  • X 1 to X 3 each independently represents an oxygen atom or a sulfur atom
  • n 1 to n 3 each independently represents 1 or 2
  • m 1 to m 3 each independently represents an integer of 0 to 6 Represents.
  • the alkyl group, aryl group or heteroaryl group in R 22 , R 25 and R 28 may have a substituent.
  • the alkyl group in R 22 , R 25 and R 28 is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.
  • the aryl group in R 22 , R 25 and R 28 is an aryl group having 6 to 30 carbon atoms which may have a substituent. preferable.
  • the heteroaryl group in R 1 is preferably a heteroaryl group having 4 to 30 carbon atoms in total which may have a substituent.
  • At least one of the heteroaryl groups in R 22 , R 25 and R 28 may be a heteroaromatic ring, such as a heteroaromatic ring and benzene.
  • the ring may be condensed.
  • R 23 , R 26 and R 29 are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group. preferable.
  • one or two of R 23 , R 26 and R 29 present in the compound are an alkyl group, an aryl group or a halogen atom. It is more preferable that one is an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.
  • the alkyl group for R 23 , R 26 and R 29 is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferred is an alkyl group of 6.
  • the aryl group for R 23 , R 26 and R 29 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
  • X 1 to X 3 each independently represents O or S, and is preferably O.
  • the ring containing X 1 to X 3 as a ring member is a 5-membered ring or a 6-membered ring.
  • n 1 to n 3 each independently represents 1 or 2, and when X 1 to X 3 are O, n 1 to n 3 are each independently In addition, when X 1 to X 3 are S, n 1 to n 3 are each preferably 2 independently.
  • R 24 , R 27 and R 30 each independently represent a halogen atom, alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group or alkoxysulfonyl group.
  • R 24 , R 27 and R 30 are preferably each independently an alkyl group or an alkyloxy group.
  • the alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R 24 , R 27 and R 30 may have a substituent.
  • the alkyl group in R 24 , R 27 and R 30 is an alkyl group having 1 to 30 carbon atoms which may have a substituent. It is preferable.
  • the alkyloxy group in R 24 , R 27 and R 30 is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. Preferably there is.
  • m 1 to m 3 each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, preferably 0 or 1. More preferably, it is particularly preferably 0.
  • the substitution of (OS-3) to (OS-5) described in paragraph numbers 0092 to 0109 of JP2011-221494A The preferred range of groups is likewise preferred.
  • the compound containing the oxime sulfonate structure represented by the general formula (B1) is particularly an oxime sulfonate compound represented by any of the following general formulas (OS-6) to (OS-11). preferable.
  • R 301 to R 306 represent an alkyl group, an aryl group, or a heteroaryl group
  • R 307 represents a hydrogen atom or a bromine atom
  • R 308 to R 310 , R 313 , R 316 and R 318 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group
  • R 311 and R 314 each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group
  • R 312 , R 315 , R 317 and R 319 each independently represent a hydrogen atom or a methyl group.
  • oxime sulfonate compounds represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. However, the present invention is not limited to these.
  • the photoacid generator is based on 100 parts by mass of all resin components (preferably a solid content, more preferably a total of copolymers) in the photosensitive resin composition. 0.1 to 10 parts by mass is preferably used, and 0.5 to 10 parts by mass is more preferably used. Two or more kinds can be used in combination.
  • the photosensitive resin composition of the present invention is characterized by containing an alicyclic epoxy compound having a molecular weight of less than 1000 (hereinafter sometimes simply referred to as “alicyclic epoxy compound”) as a crosslinking agent.
  • the alicyclic epoxy compound preferably has 1 to 5 alicyclic epoxy groups, more preferably 1 to 3, more preferably 1 or 2.
  • the alicyclic epoxy group possessed by the alicyclic epoxy compound used in the present invention is preferably an alicyclic epoxy group represented by the following.
  • the alicyclic epoxy compound is preferably represented by the following formula (1).
  • Formula (1) (In the formula (1), n represents an integer of 1 to 4.
  • R 1 represents an organic group having 1 to 30 carbon atoms.)
  • R 1 represents an organic group having 1 to 30 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic or aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond. R 1 is an n-valent linking group.
  • the number of carbon atoms of the organic group represented by R 1 is preferably 1 to 15, more preferably 1 to 8, and still more preferably 1 to 6.
  • the organic group is at least a hydrocarbon group, a hydrocarbon group, and —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms).
  • R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
  • a group consisting of one combination is preferred, and a hydrocarbon group or a group consisting of a hydrocarbon group and —O— and / or —CO— is more preferred.
  • the hydrocarbon group is preferably a linear or branched group, and more preferably a linear group.
  • the hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group.
  • N represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.
  • R 2 represents an organic group having 1 to 15 carbon atoms.
  • R 2 represents an organic group having 1 to 15 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic ring or an aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond.
  • R 2 is a divalent linking group.
  • the organic group of R 2 preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • the organic group is at least a hydrocarbon group, a hydrocarbon group, and —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms).
  • R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
  • a group consisting of one combination is preferred, and a hydrocarbon group or a group consisting of a hydrocarbon group and —O— and / or —CO— is more preferred.
  • the hydrocarbon group is preferably a linear or branched group, and more preferably a linear group.
  • the hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group.
  • the hydrocarbon group is preferably an alkylene group.
  • R 3 represents an organic group having 1 to 15 carbon atoms.
  • R 3 represents an organic group having 1 to 15 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic or aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond.
  • R 3 is a divalent linking group.
  • the number of carbon atoms in the organic group of R 3 is preferably 1-8, and more preferably 1-6.
  • the organic group is at least a hydrocarbon group, a hydrocarbon group, and —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms).
  • R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
  • a group consisting of one combination is preferred, and a hydrocarbon group or a group consisting of a hydrocarbon group and —O— and / or —CO— is more preferred.
  • the hydrocarbon group is preferably a linear or branched group, and more preferably a linear group.
  • the hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group.
  • the hydrocarbon group is preferably an alkylene group.
  • the alicyclic epoxy compound is preferably represented by the following formula (X-1).
  • Formula (X-1) (In the formula (X-1), R 4 represents an organic group having 1 to 27 carbon atoms, R 5 represents a substituent having 1 to 27 carbon atoms, except for one alicyclic epoxy group. The number is 3-30.)
  • R 4 represents an organic group having 1 to 27 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic or aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond.
  • the number of carbon atoms in the organic group represented by R 4 is preferably 1 to 15, more preferably 1 to 8, and further preferably 1 to 6.
  • the organic group is at least a hydrocarbon group, a hydrocarbon group, and —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms).
  • R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
  • a group consisting of one combination is preferred, and a hydrocarbon group or a group consisting of a hydrocarbon group and —O— and / or —CO— is more preferred.
  • the hydrocarbon group is preferably a linear or branched group, and more preferably a linear group.
  • the hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group.
  • Each R 5 represents a substituent having 1 to 27 carbon atoms, and may be independently branched, have an unsaturated bond, or have an aliphatic ring or aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Furthermore, they are at least one substituent selected from an epoxy group, an oxetanyl group, an ethylenically unsaturated group, an alkoxysilane group, an isocyanate group, a blocked isocyanate group, a thiol group, a carboxyl group, a hydroxyl group, and a succinic anhydride group. May be substituted.
  • Two R 5 s in formula (X-1) may be the same or different and are preferably the same.
  • the carbon number of the substituent of R 5 is preferably 1 to 15, more preferably 1 to 8, and further preferably 1 to 6.
  • the substituent is at least one of an epoxy group, a hydroxyl group, a hydrocarbon group, —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms).
  • R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms.
  • a group consisting of two combinations is preferred, from a group consisting of a hydroxyl group, a hydrocarbon group, a combination of —O— and / or —CO—, and a combination of an epoxy group, a hydrocarbon group and —O— and / or —CO—.
  • the epoxy group is preferably an alicyclic epoxy group.
  • the hydrocarbon group is preferably a linear or branched group, and more preferably a linear group.
  • the hydrocarbon group preferably has 1 to
  • the number of carbon atoms excluding one alicyclic epoxy group that is, in the six-membered ring containing R 4 , 2 R 5 , and 3 nitrogen atoms in the formula (X-1)
  • the total number of carbon atoms of the three carbon atoms is preferably 3 to 30, more preferably 5 to 25, and even more preferably 5 to 20.
  • a preferred embodiment of the alicyclic epoxy compound is exemplified by a compound represented by the following formula (X-2).
  • Formula (X-2) (In the formula (X-2), R 4 represents an organic group having 1 to 27 carbon atoms, and R 5 represents a substituent having 1 to 27 carbon atoms, except for one alicyclic epoxy group. (The number of carbon atoms is 3 to 30.)
  • R 4 has the same meaning as R 4 in formula (X-1), and the preferred range is also the same.
  • R 5 has the same meaning as R 5 in formula (X-1), and the preferred range is also the same.
  • Two R 4 s in formula (X-2) may be the same or different and are preferably the same.
  • the number of carbon atoms excluding one alicyclic epoxy group that is, in the six-membered ring containing two R 4 , R 5 , and three nitrogen atoms in the formula (X-2)
  • the total number of carbon atoms of the three carbon atoms is preferably 3 to 30, more preferably 5 to 25, and even more preferably 5 to 20.
  • each R 4 represents an organic group having 1 to 27 carbon atoms. However, the number of carbon atoms excluding one alicyclic epoxy group is 3 to 30.
  • R 4 has the same meaning as R 4 in formula (X-1), and the preferred range is also the same.
  • Three R 4 s in formula (X-3) may be the same or different and are preferably the same.
  • the number of carbon atoms excluding one alicyclic epoxy group that is, in formula (X-3), three R 4 s and three carbons in a six-membered ring containing three nitrogen atoms
  • the total number of carbon atoms is preferably from 3 to 30, more preferably from 5 to 25, and even more preferably from 5 to 20.
  • the production method of the alicyclic epoxy compound used in the present invention is not limited.
  • Maruzen KK Publishing, 4th Edition Experimental Chemistry Course 20 Organic Synthesis II, 213-, 1992, Ed. by Alfred Hasfner The chemistry of heterocyclic compounds-Small Ring Heterocycles part3 oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, adhesive, Vol. 29 No. 12, 32,1985, Yoshimura, adhesive, Vol. 30, No. 5 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, JP-A-1-100388, Japanese Patent No. 2906245, Japanese Patent No. 2926262, and the like.
  • the molecular weight of the alicyclic epoxy compound used in the present invention is less than 1000, and preferably less than 500. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively.
  • the lower limit is not particularly defined, but is usually 100 or more.
  • the addition amount of the alicyclic epoxy compound in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition.
  • the amount is more preferably 5 to 8 parts by mass, and further preferably 1.0 to 5 parts by mass.
  • a plurality of alicyclic epoxy compounds may be used in combination, and in that case, all the alicyclic epoxy compounds are added together to calculate the content.
  • the photosensitive resin composition of the present invention contains (D) 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 the solvent (D).
  • 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 Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like.
  • specific examples of the (D) 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 the contents thereof are described in the present specification. Embedded in the book.
  • 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.
  • Component D 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 (D) in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, preferably 60 to 90 parts by mass, per 100 parts by mass of the total resin components in the photosensitive resin composition. More preferably it is.
  • 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.
  • the photosensitive resin composition of this invention contains other crosslinking agents other than an alicyclic epoxy compound as needed.
  • a crosslinking agent other than the alicyclic epoxy compound By adding a crosslinking agent other than the alicyclic epoxy compound, the cured film obtained from the photosensitive resin composition of the present invention can be made stronger.
  • the crosslinking agent is not limited as long as a crosslinking reaction is caused by heat (excluding the polymer component (A) above).
  • a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate compound, etc. Can be added.
  • the addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass, and 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition.
  • the amount is more preferably part 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.
  • a plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.
  • ⁇ Compound having two or more epoxy groups or oxetanyl groups in the molecule Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do. Of the aliphatic epoxy resins, chain aliphatic epoxy is preferably used.
  • the chain aliphatic epoxy that can be used in the present invention has a molecular weight (in the case of a polymer, a weight average molecular weight) of preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less. . As a lower limit, it can be set as 100 or more, for example.
  • a weight average molecular weight of a chain aliphatic epoxy compound is not described in a catalog etc., it can estimate by calculation of (epoxy equivalent) x (number of functional groups). Further, the viscosity of the chain aliphatic epoxy at 25 ° C.
  • the aliphatic epoxy compound used in the present invention is a resin having a linear and / or branched carbon chain and an epoxy group, and in addition to a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a chlorine atom, etc. May be combined.
  • a resin comprising a linear and / or branched carbon chain, a hydrogen atom, and an epoxy group, or a group in which a hydroxyl group is substituted on the resin is particularly preferable.
  • the number of epoxy groups is preferably 1 to 4, and more preferably 2 or 3.
  • the cycloaliphatic epoxy compound is not substantially contained. By setting it as such a structure, it exists in the tendency for the effect of this invention to be exhibited more effectively.
  • substantially not contained means that it is not added at a level that affects the effects of the present invention, for example, 1% by weight or less of the total solid content.
  • the chain aliphatic epoxy compound used in the present invention is preferably a resin represented by the following general formula (X-1).
  • Formula (X-1) (In general formula (X-1), A is a linear or branched hydrocarbon group, which may have a hydroxyl group as a substituent, and n is an integer of 1 to 4.)
  • the carbon number of A is preferably 1 to 20, preferably 1 to 15, more preferably 2 to 10, and further preferably 2 to 6.
  • n is an integer of 1 to 4, preferably 2 or 3.
  • the chain aliphatic epoxy compound used in the present invention is more preferably a resin represented by the following general formula (X-2).
  • Formula (X-2) (In the general formula (X-2), B is a linear or branched hydrocarbon group, which may have a hydroxyl group as a substituent, and n is an integer of 1 to 4.) B preferably has 1 to 18 carbon atoms, more preferably 1 to 13, and more preferably 2 to 8. n is an integer of 1 to 4, preferably 2 or 3.
  • Examples of the chain aliphatic epoxy that can be preferably used in the present invention include Denacol EX-611 (11,800 mPa ⁇ s), EX-612 (11,900 mPa ⁇ s), EX-614 (21,200 mPa ⁇ s).
  • EX-614B (5,000 mPa ⁇ s), EX-622 (11,800 mPa ⁇ s), EX-512 (1,300 mPa ⁇ s), EX-521 (4,400 mPa ⁇ s), EX-411 (800 mPa ⁇ s) S), EX-421 (650 mPa ⁇ s), EX-313 (150 mPa ⁇ s), EX-314 (170 mPa ⁇ s), EX-321 (130 mPa ⁇ s), EX-211 (20 mPa ⁇ s), EX -212 (20 mPa ⁇ s), EX-810 (20 mPa ⁇ s), EX-811 (20 mPa ⁇ s), EX-850 (20 Pa ⁇ s), EX-851 (30 mPa ⁇ s), EX-821 (40 mPa ⁇ s), EX-830 (70 mPa ⁇ s),
  • EX-321, EX-321L, EX-211 and EX-211L fall under this category.
  • Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX above, manufactured by Toagosei Co., Ltd.
  • the compound having an oxetanyl group is preferably used alone or mixed with a compound having an epoxy group.
  • alkoxymethyl group-containing crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223A and compounds having at least one ethylenically unsaturated double bond are also preferably used. The contents of which are incorporated herein by reference.
  • alkoxymethyl group-containing crosslinking agent alkoxymethylated glycoluril is preferable.
  • the content of a compound having 2 or more epoxy groups or oxetanyl groups in the molecule is 0.1 to 100 parts by weight with respect to 100 parts by weight of the solid content.
  • the amount is preferably 10 parts by weight, and more preferably 0.5 to 10 parts by weight.
  • a blocked isocyanate compound can also be preferably employed as a crosslinking agent.
  • the blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
  • 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 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.
  • an alkoxysilane compound When an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do.
  • the alkoxysilane compound a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable.
  • the alkoxy group contained in the alkoxysilane compound preferably has 1 to 5 carbon atoms.
  • 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.
  • silane coupling agents include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrialkoxysilane, ⁇ -glycidoxypropylalkyldialkoxysilane, and ⁇ -methacryloxy.
  • ⁇ -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.
  • Ph is a phenyl group.
  • the alkoxysilane compound in the photosensitive resin composition of this invention is not specifically limited to these, A well-known thing can be used.
  • the content of the alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, and preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive composition. Is more preferable.
  • the photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with (B) a photoacid generator.
  • the sensitizer absorbs actinic rays or radiation 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 in the photosensitive resin composition of the present invention is preferably 0 to 1000 parts by mass with respect to 100 parts by mass of the photoacid generator in the photosensitive resin composition. More preferably, it is more preferably 50 to 200 parts by mass. Two or more kinds can be used in combination.
  • the photosensitive resin composition of the present invention preferably contains a basic compound.
  • the basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.
  • aliphatic amines examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine. , Dicyclohexylmethylamine, diazabicyclononene, and the like.
  • aromatic amine 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, 2,4,5-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 Such as diazabicyclo [5.3
  • Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
  • Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
  • the basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. Preferably, two kinds of heterocyclic amines are used in combination.
  • the content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition, 0.005 More preferred is 1 part by mass.
  • 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.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. .
  • KP manufactured by Shin-Etsu Chemical Co., Ltd.
  • Polyflow manufactured by Kyoeisha Chemical Co., Ltd.
  • F-Top manufactured by JEMCO
  • MegaFac manufactured by DIC Corporation
  • Florard Suditomo 3M
  • Surflon manufactured by Asahi Glass Co., Ltd.
  • PolyFox manufactured by OMNOVA
  • SH-8400 Toray Dow Corning Silicone
  • the surfactant contains the structural unit A and the structural unit B represented by the following general formula (I-1), and is converted to polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent.
  • a copolymer having a weight average molecular weight (Mw) of 1,000 or more and 10,000 or less can be given as a preferred example.
  • 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 a hydrogen atom or C represents an alkyl group having 1 to 4 carbon atoms
  • L represents an alkylene group having 3 to 6 carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p is 10 mass% to 80 mass%.
  • a numerical value is represented, q represents a numerical value of 20% by mass or more and 90% by mass or less, 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-2).
  • R 405 in the general formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. A number 2 or 3 alkyl group is more preferred.
  • the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
  • the addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, and 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, the amount is 0.01 to 3 parts by mass.
  • 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.
  • phenol-based antioxidants amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used individually by 1 type and may mix 2 or more types. Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40 and ADK STAB AO.
  • ADK STAB AO-51 ADK STAB AO-60
  • ADK STAB AO-70 ADK STAB AO-80
  • ADK STAB AO-330 ADK STAB AO-412S
  • ADK STAB AO-503 ADK STAB A-611, ADK STAB A-612, ADK STAB A -613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB PEP-36Z, ADK STAB HP-1 ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 13510, ADK STAB 3010, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS-90 -91 (above, manufactured by ADEKA Corporation), Irga
  • the content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% 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.
  • additives other than antioxidants various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.
  • an acid proliferating agent in the photosensitive resin composition of the present invention, 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.
  • the acid strength is preferably 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less.
  • the acid proliferating agent examples include paragraph numbers 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39 of JP-T 9-512498.
  • the compounds described on line 12 to page 47, line 2 can be mentioned, the contents of which are incorporated herein.
  • the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.
  • the content of the acid proliferating agent in the photosensitive composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator, from the viewpoint of dissolution contrast between the exposed and unexposed parts. It is preferably 20 to 500 parts by mass.
  • the photosensitive resin composition of the present invention can contain a development accelerator.
  • a development accelerator the description 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 in the photosensitive resin composition of the present invention is preferably 0 to 30 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. 1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
  • 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 a filter having a pore size of 0.2 ⁇ m or the like.
  • the method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
  • substrate (2) A step of removing the solvent from the applied photosensitive resin composition; (3) The process of exposing the photosensitive resin composition from which the solvent was removed with actinic rays; (4) A step of developing the exposed photosensitive resin composition with an aqueous developer; (5) A post-baking step of thermosetting the developed photosensitive resin composition.
  • Each step will be described below in order.
  • 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, silicone, 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 Made of synthetic resin such as aromatic ether, maleimide
  • 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. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
  • 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 actinic rays through a mask having a predetermined pattern.
  • the photoacid generator is decomposed to generate an acid.
  • the acid-decomposable group contained in the coating film component is hydrolyzed to produce a carboxyl group or a phenolic hydroxyl group.
  • an exposure light source using actinic light a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc.
  • g-line (436 nm), i-line (365 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 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.
  • various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
  • 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. or higher and 100 ° C. or lower.
  • the acid-decomposable group in the present invention has 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, PEB is not necessarily performed.
  • a positive image can also be formed by development.
  • a polymer 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 and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used.
  • An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
  • Preferred examples of the developer include 0.4% aqueous solution, 0.5% aqueous solution, 0.7% aqueous solution and 2.38% aqueous solution of tetraethylammonium hydroxide.
  • 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 either a liquid piling method or a dipping method. After development, washing with running water is usually performed for 30 to 300 seconds to form a desired pattern.
  • 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 acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and crosslinked with an epoxy group, a crosslinking agent, etc.
  • a cured 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 with such a crosslinking reaction, it is possible to form a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like.
  • 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 is re-exposed (post-exposure) with actinic rays to the substrate on which the pattern has been formed prior to post-baking, and then post-baked.
  • An acid is generated from the photoacid generator present in the unexposed portion, and can function as a catalyst for accelerating the cross-linking process, thereby promoting 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 photosensitive resin 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.
  • 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 physical properties, it is useful for applications of organic EL display devices and liquid crystal display devices.
  • the liquid crystal display device of the present invention comprises 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 methods that can be adopted by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (Optical). 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, -346054 can be used as the 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 in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc.
  • FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10.
  • the color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto.
  • the elements of the TFT 16 corresponding to are arranged.
  • Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17.
  • 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 can be used as the second interphase insulating film (48) of JP 2011-145686 A or the interphase insulating film (520) of JP 2009-258758 A.
  • the organic EL display device of the present invention comprises 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 layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is 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-
  • MATHF 2-tetrahydrofuranyl methacrylate (synthetic product)
  • MAEVE 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
  • MACHOE 1- (cyclohexyloxy) ethyl methacrylate
  • MATHP tetrahydro-2H-pyran-2-yl methacrylate
  • GMA glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
  • OXE-30 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
  • MAA Methacrylic acid (manufactured by Wako Pure Chemical Industries)
  • MMA Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
  • St Styrene (Wako Pure Chemical Industries, Ltd.)
  • DCPM Methacrylic acid
  • the ratio of the total amount of PGMEA and other components was 60:40. That is, a polymer solution having a solid content concentration of 40% was prepared. Monomers and the like were changed as shown in the following table, and other polymers were synthesized. In the following table, all solvents used PGMEA and the solid content concentration was 40 parts by mass.
  • ⁇ Adjustment of photosensitive resin composition Polymer components, photoacid generators, alicyclic epoxy compounds, other crosslinking agents, basic compounds, alkoxysilane compounds, sensitizers, surfactants, and others so that the solid content ratios shown in the table below are obtained.
  • the above components were dissolved and mixed in PGMEA until the solid content concentration became 25%, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 ⁇ m to obtain photosensitive resin compositions of various examples and comparative examples.
  • surface is a mass part.
  • B-1 DTS-105, (triarylsulfonium salt) (manufactured by Midori Chemical Co., Ltd.)
  • B-2 CGI1397 (manufactured by BASF Japan Ltd.)
  • B-3 PAI101 (Midori Chemical Co., Ltd.)
  • B-4 The following compound B-5: The following compound (synthesized according to the method described in paragraph 0108 of JP-T-2002-528451)
  • F-1 JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation) (bisphenol type epoxy compound)
  • F-2 Duranate 17B-60P (Asahi Kasei Chemicals Corporation) (isocyanate compound)
  • F-3 Denacol EX-321L (manufactured by Nagase ChemteX Corporation) (glycidyl ether epoxy compound)
  • F-4 JER828 (manufactured by Mitsubishi Chemical Holdings Corporation) (bisphenol type epoxy compound)
  • F-8 Denacol EX-211L (manufactured by Nagase ChemteX Corporation) (glycidyl ether epoxy compound)
  • F-9 OXT-221 (manufactured by Toagosei Co., Ltd.) (bifunctional oxetane compound)
  • F-10 JER1007K (manufactured by Mitsubishi Chemical Holdings Corporation) (bisphenol A type epoxy compound)
  • F-10 JER1007K (manu
  • G-1 ⁇ -glycidoxypropyltrialkoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • G-2 Bis (triethoxysilylpropyl) tetrasulfide (KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd.)
  • G-3 KBM-3103 (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) and then pre-baked on a hot plate at 95 ° C. for 140 seconds to volatilize the solvent.
  • a photosensitive resin composition layer having a thickness of 4.0 ⁇ m was formed.
  • the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (extra high pressure mercury lamp) manufactured by Canon Inc.
  • the exposed photosensitive resin composition layer was developed with an alkali developer (0.4 mass% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
  • the photosensitive resin composition of the present invention was excellent in sensitivity, excellent in heat-resistant transparency and CH uniformity after development, and both were above the practical level.
  • F-5 containing an ester bond is used as an alicyclic epoxy compound, it is possible to achieve extremely excellent CH uniformity while maintaining a certain level of sensitivity and transparency after development processing. High significance.
  • the photosensitive resin composition of the comparative example had a CH uniformity outside the practical level.
  • Example 52 was performed in the same manner as in Example 1, except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to FX-803M (gh-Line stepper) manufactured by Nikon Corporation. The evaluation of sensitivity was the same level as in Example 1.
  • Example 53 was performed in the same manner as in Example 1, except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to a 355 nm laser exposure machine, and 355 nm laser exposure was performed.
  • the 355 nm laser exposure machine “AEGIS” manufactured by Buoy Technology Co., Ltd. was used (wavelength 355 nm, pulse width 6 nsec), and the exposure amount was measured using “PE10B-V2” manufactured by OPHIR.
  • the evaluation of sensitivity was the same level as in Example 1.
  • a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 54 was obtained. That is, using the photosensitive resin composition of Example 1, a cured film 17 was formed as an interlayer insulating film. That is, as a pretreatment for improving the wettability of the substrate and the interlayer insulating film 17 in paragraph 0058 of Japanese Patent No. 3321003, the substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then the photosensitive film of Example 1 is used.
  • HMDS hexamethyldisilazane
  • the photosensitive resin composition After spin-coating the photosensitive resin composition, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent, thereby forming a photosensitive resin composition layer having a thickness of 3 ⁇ m.
  • the obtained photosensitive resin composition layer was subjected to 40 mJ / cm 2 (illuminance: 20 mW / cm 2 ) through a hole pattern mask of 10 ⁇ m ⁇ using Canon Inc. MPA 5500CF (high pressure mercury lamp). i-line).
  • the exposed photosensitive resin composition layer was developed with an alkali developer (0.4% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
  • the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (illuminance: 20 mW / cm 2 , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes.
  • a cured film was obtained.
  • 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.
  • liquid crystal display device 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 55 A liquid crystal display device of Example 55 was obtained in the same manner as in Example 54 except that the hexamethyldisilazane (HMDS) treatment was omitted.
  • the obtained liquid crystal display device was a highly reliable liquid crystal display device having good display characteristics without chipping or peeling of the pattern of the cured film.
  • Example 56 A liquid crystal display device of Example 56 was obtained in the same manner as in Example 54 except that the alkaline developer was changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 2.38% tetramethylammonium hydroxide aqueous solution. It was.
  • the obtained liquid crystal display device was a highly reliable liquid crystal display device having good display characteristics without chipping or peeling of the pattern of the cured film.
  • Example 57 A liquid crystal display device of Example 57 was obtained in the same manner as in Example 54 except that the alkaline developer was changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 0.04% KOH aqueous solution.
  • the obtained liquid crystal display device was a highly reliable liquid crystal display device having good display characteristics without chipping or peeling of the pattern of the cured film.
  • Example 58 A liquid crystal display device of Example 58 was obtained in the same manner as in Example 54 except that the step of full exposure after development and rinsing was omitted. The obtained liquid crystal display device showed good display characteristics and was a highly reliable liquid crystal display device.
  • Example 59 The liquid crystal of Example 59 is the same as Example 54 except that a step of heating on a hot plate at 100 ° C. for 3 minutes is added between the entire surface exposure step and the 230 ° C./30 minute heating step in the oven. A display device was obtained. The obtained liquid crystal display device showed good display characteristics and was a highly reliable liquid crystal display device.
  • Example 60 A liquid crystal display device of Example 60 was obtained in the same manner as in Example 54 except that a step of heating on a hot plate at 100 ° C. for 3 minutes was added between the development / rinsing process and the entire surface exposure process. The obtained liquid crystal display device showed good display characteristics and was a highly reliable liquid crystal display device.
  • Example 61 A liquid crystal display device similar to that of Example 54 was obtained by changing only the following coating process. That is, after the photosensitive resin composition of Example 1 was applied by a slit coating method, the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 3.0 ⁇ m. Formed. The obtained coating film was flat and had a good surface shape without unevenness. Further, the performance as a liquid crystal display device was as good as in Example 54.
  • Example 54 was performed in the same manner as in Example 1 except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to a UV-LED light source exposure machine. Further, the performance as a liquid crystal display device was as good as in Example 54.
  • Example 63> A liquid crystal display device similar to that of Example 54 was obtained by changing only the following coating process. That is, after the photosensitive resin composition of Example 1 was applied by a slit and spin method, the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 3.0 ⁇ m. Formed. The obtained coating film was flat and had a good surface shape without unevenness. Further, the performance as a liquid crystal display device was as good as in Example 54.
  • 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 planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 16 on a substrate, pre-baking (90 ° C./120 seconds) 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 is formed by developing with an alkaline aqueous solution (0.4% TMAH aqueous solution).
  • the entire surface was exposed so that the integrated irradiation amount was 300 mJ / cm 2 (illuminance: 20 mW / cm 2 , i-line), and heat treatment was performed at 230 ° C./30 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.
  • 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 flattening 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 resist was applied, prebaked, exposed through a mask having a desired pattern, and developed.
  • pattern processing was performed by wet etching using an ITO etchant.
  • 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 16 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.
  • 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.
  • 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

Abstract

Provided is a photosensitive resin composition. This photosensitive resin composition contains (A) a polymer component which contains a polymer that satisfies (1) and/or (2) described below, (B) a photoacid generator, (C) an alicyclic epoxy compound having a molecular weight of less than 1,000, and (D) a solvent. (1) a polymer which has (a1) a constituent unit having a residue wherein an acid group is protected with an acid-decomposable group and (a2) a constituent unit having an epoxy group (2) (a1) a polymer which has a constituent unit having a residue wherein an acid group is protected with an acid-decomposable group, and (a2) a polymer which has a constituent unit having an epoxy group

Description

感光性樹脂組成物、硬化膜の製造方法、硬化膜、有機ＥＬ表示装置および液晶表示装置Photosensitive resin composition, method for producing cured film, cured film, organic EL display device and liquid crystal display device
　本発明は、感光性樹脂組成物（以下、単に、「本発明の組成物」ということがある）に関する。また、上記感光性樹脂組成物を用いた硬化膜の製造方法、感光性組成物を硬化してなる硬化膜、上記硬化膜を用いた各種画像表示装置に関する。
　さらに詳しくは、液晶表示装置、有機ＥＬ表示装置、集積回路素子、固体撮像素子などの電子部品の平坦化膜、保護膜や層間絶縁膜の形成に好適な、感光性樹脂組成物およびそれを用いた硬化膜の製造方法に関する。 The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”). The present invention also relates to a method for producing a cured film using the photosensitive resin composition, a cured film obtained by curing the photosensitive composition, and various image display apparatuses using the cured film.
More specifically, a photosensitive resin composition suitable for forming a planarizing film, a protective film, and an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL display device, an integrated circuit element, and a solid-state image sensor, and the use thereof The present invention relates to a method for producing a cured film.
　有機ＥＬ表示装置や、液晶表示装置などには、パターン形成された層間絶縁膜が設けられている。この層間絶縁膜の形成には、必要とするパターン形状を得るための工程数が少なく、しかも十分な平坦性が得られるといったことから、感光性樹脂組成物が広く使用されている。 Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.
　上記表示装置における層間絶縁膜には、絶縁性、耐溶剤性、耐熱性、硬度、および、酸化インジウムスズ（ＩＴＯ）スパッタ適性に優れるといった硬化膜の物性に加えて、高い透明性が望まれている。このため、透明性に優れたアクリル系樹脂を膜形成成分として用いることが試みられており、例えば、特許文献１に記載のものが知られている。 In addition to the properties of the cured film, such as insulating properties, solvent resistance, heat resistance, hardness, and indium tin oxide (ITO) sputtering suitability, the interlayer insulating film in the above display device is desired to have high transparency. Yes. For this reason, it has been attempted to use an acrylic resin having excellent transparency as a film-forming component. For example, those described in Patent Document 1 are known.
特開２０１１－２０９６８１号公報JP 2011-209681 A
　しかしながら、本発明者が検討したところ、特許文献１に記載の感光性樹脂組成物では、コンタクトホールの均一性が不十分であることが分かった。本願発明は、かかる課題を解決することを目的としたものであって、高い感度および耐熱後の透明性を維持しつつ、均一なコンタクトホールを形成できる感光性樹脂組成物を提供することを目的とする。 However, when the present inventor examined, it was found that the contact hole uniformity was insufficient in the photosensitive resin composition described in Patent Document 1. The present invention aims to solve such problems, and an object thereof is to provide a photosensitive resin composition capable of forming a uniform contact hole while maintaining high sensitivity and transparency after heat resistance. And
　かかる状況のもと本願発明者が検討を行った結果、重合体成分に含まれる架橋性基の構成単位としてエポキシ基を有する構成単位を用い、かつ、架橋剤として、分子量が１０００未満の脂環式エポキシ化合物を配合することによって、高い感度および加熱後の透明性を維持しつつ、均一なコンタクトホールを形成できることを見だした。このメカニズムは定かではないが、脂環式エポキシ化合物は酸発生剤により発生する酸を素早くトラップするため、均一なコンタクトホールが形成できるものと考えられる。 As a result of investigation by the inventors of the present invention under such circumstances, an alicyclic ring having a molecular weight of less than 1000 is used as a crosslinking agent using a structural unit having an epoxy group as a structural unit of a crosslinkable group contained in a polymer component. It has been found that a uniform contact hole can be formed by blending the formula epoxy compound while maintaining high sensitivity and transparency after heating. Although this mechanism is not clear, it is considered that the alicyclic epoxy compound quickly traps the acid generated by the acid generator, so that a uniform contact hole can be formed.
　具体的には、以下の解決手段＜１＞により、好ましくは、＜２＞～＜１７＞により、上記課題は解決された。
＜１＞（Ａ）下記（１）および（２）の少なくとも一方を満たす重合体を含む重合体成分、
（１）（ａ１）酸基が酸分解性基で保護された残基を有する構成単位、および（ａ２）エポキシ基を有する構成単位、を有する重合体、
（２）（ａ１）酸基が酸分解性基で保護された残基を有する構成単位を有する重合体、および（ａ２）エポキシ基を有する構成単位を有する重合体、
（Ｂ）光酸発生剤
（Ｃ）分子量が１０００未満の脂環式エポキシ化合物、ならびに
（Ｄ）溶剤
を含有する感光性樹脂組成物。
＜２＞前記（Ｃ）脂環式エポキシ化合物が、下記式（１）で表される、請求項１に記載の感光性樹脂組成物。
式（１）
Figure JPOXMLDOC01-appb-C000007
 （式（１）中、ｎは１～４の整数を表す。Ｒ1は炭素数１～３０の有機基を表す。）
＜３＞Ｒ1は炭素数１～１５の有機基を表す、＜２＞に記載の感光性樹脂組成物。
＜４＞前記（Ｃ）脂環式エポキシ化合物が、下記式（２）で表される、＜１＞または＜２＞に記載の感光性樹脂組成物。
式（２）
Figure JPOXMLDOC01-appb-C000008
 （式（２）中、Ｒ2は炭素数１～１５の有機基を表す。）
＜５＞前記（Ｃ）脂環式エポキシ化合物が、下記式（３）で表される、＜１＞または＜２＞に記載の感光性樹脂組成物。
式（３）
Figure JPOXMLDOC01-appb-C000009
 （式（３）中、Ｒ3は炭素数１～１５の有機基を表す。）
＜６＞さらに、前記（Ｃ）脂環式エポキシ化合物以外の架橋剤を含む、＜１＞～＜５＞のいずれかに記載の感光性樹脂組成物。
＜７＞前記（Ｃ）脂環式エポキシ化合物が、下記式（Ｘ－１）で表される、＜１＞または＜２＞に記載の感光性樹脂組成物。
式（Ｘ－１）
Figure JPOXMLDOC01-appb-C000010
 （式（Ｘ－１）中、Ｒ4は炭素数１～２７の有機基を表す。Ｒ5はそれぞれ炭素数１～２７の置換基を表す。ただし、１つの脂環式エポキシ基を除いた炭素数は３～３０である。）
＜８＞前記（Ｃ）脂環式エポキシ化合物が、下記式（Ｘ－２）で表される、＜１＞、＜２＞、＜７＞のいずれか１項に記載の感光性樹脂組成物。
式（Ｘ－１）
Figure JPOXMLDOC01-appb-C000011
 （式（Ｘ－２）中、Ｒ4はそれぞれ炭素数１～２７の有機基を表す。Ｒ5は炭素数１～２７の置換基を表す。ただし、１つの脂環式エポキシ基を除いた炭素数は３～３０である。）
＜９＞前記（Ｃ）脂環式エポキシ化合物が、下記式（Ｘ－３）で表される、＜１＞、＜２＞、＜７＞、＜８＞のいずれか１項に記載の感光性樹脂組成物。
式（Ｘ－１）
Figure JPOXMLDOC01-appb-C000012
 （式（Ｘ－３）中、Ｒ4はそれぞれ炭素数１～２７の有機基を表す。ただし、１つの脂環式エポキシ基を除いた炭素数は３～３０である。）
＜１０＞前記酸分解性基がアセタールの形で保護された構造を有する基である、＜１＞～＜９＞のいずれかに記載の感光性樹脂組成物。
＜１１＞前記（Ａ）重合体成分のいずれかが、さらに、酸基を含有する重合体である、＜１＞～＜１０＞のいずれかに記載の感光性樹脂組成物。
＜１２＞前記（Ｂ）光酸発生剤が、オキシムスルホネート化合物である＜１＞～＜１１＞のいずれかに記載の感光性樹脂組成物。
＜１３＞（１）＜１＞～＜１２＞のいずれかに記載の感光性樹脂組成物を基板上に塗布する工程、
（２）塗布された感光性樹脂組成物から溶剤を除去する工程、
（３）溶剤が除去された感光性樹脂組成物を活性放射線で露光する工程、
（４）露光された感光性樹脂組成物を水性現像液により現像する工程、および、
（５）現像された感光性樹脂組成物を熱硬化するポストベーク工程、を含むことを特徴とする硬化膜の製造方法。
＜１４＞前記現像する工程後、ポストベーク工程前に、現像された感光性樹脂組成物を全面露光する工程を含む、＜１３＞に記載の硬化膜の形成方法。
＜１５＞＜１３＞または＜１４＞に記載の方法により形成された硬化膜。
＜１６＞層間絶縁膜である、＜１５＞に記載の硬化膜。
＜１７＞＜１５＞または＜１６＞に記載の硬化膜を有する有機ＥＬ表示装置または液晶表示装置。 Specifically, the above problem has been solved by the following means <1>, preferably <2> to <17>.
<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 a residue in which an acid group is protected with an acid-decomposable group, and (a2) a structural unit having an epoxy group,
(2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having an epoxy group,
(B) Photoacid generator (C) A photosensitive resin composition containing an alicyclic epoxy compound having a molecular weight of less than 1000, and (D) a solvent.
<2> The photosensitive resin composition according to claim 1, wherein the (C) alicyclic epoxy compound is represented by the following formula (1).
Formula (1)
Figure JPOXMLDOC01-appb-C000007
 (In the formula (1), n represents an integer of 1 to 4. R 1 represents an organic group having 1 to 30 carbon atoms.)
<3> The photosensitive resin composition according to <2>, wherein R 1 represents an organic group having 1 to 15 carbon atoms.
<4> The photosensitive resin composition according to <1> or <2>, wherein the (C) alicyclic epoxy compound is represented by the following formula (2).
Formula (2)
Figure JPOXMLDOC01-appb-C000008
 (In the formula (2), R 2 represents an organic group having 1 to 15 carbon atoms.)
<5> The photosensitive resin composition according to <1> or <2>, wherein the (C) alicyclic epoxy compound is represented by the following formula (3).
Formula (3)
Figure JPOXMLDOC01-appb-C000009
 (In the formula (3), R 3 represents an organic group having 1 to 15 carbon atoms.)
<6> The photosensitive resin composition according to any one of <1> to <5>, further comprising a crosslinking agent other than the (C) alicyclic epoxy compound.
<7> The photosensitive resin composition according to <1> or <2>, wherein the (C) alicyclic epoxy compound is represented by the following formula (X-1).
Formula (X-1)
Figure JPOXMLDOC01-appb-C000010
 (In the formula (X-1), R 4 represents an organic group having 1 to 27 carbon atoms. R 5 represents a substituent having 1 to 27 carbon atoms, respectively, except for one alicyclic epoxy group. (The number of carbon atoms is 3 to 30.)
<8> The photosensitive resin composition according to any one of <1>, <2>, and <7>, wherein the (C) alicyclic epoxy compound is represented by the following formula (X-2): .
Formula (X-1)
Figure JPOXMLDOC01-appb-C000011
 (In the formula (X-2), R 4 represents an organic group having 1 to 27 carbon atoms, and R 5 represents a substituent having 1 to 27 carbon atoms, except for one alicyclic epoxy group. (The number of carbon atoms is 3 to 30.)
<9> The photosensitive material according to any one of <1>, <2>, <7>, and <8>, wherein the (C) alicyclic epoxy compound is represented by the following formula (X-3): Resin composition.
Formula (X-1)
Figure JPOXMLDOC01-appb-C000012
 (In formula (X-3), each R 4 represents an organic group having 1 to 27 carbon atoms. However, the number of carbon atoms excluding one alicyclic epoxy group is 3 to 30.)
<10> The photosensitive resin composition according to any one of <1> to <9>, wherein the acid-decomposable group is a group having a structure protected in the form of an acetal.
<11> The photosensitive resin composition according to any one of <1> to <10>, wherein any of the polymer components (A) is a polymer further containing an acid group.
<12> The photosensitive resin composition according to any one of <1> to <11>, wherein the (B) photoacid generator is an oxime sulfonate compound.
<13> (1) A step of applying the photosensitive resin composition according to any one of <1> to <12> on a substrate,
(2) a step of removing the solvent from the applied photosensitive resin composition;
(3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic radiation,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
(5) A method for producing a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition.
<14> The method for forming a cured film according to <13>, including a step of exposing the entire surface of the developed photosensitive resin composition after the developing step and before the post-baking step.
<15> A cured film formed by the method according to <13> or <14>.
<16> The cured film according to <15>, which is an interlayer insulating film.
<17> An organic EL display device or a liquid crystal display device having the cured film according to <15> or <16>.
　さらに、下記手段によっても、上記課題は解決された。
＜１８＞上記いずれかに記載の感光性樹脂組成物であって、全固形分１００質量部に対し、（Ａ）重合体成分を５０～９９．９質量部、（Ｂ）光酸発生剤を０．１～１０質量部、（Ｃ）分子量が１０００未満の脂環式エポキシ化合物を０．１～１０質量部含む組成物。 Further, the above-mentioned problem has been solved by the following means.
<18> The photosensitive resin composition according to any one of the above, wherein (A) the polymer component is 50 to 99.9 parts by mass and (B) the photoacid generator is 100 parts by mass of the total solid content. A composition comprising 0.1 to 10 parts by mass of (C) 0.1 to 10 parts by mass of an alicyclic epoxy compound having a molecular weight of less than 1000.
　本発明によって、高い感度および耐熱後の透明性を維持しつつ、均一なコンタクトホールを形成できる感光性樹脂組成物を提供可能となった。 The present invention makes it possible to provide a photosensitive resin composition capable of forming a uniform contact hole while maintaining high sensitivity and transparency after heat resistance.
液晶表示装置の一例の構成概念図を示す。液晶表示装置におけるアクティブマトリックス基板の模式的断面図を示し、層間絶縁膜である硬化膜１７を有している。1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. The schematic sectional drawing of the active matrix substrate in a liquid crystal display device is shown, and it has the cured film 17 which is an interlayer insulation film. 有機ＥＬ表示装置の一例の構成概念図を示す。ボトムエミッション型の有機ＥＬ表示装置における基板の模式的断面図を示し、平坦化膜４を有している。1 shows a conceptual diagram of a configuration of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
　以下において、本発明の内容について詳細に説明する。以下に記載する構成要件の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されるものではない。尚、本願明細書において「～」とはその前後に記載される数値を下限値および上限値として含む意味で使用される。 Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
　なお、本明細書における基（原子団）の表記において、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。 In addition, in the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
　本発明の感光性樹脂組成物（以下、「本発明の組成物」ということがある。）は、（Ａ）下記（１）および（２）の少なくとも一方を満たす重合体を含む重合体成分、
（１）（ａ１）酸基が酸分解性基で保護された残基を有する構成単位、および（ａ２）エポキシ基を有する構成単位、を有する重合体、
（２）（ａ１）酸基が酸分解性基で保護された残基を有する構成単位を有する重合体、および（ａ２）エポキシ基を有する構成単位を有する重合体、
（Ｂ）光酸発生剤
（Ｃ）分子量が１０００未満の脂環式エポキシ化合物、ならびに
（Ｄ）溶剤
を含有することを特徴とする。また、本発明の感光性樹脂組成物は、化学増幅ポジ型感光性樹脂組成物であることが好ましい。
　以下、本発明の組成物について詳細に説明する。 The photosensitive resin composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) is (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 a residue in which an acid group is protected with an acid-decomposable group, and (a2) a structural unit having an epoxy group,
(2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having an epoxy group,
(B) A photoacid generator (C) includes an alicyclic epoxy compound having a molecular weight of less than 1,000, and (D) a solvent. In addition, the photosensitive resin composition of the present invention is preferably a chemically amplified positive photosensitive resin composition.
Hereinafter, the composition of the present invention will be described in detail.
＜（Ａ）重合体成分＞
　本発明の組成物は、重合体成分として、（１）（ａ１）酸基が酸分解性基で保護された基を有する構成単位および（ａ２）エポキシ基を有する構成単位を有する重合体、ならびに（２）（ａ１）酸基が酸分解性基で保護された基を有する構成単位を有する重合体および（ａ２）エポキシ基を有する構成単位を有する重合体、の少なくとも一方を含む。さらに、これら以外の重合体を含んでいてもよい。本発明における（Ａ）重合体成分（以下、「（Ａ）成分」というがある）は、特に述べない限り、上記（１）および／または（２）に加え、必要に応じて添加される他の重合体を含めたものを意味する。 <(A) Polymer component>
The composition of the present invention comprises (1) (a1) 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 an epoxy group, as a polymer component, and (2) At least one of (a1) 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 an epoxy group are included. Furthermore, polymers other than these may be included. The polymer component (A) in the present invention (hereinafter referred to as “component (A)”) is added in addition to the above (1) and / or (2) unless otherwise stated. Including those polymers.
＜＜構成単位（ａ１）＞＞
　成分Ａは、（ａ１）酸基が酸分解性基で保護された基を有する構成単位を少なくとも有する。（Ａ）成分が構成単位（ａ１）を有することにより、極めて高感度な感光性樹脂組成物とすることができる。
　本発明における「酸基が酸分解性基で保護された基」は、酸基および酸分解性基として公知のものを使用でき、特に限定されない。具体的な酸基としては、カルボキシル基、および、フェノール性水酸基が好ましく挙げられる。また、酸分解性基としては、酸により比較的分解し易い基（例えば、後述する式（Ａ１）で表される基のエステル構造、テトラヒドロピラニルエステル基、または、テトラヒドロフラニルエステル基等のアセタール系官能基）や酸により比較的分解し難い基（例えば、ｔｅｒｔ－ブチルエステル基等の第三級アルキル基、ｔｅｒｔ－ブチルカーボネート基等の第三級アルキルカーボネート基）を用いることができる。 << Structural Unit (a1) >>
Component A has (a1) at least a structural unit having a group in which an acid group is protected with an acid-decomposable group. When the component (A) has the structural unit (a1), a highly sensitive photosensitive resin composition can be obtained.
As the “group in which the acid group is protected with an acid-decomposable group” in the present invention, those known as an acid group and an acid-decomposable group can be used, and are not particularly limited. Specific examples of the acid group preferably include a carboxyl group and a phenolic hydroxyl group. The acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an acetal group such as an ester structure of a group represented by the formula (A1), a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester group) A functional group) or a group that is relatively difficult to decompose with an acid (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).
　（ａ１）酸基が酸分解性基で保護された基を有する構成単位は、酸分解性基で保護された保護カルボキシル基を有する構成単位、または、酸分解性基で保護された保護フェノール性水酸基を有する構成単位であることが好ましい。
　以下、酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）と、酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）について、順にそれぞれ説明する。 (A1) The structural unit having a group in which the acid group is protected with an acid-decomposable group is a structural unit having a protected carboxyl group protected with an acid-decomposable group, or a protected phenolic group protected with an acid-decomposable group. A structural unit having a hydroxyl group is preferred.
Hereinafter, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group and the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group will be described in order. To do.
＜＜＜（ａ１－１）酸分解性基で保護された保護カルボキシル基を有する構成単位＞＞＞
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）は、カルボキシル基を有する構成単位のカルボキシル基が、以下で詳細に説明する酸分解性基によって保護された保護カルボキシル基を有する構成単位である。
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）に用いることができる上記カルボキシル基を有する構成単位としては、特に制限はなく公知の構成単位を用いることができる。例えば、不飽和モノカルボン酸、不飽和ジカルボン酸、不飽和トリカルボン酸などの、分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位（ａ１－１－１）や、エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位（ａ１－１－２）が挙げられる。
　以下、上記カルボキシル基を有する構成単位として用いられる（ａ１－１－１）分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位と、（ａ１－１－２）エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位について、それぞれ順に説明する。 <<< (a1-1) Structural Unit Having a Protected Carboxyl Group Protected with an Acid-Decomposable Group >>>
The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a protected carboxyl in which the carboxyl group of the structural unit having a carboxyl group is protected by an acid-decomposable group described in detail below. A structural unit having a group.
The structural unit having a carboxyl group that can be used for the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group is not particularly limited, and a known structural unit can be used. For example, 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, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid, And a structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride.
Hereinafter, (a1-1-1) used as a structural unit having a carboxyl group, a structural unit derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, and (a1-1-2) ethylene The structural units having both the unsaturated group and the structure derived from the acid anhydride will be described in order.
＜＜＜＜（ａ１－１－１）分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位＞＞＞＞
　上記分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位（ａ１－１－１）として本発明で用いられる不飽和カルボン酸としては以下に挙げるようなものが用いられる。すなわち、不飽和モノカルボン酸としては、例えば、アクリル酸、メタクリル酸、クロトン酸、α－クロロアクリル酸、けい皮酸、2－（メタ）アクリロイロキシエチル－コハク酸、2－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、2－（メタ）アクリロイロキシエチル－フタル酸、などが挙げられる。また、不飽和ジカルボン酸としては、例えば、マレイン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸などが挙げられる。また、カルボキシル基を有する構成単位を得るために用いられる不飽和多価カルボン酸は、その酸無水物であってもよい。具体的には、無水マレイン酸、無水イタコン酸、無水シトラコン酸などが挙げられる。また、不飽和多価カルボン酸は、多価カルボン酸のモノ（２－メタクリロイロキシアルキル）エステルであってもよく、例えば、コハク酸モノ（２－アクリロイロキシエチル）、コハク酸モノ（２－メタクリロイロキシエチル）、フタル酸モノ（２－アクリロイロキシエチル）、フタル酸モノ（２－メタクリロイロキシエチル）などが挙げられる。さらに、不飽和多価カルボン酸は、その両末端ジカルボキシポリマーのモノ（メタ）アクリレートであってもよく、例えば、ω－カルボキシポリカプロラクトンモノアクリレート、ω－カルボキシポリカプロラクトンモノメタクリレートなどが挙げられる。また、不飽和カルボン酸としては、アクリル酸－２－カルボキシエチルエステル、メタクリル酸－２－カルボキシエチルエステル、マレイン酸モノアルキルエステル、フマル酸モノアルキルエステル、４－カルボキシスチレン等も用いることができる。
　中でも、現像性の観点から、上記分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位（ａ１－１－１）を形成するためには、アクリル酸、メタクリル酸、2－（メタ）アクリロイロキシエチル－コハク酸、2－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、2－（メタ）アクリロイロキシエチル－フタル酸、または不飽和多価カルボン酸の無水物等を用いることが好ましく、アクリル酸、メタクリル酸、2－（メタ）アクリロイロキシエチルヘキサヒドロフタル酸、を用いることがより好ましい。
　上記分子中に少なくとも１個のカルボキシル基を有する不飽和カルボン酸等に由来する構成単位（ａ１－１－１）は、１種単独で構成されていてもよいし、２種以上で構成されていてもよい。 <<<<< (a1-1-1) Structural Unit Derived from Unsaturated Carboxylic Acid etc. Having at least One Carboxyl Group in the Molecule >>>>
Examples of the unsaturated carboxylic acid used in the present invention as the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule include those listed below. . That is, examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, 2- (meth) acryloyloxyethyl-succinic acid, and 2- (meth) acrylic acid. Examples include leuoxyethyl hexahydrophthalic acid and 2- (meth) acryloyloxyethyl-phthalic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Moreover, the acid anhydride may be sufficient as unsaturated polyhydric carboxylic acid used in order to obtain the structural unit which has a carboxyl group. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester of a polyvalent carboxylic acid, such as succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2 -Methacryloyloxyethyl), mono (2-acryloyloxyethyl) phthalate, mono (2-methacryloyloxyethyl) phthalate and the like. Further, the unsaturated polyvalent carboxylic acid may be a mono (meth) acrylate of a dicarboxy polymer at both ends, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. As the unsaturated carboxylic acid, acrylic acid-2-carboxyethyl ester, methacrylic acid-2-carboxyethyl ester, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, 4-carboxystyrene and the like can also be used.
Among them, from the viewpoint of developability, in order to form the structural unit (a1-1-1) derived from an unsaturated carboxylic acid having at least one carboxyl group in the molecule, acrylic acid, methacrylic acid, 2- (meth) acryloyloxyethyl-succinic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl-phthalic acid, or unsaturated polyhydric carboxylic acid anhydride It is preferable to use acrylic acid, methacrylic acid, and 2- (meth) acryloyloxyethyl hexahydrophthalic acid.
The structural unit (a1-1-1) derived from an unsaturated carboxylic acid or the like having at least one carboxyl group in the molecule may be composed of one kind alone or two or more kinds. May be.
　＜＜＜＜（ａ１－１－２）エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位＞＞＞＞
　エチレン性不飽和基と酸無水物由来の構造とを共に有する構成単位（ａ１－１－２）は、エチレン性不飽和基を有する構成単位中に存在する水酸基と酸無水物とを反応させて得られたモノマーに由来する単位であることが好ましい。
　上記酸無水物としては、公知のものが使用でき、具体的には、無水マレイン酸、無水コハク酸、無水イタコン酸、無水フタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、無水クロレンド酸等の二塩基酸無水物；無水トリメリット酸、無水ピロメリット酸、ベンゾフェノンテトラカルボン酸無水物、ビフェニルテトラカルボン酸無水物などの酸無水物が挙げられる。これらの中では、現像性の観点から、無水フタル酸、テトラヒドロ無水フタル酸、または無水コハク酸、が好ましい。
　上記酸無水物の水酸基に対する反応率は、現像性の観点から、好ましくは１０～１００モル％、より好ましくは３０～１００モル％である。 <<<< (a1-1-2) Structural unit having both an ethylenically unsaturated group and a structure derived from an acid anhydride >>>>
The structural unit (a1-1-2) having both an ethylenically unsaturated group and a structure derived from an acid anhydride is obtained by reacting a hydroxyl group present in the structural unit having an ethylenically unsaturated group with an acid anhydride. A unit derived from the obtained monomer is preferred.
As the acid anhydride, known ones can be used, and specifically, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, etc. Dibasic acid anhydrides; acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, biphenyltetracarboxylic anhydride, and the like. Among these, phthalic anhydride, tetrahydrophthalic anhydride, or succinic anhydride is preferable from the viewpoint of developability.
The reaction rate of the acid anhydride with respect to the hydroxyl group is preferably 10 to 100 mol%, more preferably 30 to 100 mol% from the viewpoint of developability.
　＜＜＜＜構成単位（ａ１－１）に用いることができる酸分解性基＞＞＞＞
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）に用いることができる上記酸分解性基としては上述の酸分解性基を用いることができる。
　これらの酸分解性基の中でもカルボキシル基がアセタールの形で保護された保護カルボキシル基であることが、感光性樹脂組成物の基本物性、特に感度やパターン形状、コンタクトホールの形成性、感光性樹脂組成物の保存安定性の観点から好ましい。さらに酸分解性基の中でもカルボキシル基が下記一般式（ａ１－１０）で表されるアセタールの形で保護された保護カルボキシル基であることが、感度の観点からより好ましい。なお、カルボキシル基が下記一般式（ａ１－１０）で表されるアセタールの形で保護された保護カルボキシル基である場合、保護カルボキシル基の全体としては、－（Ｃ＝Ｏ）－Ｏ－ＣＲ101Ｒ102（ＯＲ103）の構造となっている。 <<<< acid-decomposable group that can be used for the structural unit (a1-1) >>>>
As the acid-decomposable group that can be used for the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group, the above-mentioned acid-decomposable groups can be used.
Among these acid-decomposable groups, it is a protected carboxyl group in which the carboxyl group is protected in the form of an acetal. It is preferable from the viewpoint of the storage stability of the composition. Further, among the acid-decomposable groups, the carboxyl group is more preferably a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10) from the viewpoint of sensitivity. When the carboxyl group is a protected carboxyl group protected in the form of an acetal represented by the following general formula (a1-10), the entire protected carboxyl group is — (C═O) —O—CR 101 The structure is R 102 (OR 103 ).
一般式（ａ１－１０）
Figure JPOXMLDOC01-appb-C000013
 　（式（ａ１－１０）中、Ｒ101およびＲ102は、それぞれ独立に水素原子またはアルキル基を表し、但し、Ｒ101とＲ102とが共に水素原子の場合を除く。Ｒ103は、アルキル基を表す。Ｒ101またはＲ102と、Ｒ103とが連結して環状エーテルを形成してもよい。） Formula (a1-10)
Figure JPOXMLDOC01-appb-C000013
 (In formula (a1-10), R 101 and R 102 each independently represents a hydrogen atom or an alkyl group, except that R 101 and R 102 are both hydrogen atoms, and R 103 represents an alkyl group. R 101 or R 102 and R 103 may be linked to form a cyclic ether.)
　上記一般式（ａ１－１０）中、Ｒ101～Ｒ103は、それぞれ独立に水素原子またはアルキル基を表し、上記アルキル基は直鎖状、分岐鎖状、環状のいずれでもよい。ここで、Ｒ101およびＲ102の双方が水素原子を表すことはなく、Ｒ101およびＲ102の少なくとも一方はアルキル基を表す。 In the general formula (a1-10), R 101 to R 103 each independently represents a hydrogen atom or an alkyl group, and the alkyl group may be linear, branched or cyclic. Here, both R 101 and R 102 do not represent a hydrogen atom, and at least one of R 101 and R 102 represents an alkyl group.
　上記一般式（ａ１－１０）において、Ｒ101、Ｒ102およびＲ103がアルキル基を表す場合、上記アルキル基は直鎖状、分岐鎖状または環状のいずれであってもよい。
　上記直鎖状または分岐鎖状のアルキル基としては、炭素数１～１２であることが好ましく、炭素数１～６であることがより好ましく、炭素数１～４であることがさらに好ましい。具体的には、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、ｎ－ブチル基、ｉ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ネオペンチル基、ｎ－ヘキシル基、テキシル基（２，３－ジメチル－２－ブチル基）、ｎ－ヘプチル基、ｎ－オクチル基、２－エチルヘキシル基、ｎ－ノニル基、ｎ－デシル基等を挙げることができる。 In the general formula (a1-10), when R 101 , R 102 and R 103 represent an alkyl group, the alkyl group may be linear, branched or cyclic.
The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n Examples include -hexyl group, texyl group (2,3-dimethyl-2-butyl group), n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group and the like.
　上記環状アルキル基としては、炭素数３～１２であることが好ましく、炭素数４～８であることがより好ましく、炭素数４～６であることがさらに好ましい。上記環状アルキル基としては、例えばシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、ノルボルニル基、イソボルニル基等を挙げることができる。 The cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and still more preferably 4 to 6 carbon atoms. Examples of the cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isobornyl group.
　上記アルキル基は、置換基を有していてもよく、置換基としては、ハロゲン原子、アリール基、アルコキシ基が例示できる。置換基としてハロゲン原子を有する場合、Ｒ101、Ｒ102、Ｒ103はハロアルキル基となり、置換基としてアリール基を有する場合、Ｒ101、Ｒ102、Ｒ103はアラルキル基となる。
　上記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が例示され、これらの中でもフッ素原子または塩素原子が好ましい。
　また、上記アリール基としては、炭素数６～２０のアリール基が好ましく、より好ましくは炭素数６～１２であり、具体的には、フェニル基、α－メチルフェニル基、ナフチル基等が例示でき、アリール基で置換されたアルキル基全体、すなわち、アラルキル基としては、ベンジル基、α－メチルベンジル基、フェネチル基、ナフチルメチル基等が例示できる。
　上記アルコキシ基としては、炭素数１～６のアルコキシ基が好ましく、より好ましくは炭素数１～４であり、メトキシ基またはエトキシ基がより好ましい。
　また、上記アルキル基が環状のアルキル基である場合、上記環状のアルキル基は置換基として炭素数１～１０の直鎖状または分岐鎖状のアルキル基を有していてもよく、アルキル基が直鎖状または分岐鎖状のアルキル基である場合には、置換基として炭素数３～１２の環状のアルキル基を有していてもよい。
　これらの置換基は、上記置換基でさらに置換されていてもよい。 The alkyl group may have a substituent, and examples of the substituent include a halogen atom, an aryl group, and an alkoxy group. When it has a halogen atom as a substituent, R 101 , R 102 and R 103 become a haloalkyl group, and when it has an aryl group as a substituent, R 101 , R 102 and R 103 become an aralkyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom or a chlorine atom is preferable.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, an α-methylphenyl group, and a naphthyl group. Examples of the entire alkyl group substituted with an aryl group, ie, an aralkyl group, include a benzyl group, an α-methylbenzyl group, a phenethyl group, and a naphthylmethyl group.
The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and more preferably a methoxy group or an ethoxy group.
When the alkyl group is a cyclic alkyl group, the cyclic alkyl group may have a linear or branched alkyl group having 1 to 10 carbon atoms as a substituent, and the alkyl group In the case of a linear or branched alkyl group, it may have a cyclic alkyl group having 3 to 12 carbon atoms as a substituent.
These substituents may be further substituted with the above substituents.
　上記一般式（ａ１－１０）において、Ｒ101、Ｒ102およびＲ103がアリール基を表す場合、上記アリール基は炭素数６～１２であることが好ましく、炭素数６～１０であることがより好ましい。上記アリール基は置換基を有していてもよく、上記置換基としては炭素数１～６のアルキル基が好ましく例示できる。アリール基としては、例えば、フェニル基、トリル基、シリル基、クメニル基、１－ナフチル基等が例示できる。 In the general formula (a1-10), when R 101 , R 102 and R 103 represent an aryl group, the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. preferable. 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 silyl group, a cumenyl group, and a 1-naphthyl group.
　また、Ｒ101、Ｒ102およびＲ103は互いに結合して、それらが結合している炭素原子と一緒になって環を形成することができる。Ｒ101とＲ102、Ｒ101とＲ103またはＲ102とＲ103が結合した場合の環構造としては、例えばシクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、テトラヒドロフラニル基、アダマンチル基およびテトラヒドロピラニル基等を挙げることができる。 R 101 , R 102 and R 103 can be bonded together 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.
　なお、上記一般式（ａ１－１０）において、Ｒ101およびＲ102のいずれか一方が、水素原子またはメチル基であることが好ましい。 Note that in the general formula (a1-10), it is preferable that any one of R 101 and R 102 be a hydrogen atom or a methyl group.
　上記一般式（ａ１－１０）で表される保護カルボキシル基を有する構成単位を形成するために用いられるラジカル重合性単量体は、市販のものを用いてもよいし、公知の方法で合成したものを用いることもできる。例えば、特開２０１１－２２１４９４号公報の段落番号００３７～００４０に記載の合成方法などで合成することができる。 As the radical polymerizable monomer used for forming the structural unit having a protected carboxyl group represented by the general formula (a1-10), a commercially available one may be used, or it may be synthesized by a known method. Things can also be used. For example, it can be synthesized by the synthesis method described in paragraph numbers 0037 to 0040 of JP2011-212494A.
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）の第一の好ましい態様は、下記一般式で表される構成単位である。
Figure JPOXMLDOC01-appb-C000014
 　（式中、Ｒ1およびＲ2は、それぞれ、水素原子、アルキル基またはアリール基を表し、少なくともＲ1およびＲ2のいずれか一方がアルキル基またはアリール基であり、Ｒ3は、アルキル基またはアリール基を表し、Ｒ1またはＲ2と、Ｒ3とが連結して環状エーテルを形成してもよく、Ｒ4は、水素原子またはメチル基を表し、Ｘは単結合またはアリーレン基を表す。）
　Ｒ1およびＲ2がアルキル基の場合、炭素数は１～１０のアルキル基が好ましい。Ｒ1およびＲ2がアリール基の場合、フェニル基が好ましい。Ｒ1およびＲ2は、それぞれ、水素原子または炭素数１～４のアルキル基が好ましい。
　Ｒ3は、アルキル基またはアリール基を表し、炭素数１～１０のアルキル基が好ましく、１～６のアルキル基がより好ましい。
　Ｘは単結合またはアリーレン基を表し、単結合が好ましい。 A first preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit represented by the following general formula.
Figure JPOXMLDOC01-appb-C000014
 (Wherein 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 is an alkyl group or an aryl group, and R 3 is an alkyl group or Represents an aryl group, 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 an arylene group; )
When R 1 and R 2 are alkyl groups, alkyl groups having 1 to 10 carbon atoms are preferred. When R 1 and R 2 are aryl groups, a phenyl group is preferred. R 1 and R 2 are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R 3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
X represents a single bond or an arylene group, and a single bond is preferred.
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）の第二の好ましい態様は、下記一般式の構造単位である。
Figure JPOXMLDOC01-appb-C000015
 　（式中、Ｒ121は水素原子または炭素数１～４のアルキル基を表し、Ｌ1はカルボニル基またはフェニレン基を表し、Ｒ122～Ｒ128はそれぞれ独立に、水素原子または炭素数１～４のアルキル基を表す。）
　Ｒ121は水素原子またはメチル基が好ましい。
　Ｌ1はカルボニル基が好ましい。
　Ｒ122～Ｒ128は、水素原子が好ましい。 A second preferred embodiment of the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is a structural unit of the following general formula.
Figure JPOXMLDOC01-appb-C000015
 (Wherein 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 1 to 4 carbon atoms. Represents an alkyl group of
R 121 is preferably a hydrogen atom or a methyl group.
L 1 is preferably a carbonyl group.
R 122 to R 128 are preferably hydrogen atoms.
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）の好ましい具体例としては、下記の構成単位が例示できる。なお、Ｒは水素原子またはメチル基を表す。 As preferred specific examples of the structural unit (a1-1) having a protected carboxyl group protected by the acid-decomposable group, the following structural units can be exemplified. R represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
＜＜＜（ａ１－２）酸分解性基で保護された保護フェノール性水酸基を有する構成単位＞＞＞
　上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）は、フェノール性水酸基を有する構成単位が、以下で詳細に説明する酸分解性基によって保護された保護フェノール性水酸基を有する構成単位である。 <<< (a1-2) Structural unit having a protected phenolic hydroxyl group protected with an acid-decomposable group >>>
The structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group is a protected phenolic group in which the structural unit having a phenolic hydroxyl group is protected by an acid-decomposable group described in detail below. A structural unit having a hydroxyl group.
＜＜＜＜（ａ１－２－１）フェノール性水酸基を有する構成単位＞＞＞＞
　上記フェノール性水酸基を有する構成単位としては、ヒドロキシスチレン系構成単位やノボラック系の樹脂における構成単位が挙げられるが、これらの中では、ヒドロキシスチレン、またはα－メチルヒドロキシスチレンに由来する構成単位が、感度の観点から好ましい。またフェノール性水酸基を有する構成単位として、下記一般式（ａ１－２０）で表される構成単位も、感度の観点から好ましい。 <<<<< (a1-2-1) Structural Unit Having Phenolic Hydroxyl Group >>>>
Examples of the structural unit having a phenolic hydroxyl group include a hydroxystyrene structural unit and a structural unit in a novolac resin. Among these, a structural unit derived from hydroxystyrene or α-methylhydroxystyrene includes: It is preferable from the viewpoint of sensitivity. As the structural unit having a phenolic hydroxyl group, a structural unit represented by the following general formula (a1-20) is also preferable from the viewpoint of sensitivity.
一般式（ａ１－２０）
Figure JPOXMLDOC01-appb-C000017
 　（一般式（ａ１－２０）中、Ｒ220は水素原子またはメチル基を表し、Ｒ221は単結合または二価の連結基を表し、Ｒ222はハロゲン原子または炭素数１～５の直鎖または分岐鎖状のアルキル基を表し、ａは１～５の整数を表し、ｂは０～４の整数を表し、ａ＋ｂは５以下である。なお、Ｒ222が２以上存在する場合、これらのＲ222は相互に異なっていてもよいし同じでもよい。） Formula (a1-20)
Figure JPOXMLDOC01-appb-C000017
 (In the general formula (a1-20), R 220 represents a hydrogen atom or a methyl group, R 221 represents a single bond or a divalent linking group, and R 222 represents a halogen atom or a straight chain of 1 to 5 carbon atoms or Represents a branched alkyl group, a represents an integer of 1 to 5, b represents an integer of 0 to 4, and a + b is 5 or less, and when R 222 is 2 or more, these R 222 may be different from each other or the same.)
　上記一般式（ａ１－２０）中、Ｒ220は水素原子またはメチル基を表し、メチル基であることが好ましい。
　また、Ｒ221は単結合または二価の連結基を示す。単結合である場合には、感度を向上させることができ、さらに硬化膜の透明性を向上させることができるので好ましい。Ｒ221の二価の連結基としてはアルキレン基が例示でき、Ｒ221がアルキレン基である具体例としては、メチレン基、エチレン基、プロピレン基、イソプロピレン基、ｎ－ブチレン基、イソブチレン基、ｔｅｒｔ－ブチレン基、ペンチレン基、イソペンチレン基、ネオペンチレン基、ヘキシレン基等が挙げられる。中でも、Ｒ221が単結合、メチレン基、エチレン基であることが好ましい。また、上記二価の連結基は、置換基を有していてもよく、置換基としては、ハロゲン原子、水酸基、アルコキシ基等が挙げられる。また、ａは１～５の整数を表すが、本発明の効果の観点や、製造が容易であるという点から、ａは１または２であることが好ましく、ａが１であることがより好ましい。
　また、ベンゼン環における水酸基の結合位置は、Ｒ221と結合している炭素原子を基準（１位）としたとき、４位に結合していることが好ましい。
　Ｒ222はハロゲン原子または炭素数１～５の直鎖または分岐鎖状のアルキル基である。具体的には、フッ素原子、塩素原子、臭素原子、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ペンチル基、イソペンチル基、ネオペンチル基等が挙げられる。中でも製造が容易であるという点から、塩素原子、臭素原子、メチル基またはエチル基であることが好ましい。
　また、ｂは０または１～４の整数を表す。 In the general formula (a1-20), R 220 represents a hydrogen atom or a methyl group, and is preferably a methyl group.
R 221 represents a single bond or a divalent linking group. A single bond is preferable because the sensitivity can be improved and the transparency of the cured film can be improved. The divalent linking group of R 221 may be exemplified alkylene groups, specific examples R 221 is an alkylene group, a methylene group, an ethylene group, a propylene group, isopropylene group, n- butylene group, isobutylene group, tert -Butylene group, pentylene group, isopentylene group, neopentylene group, hexylene group and the like. Among these, it is preferable that R 221 is a single bond, a methylene group, or an ethylene group. The divalent linking group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, and an alkoxy group. A represents an integer of 1 to 5, but a is preferably 1 or 2 and more preferably 1 from the viewpoint of the effects of the present invention and the ease of production. .
Further, the bonding position of the hydroxyl group in the benzene ring is preferably bonded to the 4-position when the carbon atom bonded to R 221 is defined as the reference (first position).
R 222 is a halogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, fluorine atom, chlorine atom, bromine atom, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, etc. It is done. Among these, a chlorine atom, a bromine atom, a methyl group, or an ethyl group is preferable from the viewpoint of easy production.
B represents 0 or an integer of 1 to 4;
＜＜＜＜構成単位（ａ１－２）に用いることができる酸分解性基＞＞＞＞
　上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）に用いることができる上記酸分解性基としては、上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）に用いることができる上記酸分解性基と同様に、公知のものを使用でき、特に限定されない。酸分解性基の中でもアセタールで保護された保護フェノール性水酸基を有する構成単位であることが、感光性樹脂組成物の基本物性、特に感度やパターン形状、感光性樹脂組成物の保存安定性、コンタクトホールの形成性の観点から好ましい。さらに、酸分解性基の中でもフェノール性水酸基が上記一般式（ａ１－１０）で表されるアセタールの形で保護された保護フェノール性水酸基であることが、感度の観点からより好ましい。なお、フェノール性水酸基が上記一般式（ａ１－１０）で表されるアセタールの形で保護された保護フェノール性水酸基である場合、保護フェノール性水酸基の全体としては、－Ａｒ－Ｏ－ＣＲ101Ｒ102（ＯＲ103）の構造となっている。なお、Ａｒはアリーレン基を表す。 <<<< acid-decomposable group that can be used for the structural unit (a1-2) >>>>
The acid-decomposable group that can be used in the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group includes a structure having a protected carboxyl group protected by the acid-decomposable group Similar to the acid-decomposable group that can be used for the unit (a1-1), known ones can be used and are not particularly limited. Among the acid-decomposable groups, a structural unit having a protected phenolic hydroxyl group protected with acetal is a basic physical property of the photosensitive resin composition, particularly sensitivity and pattern shape, storage stability of the photosensitive resin composition, contact This is preferable from the viewpoint of hole formability. Furthermore, among the acid-decomposable groups, the phenolic hydroxyl group is more preferably a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-10) from the viewpoint of sensitivity. When the phenolic hydroxyl group is a protected phenolic hydroxyl group protected in the form of an acetal represented by the general formula (a1-10), the protected phenolic hydroxyl group as a whole is —Ar—O—CR 101 R The structure is 102 (OR 103 ). Ar represents an arylene group.
　フェノール性水酸基のアセタールエステル構造の好ましい例は、Ｒ101＝Ｒ102＝Ｒ103＝メチル基やＲ101＝Ｒ102＝メチル基でＲ103＝ベンジル基の組み合わせが例示できる。 Preferable examples of the acetal ester structure of the phenolic hydroxyl group include a combination of R 101 = R 102 = R 103 = methyl group, R 101 = R 102 = methyl group and R 103 = benzyl group.
　また、フェノール性水酸基がアセタールの形で保護された保護フェノール性水酸基を有する構成単位を形成するために用いられるラジカル重合性単量体としては、例えば、特開２０１１－２１５５９０号公報の段落番号００４２に記載のものなどが挙げられる。
　これらの中で、４－ヒドロキシフェニルメタクリレートの１－アルコキシアルキル保護体、４－ヒドロキシフェニルメタクリレートのテトラヒドロピラニル保護体、が透明性の観点から好ましい。 Examples of the radical polymerizable monomer used for forming a structural unit having a protected phenolic hydroxyl group in which the phenolic hydroxyl group is protected in the form of an acetal include paragraph number 0042 of JP2011-215590A. And the like.
Among these, a 1-alkoxyalkyl protector of 4-hydroxyphenyl methacrylate and a tetrahydropyranyl protector of 4-hydroxyphenyl methacrylate are preferable from the viewpoint of transparency.
　フェノール性水酸基のアセタール保護基の具体例としては、１－アルコキシアルキル基が挙げられ、例えば、１－エトキシエチル基、１－メトキシエチル基、１－ｎ－ブトキシエチル基、１－イソブトキシエチル基、１－（２－クロロエトキシ）エチル基、１－（２－エチルヘキシルオキシ）エチル基、１－ｎ－プロポキシエチル基、１－シクロヘキシルオキシエチル基、１－（２－シクロヘキシルエトキシ）エチル基、１－ベンジルオキシエチル基などを挙げることができ、これらは単独または２種類以上を組み合わせて使用することができる。 Specific examples of the acetal protecting group for the phenolic hydroxyl group include a 1-alkoxyalkyl group, such as a 1-ethoxyethyl group, a 1-methoxyethyl group, a 1-n-butoxyethyl group, and a 1-isobutoxyethyl group. 1- (2-chloroethoxy) ethyl group, 1- (2-ethylhexyloxy) ethyl group, 1-n-propoxyethyl group, 1-cyclohexyloxyethyl group, 1- (2-cyclohexylethoxy) ethyl group, 1 -A benzyloxyethyl group etc. can be mentioned, These can be used individually or in combination of 2 or more types.
　上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）を形成するために用いられるラジカル重合性単量体は、市販のものを用いてもよいし、公知の方法で合成したものを用いることもできる。例えば、フェノール性水酸基を有する化合物を酸触媒の存在下でビニルエーテルと反応させることにより合成することができる。上記の合成はフェノール性水酸基を有するモノマーをその他のモノマーと予め共重合させておき、その後に酸触媒の存在下でビニルエーテルと反応させてもよい。 As the radical polymerizable monomer used for forming the structural unit (a1-2) having a protected phenolic hydroxyl group protected by the acid-decomposable group, a commercially available one may be used, or a known method may be used. What was synthesize | combined by can also be used. For example, it can be synthesized by reacting a compound having a phenolic hydroxyl group with vinyl ether in the presence of an acid catalyst. In the above synthesis, a monomer having a phenolic hydroxyl group may be previously copolymerized with another monomer, and then reacted with vinyl ether in the presence of an acid catalyst.
　上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）の好ましい具体例としては、下記の構成単位が例示できるが、本発明はこれらに限定されるものではない。 As preferred specific examples of the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group, the following structural units can be exemplified, but the present invention is not limited thereto.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
＜＜＜構成単位（ａ１）の好ましい態様＞＞＞
　上記構成単位（ａ１）を含有する重合体が、実質的に、構成単位（ａ２）を含まない場合、構成単位（ａ１）は、該構成単位（ａ１）を含有する重合体中、２０～１００モル％が好ましく、３０～９０モル％がより好ましい。
　上記構成単位（ａ１）を含有する重合体が、下記構成単位（ａ２）を含有する場合、構成単位（ａ１）は、該構成単位（ａ１）と構成単位（ａ２）を含有する重合体中、感度の観点から３～７０モル％が好ましく、１０～６０モル％がより好ましい。また、特に上記構成単位（ａ１）に用いることができる上記酸分解性基がカルボキシル基がアセタールの形で保護された保護カルボキシル基を有する構成単位である場合、２０～５０モル％が好ましい。 <<< Preferred Aspect of Structural Unit (a1) >>>
When the polymer containing the structural unit (a1) does not substantially contain the structural unit (a2), the structural unit (a1) is 20 to 100 in the polymer containing the structural unit (a1). The mol% is preferable, and 30 to 90 mol% is more preferable.
When the polymer containing the structural unit (a1) contains the following structural unit (a2), the structural unit (a1) is a polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of sensitivity, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%. In particular, when the acid-decomposable group that can be used in the structural unit (a1) is a structural unit having a protected carboxyl group in which the carboxyl group is protected in the form of an acetal, the content is preferably 20 to 50 mol%.
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）は、上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）に比べると、現像が速いという特徴がある。よって、速く現像したい場合には酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）が好ましい。逆に現像を遅くしたい場合には酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）を用いることが好ましい。
　上記酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）は、上記酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）に比べると、現像が速いという特徴がある。よって、速く現像したい場合には酸分解性基で保護された保護カルボキシル基を有する構成単位（ａ１－１）が好ましい。逆に現像を遅くしたい場合には酸分解性基で保護された保護フェノール性水酸基を有する構成単位（ａ１－２）を用いることが好ましい。 The structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, when it is desired to develop quickly, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-2) 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 is more developed than the structural unit (a1-2) having a protected phenolic hydroxyl group protected with the acid-decomposable group. Is characterized by being fast. Therefore, when it is desired to develop quickly, the structural unit (a1-1) having a protected carboxyl group protected with an acid-decomposable group is preferred. Conversely, when it is desired to delay the development, it is preferable to use the structural unit (a1-2) having a protected phenolic hydroxyl group protected with an acid-decomposable group.
＜＜（ａ２）エポキシ基を有する構成単位＞＞
　（Ａ）成分は、エポキシ基を有する構成単位（ａ２）を有する。上記エポキシ基を有する構成単位（ａ２）は、１つの構成単位中にエポキシ基を少なくとも１つ有していればよくエポキシ基を合計１～３つ有することが好ましく、エポキシ基を合計１または２つ有することがより好ましく、エポキシ基を１つ有することがさらに好ましい。 << (a2) Structural Unit Having Epoxy Group >>
The component (A) has a structural unit (a2) having an epoxy group. The structural unit (a2) having an epoxy group may have at least one epoxy group in one structural unit, and preferably has 1 to 3 epoxy groups in total, and 1 or 2 epoxy groups in total. It is more preferable to have one, and it is still more preferable to have one epoxy group.
　エポキシ基を有する構成単位を形成するために用いられるラジカル重合性単量体の具体例としては、例えば、アクリル酸グリシジル、メタクリル酸グリシジル、α－エチルアクリル酸グリシジル、α－ｎ－プロピルアクリル酸グリシジル、α－ｎ－ブチルアクリル酸グリシジル、アクリル酸－３，４－エポキシブチル、メタクリル酸－３，４－エポキシブチル、アクリル酸－３，４－エポキシシクロヘキシルメチル、メタクリル酸－３，４－エポキシシクロヘキシルメチル、α－エチルアクリル酸－３，４－エポキシシクロヘキシルメチル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、特許第４１６８４４３号公報の段落番号００３１～００３５に記載の脂環式エポキシ骨格を含有する化合物などが挙げられ、これらの内容は本願明細書に組み込まれる。
　上記エポキシ基を有する構成単位（ａ２）を形成するために用いられるラジカル重合性単量体の具体例としては、メタクリル酸エステル構造を含有するモノマー、アクリル酸エステル構造を含有するモノマーであることが好ましい。 Specific examples of the radical polymerizable monomer used for forming the structural unit having an epoxy group include, for example, glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, and glycidyl α-n-propyl acrylate. Glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexyl methacrylate Methyl, α-ethylacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, described in paragraph Nos. 0031 to 0035 of Japanese Patent No. 4168443 Alicyclic And compounds containing epoxy backbone can be cited, the contents of which are hereby incorporated herein.
Specific examples of the radical polymerizable monomer used for forming the structural unit (a2) having the epoxy group include a monomer containing a methacrylic ester structure and a monomer containing an acrylic ester structure. preferable.
　これらの中でも好ましいものは、メタクリル酸グリシジル、アクリル酸３，４－エポキシシクロヘキシルメチル、メタクリル酸３，４－エポキシシクロヘキシルメチル、アクリル酸（３－エチルオキセタン－３－イル）メチル、および、メタクリル酸（３－エチルオキセタン－３－イル）メチルである。これらの構成単位は、１種単独または２種類以上を組み合わせて使用することができる。 Among these, preferred are glycidyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, methyl (3-ethyloxetane-3-yl) methacrylate, and methacrylic acid ( 3-ethyloxetane-3-yl) methyl. These structural units can be used individually by 1 type or in combination of 2 or more types.
　上記エポキシ基を有する構成単位（ａ２）の好ましい具体例としては、下記の構成単位が例示できる。なお、Ｒは、水素原子またはメチル基を表す。 Preferred examples of the structural unit (a2) having an epoxy group include the following structural units. R represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
＜＜＜構成単位（ａ２）の好ましい態様＞＞＞
　上記構成単位（ａ２）を含有する重合体が、実質的に、構成単位（ａ１）を含まない場合、構成単位（ａ２）は、該構成単位（ａ２）を含有する重合体中、５～９０モル％が好ましく、２０～８０モル％がより好ましい。
　上記構成単位（ａ２）を含有する重合体が、上記構成単位（ａ１）を含有する場合、構成単位（ａ２）は、該構成単位（ａ１）と構成単位（ａ２）を含有する重合体中、薬品耐性の観点から３～７０モル％が好ましく、１０～６０モル％がより好ましい。
　本発明では、さらに、いずれの態様にかかわらず、（Ａ）成分の全構成単位中、構成単位（ａ２）を３～７０モル％含有することが好ましく、１０～６０モル％含有することがより好ましく、２０～６０モル％含有することが最も好ましい。
　さらに、構成単位（ａ２）が有するエポキシ基は脂環式エポキシ基でないことが好ましい。 <<< Preferred Aspect of Structural Unit (a2) >>>
When the polymer containing the structural unit (a2) does not substantially contain the structural unit (a1), the structural unit (a2) is 5 to 90% in the polymer containing the structural unit (a2). The mol% is preferable, and 20 to 80 mol% is more preferable.
When the polymer containing the structural unit (a2) contains the structural unit (a1), the structural unit (a2) is a polymer containing the structural unit (a1) and the structural unit (a2). From the viewpoint of chemical resistance, it is preferably 3 to 70 mol%, more preferably 10 to 60 mol%.
In the present invention, the structural unit (a2) is preferably contained in an amount of 3 to 70 mol%, more preferably 10 to 60 mol% in all the structural units of the component (A), regardless of any embodiment. The content is preferably 20 to 60 mol%, and most preferably.
Furthermore, it is preferable that the epoxy group which the structural unit (a2) has is not an alicyclic epoxy group.
　上記の数値の範囲内であると、感光性樹脂組成物から得られる硬化膜の透明性および薬品耐性が良好となる。 Within the above numerical range, the transparency and chemical resistance of the cured film obtained from the photosensitive resin composition are improved.
＜＜（ａ３）その他の構成単位＞＞
　本発明において、（Ａ）成分は、上記構成単位（ａ１）および／または（ａ２）に加えて、これら以外の他の構成単位（ａ３）を有していてもよい。これらの構成単位は、上記重合体成分（１）および／または（２）が含んでいてもよい。また、上記重合体成分（１）または（２）とは別に、実質的に（ａ１）および（ａ２）を含まずに他の構成単位（ａ３）を有する重合体成分を有していてもよい。上記重合体成分（１）または（２）とは別に、実質的に（ａ１）および（ａ２）を含まずに他の構成単位（ａ３）を有する重合体成分を含む場合、該重合体成分の配合量は、全重合体成分中、６０質量％以下であることが好ましく、４０質量％以下であることがより好ましく、２０質量％以下であることがさらに好ましい。 << (a3) Other structural units >>
In the present invention, the component (A) may have another structural unit (a3) in addition to the structural units (a1) and / or (a2). These structural units may be contained in the polymer component (1) and / or (2). Further, apart from the polymer component (1) or (2), it may have a polymer component having other structural unit (a3) substantially not containing (a1) and (a2). . Apart from the polymer component (1) or (2), in the case of containing a polymer component having other structural unit (a3) substantially not containing (a1) and (a2), The blending amount is preferably 60% by mass or less, more preferably 40% by mass or less, and still more preferably 20% by mass or less in all polymer components.
　その他の構成単位（ａ３）となるモノマーとしては、特に制限はなく、例えば、スチレン類、（メタ）アクリル酸アルキルエステル、（メタ）アクリル酸環状アルキルエステル、（メタ）アクリル酸アリールエステル、不飽和ジカルボン酸ジエステル、ビシクロ不飽和化合物類、マレイミド化合物類、不飽和芳香族化合物、共役ジエン系化合物、不飽和モノカルボン酸、不飽和ジカルボン酸、不飽和ジカルボン酸無水物、その他の不飽和化合物を挙げることができる。また、後述するとおり、酸基を有する構成単位を有していてもよい。その他の構成単位（ａ３）となるモノマーは、単独または２種類以上を組み合わせて使用することができる。 There is no restriction | limiting in particular as a monomer used as another structural unit (a3), For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated Dicarboxylic acid diesters, bicyclounsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated diene compounds, unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides, and other unsaturated compounds be able to. Moreover, you may have the structural unit which has an acid group so that it may mention later. The monomer which becomes another structural unit (a3) can be used individually or in combination of 2 or more types.
　以下に、本発明の重合体成分の好ましい実施形態を挙げるが、本発明はこれらに限定されるものではない。 Hereinafter, preferred embodiments of the polymer component of the present invention will be described, but the present invention is not limited thereto.
（第１の実施形態）
　重合体成分（１）が、さらに、１種または２種以上のその他の構成単位（ａ３）を有する態様。
（第２の実施形態）
　重合体成分（２）の（ａ１）酸基が酸分解性基で保護された基を有する構成単位を有する重合体が、さらに、１種または２種以上のその他の構成単位（ａ３）を有する態様。
（第３の実施形態）
　重合体成分（２）の（ａ２）エポキシ基を有する構成単位を有する重合体が、さらに、１種または２種以上のその他の構成単位（ａ３）を有する態様。 (First embodiment)
The aspect in which the polymer component (1) further has one or more other structural units (a3).
(Second Embodiment)
The polymer having a structural unit having a group in which the (a1) acid group of the polymer component (2) is protected by an acid-decomposable group further has one or more other structural units (a3). Aspect.
(Third embodiment)
The aspect which the polymer which has a structural unit which has (a2) epoxy group of the polymer component (2) further has 1 type, or 2 or more types of other structural units (a3).
（第４の実施形態）
　上記第１～第３の実施形態のいずれかにおいて、その他の構成単位（ａ３）として、少なくとも酸基を含む構成単位を含む態様。 (Fourth embodiment)
In any one of the first to third embodiments, the other structural unit (a3) includes a structural unit containing at least an acid group.
（第５の実施形態）
　上記重合体成分（１）または（２）とは別に、さらに、実質的に（ａ１）および（ａ２）を含まずに他の構成単位（ａ３）を有する重合体を有する態様。 (Fifth embodiment)
In addition to the polymer component (1) or (2), an embodiment having a polymer having another structural unit (a3) substantially not containing (a1) and (a2).
（第６の実施形態）
　上記第１～第５の実施形態の２以上の組み合わせからなる形態。
（第７の実施形態）
　重合体成分（２）を少なくとも含む態様。特に、上記第１～第６の実施形態において、少なくとも重合体成分（２）を含む態様。 (Sixth embodiment)
A form comprising a combination of two or more of the first to fifth embodiments.
(Seventh embodiment)
An embodiment comprising at least the polymer component (2). In particular, in the first to sixth embodiments, at least the polymer component (2) is included.
　構成単位（ａ３）は、具体的には、スチレン、ｔｅｒｔ－ブトキシスチレン、メチルスチレン、ヒドロキシスチレン、α－メチルスチレン、アセトキシスチレン、メトキシスチレン、エトキシスチレン、クロロスチレン、ビニル安息香酸メチル、ビニル安息香酸エチル、４－ヒドロキシ安息香酸（３－メタクリロイルオキシプロピル）エステル、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸イソボルニル、アクリロニトリル、エチレングリコールモノアセトアセテートモノ（メタ）アクリレートなどによる構成単位を挙げることができる。この他、特開２００４－２６４６２３号公報の段落番号００２１～００２４に記載の化合物を挙げることができる。 The structural unit (a3) specifically includes styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, vinylbenzoic acid. Ethyl, 4-hydroxybenzoic acid (3-methacryloyloxypropyl) ester, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) acrylic acid Isopropyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate Mention may be made of a structural unit due to theft. In addition, compounds described in paragraph numbers 0021 to 0024 of JP-A No. 2004-264623 can be exemplified.
　また、その他の構成単位（ａ３）としてスチレン類、脂肪族環式骨格を有する基が、電気特性の観点で好ましい。具体的にはスチレン、ｔｅｒｔ－ブトキシスチレン、メチルスチレン、ヒドロキシスチレン、α－メチルスチレン、ジシクロペンタニル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート等が挙げられる。 Further, as other structural unit (a3), styrenes and groups having an aliphatic cyclic skeleton are preferable from the viewpoint of electrical characteristics. Specifically, styrene, tert-butoxystyrene, methylstyrene, hydroxystyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, etc. Can be mentioned.
　さらにまた、その他の構成単位（ａ３）として（メタ）アクリル酸アルキルエステルが、密着性の観点で好ましい。具体的には（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ｎ－ブチル等が挙げられ、（メタ）アクリル酸メチルがより好ましい。重合体（Ａ）を構成する構成単位中、上記の構成単位（ａ３）の含有率は、６０モル％以下が好ましく、５０モル％以下がより好ましく、４０モル％以下がさらに好ましい。下限値としては、０モル％でもよいが、例えば、１モル％以上とすることができ、さらには、５モル％以上とすることができる。上記の数値の範囲内であると、感光性樹脂組成物から得られる硬化膜の諸特性が良好となる。 Furthermore, as other structural unit (a3), (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and n-butyl (meth) acrylate, and methyl (meth) acrylate is more preferable. In the structural unit constituting the polymer (A), the content of the structural unit (a3) is preferably 60 mol% or less, more preferably 50 mol% or less, and further preferably 40 mol% or less. As a lower limit, although 0 mol% may be sufficient, it can be set as 1 mol% or more, for example, Furthermore, it can be set as 5 mol% or more. When it is within the above numerical range, various properties of the cured film obtained from the photosensitive resin composition are improved.
　その他の構成単位（ａ３）として、酸基を含むことが好ましい。酸基を含むことにより、アルカリ性の現像液に溶けやすくなり、本発明の効果がより効果的に発揮される。本発明における酸基とは、ｐＫａが７より小さいプロトン解離性基を意味する。酸基は、通常、酸基を形成しうるモノマーを用いて、酸基を含む構成単位として、重合体に組み込まれる。このような酸基を含む構成単位を重合体中に含めることにより、アルカリ性の現像液に対して溶けやすくなる傾向にある。
　本発明で用いられる酸基としては、カルボン酸基由来のもの、スルホンアミド基に由来のもの、ホスホン酸基に由来のもの、スルホン酸基に由来のもの、フェノール性水酸基に由来するもの、スルホンアミド基、スルホニルイミド基等が例示され、カルボン酸基由来のものおよび／またはフェノール性水酸基に由来のものが好ましい。
　本発明で用いられる酸基を含む構成単位は、スチレンに由来する構成単位や、ビニル化合物に由来する構成単位、（メタ）アクリル酸および／またはそのエステルに由来する構成単位であることがより好ましい。 The other structural unit (a3) preferably contains an acid group. By containing an acid group, it becomes easy to dissolve in an alkaline developer, and the effects of the present invention are more effectively exhibited. The acid group in the present invention means a proton dissociable group having a pKa of less than 7. The acid group is usually incorporated into the polymer as a structural unit containing an acid group using a monomer capable of forming an acid group. By including such a structural unit containing an acid group in the polymer, the polymer tends to be easily dissolved in an alkaline developer.
Acid groups used in the present invention include those derived from carboxylic acid groups, those derived from sulfonamide groups, those derived from phosphonic acid groups, those derived from sulfonic acid groups, those derived from phenolic hydroxyl groups, sulfones Amide groups, sulfonylimide groups and the like are exemplified, and those derived from carboxylic acid groups and / or those derived from phenolic hydroxyl groups are preferred.
The structural unit containing an acid group used in the present invention is more preferably a structural unit derived from styrene, a structural unit derived from a vinyl compound, a structural unit derived from (meth) acrylic acid and / or an ester thereof. .
　本発明では、特に、カルボキシル基を有する構成単位、または、フェノール性水酸基を有する構成単位を含有することが、感度の観点で好ましい。 In the present invention, it is particularly preferable from the viewpoint of sensitivity to contain a structural unit having a carboxyl group or a structural unit having a phenolic hydroxyl group.
　酸基を含む構成単位は、全重合体成分の構成単位の１～８０モル％が好ましく、１～５０モル％がより好ましく、５～４０モル％がさらに好ましく、５～３０モル％が特に好ましく、５～２０モル％が特に好ましい。 The structural unit containing an acid group is preferably 1 to 80% by mole, more preferably 1 to 50% by mole, still more preferably 5 to 40% by mole, and particularly preferably 5 to 30% by mole of the structural unit of all polymer components. 5 to 20 mol% is particularly preferable.
　本発明では、上記重合体成分（１）または（２）とは別に、実質的に（ａ１）および（ａ２）を含まずに他の構成単位（ａ３）を有する重合体を含んでいても良い。 In the present invention, in addition to the polymer component (1) or (2), a polymer having other structural unit (a3) without substantially containing (a1) and (a2) may be included. .
　このような重合体としては、側鎖にカルボキシル基を有する樹脂が好ましい。例えば、特開昭５９－４４６１５号、特公昭５４－３４３２７号、特公昭５８－１２５７７号、特公昭５４－２５９５７号、特開昭５９－５３８３６号、特開昭５９－７１０４８号の各公報に記載されているような、メタクリル酸共重合体、アクリル酸共重合体、イタコン酸共重合体、クロトン酸共重合体、マレイン酸共重合体、部分エステル化マレイン酸共重合体等、並びに側鎖にカルボキシル基を有する酸性セルロース誘導体、水酸基を有するポリマーに酸無水物を付加させたもの等が挙げられ、さらに側鎖に（メタ）アクリロイル基を有する高分子重合体も好ましいものとして挙げられる。 Such a polymer is preferably a resin having a carboxyl group in the side chain. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048 As described, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and side chain Examples thereof include acidic cellulose derivatives having a carboxyl group, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, and high molecular polymers having a (meth) acryloyl group in the side chain.
　例えば、ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、２－ヒドロキシエチル（メタ）アクリレート／ベンジル（メタ）アクリレート／（メタ）アクリル酸共重合体、特開平７－１４０６５４号公報に記載の、２－ヒドロキシプロピル（メタ）アクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシ－３－フェノキシプロピルアクリレート／ポリメチルメタクリレートマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／メチルメタクリレート／メタクリル酸共重合体、２－ヒドロキシエチルメタクリレート／ポリスチレンマクロモノマー／ベンジルメタクリレート／メタクリル酸共重合体などが挙げられる。
　その他にも、特開平７－２０７２１１号公報、特開平８－２５９８７６号公報、特開平１０－３００９２２号公報、特開平１１－１４０１４４号公報、特開平１１－１７４２２４号公報、特開２０００－５６１１８号公報、特開２００３－２３３１７９号公報、特開２００９－５２０２０号公報等に記載の公知の高分子化合物を使用することができ、これらの内容は本願明細書に組み込まれる。 For example, benzyl (meth) acrylate / (meth) acrylic acid copolymer, 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, described in JP-A-7-140654 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2 -Hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid Copolymer and the like.
In addition, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118 Known polymer compounds described in JP-A-2003-233179, JP-A-2009-52020, and the like can be used, and the contents thereof are incorporated herein.
　これらの重合体として、市販されている、ＳＭＡ　１０００Ｐ、ＳＭＡ　２０００Ｐ、ＳＭＡ　３０００Ｐ、ＳＭＡ　１４４０Ｆ、ＳＭＡ　１７３５２Ｐ、ＳＭＡ　２６２５Ｐ、ＳＭＡ　３８４０Ｆ（以上、サートマー社製）、ＡＲＵＦＯＮ　ＵＣ－３０００、ＡＲＵＦＯＮ　ＵＣ－３５１０、ＡＲＵＦＯＮ　ＵＣ－３９００、ＡＲＵＦＯＮ　ＵＣ－３９１０、ＡＲＵＦＯＮ　ＵＣ－３９２０、ＡＲＵＦＯＮ　ＵＣ－３０８０（以上、東亞合成（株）製）、Ｊｏｎｃｒｙｌ  ６８０、Ｊｏｎｃｒｙｌ  ６８２、Ｊｏｎｃｒｙｌ　６９０、Ｊｏｎｃｒｙｌ　６７８、Ｊｏｎｃｒｙｌ　６７、Ｊｏｎｃｒｙｌ　５８６（以上、ＢＡＳＦ製）等も用いることもできる。
　これらの他の重合体は、１種類のみ含んでいてもよいし、２種類以上含んでいてもよい。 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 are commercially available as these polymers. UC-3900, ARUFON UC-3910, ARUFON UC-3920, ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), Joncryl 680, Joncryl 682, Joncryl 690, Joncryl 678, JoncrJr 67 Etc.) can also be used.
These other polymers may contain only 1 type, and may contain 2 or more types.
＜＜（Ａ）重合体の分子量＞＞
　（Ａ）重合体の分子量は、ポリスチレン換算重量平均分子量で、好ましくは１，０００～２００，０００、より好ましくは２，０００～５０，０００の範囲であり、さらに好ましくは１０，０００～５０，０００の範囲である。上記の数値の範囲内であると、諸特性が良好である。数平均分子量と重量平均分子量の比（分散度）は１．０～５．０が好ましく１．５～３．５がより好ましい。 << (A) Molecular Weight of Polymer >>
The molecular weight of the polymer (A) is a polystyrene-equivalent weight average molecular weight, preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and still more preferably 10,000 to 50,000. 000 range. Various characteristics are favorable in the range of said numerical value. The ratio (dispersity) between the number average molecular weight and the weight average molecular weight is preferably 1.0 to 5.0, more preferably 1.5 to 3.5.
＜＜（Ａ）重合体の製造方法＞＞
　また、（Ａ）成分の合成法についても、様々な方法が知られているが、一例を挙げると、少なくとも上記（ａ１）および上記（ａ３）で表される構成単位を形成するために用いられるラジカル重合性単量体を含むラジカル重合性単量体混合物を有機溶剤中、ラジカル重合開始剤を用いて重合することにより合成することができる。また、いわゆる高分子反応で合成することもできる。 << (A) Polymer Production Method >>
Various methods for synthesizing the component (A) are known. To give an example, the component (A) is used to form at least the structural units represented by (a1) and (a3). It can be synthesized by polymerizing a radical polymerizable monomer mixture containing a radical polymerizable monomer in an organic solvent using a radical polymerization initiator. It can also be synthesized by a so-called polymer reaction.
　本発明の感光性樹脂組成物は、全固形分１００質量部に対し、（Ａ）成分を５０～９９．９質量部の割合で含むことが好ましく、７０～９８質量部の割合で含むことがより好ましい。 The photosensitive resin composition of the present invention preferably contains the component (A) in a proportion of 50 to 99.9 parts by mass, and in a proportion of 70 to 98 parts by mass with respect to 100 parts by mass of the total solid content. More preferred.
＜（Ｂ）光酸発生剤＞
　本発明の感光性樹脂組成物は、（Ｂ）光酸発生剤を含有する。本発明で使用される光酸発生剤（「（Ｂ）成分」ともいう。）としては、波長３００ｎｍ以上、好ましくは波長３００～４５０ｎｍの活性光線に感応し、酸を発生する化合物が好ましいが、その化学構造に制限されるものではない。また、波長３００ｎｍ以上の活性光線に直接感応しない光酸発生剤についても、増感剤と併用することによって波長３００ｎｍ以上の活性光線に感応し、酸を発生する化合物であれば、増感剤と組み合わせて好ましく用いることができる。本発明で使用される光酸発生剤としては、ｐＫａが４以下の酸を発生する光酸発生剤が好ましく、ｐＫａが３以下の酸を発生する光酸発生剤がより好ましく、２以下の酸を発生する光酸発生剤が最も好ましい。 <(B) Photoacid generator>
The photosensitive resin composition of the present invention contains (B) a photoacid generator. As the photoacid generator (also referred to as “component (B)”) used in the present invention, 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. The chemical structure is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. The photoacid generator used in the present invention 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. Most preferred are photoacid generators that generate.
　光酸発生剤の例として、トリクロロメチル－ｓ－トリアジン類、スルホニウム塩やヨードニウム塩、第四級アンモニウム塩類、ジアゾメタン化合物、イミドスルホネート化合物、および、オキシムスルホネート化合物などを挙げることができる。これらの中でも、絶縁性の観点から、オキシムスルホネート化合物を用いることが好ましい。これら光酸発生剤は、１種単独または２種類以上を組み合わせて使用することができる。トリクロロメチル－ｓ－トリアジン類、ジアリールヨードニウム塩類、トリアリールスルホニウム塩類、第四級アンモニウム塩類、およびジアゾメタン誘導体の具体例としては、特開２０１１－２２１４９４号公報の段落番号００８３～００８８に記載の化合物が例示できる。 Examples of the photoacid generator include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, it is preferable to use an oxime sulfonate compound from the viewpoint of insulation. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane derivatives include the compounds described in paragraph numbers 0083 to 0088 of JP2011-212494A. It can be illustrated.
　オキシムスルホネート化合物、すなわち、オキシムスルホネート構造を有する化合物としては、下記一般式（Ｂ１）で表されるオキシムスルホネート構造を含有する化合物が好ましく例示できる。 Preferred examples of the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure include compounds having an oxime sulfonate structure represented by the following general formula (B1).
一般式（Ｂ１）
Figure JPOXMLDOC01-appb-C000022
 （一般式（Ｂ１）中、Ｒ21は、アルキル基またはアリール基を表す。波線は他の基との結合を表す。） General formula (B1)
Figure JPOXMLDOC01-appb-C000022
 (In the general formula (B1), R 21 represents an alkyl group or an aryl group. A wavy line represents a bond with another group.)
　いずれの基も置換されてもよく、Ｒ21におけるアルキル基は直鎖状でも分岐状でも環状でもよい。許容される置換基は以下に説明する。
　Ｒ21のアルキル基としては、炭素数１～１０の、直鎖状または分岐状アルキル基が好ましい。Ｒ21のアルキル基は、炭素数６～１１のアリール基、炭素数１～１０のアルコキシ基、または、環状のアルキル基（７，７－ジメチル－２－オキソノルボルニル基などの有橋式脂環基を含む、好ましくはビシクロアルキル基等）で置換されてもよい。
　Ｒ21のアリール基としては、炭素数６～１１のアリール基が好ましく、フェニル基またはナフチル基がより好ましい。Ｒ21のアリール基は、低級アルキル基、アルコキシ基あるいはハロゲン原子で置換されてもよい。 Any group may be substituted, and the alkyl group in R 21 may be linear, branched or cyclic. Acceptable substituents are described below.
The alkyl group for R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R 21 is a bridged type such as an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cyclic alkyl group (7,7-dimethyl-2-oxonorbornyl group). It may be substituted with an alicyclic group, preferably a bicycloalkyl group.
As the aryl group for R 21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R 21 may be substituted with a lower alkyl group, an alkoxy group, or a halogen atom.
　上記一般式（Ｂ１）で表されるオキシムスルホネート構造を含有する上記化合物は、下記一般式（Ｂ２）で表されるオキシムスルホネート化合物であることも好ましい。 The above compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B2).
Figure JPOXMLDOC01-appb-C000023
 （式（Ｂ２）中、Ｒ42は、アルキル基またはアリール基を表し、Ｘは、アルキル基、アルコキシ基、または、ハロゲン原子を表し、ｍ４は、０～３の整数を表し、ｍ４が２または３であるとき、複数のＸは同一でも異なっていてもよい。）
Figure JPOXMLDOC01-appb-C000023
 (In the formula (B2), R 42 represents an alkyl group or an aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, m4 represents an integer of 0 to 3, and m4 represents 2 or When X is 3, the plurality of X may be the same or different.)
　Ｘとしてのアルキル基は、炭素数１～４の直鎖状または分岐状アルキル基が好ましい。
Ｘとしてのアルコキシ基は、炭素数１～４の直鎖状または分岐状アルコキシ基が好ましい。
　Ｘとしてのハロゲン原子は、塩素原子またはフッ素原子が好ましい。　ｍ４は、０または１が好ましい。上記一般式（Ｂ２）中、ｍ４が１であり、Ｘがメチル基であり、Ｘの置換位置がオルト位であり、Ｒ42が炭素数１～１０の直鎖状アルキル基、７，７－ジメチル－２－オキソノルボルニルメチル基、またはｐ－トルイル基である化合物が特に好ましい。 The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
The alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms.
The halogen atom as X is preferably a chlorine atom or a fluorine atom. m4 is preferably 0 or 1. In the above general formula (B2), m4 is 1, X is a methyl group, the substitution position of X is the ortho position, R 42 is a linear alkyl group having 1 to 10 carbon atoms, 7,7- A compound that is a dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.
　上記一般式（Ｂ１）で表されるオキシムスルホネート構造を含有する化合物は、下記一般式（Ｂ３）で表されるオキシムスルホネート化合物であることも好ましい。 The compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably an oxime sulfonate compound represented by the following general formula (B3).
Figure JPOXMLDOC01-appb-C000024
 （式（Ｂ３）中、Ｒ43は式（Ｂ２）におけるＲ42と同義であり、Ｘ1は、ハロゲン原子、水酸基、炭素数１～４のアルキル基、炭素数１～４のアルコキシ基、シアノ基またはニトロ基を表し、ｎ４は０～５の整数を表す。）
Figure JPOXMLDOC01-appb-C000024
 (In the formula (B3), R 43 has the same meaning as R 42 in the formula (B2), and X 1 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, cyano Represents a group or a nitro group, and n4 represents an integer of 0 to 5.)
　上記一般式（Ｂ３）におけるＲ43としては、メチル基、エチル基、ｎ－プロピル基、ｎ－ブチル基、ｎ－オクチル基、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロ－ｎ－プロピル基、パーフルオロ－ｎ－ブチル基、ｐ－トリル基、４－クロロフェニル基またはペンタフルオロフェニル基が好ましく、ｎ－オクチル基が特に好ましい。
　Ｘ1としては、炭素数１～５のアルコキシ基が好ましく、メトキシ基がより好ましい。
　ｎ４としては、０～２が好ましく、０～１が特に好ましい。 R 43 in the above general formula (B3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n-propyl group. Perfluoro-n-butyl group, p-tolyl group, 4-chlorophenyl group or pentafluorophenyl group is preferred, and n-octyl group is particularly preferred.
X 1 is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably a methoxy group.
n4 is preferably from 0 to 2, particularly preferably from 0 to 1.
　上記一般式（Ｂ３）で表される化合物の具体例としては、α－（メチルスルホニルオキシイミノ）ベンジルシアニド、α－（エチルスルホニルオキシイミノ）ベンジルシアニド、α－（ｎ－プロピルスルホニルオキシイミノ）ベンジルシアニド、α－（ｎ－ブチルスルホニルオキシイミノ）ベンジルシアニド、α－（４－トルエンスルホニルオキシイミノ）ベンジルシアニド、α－〔（メチルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（エチルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（ｎ－プロピルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（ｎ－ブチルスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリル、α－〔（４－トルエンスルホニルオキシイミノ）－４－メトキシフェニル〕アセトニトリルを挙げることができる。 Specific examples of the compound represented by the general formula (B3) include α- (methylsulfonyloxyimino) benzyl cyanide, α- (ethylsulfonyloxyimino) benzyl cyanide, α- (n-propylsulfonyloxyimino). ) Benzyl cyanide, α- (n-butylsulfonyloxyimino) benzyl cyanide, α- (4-toluenesulfonyloxyimino) benzyl cyanide, α-[(methylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(ethylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-propylsulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(n-butylsulfonyloxyimino) -4- Methoxyphenyl] acetonitrile, α-[(4 It can be given toluenesulfonyl) -4-methoxyphenyl] acetonitrile.
　好ましいオキシムスルホネート化合物の具体例としては、下記化合物（ｉ）～（ｖｉｉｉ）等が挙げられ、１種単独で使用、または、２種類以上を併用することができる。化合物（ｉ）～（ｖｉｉｉ）は、市販品として、入手することができる。また、他の種類の（Ｂ）光酸発生剤と組み合わせて使用することもできる。 Specific examples of preferable oxime sulfonate compounds include the following compounds (i) to (viii), and the like can be used singly or in combination of two or more. Compounds (i) to (viii) can be obtained as commercial products. Moreover, it can also be used in combination with another kind of (B) photo-acid generator.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　上記一般式（Ｂ１）で表されるオキシムスルホネート構造を含有する化合物としては、下記一般式（ＯＳ－１）で表される化合物であることも好ましい。 The compound containing an oxime sulfonate structure represented by the above general formula (B1) is also preferably a compound represented by the following general formula (OS-1).
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　上記一般式（ＯＳ－１）中、Ｒ101は、水素原子、アルキル基、アルケニル基、アルコキシ基、アルコキシカルボニル基、アシル基、カルバモイル基、スルファモイル基、スルホ基、シアノ基、アリール基、または、ヘテロアリール基を表す。Ｒ102は、アルキル基、または、アリール基を表す。
　Ｘ101は－Ｏ－、－Ｓ－、－ＮＨ－、－ＮＲ105－、－ＣＨ2－、－ＣＲ106Ｈ－、または、－ＣＲ105Ｒ107－を表し、Ｒ105～Ｒ107はアルキル基、または、アリール基を表す。
　Ｒ121～Ｒ124は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルケニル基、アルコキシ基、アミノ基、アルコキシカルボニル基、アルキルカルボニル基、アリールカルボニル基、アミド基、スルホ基、シアノ基、または、アリール基を表す。Ｒ121～Ｒ124のうち２つは、それぞれ互いに結合して環を形成してもよい。
　Ｒ121～Ｒ124としては、水素原子、ハロゲン原子、および、アルキル基が好ましく、また、Ｒ121～Ｒ124のうち少なくとも２つが互いに結合してアリール基を形成する態様もまた、好ましく挙げられる。中でも、Ｒ121～Ｒ124がいずれも水素原子である態様が感度の観点から好ましい。
　既述の官能基は、いずれも、さらに置換基を有していてもよい。 In the general formula (OS-1), R 101 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group, or Represents a heteroaryl group. R102 represents an alkyl group or an aryl group.
X 101 represents —O—, —S—, —NH—, —NR 105 —, —CH 2 —, —CR 106 H—, or —CR 105 R 107 —, wherein R 105 to R 107 are alkyl groups. Or an aryl group.
R 121 to R 124 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group, Or an aryl group is represented. Two of R 121 to R 124 may be bonded to each other to form a ring.
R 121 to R 124 are preferably a hydrogen atom, a halogen atom and an alkyl group, and an embodiment in which at least two of R 121 to R 124 are bonded to each other to form an aryl group is also preferred. Among these, an embodiment in which R 121 to R 124 are all hydrogen atoms is preferable from the viewpoint of sensitivity.
Any of the aforementioned functional groups may further have a substituent.
　上記一般式（ＯＳ－１）で表される化合物は、下記一般式（ＯＳ－２）で表される化合物であることがより好ましい。 The compound represented by the general formula (OS-1) is more preferably a compound represented by the following general formula (OS-2).
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　上記一般式（ＯＳ－２）中、Ｒ101、Ｒ102、Ｒ121～Ｒ124は、それぞれ式（ＯＳ－１）におけるのと同義であり、好ましい例もまた同様である。
　これらの中でも、上記一般式（ＯＳ－１）および上記一般式（ＯＳ－２）におけるＲ101がシアノ基、または、アリール基である態様がより好ましく、上記一般式（ＯＳ－２）で表され、Ｒ101がシアノ基、フェニル基またはナフチル基である態様が最も好ましい。 In the general formula (OS-2), R 101 , R 102 and R 121 to R 124 have the same meanings as in the formula (OS-1), and preferred examples thereof are also the same.
Among these, an embodiment in which R 101 in the general formula (OS-1) and the general formula (OS-2) is a cyano group or an aryl group is more preferable, and is represented by the general formula (OS-2). And R 101 is most preferably a cyano group, a phenyl group, or a naphthyl group.
　また、上記オキシムスルホネート化合物においてオキシムやベンゾチアゾール環の立体構造（Ｅ，Ｚ等）のついてはそれぞれ、どちらか一方であっても、混合物であってもよい。 In the oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture.
　本発明に好適に用いうる上記一般式（ＯＳ－１）で表される化合物の具体例としては、特開２０１１－２２１４９４号公報の段落番号０１２８～０１３２に記載の化合物（例示化合物ｂ－１～ｂ－３４）が挙げられるが、本発明はこれに限定されない。 Specific examples of the compound represented by the general formula (OS-1) that can be suitably used in the present invention include compounds described in paragraph numbers 0128 to 0132 of JP2011-221494A (exemplified compounds b-1 to b-34), but the present invention is not limited thereto.
　本発明では、上記一般式（Ｂ１）で表されるオキシムスルホネート構造を含有する化合物としては、下記一般式（ＯＳ－３）、下記一般式（ＯＳ－４）または下記一般式（ＯＳ－５）で表されるオキシムスルホネート化合物であることが好ましい。 In the present invention, the compound containing the oxime sulfonate structure represented by the above general formula (B1) includes the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS-5). It is preferable that it is an oxime sulfonate compound represented by these.
Figure JPOXMLDOC01-appb-C000028
 　（一般式（ＯＳ－３）～一般式（ＯＳ－５）中、Ｒ22、Ｒ25およびＲ28はそれぞれ独立にアルキル基、アリール基またはヘテロアリール基を表し、Ｒ23、Ｒ26およびＲ29はそれぞれ独立に水素原子、アルキル基、アリール基またはハロゲン原子を表し、Ｒ24、Ｒ27およびＲ30はそれぞれ独立にハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基またはアルコキシスルホニル基を表し、Ｘ1～Ｘ3はそれぞれ独立に酸素原子または硫黄原子を表し、ｎ1～ｎ3はそれぞれ独立に１または２を表し、ｍ1～ｍ3はそれぞれ独立に０～６の整数を表す。）
Figure JPOXMLDOC01-appb-C000028
 (In the general formula (OS-3) to general formula (OS-5), R 22 , R 25 and R 28 each independently represents an alkyl group, an aryl group or a heteroaryl group; R 23 , R 26 and R 29 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a halogen atom, and R 24 , R 27 and R 30 each independently represent a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group. X 1 to X 3 each independently represents an oxygen atom or a sulfur atom, n 1 to n 3 each independently represents 1 or 2, and m 1 to m 3 each independently represents an integer of 0 to 6 Represents.)
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25およびＲ28におけるアルキル基、アリール基またはヘテロアリール基は、置換基を有していてもよい。
　上記式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25およびＲ28におけるアルキル基としては、置換基を有していてもよい総炭素数１～３０のアルキル基であることが好ましい。 In the general formulas (OS-3) to (OS-5), the alkyl group, aryl group or heteroaryl group in R 22 , R 25 and R 28 may have a substituent.
In the above formulas (OS-3) to (OS-5), the alkyl group in R 22 , R 25 and R 28 is an alkyl group having 1 to 30 carbon atoms which may have a substituent. Is preferred.
　また、上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25およびＲ28におけるアリール基としては、置換基を有してもよい総炭素数６～３０のアリール基が好ましい。 In the general formulas (OS-3) to (OS-5), the aryl group in R 22 , R 25 and R 28 is an aryl group having 6 to 30 carbon atoms which may have a substituent. preferable.
　また、上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ1におけるヘテロアリール基としては、置換基を有してもよい総炭素数４～３０のヘテロアリール基が好ましい。 In the general formulas (OS-3) to (OS-5), the heteroaryl group in R 1 is preferably a heteroaryl group having 4 to 30 carbon atoms in total which may have a substituent.
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ22、Ｒ25およびＲ28におけるヘテロアリール基は、少なくとも１つの環が複素芳香環であればよく、例えば、複素芳香環とベンゼン環とが縮環していてもよい。 In the general formulas (OS-3) to (OS-5), at least one of the heteroaryl groups in R 22 , R 25 and R 28 may be a heteroaromatic ring, such as a heteroaromatic ring and benzene. The ring may be condensed.
上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ23、Ｒ26およびＲ29は、水素原子、アルキル基またはアリール基であることが好ましく、水素原子またはアルキル基であることがより好ましい。
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、化合物中に２以上存在するＲ23、Ｒ26およびＲ29のうち、１つまたは２つがアルキル基、アリール基またはハロゲン原子であることが好ましく、１つがアルキル基、アリール基またはハロゲン原子であることがより好ましく、１つがアルキル基であり、かつ残りが水素原子であることが特に好ましい。 In the general formulas (OS-3) to (OS-5), R 23 , R 26 and R 29 are preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group. preferable.
In the above general formulas (OS-3) to (OS-5), one or two of R 23 , R 26 and R 29 present in the compound are an alkyl group, an aryl group or a halogen atom. It is more preferable that one is an alkyl group, an aryl group or a halogen atom, and it is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.
　Ｒ23、Ｒ26およびＲ29におけるアルキル基としては、置換基を有してもよい総炭素数１～１２のアルキル基であることが好ましく、置換基を有してもよい総炭素数１～６のアルキル基であることがより好ましい。 The alkyl group for R 23 , R 26 and R 29 is preferably an alkyl group having 1 to 12 carbon atoms which may have a substituent, and 1 to 1 carbon atoms which may have a substituent. More preferred is an alkyl group of 6.
　Ｒ23、Ｒ26およびＲ29におけるアリール基としては、置換基を有してもよい総炭素数６～３０のアリール基であることが好ましい。 The aryl group for R 23 , R 26 and R 29 is preferably an aryl group having 6 to 30 carbon atoms which may have a substituent.
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｘ1～Ｘ3はそれぞれ独立にＯまたはＳを表し、Ｏであることが好ましい。
上記一般式（ＯＳ－３）～（ＯＳ－５）において、Ｘ1～Ｘ3を環員として含む環は、５員環または６員環である。
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、ｎ1～ｎ3はそれぞれ独立に１または２を表し、Ｘ1～Ｘ3がＯである場合、ｎ1～ｎ3はそれぞれ独立に１であることが好ましく、また、Ｘ1～Ｘ3がＳである場合、ｎ1～ｎ3はそれぞれ独立に２であることが好ましい。 In the general formulas (OS-3) to (OS-5), X 1 to X 3 each independently represents O or S, and is preferably O.
In the general formulas (OS-3) to (OS-5), the ring containing X 1 to X 3 as a ring member is a 5-membered ring or a 6-membered ring.
In the general formulas (OS-3) to (OS-5), n 1 to n 3 each independently represents 1 or 2, and when X 1 to X 3 are O, n 1 to n 3 are each independently In addition, when X 1 to X 3 are S, n 1 to n 3 are each preferably 2 independently.
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ24、Ｒ27およびＲ30はそれぞれ独立にハロゲン原子、アルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基またはアルコキシスルホニル基を表す。その中でも、Ｒ24、Ｒ27およびＲ30はそれぞれ独立にアルキル基またはアルキルオキシ基であることが好ましい。
　Ｒ24、Ｒ27およびＲ30におけるアルキル基、アルキルオキシ基、スルホン酸基、アミノスルホニル基およびアルコキシスルホニル基は、置換基を有していてもよい。
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ24、Ｒ27およびＲ30におけるアルキル基としては、置換基を有していてもよい総炭素数１～３０のアルキル基であることが好ましい。 In the general formulas (OS-3) to (OS-5), R 24 , R 27 and R 30 each independently represent a halogen atom, alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group or alkoxysulfonyl group. To express. Among them, R 24 , R 27 and R 30 are preferably each independently an alkyl group or an alkyloxy group.
The alkyl group, alkyloxy group, sulfonic acid group, aminosulfonyl group and alkoxysulfonyl group in R 24 , R 27 and R 30 may have a substituent.
In the general formulas (OS-3) to (OS-5), the alkyl group in R 24 , R 27 and R 30 is an alkyl group having 1 to 30 carbon atoms which may have a substituent. It is preferable.
　上記一般式（ＯＳ－３）～（ＯＳ－５）中、Ｒ24、Ｒ27およびＲ30におけるアルキルオキシ基としては、置換基を有してもよい総炭素数１～３０のアルキルオキシ基であることが好ましい。 In the general formulas (OS-3) to (OS-5), the alkyloxy group in R 24 , R 27 and R 30 is an alkyloxy group having 1 to 30 carbon atoms which may have a substituent. Preferably there is.
　また、上記一般式（ＯＳ－３）～（ＯＳ－５）中、ｍ1～ｍ3はそれぞれ独立に０～６の整数を表し、０～２の整数であることが好ましく、０または１であることがより好ましく、０であることが特に好ましい。
　また、上記（ＯＳ－３）～（ＯＳ－５）のそれぞれの置換基について、特開２０１１－２２１４９４号公報の段落番号００９２～０１０９に記載の（ＯＳ－３）～（ＯＳ－５）の置換基の好ましい範囲も同様に好ましい。 In the general formulas (OS-3) to (OS-5), m 1 to m 3 each independently represents an integer of 0 to 6, preferably an integer of 0 to 2, preferably 0 or 1. More preferably, it is particularly preferably 0.
In addition, with respect to each of the substituents of (OS-3) to (OS-5) described above, the substitution of (OS-3) to (OS-5) described in paragraph numbers 0092 to 0109 of JP2011-221494A The preferred range of groups is likewise preferred.
　また、上記一般式（Ｂ１）で表されるオキシムスルホネート構造を含有する化合物は、下記一般式（ＯＳ－６）～（ＯＳ－１１）のいずれかで表されるオキシムスルホネート化合物であることが特に好ましい。 The compound containing the oxime sulfonate structure represented by the general formula (B1) is particularly an oxime sulfonate compound represented by any of the following general formulas (OS-6) to (OS-11). preferable.
Figure JPOXMLDOC01-appb-C000029
 （式（ＯＳ－６）～（ＯＳ－１１）中、Ｒ301～Ｒ306はアルキル基、アリール基またはヘテロアリール基を表し、Ｒ307は、水素原子または臭素原子を表し、Ｒ308～Ｒ310、Ｒ313、Ｒ316およびＲ318はそれぞれ独立に水素原子、炭素数１～８のアルキル基、ハロゲン原子、クロロメチル基、ブロモメチル基、ブロモエチル基、メトキシメチル基、フェニル基またはクロロフェニル基を表し、Ｒ311およびＲ314はそれぞれ独立に水素原子、ハロゲン原子、メチル基またはメトキシ基を表し、Ｒ312、Ｒ315、Ｒ317およびＲ319はそれぞれ独立には水素原子またはメチル基を表す。）
Figure JPOXMLDOC01-appb-C000029
 (In the formulas (OS-6) to (OS-11), R 301 to R 306 represent an alkyl group, an aryl group, or a heteroaryl group, R 307 represents a hydrogen atom or a bromine atom, and R 308 to R 310 , R 313 , R 316 and R 318 each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group; R 311 and R 314 each independently represent a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R 312 , R 315 , R 317 and R 319 each independently represent a hydrogen atom or a methyl group.)
　上記一般式（ＯＳ－６）～（ＯＳ－１１）における好ましい範囲は、特開２０１１－２２１４９４号公報の段落番号０１１０～０１１２に記載される（ＯＳ－６）～（ＯＳ－１１）の好ましい範囲と同様である。 Preferred ranges in the above general formulas (OS-6) to (OS-11) are preferred ranges of (OS-6) to (OS-11) described in paragraph numbers 0110 to 0112 of JP2011-221494A. It is the same.
　上記一般式（ＯＳ－３）～上記一般式（ＯＳ－５）で表されるオキシムスルホネート化合物の具体例としては、特開２０１１－２２１４９４号公報の段落番号０１１４～０１２０に記載の化合物が挙げられるが、本発明は、これらに限定されるものではない。 Specific examples of the oxime sulfonate compounds represented by the general formula (OS-3) to the general formula (OS-5) include compounds described in paragraph numbers 0114 to 0120 of JP2011-221494A. However, the present invention is not limited to these.
　本発明の感光性樹脂組成物において、（Ｂ）光酸発生剤は、感光性樹脂組成物中の全樹脂成分（好ましくは固形分、より好ましくは共重合体の合計）１００質量部に対して、０．１～１０質量部使用することが好ましく、０．５～１０質量部使用することがより好ましい。２種以上を併用することもできる。 In the photosensitive resin composition of the present invention, (B) the photoacid generator is based on 100 parts by mass of all resin components (preferably a solid content, more preferably a total of copolymers) in the photosensitive resin composition. 0.1 to 10 parts by mass is preferably used, and 0.5 to 10 parts by mass is more preferably used. Two or more kinds can be used in combination.
＜（Ｃ）分子量が１０００未満の脂環式エポキシ化合物＞
　本発明の感光性樹脂組成物は、架橋剤として分子量が１０００未満の脂環式エポキシ化合物（以下、単に「脂環式エポキシ化合物」ということがある。）を含有することを特徴とする。
　脂環式エポキシ化合物は、脂環式エポキシ基を１～５個有していることがより好ましく、１～３個有していることがより好ましく、１個または２個有することがさらに好ましい。
　本発明で用いる脂環式エポキシ化合物が有する脂環式エポキシ基は、好ましくは下記で表される脂環式エポキシ基である。
Figure JPOXMLDOC01-appb-C000030
 <(C) Alicyclic epoxy compound having a molecular weight of less than 1000>
The photosensitive resin composition of the present invention is characterized by containing an alicyclic epoxy compound having a molecular weight of less than 1000 (hereinafter sometimes simply referred to as “alicyclic epoxy compound”) as a crosslinking agent.
The alicyclic epoxy compound preferably has 1 to 5 alicyclic epoxy groups, more preferably 1 to 3, more preferably 1 or 2.
The alicyclic epoxy group possessed by the alicyclic epoxy compound used in the present invention is preferably an alicyclic epoxy group represented by the following.
Figure JPOXMLDOC01-appb-C000030
　脂環式エポキシ化合物は、下記式（１）で表されることが好ましい。
式（１）
Figure JPOXMLDOC01-appb-C000031
 （式（１）中、ｎは１～４の整数を表す。Ｒ1は炭素数１～３０の有機基を表す。） The alicyclic epoxy compound is preferably represented by the following formula (1).
Formula (1)
Figure JPOXMLDOC01-appb-C000031
 (In the formula (1), n represents an integer of 1 to 4. R 1 represents an organic group having 1 to 30 carbon atoms.)
　Ｒ1は炭素数１～３０の有機基を表し、分岐していても不飽和結合を有していてもよく、脂肪族環または芳香環の環状構造を有してもよい。また、これらの基は、酸素、硫黄、窒素、リン、ホウ素、ハロゲン原子を有していてもよい。また、置換基を有していてもよく、置換基同士が互いに結合を形成していても良い。また、Ｒ1はｎ価の連結基である。 R 1 represents an organic group having 1 to 30 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic or aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond. R 1 is an n-valent linking group.
　Ｒ1の有機基の炭素数は、１～１５が好ましく、１～８がより好ましく、１～６がさらに好ましい。有機基は、炭化水素基または、炭化水素基と、－Ｏ－、－ＣＯ－、－Ｓ－および－ＮＲ－（Ｒは、水素原子または炭素数１～７のアルキル基を表す。）の少なくとも１つの組み合わせからなる基が好ましく、炭化水素基、または、炭化水素基と、－Ｏ－および／または－ＣＯ－の組み合わせからなる基がより好ましい。炭化水素基は、直鎖または分岐の基が好ましく、直鎖の基がより好ましい。炭化水素基の炭素数は、１～４が好ましい。１つの有機基に２以上の炭化水素基が含まれていてもよい。 The number of carbon atoms of the organic group represented by R 1 is preferably 1 to 15, more preferably 1 to 8, and still more preferably 1 to 6. The organic group is at least a hydrocarbon group, a hydrocarbon group, and —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). A group consisting of one combination is preferred, and a hydrocarbon group or a group consisting of a hydrocarbon group and —O— and / or —CO— is more preferred. The hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group.
　ｎは１～４の整数を表し、１～３の整数が好ましく、１または２がより好ましい。 N represents an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably 1 or 2.
　脂環式エポキシ化合物の好ましい態様としては、下記式（２）で表される化合物が例示される。
式（２）
Figure JPOXMLDOC01-appb-C000032
 （式（２）中、Ｒ2は炭素数１～１５の有機基を表す。）
　Ｒ2は炭素数１～１５の有機基を表し、分岐していても不飽和結合を有していてもよく、脂肪族環または芳香環の環状構造を有してもよい。また、これらの基は、酸素、硫黄、窒素、リン、ホウ素、ハロゲン原子を有していてもよい。また、置換基を有していてもよく、置換基同士が互いに結合を形成していても良い。また、Ｒ2は２価の連結基である。 As a preferable aspect of an alicyclic epoxy compound, the compound represented by following formula (2) is illustrated.
Formula (2)
Figure JPOXMLDOC01-appb-C000032
 (In the formula (2), R 2 represents an organic group having 1 to 15 carbon atoms.)
R 2 represents an organic group having 1 to 15 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic ring or an aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond. R 2 is a divalent linking group.
　Ｒ2の有機基の炭素数は、１～８が好ましく、１～６がより好ましい。有機基は、炭化水素基または、炭化水素基と、－Ｏ－、－ＣＯ－、－Ｓ－および－ＮＲ－（Ｒは、水素原子または炭素数１～７のアルキル基を表す。）の少なくとも１つの組み合わせからなる基が好ましく、炭化水素基、または、炭化水素基と、－Ｏ－および／または－ＣＯ－の組み合わせからなる基がより好ましい。炭化水素基は、直鎖または分岐の基が好ましく、直鎖の基がより好ましい。炭化水素基の炭素数は、１～４が好ましい。１つの有機基に２以上の炭化水素基が含まれていてもよい。炭化水素基はアルキレン基が好ましい。 The organic group of R 2 preferably has 1 to 8 carbon atoms, and more preferably 1 to 6 carbon atoms. The organic group is at least a hydrocarbon group, a hydrocarbon group, and —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). A group consisting of one combination is preferred, and a hydrocarbon group or a group consisting of a hydrocarbon group and —O— and / or —CO— is more preferred. The hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group. The hydrocarbon group is preferably an alkylene group.
　脂環式エポキシ化合物の好ましい態様としては、下記式（３）で表される化合物も例示される。
式（３）
Figure JPOXMLDOC01-appb-C000033
 （式（３）中、Ｒ3は炭素数１～１５の有機基を表す。）
　Ｒ3は炭素数１～１５の有機基を表し、分岐していても不飽和結合を有していてもよく、脂肪族環または芳香環の環状構造を有してもよい。また、これらの基は、酸素、硫黄、窒素、リン、ホウ素、ハロゲン原子を有していてもよい。また、置換基を有していてもよく、置換基同士が互いに結合を形成していても良い。また、Ｒ3は２価の連結基である。 As a preferable aspect of an alicyclic epoxy compound, the compound represented by following formula (3) is also illustrated.
Formula (3)
Figure JPOXMLDOC01-appb-C000033
 (In the formula (3), R 3 represents an organic group having 1 to 15 carbon atoms.)
R 3 represents an organic group having 1 to 15 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic or aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond. R 3 is a divalent linking group.
　Ｒ3の有機基の炭素数は、１～８が好ましく、１～６がより好ましい。有機基は、炭化水素基または、炭化水素基と、－Ｏ－、－ＣＯ－、－Ｓ－および－ＮＲ－（Ｒは、水素原子または炭素数１～７のアルキル基を表す。）の少なくとも１つの組み合わせからなる基が好ましく、炭化水素基、または、炭化水素基と、－Ｏ－および／または－ＣＯ－の組み合わせからなる基がより好ましい。炭化水素基は、直鎖または分岐の基が好ましく、直鎖の基がより好ましい。炭化水素基の炭素数は、１～４が好ましい。１つの有機基に２以上の炭化水素基が含まれていてもよい。炭化水素基はアルキレン基が好ましい。 The number of carbon atoms in the organic group of R 3 is preferably 1-8, and more preferably 1-6. The organic group is at least a hydrocarbon group, a hydrocarbon group, and —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). A group consisting of one combination is preferred, and a hydrocarbon group or a group consisting of a hydrocarbon group and —O— and / or —CO— is more preferred. The hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group. The hydrocarbon group is preferably an alkylene group.
　上記式（１）～（３）の具体例としては、以下のような化合物が挙げられるが、本発明では特にこれに限定されるものではない。
Figure JPOXMLDOC01-appb-C000034
 Specific examples of the above formulas (1) to (3) include the following compounds, but the present invention is not particularly limited thereto.
Figure JPOXMLDOC01-appb-C000034
 また、脂環式エポキシ化合物は、下記式（Ｘ－１）で表されることが好ましい。
 式（Ｘ－１）
Figure JPOXMLDOC01-appb-C000035
 （式（Ｘ－１）中、Ｒ4は炭素数１～２７の有機基を表す。Ｒ5は炭素数１～２７の置換基を表す。ただし、１つの脂環式エポキシ基を除いた炭素数は３～３０である。） The alicyclic epoxy compound is preferably represented by the following formula (X-1).
Formula (X-1)
Figure JPOXMLDOC01-appb-C000035
 (In the formula (X-1), R 4 represents an organic group having 1 to 27 carbon atoms, R 5 represents a substituent having 1 to 27 carbon atoms, except for one alicyclic epoxy group. The number is 3-30.)
　Ｒ4は炭素数１～２７の有機基を表し、分岐していても不飽和結合を有していてもよく、脂肪族環または芳香環の環状構造を有してもよい。また、これらの基は、酸素、硫黄、窒素、リン、ホウ素、ハロゲン原子を有していてもよい。また、置換基を有していてもよく、置換基同士が互いに結合を形成していても良い。 R 4 represents an organic group having 1 to 27 carbon atoms, may be branched or have an unsaturated bond, and may have an aliphatic or aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Moreover, you may have a substituent and substituents may mutually form a bond.
　Ｒ4の有機基の炭素数は、１～１５が好ましく、１～８がより好ましく、１～６がさらに好ましい。有機基は、炭化水素基または、炭化水素基と、－Ｏ－、－ＣＯ－、－Ｓ－および－ＮＲ－（Ｒは、水素原子または炭素数１～７のアルキル基を表す。）の少なくとも１つの組み合わせからなる基が好ましく、炭化水素基、または、炭化水素基と、－Ｏ－および／または－ＣＯ－の組み合わせからなる基がより好ましい。炭化水素基は、直鎖または分岐の基が好ましく、直鎖の基がより好ましい。炭化水素基の炭素数は、１～４が好ましい。１つの有機基に２以上の炭化水素基が含まれていてもよい。 The number of carbon atoms in the organic group represented by R 4 is preferably 1 to 15, more preferably 1 to 8, and further preferably 1 to 6. The organic group is at least a hydrocarbon group, a hydrocarbon group, and —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). A group consisting of one combination is preferred, and a hydrocarbon group or a group consisting of a hydrocarbon group and —O— and / or —CO— is more preferred. The hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group.
　Ｒ5はそれぞれ炭素数１～２７の置換基を表し、それぞれ独立に分岐していても不飽和結合を有していてもよく、脂肪族環または芳香環の環状構造を有してもよい。また、これらの基は、酸素、硫黄、窒素、リン、ホウ素、ハロゲン原子を有していてもよい。さらに、それらがエポキシ基、オキセタニル基、エチレン性不飽和基、アルコキシシラン基、イソシアネート基、ブロックイソシアネート基、チオール基、カルボキシル基、水酸基およびコハク酸無水物基から選択される少なくとも１種の置換基により置換されていてもよい。
　式（Ｘ－１）中の２つのＲ5は、同一であっても異なっていてもよく、同一であることが好ましい。 Each R 5 represents a substituent having 1 to 27 carbon atoms, and may be independently branched, have an unsaturated bond, or have an aliphatic ring or aromatic ring structure. These groups may have oxygen, sulfur, nitrogen, phosphorus, boron, or halogen atoms. Furthermore, they are at least one substituent selected from an epoxy group, an oxetanyl group, an ethylenically unsaturated group, an alkoxysilane group, an isocyanate group, a blocked isocyanate group, a thiol group, a carboxyl group, a hydroxyl group, and a succinic anhydride group. May be substituted.
Two R 5 s in formula (X-1) may be the same or different and are preferably the same.
　Ｒ5の置換基の炭素数は、１～１５が好ましく、１～８がより好ましく、１～６がさらに好ましい。置換基は、エポキシ基、水酸基、炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－および－ＮＲ－（Ｒは、水素原子または炭素数１～７のアルキル基を表す。）の少なくとも１つの組み合わせからなる基が好ましく、水酸基、炭化水素基、－Ｏ－および／または－ＣＯ－の組み合わせからなる基、ならびにエポキシ基、炭化水素基と、－Ｏ－および／または－ＣＯ－の組み合わせからなる基がより好ましい。エポキシ基は、脂環式エポキシ基が好ましい。また、炭化水素基は、直鎖または分岐の基が好ましく、直鎖の基がより好ましい。炭化水素基の炭素数は、１～４が好ましい。１つの有機基に２以上の炭化水素基が含まれていてもよい。 The carbon number of the substituent of R 5 is preferably 1 to 15, more preferably 1 to 8, and further preferably 1 to 6. The substituent is at least one of an epoxy group, a hydroxyl group, a hydrocarbon group, —O—, —CO—, —S—, and —NR— (R represents a hydrogen atom or an alkyl group having 1 to 7 carbon atoms). A group consisting of two combinations is preferred, from a group consisting of a hydroxyl group, a hydrocarbon group, a combination of —O— and / or —CO—, and a combination of an epoxy group, a hydrocarbon group and —O— and / or —CO—. Is more preferred. The epoxy group is preferably an alicyclic epoxy group. Further, the hydrocarbon group is preferably a linear or branched group, and more preferably a linear group. The hydrocarbon group preferably has 1 to 4 carbon atoms. Two or more hydrocarbon groups may be contained in one organic group.
　式（Ｘ－１）中、１つの脂環式エポキシ基を除いた炭素数、すなわち式（Ｘ－１）中、Ｒ4、２つのＲ5、および３つの窒素原子を含む６員環内の３つの炭素原子の合計炭素数は３～３０であることが好ましく、５～２５であることがより好ましく、５～２０であることがさらに好ましい。 In the formula (X-1), the number of carbon atoms excluding one alicyclic epoxy group, that is, in the six-membered ring containing R 4 , 2 R 5 , and 3 nitrogen atoms in the formula (X-1) The total number of carbon atoms of the three carbon atoms is preferably 3 to 30, more preferably 5 to 25, and even more preferably 5 to 20.
　また、脂環式エポキシ化合物の好ましい態様としては、下記式（Ｘ－２）で表される化合物が例示される。
式（Ｘ－２）
Figure JPOXMLDOC01-appb-C000036
 （式（Ｘ－２）中、Ｒ4はそれぞれ炭素数１～２７の有機基を表す。Ｒ5は炭素数１～２７の置換基を表す。ただし、１つの脂環式エポキシ基を除いた炭素数は３～３０である。） A preferred embodiment of the alicyclic epoxy compound is exemplified by a compound represented by the following formula (X-2).
Formula (X-2)
Figure JPOXMLDOC01-appb-C000036
 (In the formula (X-2), R 4 represents an organic group having 1 to 27 carbon atoms, and R 5 represents a substituent having 1 to 27 carbon atoms, except for one alicyclic epoxy group. (The number of carbon atoms is 3 to 30.)
　Ｒ4は、式（Ｘ－１）中のＲ4と同義であり、好ましい範囲も同様である。
　Ｒ5は、式（Ｘ－１）中のＲ5と同義であり、好ましい範囲も同様である。
　式（Ｘ－２）中の２つのＲ4は、同一であっても異なっていてもよく、同一であることが好ましい。 R 4 has the same meaning as R 4 in formula (X-1), and the preferred range is also the same.
R 5 has the same meaning as R 5 in formula (X-1), and the preferred range is also the same.
Two R 4 s in formula (X-2) may be the same or different and are preferably the same.
　式（Ｘ－２）中、１つの脂環式エポキシ基を除いた炭素数、すなわち式（Ｘ－２）中、２つのＲ4、Ｒ5、および３つの窒素原子を含む６員環内の３つの炭素原子の合計炭素数は３～３０であることが好ましく、５～２５であることがより好ましく、５～２０であることがさらに好ましい。 In the formula (X-2), the number of carbon atoms excluding one alicyclic epoxy group, that is, in the six-membered ring containing two R 4 , R 5 , and three nitrogen atoms in the formula (X-2) The total number of carbon atoms of the three carbon atoms is preferably 3 to 30, more preferably 5 to 25, and even more preferably 5 to 20.
　脂環式エポキシ化合物の好ましい態様としては、下記式（Ｘ－３）で表される化合物も例示される。
式（Ｘ－３）
Figure JPOXMLDOC01-appb-C000037
 （式（Ｘ－３）中、Ｒ4はそれぞれ炭素数１～２７の有機基を表す。ただし、１つの脂環式エポキシ基を除いた炭素数は３～３０である。） As a preferred embodiment of the alicyclic epoxy compound, a compound represented by the following formula (X-3) is also exemplified.
Formula (X-3)
Figure JPOXMLDOC01-appb-C000037
 (In formula (X-3), each R 4 represents an organic group having 1 to 27 carbon atoms. However, the number of carbon atoms excluding one alicyclic epoxy group is 3 to 30.)
　Ｒ4は、式（Ｘ－１）中のＲ4と同義であり、好ましい範囲も同様である。
　式（Ｘ－３）中の３つのＲ4は、同一であっても異なっていてもよく、同一であることが好ましい。 R 4 has the same meaning as R 4 in formula (X-1), and the preferred range is also the same.
Three R 4 s in formula (X-3) may be the same or different and are preferably the same.
　式（Ｘ－３）中、１つの脂環式エポキシ基を除いた炭素数、すなわち式（Ｘ－３）中、３つのＲ4、および３つの窒素原子を含む６員環内の３つの炭素原子の合計炭素数は３～３０であることが好ましく、５～２５であることがより好ましく、５～２０であることがさらに好ましい。 In formula (X-3), the number of carbon atoms excluding one alicyclic epoxy group, that is, in formula (X-3), three R 4 s and three carbons in a six-membered ring containing three nitrogen atoms The total number of carbon atoms is preferably from 3 to 30, more preferably from 5 to 25, and even more preferably from 5 to 20.
　上記式（Ｘ－１）～（Ｘ－３）の具体例としては、以下のような化合物が挙げられるが、本発明では特にこれに限定されるものではない。
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
 Specific examples of the above formulas (X-1) to (X-3) include the following compounds, but the present invention is not particularly limited thereto.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
　本発明で用いる脂環式エポキシ化合物は、その製法は問わないが、例えば、丸善ＫＫ出版、第四版実験化学講座２０有機合成ＩＩ、２１３～、平成４年、Ｅｄ．ｂｙ　Ａｌｆｒｅｄ　Ｈａｓｆｎｅｒ，　Ｔｈｅ　ｃｈｅｍｉｓｔｒｙ　ｏｆ　ｈｅｔｅｒｏｃｙｃｌｉｃ　ｃｏｍｐｏｕｎｄｓ－Ｓｍａｌｌ　Ｒｉｎｇ　Ｈｅｔｅｒｏｃｙｃｌｅｓ　ｐａｒｔ３　ｏｘｉｒａｎｅｓ，　Ｊｏｈｎ＆Ｗｉｌｅｙ　ａｎｄ　Ｓｏｎｓ，　Ａｎ　Ｉｎｔｅｒｓｃｉｅｎｃｅ　Ｐｕｂｌｉｃａｔｉｏｎ，　Ｎｅｗ　Ｙｏｒｋ，　１９８５、吉村、接着、２９巻１２号、３２、１９８５、吉村、接着、３０巻５号、４２、１９８６、吉村、接着、３０巻７号、４２、１９８６、特開平１－１００３７８号、特許第２９０６２４５号、特許第２９２６２６２号の各公報等の文献を参考にして合成できる。 The production method of the alicyclic epoxy compound used in the present invention is not limited. For example, Maruzen KK Publishing, 4th Edition Experimental Chemistry Course 20 Organic Synthesis II, 213-, 1992, Ed. by Alfred Hasfner, The chemistry of heterocyclic compounds-Small Ring Heterocycles part3 oxiranes, John & Wiley and Sons, An Interscience Publication, New York, 1985, Yoshimura, adhesive, Vol. 29 No. 12, 32,1985, Yoshimura, adhesive, Vol. 30, No. 5 42, 1986, Yoshimura, Adhesion, Vol. 30, No. 7, 42, 1986, JP-A-1-100388, Japanese Patent No. 2906245, Japanese Patent No. 2926262, and the like.
　本発明で用いる脂環式エポキシ化合物の分子量は、１０００未満であり、５００未満であることが好ましい。このような範囲とすることにより、本発明の効果がより効果的に発揮される傾向にある。下限値については、特に定めるものではないが、通常、１００以上である。 The molecular weight of the alicyclic epoxy compound used in the present invention is less than 1000, and preferably less than 500. By setting it as such a range, it exists in the tendency for the effect of this invention to be exhibited more effectively. The lower limit is not particularly defined, but is usually 100 or more.
　本発明の感光性樹脂組成物中における脂環式エポキシ化合物の添加量は、感光性樹脂組成物の全固形分１００質量部に対し、０．１～１０質量部であることが好ましく、０．５～８質量部であることがより好ましく、１．０～５質量部であることがさらに好ましい。脂環式エポキシ化合物は複数を併用することもでき、その場合は脂環式エポキシ化合物を全て合算して含有量を計算する。 The addition amount of the alicyclic epoxy compound in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. The amount is more preferably 5 to 8 parts by mass, and further preferably 1.0 to 5 parts by mass. A plurality of alicyclic epoxy compounds may be used in combination, and in that case, all the alicyclic epoxy compounds are added together to calculate the content.
＜（Ｄ）溶剤＞
　本発明の感光性樹脂組成物は、（Ｄ）溶剤を含有する。本発明の感光性樹脂組成物は、本発明の必須成分と、さらに後述の任意の成分を（Ｄ）溶剤に溶解した溶液として調製されることが好ましい。
　本発明の感光性樹脂組成物に使用される（Ｄ）溶剤としては、公知の溶剤を用いることができ、エチレングリコールモノアルキルエーテル類、エチレングリコールジアルキルエーテル類、エチレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類、プロピレングリコールジアルキルエーテル類、プロピレングリコールモノアルキルエーテルアセテート類、ジエチレングリコールジアルキルエーテル類、ジエチレングリコールモノアルキルエーテルアセテート類、ジプロピレングリコールモノアルキルエーテル類、ジプロピレングリコールジアルキルエーテル類、ジプロピレングリコールモノアルキルエーテルアセテート類、エステル類、ケトン類、アミド類、ラクトン類等が例示できる。また、本発明の感光性樹脂組成物に使用される（Ｄ）溶剤の具体例としては特開２０１１－２２１４９４号公報の段落番号０１７４～０１７８に記載の溶剤も挙げられ、これらの内容は本願明細書に組み込まれる。 <(D) Solvent>
The photosensitive resin composition of the present invention contains (D) 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 the solvent (D).
As the solvent (D) used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene. Glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol Examples include monoalkyl ether acetates, esters, ketones, amides, lactones and the like. In addition, specific examples of the (D) 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 the contents thereof are described in the present specification. Embedded in the book.
　また、これらの溶剤にさらに必要に応じて、ベンジルエチルエーテル、ジヘキシルエーテル、エチレングリコールモノフェニルエーテルアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、イソホロン、カプロン酸、カプリル酸、１－オクタノール、１－ノナール、ベンジルアルコール、アニソール、酢酸ベンジル、安息香酸エチル、シュウ酸ジエチル、マレイン酸ジエチル、炭酸エチレン、炭酸プロピレン等の溶剤を添加することもできる。これら溶剤は、１種単独でまたは２種以上を混合して使用することができる。本発明に用いることができる溶剤は、１種単独、または、２種を併用することが好ましく、２種を併用することがより好ましく、プロピレングリコールモノアルキルエーテルアセテート類またはジアルキルエーテル類、ジアセテート類とジエチレングリコールジアルキルエーテル類、あるいは、エステル類とブチレングリコールアルキルエーテルアセテート類とを併用することがさらに好ましい。 In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonal as necessary for these solvents , Benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate and the like can also be added. These solvents can be used alone or in combination of two or more. The solvent that can be used in the present invention is a single type or a combination of two types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. And diethylene glycol dialkyl ethers or esters and butylene glycol alkyl ether acetates are more preferably used in combination.
　また、成分Ｄとしては、沸点１３０℃以上１６０℃未満の溶剤、沸点１６０℃以上の溶剤、または、これらの混合物であることが好ましい。
　沸点１３０℃以上１６０℃未満の溶剤としては、プロピレングリコールモノメチルエーテルアセテート（沸点１４６℃）、プロピレングリコールモノエチルエーテルアセテート(沸点１５８℃)、プロピレングリコールメチル－ｎ－ブチルエーテル（沸点１５５℃）、プロピレングリコールメチル－ｎ－プロピルエーテル（沸点１３１℃）が例示できる。
　沸点１６０℃以上の溶剤としては、３－エトキシプロピオン酸エチル（沸点１７０℃）、ジエチレングリコールメチルエチルエーテル（沸点１７６℃）、プロピレングリコールモノメチルエーテルプロピオネート（沸点１６０℃）、ジプロピレングリコールメチルエーテルアセテート（沸点２１３℃）、３－メトキシブチルエーテルアセテート（沸点１７１℃）、ジエチレングリコールジエチエルエーテル（沸点１８９℃）、ジエチレングリコールジメチルエーテル（沸点１６２℃）、プロピレングリコールジアセテート（沸点１９０℃）、ジエチレングリコールモノエチルエーテルアセテート（沸点２２０℃）、ジプロピレングリコールジメチルエーテル（沸点１７５℃）、１，３－ブチレングリコールジアセテート（沸点２３２℃）が例示できる。 Component D is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), 1,3-butylene glycol diacetate (boiling point 232 ° C) It can be.
　本発明の感光性樹脂組成物における（Ｄ）溶剤の含有量は、感光性樹脂組成物中の全樹脂成分１００質量部当たり、５０～９５質量部であることが好ましく、６０～９０質量部であることがさらに好ましい。 The content of the solvent (D) in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass, preferably 60 to 90 parts by mass, per 100 parts by mass of the total resin components in the photosensitive resin composition. More preferably it is.
＜その他の成分＞
　本発明の感光性樹脂組成物には、上記成分に加えて、必要に応じて、他の架橋剤、アルコキシシラン化合物、増感剤、塩基性化合物、界面活性剤、酸化防止剤を好ましく加えることができる。さらに本発明の感光性樹脂組成物には、酸増殖剤、現像促進剤、可塑剤、熱ラジカル発生剤、熱酸発生剤、紫外線吸収剤、増粘剤、および、有機または無機の沈殿防止剤などの公知の添加剤を加えることができる。 <Other ingredients>
In addition to the above-mentioned components, other crosslinking agents, alkoxysilane compounds, sensitizers, basic compounds, surfactants and antioxidants are preferably added to the photosensitive resin composition of the present invention as necessary. Can do. Furthermore, the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives such as can be added.
他の架橋剤
　本発明の感光性樹脂組成物は、必要に応じ、脂環式エポキシ化合物以外の他の架橋剤を含有することが好ましい。脂環式エポキシ化合物以外の他の架橋剤を添加することにより、本発明の感光性樹脂組成物により得られる硬化膜をより強固な膜とすることができる。
　架橋剤としては、熱によって架橋反応が起こるものであれば制限は無い（上記（Ａ）重合体成分を除く）。例えば、以下に述べる分子内に２個以上のエポキシ基またはオキセタニル基を有する化合物、アルコキシメチル基含有架橋剤、または、少なくとも１個のエチレン性不飽和二重結合を有する化合物、ブロックイソシアネート化合物等を添加することができる。
　本発明の感光性樹脂組成物中における架橋剤の添加量は、感光性樹脂組成物の全固形分１００質量部に対し、０．０１～５０質量部であることが好ましく、０．１～３０質量部であることがより好ましく、０．５～２０質量部であることがさらに好ましい。この範囲で添加することにより、機械的強度および耐溶剤性に優れた硬化膜が得られる。架橋剤は複数を併用することもでき、その場合は架橋剤を全て合算して含有量を計算する。 Other crosslinking agent It is preferable that the photosensitive resin composition of this invention contains other crosslinking agents other than an alicyclic epoxy compound as needed. By adding a crosslinking agent other than the alicyclic epoxy compound, the cured film obtained from the photosensitive resin composition of the present invention can be made stronger.
The crosslinking agent is not limited as long as a crosslinking reaction is caused by heat (excluding the polymer component (A) above). For example, a compound having two or more epoxy groups or oxetanyl groups in the molecule described below, an alkoxymethyl group-containing crosslinking agent, a compound having at least one ethylenically unsaturated double bond, a blocked isocyanate compound, etc. Can be added.
The addition amount of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 50 parts by mass, and 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. The amount is more preferably part 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. A plurality of crosslinking agents may be used in combination. In that case, the content is calculated by adding all the crosslinking agents.
＜分子内に２個以上のエポキシ基またはオキセタニル基を有する化合物＞
　分子内に２個以上のエポキシ基を有する化合物の具体例としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、脂肪族エポキシ樹脂等を挙げることができる。また、脂肪族エポキシ樹脂の中でも鎖状脂肪族エポキシが好適に用いられる。 <Compound having two or more epoxy groups or oxetanyl groups in the molecule>
Specific examples of compounds having two or more epoxy groups in the molecule include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, aliphatic epoxy resins, and the like. Can do. Of the aliphatic epoxy resins, chain aliphatic epoxy is preferably used.
　これらは市販品として入手できる。例えば、ＪＥＲ１５７Ｓ７０、ＪＥＲ１５７Ｓ６５、ＪＥＲ８２８、ＪＥＲ１００７Ｋ（（株）三菱ケミカルホールディングス製）など、特開２０１１－２２１４９４号公報の段落番号０１８９に記載の市販品などが挙げられる。
　その他にも、ＡＤＥＫＡ　ＲＥＳＩＮ　ＥＰ－４０００Ｓ、同ＥＰ－４００３Ｓ、同ＥＰ－４０１０Ｓ、同ＥＰ－４０１１Ｓ（以上、（株）ＡＤＥＫＡ製）、ＮＣ－２０００、ＮＣ－３０００、ＮＣ－７３００、ＸＤ－１０００、ＥＰＰＮ－５０１、ＥＰＰＮ－５０２（以上、（株）ＡＤＥＫＡ製） These are available as commercial products. Examples thereof include commercially available products described in paragraph number 0189 of JP2011-212494, such as JER157S70, JER157S65, JER828, JER1007K (manufactured by Mitsubishi Chemical Holdings Corporation).
In addition, ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation)
　本発明に用いることができる鎖状脂肪族エポキシは分子量（ポリマーの場合は、重量平均分子量）が２０００以下であることが好ましく、１５００以下であることがより好ましく、１０００以下であることがさらに好ましい。下限値としては、例えば、１００以上とすることができる。なお鎖状脂肪族エポキシ化合物の重量平均分子量がカタログなどに記載されていない場合は、（エポキシ当量）×（官能基数）の計算により推定することができる。また、鎖状脂肪族エポキシの２５℃における粘度が３０００ｍＰａ・ｓ以下であることが好ましく、２０００ｍＰａ・ｓ以下であることがより好ましく、１０００ｍＰａ・ｓ以下であることがさらに好ましい。下限値としては、特に定めるものではないが、例えば、５ｍＰａ・ｓ以上とすることができる。
　本発明で用いる脂肪族エポキシ化合物は、直鎖および／または分岐の炭素鎖とエポキシ基を有する樹脂であって、炭素鎖に、水素原子以外に、酸素原子、窒素原子、硫黄原子、塩素原子などが結合していてもよい。本発明は、特に、直鎖および／または分岐の炭素鎖と、水素原子、エポキシ基とからなる樹脂または、該樹脂に水酸基が置換している基が好ましい。エポキシ基の数は、１～４が好ましく、２または３がより好ましい。
　本発明では、また、環状脂肪族エポキシ化合物を実質的に含まないことが好ましい。このような構成とすることにより、本発明の効果がより効果的に発揮される傾向にある。ここで、実質的に含まないとは、本発明の効果に影響を与えるレベルで添加されていないことをいい、例えば、全固形分の１重量％以下であることをいう。 The chain aliphatic epoxy that can be used in the present invention has a molecular weight (in the case of a polymer, a weight average molecular weight) of preferably 2000 or less, more preferably 1500 or less, and even more preferably 1000 or less. . As a lower limit, it can be set as 100 or more, for example. In addition, when the weight average molecular weight of a chain aliphatic epoxy compound is not described in a catalog etc., it can estimate by calculation of (epoxy equivalent) x (number of functional groups). Further, the viscosity of the chain aliphatic epoxy at 25 ° C. is preferably 3000 mPa · s or less, more preferably 2000 mPa · s or less, and further preferably 1000 mPa · s or less. The lower limit is not particularly defined, but can be set to 5 mPa · s or more, for example.
The aliphatic epoxy compound used in the present invention is a resin having a linear and / or branched carbon chain and an epoxy group, and in addition to a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a chlorine atom, etc. May be combined. In the present invention, a resin comprising a linear and / or branched carbon chain, a hydrogen atom, and an epoxy group, or a group in which a hydroxyl group is substituted on the resin is particularly preferable. The number of epoxy groups is preferably 1 to 4, and more preferably 2 or 3.
In the present invention, it is also preferable that the cycloaliphatic epoxy compound is not substantially contained. By setting it as such a structure, it exists in the tendency for the effect of this invention to be exhibited more effectively. Here, “substantially not contained” means that it is not added at a level that affects the effects of the present invention, for example, 1% by weight or less of the total solid content.
　本発明で用いる鎖状脂肪族エポキシ化合物は、好ましくは下記一般式（Ｘ－１）で表される樹脂である。
一般式（Ｘ－１）
Figure JPOXMLDOC01-appb-C000040
 （一般式（Ｘ－１）中、Ａは直鎖または分岐の炭化水素基であり、置換基として水酸基を有していてもよく、ｎは１～４の整数である。）
　Ａの炭素数は、１～２０が好ましく、１～１５が好ましく、２～１０がより好ましく、２～６がさらに好ましい。ｎは１～４の整数であり、２または３が好ましい。 The chain aliphatic epoxy compound used in the present invention is preferably a resin represented by the following general formula (X-1).
Formula (X-1)
Figure JPOXMLDOC01-appb-C000040
 (In general formula (X-1), A is a linear or branched hydrocarbon group, which may have a hydroxyl group as a substituent, and n is an integer of 1 to 4.)
The carbon number of A is preferably 1 to 20, preferably 1 to 15, more preferably 2 to 10, and further preferably 2 to 6. n is an integer of 1 to 4, preferably 2 or 3.
　本発明で用いる鎖状脂肪族エポキシ化合物は、さらに好ましくは下記一般式（Ｘ－２）で表される樹脂であることがより好ましい。
一般式（Ｘ－２）
Figure JPOXMLDOC01-appb-C000041
 （一般式（Ｘ－２）中、Ｂは直鎖または分岐の炭化水素基であり、置換基として水酸基を有していてもよく、ｎは１～４の整数である。）
　Ｂの炭素数は、１～１８が好ましく、１～１３が好ましく、２～８がより好ましい。ｎは１～４の整数であり、２または３が好ましい。 The chain aliphatic epoxy compound used in the present invention is more preferably a resin represented by the following general formula (X-2).
Formula (X-2)
Figure JPOXMLDOC01-appb-C000041
 (In the general formula (X-2), B is a linear or branched hydrocarbon group, which may have a hydroxyl group as a substituent, and n is an integer of 1 to 4.)
B preferably has 1 to 18 carbon atoms, more preferably 1 to 13, and more preferably 2 to 8. n is an integer of 1 to 4, preferably 2 or 3.
　本発明で好ましく用いることができる、鎖状脂肪族エポキシとしては、デナコールＥＸ－６１１（１１，８００ｍＰａ・ｓ）、ＥＸ－６１２（１１，９００ｍＰａ・ｓ）、ＥＸ－６１４（２１，２００ｍＰａ・ｓ）、ＥＸ－６１４Ｂ（５，０００ｍＰａ・ｓ）、ＥＸ－６２２（１１，８００ｍＰａ・ｓ）、ＥＸ－５１２（１，３００ｍＰａ・ｓ）、ＥＸ－５２１（４，４００ｍＰａ・ｓ）、ＥＸ－４１１（８００ｍＰａ・ｓ）、ＥＸ－４２１（６５０ｍＰａ・ｓ）、ＥＸ－３１３（１５０ｍＰａ・ｓ）、ＥＸ－３１４（１７０ｍＰａ・ｓ）、ＥＸ－３２１（１３０ｍＰａ・ｓ）、ＥＸ－２１１（２０ｍＰａ・ｓ）、ＥＸ－２１２（２０ｍＰａ・ｓ）、ＥＸ－８１０（２０ｍＰａ・ｓ）、ＥＸ－８１１（２０ｍＰａ・ｓ）、ＥＸ－８５０（２０ｍＰａ・ｓ）、ＥＸ－８５１（３０ｍＰａ・ｓ）、ＥＸ－８２１（４０ｍＰａ・ｓ）、ＥＸ－８３０（７０ｍＰａ・ｓ）、ＥＸ－８３２（９０ｍＰａ・ｓ）、ＥＸ－８４１（１１０ｍＰａ・ｓ）、ＥＸ－９１１（２０ｍＰａ・ｓ）、ＥＸ－９４１（２５ｍＰａ・ｓ）、ＥＸ－９２０（２０ｍＰａ・ｓ）、ＥＸ－９３１（１２０ｍＰａ・ｓ）、ＥＸ－２１２Ｌ（１５ｍＰａ・ｓ）、ＥＸ－２１４Ｌ（１５ｍＰａ・ｓ）、ＥＸ－３２１Ｌ（８００ｍＰａ・ｓ）、ＥＸ－８５０Ｌ（９０ｍＰａ・ｓ）、ＥＸ－２１１Ｌ（２０ｍＰａ・ｓ）、ＥＸ－９４６Ｌ（５０ｍＰａ・ｓ）、ＥＸ－９４６Ｌ（５０ｍＰａ・ｓ）、ＤＬＣ－２０１（１０ｍＰａ・ｓ）、ＤＬＣ－２０３（８ｍＰａ・ｓ）、ＤＬＣ－２０４（１，７００ｍＰａ・ｓ）、ＤＬＣ－２０５（１５ｍＰａ・ｓ）、ＤＬＣ－２０６（２０ｍＰａ・ｓ）、ＤＬＣ－３０１（６０ｍＰａ・ｓ）、ＤＬＣ－４０２（１５０ｍＰａ・ｓ）（以上ナガセケムテック製、カッコ内は２５℃での粘度）、ＹＨ－３００（１４０～１６０ｍＰａ・ｓ）、ＹＨ－３０１（１６０～２２０ｍＰａ・ｓ）、ＹＨ－３０２（７００～１１００ｍＰａ・ｓ）、ＹＨ－３１５（７００～１１００ｍＰａ・ｓ）、ＹＨ－３２４（３５００～５５００ｍＰａ・ｓ）、ＹＨ－３２５（４０００～６０００ｍＰａ・ｓ）（以上新日鐵化学製）などが挙げられる。
　これらのうち、下記に示されるトリメチロールプロパントリグリシジルエーテルまたはネオペンチルグリコールジグリシジルエーテルを含むものであることが特に好ましい。上記のうちＥＸ－３２１、ＥＸ－３２１Ｌ、ＥＸ－２１１、ＥＸ－２１１Ｌ（以上ナガセケムテック製）がそれに該当する。
Figure JPOXMLDOC01-appb-C000042
 Examples of the chain aliphatic epoxy that can be preferably used in the present invention include Denacol EX-611 (11,800 mPa · s), EX-612 (11,900 mPa · s), EX-614 (21,200 mPa · s). EX-614B (5,000 mPa · s), EX-622 (11,800 mPa · s), EX-512 (1,300 mPa · s), EX-521 (4,400 mPa · s), EX-411 (800 mPa · s) S), EX-421 (650 mPa · s), EX-313 (150 mPa · s), EX-314 (170 mPa · s), EX-321 (130 mPa · s), EX-211 (20 mPa · s), EX -212 (20 mPa · s), EX-810 (20 mPa · s), EX-811 (20 mPa · s), EX-850 (20 Pa · s), EX-851 (30 mPa · s), EX-821 (40 mPa · s), EX-830 (70 mPa · s), EX-832 (90 mPa · s), EX-841 (110 mPa · s), EX-911 (20 mPa · s), EX-941 (25 mPa · s), EX-920 (20 mPa · s), EX-931 (120 mPa · s), EX-212L (15 mPa · s), EX-214L (15 mPa · s)・ S), EX-321L (800 mPa · s), EX-850L (90 mPa · s), EX-211L (20 mPa · s), EX-946L (50 mPa · s), EX-946L (50 mPa · s), DLC -201 (10 mPa · s), DLC-203 (8 mPa · s), DLC-204 (1,700 mPa · s), DLC-205 15 mPa · s), DLC-206 (20 mPa · s), DLC-301 (60 mPa · s), DLC-402 (150 mPa · s) (manufactured by Nagase Chemtech, the viscosity in parentheses is 25 ° C.), YH- 300 (140 to 160 mPa · s), YH-301 (160 to 220 mPa · s), YH-302 (700 to 1100 mPa · s), YH-315 (700 to 1100 mPa · s), YH-324 (3500 to 5500 mPa · s) s), YH-325 (4000 to 6000 mPa · s) (manufactured by Nippon Steel Chemical Co., Ltd.) and the like.
Among these, it is particularly preferable to contain trimethylolpropane triglycidyl ether or neopentyl glycol diglycidyl ether shown below. Among these, EX-321, EX-321L, EX-211 and EX-211L (manufactured by Nagase Chemtech) fall under this category.
Figure JPOXMLDOC01-appb-C000042
　分子内に２個以上のオキセタニル基を有する化合物の具体例としては、アロンオキセタンＯＸＴ－１２１、ＯＸＴ－２２１、ＯＸ－ＳＱ、ＰＮＯＸ（以上、東亞合成（株）製）を用いることができる。 As specific examples of the compound having two or more oxetanyl groups in the molecule, Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.) can be used.
　また、オキセタニル基を有する化合物は、単独でまたはエポキシ基を有する化合物と混合して使用することが好ましい。 In addition, the compound having an oxetanyl group is preferably used alone or mixed with a compound having an epoxy group.
　また、その他の架橋剤としては特開２０１２－８２２３号公報の段落番号０１０７～０１０８に記載のアルコキシメチル基含有架橋剤、および少なくとも１個のエチレン性不飽和二重結合を有する化合物なども好ましく用いることができ、これらの内容は本願明細書に組み込まれる。アルコキシメチル基含有架橋剤としては、アルコキシメチル化グリコールウリルが好ましい。 As other crosslinking agents, alkoxymethyl group-containing crosslinking agents described in paragraphs 0107 to 0108 of JP2012-8223A and compounds having at least one ethylenically unsaturated double bond are also preferably used. The contents of which are incorporated herein by reference. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.
　本発明の感光性樹脂組成物における分子内に２個以上のエポキシ基またはオキセタニル基を有する化合物（特に、鎖状エポキシ化合物）の含有量は、固形分１００重量部に対して、０．１～１０重量部であることが好ましく、０．５～１０重量部であることがより好ましい。 In the photosensitive resin composition of the present invention, the content of a compound having 2 or more epoxy groups or oxetanyl groups in the molecule (particularly a chain epoxy compound) is 0.1 to 100 parts by weight with respect to 100 parts by weight of the solid content. The amount is preferably 10 parts by weight, and more preferably 0.5 to 10 parts by weight.
＜ブロックイソシアネート化合物＞
　本発明の感光性樹脂組成物では、架橋剤として、ブロックイソシアネート系化合物も好ましく採用できる。ブロックイソシアネート化合物は、ブロックイソシアネート基を有する化合物であれば特に制限はないが、硬化性の観点から、１分子内に２以上のブロックイソシアネート基を有する化合物であることが好ましい。
　なお、本発明におけるブロックイソシアネート基とは、熱によりイソシアネート基を生成することが可能な基であり、例えば、ブロック剤とイソシアネート基とを反応させイソシアネート基を保護した基が好ましく例示できる。また、前記ブロックイソシアネート基は、９０℃～２５０℃の熱によりイソシアネート基を生成することが可能な基であることが好ましい。
　また、ブロックイソシアネート化合物としては、その骨格は特に限定されるものではなく、１分子中にイソシアネート基を２個有するものであればどのようなものでもよく、脂肪族、脂環族または芳香族のポリイソシアネートであってよいが、例えば２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、イソホロンジイソシアネート、１，６－ヘキサメチレンジイソシアネート、１，３－トリメチレンジイソシアネート、１，４－テトラメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、１，９－ノナメチレンジイソシアネート、１，１０－デカメチレンジイソシアネート、１，４－シクロヘキサンジイソシアネート、２，２’－ジエチルエーテルジイソシアネート、ジフェニルメタン－４，４’－ジイソシアネート、ｏ－キシレンジイソシアネート、ｍ－キシレンジイソシアネート、ｐ－キシレンジイソシアネート、メチレンビス（シクロヘキシルイソシアネート）、シクロヘキサン－１，３－ジメチレンジイソシアネート、シクロヘキサン－１，４－ジメチレレンジイソシアネート、１，５－ナフタレンジイソシアネート、ｐ－フェニレンジイソシアネート、３，３’－メチレンジトリレン－４，４’－ジイソシアネート、４，４’－ジフェニルエーテルジイソシアネート、テトラクロロフェニレンジイソシアネート、ノルボルナンジイソシアネート、水素化１，３－キシリレンジイソシアネート、水素化１，４－キシリレンジイソシアネート等のイソシアネート化合物およびこれらの化合物から派生するプレポリマー型の骨格の化合物を好適に用いることができる。これらの中でも、トリレンジイソシアネート（ＴＤＩ）やジフェニルメタンジイソシアネート（ＭＤＩ）、ヘキサメチレンジイソシアネート（ＨＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）が特に好ましい。 <Block isocyanate compound>
In the photosensitive resin composition of the present invention, a blocked isocyanate compound can also be preferably employed as a crosslinking agent. The blocked isocyanate compound is not particularly limited as long as it is a compound having a blocked isocyanate group, but is preferably a compound having two or more blocked isocyanate groups in one molecule from the viewpoint of curability.
In addition, the blocked isocyanate group in this invention is a group which can produce | generate an isocyanate group with a heat | fever, For example, the group which reacted the blocking agent and the isocyanate group and protected the isocyanate group can illustrate preferably. The blocked isocyanate group is preferably a group capable of generating an isocyanate group by heat at 90 ° C. to 250 ° C.
Further, the skeleton of the blocked isocyanate compound is not particularly limited and may be any as long as it has two isocyanate groups in one molecule, and is aliphatic, alicyclic or aromatic. Polyisocyanates may be used, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetramethylene Diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 2 2'-diethyl ether diisocyanate, diphenylmethane-4,4'-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, methylene bis (cyclohexyl isocyanate), cyclohexane-1,3-dimethylene diisocyanate, cyclohexane-1 , 4-dimethylene diisocyanate, 1,5-naphthalene diisocyanate, p-phenylene diisocyanate, 3,3'-methylene ditolylene-4,4'-diisocyanate, 4,4'-diphenyl ether diisocyanate, tetrachlorophenylene diisocyanate, norbornane diisocyanate , Isocyanation of hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate, etc. A compound and a prepolymer type skeleton compound derived from these compounds can be preferably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
　本発明の感光性樹脂組成物におけるブロックイソシアネート化合物の母構造としては、ビウレット型、イソシアヌレート型、アダクト型、２官能プレポリマー型等を挙げることができる。
　前記ブロックイソシアネート化合物のブロック構造を形成するブロック剤としては、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物、メルカプタン化合物、イミダゾール系化合物、イミド系化合物等を挙げることができる。これらの中でも、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物から選ばれるブロック剤が特に好ましい。 Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
　前記オキシム化合物としては、オキシム、および、ケトオキシムが挙げられ、具体的には、アセトキシム、ホルムアルドキシム、シクロヘキサンオキシム、メチルエチルケトンオキシム、シクロヘキサノンオキシム、ベンゾフェノンオキシム、アセトキシム等が例示できる。
　前記ラクタム化合物としてはε－カプロラクタム、γ－ブチロラクタム等が例示できる。
　前記フェノール化合物としては、フェノール、ナフトール、クレゾール、キシレノール、ハロゲン置換フェノール等が例示できる。
　前記アルコール化合物としては、メタノール、エタノール、プロパノール、ブタノール、シクロヘキサノール、エチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル、乳酸アルキル等が例示できる。
　前記アミン化合物としては、１級アミンおよび２級アミンが上げられ、芳香族アミン、脂肪族アミン、脂環族アミンいずれでもよく、アニリン、ジフェニルアミン、エチレンイミン、ポリエチレンイミン等が例示できる。
　前記活性メチレン化合物としては、マロン酸ジエチル、マロン酸ジメチル、アセト酢酸エチル、アセト酢酸メチル等が例示できる。
　前記ピラゾール化合物としては、ピラゾール、メチルピラゾール、ジメチルピラゾール等が例示できる、
　前記メルカプタン化合物としては、アルキルメルカプタン、アリールメルカプタン等が例示できる。 Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.
　本発明の感光性樹脂組成物に使用できるブロックイソシアネート化合物は、市販品として入手可能であり、例えば、コロネートＡＰステーブルＭ、コロネート２５０３、２５１５、２５０７、２５１３、２５５５、ミリオネートＭＳ－５０（以上、日本ポリウレタン工業（株）製）、タケネートＢ－８３０、Ｂ－８１５Ｎ、Ｂ－８２０ＮＳＵ、Ｂ－８４２Ｎ、Ｂ－８４６Ｎ、Ｂ－８７０Ｎ、Ｂ－８７４Ｎ、Ｂ－８８２Ｎ（以上、三井化学（株）製）、デュラネート１７Ｂ－６０ＰＸ、１７Ｂ－６０Ｐ、ＴＰＡ－Ｂ８０Ｘ、ＴＰＡ－Ｂ８０Ｅ、ＭＦ－Ｂ６０Ｘ、ＭＦ－Ｂ６０Ｂ、ＭＦ－Ｋ６０Ｘ、ＭＦ－Ｋ６０Ｂ、Ｅ４０２－Ｂ８０Ｂ、ＳＢＮ－７０Ｄ、ＳＢＢ－７０Ｐ、Ｋ６０００（以上、旭化成ケミカルズ（株）製）、デスモジュールＢＬ１１００、ＢＬ１２６５　ＭＰＡ／Ｘ、ＢＬ３５７５／１、ＢＬ３２７２ＭＰＡ、ＢＬ３３７０ＭＰＡ、ＢＬ３４７５ＢＡ／ＳＮ、ＢＬ５３７５ＭＰＡ、ＶＰＬＳ２０７８／２、ＢＬ４２６５ＳＮ、ＰＬ３４０、ＰＬ３５０、スミジュールＢＬ３１７５（以上、住化バイエルウレタン（株）製）等を好ましく使用することができる。 The blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above , Manufactured by Asahi Kasei Chemicals Corporation, Death Module B 1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) etc. are preferably used can do.
アルコキシシラン化合物
　本発明の感光性樹脂組成物は、アルコキシシラン化合物を含有させてもよい。アルコキシシラン化合物を用いると、本発明の感光性樹脂組成物により形成された膜と基板との密着性を向上できたり、本発明の感光性樹脂組成物により形成された膜の性質を調整することができる。アルコキシシラン化合物としては、ジアルコキシシラン化合物またはトリアルコキシシラン化合物が好ましく、トリアルコキシシラン化合物がより好ましい。アルコキシシラン化合物が有するアルコキシ基の炭素数は１～５が好ましい。
　本発明の感光性樹脂組成物に用いることができるアルコキシシラン化合物は、基材となる無機物、例えば、シリコン、酸化シリコン、窒化シリコン等のシリコン化合物、金、銅、モリブデン、チタン、アルミニウム等の金属と絶縁膜との密着性を向上させる化合物であることが好ましい。具体的には、公知のシランカップリング剤等も有効である。
　シランカップリング剤としては、例えば、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－グリシドキシプロピルトリアルコキシシラン、γ－グリシドキシプロピルアルキルジアルコキシシラン、γ－メタクリロキシプロピルトリアルコキシシラン、γ－メタクリロキシプロピルアルキルジアルコキシシラン、γ－クロロプロピルトリアルコキシシラン、γ－メルカプトプロピルトリアルコキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリアルコキシシラン、ビニルトリアルコキシシラン、ビス（トリエトキシシリルプロピル）テトラスルフィドが挙げられる。これらのうち、γ－グリシドキシプロピルトリアルコキシシランやγ－メタクリロキシプロピルトリアルコキシシランがより好ましく、γ－グリシドキシプロピルトリアルコキシシランがさらに好ましく、３－グリシドキシプロピルトリメトキシシランがよりさらに好ましい。これらは１種単独または２種以上を組み合わせて使用することができる。 Alkoxysilane Compound The photosensitive resin composition of the present invention may contain an alkoxysilane compound. When an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do. As the alkoxysilane compound, a dialkoxysilane compound or a trialkoxysilane compound is preferable, and a trialkoxysilane compound is more preferable. The alkoxy group contained in the alkoxysilane compound preferably has 1 to 5 carbon atoms.
The alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. Preferably, the compound improves the adhesion between the insulating film and the insulating film. Specifically, a known silane coupling agent or the like is also effective.
Examples of silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Bis (triethoxysilylpropyl) tetrasulfide. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.
　また、下記の化合物も好ましく採用できる。
Figure JPOXMLDOC01-appb-C000043
 The following compounds can also be preferably employed.
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
　上記において、Ｐｈはフェニル基である。 In the above, Ph is a phenyl group.
　本発明の感光性樹脂組成物におけるアルコキシシラン化合物は、特にこれらに限定することなく、公知のものを使用することができる。
　本発明の感光性樹脂組成物におけるアルコキシシラン化合物の含有量は、感光性組成物中の全固形分１００質量部に対して、０．１～３０質量部が好ましく、０．５～２０質量部がより好ましい。 The alkoxysilane compound in the photosensitive resin composition of this invention is not specifically limited to these, A well-known thing can be used.
The content of the alkoxysilane compound in the photosensitive resin composition of the present invention is preferably 0.1 to 30 parts by mass, and preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive composition. Is more preferable.
増感剤
　本発明の感光性樹脂組成物は、（Ｂ）光酸発生剤との組み合わせにおいて、その分解を促進させるために、増感剤を含有することが好ましい。増感剤は、活性光線または放射線を吸収して電子励起状態となる。電子励起状態となった増感剤は、光酸発生剤と接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより光酸発生剤は化学変化を起こして分解し、酸を生成する。好ましい増感剤の例としては、以下の化合物類に属しており、かつ３５０ｎｍから４５０ｎｍの波長域のいずれかに吸収波長を有する化合物を挙げることができる。 Sensitizer The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote its decomposition in combination with (B) a photoacid generator. The sensitizer absorbs actinic rays or radiation and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.
　多核芳香族類（例えば、ピレン、ペリレン、トリフェニレン、アントラセン、９，１０－ジブトキシアントラセン、９，１０－ジエトキシアントラセン，３，７－ジメトキシアントラセン、９，１０－ジプロピルオキシアントラセン）、キサンテン類（例えば、フルオレッセイン、エオシン、エリスロシン、ローダミンＢ、ローズベンガル）、キサントン類（例えば、キサントン、チオキサントン、ジメチルチオキサントン、ジエチルチオキサントン）、シアニン類（例えばチアカルボシアニン、オキサカルボシアニン）、メロシアニン類（例えば、メロシアニン、カルボメロシアニン）、ローダシアニン類、オキソノール類、チアジン類（例えば、チオニン、メチレンブルー、トルイジンブルー）、アクリジン類（例えば、アクリジンオレンジ、クロロフラビン、アクリフラビン）、アクリドン類（例えば、アクリドン、１０－ブチル－２－クロロアクリドン）、アントラキノン類（例えば、アントラキノン）、スクアリウム類（例えば、スクアリウム）、スチリル類、ベーススチリル類（例えば、２－［２－［４－（ジメチルアミノ）フェニル］エテニル］ベンゾオキサゾール）、クマリン類（例えば、７－ジエチルアミノ４－メチルクマリン、７－ヒドロキシ４－メチルクマリン、２，３，６，７－テトラヒドロ－９－メチル－１Ｈ，５Ｈ，１１Ｈ［１］ベンゾピラノ［６，７，８－ｉｊ］キノリジン－１１－ノン）。
　これら増感剤の中でも、多核芳香族類、アクリドン類、スチリル類、ベーススチリル類、クマリン類が好ましく、多核芳香族類がより好ましい。多核芳香族類の中でもアントラセン誘導体が最も好ましい。 Polynuclear aromatics (eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene), xanthenes (Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), xanthones (eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine oleoresin) Di, chloroflavin, acriflavine), acridones (eg, acridone, 10-butyl-2-chloroacridone), anthraquinones (eg, anthraquinone), squaliums (eg, squalium), styryls, base styryls ( For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins (for example, 7-diethylamino 4-methylcoumarin, 7-hydroxy 4-methylcoumarin, 2,3,6,7 -Tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-non).
Among these sensitizers, polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.
　本発明の感光性樹脂組成物中における増感剤の添加量は、感光性樹脂組成物の光酸発生剤１００質量部に対し、０～１０００質量部であることが好ましく、１０～５００質量部であることがより好ましく、５０～２００質量部であることがさらに好ましい。
　２種以上を併用することもできる。 The addition amount of the sensitizer in the photosensitive resin composition of the present invention is preferably 0 to 1000 parts by mass with respect to 100 parts by mass of the photoacid generator in the photosensitive resin composition. More preferably, it is more preferably 50 to 200 parts by mass.
Two or more kinds can be used in combination.
塩基性化合物
　本発明の感光性樹脂組成物は、塩基性化合物を含有することが好ましい。
　塩基性化合物としては、化学増幅レジストで用いられるものの中から任意に選択して使用することができる。例えば、脂肪族アミン、芳香族アミン、複素環式アミン、第四級アンモニウムヒドロキシド、およびカルボン酸の第四級アンモニウム塩等が挙げられる。 Basic Compound The photosensitive resin composition of the present invention preferably contains a basic compound.
The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids.
　脂肪族アミンとしては、例えば、トリメチルアミン、ジエチルアミン、トリエチルアミン、ジ－ｎ－プロピルアミン、トリ－ｎ－プロピルアミン、ジ－ｎ－ペンチルアミン、トリ－ｎ－ペンチルアミン、ジエタノールアミン、トリエタノールアミン、ジシクロヘキシルアミン、ジシクロヘキシルメチルアミン、ジアザビシクロノネンなどが挙げられる。
　芳香族アミンとしては、例えば、アニリン、ベンジルアミン、Ｎ，Ｎ－ジメチルアニリン、ジフェニルアミンなどが挙げられる。 Examples of aliphatic amines include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine. , Dicyclohexylmethylamine, diazabicyclononene, and the like.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
　複素環式アミンとしては、例えば、ピリジン、２－メチルピリジン、４－メチルピリジン、２－エチルピリジン、４－エチルピリジン、２－フェニルピリジン、４－フェニルピリジン、Ｎ－メチル－４－フェニルピリジン、４－ジメチルアミノピリジン、イミダゾール、ベンズイミダゾール、４－メチルイミダゾール、２－フェニルベンズイミダゾール、２，４，５－トリフェニルイミダゾール、ニコチン、ニコチン酸、ニコチン酸アミド、キノリン、８－オキシキノリン、ピラジン、ピラゾール、ピリダジン、プリン、ピロリジン、ピペリジン、ピペラジン、モルホリン、４－メチルモルホリン、Ｎ－シクロヘキシル－Ｎ’－［２－（４－モルホリニル）エチル］チオ尿素、１，５－ジアザビシクロ［４．３．０］－５－ノネン、１，８－ジアザビシクロ［５．３．０］－７－ウンデセンなどが挙げられる。 Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-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 Such as diazabicyclo [5.3.0] -7-undecene and the like.
　第四級アンモニウムヒドロキシドとしては、例えば、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラ－ｎ－ブチルアンモニウムヒドロキシド、テトラ－ｎ－ヘキシルアンモニウムヒドロキシドなどが挙げられる。 Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
　カルボン酸の第四級アンモニウム塩としては、例えば、テトラメチルアンモニウムアセテート、テトラメチルアンモニウムベンゾエート、テトラ－ｎ－ブチルアンモニウムアセテート、テトラ－ｎ－ブチルアンモニウムベンゾエートなどが挙げられる。 Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.
　本発明に用いることができる塩基性化合物は、１種単独で使用しても、２種以上を併用してもよいが、２種以上を併用することが好ましく、２種を併用することがより好ましく、複素環式アミンを２種併用することが更に好ましい。 The basic compounds that can be used in the present invention may be used singly or in combination of two or more. However, it is preferable to use two or more in combination, and it is more preferable to use two in combination. Preferably, two kinds of heterocyclic amines are used in combination.
　本発明の感光性樹脂組成物における塩基性化合物の含有量は、感光性樹脂組成物中の全固形分１００質量部に対して、０．００１～３質量部であることが好ましく、０．００５～１質量部であることがより好ましい。 The content of the basic compound in the photosensitive resin composition of the present invention is preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition, 0.005 More preferred is 1 part by mass.
界面活性剤
　本発明の感光性樹脂組成物は、界面活性剤を含有してもよい。界面活性剤としては、アニオン系、カチオン系、ノニオン系、または、両性のいずれでも使用することができるが、好ましい界面活性剤はノニオン界面活性剤である。
　ノニオン系界面活性剤の例としては、ポリオキシエチレン高級アルキルエーテル類、ポリオキシエチレン高級アルキルフェニルエーテル類、ポリオキシエチレングリコールの高級脂肪酸ジエステル類、シリコーン系、フッ素系界面活性剤を挙げることができる。また、以下商品名で、ＫＰ（信越化学工業（株）製）、ポリフロー（共栄社化学（株）製）、エフトップ（ＪＥＭＣＯ社製）、メガファック（ＤＩＣ（株）製）、フロラード（住友スリーエム（株）製）、アサヒガード、サーフロン（旭硝子（株）製）、ＰｏｌｙＦｏｘ（ＯＭＮＯＶＡ社製）、ＳＨ－８４００（東レ・ダウコーニングシリコーン）等の各シリーズを挙げることができる。
　また、界面活性剤として、下記一般式（Ｉ－１）で表される構成単位Ａおよび構成単位Ｂを含み、テトラヒドロフラン（ＴＨＦ）を溶剤とした場合のゲルパーミエーションクロマトグラフィーで測定されるポリスチレン換算の重量平均分子量（Ｍｗ）が１，０００以上１０，０００以下である共重合体を好ましい例として挙げることができる。 Surfactant The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFac (manufactured by DIC Corporation), Florard (Sumitomo 3M) Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), and the like.
In addition, the surfactant contains the structural unit A and the structural unit B represented by the following general formula (I-1), and is converted to polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A copolymer having a weight average molecular weight (Mw) of 1,000 or more and 10,000 or less can be given as a preferred example.
　一般式（Ｉ－１）
Figure JPOXMLDOC01-appb-C000045
 　（式（Ｉ－１）中、Ｒ401およびＲ403はそれぞれ独立に、水素原子またはメチル基を表し、Ｒ402は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ404は水素原子または炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐおよびｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｓは１以上１０以下の整数を表す。） Formula (I-1)
Figure JPOXMLDOC01-appb-C000045
 (In the formula (I-1), R 401 and R 403 each independently represent a hydrogen atom or a methyl group, R 402 represents a linear alkylene group having 1 to 4 carbon atoms, and R 404 represents a hydrogen atom or C represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is 10 mass% to 80 mass%. A numerical value is represented, q represents a numerical value of 20% by mass or more and 90% by mass or less, r represents an integer of 1 to 18 and s represents an integer of 1 to 10)
　上記Ｌは、下記一般式（Ｉ－２）で表される分岐アルキレン基であることが好ましい。一般式（Ｉ－２）におけるＲ405は、炭素数１以上４以下のアルキル基を表し、相溶性と被塗布面に対する濡れ性の点で、炭素数１以上３以下のアルキル基が好ましく、炭素数２または３のアルキル基がより好ましい。ｐとｑとの和（ｐ＋ｑ）は、ｐ＋ｑ＝１００、すなわち、１００質量％であることが好ましい。 L is preferably a branched alkylene group represented by the following general formula (I-2). R 405 in the general formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. A number 2 or 3 alkyl group is more preferred. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.
　一般式（Ｉ－２）
Figure JPOXMLDOC01-appb-C000046
 Formula (I-2)
Figure JPOXMLDOC01-appb-C000046
　上記共重合体の重量平均分子量（Ｍｗ）は、１，５００以上５，０００以下がより好ましい。 The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
　これらの界面活性剤は、１種単独でまたは２種以上を混合して使用することができる。
　本発明の感光性樹脂組成物における界面活性剤の添加量は、感光性樹脂組成物中の全固形分１００質量部に対して、１０質量部以下であることが好ましく、０．００１～１０質量部であることがより好ましく、０．０１～３質量部であることがさらに好ましい。 These surfactants can be used individually by 1 type or in mixture of 2 or more types.
The addition amount of the surfactant in the photosensitive resin composition of the present invention is preferably 10 parts by mass or less, and 0.001 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. More preferably, the amount is 0.01 to 3 parts by mass.
酸化防止剤
　本発明の感光性樹脂組成物は、酸化防止剤を含有してもよい。酸化防止剤としては、公知の酸化防止剤を含有することができる。酸化防止剤を添加することにより、硬化膜の着色を防止できる、または、分解による膜厚減少を低減でき、また、耐熱透明性に優れるという利点がある。
　このような酸化防止剤としては、例えば、リン系酸化防止剤、アミド類、ヒドラジド類、ヒンダードアミン系酸化防止剤、イオウ系酸化防止剤、フェノール系酸化防止剤、アスコルビン酸類、硫酸亜鉛、糖類、亜硝酸塩、亜硫酸塩、チオ硫酸塩、ヒドロキシルアミン誘導体などを挙げることができる。これらの中では、硬化膜の着色、膜厚減少の観点から特にフェノール系酸化防止剤、アミド系酸化防止剤、ヒドラジド系酸化防止剤、イオウ系酸化防止剤が好ましい。これらは１種単独で用いてもよいし、２種以上を混合してもよい。
　フェノール系酸化防止剤の市販品としては、例えば、アデカスタブＡＯ－１５、アデカスタブＡＯ－１８、アデカスタブＡＯ－２０、アデカスタブＡＯ－２３、アデカスタブＡＯ－３０、アデカスタブＡＯ－３７、アデカスタブＡＯ－４０、アデカスタブＡＯ－５０、アデカスタブＡＯ－５１、アデカスタブＡＯ－６０、アデカスタブＡＯ－７０、アデカスタブＡＯ－８０、アデカスタブＡＯ－３３０、アデカスタブＡＯ－４１２Ｓ、アデカスタブＡＯ－５０３、アデカスタブＡ－６１１、アデカスタブＡ－６１２、アデカスタブＡ－６１３、アデカスタブＰＥＰ－４Ｃ、アデカスタブＰＥＰ－８、アデカスタブＰＥＰ－８Ｗ、アデカスタブＰＥＰ－２４Ｇ、アデカスタブＰＥＰ－３６、アデカスタブＰＥＰ－３６Ｚ、アデカスタブＨＰ－１０、アデカスタブ２１１２、アデカスタブ２６０、アデカスタブ５２２Ａ、アデカスタブ１１７８、アデカスタブ１５００、アデカスタブＣ、アデカスタブ１３５Ａ、アデカスタブ３０１０、アデカスタブＴＰＰ、アデカスタブＣＤＡ－１、アデカスタブＣＤＡ－６、アデカスタブＺＳ－２７、アデカスタブＺＳ－９０、アデカスタブＺＳ－９１（以上、（株）ＡＤＥＫＡ製）、イルガノックス２４５ＦＦ、イルガノックス１０１０ＦＦ、イルガノックス１０１０、イルガノックスＭＤ１０２４、イルガノックス１０３５ＦＦ、イルガノックス１０３５、イルガノックス１０９８、イルガノックス１３３０、イルガノックス１５２０Ｌ、イルガノックス３１１４、イルガノックス１７２６、イルガフォス１６８、イルガモッド２９５（ＢＡＳＦ（株）製）などが挙げられる。中でも、アデカスタブＡＯ－６０、アデカスタブＡＯ－８０、イルガノックス１７２６、イルガノックス１０３５、イルガノックス１０９８を好適に使用することができる。 Antioxidant The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By adding an antioxidant, there is an advantage that coloring of the cured film can be prevented, or a decrease in film thickness due to decomposition can be reduced, and heat-resistant transparency is excellent.
Examples of such antioxidants include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acids, zinc sulfate, sugars, Examples thereof include nitrates, sulfites, thiosulfates, and hydroxylamine derivatives. Among these, phenol-based antioxidants, amide-based antioxidants, hydrazide-based antioxidants, and sulfur-based antioxidants are particularly preferable from the viewpoint of coloring the cured film and reducing the film thickness. These may be used individually by 1 type and may mix 2 or more types.
Examples of commercially available phenolic antioxidants include ADK STAB AO-15, ADK STAB AO-18, ADK STAB AO-20, ADK STAB AO-23, ADK STAB AO-30, ADK STAB AO-37, ADK STAB AO-40 and ADK STAB AO. -50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB AO-503, ADK STAB A-611, ADK STAB A-612, ADK STAB A -613, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, ADK STAB PEP-36Z, ADK STAB HP-1 ADK STAB 2112, ADK STAB 260, ADK STAB 1522, ADK STAB 1178, ADK STAB 1500, ADK STAB C, ADK STAB 13510, ADK STAB 3010, ADK STAB CDA-1, ADK STAB CDA-6, ADK STAB ZS-27, ADK STAB ZS-90 -91 (above, manufactured by ADEKA Corporation), Irganox 245FF, Irganox 1010FF, Irganox 1010, Irganox MD1024, Irganox 1035FF, Irganox 1035, Irganox 1098, Irganox 1330, Irganox 1520L, Irganox 3114, Irganox 1726, Irgafos 168, Irgamod 295 (BAS Co., Ltd.), and the like. Among them, ADK STAB AO-60, ADK STAB AO-80, IRGANOX 1726, IRGANOX 1035, and IRGANOX 1098 can be preferably used.
　酸化防止剤の含有量は、感光性樹脂組成物の全固形分に対して、０．１～１０質量％であることが好ましく、０．２～５質量％であることがより好ましく、０．５～４質量％であることが特に好ましい。この範囲にすることで、形成された膜の十分な透明性が得られ、且つ、パターン形成時の感度も良好となる。
　また、酸化防止剤以外の添加剤として、“高分子添加剤の新展開（（株）日刊工業新聞社）”に記載の各種紫外線吸収剤や、金属不活性化剤等を本発明の感光性樹脂組成物に添加してもよい。 The content of the antioxidant is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on the total solid content of the photosensitive resin composition. It is particularly preferably 5 to 4% 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.
As additives other than antioxidants, various ultraviolet absorbers described in “New Development of Polymer Additives (Nikkan Kogyo Shimbun Co., Ltd.)”, metal deactivators, and the like are used in the present invention. You may add to a resin composition.
〔酸増殖剤〕
　本発明の感光性樹脂組成物は、感度向上を目的に、酸増殖剤を用いることができる。
　本発明に用いることができる酸増殖剤は、酸触媒反応によってさらに酸を発生して反応系内の酸濃度を上昇させることができる化合物であり、酸が存在しない状態では安定に存在する化合物である。このような化合物は、１回の反応で１つ以上の酸が増えるため、反応の進行に伴って加速的に反応が進むが、発生した酸自体が自己分解を誘起するため、ここで発生する酸の強度は、酸解離定数、ｐＫａとして３以下であるのが好ましく、特に２以下であるのが好ましい。
　酸増殖剤の具体例としては、特開平１０－１５０８号公報の段落番号０２０３～０２２３、特開平１０－２８２６４２号公報の段落番号００１６～００５５、および、特表平９－５１２４９８号公報第３９頁１２行目～第４７頁２行目に記載の化合物を挙げることができ、これらの内容は本願明細書に組み込まれる。
　本発明で用いることができる酸増殖剤としては、酸発生剤から発生した酸によって分解し、ジクロロ酢酸、トリクロロ酢酸、メタンスルホン酸、ベンゼンスルホン酸、トリフルオロメタンスルホン酸、フェニルホスホン酸などのｐＫａが３以下の酸を発生させる化合物を挙げることができる。
　具体的には
Figure JPOXMLDOC01-appb-C000047
 等を挙げることができる。
　酸増殖剤の感光性組成物への含有量は、光酸発生剤１００質量部に対して、１０～１，０００質量部とするのが、露光部と未露光部との溶解コントラストの観点から好ましく、２０～５００質量部とするのがさらに好ましい。 [Acid multiplication agent]
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there. In such a compound, since one or more acids increase in one reaction, the reaction proceeds at an accelerated rate as the reaction proceeds. However, the generated acid itself induces self-decomposition, and is generated here. The acid strength is preferably 3 or less as an acid dissociation constant, pKa, and particularly preferably 2 or less.
Specific examples of the acid proliferating agent include paragraph numbers 0203 to 0223 of JP-A-10-1508, paragraphs 0016 to 0055 of JP-A-10-282642, and page 39 of JP-T 9-512498. The compounds described on line 12 to page 47, line 2 can be mentioned, the contents of which are incorporated herein.
Examples of the acid proliferating agent that can be used in the present invention include pKa such as dichloroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, and phenylphosphonic acid, which are decomposed by an acid generated from the acid generator. Examples include compounds that generate 3 or less acids.
In particular
Figure JPOXMLDOC01-appb-C000047
 Etc.
The content of the acid proliferating agent in the photosensitive composition is 10 to 1,000 parts by mass with respect to 100 parts by mass of the photoacid generator, from the viewpoint of dissolution contrast between the exposed and unexposed parts. It is preferably 20 to 500 parts by mass.
〔現像促進剤〕
　本発明の感光性樹脂組成物は、現像促進剤を含有することができる。
　現像促進剤としては、特開２０１２－０４２８３７号公報の段落番号０１７１～０１７２の記載を参酌でき、かかる内容は本願明細書に組み込まれる。 [Development accelerator]
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, the description in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
　現像促進剤は、１種を単独で用いてもよいし、２種以上を併用することも可能である。
　本発明の感光性樹脂組成物における現像促進剤の添加量は、感度と残膜率の観点から、感光性組成物の全固形分１００質量部に対し、０～３０質量部が好ましく、０．１～２０質量部がより好ましく、０．５～１０質量部であることが最も好ましい。
　また、その他の添加剤としては特開２０１２－８２２３号公報の段落番号０１２０～０１２１に記載の熱ラジカル発生剤、ＷＯ２０１１／１３６０７４Ａ１に記載の窒素含有化合物および熱酸発生剤も用いることができ、これらの内容は本願明細書に組み込まれる。 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 in the photosensitive resin composition of the present invention is preferably 0 to 30 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. 1 to 20 parts by mass is more preferable, and 0.5 to 10 parts by mass is most preferable.
In addition, as other additives, thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, nitrogen-containing compounds and thermal acid generators described in WO2011-133604A1, can be used. Is incorporated herein by reference.
＜感光性樹脂組成物の調製方法＞
　各成分を所定の割合でかつ任意の方法で混合し、撹拌溶解して感光性樹脂組成物を調製する。例えば、成分を、それぞれ予め溶剤に溶解させた溶液とした後、これらを所定の割合で混合して樹脂組成物を調製することもできる。以上のように調製した組成物溶液は、孔径０．２μｍのフィルター等を用いてろ過した後に、使用に供することもできる。 <Method for preparing photosensitive resin composition>
Each component is mixed in a predetermined ratio and by any method, stirred and dissolved to prepare a photosensitive resin composition. For example, a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio. The composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.
［硬化膜の製造方法］
　次に、本発明の硬化膜の製造方法を説明する。
　本発明の硬化膜の製造方法は、以下の（１）～（５）の工程を含むことが好ましい。
　（１）本発明の感光性樹脂組成物を基板上に塗布する工程；
　（２）塗布された感光性樹脂組成物から溶剤を除去する工程；
　（３）溶剤が除去された感光性樹脂組成物を活性光線により露光する工程；
　（４）露光された感光性樹脂組成物を水性現像液により現像する工程；
　（５）現像された感光性樹脂組成物を熱硬化するポストベーク工程。
　以下に各工程を順に説明する。 [Method for producing cured film]
Next, the manufacturing method of the cured film of this invention is demonstrated.
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) The process of apply | coating the photosensitive resin composition of this invention on a board | substrate;
(2) A step of removing the solvent from the applied photosensitive resin composition;
(3) The process of exposing the photosensitive resin composition from which the solvent was removed with actinic rays;
(4) A step of developing the exposed photosensitive resin composition with an aqueous developer;
(5) A post-baking step of thermosetting the developed photosensitive resin composition.
Each step will be described below in order.
　（１）の塗布工程では、本発明の感光性樹脂組成物を基板上に塗布して溶剤を含む湿潤膜とすることが好ましい。感光性樹樹脂組成物を基板へ塗布する前にアルカリ洗浄やプラズマ洗浄といった基板の洗浄を行うことが好ましく、さらに基板洗浄後にヘキサメチルジシラザンで基板表面を処理することがより好ましい。この処理を行うことにより、感光性樹脂組成物の基板への密着性が向上する傾向にある。ヘキサメチルジシラザンで基板表面を処理する方法としては、特に限定されないが、例えば、ヘキサメチルジシラザン蒸気に中に基板を晒しておく方法等が挙げられる。
　上記の基板としては、無機基板、樹脂、樹脂複合材料などが挙げられる。
　無機基板としては、例えばガラス、石英、シリコーン、シリコンナイトライド、および、それらのような基板上にモリブデン、チタン、アルミ、銅などを蒸着した複合基板が挙げられる。
　樹脂としては、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリブチレンナフタレート、ポリスチレン、ポリカーボネート、ポリスルホン、ポリエーテルスルホン、ポリアリレート、アリルジグリコールカーボネート、ポリアミド、ポリイミド、ポリアミドイミド、ポリエーテルイミド、ポリベンズアゾール、ポリフェニレンサルファイド、ポリシクロオレフィン、ノルボルネン樹脂、ポリクロロトリフルオロエチレン等のフッ素樹脂、液晶ポリマー、アクリル樹脂、エポキシ樹脂、シリコーン樹脂、アイオノマー樹脂、シアネート樹脂、架橋フマル酸ジエステル、環状ポリオレフィン、芳香族エーテル、マレイミドーオレフィン、セルロース、エピスルフィド化合物等の合成樹脂からなる基板が挙げられる
　これらの基板は、上記の形態のまま用いられる場合は少なく、通常、最終製品の形態によって、例えばＴＦＴ素子のような多層積層構造が形成されている。
　基板への塗布方法は特に限定されず、例えば、スリットコート法、スプレー法、ロールコート法、回転塗布法、流延塗布法、スリットアンドスピン法等の方法を用いることができる。さらに、特開２００９－１４５３９５号公報に記載されているような、所謂プリウェット法を適用することも可能である。
　塗布したときのウエット膜厚は特に限定されるものではなく、用途に応じた膜厚で塗布することができるが、通常は０．５～１０μｍの範囲で使用される。 In the application step (1), the photosensitive resin composition of the present invention is preferably applied onto a substrate to form a wet film containing a solvent. Before applying the photosensitive resin resin composition to the substrate, it is preferable to perform substrate cleaning such as alkali cleaning or plasma cleaning, and it is more preferable to treat the substrate surface with hexamethyldisilazane after substrate cleaning. By performing this treatment, the adhesiveness of the photosensitive resin composition to the substrate tends to be improved. The method for treating the substrate surface with hexamethyldisilazane is not particularly limited, and examples thereof include a method in which the substrate is exposed to hexamethyldisilazane vapor.
Examples of the substrate include inorganic substrates, resins, and resin composite materials.
Examples of the inorganic substrate include glass, quartz, silicone, 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 Made of synthetic resin such as aromatic ether, maleimide-olefin, cellulose, episulfide compound These substrates which may be mentioned are less if used while the above embodiment, normally, depending on the form of the final product, for example, multi-layered structure such as a TFT element is formed.
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. Furthermore, it is also possible to apply a so-called pre-wet method as described in JP-A-2009-145395.
The wet film thickness when applied is not particularly limited, and can be applied with a film thickness according to the application, but it is usually used in the range of 0.5 to 10 μm.
　（２）の溶剤除去工程では、塗布された上記の膜から、減圧（バキューム）および／または加熱により、溶剤を除去して基板上に乾燥塗膜を形成させる。溶剤除去工程の加熱条件は、好ましくは７０～１３０℃で３０～３００秒間程度である。温度と時間が上記範囲である場合、パターンの密着性がより良好で、且つ残渣もより低減できる傾向にある。 (2) In the solvent removal step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.
　（３）の露光工程では、塗膜を設けた基板に所定のパターンを有するマスクを介して、活性光線を照射する。この工程では、光酸発生剤が分解し酸が発生する。発生した酸の触媒作用により、塗膜成分中に含まれる酸分解性基が加水分解されて、カルボキシル基またはフェノール性水酸基が生成する。
　活性光線による露光光源としては、低圧水銀灯、高圧水銀灯、超高圧水銀灯、ケミカルランプ、ＬＥＤ光源、エキシマレーザー発生装置などを用いることができ、ｇ線（４３６ｎｍ）、ｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）などの波長３００ｎｍ以上４５０ｎｍ以下の波長を有する活性光線が好ましく使用できる。また、必要に応じて長波長カットフィルター、短波長カットフィルター、バンドパスフィルターのような分光フィルターを通して照射光を調整することもできる。
　露光装置としては、ミラープロジェクションアライナー、ステッパー、スキャナー、プロキシミティ、コンタクト、マイクロレンズアレイ、レーザー露光、など各種方式の露光機を用いることができる。
　酸触媒の生成した領域において、上記の加水分解反応を加速させるために、露光後加熱処理：Ｐｏｓｔ　Ｅｘｐｏｓｕｒｅ　Ｂａｋｅ（以下、「ＰＥＢ」ともいう。）を行うことができる。ＰＥＢにより、酸分解性基からのカルボキシル基またはフェノール性水酸基の生成を促進させることができる。ＰＥＢを行う場合の温度は、３０℃以上１３０℃以下であることが好ましく、４０℃以上１１０℃以下がより好ましく、５０℃以上１００℃以下が特に好ましい。
　ただし、本発明における酸分解性基は、酸分解の活性化エネルギーが低く、露光による酸発生剤由来の酸により容易に分解し、カルボキシル基またはフェノール性水酸基を生じるため、必ずしもＰＥＢを行うことなく、現像によりポジ画像を形成することもできる。 In the exposure step (3), the substrate provided with the coating film is irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to produce a carboxyl group or a phenolic hydroxyl group.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, etc. can be used, and g-line (436 nm), i-line (365 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as 405 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
In order to accelerate the hydrolysis reaction in the region where the acid catalyst is generated, post-exposure heat treatment: Post Exposure Bake (hereinafter also referred to as “PEB”) can be performed. PEB can promote the formation of a carboxyl group or a phenolic hydroxyl group from an acid-decomposable group. The temperature for performing PEB is preferably 30 ° C. or higher and 130 ° C. or lower, more preferably 40 ° C. or higher and 110 ° C. or lower, and particularly preferably 50 ° C. or higher and 100 ° C. or lower.
However, since the acid-decomposable group in the present invention has 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, PEB is not necessarily performed. A positive image can also be formed by development.
　（４）の現像工程では、遊離したカルボキシル基またはフェノール性水酸基を有する重合体を、アルカリ性現像液を用いて現像する。アルカリ性現像液に溶解しやすいカルボキシル基またはフェノール性水酸基を有する樹脂組成物を含む露光部領域を除去することにより、ポジ画像が形成する。
　現像工程で使用する現像液には、塩基性化合物が含まれることが好ましい。塩基性化合物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物類；炭酸ナトリウム、炭酸カリウムなどのアルカリ金属炭酸塩類；重炭酸ナトリウム、重炭酸カリウムなどのアルカリ金属重炭酸塩類；テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリンヒドロキシド等のアンモニウムヒドロキシド類；ケイ酸ナトリウム、メタケイ酸ナトリウムなどの水溶液を使用することができる。また、上記アルカリ類の水溶液にメタノールやエタノールなどの水溶性有機溶剤や界面活性剤を適当量添加した水溶液を現像液として使用することもできる。
　好ましい現像液として、テトラエチルアンモニウムヒドロキシドの０．４％水溶液、０．５％水溶液、０．７％水溶液、２．３８％水溶液を挙げる事ができる。
　現像液のｐＨは、好ましくは１０．０～１４．０である。
　現像時間は、好ましくは３０～５００秒間であり、また、現像の手法は液盛り法、ディップ法等の何れでもよい。現像後は、流水洗浄を、通常、３０～３００秒間行い、所望のパターンを形成させることができる。
　現像の後に、リンス工程を行うこともできる。リンス工程では、現像後の基板を純水などで洗うことで、付着している現像液除去、現像残渣除去を行う。リンス方法は公知の方法を用いることができる。例えばシャワーリンスやディップリンスなどを挙げる事ができる。 In the developing step (4), a polymer 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 and choline hydroxide; aqueous solutions such as sodium silicate and sodium metasilicate can be used. An aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the alkaline aqueous solution can also be used as a developer.
Preferred examples of the developer include 0.4% aqueous solution, 0.5% aqueous solution, 0.7% aqueous solution and 2.38% aqueous solution of tetraethylammonium hydroxide.
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 either a liquid piling method or a dipping method. After development, washing with running water is usually performed for 30 to 300 seconds to form a desired pattern.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.
　（５）のポストベーク工程では、得られたポジ画像を加熱することにより、酸分解性基を熱分解しカルボキシル基またはフェノール性水酸基を生成させ、エポキシ基、架橋剤等と架橋させることにより、硬化膜を形成することができる。この加熱は、ホットプレートやオーブン等の加熱装置を用いて、所定の温度、例えば１８０～２５０℃で所定の時間、例えばホットプレート上なら５～９０分間、オーブンならば３０～１２０分間、加熱処理をすることが好ましい。このような架橋反応を進行させることにより、耐熱性、硬度等により優れた保護膜や層間絶縁膜を形成することができる。また、加熱処理を行う際は窒素雰囲気下で行うことにより、透明性をより向上させることもできる。
　ポストベークの前に、比較的低温でベークを行った後にポストベークすることもできる（ミドルベーク工程の追加）。ミドルベークを行う場合は、９０～１５０℃で１～６０分加熱した後に、２００℃以上の高温でポストベークすることが好ましい。また、ミドルベーク、ポストベークを３段階以上の多段階に分けて加熱する事もできる。このようなミドルベーク、ポストベークの工夫により、パターンのテーパー角を調整することができる。これらの加熱は、ホットプレート、オーブン、赤外線ヒーターなど、公知の加熱方法を使用することができる。
　なお、選択する各材料の特性により、架橋度が不足すると予想される場合は、ポストベークに先立ち、パターンを形成した基板に活性光線により全面再露光（ポスト露光）した後、ポストベークすることにより未露光部分に存在する光酸発生剤から酸を発生させ、架橋工程を促進する触媒として機能させることができ、膜の硬化反応を促進することができる。ポスト露光工程を含む場合の好ましい露光量としては、１００～３，０００ｍＪ／ｃｍ2が好ましく、１００～５００ｍＪ／ｃｍ2が特に好ましい。一方、上記以外の場合においては、再露光工程を行わないことが好ましい。生産性を向上させると共に、高温・高湿状態での安定性を高めることができる。 In the post-baking step of (5), by heating the obtained positive image, the acid-decomposable group is thermally decomposed to generate a carboxyl group or a phenolic hydroxyl group, and crosslinked with an epoxy group, a crosslinking agent, etc. A cured 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 with such a crosslinking reaction, it is possible to form a protective film and an interlayer insulating film that are superior in heat resistance, hardness, and the like. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When middle baking is performed, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
If the degree of cross-linking is expected to be insufficient due to the characteristics of each material to be selected, the entire surface is re-exposed (post-exposure) with actinic rays to the substrate on which the pattern has been formed prior to post-baking, and then post-baked. An acid is generated from the photoacid generator present in the unexposed portion, and can function as a catalyst for accelerating the cross-linking process, thereby promoting 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. On the other hand, in cases other than the above, it is preferable not to perform the re-exposure step. In addition to improving productivity, stability at high temperatures and high humidity can be increased.
　さらに、本発明の感光性樹脂組成物より得られた硬化膜は、ドライエッチングレジストとして使用することもできる。ポストベーク工程により熱硬化して得られた硬化膜をドライエッチングレジストとして使用する場合、エッチング処理としてはアッシング、プラズマエッチング、オゾンエッチングなどのドライエッチング処理を行うことができる。 Furthermore, the cured film obtained from the photosensitive resin composition of the present invention can also be used as a dry etching resist. In the case where a cured film obtained by thermal curing in a post-baking process is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.
［硬化膜］
　本発明の硬化膜は、本発明の感光性樹脂組成物を硬化して得られた硬化膜である。
　本発明の硬化膜は、層間絶縁膜として好適に用いることができる。また、本発明の硬化膜は、本発明の硬化膜の形成方法により得られた硬化膜であることが好ましい。
　本発明の感光性樹脂組成物により、絶縁性に優れ、高温でベークされた場合においても高い透明性を有する層間絶縁膜が得られる。本発明の感光性樹脂組成物を用いてなる層間絶縁膜は、高い透明性を有し、硬化膜物性に優れるため、有機ＥＬ表示装置や液晶表示装置の用途に有用である。 [Curing film]
The cured film of the present invention is a cured film obtained by curing the photosensitive resin composition of the present invention.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention.
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 physical properties, it is useful for applications of organic EL display devices and liquid crystal display devices.
［液晶表示装置］
　本発明の液晶表示装置は、本発明の硬化膜を具備することを特徴とする。
　本発明の液晶表示装置としては、上記本発明の感光性樹脂組成物を用いて形成される平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の液晶表示装置を挙げることができる。
　例えば、本発明の液晶表示装置が具備するＴＦＴ（Ｔｈｉｎ－Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ）の具体例としては、アモルファスシリコン－ＴＦＴ、低温ポリシリコンーＴＦＴ、酸化物半導体ＴＦＴ等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのＴＦＴに組み合わせて好ましく用いることができる。
　また、本発明の液晶表示装置が取りうる液晶駆動方式としてはＴＮ（ＴｗｉｓｔｅｄＮｅｍａｔｉｃ）方式、ＶＡ（Ｖｉｒｔｉｃａｌ　Ａｌｉｇｎｍｅｎｔ）方式、ＩＰＳ（Ｉｎ－Ｐｌａｃｅ－Ｓｗｉｔｃｈｉｎｇ）方式、ＦＦＳ（Ｆｒｉｎｇｓ　Ｆｉｅｌｄ　Ｓｗｉｔｃｈｉｎｇ）方式、ＯＣＢ（Ｏｐｔｉｃａｌ　Ｃｏｍｐｅｎｓａｔｅｄ　Ｂｅｎｄ）方式などが挙げられる。
　パネル構成においては、ＣＯＡ（Ｃｏｌｏｒ　Ｆｉｌｔｅｒ　ｏｎ　Ａｌｌａｙ）方式の液晶表示装置でも本発明の硬化膜を用いることができ、例えば、特開２００５－２８４２９１号公報の有機絶縁膜（１１５）や、特開２００５－３４６０５４号公報の有機絶縁膜（２１２）として用いることができる。
　また、本発明の液晶表示装置が取りうる液晶配向膜の具体的な配向方式としてはラビング配向法、光配向方などが挙げられる。また、特開２００３－１４９６４７号公報や特開２０１１－２５７７３４号公報に記載のＰＳＡ（Ｐｏｌｙｍｅｒ　Ｓｕｓｔａｉｎｅｄ　Ａｌｉｇｎｍｅｎｔ）技術によってポリマー配向支持されていてもよい。
　また、本発明の感光性樹脂組成物および本発明の硬化膜は、上記用途に限定されず種々の用途に使用することができる。例えば、平坦化膜や層間絶縁膜以外にも、カラーフィルターの保護膜や、液晶表示装置における液晶層の厚みを一定に保持するためのスペーサーや固体撮像素子においてカラーフィルター上に設けられるマイクロレンズ等に好適に用いることができる。
　図１は、アクティブマトリックス方式の液晶表示装置１０の一例を示す概念的断面図である。このカラー液晶表示装置１０は、背面にバックライトユニット１２を有する液晶パネルであって、液晶パネルは、偏光フィルムが貼り付けられた２枚のガラス基板１４，１５の間に配置されたすべての画素に対応するＴＦＴ１６の素子が配置されている。ガラス基板上に形成された各素子には、硬化膜１７中に形成されたコンタクトホール１８を通して、画素電極を形成するＩＴＯ透明電極１９が配線されている。ＩＴＯ透明電極１９の上には、液晶２０の層とブラックマトリックスを配置したＲＧＢカラーフィルター２２が設けられている。
　バックライトの光源としては、特に限定されず公知の光源を用いることができる。例えば白色ＬＥＤ、青色・赤色・緑色などの多色ＬＥＤ、蛍光灯（冷陰極管）、有機ＥＬなどを挙げる事ができる。
　また、液晶表示装置は、３Ｄ（立体視）型のものとしたり、タッチパネル型のものとしたりすることも可能である。さらにフレキシブル型にすることも可能であり、特開２０１１－１４５６８６号公報の第２相間絶縁膜（４８）や、特開２００９－２５８７５８号公報の相間絶縁膜（５２０）として用いることができる。 [Liquid Crystal Display]
The liquid crystal display device of the present invention comprises the cured film of the present invention.
The liquid crystal display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and known liquid crystal displays having various structures. An apparatus can be mentioned.
For example, specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
Further, the liquid crystal driving methods that can be adopted by the liquid crystal display device of the present invention include TN (Twisted Nematic) method, VA (Virtual Alignment) method, IPS (In-Place-Switching) method, FFS (Frings Field Switching) method, OCB (Optical). Compensated Bend) method and the like.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of JP-A-2005-284291, -346054 can be used as the organic insulating film (212).
Specific examples of the alignment method of the liquid crystal alignment film that the liquid crystal display device of the present invention can take include a rubbing alignment method and a photo alignment method. Further, the polymer orientation may be supported by a PSA (Polymer Sustained Alignment) technique described in JP-A Nos. 2003-149647 and 2011-257734.
Moreover, the photosensitive resin composition of this invention and the cured film of this invention are not limited to the said use, It can be used for various uses. For example, in addition to the planarization film and interlayer insulating film, a protective film for the color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, a microlens provided on the color filter in the solid-state imaging device, etc. Can be suitably used.
FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and can be used as the second interphase insulating film (48) of JP 2011-145686 A or the interphase insulating film (520) of JP 2009-258758 A.
［有機ＥＬ表示装置］
　本発明の有機ＥＬ表示装置は、本発明の硬化膜を具備することを特徴とする。
　本発明の有機ＥＬ表示装置としては、上記本発明の感光性樹脂組成物を用いて形成される平坦化膜や層間絶縁膜を有すること以外は特に制限されず、様々な構造をとる公知の各種有機ＥＬ表示装置や液晶表示装置を挙げることができる。
　例えば、本発明の有機ＥＬ表示装置が具備するＴＦＴ（Ｔｈｉｎ－Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ）の具体例としては、アモルファスシリコン－ＴＦＴ、低温ポリシリコンーＴＦＴ、酸化物半導体ＴＦＴ等が挙げられる。本発明の硬化膜は電気特性に優れるため、これらのＴＦＴに組み合わせて好ましく用いることができる。
　図２は、有機ＥＬ表示装置の一例の構成概念図である。ボトムエミッション型の有機ＥＬ表示装置における基板の模式的断面図を示し、平坦化膜４を有している。
　ガラス基板６上にボトムゲート型のＴＦＴ１を形成し、このＴＦＴ１を覆う状態でＳｉ3Ｎ4から成る絶縁膜３が形成されている。絶縁膜３に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してＴＦＴ１に接続される配線２（高さ１．０μｍ）が絶縁膜３上に形成されている。配線２は、ＴＦＴ１間または、後の工程で形成される有機ＥＬ素子とＴＦＴ１とを接続するためのものである。
　さらに、配線２の形成による凹凸を平坦化するために、配線２による凹凸を埋め込む状態で絶縁膜３上に平坦化層４が形成されている。
　平坦化膜４上には、ボトムエミッション型の有機ＥＬ素子が形成されている。すなわち、平坦化膜４上に、ＩＴＯからなる第一電極５が、コンタクトホール７を介して配線２に接続させて形成されている。また、第一電極５は、有機ＥＬ素子の陽極に相当する。
　第一電極５の周縁を覆う形状の絶縁膜８が形成されており、この絶縁膜８を設けることによって、第一電極５とこの後の工程で形成する第二電極との間のショートを防止することができる。
　さらに、図２には図示していないが、所望のパターンマスクを介して、正孔輸送層、有機発光層、電子輸送層を順次蒸着して設け、次いで、基板上方の全面にＡｌから成る第二電極を形成し、封止用ガラス板と紫外線硬化型エポキシ樹脂を用いて貼り合わせることで封止し、各有機ＥＬ素子にこれを駆動するためのＴＦＴ１が接続されてなるアクティブマトリックス型の有機ＥＬ表示装置が得られる。 [Organic EL display device]
The organic EL display device of the present invention comprises the cured film of the present invention.
The organic EL display device of the present invention is not particularly limited except that it has a flattening film and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and various known structures having various structures. Examples thereof include an organic EL display device and a liquid crystal display device.
For example, specific examples of TFT (Thin-Film Transistor) included in the organic EL display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
FIG. 2 is a conceptual diagram of an example of an organic EL display device. A schematic cross-sectional view of a substrate in a bottom emission type organic EL display device is shown, and a planarizing film 4 is provided.
A bottom gate type TFT 1 is formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 is formed so as to cover the TFT 1. A contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height: 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. The wiring 2 is for connecting the TFT 1 with an organic EL element formed between the TFTs 1 or in a later process.
Further, in order to flatten the unevenness due to the formation of the wiring 2, the flattening layer 4 is formed on the insulating film 3 in a state where the unevenness due to the wiring 2 is embedded.
On the planarizing film 4, a bottom emission type organic EL element is formed. That is, the first electrode 5 made of ITO is formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. The first electrode 5 corresponds to the anode of the organic EL element.
An insulating film 8 having a shape covering the periphery of the first electrode 5 is formed. By providing the insulating film 8, a short circuit between the first electrode 5 and the second electrode formed in the subsequent process is prevented. can do.
Further, although not shown in FIG. 2, a hole transport layer, an organic light emitting layer, and an electron transport layer are sequentially deposited through a desired pattern mask, and then a second layer made of Al is formed on the entire surface above the substrate. An active matrix organic material in which two electrodes are formed and sealed by bonding using a sealing glass plate and an ultraviolet curable epoxy resin, and each organic EL element is connected to a TFT 1 for driving it. An EL display device is obtained.
　本発明の感光性樹脂組成物は、硬化性および硬化膜特性に優れるため、ＭＥＭＳデバイスの構造部材として、本発明の感光性樹脂組成物を用いて形成されたレジストパターンを隔壁としたり、機械駆動部品の一部として組み込んで使用される。このようなＭＥＭＳ用デバイスとしては、例えばＳＡＷフィルター、ＢＡＷフィルター、ジャイロセンサー、ディスプレイ用マイクロシャッター、イメージセンサー、電子ペーパー、インクジェットヘッド、バイオチップ、封止剤等の部品が挙げられる。より具体的な例は、特表２００７－５２２５３１号公報、特開２００８－２５０２００号公報、特開２００９－２６３５４４号公報等に例示されている。 Since the photosensitive resin composition of the present invention is excellent in curability and cured film characteristics, a resist pattern formed using the photosensitive resin composition of the present invention as a structural member of a MEMS device can be used as a partition wall or mechanically driven. Used as part of the part. Examples of such MEMS devices include parts such as SAW filters, BAW filters, gyro sensors, display micro shutters, image sensors, electronic paper, inkjet heads, biochips, sealants, and the like. More specific examples are exemplified in JP-T-2007-522531, JP-A-2008-250200, JP-A-2009-263544, and the like.
　本発明の感光性樹脂組成物は、平坦性や透明性に優れるため、例えば特開２０１１－１０７４７６号公報の図２に記載のバンク層（１６）および平坦化膜（５７）、特開２０１０－９７９３号公報の図４（ａ）に記載の隔壁（１２）および平坦化膜（１０２）、特開２０１０－２７５９１号公報の図１０に記載のバンク層（２２１）および第３層間絶縁膜（２１６ｂ）、特開２００９－１２８５７７号公報の図４（ａ）に記載の第２層間絶縁膜（１２５）および第３層間絶縁膜（１２６）、特開２０１０－１８２６３８号公報の図３に記載の平坦化膜（１２）および画素分離絶縁膜（１４）などの形成に用いることもできる。 Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010- The partition wall (12) and the planarization film (102) described in FIG. 4 (a) of Japanese Patent No. 9793, the bank layer (221) and the third interlayer insulating film (216b) described in FIG. 10 of Japanese Patent Application Laid-Open No. 2010-27591. ), The second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and the flatness described in FIG. 3 of JP-A-2010-182638. It can also be used to form a chemical film (12) and a pixel isolation insulating film (14).
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。なお、特に断りのない限り、「部」、「％」は質量基準である。 The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.
　以下の合成例において、以下の符号はそれぞれ以下の化合物を表す。
ＭＡＴＨＦ：２－テトラヒドロフラニルメタクリレート（合成品）
ＭＡＥＶＥ：１－エトキシエチルメタクリレート（和光純薬工業社製）
ＭＡＣＨＯＥ：１－（シクロヘキシルオキシ）エチルメタクリレート
ＭＡＴＨＰ：テトラヒドロ－２Ｈ－ピラン－２－イルメタクリレート
ＧＭＡ：グリシジルメタクリレート（和光純薬工業社製）
ＯＸＥ－３０：３－エチル－３－オキセタニルメチルメタクリレート（大阪有機化学工業社製）
ＭＡＡ：メタクリル酸（和光純薬工業社製）
ＭＭＡ：メチルメタクリレート（和光純薬工業社製）
Ｓｔ：スチレン（和光純薬工業社製）
ＤＣＰＭ：ジシクロペンタニルメタクリレート
ＨＥＭＡ：ヒドロキシエチルメタクリレート（和光純薬社製）
Ｖ－６５：２，２‘－アゾビス（２，４－ジメチルバレロニトリル）（和光純薬工業社製）
ＰＧＭＥＡ：メトキシプロピルアセテート（昭和電工社製） In the following synthesis examples, the following symbols represent the following compounds, respectively.
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
MAEVE: 1-ethoxyethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
MACHOE: 1- (cyclohexyloxy) ethyl methacrylate MATHP: tetrahydro-2H-pyran-2-yl methacrylate GMA: glycidyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.)
OXE-30: 3-ethyl-3-oxetanylmethyl methacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
MAA: Methacrylic acid (manufactured by Wako Pure Chemical Industries)
MMA: Methyl methacrylate (Wako Pure Chemical Industries, Ltd.)
St: Styrene (Wako Pure Chemical Industries, Ltd.)
DCPM: Dicyclopentanyl methacrylate HEMA: Hydroxyethyl methacrylate (Wako Pure Chemical Industries, Ltd.)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
PGMEA: Methoxypropyl acetate (manufactured by Showa Denko)
＜ＭＡＴＨＦの合成＞
　メタクリル酸（８６ｇ、１ｍｏｌ）を１５℃に冷却しておき、カンファースルホン酸（４．６ｇ、０．０２ｍｏｌ）添加した。その溶液に、２－ジヒドロフラン（７１ｇ、１ｍｏｌ、１．０当量）を滴下した。１時間撹拌した後に、飽和炭酸水素ナトリウム（５００ｍＬ）を加え、酢酸エチル（５００ｍＬ）で抽出し、硫酸マグネシウムで乾燥後、不溶物を濾過後４０℃以下で減圧濃縮し、残渣の黄色油状物を減圧蒸留して沸点（ｂｐ．）５４～５６℃／３．５ｍｍＨｇ留分のメタクリル酸テトラヒドロ－２Ｈ－フラン－２－イル（ＭＡＴＨＦ）１２５ｇを無色油状物として得た（収率８０％）。 <Synthesis of MATHF>
Methacrylic acid (86 g, 1 mol) was cooled to 15 ° C., and camphorsulfonic acid (4.6 g, 0.02 mol) was added. To the solution, 2-dihydrofuran (71 g, 1 mol, 1.0 equivalent) was added dropwise. After stirring for 1 hour, saturated sodium bicarbonate (500 mL) was added, extracted with ethyl acetate (500 mL), dried over magnesium sulfate, insolubles were filtered and concentrated under reduced pressure at 40 ° C. or lower to give a residual yellow oily product. Distillation under reduced pressure afforded 125 g of tetrahydro-2H-furan-2-yl methacrylate (MATHF) as a colorless oily substance (yield 80%) at a boiling point (bp.) Of 54 to 56 ° C./3.5 mmHg.
＜重合体Ｐ－１の合成例＞
　３つ口フラスコにＰＧＭＥＡ（８９ｇ）を入れ、窒素雰囲気下において９０℃に昇温した。その溶液にＭＡＣＨＯＥ（全単量体成分中の４０ｍｏｌ％となる量）、ＧＭＡ（全単量体成分中の３０ｍｏｌ％となる量）、ＭＡＡ（全単量体成分中の１０ｍｏｌ％となる量）、ＭＭＡ（全単量体成分中の２０ｍｏｌ％となる量）、Ｖ－６５（全単量体成分の合計１００ｍｏｌ％に対して４ｍｏｌ％に相当）を溶解させ、２時間かけて滴下した。滴下終了後２時間攪拌し、反応を終了させた。それにより重合体Ｐ－１を得た。なお、ＰＧＭＥＡとその他の成分の合計量の比を６０：４０とした。即ち、固形分濃度４０％の重合体溶液を調製した。
　モノマー種類等を下記表に示す通りに変更し、他の重合体を合成した。下記表中、溶剤は全てＰＧＭＥＡを使用し、固形分濃度は４０質量部とした。 <Synthesis Example of Polymer P-1>
PGMEA (89 g) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. MACHOE (amount to be 40 mol% in all monomer components), GMA (amount to be 30 mol% in all monomer components), MAA (amount to be 10 mol% in all monomer components) MMA (amount to be 20 mol% in all monomer components) and V-65 (corresponding to 4 mol% with respect to 100 mol% in total of all monomer components) were dissolved and added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred for 2 hours to complete the reaction. Thereby, a polymer P-1 was obtained. The ratio of the total amount of PGMEA and other components was 60:40. That is, a polymer solution having a solid content concentration of 40% was prepared.
Monomers and the like were changed as shown in the following table, and other polymers were synthesized. In the following table, all solvents used PGMEA and the solid content concentration was 40 parts by mass.
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
＜感光性樹脂組成物の調整＞
　下記表記載の固形分比となるように、重合体成分、光酸発生剤、脂環式エポキシ化合物、他の架橋剤、塩基性化合物、アルコキシシラン化合物、増感剤、界面活性剤、およびその他の成分をＰＧＭＥＡに固形分濃度２５％になるまで溶解混合し、口径０．２μｍのポリテトラフルオロエチレン製フィルターで濾過して、各種実施例および比較例の感光性樹脂組成物を得た。なお、表中の添加量は、質量部である。 <Adjustment of photosensitive resin composition>
Polymer components, photoacid generators, alicyclic epoxy compounds, other crosslinking agents, basic compounds, alkoxysilane compounds, sensitizers, surfactants, and others so that the solid content ratios shown in the table below are obtained The above components were dissolved and mixed in PGMEA until the solid content concentration became 25%, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain photosensitive resin compositions of various examples and comparative examples. In addition, the addition amount in a table | surface is a mass part.
　実施例および比較例に用いた各化合物を示す略号の詳細は、以下の通りである。 Details of the abbreviations indicating each compound used in Examples and Comparative Examples are as follows.
（重合体成分）
Ｐ－１７：Ｊｏｎｃｒｙｌ ６８０（ＢＡＳＦ製）
Ｐ－１８：Ｊｏｎｃｒｙｌ ６７（ＢＡＳＦ製）
Ｐ－１９：ＡＲＵＦＯＮ　ＵＣ－３９１０（東亞合成（株）製）
Ｐ－２３：ＳＭＡ－３０００Ｐ（Ｃｒａｙ Ｖａｌｌｅｙ ＵＳＡ、ＬＬＣ製） (Polymer component)
P-17: Joncryl 680 (manufactured by BASF)
P-18: Joncryl 67 (BASF)
P-19: ARUFON UC-3910 (manufactured by Toagosei Co., Ltd.)
P-23: SMA-3000P (Cray Valley USA, manufactured by LLC)
（光酸発生剤）
Ｂ－１：ＤＴＳ－１０５、（トリアリールスルホニウム塩）（みどり化学社製）
Ｂ－２：ＣＧＩ１３９７（ＢＡＳＦジャパン（株）製）
Figure JPOXMLDOC01-appb-C000049
 Ｂ－３：ＰＡＩ１０１（みどり化学（株）製）
Figure JPOXMLDOC01-appb-C000050
 Ｂ－４：下記の化合物
Figure JPOXMLDOC01-appb-C000051
 Ｂ－５：下記の化合物（特表２００２－５２８４５１号公報の段落０１０８に記載の方法に従って合成した）
Figure JPOXMLDOC01-appb-C000052
 (Photoacid generator)
B-1: DTS-105, (triarylsulfonium salt) (manufactured by Midori Chemical Co., Ltd.)
B-2: CGI1397 (manufactured by BASF Japan Ltd.)
Figure JPOXMLDOC01-appb-C000049
 B-3: PAI101 (Midori Chemical Co., Ltd.)
Figure JPOXMLDOC01-appb-C000050
 B-4: The following compound
Figure JPOXMLDOC01-appb-C000051
 B-5: The following compound (synthesized according to the method described in paragraph 0108 of JP-T-2002-528451)
Figure JPOXMLDOC01-appb-C000052
〔Ｂ－４の合成〕
　２－ナフトール（１０ｇ）、クロロベンゼン（３０ｍＬ）の懸濁溶液に塩化アルミニウム（１０．６ｇ）、２－クロロプロピオニルクロリド（１０．１ｇ）を添加し、混合液を４０℃に加熱して２時間反応させた。氷冷下、反応液に４ＮＨＣｌ水溶液（６０ｍＬ）を滴下し、酢酸エチル（５０ｍＬ）を添加して分液した。有機層に炭酸カリウム（１９．２ｇ）を加え、４０℃で１時間反応させた後、２ＮＨＣｌ水溶液（６０ｍＬ）を添加して分液し、有機層を濃縮後、結晶をジイソプロピルエーテル（１０ｍＬ）でリスラリーし、ろ過、乾燥してケトン化合物（６．５ｇ）を得た。
　得られたケトン化合物（３．０ｇ）、メタノール（３０ｍＬ）の懸濁溶液に酢酸（７．３ｇ）、５０質量％ヒドロキシルアミン水溶液（８．０ｇ）を添加し、加熱還流した。放冷後、水（５０ｍＬ）を加え、析出した結晶をろ過、冷メタノール洗浄後、乾燥してオキシム化合物（２．４ｇ）を得た。
　得られたオキシム化合物（１．８ｇ）をアセトン（２０ｍＬ）に溶解させ、氷冷下トリエチルアミン（１．５ｇ）、ｐ－トルエンスルホニルクロリド（２．４ｇ）を添加し、室温に昇温して１時間反応させた。反応液に水（５０ｍＬ）を添加し、析出した結晶をろ過後、メタノール（２０ｍＬ）でリスラリーし、ろ過、乾燥してＢ－４（２．３ｇ）を得た。
　なお、Ｂ－４の1Ｈ－ＮＭＲスペクトル（３００ＭＨｚ、ＣＤＣｌ3）は、δ＝８．３（ｄ，１Ｈ），８．０（ｄ，２Ｈ），７．９（ｄ，１Ｈ），７．８（ｄ，１Ｈ），７．６（ｄｄ，１Ｈ），７．４（ｄｄ，１Ｈ）７．３（ｄ，２Ｈ），７．１（ｄ．１Ｈ），５．６（ｑ，１Ｈ），２．４（ｓ，３Ｈ），１．７（ｄ，３Ｈ）であった。 [Synthesis of B-4]
Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a suspension of 2-naphthol (10 g) and chlorobenzene (30 mL), and the mixture was heated to 40 ° C. for 2 hours. I let you. Under ice-cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added for liquid separation. Potassium carbonate (19.2 g) was added to the organic layer, reacted at 40 ° C. for 1 hour, 2N HCl aqueous solution (60 mL) was added and separated, and the organic layer was concentrated, and the crystals were diluted with diisopropyl ether (10 mL). The slurry was reslurried, filtered and dried to obtain a ketone compound (6.5 g).
Acetic acid (7.3 g) and a 50 mass% aqueous hydroxylamine solution (8.0 g) were added to a suspension of the obtained ketone compound (3.0 g) and methanol (30 mL), and the mixture was heated to reflux. After allowing to cool, water (50 mL) was added, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).
The obtained oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice cooling, and the temperature was raised to room temperature. Reacted for hours. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered, reslurried with methanol (20 mL), filtered and dried to obtain B-4 (2.3 g).
The 1 H-NMR spectrum (300 MHz, CDCl 3 ) of B-4 has δ = 8.3 (d, 1H), 8.0 (d, 2H), 7.9 (d, 1H), 7. 8 (d, 1H), 7.6 (dd, 1H), 7.4 (dd, 1H) 7.3 (d, 2H), 7.1 (d.1H), 5.6 (q, 1H) , 2.4 (s, 3H), 1.7 (d, 3H).
（脂環式エポキシ化合物）
Ｆ－５：下記化合物１（ダイセル化学工業（株）製、セロキサイド2021P）
Figure JPOXMLDOC01-appb-C000053
 Ｆ－６：下記化合物２（合成品）
Figure JPOXMLDOC01-appb-C000054
 Ｆ－７：下記化合物３（ダイセル化学工業（株）製、セロキサイド2000）
Figure JPOXMLDOC01-appb-C000055
 Ｆ－１１；下記化合物４（下記で示される化合物）
Figure JPOXMLDOC01-appb-C000056
 Ｆ－１２；下記化合物５（下記で示される化合物）
Figure JPOXMLDOC01-appb-C000057
 Ｆ－１３；下記化合物６（下記で示される化合物）
Figure JPOXMLDOC01-appb-C000058
 (Alicyclic epoxy compound)
F-5: Compound 1 below (Daicel Chemical Industries, Celoxide 2021P)
Figure JPOXMLDOC01-appb-C000053
 F-6: Compound 2 below (Synthetic product)
Figure JPOXMLDOC01-appb-C000054
 F-7: Compound 3 below (Daicel Chemical Industries, Celoxide 2000)
Figure JPOXMLDOC01-appb-C000055
 F-11; Compound 4 below (compound shown below)
Figure JPOXMLDOC01-appb-C000056
 F-12; the following compound 5 (compound shown below)
Figure JPOXMLDOC01-appb-C000057
 F-13; Compound 6 (compound shown below)
Figure JPOXMLDOC01-appb-C000058
（Ｆ－６の合成）
　丸善ＫＫ出版、第四版実験化学講座２０有機合成ＩＩ、２１３～に記載の方法に従って合成した。 (Synthesis of F-6)
It was synthesized according to the method described in Maruzen KK Publishing, 4th edition Experimental Chemistry Course 20 Organic Synthesis II, 213-.
（Ｆ－１１～Ｆ－１３の合成）
　特開２０１２－９２０６２号公報に記載の方法に従って合成した。 (Synthesis of F-11 to F-13)
The compound was synthesized according to the method described in JP2012-92062A.
（脂環式エポキシ化合物以外の架橋剤）
Ｆ－１：ＪＥＲ１５７Ｓ６５（（株）三菱ケミカルホールディングス製）（ビスフェノール型エポキシ化合物）
Ｆ－２：デュラネート１７Ｂ－６０Ｐ（旭化成ケミカルズ（株）製）（イソシアネート化合物）
Ｆ－３：デナコールＥＸ－３２１Ｌ（ナガセケムテックス（株）製）（グリシジルエーテルエポキシ化合物）
Ｆ－４：ＪＥＲ８２８（（株）三菱ケミカルホールディングス製）（ビスフェノール型エポキシ化合物）
Ｆ－８：デナコールＥＸ－２１１Ｌ（ナガセケムテックス（株）製）（グリシジルエーテルエポキシ化合物）
Ｆ－９：ＯＸＴ－２２１（東亞合成（株）製）（二官能オキセタン化合物）
Ｆ－１０：（ＪＥＲ１００７Ｋ（（株）三菱ケミカルホールディングス製）（ビスフェノールＡ型エポキシ化合物）
Ｆ－１１：タケネートＢ－８７０Ｎ（三井化学（株）製） (Crosslinking agent other than alicyclic epoxy compound)
F-1: JER157S65 (manufactured by Mitsubishi Chemical Holdings Corporation) (bisphenol type epoxy compound)
F-2: Duranate 17B-60P (Asahi Kasei Chemicals Corporation) (isocyanate compound)
F-3: Denacol EX-321L (manufactured by Nagase ChemteX Corporation) (glycidyl ether epoxy compound)
F-4: JER828 (manufactured by Mitsubishi Chemical Holdings Corporation) (bisphenol type epoxy compound)
F-8: Denacol EX-211L (manufactured by Nagase ChemteX Corporation) (glycidyl ether epoxy compound)
F-9: OXT-221 (manufactured by Toagosei Co., Ltd.) (bifunctional oxetane compound)
F-10: (JER1007K (manufactured by Mitsubishi Chemical Holdings Corporation) (bisphenol A type epoxy compound)
F-11: Takenate B-870N (Mitsui Chemicals)
（アルコキシシラン化合物）
Ｇ－１：γ－グリシドキシプロピルトリアルコキシシラン（ＫＢＭ－４０３、信越化学工業社製）
Ｇ－２：ビス（トリエトキシシリルプロピル）テトラスルフィド（ＫＢＥ－８４６、信越化学工業社製）
Ｇ－３：ＫＢＭ－３１０３（信越化学工業（株）製） (Alkoxysilane compound)
G-1: γ-glycidoxypropyltrialkoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.)
G-2: Bis (triethoxysilylpropyl) tetrasulfide (KBE-846, manufactured by Shin-Etsu Chemical Co., Ltd.)
G-3: KBM-3103 (manufactured by Shin-Etsu Chemical Co., Ltd.)
（増感剤）
Ｅ－１：下記構造のジブトキシアントラセン（川崎化成社製）
Figure JPOXMLDOC01-appb-C000059
 (Sensitizer)
E-1: Dibutoxyanthracene having the following structure (manufactured by Kawasaki Kasei Co., Ltd.)
Figure JPOXMLDOC01-appb-C000059
（塩基性化合物）
Ｓ－４：ジアザビシクロノネン
Ｓ－５：２，４，５－トリフェニルイミダゾール
Ｓ－６：Ｎ－シクロヘキシル－Ｎ’－［２－（４－モルホリニル）エチル］チオ尿素 (Basic compound)
S-4: Diazabicyclononene S-5: 2,4,5-triphenylimidazole S-6: N-cyclohexyl-N ′-[2- (4-morpholinyl) ethyl] thiourea
（界面活性剤）
Ｗ－１：下記構造式で示されるパーフルオロアルキル基含有ノニオン界面活性剤（Ｆ－５５４，ＤＩＣ製）
Figure JPOXMLDOC01-appb-C000060
 (Surfactant)
W-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC)
Figure JPOXMLDOC01-appb-C000060
（酸化防止剤）
Ｊ－１：イルガノックス１０９８（ＢＡＳＦ製）
Ｊ－２：イルガノックス１０３５（ＢＡＳＦ製）
Ｊ－３：アデカスタブＡＯ－６０（ＡＤＥＫＡ製） (Antioxidant)
J-1: Irganox 1098 (BASF)
J-2: Irganox 1035 (manufactured by BASF)
J-3: ADK STAB AO-60 (manufactured by ADEKA)
Figure JPOXMLDOC01-appb-T000061
Figure JPOXMLDOC01-appb-T000061
Figure JPOXMLDOC01-appb-T000062
Figure JPOXMLDOC01-appb-T000062
＜感度の評価＞
　ガラス基板（コーニング１７３７、０．７ｍｍ厚（コーニング社製））上に、各感光性樹脂組成物をスリット塗布した後、９５℃／１４０秒ホットプレート上でプリベークして溶剤を揮発させ、膜厚４．０μｍの感光性樹脂組成物層を形成した。
　次に、得られた感光性樹脂組成物層を、キヤノン（株）製　ＭＰＡ　５５００ＣＦ（超高圧水銀ランプ）を用いて、所定のマスクを介して露光した。そして、露光後の感光性樹脂組成物層を、アルカリ現像液（０．４質量％のテトラメチルアンモニウムヒドロキシド水溶液）で２３℃／６０秒間現像した後、超純水で２０秒リンスした。
　これらの操作により５μｍのホールを解像する時の最適ｉ線露光量（Ｅｏｐｔ）を感度とした。Ｃ以上が実用レベルである。
　Ａ：２０ｍＪ／ｃｍ2未満
　Ｂ：２０ｍＪ／ｃｍ2以上、４０ｍＪ／ｃｍ2未満
　Ｃ：４０ｍＪ／ｃｍ2以上、８０ｍＪ／ｃｍ2未満
　Ｄ：８０ｍＪ／ｃｍ2以上、１６０ｍＪ／ｃｍ2未満
　Ｅ：１６０ｍＪ／ｃｍ2以上 <Evaluation of sensitivity>
Each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (manufactured by Corning)) and then pre-baked on a hot plate at 95 ° C. for 140 seconds to volatilize the solvent. A photosensitive resin composition layer having a thickness of 4.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed through a predetermined mask using MPA 5500CF (extra high pressure mercury lamp) manufactured by Canon Inc. The exposed photosensitive resin composition layer was developed with an alkali developer (0.4 mass% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds.
The optimum i-line exposure (Eopt) when resolving a 5 μm hole by these operations was taken as the sensitivity. C and above are practical levels.
A: 20mJ / cm 2 less B: 20mJ / cm 2 or more, 40 mJ / cm 2 less than C: 40mJ / cm 2 or more, 80 mJ / cm 2 less than D: 80mJ / cm 2 or more, 160 mJ / cm 2 less than E: 160 mJ / cm 2 or more
＜耐熱透明性の評価＞
　ガラス基板（イーグル２０００　コーニング社製）に各感光性樹脂組成物の溶液をスピン塗布した後、９０℃で１２０秒間ホットプレート上においてプリベークして膜厚３μｍの塗膜を形成した。得られた塗膜を０．４％のテトラメチルアンモニウムヒドロキシド水溶液により２３℃で６０秒間液盛り法で現像し、更に超純水で４５秒間リンスした後、キャノン（株）製ＰＬＡ－５０１Ｆ露光機（超高圧水銀ランプ）で積算照射量が３００ｍＪ／ｃｍ2（照度：２０ｍＷ／ｃｍ2）となるように露光し、その後、この基板をオーブンにて２３０℃で１時間加熱して硬化膜を得た。得られた硬化膜をオーブンにて２３０℃で２時間更に加熱した後、光線透過率を分光光度計「１５０－２０型ダブルビーム（（株）日立製作所製）」を用いて４００～８００ｎｍの範囲の波長で測定した。
　評価基準は下記の通りであり、Ｂ以上が実用レベルである。なお、最低光線透過率の値は、２３０℃で２時間加熱後の膜厚２μｍ当たりの値に換算している。
　Ａ：９２％以上
　Ｂ：８７％以上９２％未満
　Ｃ：８５％以上８７％未満
　Ｄ：８２％以上８５％未満
　Ｅ：８２％未満 <Evaluation of heat-resistant transparency>
A solution of each photosensitive resin composition was spin-coated on a glass substrate (Eagle 2000 Corning), and then pre-baked on a hot plate at 90 ° C. for 120 seconds to form a coating film having a thickness of 3 μm. The resulting coating film was developed with a 0.4% aqueous solution of tetramethylammonium hydroxide at 23 ° C. for 60 seconds, rinsed with ultrapure water for 45 seconds, and then exposed to PLA-501F manufactured by Canon Inc. Machine (extra-high pressure mercury lamp) so that the integrated dose is 300 mJ / cm 2 (illuminance: 20 mW / cm 2 ), and then this substrate is heated in an oven at 230 ° C. for 1 hour to form a cured film. Obtained. The obtained cured film was further heated in an oven at 230 ° C. for 2 hours, and the light transmittance was in the range of 400 to 800 nm using a spectrophotometer “150-20 type double beam (manufactured by Hitachi, Ltd.)”. Measured at a wavelength of.
The evaluation criteria are as follows, and B or higher is a practical level. In addition, the value of the minimum light transmittance is converted into a value per 2 μm of film thickness after heating at 230 ° C. for 2 hours.
A: 92% or more B: 87% or more and less than 92% C: 85% or more and less than 87% D: 82% or more and less than 85% E: Less than 82%
＜コンタクトホール（ＣＨ）均一性の評価＞
　各感光性樹脂組成物を５５０ｍｍ×６５０ｍｍガラス基板上にスピン塗布し、ホットプレート上でプリベーク（９５℃×１４０秒）した後、キヤノン（株）製　ＭＰＡ　５５００ＣＦ（超高圧水銀ランプ）を用いて、所定のマスクを介して露光した。この時の露光量は、感度評価の結果に基づき以下のように変更した。
　感度Ａ・・・１５ｍＪ／ｃｍ2
　感度Ｂ・・・３０ｍＪ／ｃｍ2
　感度Ｃ・・・６０ｍＪ／ｃｍ2
　感度Ｄ・・・１２０ｍＪ／ｃｍ2
　感度Ｅ・・・２００ｍＪ／ｃｍ2
　その後、アルカリ水溶液にて現像してコンタクトホール（ＣＨ）パターンを形成した。かかるＣＨパターン付き基板を１０枚準備し、基板１枚ごとに５０点、光学式計測器ZYGO New View7200（ZYGO corp.製）にて、１０μｍの設定ＣＨサイズに対する差がどの程度あるか、実ＣＨサイズを計測した。評価基準は下記の通りであり、Ｄ以上が実用レベルである。
Ａ：平均のＣＨサイズ差が０．２μｍ以下
Ｂ：平均のＣＨサイズ差が０．２μｍより大きく０．４μｍ以下
Ｃ：平均のＣＨサイズ差が０．４μｍより大きく０．６μｍ以下
Ｄ：平均のＣＨサイズ差が０．６μｍより大きく０．８μｍ以下
Ｅ：平均のＣＨサイズ差が０．８μｍより大きく１．０μｍ以下
Ｆ：平均のＣＨサイズ差が１．０μｍより大きく１．２μｍ以下
Ｇ：平均のＣＨサイズ差が１．２μｍより大きく１．４μｍ以下
Ｈ：平均のＣＨサイズ差が１．４μｍより大きい <Evaluation of contact hole (CH) uniformity>
Each photosensitive resin composition was spin-coated on a 550 mm × 650 mm glass substrate, pre-baked on a hot plate (95 ° C. × 140 seconds), and then MPA 5500CF (extra-high pressure mercury lamp) manufactured by Canon Inc. was used. It exposed through the predetermined mask. The exposure amount at this time was changed as follows based on the result of sensitivity evaluation.
Sensitivity A: 15 mJ / cm 2
Sensitivity B ... 30mJ / cm 2
Sensitivity C ... 60mJ / cm 2
Sensitivity D ... 120mJ / cm 2
Sensitivity E ... 200mJ / cm 2
Then, it developed with alkaline aqueous solution and formed the contact hole (CH) pattern. Prepare 10 such substrates with CH pattern, 50 points for each substrate, and how much difference there is with respect to the set CH size of 10 μm with optical measuring instrument ZYGO New View 7200 (manufactured by ZYGO corp.) The size was measured. The evaluation criteria are as follows, and D or higher is a practical level.
A: Average CH size difference is 0.2 μm or less B: Average CH size difference is greater than 0.2 μm and 0.4 μm or less C: Average CH size difference is greater than 0.4 μm and 0.6 μm or less D: Average CH size difference greater than 0.6 μm and 0.8 μm or less E: Average CH size difference greater than 0.8 μm and 1.0 μm or less F: Average CH size difference greater than 1.0 μm and 1.2 μm or less G: Average CH size difference of greater than 1.2 μm and 1.4 μm or less H: Average CH size difference of greater than 1.4 μm
Figure JPOXMLDOC01-appb-T000063
Figure JPOXMLDOC01-appb-T000063
　上記結果から明らかなとおり、本発明の感光性樹脂組成物は、感度に優れ、また、現像処理後の耐熱透明性およびＣＨ均一性に優れ、いずれも実用レベル以上であった。特に、脂環式エポキシ化合物として、エステル結合を含むＦ－５を用いたときは、感度および現像処理後の透明性について、一定レベルを維持しつつ、極めて優れたＣＨ均一性を達成できることから技術的意義が高い。これに対し、比較例の感光性樹脂組成物は、ＣＨ均一性が実用レベル外であった。 As is clear from the above results, the photosensitive resin composition of the present invention was excellent in sensitivity, excellent in heat-resistant transparency and CH uniformity after development, and both were above the practical level. In particular, when F-5 containing an ester bond is used as an alicyclic epoxy compound, it is possible to achieve extremely excellent CH uniformity while maintaining a certain level of sensitivity and transparency after development processing. High significance. In contrast, the photosensitive resin composition of the comparative example had a CH uniformity outside the practical level.
＜実施例５２＞
　実施例５２は、実施例１において、露光機を、キヤノン（株）製　ＭＰＡ　５５００ＣＦから、Ｎｉｋｏｎ（株）製ＦＸ－８０３Ｍ（ｇｈ－Ｌｉｎｅ　ステッパ）に変更した以外は同様に行った。感度の評価は実施例１と同レベルであった。 <Example 52>
Example 52 was performed in the same manner as in Example 1, except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to FX-803M (gh-Line stepper) manufactured by Nikon Corporation. The evaluation of sensitivity was the same level as in Example 1.
＜実施例５３＞
　実施例５３は、実施例１において、露光機を、キヤノン（株）製　ＭＰＡ　５５００ＣＦから、３５５ｎｍレーザー露光機に変更して３５５ｎｍレーザー露光を行った以外は同様に行った。ここで、３５５ｎｍレーザー露光機としては、株式会社ブイテクノロジー社製の「ＡＥＧＩＳ」を使用し（波長３５５ｎｍ、パルス幅６ｎｓｅｃ）、露光量はＯＰＨＩＲ社製の「ＰＥ１０Ｂ－Ｖ２」を用いて測定した。
　感度の評価は実施例１と同レベルであった。 <Example 53>
Example 53 was performed in the same manner as in Example 1, except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to a 355 nm laser exposure machine, and 355 nm laser exposure was performed. Here, as the 355 nm laser exposure machine, “AEGIS” manufactured by Buoy Technology Co., Ltd. was used (wavelength 355 nm, pulse width 6 nsec), and the exposure amount was measured using “PE10B-V2” manufactured by OPHIR.
The evaluation of sensitivity was the same level as in Example 1.
＜実施例５４＞
　特許第３３２１００３号公報の図１に記載のアクティブマトリクス型液晶表示装置において、層間絶縁膜として硬化膜１７を以下のようにして形成し、実施例５４の液晶表示装置を得た。すなわち、実施例１の感光性樹脂組成物を用い、層間絶縁膜として硬化膜１７を形成した。
　すなわち、特許第３３２１００３号公報の段落００５８の基板と層間絶縁膜１７の濡れ性を向上させる前処理として、基板をヘキサメチルジシラザン（ＨＭＤＳ）蒸気下に３０秒曝し、その後、実施例１の感光性樹脂組成物をスピンコート塗布した後、９０℃で２分ホットプレート上でプリベークして溶剤を揮発させ、膜厚３μｍの感光性樹脂組成物層を形成した。次に、得られた感光性樹脂組成物層を、キヤノン（株）製　ＭＰＡ　５５００ＣＦ（高圧水銀灯）を用いて、１０μｍφのホールパターンのマスクを介して４０ｍＪ／ｃｍ2（照度：２０ｍＷ／ｃｍ2、ｉ線）となるよう露光した。そして、露光後の感光性樹脂組成物層を、アルカリ現像液（０．４％のテトラメチルアンモニウムヒドロキシド水溶液）で２３℃／６０秒間現像した後、超純水で２０秒リンスした。続いて超高圧水銀灯を用いて積算照射量が３００ｍＪ／ｃｍ2（照度：２０ｍＷ／ｃｍ2、ｉ線）となるように全面露光し、その後、この基板をオーブンにて２３０℃で３０分加熱して硬化膜を得た。
　前記感光性樹脂組成物を塗布する際の塗布性は良好で、露光、現像、焼成の後に得られた硬化膜には、しわやクラックの発生は認められなかった。 <Example 54>
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 54 was obtained. That is, using the photosensitive resin composition of Example 1, a cured film 17 was formed as an interlayer insulating film.
That is, as a pretreatment for improving the wettability of the substrate and the interlayer insulating film 17 in paragraph 0058 of Japanese Patent No. 3321003, the substrate is exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and then the photosensitive film of Example 1 is used. After spin-coating the photosensitive resin composition, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to volatilize the solvent, thereby forming a photosensitive resin composition layer having a thickness of 3 μm. Next, the obtained photosensitive resin composition layer was subjected to 40 mJ / cm 2 (illuminance: 20 mW / cm 2 ) through a hole pattern mask of 10 μmφ using Canon Inc. MPA 5500CF (high pressure mercury lamp). i-line). The exposed photosensitive resin composition layer was developed with an alkali developer (0.4% tetramethylammonium hydroxide aqueous solution) at 23 ° C./60 seconds, and then rinsed with ultrapure water for 20 seconds. Subsequently, the whole surface was exposed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (illuminance: 20 mW / cm 2 , i-line), and then the substrate was heated in an oven at 230 ° C. for 30 minutes. Thus, a cured film was obtained.
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.
　得られた液晶表示装置に対して、駆動電圧を印加したところ、良好な表示特性を示し、信頼性の高い液晶表示装置であることが分かった。 When a driving voltage was applied to the obtained liquid crystal display device, it was found that the liquid crystal display device showed good display characteristics and high reliability.
＜実施例５５＞
　実施例５４から、ヘキサメチルジシラザン（ＨＭＤＳ）処理を省いた他は同様にし、実施例５５の液晶表示装置を得た。得られた液晶表示装置は、硬化膜のパターンの欠けや剥がれの無く、良好な表示特性を示し、信頼性の高い液晶表示装置であった。 <Example 55>
A liquid crystal display device of Example 55 was obtained in the same manner as in Example 54 except that the hexamethyldisilazane (HMDS) treatment was omitted. The obtained liquid crystal display device was a highly reliable liquid crystal display device having good display characteristics without chipping or peeling of the pattern of the cured film.
＜実施例５６＞
　実施例５４から、アルカリ現像液を０．４％のテトラメチルアンモニウムヒドロキシド水溶液から、２．３８％のテトラメチルアンモニウムヒドロキシド水溶液に変更した他は同様にし、実施例５６の液晶表示装置を得た。得られた液晶表示装置は、硬化膜のパターンの欠けや剥がれの無く、良好な表示特性を示し、信頼性の高い液晶表示装置であった。 <Example 56>
A liquid crystal display device of Example 56 was obtained in the same manner as in Example 54 except that the alkaline developer was changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 2.38% tetramethylammonium hydroxide aqueous solution. It was. The obtained liquid crystal display device was a highly reliable liquid crystal display device having good display characteristics without chipping or peeling of the pattern of the cured film.
＜実施例５７＞
　実施例５４から、アルカリ現像液を０．４％のテトラメチルアンモニウムヒドロキシド水溶液から、０．０４％のＫＯＨ水溶液に変更した他は同様にし、実施例５７の液晶表示装置を得た。得られた液晶表示装置は、硬化膜のパターンの欠けや剥がれの無く、良好な表示特性を示し、信頼性の高い液晶表示装置であった。 <Example 57>
A liquid crystal display device of Example 57 was obtained in the same manner as in Example 54 except that the alkaline developer was changed from a 0.4% tetramethylammonium hydroxide aqueous solution to a 0.04% KOH aqueous solution. The obtained liquid crystal display device was a highly reliable liquid crystal display device having good display characteristics without chipping or peeling of the pattern of the cured film.
＜実施例５８＞
　実施例５４から、現像・リンス後の全面露光の工程を省いた他は同様にし、実施例５８の液晶表示装置を得た。得られた液晶表示装置は良好な表示特性を示し、信頼性の高い液晶表示装置であった。 <Example 58>
A liquid crystal display device of Example 58 was obtained in the same manner as in Example 54 except that the step of full exposure after development and rinsing was omitted. The obtained liquid crystal display device showed good display characteristics and was a highly reliable liquid crystal display device.
＜実施例５９＞
　実施例５４から、全面露光の工程とオーブンでの２３０℃／３０分の加熱工程の間に、１００℃で３分ホットプレート上で加熱する工程を追加した他は同様にし、実施例５９の液晶表示装置を得た。得られた液晶表示装置は良好な表示特性を示し、信頼性の高い液晶表示装置であった。 <Example 59>
The liquid crystal of Example 59 is the same as Example 54 except that a step of heating on a hot plate at 100 ° C. for 3 minutes is added between the entire surface exposure step and the 230 ° C./30 minute heating step in the oven. A display device was obtained. The obtained liquid crystal display device showed good display characteristics and was a highly reliable liquid crystal display device.
＜実施例６０＞
　実施例５４から、現像・リンスの工程と全面露光の工程の間に、１００℃で３分ホットプレート上で加熱する工程を追加した他は同様にし、実施例６０の液晶表示装置を得た。得られた液晶表示装置は良好な表示特性を示し、信頼性の高い液晶表示装置であった。 <Example 60>
A liquid crystal display device of Example 60 was obtained in the same manner as in Example 54 except that a step of heating on a hot plate at 100 ° C. for 3 minutes was added between the development / rinsing process and the entire surface exposure process. The obtained liquid crystal display device showed good display characteristics and was a highly reliable liquid crystal display device.
＜実施例６１＞
　実施例５４と以下の塗布プロセスのみ変更して、同様の液晶表示装置を得た。すなわち、実施例１の感光性樹脂組成物をスリットコート法にて塗布した後、９０℃／１２０秒ホットプレート上で加熱により溶剤を除去し、膜厚３．０μｍの感光性樹脂組成物層を形成した。得られた塗膜は、平坦でムラの無い良好な面状であった。また液晶表示装置としての性能も実施例５４と同様に良好であった。 <Example 61>
A liquid crystal display device similar to that of Example 54 was obtained by changing only the following coating process. That is, after the photosensitive resin composition of Example 1 was applied by a slit coating method, the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 3.0 μm. Formed. The obtained coating film was flat and had a good surface shape without unevenness. Further, the performance as a liquid crystal display device was as good as in Example 54.
＜実施例６２＞
　実施例５４は、実施例１において、露光機を、キヤノン（株）製　ＭＰＡ　５５００ＣＦから、ＵＶ－ＬＥＤ光源露光機に変更した以外は同様に行った。また液晶表示装置としての性能も実施例５４と同様に良好であった。 <Example 62>
Example 54 was performed in the same manner as in Example 1 except that the exposure machine was changed from MPA 5500CF manufactured by Canon Inc. to a UV-LED light source exposure machine. Further, the performance as a liquid crystal display device was as good as in Example 54.
＜実施例６３＞
　実施例５４と以下の塗布プロセスのみ変更して、同様の液晶表示装置を得た。すなわち、実施例１の感光性樹脂組成物をスリットアンドスピン法にて塗布した後、９０℃／１２０秒ホットプレート上で加熱により溶剤を除去し、膜厚３．０μｍの感光性樹脂組成物層を形成した。得られた塗膜は、平坦でムラの無い良好な面状であった。また液晶表示装置としての性能も実施例５４と同様に良好であった。 <Example 63>
A liquid crystal display device similar to that of Example 54 was obtained by changing only the following coating process. That is, after the photosensitive resin composition of Example 1 was applied by a slit and spin method, the solvent was removed by heating on a hot plate at 90 ° C./120 seconds to form a photosensitive resin composition layer having a thickness of 3.0 μm. Formed. The obtained coating film was flat and had a good surface shape without unevenness. Further, the performance as a liquid crystal display device was as good as in Example 54.
＜実施例６４＞
　薄膜トランジスター（ＴＦＴ）を用いた有機ＥＬ表示装置を以下の方法で作製した（図２参照）。
　ガラス基板６上にボトムゲート型のＴＦＴ１を形成し、このＴＦＴ１を覆う状態でＳｉ3Ｎ4から成る絶縁膜３を形成した。次に、この絶縁膜３に、ここでは図示を省略したコンタクトホールを形成した後、このコンタクトホールを介してＴＦＴ１に接続される配線２（高さ１．０μｍ）を絶縁膜３上に形成した。この配線２は、ＴＦＴ１間または、後の工程で形成される有機ＥＬ素子とＴＦＴ１とを接続するためのものである。 <Example 64>
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 2).
A bottom gate type TFT 1 was formed on a glass substrate 6, and an insulating film 3 made of Si 3 N 4 was formed so as to cover the TFT 1. Next, a contact hole (not shown) is formed in the insulating film 3, and then a wiring 2 (height 1.0 μm) connected to the TFT 1 through the contact hole is formed on the insulating film 3. . The wiring 2 is used to connect the TFT 1 with an organic EL element formed between TFTs 1 or in a later process.
　さらに、配線２の形成による凹凸を平坦化するために、配線２による凹凸を埋め込む状態で絶縁膜３上へ平坦化膜４を形成した。絶縁膜３上への平坦化膜４の形成は、実施例１６の感光性樹脂組成物を基板上にスピン塗布し、ホットプレート上でプリベーク（９０℃／１２０秒）した後、マスク上から高圧水銀灯を用いてｉ線（３６５ｎｍ）を４５ｍＪ／ｃｍ2（照度２０ｍＷ／ｃｍ2）照射した後、アルカリ水溶液（０．４％のＴＭＡＨ水溶液）にて現像してパターンを形成し、超高圧水銀灯を用いて積算照射量が３００ｍＪ／ｃｍ2（照度：２０ｍＷ／ｃｍ2、ｉ線）となるように全面露光し、２３０℃／３０分間の加熱処理を行った。
　感光性樹脂組成物を塗布する際の塗布性は良好で、露光、現像、焼成の後に得られた硬化膜には、しわやクラックの発生は認められなかった。さらに、配線２の平均段差は５００ｎｍ、作製した平坦化膜４の膜厚は２，０００ｎｍであった。 Further, in order to flatten the unevenness due to the formation of the wiring 2, the planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarization film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 16 on a substrate, pre-baking (90 ° C./120 seconds) 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 is formed by developing with an alkaline aqueous solution (0.4% TMAH aqueous solution). Using this, the entire surface was exposed so that the integrated irradiation amount was 300 mJ / cm 2 (illuminance: 20 mW / cm 2 , i-line), and heat treatment was performed at 230 ° C./30 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.
　次に、得られた平坦化膜４上に、ボトムエミッション型の有機ＥＬ素子を形成した。まず、平坦化膜４上に、ＩＴＯからなる第一電極５を、コンタクトホール７を介して配線２に接続させて形成した。その後、レジストを塗布、プリベークし、所望のパターンのマスクを介して露光し、現像した。このレジストパターンをマスクとして、ＩＴＯエッチャント用いたウエットエッチングによりパターン加工を行った。その後、レジスト剥離液（リムーバ１００、ＡＺエレクトロニックマテリアルズ社製）を用いて上記レジストパターンを５０℃で剥離した。こうして得られた第一電極５は、有機ＥＬ素子の陽極に相当する。 Next, a bottom emission type organic EL element was formed on the obtained flattening film 4. First, a first electrode 5 made of ITO was formed on the planarizing film 4 so as to be connected to the wiring 2 through the contact hole 7. Thereafter, a resist was applied, prebaked, exposed through a mask having a desired pattern, and developed. Using this resist pattern as a mask, pattern processing was performed by wet etching using an ITO etchant. Thereafter, the resist pattern was stripped at 50 ° C. using a resist stripper (remover 100, manufactured by AZ Electronic Materials). The first electrode 5 thus obtained corresponds to the anode of the organic EL element.
　次に、第一電極５の周縁を覆う形状の絶縁膜８を形成した。絶縁膜８には、実施例１６の感光性樹脂組成物を用い、上記と同様の方法で絶縁膜８を形成した。この絶縁膜８を設けることによって、第一電極５とこの後の工程で形成する第二電極との間のショートを防止することができる。 Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. As the insulating film 8, the photosensitive resin composition of Example 16 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.
　さらに、真空蒸着装置内で所望のパターンマスクを介して、正孔輸送層、有機発光層、電子輸送層を順次蒸着して設けた。次いで、基板上方の全面にＡｌから成る第二電極を形成した。得られた上記基板を蒸着機から取り出し、封止用ガラス板と紫外線硬化型エポキシ樹脂を用いて貼り合わせることで封止した。 Further, a hole transport layer, an organic light emitting layer, and an electron transport layer were sequentially deposited through a desired pattern mask in a vacuum deposition apparatus. Next, a second electrode made of Al was formed on the entire surface above the substrate. The obtained board | substrate was taken out from the vapor deposition machine, and it sealed by bonding together using the glass plate for sealing, and an ultraviolet curable epoxy resin.
　以上のようにして、各有機ＥＬ素子にこれを駆動するためのＴＦＴ１が接続してなるアクティブマトリックス型の有機ＥＬ表示装置が得られた。駆動回路を介して電圧を印加したところ、良好な表示特性を示し、信頼性の高い有機ＥＬ表示装置であることが分かった。 As described above, an active matrix type organic EL display device in which each organic EL element is connected to the TFT 1 for driving it was obtained. When a voltage was applied via the drive circuit, it was found that the organic EL display device showed good display characteristics and high reliability.
　１：ＴＦＴ（薄膜トランジスター）
　２：配線
　３：絶縁膜
　４：平坦化膜
　５：第一電極
　６：ガラス基板
　７：コンタクトホール
　８：絶縁膜
　１０：液晶表示装置
　１２：バックライトユニット
　１４，１５：ガラス基板
　１６：ＴＦＴ
　１７：硬化膜
　１８：コンタクトホール
　１９：ＩＴＯ透明電極
　２０：液晶
　２２：カラーフィルター 1: TFT (Thin Film Transistor)
2: Wiring 3: Insulating film 4: Flattened film 5: First electrode 6: Glass substrate 7: Contact hole 8: Insulating film 10: Liquid crystal display device 12: Backlight unit 14, 15: Glass substrate 16: TFT
17: Cured film 18: Contact hole 19: ITO transparent electrode 20: Liquid crystal 22: Color filter

Claims (17)

  1. （Ａ）下記（１）および（２）の少なくとも一方を満たす重合体を含む重合体成分、
    （１）（ａ１）酸基が酸分解性基で保護された残基を有する構成単位、および（ａ２）エポキシ基を有する構成単位、を有する重合体、
    （２）（ａ１）酸基が酸分解性基で保護された残基を有する構成単位を有する重合体、および（ａ２）エポキシ基を有する構成単位を有する重合体、
    （Ｂ）光酸発生剤
    （Ｃ）分子量が１０００未満の脂環式エポキシ化合物、ならびに
    （Ｄ）溶剤
    を含有する感光性樹脂組成物。     (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 a residue in which an acid group is protected with an acid-decomposable group, and (a2) a structural unit having an epoxy group,
    (2) (a1) a polymer having a structural unit having a residue in which an acid group is protected with an acid-decomposable group, and (a2) a polymer having a structural unit having an epoxy group,
    (B) Photoacid generator (C) A photosensitive resin composition containing an alicyclic epoxy compound having a molecular weight of less than 1000, and (D) a solvent.
  2. 前記（Ｃ）脂環式エポキシ化合物が、下記式（１）で表される、請求項１に記載の感光性樹脂組成物。
    式（１）
    Figure JPOXMLDOC01-appb-C000001
     （式（１）中、ｎは１～４の整数を表す。Ｒ1は炭素数１～３０の有機基を表す。）     The photosensitive resin composition according to claim 1, wherein the (C) alicyclic epoxy compound is represented by the following formula (1).
    Formula (1)
    Figure JPOXMLDOC01-appb-C000001
     (In the formula (1), n represents an integer of 1 to 4. R 1 represents an organic group having 1 to 30 carbon atoms.)
  3. Ｒ1は炭素数１～１５の有機基を表す、請求項２に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 2, wherein R 1 represents an organic group having 1 to 15 carbon atoms.
  4. 前記（Ｃ）脂環式エポキシ化合物が、下記式（２）で表される、請求項１または２に記載の感光性樹脂組成物。
    式（２）
    Figure JPOXMLDOC01-appb-C000002
     （式（２）中、Ｒ2は炭素数１～１５の有機基を表す。）     The photosensitive resin composition according to claim 1 or 2, wherein the (C) alicyclic epoxy compound is represented by the following formula (2).
    Formula (2)
    Figure JPOXMLDOC01-appb-C000002
     (In the formula (2), R 2 represents an organic group having 1 to 15 carbon atoms.)
  5. 前記（Ｃ）脂環式エポキシ化合物が、下記式（３）で表される、請求項１または２に記載の感光性樹脂組成物。
    式（３）
    Figure JPOXMLDOC01-appb-C000003
     （式（３）中、Ｒ3は炭素数１～１５の有機基を表す。）     The photosensitive resin composition according to claim 1 or 2, wherein the (C) alicyclic epoxy compound is represented by the following formula (3).
    Formula (3)
    Figure JPOXMLDOC01-appb-C000003
     (In the formula (3), R 3 represents an organic group having 1 to 15 carbon atoms.)
  6. さらに、前記（Ｃ）脂環式エポキシ化合物以外の架橋剤を含む、請求項１～５のいずれか１項に記載の感光性樹脂組成物。 6. The photosensitive resin composition according to claim 1, further comprising a crosslinking agent other than the (C) alicyclic epoxy compound.
  7. 前記（Ｃ）脂環式エポキシ化合物が、下記式（Ｘ－１）で表される、請求項１または２に記載の感光性樹脂組成物。
    式（Ｘ－１）
    Figure JPOXMLDOC01-appb-C000004
     （式（Ｘ－１）中、Ｒ4は炭素数１～２７の有機基を表す。Ｒ5はそれぞれ炭素数１～２７の置換基を表す。ただし、１つの脂環式エポキシ基を除いた炭素数は３～３０である。）     The photosensitive resin composition according to claim 1 or 2, wherein the (C) alicyclic epoxy compound is represented by the following formula (X-1).
    Formula (X-1)
    Figure JPOXMLDOC01-appb-C000004
     (In the formula (X-1), R 4 represents an organic group having 1 to 27 carbon atoms. R 5 represents a substituent having 1 to 27 carbon atoms, respectively, except for one alicyclic epoxy group. (The number of carbon atoms is 3 to 30.)
  8. 前記（Ｃ）脂環式エポキシ化合物が、下記式（Ｘ－２）で表される、請求項１、２、７のいずれか１項に記載の感光性樹脂組成物。
    式（Ｘ－１）
    Figure JPOXMLDOC01-appb-C000005
     （式（Ｘ－２）中、Ｒ4はそれぞれ炭素数１～２７の有機基を表す。Ｒ5は炭素数１～２７の置換基を表す。ただし、１つの脂環式エポキシ基を除いた炭素数は３～３０である。）     The photosensitive resin composition according to claim 1, wherein the (C) alicyclic epoxy compound is represented by the following formula (X-2).
    Formula (X-1)
    Figure JPOXMLDOC01-appb-C000005
     (In the formula (X-2), R 4 represents an organic group having 1 to 27 carbon atoms, and R 5 represents a substituent having 1 to 27 carbon atoms, except for one alicyclic epoxy group. (The number of carbon atoms is 3 to 30.)
  9. 前記（Ｃ）脂環式エポキシ化合物が、下記式（Ｘ－３）で表される、請求項１、２、７、８のいずれか１項に記載の感光性樹脂組成物。
    式（Ｘ－１）
    Figure JPOXMLDOC01-appb-C000006
     （式（Ｘ－３）中、Ｒ4はそれぞれ炭素数１～２７の有機基を表す。ただし、１つの脂環式エポキシ基を除いた炭素数は３～３０である。）     The photosensitive resin composition according to any one of claims 1, 2, 7, and 8, wherein the (C) alicyclic epoxy compound is represented by the following formula (X-3).
    Formula (X-1)
    Figure JPOXMLDOC01-appb-C000006
     (In formula (X-3), each R 4 represents an organic group having 1 to 27 carbon atoms. However, the number of carbon atoms excluding one alicyclic epoxy group is 3 to 30.)
  10. 前記酸分解性基がアセタールの形で保護された構造を有する基である、請求項１～９のいずれか１項に記載の感光性樹脂組成物。 10. The photosensitive resin composition according to claim 1, wherein the acid-decomposable group is a group having a structure protected in the form of an acetal.
  11. 前記（Ａ）重合体成分のいずれかが、さらに、酸基を含有する重合体である、請求項１～１０のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 10, wherein any one of the polymer components (A) is a polymer further containing an acid group.
  12. 前記（Ｂ）光酸発生剤が、オキシムスルホネート化合物である請求項１～１１のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 11, wherein the photoacid generator (B) is an oxime sulfonate compound.
  13. （１）請求項１～１２のいずれか１項に記載の感光性樹脂組成物を基板上に塗布する工程、
    （２）塗布された感光性樹脂組成物から溶剤を除去する工程、
    （３）溶剤が除去された感光性樹脂組成物を活性放射線で露光する工程、
    （４）露光された感光性樹脂組成物を水性現像液により現像する工程、および、
    （５）現像された感光性樹脂組成物を熱硬化するポストベーク工程、を含むことを特徴とする硬化膜の製造方法。     (1) a step of applying the photosensitive resin composition according to any one of claims 1 to 12 on a substrate;
    (2) a step of removing the solvent from the applied photosensitive resin composition;
    (3) A step of exposing the photosensitive resin composition from which the solvent has been removed with actinic radiation,
    (4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and
    (5) A method for producing a cured film, comprising a post-baking step of thermosetting the developed photosensitive resin composition.
  14. 前記現像する工程後、ポストベーク工程前に、現像された感光性樹脂組成物を全面露光する工程を含む、請求項１３に記載の硬化膜の形成方法。 The method for forming a cured film according to claim 13, comprising a step of exposing the entire surface of the developed photosensitive resin composition after the developing step and before the post-baking step.
  15. 請求項１３または１４に記載の方法により形成された硬化膜。 A cured film formed by the method according to claim 13 or 14.
  16. 層間絶縁膜である、請求項１５に記載の硬化膜。 The cured film according to claim 15, which is an interlayer insulating film.
  17. 請求項１５または１６に記載の硬化膜を有する有機ＥＬ表示装置または液晶表示装置。 An organic EL display device or a liquid crystal display device having the cured film according to claim 15 or 16.
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