WO2015087832A1 - Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device and organic el display device - Google Patents

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

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Publication number
WO2015087832A1
WO2015087832A1 PCT/JP2014/082414 JP2014082414W WO2015087832A1 WO 2015087832 A1 WO2015087832 A1 WO 2015087832A1 JP 2014082414 W JP2014082414 W JP 2014082414W WO 2015087832 A1 WO2015087832 A1 WO 2015087832A1
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group
resin composition
photosensitive resin
general formula
acid
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PCT/JP2014/082414
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French (fr)
Japanese (ja)
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雨宮　拓馬
豪 安藤
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富士フイルム株式会社
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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
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/10—OLED displays
    • H10K59/12—Active-matrix OLED [AMOLED] displays
    • H10K59/124—Insulating layers formed between TFT elements and OLED elements

Definitions

  • the present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”). Moreover, it is related with the manufacturing method of the cured film using the said photosensitive resin composition, the cured film formed by hardening
  • the present invention relates to an article and a method for producing a cured film using the article.
  • Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film.
  • photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.
  • the photosensitive resin composition for interlayer insulating films and interlayer insulating films in the display device are required to have high sensitivity, high resolution, high transparency, and solvent resistance.
  • an attempt has been made to use an acrylic resin as a film forming component For example, those described in Patent Documents 1 and 2 are known.
  • PBO Polybenzoxazole
  • Patent Documents 3 to 5 have higher tensile strength than acrylic resins, but the hardness of the cured film is low, and there are problems in scratch resistance tests such as pencil hardness tests. .
  • Patent Document 3 shows that the elongation at break is improved by adding a crosslinkable group to the terminal of the polybenzoxazole precursor, but there is a problem that the hardness is inferior.
  • the present invention has been made to solve the above problems, and is a photosensitive resin composition excellent in sensitivity, transmittance, pencil hardness, and electrical properties after high-humidity treatment, a method for producing a cured film, a cured film, An object is to provide a liquid crystal display device and an organic EL display device.
  • a photosensitive resin composition comprising (B) a photoacid generator and (C) a solvent; (1) (a-1) a repeating unit represented by general formula (1), wherein at least one of R 1 and R 2 is an acid-decomposable group, and (a-2) general formula A repeating unit represented by (1), wherein at least one of R 1 and R 2 is a crosslinkable group; (2) (a-3) A repeating unit represented by the general formula (1), wherein one of R 1 and R 2 includes an acid-decomposable group and the other includes a repeating unit that is a crosslinkable group.
  • X represents a tetravalent organic group
  • Y represents a divalent organic group.
  • R 1 and R 2 are each independently a hydrogen atom, a crosslinkable group, an alkyl group, acid-decomposable. Represents a group or —CORc, where Rc represents an alkyl group or an aryl group.
  • X represents a tetravalent organic group
  • Y represents a divalent organic group.
  • R 1 and R 2 are each independently a hydrogen atom, a crosslinkable group, an alkyl group, acid-decomposable. Represents a group or —CORc, where Rc represents an alkyl group or an aryl group.
  • Formula (X) (In the general formula (X), Z represents a single bond, a carbon atom or a sulfur atom, R 11 represents a monovalent organic group. N represents 0 or 1, and when Z is a single bond, a is 0. When Z is a carbon atom, a is 1, and when Z is a sulfur atom, a is 2. When n is 0, two R 11 are bonded to each other to form a ring.
  • the polybenzoxazole precursor includes m repeating units represented by the general formula (1) and n repeating units represented by the general formula (3), and m is 3 to 1000
  • Y 1 is independently an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or these, —CH 2 —, an oxygen atom, a sulfur atom, — Represents a group composed of a combination with at least one of SO 2 —, —CO—, —NHCO—, and —C (CF 3 ) 2 —, and X 2 represents an arylene group, a divalent heterocyclic group, a divalent group, Or a cyclic aliphatic group of the above, or at least one of —CH 2 —, oxygen atom, sulfur atom, —SO 2 —, —CO—, —NHCO—, and —C (CF 3 ) 2 —.
  • ⁇ 5> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the crosslinkable group is selected from an epoxy group, an oxetanyl group, a carbon-carbon unsaturated bond group, and a blocked isocyanate group.
  • the acid-decomposable group is a group capable of leaving by the action of an acid; provided that each R 5 is independently a hydrogen atom Or an alkyl group having 1 to 4 carbon atoms, and R 4 represents a group capable of leaving by the action of an acid.
  • the group capable of leaving by the action of an acid is an alkoxycarbonyl group, an alkoxyalkyl group, an alkylsilyl group, a group constituting an acetal, or a group constituting a ketal, described in ⁇ 6> or ⁇ 7> Photosensitive resin composition.
  • ⁇ 9> (1) A step of applying the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 8> to at least one surface of 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 rays, (4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and (5) a post-baking step of thermosetting the developed photosensitive resin composition, The manufacturing method of the cured film containing this.
  • the method for producing a cured film according to ⁇ 9> including a step of exposing the entire surface of the developed photosensitive resin composition after the step of (4) developing and before the step of (5) post-baking.
  • ⁇ 11> A cured film obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 8> or a cured film formed by the method according to ⁇ 9> or ⁇ 10>.
  • ⁇ 12> The cured film according to ⁇ 11>, which is an interlayer insulating film.
  • ⁇ 13> A liquid crystal display device or an organic EL display device having the cured film according to ⁇ 11> or ⁇ 12>.
  • the present invention it is possible to provide a photosensitive resin composition excellent in sensitivity, transmittance, pencil hardness, and electrical characteristics after high-humidity treatment, a method for producing a cured film, a cured film, a liquid crystal display device, and an organic EL display device It became.
  • 1 is a conceptual diagram of a configuration of an example of a liquid crystal display device.
  • 1 is a schematic cross-sectional view of an active matrix substrate in a liquid crystal display device.
  • 1 shows a conceptual diagram of a configuration of an example of an organic EL display device.
  • 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device.
  • the description which does not describe substitution and non-substitution includes what has a substituent with what does not have 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).
  • (meth) acrylic acid means acrylic acid and / or methacrylic acid.
  • the solid content concentration in the present invention refers to the solid content concentration at 25 ° C.
  • a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by GPC measurement.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column.
  • 0.0 mm ID ⁇ 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.
  • Photosensitive resin composition comprises (A) a polybenzoxazole precursor containing a repeating unit represented by the general formula (1) and satisfying the following (1) and / or (2): , (B) a photoacid generator, and (C) a solvent.
  • X represents a tetravalent organic group
  • Y represents a divalent organic group.
  • R 1 and R 2 are each independently a hydrogen atom, a crosslinkable group, an alkyl group, acid-decomposable.
  • Rc represents an alkyl group or an aryl group.
  • Patent Document 3 Japanese Patent Laid-Open No. 2008-224970
  • a crosslinkable group is added to the terminal of the polybenzoxazole precursor.
  • the elongation at break (confirmation of examples in the reference) is improved, but the pencil hardness is inferior.
  • it can withstand breaking elongation, but tends not to withstand a large force.
  • it is also known to bond an acrylic resin with a crosslinkable group, but there is a problem that electrical properties after high humidity treatment are inferior.
  • the present invention by using a polybenzoxazole precursor and adding a crosslinkable group to the main chain, high pencil hardness and electrical properties after high humidity treatment are achieved.
  • the present invention is significant in that a high pencil hardness that does not deform with some force can be achieved.
  • the photosensitive resin composition of the present invention is preferably used as 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 (A) a polybenzoxazole precursor having a repeating unit represented by the general formula (1) (hereinafter simply referred to as “(A) polybenzoxazole precursor”, “component (A)”. Sometimes).
  • the (A) polybenzoxazole precursor used in the present invention preferably further has a crosslinkable group at the terminal.
  • the terminal may be one terminal, but more preferably has a crosslinkable group at both terminals.
  • the terminal of the polybenzoxazole precursor means the main chain terminal of the polybenzoxazole precursor.
  • the repeating unit represented by the general formula (1) may contain only one type or two or more types.
  • the polybenzoxazole precursor preferably contains 70 mol% or more, more preferably 80 mol% or more of the repeating unit represented by the general formula (1) with respect to all repeating units. Preferably it is 90 mol% or more.
  • the polybenzoxazole precursor preferably contains at least 60 to 3 mol% of repeating units containing an acid-decomposable group, and preferably contains 30 to 5 mol% of all repeating units. Is more preferable.
  • the polybenzoxazole precursor (A) preferably contains at least 40 to 1 mol% of repeating units containing a crosslinkable group, and preferably contains 30 to 5 mol% of all repeating units.
  • the polybenzoxazole precursor containing a crosslinkable group contains, in particular, a repeating unit containing the above-mentioned proportion of an acid-decomposable group, a repeating unit containing the above-mentioned proportion of the crosslinkable group, and further has a crosslinking property at the end.
  • it contains a group.
  • the repeating unit represented by the general formula (1) is (a-1) the repeating unit represented by the general formula (1), wherein at least one of R 1 and R 2 is acid-decomposable.
  • a certain repeating unit (a repeating unit including a crosslinkable group) may be included, or (a-3) a repeating unit including an acid-decomposable group and a crosslinkable group may be included.
  • the polybenzoxazole precursor may contain (a-1) a repeating unit containing an acid-decomposable group.
  • the repeating unit containing an acid-decomposable group is represented by the following general formula (1-1).
  • the repeating unit represented by the general formula (1) may contain only one type or two or more types.
  • R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, an acid-decomposable group, Or represents —CORc, where Rc represents an alkyl group or an aryl group, and at least one of R 1 and R 2 is an acid-decomposable group.
  • X represents a tetravalent organic group.
  • the tetravalent organic group represented by X is not particularly limited, but preferably has at least one cyclic structure, more preferably 1 to 2 cyclic structures.
  • the cyclic structure may be any of an aromatic ring, a heterocyclic ring, and an aliphatic ring, and preferably includes an aromatic ring and / or a heterocyclic ring, and more preferably includes an aromatic ring. By setting it as such a cyclic structure, the effect of this invention is exhibited more effectively.
  • the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring.
  • heterocyclic ring furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline ring
  • Examples include pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring.
  • the aliphatic ring examples include a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring.
  • the ring may be condensed, —O—, —S—, a fluorine-substituted alkylene group (preferably —C (CF 3 ) 2 —), —CH 2 — , —SO 2 —, or —NHCO— may be bonded to a plurality of cyclic structures via a linking group.
  • the linking group is preferably —O—, —S—, —C (CF 3 ) 2 —, —CH 2 —, —SO 2 —, or —NHCO—, where —C (CF 3 ) 2 — is More preferred.
  • the X moiety preferably contains a fluorine-substituted alkylene group. By including a fluorine-substituted alkylene group, the transparency of the composition of the present invention tends to be further improved.
  • X include, but are not limited to, the following.
  • X 1 represents a linking group.
  • NH and R 1 bonded to X, and NH and R 2 are preferably bonded so as to be in the ortho position (adjacent position) in the cyclic structure.
  • X is preferably (2) or (10), more preferably (2).
  • X 1 is a fluorine-substituted alkylene group (preferably —C (CF 3 ) 2 —), since the transparency of the composition of the present invention is further improved.
  • R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, an acid-decomposable group, or —CORc, and one of R 1 and R 2 is an acid-decomposable group.
  • the alkyl group may or may not have a substituent.
  • the alkyl group may be linear, branched or cyclic, and in the case of a linear or branched alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 15 carbon atoms Is more preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable.
  • an alkyl group having 3 to 15 carbon atoms is preferable, an alkyl group having 5 to 15 carbon atoms is more preferable, and an alkyl group having 5 to 10 carbon atoms is more preferable.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.
  • the substituent include a halogen atom, a cyano group, an amide group, and a sulfonylamide group.
  • An acid-decomposable group is a group capable of leaving by the action of an acid, or a group that leaves by the action of an acid to generate an alkali-soluble group such as a hydroxyl group or a carboxyl group, such as —C (R 5 ) 2 —COOR 4.
  • R 5 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 4 represents a group capable of leaving by the action of an acid.
  • the acid acting as an acid usually means an acid generated from an acid generator described later.
  • Examples of the group capable of leaving by the action of an acid include vinyl ether substituents, alkoxycarbonyl groups (preferably having 2 to 5 carbon atoms), alkoxyalkyl groups (preferably having 2 to 5 carbon atoms), alkylsilyl groups (preferably carbon atoms). And a group constituting an acetal or a ketal. From the viewpoint of sensitivity, an acetal group or a ketal group is preferable. As group which comprises acetal or ketal, what has the following structure is mentioned, for example. (In the formula, R 1x and R 2x each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R 1x and R 2x represents an alkyl group or an aryl group.
  • R 3x represents an alkyl group. Alternatively, it represents an aryl group, and R 1x or R 2x and R 3x may be linked to form a cyclic ether.
  • the alkyl group represented by R 1x and R 2x is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
  • the aryl group represented by R 1x and R 2x is preferably an aryl group having 6 to 10 carbon atoms, and more preferably a phenyl group.
  • R 1x and R 2x are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 3X represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 16 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
  • aryl group an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable.
  • the group capable of leaving by the action of an acid include alkoxycarbonyl groups such as t-butoxycarbonyl group, alkoxyalkyl groups such as methoxymethyl group and ethoxyethyl group, alkylsilyl groups such as methylsilyl group and ethylsilyl group, tetrahydro Pyranyl group, tetrahydrofuranyl group, alkoxy-substituted tetrahydropyranyl group, alkoxy-substituted tetrahydrofuranyl group and the like are exemplified as typical examples, but are not limited thereto.
  • the most preferable group as a group capable of leaving by the action of an acid is an ethoxyethyl group, a tetrahydropyranyl group or a tetrahydrofuranyl group. These may be used alone or in combination of two or more.
  • the structure of a group preferable as a group capable of leaving by the action of an acid is shown.
  • Rc represents an alkyl group or an aryl group, and these groups may or may not have a substituent.
  • the alkyl group represented by Rc has the same meaning as the alkyl group represented by R 1 and R 2 , and the preferred range is also the same.
  • the aryl group represented by Rc is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further preferably an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group.
  • the substituent that the aryl group may have is the same as the substituent that the alkyl group may have.
  • Y represents a divalent organic group.
  • the divalent organic group represented by Y is not particularly limited, but preferably has at least one cyclic structure, and more preferably has 1 to 2 cyclic structures.
  • the cyclic structure may be any of an arylene group, a divalent cyclic aliphatic group, and a divalent heterocyclic group, and preferably includes an arylene group and / or a divalent heterocyclic ring, and includes an arylene group. It is more preferable.
  • the divalent organic group represented by Y includes an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or a methylene group, an oxygen atom, a sulfur atom, —SO 2.
  • arylene group an arylene group having 6 to 20 carbon atoms is preferable, an arylene group having 6 to 14 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is more preferable.
  • Specific examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a naphthylene group, and an anthracenylene group.
  • Examples of the divalent cyclic aliphatic group include a cyclic alkylene group, a cyclic alkenylene group, and a cyclic alkynylene group.
  • a cyclic alkylene group an alkylene group having 3 to 20 carbon atoms is preferable, a cyclic alkylene group having 3 to 18 carbon atoms is more preferable, and a cyclic alkylene group having 3 to 15 carbon atoms is more preferable.
  • the cyclic alkenylene group is preferably an alkenylene group having 3 to 20 carbon atoms, more preferably a cyclic alkenylene group having 3 to 18 carbon atoms, and further preferably a cyclic alkenylene group having 3 to 15 carbon atoms.
  • cyclic alkynylene group a cyclic alkynylene group having 3 to 20 carbon atoms is preferable, a cyclic alkynylene group having 3 to 18 carbon atoms is more preferable, and a cyclic alkynylene group having 3 to 15 carbon atoms is more preferable.
  • divalent cycloaliphatic group include 1,4-cyclohexylene group, 1,3-cyclohexylene group, 1,2-cyclohexylene group, and octylene group.
  • the divalent heterocyclic group preferably has a 5-membered, 6-membered or 7-membered heterocyclic ring.
  • a 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is more preferable.
  • a nitrogen atom, an oxygen atom and a sulfur atom are preferable.
  • the heterocycle is preferably an aromatic heterocycle.
  • the aromatic heterocyclic ring is generally an unsaturated heterocyclic ring, and an unsaturated heterocyclic ring having the most double bond is more preferable.
  • heterocycles include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, Pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring Is included.
  • Y represents an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or a methylene group, an oxygen atom, a sulfur atom, —SO 2 —, —CO—, —NHCO—, and — C (CF 3) 2 - in can be a group comprising a combination of at least one, and specific examples thereof include the following groups.
  • A represents a methylene group, an oxygen atom, a sulfur atom, —SO 2 —, —CO—, —NHCO—, or —C (CF 3 ) 2 —.
  • Y is preferably 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group or octylene group.
  • the polybenzoxazole precursor may contain (a-2) a repeating unit containing a crosslinkable group.
  • A-2) The repeating unit containing a crosslinkable group is represented by the following general formula (2-1).
  • the repeating unit represented by the general formula (2-1) may include only one type, or may include two or more types.
  • Formula (2-1) (In general formula (2-1), X represents a tetravalent organic group and Y represents a divalent organic group.
  • R 1 and R 2 each independently represents a hydrogen atom, a crosslinkable group, an alkyl group, or -CORc, Rc represents an alkyl group or an aryl group, and at least one of R 1 and R 2 is a crosslinkable group.
  • X represents a tetravalent organic group.
  • X and Y have the same meanings as X and Y in the general formula (1-1) in the repeating unit (a-1) containing an acid-decomposable group, respectively, and preferred ranges are also the same.
  • R 1 and R 2 each independently represents a hydrogen atom, a crosslinkable group, an alkyl group, or —CORc.
  • One of R 1 and R 2 is a crosslinkable group.
  • R 1 and R 2 of the alkyl and -CORc has the same meaning as R 1 and R 2 in the general formula (1-1) in the repeating unit comprising (a-1) acid-decomposable groups, preferred The range is the same.
  • the crosslinkable group is not limited as long as a crosslinking reaction is caused by heat. From the viewpoint of mechanical strength and solvent resistance, those which react with the carboxy group, hydroxy group or carbon-carbon unsaturated bond of component (A) are preferred. Specifically, a group containing at least one of an epoxy group, an oxetanyl group, a carbon-carbon unsaturated bond group and a blocked isocyanate group is preferable, and at least one of an epoxy group, an oxetanyl group, a carbon-carbon unsaturated bond group and a blocked isocyanate group The group containing is more preferable. Nate groups are more preferred.
  • crosslinkable group examples include the following, but are not limited thereto.
  • the crosslinkable group may be bonded via a linking group or the like, and is preferably directly bonded to the oxygen atom in the formula (2-1).
  • the polybenzoxazole precursor is preferably a repeating unit in which one of R 1 and R 2 in the general formula (1) is an acid-decomposable group and the other is a crosslinkable group.
  • X and Y in the general formula (1) have the same meanings as X and Y in the general formula (1-1), and the preferred ranges are also the same.
  • a preferred embodiment of the acid-decomposable group is the same as the acid-decomposable group in the general formula (1-1).
  • a preferred embodiment of the crosslinkable group is the same as that of the crosslinkable group in the general formula (2-1).
  • repeating unit (a-3) in which at least one of R 1 and R 2 in the general formula (1) is an acid-decomposable group and the other is a crosslinkable group,
  • the repeating unit of 1) and / or (a-2) may also be included.
  • repeating unit (a-4) Other repeating unit
  • the polybenzoxazole precursor may contain other repeating units.
  • Examples of other repeating units include repeating units represented by the general formula (3) or the general formula (4).
  • X, Y, and Rc have the same meanings as X, Y, and Rc in general formula (1-1), and the preferred ranges are also the same. This is the same as the preferred range of the alkyl group or —CORc as R 3 and R 4 and the alkyl group or —CORc in R 1 and R 2 of formula (1-1).
  • Y 1 each independently represents an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or these, —CH 2 —, an oxygen atom, a sulfur atom, — Represents a group composed of a combination with at least one of SO 2 —, —CO—, —NHCO—, and —C (CF 3 ) 2 —
  • X 2 represents an arylene group, a divalent heterocyclic group, a divalent group, Or a cyclic aliphatic group of the above, or at least one of —CH 2 —, oxygen atom, sulfur atom, —SO 2 —, —CO—, —NHCO—, and —C (CF 3 ) 2 —.
  • Y 1 is independently an arylene group, divalent cycloaliphatic group, divalent heterocyclic group, or a methylene group, oxygen atom, sulfur atom, —SO 2 —, —CO—, —NHCO. And a group consisting of a combination with at least one of — and —C (CF 3 ) 2 —.
  • arylene group an arylene group having 6 to 20 carbon atoms is preferable, an arylene group having 6 to 14 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is more preferable.
  • the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a naphthylene group, and an anthracenylene group.
  • the divalent heterocyclic group preferably has a 5-membered, 6-membered or 7-membered heterocyclic ring. A 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is more preferable.
  • the hetero atom constituting the heterocyclic ring a nitrogen atom, an oxygen atom and a sulfur atom are preferable.
  • the heterocycle is preferably an aromatic heterocycle.
  • the aromatic heterocycle is generally an unsaturated heterocycle.
  • An unsaturated heterocyclic ring having the most double bond is more preferable.
  • Specific heterocycles include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, Pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring Is included.
  • Examples of the divalent cyclic aliphatic group include a cyclic alkylene group, a cyclic alkenylene group, and a cyclic alkynylene group.
  • a cyclic alkylene group having 3 to 20 carbon atoms is preferable, a cyclic alkylene group having 3 to 18 carbon atoms is more preferable, and a cyclic alkylene group having 3 to 15 carbon atoms is more preferable.
  • cyclic alkenylene group a cyclic alkenylene group having 3 to 20 carbon atoms is preferable, a cyclic alkenylene group having 3 to 18 carbon atoms is more preferable, and a cyclic alkenylene group having 3 to 15 carbon atoms is more preferable.
  • cyclic alkynylene group a cyclic alkynylene group having 3 to 20 carbon atoms is preferable, a cyclic alkynylene group having 3 to 18 carbon atoms is more preferable, and a cyclic alkynylene group having 3 to 15 carbon atoms is more preferable.
  • divalent cycloaliphatic group examples include 1,4-cyclohexylene group, 1,3-cyclohexylene group, 1,2-cyclohexylene group, and octylene group.
  • Y 1 represents an arylene group, a divalent heterocyclic group, a divalent cycloaliphatic group, or a methylene group, an oxygen atom, a sulfur atom, —SO 2 —, —CO—, —NHCO—, and -C (CF 3) 2 - in can be a group comprising a combination of at least one of these and, -C (CF 3) 2 -, more preferably a group consisting of an arylene group And more preferably a group consisting of a combination of —C (CF 3 ) 2 —.
  • Y 1 is preferably a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, an octylene group, or the following exemplified compounds, and includes a 1,4-phenylene group, a 1,3-phenylene group, , 2-phenylene group and octylene group are more preferable.
  • X 2 represents an arylene group, divalent heterocyclic group, divalent cycloaliphatic group, or a methylene group, oxygen atom, sulfur atom, —SO 2 —, —CO—, —NHCO—, and A group consisting of a combination of at least one of —C (CF 3 ) 2 — is represented, and these groups may contain a silicon atom.
  • An arylene group represented by X 2 , a divalent heterocyclic group, and a divalent cyclic aliphatic group are an arylene group represented by Y 1 in formula (1-2), a divalent heterocyclic group, and a divalent cyclic group. It is synonymous with an aliphatic group, and its preferable range is also the same.
  • X 2 represents an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or a methylene group, an oxygen atom, a sulfur atom, —SO 2 —, —CO—, —NHCO—, and
  • the group may be a combination of at least one of —C (CF 3 ) 2 —, and specific examples thereof include the following groups.
  • A represents a methylene group, an oxygen atom, a sulfur atom, —SO 2 —, —CO—, —NHCO—, or —C (CF 3 ) 2 —.
  • the polybenzoxazole precursor which has (A) a crosslinkable group contains the repeating unit containing a silicon atom, for example.
  • Specific examples include the following repeating units.
  • Y 1 represents an arylene group, divalent cycloaliphatic group, divalent heterocyclic group, or these, —CH 2 —, oxygen atom, sulfur atom, —SO 2 —, —CO Represents a group composed of a combination of at least one of —, —NHCO—, and —C (CF 3 ) 2 —, and X 3 represents a group containing a silicon atom.
  • Y 1 has the same meaning as Y 1 in the general formula (3), and preferred ranges are also the same.
  • X 3 is preferably a group represented by the following. (R 5 and R 6 each independently represent a divalent organic group, and R 7 and R 8 each independently represent a monovalent organic group.)
  • the divalent organic group represented by R 5 and R 6 is not particularly limited, but may be a linear or branched alkylene group having 1 to 20 carbon atoms and a substituent, which may have a specific substituent.
  • As the linear or branched alkylene group having 1 to 20 carbon atoms an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 6 carbon atoms is more preferable.
  • Specific examples include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and a t-butylene group.
  • arylene group having 6 to 20 carbon atoms an arylene group having 6 to 14 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is more preferable.
  • Specific examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a naphthylene group, and an anthracenylene group.
  • the divalent cycloaliphatic group having 3 to 20 carbon atoms is preferably a divalent cycloaliphatic group having 3 to 10 carbon atoms, and more preferably a divalent cycloaliphatic group having 5 to 6 carbon atoms.
  • Examples of the divalent cycloaliphatic group include a 1,4-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,2-cyclohexylene group.
  • These linear or branched alkylene groups having 1 to 20 carbon atoms, arylene groups having 6 to 20 carbon atoms, and divalent cyclic aliphatic groups having 3 to 20 carbon atoms may have a substituent.
  • Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.
  • the group formed by combining a straight chain or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent cyclic aliphatic group having 3 to 20 carbon atoms is not particularly limited.
  • a group formed by combining groups formed by combining divalent cycloaliphatic groups having 3 to 20 carbon atoms is preferable.
  • Specific examples of the group formed by combining a linear or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent cyclic aliphatic group having 3 to 20 carbon atoms are as follows: Although the following are mentioned, it is not limited to these.
  • the monovalent organic group represented by R 7 and R 8 represents a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent.
  • the linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
  • examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group.
  • the aryl group which may have a substituent is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further preferably an aryl group having 6 to 10 carbon atoms.
  • Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group. These linear or branched alkyl groups and aryl groups having 1 to 20 carbon atoms may have a substituent.
  • the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.
  • X 3 include the following, but are not limited thereto.
  • the repeating unit represented by the general formula (3) may include only one type or two or more types.
  • the polybenzoxazole precursor used in the present invention may contain a repeating unit other than the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (3).
  • such other repeating units are preferably 5 mol% or less of all repeating units.
  • the polybenzoxazole precursor is composed of m repeating units represented by the general formula (1) (the total of the above (a-1) to (a-3)) and n general formulas described later ( 3), m represents 3 to 1000, preferably 5 to 300, and more preferably 10 to 100. n represents 0 to 1000, preferably 0 to 300, and more preferably 0 to 100. However, m + n represents 3 to 1000, preferably 5 to 600, and more preferably 10 to 200.
  • the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (3) may be so-called random polymers.
  • the polybenzoxazole precursor in the present invention can have an embodiment having a crosslinkable group at the terminal.
  • membrane hardness can be improved.
  • the terminal having a crosslinkable group may be one terminal, but is preferably both terminals.
  • the terminal of a polybenzoxazole precursor is not specifically limited, It is preferable that a crosslinkable group is included.
  • the crosslinkable group is preferably a group containing at least one selected from an epoxy group, an oxetanyl group, a carbon-carbon unsaturated bond group, and a blocked isocyanate group.
  • the terminal of the (A) polybenzoxazole precursor in the present invention is preferably a group represented by the general formula (X).
  • Formula (X) (In the general formula (X), Z represents a single bond, a carbon atom or a sulfur atom, R 11 represents a monovalent organic group. N represents 0 or 1, and when Z is a single bond, a is 0. When Z is a carbon atom, a is 1, and when Z is a sulfur atom, a is 2. When n is 0, two R 11 are bonded to each other to form a ring. May be good.)
  • Z represents a single bond, a carbon atom or a sulfur atom, preferably a single bond or a carbon atom.
  • R 11 represents a monovalent organic group.
  • the monovalent organic group represented by R 11 is not particularly limited, and examples thereof include those having a formula weight of 20 to 500 per molecule.
  • the atom constituting the monovalent organic group represented by R 11 is preferably selected from a carbon atom, an oxygen atom, a nitrogen atom, a hydrogen atom, and a sulfur atom, and a carbon atom, an oxygen atom, a nitrogen atom, and a hydrogen atom More preferably, it is selected from.
  • R 11 is an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) or an alkenyl group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms).
  • An alkynyl group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), an aryl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), an alkoxy group (preferably having a carbon number) 1 to 10, more preferably 1 to 6 carbon atoms), carboxyl group, crosslinkable group, oxygen atom, carbonyl group, sulfonyl group, arylene group (preferably 6 to 20 carbon atoms, more preferably 6 to 6 carbon atoms) 10) an alkylene group (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkenylene group (preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), A nylene group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms) and an alkenyl group, alkynyl group, aryl group, carbonyl group, carboxyl group, crosslinkable group,
  • the crosslinkable group represented by R 11 is synonymous with the crosslinkable group represented by R 1 in formula (1), and the preferred range is also the same.
  • These groups may have a substituent, and examples of the substituent include a hydroxyl group, an alkyl group, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.
  • the terminal of the polybenzoxazole precursor is not a crosslinkable group, it may be sealed with a sealing group.
  • a sealing group in this case is an acetyl group.
  • the polybenzoxazole precursor has no crosslinkable group at the terminal.
  • the polybenzoxazole precursor (A) has a weight average molecular weight of preferably 3000 to 200,000, more preferably 4000 to 100,000, and most preferably 5000 to 50000. By setting it as this range, the lithography performance and the cured film physical properties can be made excellent.
  • the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.
  • the number average molecular weight of the (A) polybenzoxazole precursor is preferably 1000 to 50000, more preferably 2000 to 40000, and still more preferably 3000 to 30000.
  • the number average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.
  • the content of the (A) polybenzoxazole precursor in the composition of the present invention is preferably 50% by mass or more, more preferably 60% by mass, and particularly preferably 70% by mass or more in terms of solid content.
  • the total amount becomes the said range.
  • the polybenzoxazole precursor containing a crosslinkable group used in the present invention can be synthesized in consideration of the description in JP-A-2008-224907.
  • X a group represented by the general formula (X).
  • capping the terminal amino group via a carbonyl group or sulfonyl group capping as an amide using an acid anhydride or acid derivative, or a monofunctional amine or acid chloride during the polymerization reaction It can be synthesized at once by mixing.
  • the photosensitive resin composition of the present invention contains (B) a photoacid generator.
  • the photoacid generator used in the present invention is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure.
  • a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
  • 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.
  • pKa basically refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement. Specifically, the pKa described in the chemical handbook can be referred to.
  • 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 viewpoints of sensitivity and 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
  • paragraph numbers 0083 to 0088 of JP2011-221494A WO11 / 087011.
  • the compounds described in paragraph numbers 0065 to 0072 of the publication can be exemplified, and the contents thereof are incorporated in the present specification.
  • the triarylsulfonium salt a triarylsulfonium salt having the following structure can be preferably used.
  • imide sulfonate compound the imide sulfonate compound of the following structure can be used preferably.
  • Triarylsulfonium salts and imide sulfonate compounds are preferably used together with a sensitizer described later.
  • each R independently represents a group consisting of a hydrogen atom and a carbon atom and / or an oxygen atom (excluding other than C, H and O), and the sum of the carbon atom and the oxygen atom is 16 or less.
  • R 1 represents a monovalent organic group having 16 or less carbon atoms.
  • R independently represents a group consisting of a hydrogen atom and a carbon atom and / or an oxygen atom (excluding other than C, H and O), and the sum of the carbon atom and the oxygen atom is 16 or less.
  • R is preferably a hydrogen atom or an alkylene oxide group having 8 or less carbon atoms.
  • R 1 represents a monovalent organic group having 16 or less carbon atoms.
  • R 1 preferably does not contain other than C, H, O, and F.
  • Examples of R 1 include a methyl group, a trifluoromethyl group, a propyl group, a phenyl group, and a tosyl group.
  • imide sulfonate compound examples include the compounds described in paragraph numbers 0065 to 0075 of WO2011 / 087011, and the following compounds.
  • 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 (B1-1).
  • General formula (B1-1) (In the general formula (B1-1), R 21 represents an alkyl group or an aryl group. The wavy line represents a bond with another group.)
  • 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 represented by R 21 has a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group). It may be substituted with a bridged alicyclic group, preferably a bicycloalkyl group or the like.
  • 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 compound containing the oxime sulfonate structure represented by the general formula (B1-1) is preferably an oxime sulfonate compound represented by the following general formula (B1-2).
  • General formula (B1-2) (In the formula (B1-2), R 42 represents an optionally substituted alkyl group or aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, and m4 represents 0-3. Represents an integer, and when m4 is 2 or 3, a plurality of Xs 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.
  • m4 is 1, X is a methyl group, the substitution position of X is an ortho position, R 42 is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound which is a 7-dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.
  • the compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-3).
  • General formula (B1-3) (In the formula (B1-3), R 43 has the same meaning as R 42 in the formula (B1-2), and X 1 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents an alkoxy group, a cyano group or a nitro group, and n4 represents an integer of 0 to 5.)
  • R 43 in the above general formula (B1-3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n—.
  • a propyl group, a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.
  • 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.
  • the description in paragraphs 0080 to 0082 of JP2012-163937A can be referred to. Incorporated in the description.
  • the compound containing an oxime sulfonate structure represented by the general formula (B1-1) 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, for example, a compound represented by the general formula (OS-2) described in paragraph numbers 0087 to 0089 of JP2012-163937A Which is incorporated herein by reference.
  • 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.
  • the compound containing the oxime sulfonate structure represented by the general formula (B1-1) is represented by the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS- The oxime sulfonate compound represented by 5) is preferred.
  • 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 compound containing an oxime sulfonate structure represented by the above general formula (B1-1) is, for example, a compound represented by the general formula (OS-6) described in paragraph 0117 of JP2012-163937A. Particularly preferred is a compound represented by any of (OS-11), the contents of which are incorporated herein. 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. The contents of which are incorporated herein by reference.
  • oxime sulfonate compound 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. The contents of which are incorporated herein by reference. The present invention is not limited to these.
  • the compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-4).
  • General formula (B1-4) (In the general formula (B1-4), R 1 represents an alkyl group or an aryl group, R 2 represents an alkyl group, an aryl group, or a heteroaryl group. R 3 to R 6 each represents a hydrogen atom. Represents an alkyl group, an aryl group, or a halogen atom, provided that R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 may combine to form an alicyclic ring or aromatic ring. , -O- or S-.
  • R 1 represents an alkyl group or an aryl group.
  • the alkyl group is preferably a branched alkyl group or a cyclic alkyl group.
  • the alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable. When the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable.
  • alkyl group examples include propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, hexyl group. 2-ethylhexyl group, cyclohexyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
  • the aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms.
  • Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
  • the alkyl group and aryl group represented by R 1 may have a substituent.
  • substituents examples include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), an alkenyl group, an alkynyl group, Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, A nitro group, a hydrazino group, a heterocyclic group, etc. are mentioned. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.
  • R 1 is preferably an alkyl group from the viewpoint of transparency, and R 1 has a branched structure having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity.
  • An alkyl group, an alkyl group having a cyclic structure having 5 to 7 carbon atoms, or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. .
  • an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.
  • R 2 represents an alkyl group, an aryl group, or a heteroaryl group.
  • the alkyl group represented by R 2 is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
  • Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. It is a group.
  • As the aryl group an aryl group having 6 to 10 carbon atoms is preferable.
  • Examples of the aryl group include a phenyl group, a naphthyl group, a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
  • Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
  • the alkyl group, aryl group, and heteroaryl group represented by R 2 may have a substituent. As a substituent, it is synonymous with the substituent which the alkyl group and aryl group which R ⁇ 1 > may have.
  • R 2 is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group.
  • As the substituent for the phenyl group a methyl group is preferred.
  • R 3 to R 6 each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom).
  • the alkyl group represented by R 3 to R 6 has the same meaning as the alkyl group represented by R 2 , and the preferred range is also the same.
  • the aryl group represented by R 3 to R 6 has the same meaning as the aryl group represented by R 1 , and the preferred range is also the same.
  • R 3 to R 6 may combine to form a ring, and the ring may form an alicyclic ring or an aromatic ring. It is preferable that a benzene ring is more preferable.
  • R 3 to R 6 are each a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6.
  • a benzene ring is preferably formed, and a hydrogen atom, a methyl group, a fluorine atom, a chloro atom, a bromine atom, or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 are combined to form a benzene ring Is more preferable.
  • Preferred embodiments of R 3 to R 6 are as follows.
  • At least two are hydrogen atoms.
  • the number of alkyl groups, aryl groups, or halogen atoms is one or less.
  • Aspect 3) R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 are combined to form a benzene ring.
  • X represents —O— or S—.
  • Ts represents a tosyl group (p-toluenesulfonyl group)
  • Me represents a methyl group
  • Bu represents an n-butyl group
  • Ph represents a phenyl group.
  • the content of the (B) photoacid generator is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. 5 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is even more preferable. Only 1 type may be used for a photo-acid generator, and it can also use 2 or more types together. A photo-acid generator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of photo-acid generators, the total amount becomes the said range.
  • the photosensitive resin composition of the present invention contains (C) a solvent.
  • the photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in a solvent.
  • a solvent used for the preparation of the composition of the present invention a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
  • known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl.
  • Ethers propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, diethylene glycol dialkyl ethers such as diethylene glycol ethyl methyl ether, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, Dipropylene glycol dialkyl ethers, dipropylene glycol mono Ruki ether acetates, esters, ketones, amides, lactones such as ⁇ - butyrolactone, pyrrolidones and the like.
  • the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraphs 0174 to 0178 of JP2011-221494A, and paragraphs of 0167 to 167290 of JP2012-194290A. Also included are the solvents described in 0168, the contents of which are incorporated herein.
  • the solvent that can be used in the present invention is a single type or a combination of two or more types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. It is more preferable to use a combination of styrene and diethylene glycol dialkyl ether or an ester and butylene glycol alkyl ether acetate.
  • the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
  • Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
  • Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate.
  • the content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass and more preferably 60 to 90 parts by mass with respect to 100 parts by mass of all components in the photosensitive resin composition.
  • a solvent may be used individually by 1 type, or may use 2 or more types together. When two or more kinds of solvents are used, the total amount falls within the above range.
  • the photosensitive resin composition of the present invention may contain a crosslinking agent.
  • the crosslinking agent is a compound containing at least two crosslinking groups in the molecule, and the crosslinking group means a group that reacts with the crosslinking group / benzene ring / hydroxy group of the polybenzoxazole precursor by heat. To do.
  • crosslinking group a methylol group, an epoxy group, an oxetanyl group, an alkoxymethyl group, a blocked isocyanate group, a methacryloyl group and an acryloyl group are preferable, and a methylol group, an epoxy group, an alkoxymethyl group, a blocked isocyanate group, a methacryloyl group and an acryloyl group are preferable. More preferred.
  • the number of cross-linking groups in one molecule of the cross-linking agent is preferably 3 or more, and more preferably 4 or more.
  • the cross-linking group may have two or more of the same type of cross-linking group in the molecule, or may have two or more different types of cross-linking groups in the molecule.
  • These crosslinking agents react with (A) a polybenzoxazole precursor (particularly, a benzene ring and / or a phenolic hydroxyl group in the precursor) to form a crosslinked structure between (A) the polybenzoxazole precursor,
  • the cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
  • the molecular weight of the crosslinking agent used in the present invention is preferably 150 to 30000, and more preferably 200 to 10000. By setting it as such a range, the effect of this invention is exhibited more effectively.
  • the content of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 200 parts by mass with respect to a total of 100 parts by mass of the component (A) when the crosslinking agent is blended.
  • the amount is more preferably 1 to 100 parts by mass, and further preferably 5 to 60 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.
  • composition of the present invention can be configured to be substantially free of a crosslinking agent.
  • the configuration not actually included means that the cross-linking agent is, for example, 1% by mass or less of the solid content of the composition.
  • a compound having two or more epoxy groups in the molecule can be used as a crosslinking agent.
  • 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 epoxy group containing An acrylic resin having a structural unit can be given.
  • JER152, JER157S70, JER157S65, JER806, JER828, JER1007 are commercially available products described in paragraph No. 0189 of JP2011-221494, etc.
  • crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule is a crosslinking agent having two or more structures represented by the following general formula (1) or general formula (2) in the molecule. , One or both of an alkoxymethyl group and a methylol group are contained in the molecule in a total of two or more.
  • -CH 2 OR 1 (1) In the formula, R 1 represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
  • the alkoxymethyl group or methylol group is preferably bonded to a nitrogen atom or a carbon atom forming an aromatic ring.
  • Alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, and alkoxymethylated urea convert methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylol group of methylolated urea to alkoxymethyl group, respectively.
  • Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group, and the methoxymethyl group is particularly preferable from the viewpoint of outgas generation amount.
  • alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril are mentioned as preferred crosslinkable compounds, from the viewpoint of transparency Alkoxymethylated glycoluril and methylolated glycoluril are particularly preferred.
  • the alkoxymethyl group-containing crosslinking agent described in paragraph No. 0107 of JP2012-8223A can be preferably used, and the contents thereof are incorporated in the present specification.
  • Preferred structures of the crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule include compounds represented by the following formulas (8-1) to (8-4).
  • R 7 and R each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R 8 to R 11 each independently represents Represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxyl group
  • X 2 represents a single bond, a methylene group or an oxygen atom.
  • the alkyl group represented by R 7 and R has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • the alkyl group represented by R 8 to R 11 preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
  • the alkoxyl group represented by R 8 to R 11 preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group.
  • X 2 is preferably a single bond or a methylene group.
  • R 7 to R 11 and X 2 may be substituted with an alkyl group such as a methyl group or an ethyl group, or a halogen atom.
  • a plurality of R 7 , R, and R 8 to R 11 may be the same or different.
  • Specific examples of the compound represented by the formula (8-2) include N, N, N, N-tetramethylolglycoluril, N, N, N, N-tetramethylolglycoluril having 1 to 1 methylol groups. 4 methoxymethylated compounds, N, N, N, N-tetramethylolglycoluril methylol group having 1 to 4 ethoxymethylated compounds, N, N, N, N-tetramethylolglycoluril methylol N-propoxymethylated compounds having 1 to 4 groups, isopropoxymethylated compounds having 1 to 4 methylol groups in N, N, N, N-tetramethylolglycoluril, N, N, N, N -N-butoxymethylated compound having 1 to 4 methylol groups of tetramethylol glycoluril, N, N, N, N-tetramethylolglycol Methylol groups
  • Ruuriru can be exemplified
  • Specific examples of the compound represented by the formula (8-4) include N, N, N, N, N, N-hexamethylol melamine, N, N, N, N, N-hexamethylol melamine.
  • 1-6 methoxymethylated methylol groups 1-6 methoxymethylated methylol groups of N, N, N, N, N, N-hexamethylolmelamine, N, N, N, N, N, N-hexamethylolmelamine 1-6 methylol groups n-propoxymethylated, N, N, N, N, N, N-hexamethylolmelamine 1-6 methylol groups isopropoxymethyl Compound, N, N, N, N, N, N-hexamethylol compound in which 1 to 6 methylol groups of melamine are n-butoxymethylated, N, N, N, N, N-hexamethylol Mela Methylol groups of the emission can be cited 1-6 ter
  • X represents a single bond or a monovalent to tetravalent organic group
  • R 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group
  • n is an integer of 1 to 4.
  • p and q are each independently an integer of 0 to 4.
  • two Y's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and may contain an oxygen atom or a fluorine atom
  • R 13 to R 16 are each independently a hydrogen atom.
  • m and n are each independently an integer of 1 to 3
  • p and q are each independently an integer of 0 to 4.
  • Crosslinking agents containing two or more alkoxymethyl groups or methylol groups in these molecules are also available as commercial products, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicarax MX-750, -032, -706, -708, -40 , -31, -270, -280, -290, -750LM, Nicarak MS-11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.), etc. are preferably used. it can. These can be used alone or in combination of two or more.
  • a compound containing two or more blocked isocyanate groups in the molecule can be used as a crosslinking agent.
  • the blocked isocyanate group in the present invention is a group capable of generating an isocyanate group by heat.
  • a group obtained by reacting a blocking agent with an isocyanate group to protect the isocyanate group can be preferably exemplified.
  • 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 any skeleton having two or more isocyanate groups in one molecule may be used, and may be aliphatic, alicyclic or aromatic.
  • tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
  • 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.
  • the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to.
  • a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
  • Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
  • Examples of the lactam compound include ⁇ -caprolactam and ⁇ -butyrolactam.
  • Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
  • Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
  • Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
  • Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
  • Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
  • Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.
  • the blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available.
  • Coronate AP Stable M Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above , Manufactured by Asahi Kasei Chemicals Corporation, Death Module B 1100, BL1265 MPA / X, BL
  • a compound containing two or more methacryloyl groups or acryloyl groups in the molecule may be used as a crosslinking agent.
  • the compound containing a methacryloyl group or an acryloyl group is a compound selected from the group consisting of acrylic acid esters and methacrylic acid esters. It is preferable that the acryloyl group and the methacryloyl group are compounds having two or more, more preferably trifunctional or more in one molecule.
  • bifunctional (meth) acrylate examples include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.
  • Examples of the tri- or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, and pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
  • Preferable commercially available products are KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., NK ester series manufactured by Shin-Nakamura Chemical Co., Ltd., bifunctional A-200, A-400, A-600, A-1000, ABE-300, A- BPE-4, A-BPE-10, A-BPE-20, A-BPE-30, A-BPP-3, A-DOD, A-DCP, A-IBD-2E, A-NPG, 701A, A- B1206PE, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, BD, HD- N, NOD, IND, BPE-100, BPE-200, BPE-300, BPE-500, BPE-900, BPE-1300N, NPG, DCP, 1206PE, 701, 3 G, 9PG, tri
  • the photosensitive resin composition of the present invention may use a compound containing an oxetane group as a crosslinking agent. It is preferable that there are two or more oxetane groups in the molecule.
  • Examples of the compound having two or more oxetanyl groups in the molecule include the compounds described in paragraphs 0134 to 0145 of JP-A-2008-224970, the contents of which are incorporated herein.
  • Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX above, manufactured by Toagosei Co., Ltd. can be used.
  • the photosensitive resin composition of the present invention may contain a compound in which at least a part of the acid group is protected with an acid-decomposable group (hereinafter also referred to as “dissolution inhibitor” or “(E) compound”).
  • the compound (E) is a compound that has an acid group and at least a part of the acid group is protected by a protecting group, and the protecting group is removed by the action of the acid to increase alkali solubility. is there.
  • the compound (E) plays a role of decreasing the alkali solubility in the non-exposed area and increasing the alkali solubility in the exposed area.
  • As the acid group a carboxy group or a phenolic hydroxyl group is preferable.
  • the acid-decomposable group is not particularly limited as long as it is a group that decomposes by the action of an acid, and examples thereof include an acetal group, a ketal group, a silyl group, a silyl ether group, and a tertiary alkyl ester group. In view of the above, an acetal group is preferable.
  • the protecting group examples include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, And trimethylsilyl ether group. From the viewpoint of sensitivity, an ethoxyethyl group and a tetrahydrofuranyl group are preferred.
  • the compound (E) may be a polymer (for example, a molecular weight exceeding 5000 or even exceeding 10,000) or a low molecule (for example, 5000 or less). Is preferably 3000 or less, and more preferably 1000 or less.
  • the molecular weight is a number average molecular weight determined by polystyrene conversion.
  • 150 or more are preferred and 300 or more are more preferred.
  • a compound (E) contains either an aromatic ring, a heterocyclic ring, and an alicyclic structure from a viewpoint of a dissolution inhibitory ability improvement.
  • the compound (E) preferably has two or more acid groups protected in the molecule from the viewpoint of improving sensitivity. Moreover, it is preferable that a (E) compound contains an aromatic ring and / or a heterocyclic ring from a viewpoint of a compatibility improvement with (A) component. Moreover, it is preferable not to contain other than C, H, O, and N atom from a viewpoint of compatibility improvement with (A) component.
  • a (E) compound contains an aromatic ring and / or a heterocyclic ring from a viewpoint of a compatibility improvement with (A) component.
  • the compound (E) is preferably a compound represented by the following general formula (E-1-1).
  • Formula (E-1-1) (In the general formula (E-1-1), R represents a monovalent to hexavalent organic group having a molecular weight of 2000 or less, and R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, or an aryl group. , R 1 and R 2 are an alkyl group or an aryl group, and R 3 represents an alkyl group or an aryl group, and may combine with R 1 or R 2 to form a cyclic ether.
  • N1 represents an integer of 1 to 6.
  • R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R 1 and R 2 is an alkyl group or an aryl group.
  • an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.
  • the alkyl group may have a substituent.
  • the alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.
  • aryl group an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable.
  • the aryl group may have a substituent.
  • a phenyl group, a naphthyl group, an anthracenyl group etc. are mentioned, for example, A phenyl group is especially preferable.
  • R 3 represents an alkyl group or an aryl group, and may combine with R 1 or R 2 to form a cyclic ether.
  • the alkyl group is preferably an alkyl group having 1 to 16 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and further an alkyl group having 1 to 4 carbon atoms. preferable.
  • the alkyl group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, and a hexyl group.
  • the aryl group an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable.
  • Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group.
  • R 3 may be linked to R 1 or R 2 to form a cyclic ether.
  • the cyclic ether formed by linking to R 1 or R 2 is preferably a 3- to 6-membered cyclic ether, more preferably a 5- to 6-membered cyclic ether.
  • R 1 and R 2 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 3 is preferably bonded to an alkyl group having 1 to 4 carbon atoms, R 1 or R 2 to form a tetrahydrofuranyl group.
  • R 1 to R 3 may have a substituent.
  • substituents include an alkyl group having 1 to 6 carbon atoms and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and these substituents may further have a substituent.
  • R represents a monovalent to hexavalent organic group having a molecular weight of 2000 or less.
  • the organic group represented by R is a 1 to 6 valent organic group having a molecular weight of 2000 or less, preferably a 1 to 6 valent organic group having a molecular weight of 1500 or less, and a 1 to 6 valent organic group having a molecular weight of 1000 or less. More preferred.
  • the organic group represented by R is preferably an organic group containing an aromatic ring or a heterocyclic ring and containing no atoms other than C, H, O, and N atoms, and is an organic group containing a cyclic structure and / or a carbonyl group.
  • a group composed of a combination of an aromatic group, a cycloaliphatic group, a carbonyl group, an alkylene group, a phenylene group, and an oxygen atom is more preferable.
  • R is preferably the following organic group when the acid group is a phenolic hydroxy group.
  • a wavy line represents a bonding site with an oxygen atom
  • R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • m and n each independently represents 0 to 4 Represents an integer.
  • R is preferably the following organic group when the acid group is a carboxy group.
  • a wavy line represents a bonding site with an oxygen atom
  • R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 8 carbon atoms).
  • M and n each independently represents an integer of 0 to 4 (preferably 0).
  • the compound (E) is preferably a compound represented by the following general formula (E-1-2).
  • Formula (E-1-2) (In general formula (E-1-2), R 1 represents an n1-valent organic group, Ar represents an optionally substituted aryl group, a represents an integer of 0 or more, and n1 represents 2) (An integer greater than or equal to 1 is shown, where n1-a is an integer greater than or equal to 1.)
  • R 1 represents an n1-valent organic group, preferably a 2- to 8-valent organic group, more preferably a 2- to 6-valent organic group.
  • R 1 is preferably a hydrocarbon group having 2 to 15 carbon atoms, or a group mainly having a hydrocarbon group in which 1 to 2 oxygen atoms form an ether bond in the hydrocarbon group.
  • R 1 represents an aliphatic hydrocarbon structure (for example, a linear alkylene structure, a branched alkylene structure, a cycloalkylene structure, a norbornane structure, a norbornene structure, a norbornane skeleton, or a structure in which a norbornene skeleton and a cycloalkylene skeleton are condensed).
  • Aromatic hydrocarbon structures eg, benzene structures
  • aralkyl structures structures in which these structures are combined
  • structures in which these structures are combined through ether bonds and other tetrahydropyran structures
  • R 1 an alkylene structure, an alicyclic structure, an ether structure, an aralkyl structure, or a combination of these is particularly preferable as a basic skeleton.
  • Ar represents an optionally substituted aryl group.
  • aryl group an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable.
  • Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group.
  • a represents an integer of 0 or more, preferably an integer of 0 to 3, and more preferably 0.
  • n represents an integer of 2 or more, preferably an integer of 2 to 8, more preferably an integer of 2 to 6, and more preferably 2.
  • Na is an integer of 1 or more, preferably 1-7.
  • Ar represents an optionally substituted aryl group, and specific examples thereof include a phenyl group and a naphthyl group. Examples of the substituent include a halogen atom such as a chlorine atom; a methyl group, a tert-butyl group and the like.
  • Preferred examples include alkyl groups; alkoxy groups such as methoxy groups.
  • the compound represented by the general formula (E-1-2) preferably contains no atoms other than C, H, O, and N atoms from the viewpoint of improving compatibility with the component (A).
  • the compound (E) is a polymer, it is preferably a compound having a repeating unit represented by the following general formula (E-1-3).
  • General formula (E-1-3) (In the general formula (E-1-3), R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, or an aryl group, and one of R 1 and R 2 is an alkyl group or an aryl group.
  • R 3 represents an alkyl group or an aryl group, and may combine with R 1 or R 2 to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents 2 Represents a valent organic group.
  • R 1 and R 2 has the same meaning as R 1 and R 2 in the general formula (E-1-1), and preferred ranges are also the same.
  • R 3 has the same meaning as R 3 in formula (E-1-1), and the preferred range is also the same.
  • X represents a divalent organic group.
  • Examples of the divalent organic group represented by X include a phenylene group, a carbonyl group, and a p-phenylenecarbonyl group.
  • Preferable specific examples of the compound having a repeating unit represented by the general formula (E-1-3) include a polymer having any one of the following structural units.
  • R 4 represents a hydrogen atom or a methyl group.
  • the weight average molecular weight of the compound having a repeating unit represented by the general formula (E-1-3) is preferably 2000 to 50000, more preferably 3000 to 20000.
  • the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.
  • the other component is preferably a compound having a repeating unit represented by the following general formula (E-1-4).
  • General formula (E-1-4) (In the general formula (E-1-4), R 41 represents a hydrogen atom or a methyl group, X represents a single bond or a divalent organic group, and R 42 may have a substituent. Represents an aryl group or a hydroxyl group.)
  • X represents a single bond or a divalent organic group
  • examples of the divalent organic group represented by X include a phenylene group, a carbonyl group, a carboxyl group, and a p-phenylenecarbonyl group.
  • R 42 represents an aryl group which may have a substituent or a hydroxyl group
  • the aryl group which may have a substituent includes an aryl represented by R 1 in formula (E-1-1) It is synonymous with group, and its preferable range is also the same.
  • the aryl group may have a substituent.
  • the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a hydroxyl group, and the like, and these substituents may further have a substituent. Good.
  • Preferable specific examples of the compound having a repeating unit represented by the general formula (E-1-4) include a polymer having any one of the following structural units.
  • R 4 represents a hydrogen atom or a methyl group.
  • the compounds (1) to (3) are preferably used from the viewpoint of compatibility with the component (A). From the viewpoint, it is preferable to use the compounds (4) to (5) having an acid group.
  • the content of the compound (E) is 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the (A) polybenzoxazole precursor.
  • the content is 5 to 50 parts by mass, film physical properties and sensitivity can be improved.
  • 2 or more types of (E) compounds can be used, and when using 2 or more types, the total amount becomes the said range.
  • (E) compound can also be made into 1 mass% or less of the total solid of the composition of this invention.
  • a sensitizer, an alkoxysilane compound, a basic compound, a surfactant, and an antioxidant can be preferably added to the photosensitive resin composition of the present invention as necessary.
  • the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor.
  • Known additives such as can be added.
  • compounds described in paragraph numbers 0201 to 0224 of JP2012-8859A can be used, and the contents thereof are incorporated in the present specification.
  • the photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote the decomposition in combination with the photoacid generator.
  • the sensitizer absorbs actinic rays and enters an electronically excited state.
  • the sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur.
  • a photo-acid generator raise
  • Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.
  • Polynuclear aromatics eg, pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10-dipropyloxyanthracene
  • xanthenes Eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal
  • xanthones eg, xanthone, thioxanthone, dimethylthioxanthone, diethylthioxanthone
  • cyanines eg, thiacarbocyanine, oxacarbocyanine
  • merocyanines For example, merocyanine, carbomerocyanine), rhodocyanines, oxonols, thiazines (eg, thionine, methylene blue, to
  • polynuclear aromatics polynuclear aromatics, acridones, styryls, base styryls, and coumarins are preferable, and polynuclear aromatics are more preferable.
  • polynuclear aromatics anthracene derivatives are most preferred.
  • the content of the sensitizer is 0.001 to 100 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. It is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass. Two or more sensitizers can be used in combination. When two or more kinds of sensitizers are used, the total amount is within the above range.
  • the photosensitive resin composition of the present invention may contain an alkoxysilane compound as an adhesion improver (adhesion aid).
  • an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do.
  • the alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum.
  • the compound improves the adhesion between the insulating film and the insulating film.
  • a known silane coupling agent or the like is also effective.
  • silane coupling agents include ⁇ -glycid such as ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and ⁇ -glycidoxypropyltrimethoxysilane.
  • ⁇ -methacryloxypropyltrialkoxysilane such as xylpropyltrialkoxysilane, ⁇ -glycidoxypropyl dialkoxysilane, 3-methacryloxypropylmethyldimethoxysilane, ⁇ -methacryloxypropyl dialkoxysilane, ⁇ -chloropropyltrialkoxy Examples thereof include silane, ⁇ -mercaptopropyltrialkoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrialkoxysilane, and vinyltrialkoxysilane.
  • ⁇ -glycidoxypropyltrialkoxysilane and ⁇ -methacryloxypropyltrialkoxysilane are more preferable, ⁇ -glycidoxypropyltrialkoxysilane is more preferable, and ⁇ -glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.
  • an alkoxysilane compound A well-known thing can be used for an alkoxysilane compound, without specifically limiting to these.
  • the content of the alkoxysilane compound is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. 0.5 to 20 parts by mass is more preferable.
  • An alkoxysilane compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of alkoxysilane compounds, the total amount becomes the said range.
  • the photosensitive resin composition of the present invention may contain a basic compound.
  • the basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in paragraph numbers 0204 to 0207 of JP2011-221494A and compounds described in paragraph numbers 0141 to 0145 of JP2012-133301A. It is incorporated herein.
  • aliphatic amine examples include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like.
  • examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
  • aromatic amine examples include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
  • heterocyclic amine examples include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 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-di And azabicyclo
  • Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
  • Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
  • the basic compounds that can be used in the present invention may be used singly or in combination of two or more.
  • the content of the basic compound is 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid component in the photosensitive resin composition.
  • the amount is preferably 0.005 to 1 part by mass.
  • the total amount becomes the said range.
  • the photosensitive resin composition of the present invention preferably contains a surfactant.
  • a surfactant any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
  • examples of the surfactant used in the composition of the present invention include those described in paragraph Nos. 0201 to 0205 in JP2012-88459A, and paragraphs 0185 to 0188 in JP2011-215580A. Can be used and these descriptions are incorporated herein.
  • nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. .
  • the following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No.
  • the surfactant is measured by gel permeation chromatography using the structural unit A and the structural unit B represented by the following general formula (I-1-1) and using tetrahydrofuran (THF) as a solvent.
  • a preferred example is a copolymer having a polystyrene-reduced weight average molecular weight (Mw) of 1,000 or more and 10,000 or less.
  • R 401 and R 403 each independently represent a hydrogen atom or a methyl group
  • R 402 represents a linear alkylene group having 1 to 4 carbon atoms
  • R 404 represents hydrogen.
  • L represents an alkylene group having 3 to 6 carbon atoms
  • p and q are mass percentages representing a polymerization ratio
  • p is 10 mass% to 80 mass%.
  • the following numerical values are represented, q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.
  • L is preferably a branched alkylene group represented by the following general formula (I-1-2).
  • R 405 in formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. And an alkyl group having 2 or 3 carbon atoms is more preferred.
  • the weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
  • These surfactants can be used individually by 1 type or in mixture of 2 or more types.
  • the content of the surfactant is preferably 10 parts by mass or less with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. 0.001 to 10 parts by mass is more preferable, and 0.01 to 3 parts by mass is even more preferable.
  • Surfactant may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of surfactant, the total amount becomes the said range.
  • an acid proliferating agent can be used for the purpose of improving sensitivity.
  • the acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
  • Specific examples of such an acid proliferating agent include acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.
  • the content of the acid proliferating agent in the photosensitive composition should be 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 part and the unexposed part, it is preferably 20 to 500 parts by mass.
  • the acid proliferating agent may be used alone or in combination of two or more. When two or more kinds of acid proliferating agents are used, the total amount is within the above range.
  • the photosensitive resin composition of the present invention can contain a development accelerator.
  • a development accelerator those described in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
  • a development accelerator may be used individually by 1 type, and can also use 2 or more types together.
  • the content of the development accelerator is 0 with respect to 100 parts by mass of the total solid content of the photosensitive resin composition from the viewpoint of sensitivity and residual film ratio. Is preferably 30 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass.
  • the total amount is within the above range.
  • the photosensitive resin composition of the present invention may contain an antioxidant.
  • an antioxidant a well-known antioxidant can be contained. By containing the antioxidant, there is an advantage that coloring of the cured film can be prevented, or the film thickness reduction due to decomposition by light or heat can be reduced, and the heat-resistant transparency is excellent.
  • the antioxidant include phosphorus antioxidants, amides, hydrazides, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, saccharides, nitrites, sulfites, thiosulfates, Examples include hydroxylamine derivatives.
  • a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant are preferable, and a phenolic antioxidant is more preferable from the viewpoints of coloring the cured film by light and heat and reducing the film thickness.
  • These may be used individually by 1 type and may mix 2 or more types.
  • the combined use of a phenol-based antioxidant and a sulfur-based antioxidant is preferable.
  • Preferred commercial products 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, ADK STAB AO-50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB AO-503, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, Examples include ADK STAB PEP-36Z and ADK STAB HP-10 (above, manufactured by ADEKA Corporation).
  • the content of the antioxidant is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid components of the photosensitive resin composition.
  • the amount is preferably 0.2 to 5 parts by mass, and particularly preferably 0.5 to 4 parts by mass.
  • the total amount becomes the said range.
  • thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, nitrogen-containing compounds and thermal acid generators described in WO2011-133604A1 can be used. Is incorporated herein by reference.
  • a resin composition can be prepared by preparing a solution in which components are dissolved in a solvent in advance and then mixing them in a predetermined ratio.
  • the composition solution prepared as described above can be used after being filtered using a filter having a pore size of 0.2 ⁇ m or the like.
  • the solid content concentration of the composition of the present invention at 25 ° C. is preferably 1 to 60% by mass, more preferably 3 to 40% by mass, further preferably 5 to 30% by mass, and particularly preferably 5 to 17% by mass.
  • the viscosity at 25 ° C. of the composition of the present invention is preferably 1 to 100 mPa ⁇ s, more preferably 2 to 60 mPa ⁇ s, and most preferably 3 to 40 mPa ⁇ s.
  • the viscosity can be measured, for example, using a viscometer RE85L (rotor: 1 ° 34 ′ ⁇ R24 measurement range 0.6 to 1200 mPa ⁇ s) manufactured by Toki Sangyo Co., Ltd., with the temperature adjusted to 25 ° C. .
  • the method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
  • 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 photosensitive resin composition can be applied onto the substrate by a known coating method such as slit coating, spin coating, or inkjet coating. Of these, slit coating is preferred. Since the slit coat can be efficiently applied to a large substrate, the productivity is high. And large-sized substrate refers to a substrate area of 300000Mm 2 more 12000000Mm 2 or less.
  • the relative movement speed of the substrate and the slit die is preferably 20 to 180 mm / sec. It is also possible to combine spin coating after slit coating.
  • the coating film thickness (dry film thickness) is not particularly limited, and can be applied with a film thickness according to the application, but is usually used in the range of 0.5 to 10 ⁇ m.
  • the solvent removal step (2) the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate.
  • the heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.
  • the substrate provided with the coating film is irradiated with an actinic ray having a predetermined pattern.
  • the photoacid generator is decomposed to generate an acid. Due to the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to generate a carboxyl group or a phenolic hydroxyl group.
  • a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used, and i-line (365 nm), h-line (405 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as 436 nm), can be preferably used.
  • irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
  • the exposure amount is preferably 1 to 500 mJ / cm 2 .
  • various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, laser exposure, and immersion exposure can be used.
  • the super-resolution technique includes multiple exposure in which exposure is performed a plurality of times, a method using a phase shift mask, and an annular illumination method. By using these super-resolution techniques, it is possible to form a higher definition pattern, which is preferable.
  • 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.
  • a copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer.
  • a positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
  • the developer used in the development step preferably contains an aqueous solution of a basic compound.
  • Examples of basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and other tetraalkylammonium hydroxides: Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkylamines such as diamine; Alcoholamines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo- [5.4.0] -7-unde
  • sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
  • 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.
  • the pH of the developer is preferably 10.0 to 14.0.
  • the development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
  • a rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like.
  • a known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.
  • the obtained positive image is heated to thermally decompose the acid-decomposable group to generate a carboxyl group or a phenolic hydroxyl group, to crosslink the crosslinkable group, the crosslinking agent, and the like.
  • a cured film can be formed by promoting cyclized PBO. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 400 ° C. for a predetermined time, for example, 5 to 120 minutes on a hot plate, 30 to 360 minutes for an oven.
  • a protective film and an interlayer insulating film that are superior in heat resistance, hardness and the like can be formed.
  • the transparency can be further improved.
  • 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.
  • heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
  • post-exposure the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film.
  • the preferred exposure amount in the case of including a post-exposure step preferably 100 ⁇ 3,000mJ / cm 2, particularly preferably 100 ⁇ 500mJ / cm 2.
  • the cured film obtained from the photosensitive resin composition of the present invention can also be used as an etching resist.
  • dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.
  • the cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition.
  • the cured film of the present invention can be suitably used as an interlayer insulating film.
  • the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention mentioned above.
  • the photosensitive resin composition of the present invention With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film properties, it is useful for liquid crystal display devices and organic EL display devices.
  • the transmittance of the cured film of the present invention at a wavelength of 400 nm is preferably 85 to 100%, more preferably 90 to 100%, and still more preferably 95 to 100%.
  • the transmittance at a wavelength of 400 nm can be measured, for example, with a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.).
  • 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 protective film, a planarizing film, and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and is known in various structures.
  • the liquid crystal display device can be mentioned.
  • specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
  • the liquid crystal driving method that can be adopted by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (Optical) method. Compensated Bend) method and the like.
  • the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device.
  • the organic insulating film (115) of JP-A-2005-284291, -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. For example, it can be suitably used for a color filter protective film, a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens provided on a color filter in a solid-state imaging device, or the like.
  • the color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto.
  • the elements of the TFT 16 corresponding to are arranged.
  • Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17.
  • an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
  • the light source of the backlight is not particularly limited, and a known light source can be used.
  • the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and used as the second interlayer insulating film (48) described in Japanese Patent Application Laid-Open No. 2011-145686 and the interlayer insulating film (520) described in Japanese Patent Application Laid-Open No. 2009-258758. Can do. Further, even in a static drive type liquid crystal display device, a pattern with high designability can be displayed by applying the present invention. As an example, the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in JP-A-2001-125086.
  • the organic EL display device of the present invention includes 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-
  • spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.
  • Synthesis Example A-1 Synthesis of Resin A-1 In a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 293 g (0.8 mol) of hexafluoro-2,2-bis (3-amino- 4-Hydroxyphenyl) propane (Nippon Kayaku Co., Ltd.), 158.2 g (2.0 mol) of pyridine and 1.2 kg of N-methyl-2-pyrrolidone (NMP) were added. This was stirred at room temperature and then cooled to ⁇ 25 ° C. with a dry ice / acetone bath. To this solution, while maintaining the reaction temperature at ⁇ 20 ° C.
  • Synthesis Examples A-2 to A-14 Synthesis of Resins A-2 to 14 Resins A-2 to A-14 were synthesized in the same manner as Resin A-1.
  • the apparatus used in these syntheses, the amount of pyridine, the amount of solvent, the method for taking out the polymer, etc. are all the same apparatus and conditions as in Synthesis Example A-1.
  • all of the acid dichloride was mixed and placed on the dropping liquid side.
  • the amount of monomer used and the molecular weight of the resulting polymer are shown in the table below.
  • bis-APAF represents hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane
  • ODC represents 4,4′-oxybisbenzoyl chloride
  • IC represents isophthalic acid chloride.
  • Seb-C represents sebacic acid dichloride (manufactured by ALDRICH)
  • Adi-C represents adipic acid dichloride (manufactured by ALDRICH)
  • CHD-C represents 1,4-cyclohexanedicarboxylic acid dichloride (manufactured by Tokyo Chemical Industry 1, 4-cyclohexanedicarboxylic acid obtained by acidification by a conventional method)
  • AcCl represents acetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.).
  • a molecular weight (GPC) represents the numerical value x1000 in a table
  • the molecular weight is an Mw value measured by gel permeation chromatography in terms of polystyrene, and represents a numerical value x 1000 in the table (hereinafter the same as the molecular weight of the resin).
  • Synthesis Example B-101 Synthesis of Resin B-101 To a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube is added 150 g of the resin A-1 obtained in Synthesis Example A-1, and propylene glycol-1 -1.5 L of monomethyl ether-2-acetate (PGMEA) was added, 17.05 g (0.168 mmol) of triethylamine and 10.39 g (0.112 mol) of epichlorohydrin were added, and the mixture was stirred at room temperature for 3 hours. The reaction solution was diluted with 1.5 L of acetone, poured into 20 L of hexane that was vigorously stirred, and the precipitated white powder was collected by filtration.
  • PGMEA monomethyl ether-2-acetate
  • the polymer was dried under vacuum at 40 ° C. for 4 hours, 120 g of this polymer was dissolved in 2 L acetone, poured into 10 L of vigorously stirred water, and deionized water and water / methanol (50/50 mass ratio) ) Washed with the mixture. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin B-101.
  • Synthesis Examples B-102 to B-114 Synthesis of Resins B-102 to B-114 Resins B-102 to B-114 were synthesized in the same manner as Resin B-101. The equipment used in these syntheses, the amount of solvent, the method for taking out the polymer, etc. are all the same as in Synthesis Example B-101. The amount of monomer used and the molecular weight of the resulting polymer are shown in the table below.
  • ECH represents epichlorohydrin
  • NEt 3 represents triethylamine.
  • the molecular weight represents a numerical value x 1000 in the table.
  • the introduction rate means that the acid-decomposable group (crosslinkable group) of the OH group reacted with the total hydroxyl groups (molar amount) in the polybenzoxazole precursor before introducing the acid-decomposable group (crosslinkable group). It means molar amount (the same applies hereinafter).
  • Synthesis Example C-101 Synthesis of Resin C-101
  • Resin A-1 150 g was added to a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, and 1-methyl-2-pyrrolidone (NMP) was added.
  • NMP 1-methyl-2-pyrrolidone
  • the reaction solution was diluted with 1.5 L of acetone, poured into 20 L of hexane that was vigorously stirred, and the precipitated white powder was collected by filtration.
  • the polymer was dried under vacuum at 40 ° C. for 4 hours, 120 g of this polymer was dissolved in 2 L acetone, poured into 10 L of vigorously stirred water, and deionized water and water / methanol (50/50 mass ratio) ) Washed with the mixture. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin C-101.
  • Synthesis Examples C-102 to C-114 Synthesis of Resins C-102 to C-114 Resins C-102 to C-114 were synthesized in the same manner as Resin C-101.
  • the apparatus used in these syntheses, the amount of potassium iodide, the amount of solvent, the method for taking out the polymer, etc. are all the same conditions as in Synthesis Example C-101.
  • the amount of monomer used and the molecular weight of the resulting polymer are shown in the table below.
  • NEt 3 represents triethylamine.
  • Synthesis Example D-101 Synthesis of Resin D-101 Resin A-1 (150 g) was added to a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, and 1-methyl-2-pyrrolidone (NMP) was added. 1.5 L, triethylamine (17.05 g, 0.168 mol), intermediate D (23.22 g, 0.112 mol) and potassium iodide (33.2 g, 0.20 mol) were added, and 3 hours at room temperature. Stir. The reaction solution was diluted with 1.5 L of acetone, poured into 20 L of hexane that was vigorously stirred, and the precipitated white powder was collected by filtration.
  • NMP 1-methyl-2-pyrrolidone
  • the polymer was dried under vacuum at 40 ° C. for 4 hours, 120 g of this polymer was dissolved in 2 L acetone, poured into 10 L of vigorously stirred water, and deionized water and water / methanol (50/50 mass ratio) ) Washed with the mixture. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin D-101.
  • Synthesis Examples D-102 to D-114 Synthesis of Resins D-102 to D-114 Resins D-102 to D-114 were synthesized in the same manner as Resin D-101.
  • the apparatus used in these syntheses, the amount of potassium iodide, the amount of solvent, the method for taking out the polymer, etc. are all the same conditions as in the synthesis of Resin D-101.
  • the amount of monomer used and the molecular weight of the resulting polymer are shown in the table below.
  • NEt 3 represents triethylamine.
  • the molecular weight represents a numerical value x 1000 in the table.
  • Synthesis Example B-201a Synthesis of Resin B-201a
  • Resin B-101 100 g was added to a three-necked flask and 1.6 L of propylene glycol-1-monomethyl ether-2-acetate (PGMEA) was added.
  • PGMEA propylene glycol-1-monomethyl ether-2-acetate
  • PGMEA propylene glycol-1-monomethyl ether-2-acetate
  • 9.16 g (1.18 mmol) of camphorsulfonic acid (3 mass% PGMEA solution) and 6.84 g (0.098 mol) of 2,3-dihydrofuran were added, Stir at room temperature for 4 hours.
  • 2.99 g (2.95 mmol) of triethylamine (10 mass% PGMEA solution) was added to stop the reaction.
  • the reaction solution was diluted with 1.0 L of acetone, poured into 12 L of hexane that was vigorously stirred, and the precipitated white powder was collected by filtration.
  • the polymer was dried at 40 ° C. for 4 hours under vacuum. 80 g of this polymer was dissolved in 1.3 L of acetone, poured into 10 L of vigorously stirred water and washed with deionized water and a water / methanol (50/50 mass ratio) mixture. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin B-201a.
  • Synthesis Examples B-201b to B-214a Synthesis of Resins B-201b to B-214a Resins B-201b to D-214a were synthesized in the same manner as Resin B-201a.
  • the equipment used in these syntheses, the amount of solvent, the method for extracting the polymer, etc. are all the same equipment and conditions as in Synthesis Example B-201a.
  • the amount of monomer used and the molecular weight of the resulting polymer are shown in the table below.
  • OH group protection rate means the molar ratio% in which the acid-decomposable group has reacted with respect to the total hydroxyl groups (molar amount) in the polybenzoxazole precursor before the introduction of the acid-decomposable group and the crosslinkable group (hereinafter referred to as the following) the same).
  • DHF 2,3-dihydrofuran
  • CSA camphorsulfonic acid (3% by mass PGMEA solution)
  • 10% NEt 3 represents a 10% by mass PGMEA solution of triethylamine.
  • Synthesis Examples B-301a, C-301a, D-301a Synthesis of Resins B-301a, C-301a, D-301a For Resins B-301a, C-301a, D-301a, 2 or 3 vinyl ethers were used. Synthesis was performed in the same manner as for Resin B-201a except that dihydrofuran was changed to ethyl vinyl ether. The equipment used in these syntheses, the amount of solvent, the method for extracting the polymer, etc. are all the same equipment and conditions as in Synthesis Example B-201a. The amount of monomer used and the molecular weight of the resulting polymer are shown in the table below. In the table, EVE represents ethyl vinyl ether, 3% CSA represents camphorsulfonic acid (3% by mass PGMEA solution), and 10% NEt 3 represents triethylamine (10% by mass PGMEA solution).
  • Synthesis Example E-1 Synthesis of Resin E-1 In a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 293 g (0.8 mol) of hexafluoro-2,2-bis (3-amino- 4-Hydroxyphenyl) propane (Nippon Kayaku Co., Ltd.), 158.2 g (2.0 mol) of pyridine, and 1.2 kg of N-methyl-2-pyrrolidone (NMP) were added. This was stirred at room temperature and then cooled to ⁇ 25 ° C. with a dry ice / acetone bath. To this solution, while maintaining the reaction temperature at ⁇ 20 ° C.
  • the reaction solution is diluted with 2 L of acetone, poured into 20 L of deionized water with vigorous stirring, the precipitated white powder is recovered by filtration, and deionized water and a water / methanol (50/50 mass ratio) mixture. Washed.
  • the polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin E-1.
  • the number average molecular weight of the resin E-1 was 6.4 ⁇ 10 3 in terms of polystyrene, and the degree of dispersion was 2.2. From 1 H-NMR, it was confirmed that the introduction rate of 5-norbornene-2,3-dicarboxylic anhydride was almost quantitative.
  • Synthesis Example E-101a Synthesis of Resin E-101a To a three-necked flask, 100 g of the polymer (E-1) obtained in Synthesis Example E-1 was added, and propylene glycol-1-monomethyl ether-2-acetate (PGMEA 1.6 L) and concentrated until the content was 0.9 kg. Using a thermometer, a stirrer and a nitrogen introduction tube, 9.16 g (1.18 mmol) of camphorsulfonic acid (3 mass% PGMEA solution) and 9.07 g (0.129 mol) of 2,3-dihydrofuran were added, Stir at room temperature for 4 hours.
  • PGMEA propylene glycol-1-monomethyl ether-2-acetate
  • the number average molecular weight of Resin E-101a was 6.9 ⁇ 10 3 in terms of polystyrene, and the degree of dispersion was 2.4. From 1 H-NMR, it was confirmed that the introduction rate of acid-decomposable groups was 30 mol% with respect to all the hydroxyl groups of the raw material resin E-1.
  • Synthesis Example F-1 Synthesis of Resin F-1 To a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 150 g of the polymer (E-1) obtained in Synthesis Example E-1 was added, and propylene was added. 1.5 L of glycol-1-monomethyl ether-2-acetate (PGMEA) was added, 17.91 g (0.177 mmol) of triethylamine and 10.88 g (0.118 mol) of epichlorohydrin were added, and the mixture was stirred at room temperature for 3 hours. did.
  • PGMEA glycol-1-monomethyl ether-2-acetate
  • the reaction solution was diluted with 1.5 L of acetone, poured into 20 L of hexane that was vigorously stirred, and the precipitated white powder was collected by filtration.
  • the polymer was dried under vacuum at 40 ° C. for 4 hours, 120 g of this polymer was dissolved in 2 L acetone, poured into 10 L of vigorously stirred water, and deionized water and water / methanol (50/50 mass ratio) ) Washed with the mixture.
  • the polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin F-1.
  • the number average molecular weight of the resin F-1 was 6.9 ⁇ 10 3 in terms of polystyrene, and the degree of dispersion was 2.3. From 1 H-NMR, it was confirmed that the epoxy group introduction rate into the hydroxyl group was 19 mol%.
  • Synthesis Example F-101a Synthesis of Resin F-101a To a three-necked flask, 100 g of the polymer (F-1) obtained in Synthesis Example F-1 was added, and propylene glycol-1-monomethyl ether-2-acetate (PGMEA 1.6 L) and concentrated until the content was 0.9 kg. Using a thermometer, a stirrer, and a nitrogen introduction tube, 9.16 g (1.18 mmol) of camphorsulfonic acid (3 mass% PGMEA solution) and 8.65 g (0.123 mol) of 2,3-dihydrofuran were added, Stir at room temperature for 4 hours.
  • PGMEA propylene glycol-1-monomethyl ether-2-acetate
  • the number average molecular weight of the resin F-101a was 7.0 ⁇ 10 3 in terms of polystyrene, and the degree of dispersion was 2.4. From 1 H-NMR, it was confirmed that the introduction rate of acid-decomposable groups was 31 mol% with respect to all the hydroxyl groups of the raw material resin E-1.
  • Synthesis Example F-101b Synthesis of Resin F-101b The same operation as in the synthesis of F-101a, except that the amount of 2,3-dihydrofuran was changed to 6.58 g (0.094 mol) in the synthesis of F-101a. As a result, F101b having different introduction amounts of acid-decomposable groups was obtained. The number average molecular weight of Resin F-101b was 6.9 ⁇ 10 3 in terms of polystyrene, and the dispersity was 2.3. From 1 HNMR, it was confirmed that the introduction rate of acid-decomposable groups was 23 mol% with respect to all the hydroxyl groups of the raw material resin E-1.
  • Synthesis Example G-1 Synthesis of Resin G-1 In a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 293 g (0.8 mol) of hexafluoro-2,2-bis (3-amino- 4-Hydroxyphenyl) propane (Nippon Kayaku Co., Ltd.), 126.6 g (16 mol) of pyridine and 1.2 kg of N-methyl-2-pyrrolidone (NMP) were added. This was stirred at room temperature and then cooled to ⁇ 25 ° C. with a dry ice / acetone bath. To this solution, while maintaining the reaction temperature at ⁇ 20 ° C.
  • the reaction solution is diluted with 2 L of acetone, poured into 20 L of deionized water with vigorous stirring, the precipitated white powder is recovered by filtration, and deionized water and a water / methanol (50/50 mass ratio) mixture. Washed.
  • the polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin G-1.
  • the number average molecular weight of the resin G-1 was 6.4 ⁇ 10 3 in terms of polystyrene, and the degree of dispersion was 2.1.
  • Synthesis Example G-2 Synthesis of Resin G-2 Resin G-1 (400 g) was dissolved in PGMEA to give a 15% solution. To this, 21 g of allyl chloroformate (manufactured by Tokyo Chemical Industry) and 16 g of pyridine were added and stirred at room temperature for 3 hours. did. The obtained reaction solution was washed with water, 200 g of toluene was added, and the solvent was distilled off at 50 ° C. to remove water in the system by azeotropic dehydration to obtain a solution having a solid content concentration of 15%. The water content in the system was 0.01%.
  • the white powder was collected by filtration and washed with deionized water and a water / methanol (50/50 weight ratio) mixture.
  • the polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin G-2.
  • the number average molecular weight of the resin G-2 was 6.6 ⁇ 10 3 in terms of polystyrene, and the degree of dispersion was 2.2. From 1 H-NMR, it was confirmed that the introduction rate of allyl chloroformate was quantitative and that the hydroxyl acetal group protection rate of the hydroxyl group was 21 mol%.
  • Resin M-1 Structure shown below (Polymer (A-1) described in paragraphs 0212 to 0217 of JP2011-209681A)
  • Photoacid generator B-1 Structure shown below (PAG-103, manufactured by BASF)
  • Ts represents a tosyl group.
  • Solvent MEDG Diethylene glycol ethyl methyl ether, (Hisolv EDM, manufactured by Toho Chemical Industry Co., Ltd.)
  • PGMEA Propylene glycol monomethyl ether acetate (Showa Denko)
  • GBL Gamma butyrolactone (Mitsubishi Chemical Corporation)
  • Adhesion aid KBM-403 ⁇ -glycidoxypropyltrimethoxysilane (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Surfactant W-1 Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC)
  • Sensitizer DBA 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Co., Ltd.)
  • Compound N-1 having a crosslinkable group epoxy compound having the following structure (oxetane additive (O-3) described in paragraph 0273 of JP-A-2008-224970)
  • Crude B-1-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-1-2A.
  • B-1-2A (1.7 g) and p-xylene (6 mL) were mixed, 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated at 140 ° C. for 2 hours. .
  • water and ethyl acetate were added to the reaction mixture and the phases were separated.
  • Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thickness (manufactured by Corning)) that has been surface-treated with hexamethyldisilazane vapor for 1 minute, and then heated at 90 ° C. for 120 seconds. Pre-baking was performed to volatilize the solvent, and a photosensitive resin composition layer having a thickness of 3.0 ⁇ m was formed. Next, the obtained photosensitive resin composition layer was exposed to a 6.0 ⁇ m hole pattern using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Then, it heated on a 90 degreeC and 90 second hotplate.
  • a PLA-501F exposure machine extra-high pressure mercury lamp
  • Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thickness (manufactured by Corning)) that has been surface-treated with hexamethyldisilazane vapor for 1 minute, and then heated at 90 ° C. for 120 seconds. Pre-baking was performed to volatilize the solvent, and a photosensitive resin composition layer having a thickness of 3.0 ⁇ m was formed. Next, the obtained photosensitive resin composition layer was baked at 300 ° C. for 2 hours under a nitrogen stream, and the obtained cured film was evaluated with a pencil hardness tester. The higher the hardness, the more preferable, and A to C are practical ranges.
  • Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thickness (manufactured by Corning)) that has been surface-treated with hexamethyldisilazane vapor for 1 minute, and then heated at 90 ° C. for 120 seconds. Pre-baking was performed to volatilize the solvent, and a photosensitive resin composition layer having a thickness of 3.0 ⁇ m was formed. Next, the obtained photosensitive resin composition layer was baked at 300 ° C. for 2 hours under a nitrogen stream, and the obtained cured film was exposed to 80 ° C. and 80% for 24 hours, and a film at 1 MHz before and after the test.
  • the dielectric constant was measured and evaluated according to the following criteria (A is a practical range).
  • A Dielectric constant variation before and after exposure is less than 30%, and dielectric constant after exposure is less than 3.3
  • B Dielectric constant variation before and after exposure is less than 30%, but dielectric constant after exposure is observed to be 3.3 or higher
  • C Dielectric constant variation before and after exposure is 30% or more, or 3.3 or more is observed in either dielectric constant before and after exposure.
  • Examples 1 to 32 using the photosensitive resin composition of the present invention were all good in sensitivity, transmittance, pencil hardness, and electrical properties after high humidity treatment.
  • Comparative Examples 1 to 13 that do not satisfy the requirements of the present invention were found to be inferior to the Examples in terms of sensitivity, transmittance, pencil hardness, and electrical properties after high humidity treatment. Specifically, it was found that when there is no crosslinkable group in the main chain as in Comparative Examples 1 to 7 and 13, the pencil hardness and the electrical properties after high humidity treatment are significantly inferior to those of Examples 1 to 32. .
  • the photosensitive resin compositions of Examples 1 to 32 were subjected to pattern formation in the same manner as the sensitivity evaluation except that the exposure was changed as follows in the sensitivity evaluation. That is, a predetermined photomask was set through a 150 ⁇ m interval from the coating film, and a laser having a wavelength of 355 nm was irradiated.
  • the laser device used was “AEGIS” manufactured by Buoy Technology Co., Ltd. (wavelength 355 nm, pulse width 6 nsec). In any of the examples, it was found that a pattern could be formed even by 355 nm laser exposure as in the case of an ultrahigh pressure mercury lamp.
  • UV-LED exposure Further, the photosensitive resin compositions of Examples 1 to 32 were evaluated in the same manner as the sensitivity evaluation (without PEB) except that the exposure was changed to a UV-LED light source exposure machine. It was found that pattern formation was possible.
  • Example 100 An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 1). 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, after forming a contact hole in the insulating film 3, a wiring 2 (height of 1.0 ⁇ m) connected to the TFT 1 through the contact hole was formed on the insulating film 3.
  • TFT thin film transistor
  • a planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded.
  • the planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 2 on a substrate, pre-baking on a hot plate (90 ° C. ⁇ 2 minutes), and then applying high pressure from above the mask.
  • a mercury lamp is used to irradiate i-line (365 nm) with an exposure amount corresponding to the sensitivity measured by sensitivity evaluation, heated on an 80 ° C. hot plate for 60 seconds, and then developed with an aqueous alkaline solution to form a pattern.
  • a heat treatment was performed at 60 ° C. for 60 minutes.
  • the applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking.
  • the average level difference of the wiring 2 was 500 nm
  • 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 insulating film 8 was formed using the photosensitive resin composition of Example 2 by the same method as described above.
  • 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.
  • Example 101 An organic EL display device was produced in the same manner as in Example 100 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 6. The obtained organic EL display device showed good display characteristics and was found to be a highly reliable organic EL display device.
  • Example 102 An organic EL display device was produced in the same manner as in Example 100 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 9. The obtained organic EL display device showed good display characteristics and was found to be a highly reliable organic EL display device.
  • Example 103 An organic EL display device was produced in the same manner as in Example 100 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 12. The obtained organic EL display device showed good display characteristics and was found to be a highly reliable organic EL display device.
  • Example 104 In the active matrix liquid crystal display device described in FIG. 1 and FIG. 2 of Japanese Patent No. 332003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 104 was obtained. That is, using the photosensitive resin composition of Example 2, the cured film 17 was formed as an interlayer insulating film by the same method as the method for forming the planarizing film 4 of the organic EL display device in Example 100.
  • 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 105 A liquid crystal display device was produced in the same manner as in Example 104 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 14. The obtained liquid crystal display device showed good display characteristics and was found to be a highly reliable liquid crystal display device.
  • Example 106 A liquid crystal display device was produced in the same manner as in Example 104 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 24. The obtained liquid crystal display device showed good display characteristics and was found to be a highly reliable liquid crystal display device.
  • Example 107 A liquid crystal display device was produced in the same manner as in Example 104 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 28. The obtained liquid crystal display device showed good display characteristics and was found to be a highly reliable liquid crystal display device.
  • 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 are: a photosensitive resin composition which has excellent sensitivity, transmittance, pencil hardness and electrical characteristics after a high-humidity treatment; a method for producing a cured film; a cured film; a liquid crystal display device; and an organic EL display device. A photosensitive resin composition which contains (A) a polybenzoxazole precursor containing a repeating unit represented by general formula (1) and satisfying the requirement (1) and/or (2) below, (B) a photoacid generator and (C) a solvent. (1) The polybenzoxazole precursor contains (a-1) a repeating unit which is represented by general formula (1), and wherein R1 and/or R2 is an acid-decomposable group, and (a-2) a repeating unit which is represented by general formula (1), and wherein R1 and/or R2 is a crosslinkable group. (2) The polybenzoxazole precursor contains (a-3) a repeating unit which is represented by general formula (1), and wherein one of R1 and R2 contains an acid-decomposable group and the other is a crosslinkable group.

Description

感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置および有機ＥＬ表示装置Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, and organic EL display device
　本発明は、感光性樹脂組成物（以下、単に、「本発明の組成物」ということがある）に関する。また、上記感光性樹脂組成物を用いた硬化膜の製造方法、感光性樹脂組成物を硬化してなる硬化膜、上記硬化膜を用いた各種画像表示装置に関する。
　さらに詳しくは、液晶表示装置、有機ＥＬ（有機エレクトロルミネッセンス）表示装置、集積回路素子、固体撮像素子などの電子部品の平坦化膜、保護膜や層間絶縁膜の形成に好適な、感光性樹脂組成物およびそれを用いた硬化膜の製造方法に関する。 The present invention relates to a photosensitive resin composition (hereinafter sometimes simply referred to as “the composition of the present invention”). Moreover, it is related with the manufacturing method of the cured film using the said photosensitive resin composition, the cured film formed by hardening | curing the photosensitive resin composition, and various image display apparatuses using the said cured film.
More specifically, a photosensitive resin composition suitable for forming a flattening film, a protective film and an interlayer insulating film of an electronic component such as a liquid crystal display device, an organic EL (organic electroluminescence) display device, an integrated circuit element, and a solid-state imaging element. The present invention relates to an article and a method for producing a cured film using the article.
　有機ＥＬ表示装置や、液晶表示装置などには、パターン形成された層間絶縁膜が設けられている。この層間絶縁膜の形成には、必要とするパターン形状を得るための工程数が少なく、しかも十分な平坦性が得られるといったことから、感光性樹脂組成物が広く使用されている。 Organic EL display devices, liquid crystal display devices, and the like are provided with a patterned interlayer insulating film. In forming the interlayer insulating film, photosensitive resin compositions are widely used because the number of steps for obtaining a required pattern shape is small and sufficient flatness is obtained.
　上記表示装置における層間絶縁膜用感光性樹脂組成物や層間絶縁膜には、高感度、高解像性、高透明性、耐溶剤性といった性能が必要とされる。代表的な材料として、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、２に記載のものが知られている。 The photosensitive resin composition for interlayer insulating films and interlayer insulating films in the display device are required to have high sensitivity, high resolution, high transparency, and solvent resistance. As a typical material, an attempt has been made to use an acrylic resin as a film forming component. For example, those described in Patent Documents 1 and 2 are known.
　近年、製造の効率化や表示装置の高性能化のために、従来よりも高い温度（例えば３００℃程度）での熱処理や製膜を行う試みがなされている。 In recent years, attempts have been made to perform heat treatment and film formation at a higher temperature (eg, about 300 ° C.) than in the past in order to increase production efficiency and display device performance.
　アクリル樹脂よりも耐熱性の高い材料としてポリベンゾオキサゾール（ＰＢＯ）が知られている。ＰＢＯの前駆体を用いて感光性樹脂組成物を調製し、各種微細パターンを形成する試みが行われている（特許文献３～５）。 Polybenzoxazole (PBO) is known as a material having higher heat resistance than acrylic resin. Attempts have been made to prepare photosensitive resin compositions using PBO precursors and form various fine patterns (Patent Documents 3 to 5).
特開２０１１－２０９６８１号公報JP 2011-209681 A 特開２０１１－２２１４７１号公報JP 2011-221471 A 特開２００８－２２４９７０号公報JP 2008-224970 A 特表２０１１－５１２５５２号公報Special table 2011-512552 gazette 特開２００４－１７０６１１号公報JP 2004-170611 A
　しかしながら、特許文献３～５のような従来の感光性組成物は、アクリル樹脂と比較して引張強度は強いが、硬化膜の硬度が低く、鉛筆硬度試験などの耐傷性試験において課題があった。特に、特許文献３では、ポリベンゾオキサゾール前駆体の末端に架橋性基を付与することで破断伸びが向上することが示されているが、硬度に劣るという問題があった。 However, conventional photosensitive compositions such as Patent Documents 3 to 5 have higher tensile strength than acrylic resins, but the hardness of the cured film is low, and there are problems in scratch resistance tests such as pencil hardness tests. . In particular, Patent Document 3 shows that the elongation at break is improved by adding a crosslinkable group to the terminal of the polybenzoxazole precursor, but there is a problem that the hardness is inferior.
　本発明は、上記問題を解決するためになされたものであり、感度、透過率、鉛筆硬度、および高湿処理後の電気特性に優れる感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置および有機ＥＬ表示装置を提供することを目的とする。 The present invention has been made to solve the above problems, and is a photosensitive resin composition excellent in sensitivity, transmittance, pencil hardness, and electrical properties after high-humidity treatment, a method for producing a cured film, a cured film, An object is to provide a liquid crystal display device and an organic EL display device.
　かかる状況のもと、本発明者が鋭意検討を行った結果、酸分解性基および架橋性基を有するポリベンゾオキサゾール前駆体を含有する樹脂組成物を用いることで上記課題を達成することを見出し、本発明を完成させるに至った。
　具体的には、以下の解決手段＜１＞により、好ましくは、＜２＞～＜１３＞により、上記課題は解決された。
＜１＞（Ａ）一般式（１）で表される繰り返し単位を含み、下記（１）および／または（２）を満たす、ポリベンゾオキサゾール前駆体、
（Ｂ）光酸発生剤、および
（Ｃ）溶剤
を含む、感光性樹脂組成物；
（１）（ａ－１）一般式（１）で表される繰り返し単位であって、Ｒ1およびＲ2の少なくとも一方が酸分解性基である繰り返し単位、および、（ａ－２）一般式（１）で表される繰り返し単位であって、Ｒ1およびＲ2の少なくとも一方が架橋性基である繰り返し単位を含む；
（２）（ａ－３）一般式（１）で表される繰り返し単位であって、Ｒ1およびＲ2の一方が、酸分解性基を含み、他方が架橋性基である繰り返し単位を含む。
一般式（１）
Figure JPOXMLDOC01-appb-C000004
 （一般式（１）中、Ｘは４価の有機基を表し、Ｙは２価の有機基を表す。Ｒ1およびＲ2はそれぞれ独立に水素原子、架橋性基、アルキル基、酸分解性基、または、－ＣＯＲｃを表す。Ｒｃは、アルキル基またはアリール基を表す。）
＜２＞（Ａ）ポリベンゾオキサゾール前駆体の末端に、架橋性基を含む、＜１＞に記載の感光性樹脂組成物。
＜３＞（Ａ）ポリベンゾオキサゾール前駆体の末端が、一般式（Ｘ）で表される基である、＜１＞に記載の感光性樹脂組成物。
一般式（Ｘ）
Figure JPOXMLDOC01-appb-C000005
 （一般式（Ｘ）中、Ｚは単結合、炭素原子または硫黄原子を表し、Ｒ11は１価の有機基を表す。ｎは０または１を表し、Ｚが単結合の場合、ａは０であり、Ｚが炭素原子の場合、ａは１であり、Ｚが硫黄原子の場合、ａは２である。ｎが０の場合、２つのＲ11は、互いに結合し環を形成していてもよい。）
＜４＞（Ａ）ポリベンゾオキサゾール前駆体が、ｍ個の一般式（１）で表される繰り返し単位とｎ個の一般式（３）で表される繰り返し単位を含み、ｍは３～１０００を表し、ｎは０～１０００を表し、ｍ＋ｎは３～１０００である、＜１＞～＜３＞のいずれかに記載の感光性樹脂組成物。
一般式（３）
Figure JPOXMLDOC01-appb-C000006
 （一般式（３）中、Ｙ1は、それぞれ独立にアリーレン基、２価の環状脂肪族基、２価の複素環基、または、これらと、－ＣＨ2－、酸素原子、硫黄原子、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、および－Ｃ（ＣＦ3）2－の少なくとも１種との組み合わせからなる基を表し、Ｘ2は、アリーレン基、２価の複素環基、２価の環状脂肪族基、または、これらと、－ＣＨ2－、酸素原子、硫黄原子、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、および－Ｃ（ＣＦ3）2－の少なくとも１種との組み合わせからなる基を表す。）
＜５＞架橋性基が、エポキシ基、オキセタニル基、炭素炭素不飽和結合基およびブロックイソシアネート基から選択される、＜１＞～＜４＞のいずれかに記載の感光性樹脂組成物。
＜６＞酸分解性基が、酸の作用により脱離する基である、＜１＞～＜５＞のいずれかに記載の感光性樹脂組成物；ただし、Ｒ5は、それぞれ独立に水素原子、または炭素数１～４のアルキル基を表し、Ｒ4は、酸の作用により脱離する基を表す。
＜７＞酸の作用により脱離する基が、ビニルエーテル系の置換基である、＜６＞に記載の感光性樹脂組成物。
＜８＞酸の作用により脱離する基が、アルコキシカルボニル基、アルコキシアルキル基、アルキルシリル基、アセタールを構成する基、またはケタールを構成する基である、＜６＞または＜７＞に記載の感光性樹脂組成物。
＜９＞（１）＜１＞～＜８＞のいずれかに記載の感光性樹脂組成物を基板の少なくとも一方の面に塗布する工程、
（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、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、
を含む硬化膜の製造方法。
＜１０＞（４）現像する工程後、（５）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、＜９＞に記載の硬化膜の製造方法。
＜１１＞＜１＞～＜８＞のいずれかに記載の感光性樹脂組成物を硬化してなる硬化膜または＜９＞または＜１０＞に記載の方法により形成された硬化膜。
＜１２＞層間絶縁膜である、＜１１＞に記載の硬化膜。
＜１３＞＜１１＞または＜１２＞に記載の硬化膜を有する液晶表示装置または有機ＥＬ表示装置。 Under such circumstances, as a result of intensive studies by the present inventors, it has been found that the above-mentioned problems can be achieved by using a resin composition containing a polybenzoxazole precursor having an acid-decomposable group and a crosslinkable group. The present invention has been completed.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <13>.
<1> (A) a polybenzoxazole precursor containing the repeating unit represented by the general formula (1) and satisfying the following (1) and / or (2):
A photosensitive resin composition comprising (B) a photoacid generator and (C) a solvent;
(1) (a-1) a repeating unit represented by general formula (1), wherein at least one of R 1 and R 2 is an acid-decomposable group, and (a-2) general formula A repeating unit represented by (1), wherein at least one of R 1 and R 2 is a crosslinkable group;
(2) (a-3) A repeating unit represented by the general formula (1), wherein one of R 1 and R 2 includes an acid-decomposable group and the other includes a repeating unit that is a crosslinkable group. .
General formula (1)
Figure JPOXMLDOC01-appb-C000004
 (In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group. R 1 and R 2 are each independently a hydrogen atom, a crosslinkable group, an alkyl group, acid-decomposable. Represents a group or —CORc, where Rc represents an alkyl group or an aryl group.)
<2> (A) The photosensitive resin composition as described in <1> which contains a crosslinkable group at the terminal of the polybenzoxazole precursor.
<3> (A) The photosensitive resin composition as described in <1> whose terminal of a polybenzoxazole precursor is group represented by general formula (X).
Formula (X)
Figure JPOXMLDOC01-appb-C000005
 (In the general formula (X), Z represents a single bond, a carbon atom or a sulfur atom, R 11 represents a monovalent organic group. N represents 0 or 1, and when Z is a single bond, a is 0. When Z is a carbon atom, a is 1, and when Z is a sulfur atom, a is 2. When n is 0, two R 11 are bonded to each other to form a ring. May be good.)
<4> (A) The polybenzoxazole precursor includes m repeating units represented by the general formula (1) and n repeating units represented by the general formula (3), and m is 3 to 1000 The photosensitive resin composition according to any one of <1> to <3>, wherein n represents 0 to 1000, and m + n is 3 to 1000.
General formula (3)
Figure JPOXMLDOC01-appb-C000006
 (In General Formula (3), Y 1 is independently an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or these, —CH 2 —, an oxygen atom, a sulfur atom, — Represents a group composed of a combination with at least one of SO 2 —, —CO—, —NHCO—, and —C (CF 3 ) 2 —, and X 2 represents an arylene group, a divalent heterocyclic group, a divalent group, Or a cyclic aliphatic group of the above, or at least one of —CH 2 —, oxygen atom, sulfur atom, —SO 2 —, —CO—, —NHCO—, and —C (CF 3 ) 2 —. Represents a group consisting of a combination.)
<5> The photosensitive resin composition according to any one of <1> to <4>, wherein the crosslinkable group is selected from an epoxy group, an oxetanyl group, a carbon-carbon unsaturated bond group, and a blocked isocyanate group.
<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the acid-decomposable group is a group capable of leaving by the action of an acid; provided that each R 5 is independently a hydrogen atom Or an alkyl group having 1 to 4 carbon atoms, and R 4 represents a group capable of leaving by the action of an acid.
<7> The photosensitive resin composition according to <6>, wherein the group capable of leaving by the action of an acid is a vinyl ether-based substituent.
<8> The group capable of leaving by the action of an acid is an alkoxycarbonyl group, an alkoxyalkyl group, an alkylsilyl group, a group constituting an acetal, or a group constituting a ketal, described in <6> or <7> Photosensitive resin composition.
<9> (1) A step of applying the photosensitive resin composition according to any one of <1> to <8> to at least one surface of 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 rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and (5) a post-baking step of thermosetting the developed photosensitive resin composition,
The manufacturing method of the cured film containing this.
<10> The method for producing a cured film according to <9>, including a step of exposing the entire surface of the developed photosensitive resin composition after the step of (4) developing and before the step of (5) post-baking.
<11> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <8> or a cured film formed by the method according to <9> or <10>.
<12> The cured film according to <11>, which is an interlayer insulating film.
<13> A liquid crystal display device or an organic EL display device having the cured film according to <11> or <12>.
　本発明によれば、感度、透過率、鉛筆硬度、および高湿処理後の電気特性に優れる感光性樹脂組成物、硬化膜の製造方法、硬化膜、液晶表示装置および有機ＥＬ表示装置を提供可能となった。 According to the present invention, it is possible to provide a photosensitive resin composition excellent in sensitivity, transmittance, pencil hardness, and electrical characteristics after high-humidity treatment, a method for producing a cured film, a cured film, a liquid crystal display device, and an organic EL display device It became.
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ている。1 is a conceptual diagram of a configuration of an example of a liquid crystal display device. 1 is a schematic cross-sectional view of an active matrix substrate in a liquid crystal display device. 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ている。1 shows a conceptual diagram of a configuration of an example of an organic EL display device. 1 is a schematic cross-sectional view of a substrate in a bottom emission type organic EL display device.
　以下において、本発明の内容について詳細に説明する。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. 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。
　さらに、（メタ）アクリル酸とは、アクリル酸および／またはメタクリル酸を意味する。
　本発明における固形分濃度とは、２５℃における固形分の濃度をいう。
本　明細書において、重量平均分子量および数平均分子量は、ＧＰＣ測定によるポリスチレン換算値として定義される。本明細書において、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８２２０（東ソー（株）製）を用い、カラムとしてＴＳＫｇｅｌ Ｓｕｐｅｒ　ＡＷＭ―Ｈ（東ソー（株）製、６．０ｍｍＩＤ×１５．０ｃｍを、溶離液として１０ｍｍｏｌ／Ｌ　リチウムブロミドＮＭＰ(Ｎ－メチルピロリジノン)溶液を用いることによって求めることができる。 In addition, in the description of group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what has a substituent with what does not have 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).
Furthermore, (meth) acrylic acid means acrylic acid and / or methacrylic acid.
The solid content concentration in the present invention refers to the solid content concentration at 25 ° C.
In this specification, a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value by GPC measurement. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and TSKgel Super AWM-H (manufactured by Tosoh Corporation, 6) as a column. 0.0 mm ID × 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as the eluent.
感光性樹脂組成物
　本発明の感光性樹脂組成物は、（Ａ）一般式（１）で表される繰り返し単位を含み、下記（１）および／または（２）を満たす、ポリベンゾオキサゾール前駆体、（Ｂ）光酸発生剤、および（Ｃ）溶剤を含む。
Figure JPOXMLDOC01-appb-C000007
 （一般式（１）中、Ｘは４価の有機基を表し、Ｙは２価の有機基を表す。Ｒ1およびＲ2はそれぞれ独立に水素原子、架橋性基、アルキル基、酸分解性基、または、－ＣＯＲｃを表す。Ｒｃは、アルキル基またはアリール基を表す。）
（１）（ａ－１）一般式（１）で表される繰り返し単位であって、Ｒ1およびＲ2の少なくとも一方が酸分解性基である繰り返し単位、および、（ａ－２）一般式（１）で表される繰り返し単位であって、Ｒ1およびＲ2の少なくとも一方が架橋性基である繰り返し単位を含む；
（２）（ａ－３）一般式（１）で表される繰り返し単位であって、Ｒ1およびＲ2の一方が、酸分解性基を含み、他方が架橋性基である繰り返し単位を含む。 Photosensitive resin composition The photosensitive resin composition of the present invention comprises (A) a polybenzoxazole precursor containing a repeating unit represented by the general formula (1) and satisfying the following (1) and / or (2): , (B) a photoacid generator, and (C) a solvent.
Figure JPOXMLDOC01-appb-C000007
 (In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group. R 1 and R 2 are each independently a hydrogen atom, a crosslinkable group, an alkyl group, acid-decomposable. Represents a group or —CORc, where Rc represents an alkyl group or an aryl group.)
(1) (a-1) a repeating unit represented by general formula (1), wherein at least one of R 1 and R 2 is an acid-decomposable group, and (a-2) general formula A repeating unit represented by (1), wherein at least one of R 1 and R 2 is a crosslinkable group;
(2) (a-3) A repeating unit represented by the general formula (1), wherein one of R 1 and R 2 includes an acid-decomposable group and the other includes a repeating unit that is a crosslinkable group. .
　特許文献３（特開２００８－２２４９７０号公報）では、ポリベンゾオキサゾール前駆体の末端に架橋性基を付与している。このような構成とすることにより、破断伸び（引例の実施例確認）が向上するが、鉛筆硬度に劣ってしまう。特許文献３では、また、破断伸びには耐えられるが、大きい力に耐えられない傾向にある。
　また、アクリル樹脂を架橋性基で結合させることも知られているが、高湿度処理後の電気特性が劣るという問題がある。
　本発明では、ポリベンゾオキサゾール前駆体を用い、かつ、主鎖に架橋性基を付与することにより、高い鉛筆硬度と高湿度処理後の電気特性を達成した。特に、本発明では、多少の力では変形しない、鉛筆硬度が高いものが達成できた点で意義がある。 In Patent Document 3 (Japanese Patent Laid-Open No. 2008-224970), a crosslinkable group is added to the terminal of the polybenzoxazole precursor. By adopting such a configuration, the elongation at break (confirmation of examples in the reference) is improved, but the pencil hardness is inferior. In Patent Document 3, it can withstand breaking elongation, but tends not to withstand a large force.
In addition, it is also known to bond an acrylic resin with a crosslinkable group, but there is a problem that electrical properties after high humidity treatment are inferior.
In the present invention, by using a polybenzoxazole precursor and adding a crosslinkable group to the main chain, high pencil hardness and electrical properties after high humidity treatment are achieved. In particular, the present invention is significant in that a high pencil hardness that does not deform with some force can be achieved.
　本発明の感光性樹脂組成物は、化学増幅型ポジ型感光性樹脂組成物として好ましく用いられる。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 is preferably used as a chemically amplified positive photosensitive resin composition. Hereinafter, the composition of the present invention will be described in detail.
＜（Ａ）下記一般式（１）で表される繰り返し単位を含むポリベンゾオキサゾール前駆体＞
　本発明の組成物は、（Ａ）一般式（１）で表される繰り返し単位を有するポリベンゾオキサゾール前駆体（以下、単に、「（Ａ）ポリベンゾオキサゾール前駆体」、「（Ａ）成分」ということがある）を含有する。本発明で用いる（Ａ）ポリベンゾオキサゾール前駆体は、さらに、末端に架橋性基を有していることが好ましい。末端は、片方の末端でもよいが、両方の末端に架橋性基を有していることがより好ましい。なお、本発明において、ポリベンゾオキサゾール前駆体の末端とは、ポリベンゾオキサゾール前駆体の主鎖末端を意味する。
　一般式（１）で表される繰り返し単位は１種類のみ含んでいても良いし、２種類以上含んでいても良い。（Ａ）ポリベンゾオキサゾール前駆体は、全繰り返し単位に対して、一般式（１）で表される繰り返し単位を７０モル％以上含有していることが好ましく、より好ましくは８０モル％以上、最も好ましくは９０モル％以上である。
　（Ａ）ポリベンゾオキサゾール前駆体は、全繰り返し単位に対して、少なくとも酸分解性基を含む繰り返し単位を６０～３モル％の割合で含むことが好ましく、３０～５モル％の割合で含むことがより好ましい。
　（Ａ）ポリベンゾオキサゾール前駆体は、全繰り返し単位に対して、少なくとも架橋性基を含む繰り返し単位を４０～１モル％の割合で含むことが好ましく、３０～５モル％の割合で含むことがより好ましい。
　（Ａ）架橋性基を含むポリベンゾオキサゾール前駆体は、特に、上記割合の酸分解性基を含む繰り返し単位を含み、上記割合の架橋性基を含む繰り返し単位を含み、さらに、末端に架橋性基を含むことが好ましい。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。尚、酸分解性基と架橋性基は、同じ繰り返し単位に含まれていても良いことは言うまでもない。
　具体的には、一般式（１）で表される繰り返し単位は、（ａ－１）一般式（１）で表される繰り返し単位であって、Ｒ1およびＲ2の少なくとも一方が酸分解性基である繰り返し単位（酸分解性基を含む繰り返し単位）、および（ａ－２）一般式（１）で表される繰り返し単位であって、Ｒ1およびＲ2の少なくとも一方が架橋性基である繰り返し単位（架橋性基を含む繰り返し単位）を含んでいてもよいし、（ａ－３）酸分解性基と架橋性基を含む繰り返し単位を含んでいても良い。以下これらの詳細について説明する。 <(A) Polybenzoxazole precursor containing a repeating unit represented by the following general formula (1)>
The composition of the present invention comprises (A) a polybenzoxazole precursor having a repeating unit represented by the general formula (1) (hereinafter simply referred to as “(A) polybenzoxazole precursor”, “component (A)”. Sometimes). The (A) polybenzoxazole precursor used in the present invention preferably further has a crosslinkable group at the terminal. The terminal may be one terminal, but more preferably has a crosslinkable group at both terminals. In the present invention, the terminal of the polybenzoxazole precursor means the main chain terminal of the polybenzoxazole precursor.
The repeating unit represented by the general formula (1) may contain only one type or two or more types. (A) The polybenzoxazole precursor preferably contains 70 mol% or more, more preferably 80 mol% or more of the repeating unit represented by the general formula (1) with respect to all repeating units. Preferably it is 90 mol% or more.
(A) The polybenzoxazole precursor preferably contains at least 60 to 3 mol% of repeating units containing an acid-decomposable group, and preferably contains 30 to 5 mol% of all repeating units. Is more preferable.
The polybenzoxazole precursor (A) preferably contains at least 40 to 1 mol% of repeating units containing a crosslinkable group, and preferably contains 30 to 5 mol% of all repeating units. More preferred.
(A) The polybenzoxazole precursor containing a crosslinkable group contains, in particular, a repeating unit containing the above-mentioned proportion of an acid-decomposable group, a repeating unit containing the above-mentioned proportion of the crosslinkable group, and further has a crosslinking property at the end. Preferably it contains a group. By adopting such a configuration, the effect of the present invention is more effectively exhibited. Needless to say, the acid-decomposable group and the crosslinkable group may be contained in the same repeating unit.
Specifically, the repeating unit represented by the general formula (1) is (a-1) the repeating unit represented by the general formula (1), wherein at least one of R 1 and R 2 is acid-decomposable. A repeating unit (a repeating unit containing an acid-decomposable group) as a group, and (a-2) a repeating unit represented by the general formula (1), wherein at least one of R 1 and R 2 is a crosslinkable group A certain repeating unit (a repeating unit including a crosslinkable group) may be included, or (a-3) a repeating unit including an acid-decomposable group and a crosslinkable group may be included. These details will be described below.
＜＜（ａ－１）酸分解性基を含む繰り返し単位＞＞
（Ａ）ポリベンゾオキサゾール前駆体は、（ａ－１）酸分解性基を含む繰り返し単位を含んでいてもよい。酸分解性基を含む繰り返し単位は下記一般式（１－１）で表される。一般式（１）で表される繰り返し単位は１種類のみ含んでいても良いし、２種類以上含んでいても良い。 << (a-1) Repeating unit containing acid-decomposable group >>
(A) The polybenzoxazole precursor may contain (a-1) a repeating unit containing an acid-decomposable group. The repeating unit containing an acid-decomposable group is represented by the following general formula (1-1). The repeating unit represented by the general formula (1) may contain only one type or two or more types.
一般式（１－１）
Figure JPOXMLDOC01-appb-C000008
 （一般式（１－１）中、Ｘは４価の有機基を表し、Ｙは２価の有機基を表す。Ｒ1およびＲ2はそれぞれ独立に水素原子、アルキル基、酸分解性基、または、－ＣＯＲｃを表す。Ｒｃは、アルキル基またはアリール基を表す。Ｒ1またはＲ2の少なくとも一方が酸分解性基である。） General formula (1-1)
Figure JPOXMLDOC01-appb-C000008
 (In the general formula (1-1), X represents a tetravalent organic group and Y represents a divalent organic group. R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, an acid-decomposable group, Or represents —CORc, where Rc represents an alkyl group or an aryl group, and at least one of R 1 and R 2 is an acid-decomposable group.
　Ｘは、４価の有機基を表す。Ｘが表わす４価の有機基としては特に制限はないが、環状構造を少なくとも１つ以上有することが好ましく、環状構造を１～２つ有することがより好ましい。環状構造は、芳香族環、複素環、および脂肪族環のいずれであってもよく、芳香族環および／または複素環を含むことが好ましく、芳香族環を含むことがより好ましい。このような環状構造とすることにより、本発明の効果がより効果的に発揮される。
　芳香族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環などが挙げられる。複素環としては、フラン環、チオフェン環、ピロール環、ピロリン環、ピロリジン環、オキサゾール環、イソオキサゾール環、チアゾール環、イソチアゾール環、イミダゾール環、イミダゾリン環、イミダゾリジン環、ピラゾール環、ピラゾリン環、ピラゾリジン環、トリアゾール環、フラザン環、テトラゾール環、ピラン環、チイン環、ピリジン環、ピペリジン環、オキサジン環、モルホリン環、チアジン環、ピリダジン環、ピリミジン環、ピラジン環、ピペラジン環およびトリアジン環などが挙げられる。脂肪族環としては、シクロペンタン環、シクロヘキサン環、シクロヘプタン環などが挙げられる。
　また、複数の環状構造を有する場合、環は縮環していてもよく、－Ｏ－、－Ｓ－、フッ素置換アルキレン基（好ましくは、－Ｃ（ＣＦ3）2－）、－ＣＨ2－、－ＳＯ2－、または－ＮＨＣＯ－などの連結基を介して複数の環状構造と結合していてもよい。連結基は、－Ｏ－、－Ｓ－、－Ｃ（ＣＦ3）2－、－ＣＨ2－、－ＳＯ2－、または－ＮＨＣＯ－であることが好ましく、－Ｃ（ＣＦ3）2－がより好ましい。
　本発明では、Ｘ部分がフッ素置換アルキレン基を含むことが好ましい。フッ素置換アルキレン基を含むことにより、本発明の組成物の透明性がより向上する傾向にある。 X represents a tetravalent organic group. The tetravalent organic group represented by X is not particularly limited, but preferably has at least one cyclic structure, more preferably 1 to 2 cyclic structures. The cyclic structure may be any of an aromatic ring, a heterocyclic ring, and an aliphatic ring, and preferably includes an aromatic ring and / or a heterocyclic ring, and more preferably includes an aromatic ring. By setting it as such a cyclic structure, the effect of this invention is exhibited more effectively.
Examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. As the heterocyclic ring, furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline ring, Examples include pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring. It is done. Examples of the aliphatic ring include a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring.
In the case of having a plurality of cyclic structures, the ring may be condensed, —O—, —S—, a fluorine-substituted alkylene group (preferably —C (CF 3 ) 2 —), —CH 2 — , —SO 2 —, or —NHCO— may be bonded to a plurality of cyclic structures via a linking group. The linking group is preferably —O—, —S—, —C (CF 3 ) 2 —, —CH 2 —, —SO 2 —, or —NHCO—, where —C (CF 3 ) 2 — is More preferred.
In the present invention, the X moiety preferably contains a fluorine-substituted alkylene group. By including a fluorine-substituted alkylene group, the transparency of the composition of the present invention tends to be further improved.
　Ｘの具体例としては、以下のものが挙げられるが、これらに限定されるものではない。式中、式中、Ｘ1は、連結基を表す。
Figure JPOXMLDOC01-appb-C000009
 Specific examples of X include, but are not limited to, the following. In the formula, X 1 represents a linking group.
Figure JPOXMLDOC01-appb-C000009
　Ｘと結合するＮＨおよびＲ1、ならびにＮＨおよびＲ2は、環状構造におけるオルト位（隣接位）となるように結合することが好ましい。
　Ｘとしては、（２）、（１０）が好ましく、（２）がより好ましい。特に、Ｘ1がフッ素置換アルキレン基（好ましくは、－Ｃ（ＣＦ3）2－）であると、本発明の組成物の透明性がより向上し、好ましい。 NH and R 1 bonded to X, and NH and R 2 are preferably bonded so as to be in the ortho position (adjacent position) in the cyclic structure.
X is preferably (2) or (10), more preferably (2). In particular, it is preferable that X 1 is a fluorine-substituted alkylene group (preferably —C (CF 3 ) 2 —), since the transparency of the composition of the present invention is further improved.
　Ｒ1およびＲ2は、それぞれ独立に、水素原子、アルキル基、酸分解性基、または－ＣＯＲｃを表し、Ｒ1およびＲ2の一方は、酸分解性基である。
　アルキル基は、置換基を有していても良いし、有していなくても良い。
　アルキル基としては、直鎖、分枝状、環状であってもよく、直鎖、または分枝状アルキル基の場合、炭素数１～２０のアルキル基が好ましく、炭素数１～１５のアルキル基がより好ましく、炭素数１～１０のアルキル基がさらに好ましい。環状アルキル基の場合、炭素数３～１５のアルキル基が好ましく、炭素数５～１５のアルキル基がより好ましく、炭素数５～１０のアルキル基がより好ましい。具体的なアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、オクチル基、シクロペンチル基、シクロヘキシル基、ノルボルニル基、アダマンチル基などが挙げられる。置換基としては、ハロゲン原子、シアノ基、アミド基、スルホニルアミド基などを挙げることができる。 R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, an acid-decomposable group, or —CORc, and one of R 1 and R 2 is an acid-decomposable group.
The alkyl group may or may not have a substituent.
The alkyl group may be linear, branched or cyclic, and in the case of a linear or branched alkyl group, an alkyl group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 15 carbon atoms Is more preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable. In the case of a cyclic alkyl group, an alkyl group having 3 to 15 carbon atoms is preferable, an alkyl group having 5 to 15 carbon atoms is more preferable, and an alkyl group having 5 to 10 carbon atoms is more preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an octyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. Examples of the substituent include a halogen atom, a cyano group, an amide group, and a sulfonylamide group.
　酸分解性基は、酸の作用により脱離する基、または－Ｃ(Ｒ5)2－ＣＯＯＲ4のように、酸の作用により脱離して、水酸基、カルボキシル基などのアルカリ可溶性基を生じる基を表す。
　Ｒ5は、それぞれ独立に水素原子、または炭素数１～４のアルキル基を表し、Ｒ4は、酸の作用により脱離する基を表す。ここで、酸の作用の酸は、通常、後述する酸発生剤から発生した酸を意味する。
　酸の作用により脱離する基としては、ビニルエーテル系の置換基、アルコキシカルボニル基（好ましくは炭素数２～５）、アルコキシアルキル基（好ましくは炭素数２～５）、アルキルシリル基（好ましくは炭素数１～２０）、またはアセタール若しくはケタールを構成する基を挙げることができる。感度の観点から、アセタール基またはケタール基であることが好ましい。
　アセタール若しくはケタールを構成する基としては、例えば次の構造を有するものが挙げられる。
Figure JPOXMLDOC01-appb-C000010
 （式中、Ｒ1xおよびＲ2xは、それぞれ独立に水素原子、アルキル基またはアリール基を表し、少なくともＲ1xおよびＲ2xのいずれか一方がアルキル基またはアリール基を表す。Ｒ3xは、アルキル基またはアリール基を表し、Ｒ1xまたはＲ2xと、Ｒ3xとが連結して環状エーテルを形成してもよい。）
　Ｒ1xおよびＲ2xが表わすアルキル基としては、炭素数１～１０のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましい。Ｒ1xおよびＲ2xが表わすアリール基としては、炭素数６～１０のアリール基が好ましく、フェニル基がより好ましい。Ｒ1xおよびＲ2x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。
　Ｒ3Xは、アルキル基またはアリール基を表し、炭素数１～１６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。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、炭素数６～１０のアリール基がより好ましい。 An acid-decomposable group is a group capable of leaving by the action of an acid, or a group that leaves by the action of an acid to generate an alkali-soluble group such as a hydroxyl group or a carboxyl group, such as —C (R 5 ) 2 —COOR 4. Represents.
R 5 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 4 represents a group capable of leaving by the action of an acid. Here, the acid acting as an acid usually means an acid generated from an acid generator described later.
Examples of the group capable of leaving by the action of an acid include vinyl ether substituents, alkoxycarbonyl groups (preferably having 2 to 5 carbon atoms), alkoxyalkyl groups (preferably having 2 to 5 carbon atoms), alkylsilyl groups (preferably carbon atoms). And a group constituting an acetal or a ketal. From the viewpoint of sensitivity, an acetal group or a ketal group is preferable.
As group which comprises acetal or ketal, what has the following structure is mentioned, for example.
Figure JPOXMLDOC01-appb-C000010
 (In the formula, R 1x and R 2x each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R 1x and R 2x represents an alkyl group or an aryl group. R 3x represents an alkyl group. Alternatively, it represents an aryl group, and R 1x or R 2x and R 3x may be linked to form a cyclic ether.
The alkyl group represented by R 1x and R 2x is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. The aryl group represented by R 1x and R 2x is preferably an aryl group having 6 to 10 carbon atoms, and more preferably a phenyl group. R 1x and R 2x are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R 3X represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 16 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable.
　酸の作用により脱離する基の具体例としては、ｔ－ブトキシカルボニル基等のアルコキシカルボニル基、メトキシメチル基、エトキシエチル基等のアルコキシアルキル基、メチルシリル基、エチルシリル基等のアルキルシリル基、テトラヒドロピラニル基、テトラヒドロフラニル基、アルコキシ置換テトラヒドロピラニル基、アルコキシ置換テトラヒドロフラニル基等が典型的な例として例示されるが、これらに限定されるものではない。酸の作用により脱離する基として最も好ましい基はエトキシエチル基、テトラヒドロピラニル基、テトラヒドロフラニル基である。これらは単独で用いても良いし、複数種を併用しても良い。
　酸の作用により脱離する基として好ましい基の構造を示す。
Figure JPOXMLDOC01-appb-C000011
 Specific examples of the group capable of leaving by the action of an acid include alkoxycarbonyl groups such as t-butoxycarbonyl group, alkoxyalkyl groups such as methoxymethyl group and ethoxyethyl group, alkylsilyl groups such as methylsilyl group and ethylsilyl group, tetrahydro Pyranyl group, tetrahydrofuranyl group, alkoxy-substituted tetrahydropyranyl group, alkoxy-substituted tetrahydrofuranyl group and the like are exemplified as typical examples, but are not limited thereto. The most preferable group as a group capable of leaving by the action of an acid is an ethoxyethyl group, a tetrahydropyranyl group or a tetrahydrofuranyl group. These may be used alone or in combination of two or more.
The structure of a group preferable as a group capable of leaving by the action of an acid is shown.
Figure JPOXMLDOC01-appb-C000011
　Ｒｃは、アルキル基またはアリール基を表し、これらの基も置換基を有していても良いし、有していなくても良い。
　Ｒｃが表わすアルキル基は、Ｒ1およびＲ2が表わすアルキル基と同義であり、好ましい範囲も同様である。
　Ｒｃが表わす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、炭素数６～１４のアリール基がより好ましく、炭素数６～１０のアリール基がさらに好ましい。具体的にアリール基としては、フェニル基、トルイル基、メシチル基、ナフチル基などが挙げられる。アリール基が有していてもよい置換基は、アルキル基が有していてもよい置換基と同様である。 Rc represents an alkyl group or an aryl group, and these groups may or may not have a substituent.
The alkyl group represented by Rc has the same meaning as the alkyl group represented by R 1 and R 2 , and the preferred range is also the same.
The aryl group represented by Rc is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further preferably an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group. The substituent that the aryl group may have is the same as the substituent that the alkyl group may have.
　Ｙは２価の有機基を表す。Ｙが表わす２価の有機基としては特に制限はないが、環状構造を少なくとも１つ有することが好ましく、環状構造を１～２つ有することがより好ましい。環状構造は、アリーレン基、２価の環状脂肪族基、２価の複素環基のいずれであってもよく、アリーレン基、および／または２価の複素環を含むことが好ましく、アリーレン基を含むことがより好ましい。具体的に、Ｙが表す２価の有機基としては、アリーレン基、２価の環状脂肪族基、２価の複素環基、または、これらと、メチレン基、酸素原子、硫黄原子、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、および－Ｃ（ＣＦ3）2－の少なくとも１種との組み合わせからなる基を表すことが好ましい。
　アリーレン基としては、炭素数６～２０のアリーレン基が好ましく、炭素数６～１４のアリーレン基がより好ましく、炭素数６～１０のアリーレン基がさらに好ましい。具体的なアリーレン基としては、１，４－フェニレン基、１，３－フェニレン基、１，２－フェニレン基、ナフチレン基、アントラセニレン基などが挙げられる。
　２価の環状脂肪族基としては、環状アルキレン基、環状アルケニレン基、環状アルキニレン基などが挙げられる。環状アルキレン基としては、炭素数３～２０のアルキレン基が好ましく、炭素数３～１８の環状アルキレン基がより好ましく、炭素数３～１５の環状アルキレン基がさらに好ましい。環状アルケニレン基としては、炭素数３～２０のアルケニレン基が好ましく、炭素数３～１８の環状アルケニレン基がより好ましく、炭素数３～１５の環状アルケニレン基がさらに好ましい。環状アルキニレン基としては、炭素数３～２０の環状アルキニレン基が好ましく、炭素数３～１８の環状アルキニレン基がより好ましく、炭素数３～１５の環状アルキニレン基がさらに好ましい。具体的な２価の環状脂肪族基としては、１，４－シクロヘキシレン基、１，３－シクロヘキシレン基、１，２－シクロヘキシレン基、オクチレン基などが挙げられる。
　２価の複素環基としては、５員、６員または７員の複素環を有することが好ましい。５員環または６員環がさらに好ましく、６員環がより好ましい。複素環を構成するヘテロ原子としては、窒素原子、酸素原子および硫黄原子が好ましい。複素環は、芳香族性複素環であることが好ましい。芳香族性複素環は、一般に不飽和複素環であり、最多二重結合を有する不飽和複素環がさらに好ましい。具体的な複素環としては、フラン環、チオフェン環、ピロール環、ピロリン環、ピロリジン環、オキサゾール環、イソオキサゾール環、チアゾール環、イソチアゾール環、イミダゾール環、イミダゾリン環、イミダゾリジン環、ピラゾール環、ピラゾリン環、ピラゾリジン環、トリアゾール環、フラザン環、テトラゾール環、ピラン環、チイン環、ピリジン環、ピペリジン環、オキサジン環、モルホリン環、チアジン環、ピリダジン環、ピリミジン環、ピラジン環、ピペラジン環およびトリアジン環が含まれる。
　Ｙは、アリーレン基、２価の環状脂肪族基、２価の複素環基、または、これらと、メチレン基、酸素原子、硫黄原子、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、および－Ｃ（ＣＦ3）2－の少なくとも１種との組み合わせからなる基であってもよく、具体的には、以下の基が挙げられる。式中、Ａは、メチレン基、酸素原子、硫黄原子、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、または－Ｃ（ＣＦ3）2－を表す。
Figure JPOXMLDOC01-appb-C000012
 Y represents a divalent organic group. The divalent organic group represented by Y is not particularly limited, but preferably has at least one cyclic structure, and more preferably has 1 to 2 cyclic structures. The cyclic structure may be any of an arylene group, a divalent cyclic aliphatic group, and a divalent heterocyclic group, and preferably includes an arylene group and / or a divalent heterocyclic ring, and includes an arylene group. It is more preferable. Specifically, the divalent organic group represented by Y includes an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or a methylene group, an oxygen atom, a sulfur atom, —SO 2. It preferably represents a group consisting of a combination of at least one of-, -CO-, -NHCO-, and -C (CF 3 ) 2- .
As the arylene group, an arylene group having 6 to 20 carbon atoms is preferable, an arylene group having 6 to 14 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. Specific examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a naphthylene group, and an anthracenylene group.
Examples of the divalent cyclic aliphatic group include a cyclic alkylene group, a cyclic alkenylene group, and a cyclic alkynylene group. As the cyclic alkylene group, an alkylene group having 3 to 20 carbon atoms is preferable, a cyclic alkylene group having 3 to 18 carbon atoms is more preferable, and a cyclic alkylene group having 3 to 15 carbon atoms is more preferable. The cyclic alkenylene group is preferably an alkenylene group having 3 to 20 carbon atoms, more preferably a cyclic alkenylene group having 3 to 18 carbon atoms, and further preferably a cyclic alkenylene group having 3 to 15 carbon atoms. As the cyclic alkynylene group, a cyclic alkynylene group having 3 to 20 carbon atoms is preferable, a cyclic alkynylene group having 3 to 18 carbon atoms is more preferable, and a cyclic alkynylene group having 3 to 15 carbon atoms is more preferable. Specific examples of the divalent cycloaliphatic group include 1,4-cyclohexylene group, 1,3-cyclohexylene group, 1,2-cyclohexylene group, and octylene group.
The divalent heterocyclic group preferably has a 5-membered, 6-membered or 7-membered heterocyclic ring. A 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is more preferable. As the hetero atom constituting the heterocyclic ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable. The heterocycle is preferably an aromatic heterocycle. The aromatic heterocyclic ring is generally an unsaturated heterocyclic ring, and an unsaturated heterocyclic ring having the most double bond is more preferable. Specific heterocycles include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, Pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring Is included.
Y represents an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or a methylene group, an oxygen atom, a sulfur atom, —SO 2 —, —CO—, —NHCO—, and — C (CF 3) 2 - in can be a group comprising a combination of at least one, and specific examples thereof include the following groups. In the formula, A represents a methylene group, an oxygen atom, a sulfur atom, —SO 2 —, —CO—, —NHCO—, or —C (CF 3 ) 2 —.
Figure JPOXMLDOC01-appb-C000012
　これらの中でも、Ｙとしては、１，４－フェニレン基、１，３－フェニレン基、１，２－フェニレン基、オクチレン基が好ましい。 Among these, Y is preferably 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group or octylene group.
＜＜（ａ－２）架橋性基を含む繰り返し単位＞＞
（Ａ）ポリベンゾオキサゾール前駆体は、（ａ－２）架橋性基を含む繰り返し単位を含んでいてもよい。（ａ－２）架橋性基を含む繰り返し単位は下記一般式（２－１）で表される。一般式（２－１）で表される繰り返し単位は１種類のみ含んでいても良いし、２種類以上含んでいても良い。 << (a-2) Repeating unit containing crosslinkable group >>
(A) The polybenzoxazole precursor may contain (a-2) a repeating unit containing a crosslinkable group. (A-2) The repeating unit containing a crosslinkable group is represented by the following general formula (2-1). The repeating unit represented by the general formula (2-1) may include only one type, or may include two or more types.
一般式（２－１）
（一般式（２－１）中、Ｘは４価の有機基を表し、Ｙは２価の有機基を表す。Ｒ1およびＲ2はそれぞれ独立に水素原子、架橋性基、アルキル基、または、－ＣＯＲｃを表す。Ｒｃは、アルキル基またはアリール基を表す。Ｒ1またはＲ2の少なくとも一方が架橋性基である。） Formula (2-1)
(In general formula (2-1), X represents a tetravalent organic group and Y represents a divalent organic group. R 1 and R 2 each independently represents a hydrogen atom, a crosslinkable group, an alkyl group, or -CORc, Rc represents an alkyl group or an aryl group, and at least one of R 1 and R 2 is a crosslinkable group.)
　Ｘは、４価の有機基を表す。ＸおよびＹは、それぞれ、（ａ－１）酸分解性基を含む繰り返し単位における一般式（１－１）中のＸおよびＹと同義であり、好ましい範囲も同様である。 X represents a tetravalent organic group. X and Y have the same meanings as X and Y in the general formula (1-1) in the repeating unit (a-1) containing an acid-decomposable group, respectively, and preferred ranges are also the same.
　Ｒ1およびＲ2は、それぞれ独立に、水素原子、架橋性基、アルキル基、または－ＣＯＲｃを表す。Ｒ1およびＲ2のいずれか一方は、架橋性基である。
　Ｒ1およびＲ2のとしての、アルキル基および－ＣＯＲｃは、（ａ－１）酸分解性基を含む繰り返し単位における一般式（１－１）中のＲ1およびＲ2と同義であり、好ましい範囲も同様である。 R 1 and R 2 each independently represents a hydrogen atom, a crosslinkable group, an alkyl group, or —CORc. One of R 1 and R 2 is a crosslinkable group.
As R 1 and R 2 of the alkyl and -CORc has the same meaning as R 1 and R 2 in the general formula (1-1) in the repeating unit comprising (a-1) acid-decomposable groups, preferred The range is the same.
　架橋性基としては、熱によって架橋反応が起こるものであれば制限は無い。機械的強度および耐溶剤性の観点から（Ａ）成分のカルボキシ基、ヒドロキシ基又は炭素-炭素不飽和結合と反応するものが好ましい。具体的にはエポキシ基、オキセタニル基、炭素炭素不飽和結合基およびブロックイソシアネート基の少なくとも１つを含む基が好ましく、エポキシ基、オキセタニル基、炭素炭素不飽和結合基およびブロックイソシアネート基の少なくとも１つを含む基がより好ましい。
ネート基がより好ましい。 The crosslinkable group is not limited as long as a crosslinking reaction is caused by heat. From the viewpoint of mechanical strength and solvent resistance, those which react with the carboxy group, hydroxy group or carbon-carbon unsaturated bond of component (A) are preferred. Specifically, a group containing at least one of an epoxy group, an oxetanyl group, a carbon-carbon unsaturated bond group and a blocked isocyanate group is preferable, and at least one of an epoxy group, an oxetanyl group, a carbon-carbon unsaturated bond group and a blocked isocyanate group The group containing is more preferable.
Nate groups are more preferred.
　架橋性基の具体例としては、以下のものが挙げられるが、これらに限定されるものではない。
Figure JPOXMLDOC01-appb-C000014
 Specific examples of the crosslinkable group include the following, but are not limited thereto.
Figure JPOXMLDOC01-appb-C000014
　なお、架橋性基は、連結基等を介して結合していてもよく、直接式（２－１）中の酸素原子に結合していることが好ましい。 The crosslinkable group may be bonded via a linking group or the like, and is preferably directly bonded to the oxygen atom in the formula (2-1).
＜＜（ａ－３）一般式（１）中のＲ1およびＲ2の一方が、酸分解性基であり、他方が架橋性基である繰り返し単位＞＞
　ポリベンゾオキサゾール前駆体は、一般式（１）中のＲ1およびＲ2の一方が、酸分解性基であり、他方が架橋性基である繰り返し単位であることも好ましい。本実施形態における、一般式（１）のＸ、Ｙは、一般式（１－１）における、Ｘ、Ｙと同義であり、好ましい範囲も同様である。酸分解性基の好ましい態様は、一般式（１－１）における酸分解性基と同様である。架橋性基の好ましい態様は、一般式（２－１）における架橋性基と同様である。
　本発明では、（ａ－３）一般式（１）中のＲ1およびＲ2の少なくとも一方が、酸分解性基であり、他方が架橋性基である繰り返し単位に加えて、上記（ａ－１）および／または（ａ－２）の繰り返し単位も含んでいても良い。 << (a-3) Repeating unit in which one of R 1 and R 2 in general formula (1) is an acid-decomposable group and the other is a crosslinkable group >>
The polybenzoxazole precursor is preferably a repeating unit in which one of R 1 and R 2 in the general formula (1) is an acid-decomposable group and the other is a crosslinkable group. In this embodiment, X and Y in the general formula (1) have the same meanings as X and Y in the general formula (1-1), and the preferred ranges are also the same. A preferred embodiment of the acid-decomposable group is the same as the acid-decomposable group in the general formula (1-1). A preferred embodiment of the crosslinkable group is the same as that of the crosslinkable group in the general formula (2-1).
In the present invention, in addition to the repeating unit (a-3) in which at least one of R 1 and R 2 in the general formula (1) is an acid-decomposable group and the other is a crosslinkable group, The repeating unit of 1) and / or (a-2) may also be included.
＜＜（ａ－４）他の繰り返し単位＞＞
　ポリベンゾオキサゾール前駆体は、（ａ－１）～（ａ－３）の繰り返し単位の他に、その他の繰り返し単位を含んでいてもよい。
　その他の繰り返し単位としては、例えば、一般式（３）または一般式（４）で表される繰り返し単位が例示される。 << (a-4) Other repeating unit >>
In addition to the repeating units (a-1) to (a-3), the polybenzoxazole precursor may contain other repeating units.
Examples of other repeating units include repeating units represented by the general formula (3) or the general formula (4).
＜＜＜一般式（３）で表される繰り返し単位＞＞＞
一般式（３）
Figure JPOXMLDOC01-appb-C000015
 （一般式（３）中、Ｘは４価の有機基を表し、Ｙは２価の有機基を表す。Ｒ3およびＲ4はそれぞれ独立に水素原子、アルキル基、または、－ＣＯＲｃを表す。Ｒｃは、アルキル基またはアリール基を表す。） <<< Repeating unit represented by formula (3) >>>
General formula (3)
Figure JPOXMLDOC01-appb-C000015
 (In the general formula (3), X represents a tetravalent organic group and Y represents a divalent organic group. R 3 and R 4 each independently represents a hydrogen atom, an alkyl group, or —CORc. Rc represents an alkyl group or an aryl group.)
　一般式（３）中、Ｘ、Ｙ、およびＲｃは、一般式（１－１）中のＸ、ＹおよびＲｃと同義であり、好ましい範囲も同様である。Ｒ3およびＲ4としての、アルキル基または－ＣＯＲｃや、一般式（１－１）のＲ1およびＲ2におけるアルキル基または－ＣＯＲｃの好ましい範囲と同様である。 In general formula (3), X, Y, and Rc have the same meanings as X, Y, and Rc in general formula (1-1), and the preferred ranges are also the same. This is the same as the preferred range of the alkyl group or —CORc as R 3 and R 4 and the alkyl group or —CORc in R 1 and R 2 of formula (1-1).
＜＜＜一般式（４）で表される繰り返し単位＞＞＞
一般式（４）
Figure JPOXMLDOC01-appb-C000016
 （一般式（４）中、Ｙ1は、それぞれ独立にアリーレン基、２価の環状脂肪族基、２価の複素環基、または、これらと、－ＣＨ2－、酸素原子、硫黄原子、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、および－Ｃ（ＣＦ3）2－の少なくとも１種との組み合わせからなる基を表し、Ｘ2は、アリーレン基、２価の複素環基、２価の環状脂肪族基、または、これらと、－ＣＨ2－、酸素原子、硫黄原子、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、および－Ｃ（ＣＦ3）2－の少なくとも１種との組み合わせからなる基を表す。） <<< Repeating unit represented by formula (4) >>>
General formula (4)
Figure JPOXMLDOC01-appb-C000016
 (In the general formula (4), Y 1 each independently represents an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or these, —CH 2 —, an oxygen atom, a sulfur atom, — Represents a group composed of a combination with at least one of SO 2 —, —CO—, —NHCO—, and —C (CF 3 ) 2 —, and X 2 represents an arylene group, a divalent heterocyclic group, a divalent group, Or a cyclic aliphatic group of the above, or at least one of —CH 2 —, oxygen atom, sulfur atom, —SO 2 —, —CO—, —NHCO—, and —C (CF 3 ) 2 —. Represents a group consisting of a combination.)
　Ｙ1は、それぞれ独立にアリーレン基、２価の環状脂肪族基、２価の複素環基、または、これらと、メチレン基、酸素原子、硫黄原子、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、および－Ｃ（ＣＦ3）2－の少なくとも１種との組み合わせからなる基を表す。
　アリーレン基としては、炭素数６～２０のアリーレン基が好ましく、炭素数６～１４のアリーレン基がより好ましく、炭素数６～１０のアリーレン基がさらに好ましい。具体的なアリーレン基としては、１，４－フェニレン基、１，３－フェニレン基、１，２－フェニレン基、ナフチレン基、アントラセニレン基などが挙げられる。
　２価の複素環基としては、５員、６員または７員の複素環を有することが好ましい。５員環または６員環がさらに好ましく、６員環がより好ましい。複素環を構成するヘテロ原子としては、窒素原子、酸素原子および硫黄原子が好ましい。複素環は、芳香族性複素環であることが好ましい。芳香族性複素環は、一般に不飽和複素環である。最多二重結合を有する不飽和複素環がさらに好ましい。具体的な複素環としては、フラン環、チオフェン環、ピロール環、ピロリン環、ピロリジン環、オキサゾール環、イソオキサゾール環、チアゾール環、イソチアゾール環、イミダゾール環、イミダゾリン環、イミダゾリジン環、ピラゾール環、ピラゾリン環、ピラゾリジン環、トリアゾール環、フラザン環、テトラゾール環、ピラン環、チイン環、ピリジン環、ピペリジン環、オキサジン環、モルホリン環、チアジン環、ピリダジン環、ピリミジン環、ピラジン環、ピペラジン環およびトリアジン環が含まれる。
　２価の環状脂肪族基としては、環状アルキレン基、環状アルケニレン基、環状アルキニレン基などが挙げられる。環状アルキレン基としては、炭素数３～２０の環状アルキレン基が好ましく、炭素数３～１８の環状アルキレン基がより好ましく、炭素数３～１５の環状アルキレン基がさらに好ましい。環状アルケニレン基としては、炭素数３～２０の環状アルケニレン基が好ましく、炭素数３～１８の環状アルケニレン基がより好ましく、炭素数３～１５の環状アルケニレン基がさらに好ましい。環状アルキニレン基としては、炭素数３～２０の環状アルキニレン基が好ましく、炭素数３～１８の環状アルキニレン基がより好ましく、炭素数３～１５の環状アルキニレン基がさらに好ましい。具体的な２価の環状脂肪族基としては、１，４－シクロヘキシレン基、１，３－シクロヘキシレン基、１，２－シクロヘキシレン基、オクチレン基などが挙げられる。
　Ｙ1は、アリーレン基、２価の複素環基、２価の環状脂肪族基、または、これらと、メチレン基、酸素原子、硫黄原子、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、および－Ｃ（ＣＦ3）2－の少なくとも１種との組み合わせからなる基であってもよく、これらと、－Ｃ（ＣＦ3）2－との組み合わせからなる基であることがより好ましく、アリーレン基と－Ｃ（ＣＦ3）2－との組み合わせからなる基であることがさらに好ましい。
　Ｙ1としては、１，４－フェニレン基、１，３－フェニレン基、１，２－フェニレン基、オクチレン基、下記例示化合物が好ましく、１，４－フェニレン基、１，３－フェニレン基、１，２－フェニレン基、オクチレン基がより好ましい。
Figure JPOXMLDOC01-appb-C000017
 Y 1 is independently an arylene group, divalent cycloaliphatic group, divalent heterocyclic group, or a methylene group, oxygen atom, sulfur atom, —SO 2 —, —CO—, —NHCO. And a group consisting of a combination with at least one of — and —C (CF 3 ) 2 —.
As the arylene group, an arylene group having 6 to 20 carbon atoms is preferable, an arylene group having 6 to 14 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. Specific examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a naphthylene group, and an anthracenylene group.
The divalent heterocyclic group preferably has a 5-membered, 6-membered or 7-membered heterocyclic ring. A 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is more preferable. As the hetero atom constituting the heterocyclic ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable. The heterocycle is preferably an aromatic heterocycle. The aromatic heterocycle is generally an unsaturated heterocycle. An unsaturated heterocyclic ring having the most double bond is more preferable. Specific heterocycles include furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, Pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring Is included.
Examples of the divalent cyclic aliphatic group include a cyclic alkylene group, a cyclic alkenylene group, and a cyclic alkynylene group. As the cyclic alkylene group, a cyclic alkylene group having 3 to 20 carbon atoms is preferable, a cyclic alkylene group having 3 to 18 carbon atoms is more preferable, and a cyclic alkylene group having 3 to 15 carbon atoms is more preferable. As the cyclic alkenylene group, a cyclic alkenylene group having 3 to 20 carbon atoms is preferable, a cyclic alkenylene group having 3 to 18 carbon atoms is more preferable, and a cyclic alkenylene group having 3 to 15 carbon atoms is more preferable. As the cyclic alkynylene group, a cyclic alkynylene group having 3 to 20 carbon atoms is preferable, a cyclic alkynylene group having 3 to 18 carbon atoms is more preferable, and a cyclic alkynylene group having 3 to 15 carbon atoms is more preferable. Specific examples of the divalent cycloaliphatic group include 1,4-cyclohexylene group, 1,3-cyclohexylene group, 1,2-cyclohexylene group, and octylene group.
Y 1 represents an arylene group, a divalent heterocyclic group, a divalent cycloaliphatic group, or a methylene group, an oxygen atom, a sulfur atom, —SO 2 —, —CO—, —NHCO—, and -C (CF 3) 2 - in can be a group comprising a combination of at least one of these and, -C (CF 3) 2 -, more preferably a group consisting of an arylene group And more preferably a group consisting of a combination of —C (CF 3 ) 2 —.
Y 1 is preferably a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, an octylene group, or the following exemplified compounds, and includes a 1,4-phenylene group, a 1,3-phenylene group, , 2-phenylene group and octylene group are more preferable.
Figure JPOXMLDOC01-appb-C000017
　Ｘ2は、アリーレン基、２価の複素環基、２価の環状脂肪族基、または、これらと、メチレン基、酸素原子、硫黄原子、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、および－Ｃ（ＣＦ3）2－の少なくとも１種との組み合わせからなる基を表し、これらの基はケイ素原子を含んでいてもよい。
　Ｘ2が表わすアリーレン基、２価の複素環基、２価の環状脂肪族基は、一般式（１－２）中のＹ1が表わすアリーレン基、２価の複素環基、２価の環状脂肪族基と同義であり、好ましい範囲も同様である。 X 2 represents an arylene group, divalent heterocyclic group, divalent cycloaliphatic group, or a methylene group, oxygen atom, sulfur atom, —SO 2 —, —CO—, —NHCO—, and A group consisting of a combination of at least one of —C (CF 3 ) 2 — is represented, and these groups may contain a silicon atom.
An arylene group represented by X 2 , a divalent heterocyclic group, and a divalent cyclic aliphatic group are an arylene group represented by Y 1 in formula (1-2), a divalent heterocyclic group, and a divalent cyclic group. It is synonymous with an aliphatic group, and its preferable range is also the same.
　Ｘ2は、アリーレン基、２価の環状脂肪族基、２価の複素環基、または、これらと、メチレン基、酸素原子、硫黄原子、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、および－Ｃ（ＣＦ3）2－の少なくとも１種との組み合わせからなる基であってもよく、具体的には、以下の基が挙げられる。式中、Ａは、メチレン基、酸素原子、硫黄原子、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、または－Ｃ（ＣＦ3）2－を表す。
Figure JPOXMLDOC01-appb-C000018
 X 2 represents an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or a methylene group, an oxygen atom, a sulfur atom, —SO 2 —, —CO—, —NHCO—, and The group may be a combination of at least one of —C (CF 3 ) 2 —, and specific examples thereof include the following groups. In the formula, A represents a methylene group, an oxygen atom, a sulfur atom, —SO 2 —, —CO—, —NHCO—, or —C (CF 3 ) 2 —.
Figure JPOXMLDOC01-appb-C000018
　また、その他の繰り返し単位としては、例えば、さらに、（Ａ）架橋性基を有するポリベンゾオキサゾール前駆体がケイ素原子を含む繰り返し単位を含んでいることも好ましい。具体的には、以下の繰り返し単位を含む例が例示される。
Figure JPOXMLDOC01-appb-C000019
 （上記式中、Ｙ1は、アリーレン基、２価の環状脂肪族基、２価の複素環基、または、これらと、－ＣＨ2－、酸素原子、硫黄原子、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、および－Ｃ（ＣＦ3）2－の少なくとも１種との組み合わせからなる基を表し、Ｘ3は、ケイ素原子を含む基を表す。）
　ここで、Ｙ1は、一般式（３）におけるＹ1と同義であり、好ましい範囲も同様である。Ｘ3は下記で表される基であることが好ましい。
Figure JPOXMLDOC01-appb-C000020
 （Ｒ5およびＲ6はそれぞれ独立に２価の有機基を表し、Ｒ7およびＲ8はそれぞれ独立に１価の有機基を表す。） Moreover, as another repeating unit, it is also preferable that the polybenzoxazole precursor which has (A) a crosslinkable group contains the repeating unit containing a silicon atom, for example. Specific examples include the following repeating units.
Figure JPOXMLDOC01-appb-C000019
 (In the above formula, Y 1 represents an arylene group, divalent cycloaliphatic group, divalent heterocyclic group, or these, —CH 2 —, oxygen atom, sulfur atom, —SO 2 —, —CO Represents a group composed of a combination of at least one of —, —NHCO—, and —C (CF 3 ) 2 —, and X 3 represents a group containing a silicon atom.)
Here, Y 1 has the same meaning as Y 1 in the general formula (3), and preferred ranges are also the same. X 3 is preferably a group represented by the following.
Figure JPOXMLDOC01-appb-C000020
 (R 5 and R 6 each independently represent a divalent organic group, and R 7 and R 8 each independently represent a monovalent organic group.)
　Ｒ5およびＲ6で表される２価の有機基としては特に制限はないが、具体的に置換基を有していてもよい炭素数１～２０の直鎖もしくは分岐のアルキレン基、置換基を有していてもよい炭素数６～２０のアリーレン基、置換基を有していてもよい炭素数３～２０の２価の環状脂肪族基、またはこれらを組み合わせてなる基を表す。
　炭素数１～２０の直鎖もしくは分岐のアルキレン基としては、炭素数１～１０のアルキレン基がより好ましく、炭素数１～６のアルキレン基がさらに好ましい。具体的には、メチレン基、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、ｔ－ブチレン基などが挙げられる。
　炭素数６～２０のアリーレン基としては、炭素数６～１４のアリーレン基がより好ましく、炭素数６～１０のアリーレン基がさらに好ましい。具体的なアリーレン基としては、１，４－フェニレン基、１，３－フェニレン基、１，２－フェニレン基、ナフチレン基、アントラセニレン基などが挙げられる。
　炭素数３～２０の２価の環状脂肪族基としては、炭素数３～１０の２価の環状脂肪族基が好ましく、炭素数５～６の２価の環状脂肪族基がより好ましい。２価の環状脂肪族基としては、１，４－シクロヘキシレン基、１，３－シクロヘキシレン基、１，２－シクロヘキシレン基などが挙げられる。
　これら炭素数１～２０の直鎖もしくは分岐のアルキレン基、炭素数６～２０のアリーレン基、および炭素数３～２０の２価の環状脂肪族基は置換基を有していてもよい。置換基としては、炭素数１～６のアルキル基、ハロゲン原子、シアノ基、アミド基、スルホニルアミド基などを挙げることができる。 The divalent organic group represented by R 5 and R 6 is not particularly limited, but may be a linear or branched alkylene group having 1 to 20 carbon atoms and a substituent, which may have a specific substituent. Represents an arylene group having 6 to 20 carbon atoms which may have a divalent cyclic aliphatic group having 3 to 20 carbon atoms which may have a substituent, or a combination thereof.
As the linear or branched alkylene group having 1 to 20 carbon atoms, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 6 carbon atoms is more preferable. Specific examples include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and a t-butylene group.
As the arylene group having 6 to 20 carbon atoms, an arylene group having 6 to 14 carbon atoms is more preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. Specific examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a naphthylene group, and an anthracenylene group.
The divalent cycloaliphatic group having 3 to 20 carbon atoms is preferably a divalent cycloaliphatic group having 3 to 10 carbon atoms, and more preferably a divalent cycloaliphatic group having 5 to 6 carbon atoms. Examples of the divalent cycloaliphatic group include a 1,4-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,2-cyclohexylene group.
These linear or branched alkylene groups having 1 to 20 carbon atoms, arylene groups having 6 to 20 carbon atoms, and divalent cyclic aliphatic groups having 3 to 20 carbon atoms may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.
　炭素数１～２０の直鎖もしくは分岐のアルキレン基、炭素数６～２０のアリーレン基、または炭素数３～２０の２価の環状脂肪族基を組み合わせてなる基としては、特に制限はないが、炭素数３～２０の２価の環状脂肪族基を組み合わせてなる基を組み合わせた基であることが好ましい。以下、炭素数１～２０の直鎖もしくは分岐のアルキレン基、炭素数６～２０のアリーレン基、または炭素数３～２０の２価の環状脂肪族基を組み合わせてなる基の具体例としては、以下のものが挙げられるが、これらに限定されるものではない。
Figure JPOXMLDOC01-appb-C000021
 The group formed by combining a straight chain or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent cyclic aliphatic group having 3 to 20 carbon atoms is not particularly limited. A group formed by combining groups formed by combining divalent cycloaliphatic groups having 3 to 20 carbon atoms is preferable. Specific examples of the group formed by combining a linear or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent cyclic aliphatic group having 3 to 20 carbon atoms are as follows: Although the following are mentioned, it is not limited to these.
Figure JPOXMLDOC01-appb-C000021
　Ｒ7およびＲ8で表される１価の有機基としては、置換基を有していてもよい炭素数１～２０の直鎖もしくは分岐のアルキル基もしくは炭素数６～２０のアリール基を表す。
　置換基を有していてもよい炭素数１～２０の直鎖もしくは分岐のアルキル基としては、炭素数１～１０のアルキル基が好ましく、炭素数１～６のアルキル基がより好ましい。具体的には、アルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔ－ブチル基などが挙げられる。
　置換基を有していてもよい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、炭素数６～１４のアリール基がより好ましく、炭素数６～１０のアリール基がさらに好ましい。具体的にアリール基としては、フェニル基、トルイル基、メシチル基、ナフチル基などが挙げられる。
　これら炭素数１～２０の直鎖もしくは分岐のアルキル基、アリール基は置換基を有していてもよい。置換基としては、炭素数１～６のアルキル基、ハロゲン原子、シアノ基、アミド基、スルホニルアミド基などを挙げることができる。 The monovalent organic group represented by R 7 and R 8 represents a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms which may have a substituent. .
The linear or branched alkyl group having 1 to 20 carbon atoms which may have a substituent is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms. Specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group.
The aryl group which may have a substituent is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and further preferably an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group.
These linear or branched alkyl groups and aryl groups having 1 to 20 carbon atoms may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.
　Ｘ3の具体例としては、以下のものが挙げられるが、これらに限定されるものではない。
Figure JPOXMLDOC01-appb-C000022
 Specific examples of X 3 include the following, but are not limited thereto.
Figure JPOXMLDOC01-appb-C000022
　一般式（３）で表される繰り返し単位は、１種類のみ含んでいても良いし、２種類以上含んでいても良い。また、本発明で用いるポリベンゾオキサゾール前駆体は、一般式（１）で表される繰り返し単位と一般式（３）で表される繰り返し単位以外の繰り返し単位を含んでいても良い。但し、このような他の繰り返し単位は、全繰り返し単位の５モル％以下であることが好ましい。 The repeating unit represented by the general formula (3) may include only one type or two or more types. The polybenzoxazole precursor used in the present invention may contain a repeating unit other than the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (3). However, such other repeating units are preferably 5 mol% or less of all repeating units.
（Ａ）ポリベンゾオキサゾール前駆体は、ｍ個の一般式（１）で表される繰り返し単位（上述の（ａ－１）～（ａ－３）の合計）とｎ個の後述する一般式（３）で表される繰り返し単位を含み、ｍは３～１０００を表し、５～３００が好ましく、１０～１００がより好ましい。ｎは０～１０００を表し、０～３００が好ましく、０～１００がより好ましい。ただし、ｍ＋ｎは３～１０００を表し、５～６００が好ましく、１０～２００がより好ましい。ここで、一般式（１）で表される繰り返し単位と一般式（３）で表される繰り返し単位は、いわゆるランダム重合体であってもよい。 (A) The polybenzoxazole precursor is composed of m repeating units represented by the general formula (1) (the total of the above (a-1) to (a-3)) and n general formulas described later ( 3), m represents 3 to 1000, preferably 5 to 300, and more preferably 10 to 100. n represents 0 to 1000, preferably 0 to 300, and more preferably 0 to 100. However, m + n represents 3 to 1000, preferably 5 to 600, and more preferably 10 to 200. Here, the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (3) may be so-called random polymers.
　本発明におけるポリベンゾオキサゾール前駆体は、末端に架橋性基を有している態様とすることができる。このような態様とすることによって、膜硬度等の膜物性を向上させることができる。架橋性基を有する末端は、片方の末端でもよいが、両方の末端であることが好ましい。 The polybenzoxazole precursor in the present invention can have an embodiment having a crosslinkable group at the terminal. By setting it as such an aspect, film | membrane physical properties, such as film | membrane hardness, can be improved. The terminal having a crosslinkable group may be one terminal, but is preferably both terminals.
　（Ａ）ポリベンゾオキサゾール前駆体の末端は特に限定されないが、架橋性基を含むことが好ましい。架橋性基は、エポキシ基、オキセタニル基、炭素炭素不飽和結合基およびブロックイソシアネート基から選択される少なくとも１種を含む基であることが好ましい。本発明における（Ａ）ポリベンゾオキサゾール前駆体の末端は、一般式（Ｘ）で表される基であることが好ましい。
一般式（Ｘ）
Figure JPOXMLDOC01-appb-C000023
 （一般式（Ｘ）中、Ｚは単結合、炭素原子または硫黄原子を表し、Ｒ11は１価の有機基を表す。ｎは０または１を表し、Ｚが単結合の場合、ａは０であり、Ｚが炭素原子の場合、ａは１であり、Ｚが硫黄原子の場合、ａは２である。ｎが０の場合、２つのＲ11は、互いに結合し環を形成していてもよい。） (A) Although the terminal of a polybenzoxazole precursor is not specifically limited, It is preferable that a crosslinkable group is included. The crosslinkable group is preferably a group containing at least one selected from an epoxy group, an oxetanyl group, a carbon-carbon unsaturated bond group, and a blocked isocyanate group. The terminal of the (A) polybenzoxazole precursor in the present invention is preferably a group represented by the general formula (X).
Formula (X)
Figure JPOXMLDOC01-appb-C000023
 (In the general formula (X), Z represents a single bond, a carbon atom or a sulfur atom, R 11 represents a monovalent organic group. N represents 0 or 1, and when Z is a single bond, a is 0. When Z is a carbon atom, a is 1, and when Z is a sulfur atom, a is 2. When n is 0, two R 11 are bonded to each other to form a ring. May be good.)
　Ｚは、単結合、炭素原子または硫黄原子を表し、単結合、炭素原子が好ましい。 Z represents a single bond, a carbon atom or a sulfur atom, preferably a single bond or a carbon atom.
　Ｒ11は１価の有機基を表す。Ｒ11が表わす１価の有機基としては特に制限はないが、一分子あたりの式量が２０～５００のものが例示される。また、Ｒ11が表わす１価の有機基を構成する原子は、炭素原子、酸素原子、窒素原子、水素原子、硫黄原子から選択されることが好ましく、炭素原子、酸素原子、窒素原子、水素原子から選択されることがより好ましい。
　具体的には、Ｒ11は、アルキル基（好ましくは炭素数１～１０、より好ましくは炭素数１～６）、アルケニル基（好ましくは炭素数２～１０、より好ましくは炭素数２～６）、アルキニル基（好ましくは炭素数２～１０、より好ましくは炭素数２～６）、アリール基（好ましくは炭素数６～２０、より好ましくは炭素数６～１０）、アルコキシ基（好ましくは炭素数１～１０、より好ましくは炭素数１～６）、カルボキシル基、架橋性基、ならびに、酸素原子、カルボニル基、スルホニル基、アリーレン基（好ましくは炭素数６～２０、より好ましくは炭素数６～１０）、アルキレン基（好ましくは炭素数１～１０、より好ましくは炭素数１～６）、アルケニレン基（好ましくは炭素数２～１０、より好ましくは炭素数２～６）、およびアルキニレン基（好ましくは炭素数２～１０、より好ましくは炭素数２～６）と、アルケニル基、アルキニル基、アリール基、カルボニル基、カルボキシル基、架橋性基、酸素原子、アルキレン基、アルキニレン基またはアリーレン基との組み合わせからなる基であることがより好ましい。
　Ｒ11が表わす架橋性基は、一般式（１）中のＲ1が表す架橋性基と同義であり、好ましい範囲も同様である。
　これらの基は、置換基を有していてもよく、置換基としては、水酸基、アルキル基、ハロゲン原子、シアノ基、アミド基、スルホニルアミド基などを挙げることができる。 R 11 represents a monovalent organic group. The monovalent organic group represented by R 11 is not particularly limited, and examples thereof include those having a formula weight of 20 to 500 per molecule. The atom constituting the monovalent organic group represented by R 11 is preferably selected from a carbon atom, an oxygen atom, a nitrogen atom, a hydrogen atom, and a sulfur atom, and a carbon atom, an oxygen atom, a nitrogen atom, and a hydrogen atom More preferably, it is selected from.
Specifically, R 11 is an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) or an alkenyl group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms). An alkynyl group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), an aryl group (preferably having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), an alkoxy group (preferably having a carbon number) 1 to 10, more preferably 1 to 6 carbon atoms), carboxyl group, crosslinkable group, oxygen atom, carbonyl group, sulfonyl group, arylene group (preferably 6 to 20 carbon atoms, more preferably 6 to 6 carbon atoms) 10) an alkylene group (preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkenylene group (preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), A nylene group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms) and an alkenyl group, alkynyl group, aryl group, carbonyl group, carboxyl group, crosslinkable group, oxygen atom, alkylene group, alkynylene group or It is more preferably a group consisting of a combination with an arylene group.
The crosslinkable group represented by R 11 is synonymous with the crosslinkable group represented by R 1 in formula (1), and the preferred range is also the same.
These groups may have a substituent, and examples of the substituent include a hydroxyl group, an alkyl group, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.
　一般式（Ｘ）で表される基の具体例としては、以下のものが挙げられるが、これらに限定されるものではない。式中、Ｐｈはフェニル基を表す。
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
 Specific examples of the group represented by the general formula (X) include, but are not limited to, the following. In the formula, Ph represents a phenyl group.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
　（Ａ）ポリベンゾオキサゾール前駆体の末端が架橋性基でない場合、封止基によって封止されていてもよい。この場合の封止基としては、アセチル基が例示される。 (A) When the terminal of the polybenzoxazole precursor is not a crosslinkable group, it may be sealed with a sealing group. An example of the sealing group in this case is an acetyl group.
　一方、本発明では、ポリベンゾオキサゾール前駆体の末端に架橋性基を有さない構成とすることも好ましい。このような態様にすることによって、ポリベンゾオキサゾール前駆体の分子量制御が容易になり、より均一な分子量を有する樹脂を得やすくなる。 On the other hand, in the present invention, it is also preferable that the polybenzoxazole precursor has no crosslinkable group at the terminal. By setting it as such an aspect, control of the molecular weight of a polybenzoxazole precursor becomes easy and it becomes easy to obtain resin which has a more uniform molecular weight.
　（Ａ）ポリベンゾオキサゾール前駆体は、重量平均分子量が３０００～２００，０００が好ましく、４０００～１０００００がより好ましく、５０００～５００００が最も好ましい。この範囲とすることでリソグラフィー性能と硬化膜物性とを優れたものとすることができる。ここで、重量平均分子量は、ゲルパーミエーションクロマトグラフィーのポリスチレン換算値をもって定義される。
　また、（Ａ）ポリベンゾオキサゾール前駆体は、数平均分子量が１０００～５００００が好ましく、２０００～４００００がより好ましく、３０００～３００００がさらに好ましい。ここで、数平均分子量は、ゲルパーミエーションクロマトグラフィーのポリスチレン換算値をもって定義される。 The polybenzoxazole precursor (A) has a weight average molecular weight of preferably 3000 to 200,000, more preferably 4000 to 100,000, and most preferably 5000 to 50000. By setting it as this range, the lithography performance and the cured film physical properties can be made excellent. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.
The number average molecular weight of the (A) polybenzoxazole precursor is preferably 1000 to 50000, more preferably 2000 to 40000, and still more preferably 3000 to 30000. Here, the number average molecular weight is defined as a polystyrene equivalent value of gel permeation chromatography.
　本発明の組成物中の（Ａ）ポリベンゾオキサゾール前駆体の含有量は、固形分換算で５０質量％以上が好ましく、６０質量％がより好ましく、７０質量％以上が特に好ましい。２種以上のポリベンゾオキサゾール前駆体を用いる場合は、その合計量が上記範囲となる。 The content of the (A) polybenzoxazole precursor in the composition of the present invention is preferably 50% by mass or more, more preferably 60% by mass, and particularly preferably 70% by mass or more in terms of solid content. When using 2 or more types of polybenzoxazole precursor, the total amount becomes the said range.
＜＜ポリベンゾオキサゾール前駆体の製造方法＞＞
　本発明で用いる架橋性基を含むポリベンゾオキサゾール前駆体は、特開２００８－２２４９０７号公報の記載を参酌して合成することができる。また、本発明では、架橋性基を含むポリベンゾオキサゾール前駆体を一般式（Ｘ）で表される基で封止することが好ましいが、かかる末端の封止は、末端をアミノ基とした樹脂を合成した後、末端のアミノ基を、カルボニル基またはスルホニル基を介して結合する、酸無水物または酸誘導体を用いてアミドとしてキャップする方法、或いは重合反応の際に単官能のアミン或いは酸クロリドを混ぜておくことにより一度に合成することができる。 << Method for Producing Polybenzoxazole Precursor >>
The polybenzoxazole precursor containing a crosslinkable group used in the present invention can be synthesized in consideration of the description in JP-A-2008-224907. In the present invention, it is preferable to seal the polybenzoxazole precursor containing a crosslinkable group with a group represented by the general formula (X). And then capping the terminal amino group via a carbonyl group or sulfonyl group, capping as an amide using an acid anhydride or acid derivative, or a monofunctional amine or acid chloride during the polymerization reaction It can be synthesized at once by mixing.
＜（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。なお本発明において、ｐＫａは、基本的に２５℃の水中におけるｐＫａを指す。水中で測定できないものは、測定に適する溶剤に変更し測定したものを指す。具体的には、化学便覧等に記載のｐＫａが参考にできる。 <(B) Photoacid generator>
The photosensitive resin composition of the present invention contains (B) a photoacid generator. The photoacid generator used in the present invention is preferably a compound that reacts with actinic rays having a wavelength of 300 nm or more, preferably 300 to 450 nm, and generates an acid, but is not limited to its chemical structure. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can also be used as a sensitizer if it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination. 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. In the present invention, pKa basically refers to pKa in water at 25 ° C. Those that cannot be measured in water refer to those measured after changing to a solvent suitable for measurement. Specifically, the pKa described in the chemical handbook can be referred to.
　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、感度、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、ＷＯ１１/０８７０１１号公報の段落番号００６５～００７２に記載の化合物が例示でき、これらの内容は本願明細書に組み込まれる。トリアリールスルホニウム塩類としては、下記構造のトリアリールスルホニウム塩類を好ましく使用することができる。
Figure JPOXMLDOC01-appb-C000030
 　また、イミドスルホネート化合物としては、下記構造のイミドスルホネート化合物を好ましく使用することができる。
　なお、トリアリールスルホニウム塩類、およびイミドスルホネート化合物は、後述する増感剤とともに用いることが好ましい。
Figure JPOXMLDOC01-appb-C000031
 （式中、Ｒは、それぞれ独立に、水素原子と炭素原子および／または酸素原子とからなる基を表し（Ｃ、Ｈ、Ｏ以外は含まない）、炭素原子と酸素原子との和が１６以下である。Ｒ1は、炭素原子数１６以下の１価有機基を表す。）
　Ｒは、それぞれ独立に、水素原子と炭素原子および／または酸素原子とからなる基を表し（Ｃ、Ｈ、Ｏ以外は含まない）、炭素原子と酸素原子との和が１６以下である。Ｒは、水素原子、または炭素数８以下のアルキレンオキサイド基が好ましい。
　Ｒ1は、炭素原子数１６以下の１価有機基を表す。Ｒ1は、Ｃ、Ｈ、Ｏ、Ｆ以外を含まないことが好ましい。Ｒ1としては、例えば、メチル基、トリフルオロメチル基、プロピル基、フェニル基、トシル基などが挙げられる。 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 viewpoints of sensitivity and 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 paragraph numbers 0083 to 0088 of JP2011-221494A, WO11 / 087011. The compounds described in paragraph numbers 0065 to 0072 of the publication can be exemplified, and the contents thereof are incorporated in the present specification. As the triarylsulfonium salt, a triarylsulfonium salt having the following structure can be preferably used.
Figure JPOXMLDOC01-appb-C000030
 Moreover, as an imide sulfonate compound, the imide sulfonate compound of the following structure can be used preferably.
Triarylsulfonium salts and imide sulfonate compounds are preferably used together with a sensitizer described later.
Figure JPOXMLDOC01-appb-C000031
 (In the formula, each R independently represents a group consisting of a hydrogen atom and a carbon atom and / or an oxygen atom (excluding other than C, H and O), and the sum of the carbon atom and the oxygen atom is 16 or less. R 1 represents a monovalent organic group having 16 or less carbon atoms.)
R independently represents a group consisting of a hydrogen atom and a carbon atom and / or an oxygen atom (excluding other than C, H and O), and the sum of the carbon atom and the oxygen atom is 16 or less. R is preferably a hydrogen atom or an alkylene oxide group having 8 or less carbon atoms.
R 1 represents a monovalent organic group having 16 or less carbon atoms. R 1 preferably does not contain other than C, H, O, and F. Examples of R 1 include a methyl group, a trifluoromethyl group, a propyl group, a phenyl group, and a tosyl group.
　このような化合物の具体例としては、以下の化合物が例示される。
Figure JPOXMLDOC01-appb-C000032
 Specific examples of such compounds include the following compounds.
Figure JPOXMLDOC01-appb-C000032
　このほか、イミドスルホネート化合物の具体例としてはＷＯ２０１１/０８７０１１号公報の段落番号００６５～００７５に記載の化合物や下記化合物が例示できる。 In addition, specific examples of the imide sulfonate compound include the compounds described in paragraph numbers 0065 to 0075 of WO2011 / 087011, and the following compounds.
　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含む化合物としては、下記一般式（Ｂ１－１）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。
一般式（Ｂ１－１）
Figure JPOXMLDOC01-appb-C000033
 （一般式（Ｂ１－１）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。） 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 (B1-1).
General formula (B1-1)
Figure JPOXMLDOC01-appb-C000033
 (In the general formula (B1-1), R 21 represents an alkyl group or an aryl group. The wavy line represents a bond with another group.)
　一般式（Ｂ１－１）中、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、ハロゲン原子、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、シクロアルキル基（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。 In general formula (B1-1), 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 represented by R 21 has a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group). It may be substituted with a bridged alicyclic group, preferably a bicycloalkyl group or the like.
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（Ｂ１－１）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（Ｂ１－２）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。
一般式（Ｂ１－２）
Figure JPOXMLDOC01-appb-C000034
 （式（Ｂ１－２）中、Ｒ42は、置換されていても良い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。） The compound containing the oxime sulfonate structure represented by the general formula (B1-1) is preferably an oxime sulfonate compound represented by the following general formula (B1-2).
General formula (B1-2)
Figure JPOXMLDOC01-appb-C000034
 (In the formula (B1-2), R 42 represents an optionally substituted alkyl group or aryl group, X represents an alkyl group, an alkoxy group, or a halogen atom, and m4 represents 0-3. Represents an integer, and when m4 is 2 or 3, a plurality of Xs may be the same or different.
　Ｒ42の好ましい範囲としては、上記Ｒ21の好ましい範囲と同一である。
　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。また、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。また、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（Ｂ１－２）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。 Preferred ranges of R 42, the same as the preferable range of the R 21.
The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. Further, 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 general formula (B1-2), m4 is 1, X is a methyl group, the substitution position of X is an ortho position, R 42 is a linear alkyl group having 1 to 10 carbon atoms, 7, A compound which is a 7-dimethyl-2-oxonorbornylmethyl group or a p-toluyl group is particularly preferred.
　上記一般式（Ｂ１－１）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（Ｂ１－３）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。
一般式（Ｂ１－３）
Figure JPOXMLDOC01-appb-C000035
 （式（Ｂ１－３）中、Ｒ43は式（Ｂ１－２）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。） The compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-3).
General formula (B1-3)
Figure JPOXMLDOC01-appb-C000035
 (In the formula (B1-3), R 43 has the same meaning as R 42 in the formula (B1-2), and X 1 is a halogen atom, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. Represents an alkoxy group, a cyano group or a nitro group, and n4 represents an integer of 0 to 5.)
　上記一般式（Ｂ１－３）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。
　上記一般式（Ｂ１－３）で表される化合物の具体例および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、特開２０１２－１６３９３７号公報の段落番号００８０～００８２の記載を参酌でき、この内容は本願明細書に組み込まれる。 R 43 in the above general formula (B1-3) is methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, trifluoromethyl group, pentafluoroethyl group, perfluoro-n—. A propyl group, a perfluoro-n-butyl group, a p-tolyl group, a 4-chlorophenyl group or a pentafluorophenyl group is preferable, and an n-octyl group is particularly preferable.
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.
As specific examples of the compound represented by the above general formula (B1-3) and preferable examples of the oxime sulfonate compound, the description in paragraphs 0080 to 0082 of JP2012-163937A can be referred to. Incorporated in the description.
　上記一般式（Ｂ１－１）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。
Figure JPOXMLDOC01-appb-C000036
 The compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably a compound represented by the following general formula (OS-1).
Figure JPOXMLDOC01-appb-C000036
　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。
　上記一般式（ＯＳ－１）で表される化合物は、例えば、特開２０１２－１６３９３７号公報の段落番号００８７～００８９に記載されている一般式（ＯＳ－２）で表される化合物であることが好ましく、この内容は本願明細書に組み込まれる。 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.
The compound represented by the general formula (OS-1) is, for example, a compound represented by the general formula (OS-2) described in paragraph numbers 0087 to 0089 of JP2012-163937A Which is incorporated herein by reference.
　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。
　本発明では、上記一般式（Ｂ１－１）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。
Figure JPOXMLDOC01-appb-C000037
 （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。）
　上記一般式（ＯＳ－３）～（ＯＳ－５）については、例えば、特開２０１３－４７７６５号公報の段落番号００３４～００７１の記載を参酌でき、この内容は本願明細書に組み込まれる。 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.
In the present invention, the compound containing the oxime sulfonate structure represented by the general formula (B1-1) is represented by the following general formula (OS-3), the following general formula (OS-4), or the following general formula (OS- The oxime sulfonate compound represented by 5) is preferred.
Figure JPOXMLDOC01-appb-C000037
 (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.)
With respect to the above general formulas (OS-3) to (OS-5), for example, the descriptions in paragraph numbers 0034 to 0071 of JP2013-47765A can be referred to, and the contents thereof are incorporated in the present specification.
　また、上記一般式（Ｂ１－１）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、例えば、特開２０１２－１６３９３７号公報の段落番号０１１７に記載されている、一般式（ＯＳ－６）～（ＯＳ－１１）のいずれかで表される化合物であることが特に好ましく、この内容は本願明細書に組み込まれる。
　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り、この内容は本願明細書に組み込まれる。
　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、この内容は本願明細書に組み込まれる。本発明は、これらに限定されるものではない。 In addition, the compound containing an oxime sulfonate structure represented by the above general formula (B1-1) is, for example, a compound represented by the general formula (OS-6) described in paragraph 0117 of JP2012-163937A. Particularly preferred is a compound represented by any of (OS-11), the contents of which are incorporated herein.
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. The contents of which are incorporated herein by reference.
Specific examples of the oxime sulfonate compound 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. The contents of which are incorporated herein by reference. The present invention is not limited to these.
　上記一般式（Ｂ１－１）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（Ｂ１－４）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。
一般式（Ｂ１－４）
Figure JPOXMLDOC01-appb-C000038
 （一般式（Ｂ１－４）中、Ｒ1は、アルキル基またはアリール基を表し、Ｒ2は、アルキル基、アリール基、またはヘテロアリール基を表す。Ｒ3～Ｒ6は、それぞれ、水素原子、アルキル基、アリール基、ハロゲン原子を表す。但し、Ｒ3とＲ4、Ｒ4とＲ5、またはＲ5とＲ6が結合して脂環または芳香環を形成してもよい。Ｘは、－Ｏ－またはＳ－を表す。） The compound containing an oxime sulfonate structure represented by the general formula (B1-1) is also preferably an oxime sulfonate compound represented by the following general formula (B1-4).
General formula (B1-4)
Figure JPOXMLDOC01-appb-C000038
 (In the general formula (B1-4), R 1 represents an alkyl group or an aryl group, R 2 represents an alkyl group, an aryl group, or a heteroaryl group. R 3 to R 6 each represents a hydrogen atom. Represents an alkyl group, an aryl group, or a halogen atom, provided that R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 may combine to form an alicyclic ring or aromatic ring. , -O- or S-.
　Ｒ1は、アルキル基またはアリール基を表す。アルキル基は、分岐構造を有するアルキル基または環状構造のアルキル基が好ましい。
　アルキル基の炭素数は、好ましくは３～１０である。特にアルキル基が分岐構造を有する場合、炭素数３～６のアルキル基が好ましく、環状構造を有する場合、炭素数５～７のアルキル基が好ましい。
　アルキル基としては、例えば、プロピル基、イソプロピル基、ｎ－ブチル基、ｓ－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、１，１－ジメチルプロピル基、ヘキシル基、２－エチルヘキシル基、シクロヘキシル基、オクチル基などが挙げられ、好ましくは、イソプロピル基、ｔｅｒｔ－ブチル基、ネオペンチル基、シクロヘキシル基である。
　アリール基の炭素数は、好ましくは６～１２であり、より好ましくは６～８であり、さらに好ましくは６～７である。上記アリール基としては、フェニル基、ナフチル基などが挙げられ、好ましくは、フェニル基である。
　Ｒ1が表すアルキル基およびアリール基は、置換基を有していてもよい。置換基としては、例えばハロゲン原子（フッ素原子、クロロ原子、臭素原子、ヨウ素原子）、直鎖、分岐または環状のアルキル基（例えばメチル基、エチル基、プロピル基など）、アルケニル基、アルキニル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、シアノ基、カルボキシル基、水酸基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、ヘテロ環オキシ基、アシルオキシ基、アミノ基、ニトロ基、ヒドラジノ基、ヘテロ環基などが挙げられる。また、これらの基によってさらに置換されていてもよい。好ましくは、ハロゲン原子、メチル基である。 R 1 represents an alkyl group or an aryl group. The alkyl group is preferably a branched alkyl group or a cyclic alkyl group.
The alkyl group preferably has 3 to 10 carbon atoms. In particular, when the alkyl group has a branched structure, an alkyl group having 3 to 6 carbon atoms is preferable. When the alkyl group has a cyclic structure, an alkyl group having 5 to 7 carbon atoms is preferable.
Examples of the alkyl group include propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, hexyl group. 2-ethylhexyl group, cyclohexyl group, octyl group and the like, preferably isopropyl group, tert-butyl group, neopentyl group, and cyclohexyl group.
The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 8 carbon atoms, and still more preferably 6 to 7 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The alkyl group and aryl group represented by R 1 may have a substituent. Examples of the substituent include a halogen atom (a fluorine atom, a chloro atom, a bromine atom, an iodine atom), a linear, branched or cyclic alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), an alkenyl group, an alkynyl group, Aryl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, cyano group, carboxyl group, hydroxyl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic oxy group, acyloxy group, amino group, A nitro group, a hydrazino group, a heterocyclic group, etc. are mentioned. Further, these groups may be further substituted. Preferably, they are a halogen atom and a methyl group.
　本発明の感光性樹脂組成物は、透明性の観点から、Ｒ1はアルキル基が好ましく、保存安定性と感度とを両立させる観点から、Ｒ1は、炭素数３～６の分岐構造を有するアルキル基、炭素数５～７の環状構造のアルキル基、または、フェニル基が好ましく、炭素数３～６の分岐構造を有するアルキル基、または炭素数５～７の環状構造のアルキル基がより好ましい。このようなかさ高い基（特に、かさ高いアルキル基）をＲ1として採用することにより、透明性をより向上させることが可能になる。
　かさ高い置換基の中でも、イソプロピル基、ｔｅｒｔ－ブチル基、ネオペンチル基、シクロヘキシル基が好ましく、ｔｅｒｔ－ブチル基、シクロヘキシル基がより好ましい。 In the photosensitive resin composition of the present invention, R 1 is preferably an alkyl group from the viewpoint of transparency, and R 1 has a branched structure having 3 to 6 carbon atoms from the viewpoint of achieving both storage stability and sensitivity. An alkyl group, an alkyl group having a cyclic structure having 5 to 7 carbon atoms, or a phenyl group is preferable, and an alkyl group having a branched structure having 3 to 6 carbon atoms or an alkyl group having a cyclic structure having 5 to 7 carbon atoms is more preferable. . By adopting such a bulky group (particularly a bulky alkyl group) as R 1 , it becomes possible to further improve the transparency.
Among the bulky substituents, an isopropyl group, a tert-butyl group, a neopentyl group, and a cyclohexyl group are preferable, and a tert-butyl group and a cyclohexyl group are more preferable.
　Ｒ2は、アルキル基、アリール基、またはヘテロアリール基を表す。Ｒ2が表すアルキル基としては、炭素数１～１０の、直鎖、分岐または環状のアルキル基が好ましい。上記アルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ－ブチル基、ｔｅｒｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基、シクロヘキシル基などが挙げられ、好ましくは、メチル基である。
　アリール基としては、炭素数６～１０のアリール基が好ましい。上記アリール基としては、フェニル基、ナフチル基、ｐ－トルイル基（ｐ－メチルフェニル基）などが挙げられ、好ましくは、フェニル基、ｐ－トルイル基である。
　ヘテロアリール基としては、例えば、ピロール基、インドール基、カルバゾール基、フラン基、チオフェン基などが挙げられる。
　Ｒ2が表すアルキル基、アリール基、およびヘテロアリール基は、置換基を有していてもよい。置換基としては、Ｒ1が表すアルキル基およびアリール基が有していてもよい置換基と同義である。
　Ｒ2は、アルキル基またはアリール基が好ましく、アリール基がより好ましく、フェニル基がより好ましい。フェニル基の置換基としてはメチル基が好ましい。 R 2 represents an alkyl group, an aryl group, or a heteroaryl group. The alkyl group represented by R 2 is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, and a cyclohexyl group. It is a group.
As the aryl group, an aryl group having 6 to 10 carbon atoms is preferable. Examples of the aryl group include a phenyl group, a naphthyl group, a p-toluyl group (p-methylphenyl group), and a phenyl group and a p-toluyl group are preferable.
Examples of the heteroaryl group include a pyrrole group, an indole group, a carbazole group, a furan group, and a thiophene group.
The alkyl group, aryl group, and heteroaryl group represented by R 2 may have a substituent. As a substituent, it is synonymous with the substituent which the alkyl group and aryl group which R < 1 > may have.
R 2 is preferably an alkyl group or an aryl group, more preferably an aryl group, and more preferably a phenyl group. As the substituent for the phenyl group, a methyl group is preferred.
　Ｒ3～Ｒ6は、それぞれ、水素原子、アルキル基、アリール基、またはハロゲン原子（フッ素原子、クロロ原子、臭素原子、ヨウ素原子）を表す。Ｒ3～Ｒ6が表すアルキル基としては、Ｒ2が表すアルキル基と同義であり、好ましい範囲も同様である。また、Ｒ3～Ｒ6が表すアリール基としては、Ｒ1が表すアリール基と同義であり、好ましい範囲も同様である。
　Ｒ3～Ｒ6のうち、Ｒ3とＲ4、Ｒ4とＲ5、またはＲ5とＲ6が結合して環を形成してもよく、環としては、脂環または芳香環を形成していることが好ましく、ベンゼン環がより好ましい。
　Ｒ3～Ｒ6は、水素原子、アルキル基、ハロゲン原子（フッ素原子、クロロ原子、臭素原子）、または、Ｒ3とＲ4、Ｒ4とＲ5、またはＲ5とＲ6が結合してベンゼン環を構成していることが好ましく、水素原子、メチル基、フッ素原子、クロロ原子、臭素原子またはＲ3とＲ4、Ｒ4とＲ5、またはＲ5とＲ6が結合してベンゼン環を構成していることがより好ましい。
　Ｒ3～Ｒ6の好ましい態様は以下の通りである。
（態様１）少なくとも２つは水素原子である。
（態様２）アルキル基、アリール基、またはハロゲン原子の数は、１つ以下である。
（態様３）Ｒ3とＲ4、Ｒ4とＲ5、またはＲ5とＲ6が結合してベンゼン環を構成している。
（態様４）上記態様１と２を満たす態様、および／または、上記態様１と３を満たす態様。
　Ｘは、－Ｏ－またはＳ－を表す。 R 3 to R 6 each represent a hydrogen atom, an alkyl group, an aryl group, or a halogen atom (a fluorine atom, a chloro atom, a bromine atom, or an iodine atom). The alkyl group represented by R 3 to R 6 has the same meaning as the alkyl group represented by R 2 , and the preferred range is also the same. The aryl group represented by R 3 to R 6 has the same meaning as the aryl group represented by R 1 , and the preferred range is also the same.
Among R 3 to R 6 , R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 may combine to form a ring, and the ring may form an alicyclic ring or an aromatic ring. It is preferable that a benzene ring is more preferable.
R 3 to R 6 are each a hydrogen atom, an alkyl group, a halogen atom (fluorine atom, chloro atom, bromine atom), or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6. A benzene ring is preferably formed, and a hydrogen atom, a methyl group, a fluorine atom, a chloro atom, a bromine atom, or R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 are combined to form a benzene ring Is more preferable.
Preferred embodiments of R 3 to R 6 are as follows.
(Aspect 1) At least two are hydrogen atoms.
(Aspect 2) The number of alkyl groups, aryl groups, or halogen atoms is one or less.
(Aspect 3) R 3 and R 4 , R 4 and R 5 , or R 5 and R 6 are combined to form a benzene ring.
(Aspect 4) An aspect satisfying the above aspects 1 and 2 and / or an aspect satisfying the above aspects 1 and 3.
X represents —O— or S—.
　上記一般式（Ｂ１－４）の具体例としては、以下のような化合物が挙げられるが、本発明では特にこれに限定されない。なお、例示化合物中、Ｔｓはトシル基（ｐ－トルエンスルホニル基）を表し、Ｍｅはメチル基を表し、Ｂｕはｎ－ブチル基を表し、Ｐｈはフェニル基を表す。 Specific examples of the general formula (B1-4) include the following compounds, but the present invention is not particularly limited thereto. In the exemplified compounds, Ts represents a tosyl group (p-toluenesulfonyl group), Me represents a methyl group, Bu represents an n-butyl group, and Ph represents a phenyl group.
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　本発明の感光性樹脂組成物において、（Ｂ）光酸発生剤の含有量は、感光性樹脂組成物中の全固形成分１００質量部に対して、０．１～２０質量部が好ましく、０．５～１０質量部がより好ましく、０．５～５質量部がさらに好ましい。光酸発生剤は、１種のみを用いてもよいし、２種以上を併用することもできる。光酸発生剤は、１種単独で使用しても、２種以上を併用してもよい。２種類以上の光酸発生剤を用いる場合は、その合計量が上記範囲となる。 In the photosensitive resin composition of the present invention, the content of the (B) photoacid generator is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. 5 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is even more preferable. Only 1 type may be used for a photo-acid generator, and it can also use 2 or more types together. A photo-acid generator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of photo-acid generators, the total amount becomes the said range.
＜（Ｃ）溶剤＞
　本発明の感光性樹脂組成物は、（Ｃ）溶剤を含有する。本発明の感光性樹脂組成物は、本発明の必須成分と、さらに後述の任意の成分を溶剤に溶解した溶液として調製されることが好ましい。本発明の組成物の調製に用いられる溶剤としては、必須成分および任意成分を均一に溶解し、各成分と反応しないものが用いられる。
　本発明の感光性樹脂組成物に使用される溶剤としては、公知の溶剤を用いることができ、エチレングリコールモノアルキルエーテル類、エチレングリコールジアルキルエーテル類、エチレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類、プロピレングリコールジアルキルエーテル類、プロピレングリコールモノメチルエーテルアセテートなどの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エチルメチルエーテルなどの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、γ－ブチロラクトンなどのラクトン類、ピロリドン類等が例示できる。また、本発明の感光性樹脂組成物に使用される溶剤の具体例としては特開２０１１－２２１４９４号公報の段落番号０１７４～０１７８に記載の溶剤、特開２０１２－１９４２９０号公報の段落番号０１６７～０１６８に記載の溶剤も挙げられ、これらの内容は本願明細書に組み込まれる。 <(C) Solvent>
The photosensitive resin composition of the present invention contains (C) a solvent. The photosensitive resin composition of the present invention is preferably prepared as a solution in which the essential components of the present invention and further optional components described below are dissolved in a solvent. As a solvent used for the preparation of the composition of the present invention, a solvent that uniformly dissolves essential components and optional components and does not react with each component is used.
As the solvent used in the photosensitive resin composition of the present invention, known solvents can be used, such as ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl. Ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, diethylene glycol dialkyl ethers such as diethylene glycol ethyl methyl ether, diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, Dipropylene glycol dialkyl ethers, dipropylene glycol mono Ruki ether acetates, esters, ketones, amides, lactones such as γ- butyrolactone, pyrrolidones and the like. Specific examples of the solvent used in the photosensitive resin composition of the present invention include the solvents described in paragraphs 0174 to 0178 of JP2011-221494A, and paragraphs of 0167 to 167290 of JP2012-194290A. Also included are the solvents described in 0168, the contents of which are incorporated herein.
　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、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 or more types, more preferably a combination of two types, propylene glycol monoalkyl ether acetates or dialkyl ethers, diacetates. It is more preferable to use a combination of styrene and diethylene glycol dialkyl ether or an ester and butylene glycol alkyl ether acetate.
　また、溶剤としては、沸点１３０℃以上１６０℃未満の溶剤、沸点１６０℃以上の溶剤、または、これらの混合物であることが好ましい。
　沸点１３０℃以上１６０℃未満の溶剤としては、プロピレングリコールモノメチルエーテルアセテート（沸点１４６℃）、プロピレングリコールモノエチルエーテルアセテート(沸点１５８℃)、プロピレングリコールメチル－ｎ－ブチルエーテル（沸点１５５℃）、プロピレングリコールメチル－ｎ－プロピルエーテル（沸点１３１℃）が例示できる。
　沸点１６０℃以上の溶剤としては、３－エトキシプロピオン酸エチル（沸点１７０℃）、ジエチレングリコールメチルエチルエーテル（沸点１７６℃）、プロピレングリコールモノメチルエーテルプロピオネート（沸点１６０℃）、ジプロピレングリコールメチルエーテルアセテート（沸点２１３℃）、３－メトキシブチルエーテルアセテート（沸点１７１℃）、ジエチレングリコールジエチエルエーテル（沸点１８９℃）、ジエチレングリコールジメチルエーテル（沸点１６２℃）、プロピレングリコールジアセテート（沸点１９０℃）、ジエチレングリコールモノエチルエーテルアセテート（沸点２２０℃）、ジプロピレングリコールジメチルエーテル（沸点１７５℃）、１，３－ブチレングリコールジアセテート（沸点２３２℃）、Ｎ－メチル－２－ピロリドン（沸点２０４℃）、γ－ブチロラクトン（沸点２０４℃）が例示できる。 Further, the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), propylene glycol An example is methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Boiling point 213 ° C), 3-methoxybutyl ether acetate (boiling point 171 ° C), diethylene glycol diethyl ether (boiling point 189 ° C), diethylene glycol dimethyl ether (boiling point 162 ° C), propylene glycol diacetate (boiling point 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C.), dipropylene glycol dimethyl ether (boiling point 175 ° C.), 1,3-butylene glycol diacetate (boiling point 232 ° C.), N Methyl-2-pyrrolidone (boiling point 204 ° C.), .gamma.-butyrolactone (boiling point 204 ° C.) can be exemplified.
　本発明の感光性樹脂組成物における溶剤の含有量は、感光性樹脂組成物中の全成分１００質量部当たり、５０～９５質量部であることが好ましく、６０～９０質量部であることがさらに好ましい。溶剤は、１種単独で使用しても、２種以上を併用してもよい。２種類以上の溶剤を用いる場合は、その合計量が上記範囲となる。 The content of the solvent in the photosensitive resin composition of the present invention is preferably 50 to 95 parts by mass and more preferably 60 to 90 parts by mass with respect to 100 parts by mass of all components in the photosensitive resin composition. preferable. A solvent may be used individually by 1 type, or may use 2 or more types together. When two or more kinds of solvents are used, the total amount falls within the above range.
＜（Ｄ）架橋剤＞
　本発明の感光性樹脂組成物は、架橋剤を含有していてもよい。架橋剤とは、架橋基を分子内に少なくとも２つ以上含有する化合物であり、架橋基とは、熱によりポリベンゾオキサゾール前駆体の、架橋性基/ベンゼン環/ヒドロキシ基と反応する基を意味する。架橋基としては、メチロール基、エポキシ基、オキセタニル基、アルコキシメチル基、ブロックイソシアネート基、メタクリロイル基およびアクリロイル基が好ましく、メチロール基、エポキシ基、アルコキシメチル基、ブロックイソシアネート基、メタクリロイル基およびアクリロイル基がより好ましい。
　また、架橋剤一分子中の架橋基の数は、３以上であることが好ましく、４以上であることがより好ましい。
　架橋基は、同じ種類の架橋基を分子内に２つ以上有していてもよいし、異なる種類の架橋基を分子内に２つ以上有していてもよい。
　これらの架橋剤は、（Ａ）ポリベンゾオキサゾール前駆体（特に、前駆体中のベンゼン環および／またはフェノール性水酸基）と反応し、（Ａ）ポリベンゾオキサゾール前駆体間に架橋構造を形成し、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。
　本発明で用いる架橋剤の分子量は、１５０～３００００が好ましく、２００～１００００がより好ましい。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。
　本発明の感光性樹脂組成物中における架橋剤の含有量は、架橋剤を配合する場合、上記（Ａ）成分の合計１００質量部に対し、０．０１～２００質量部であることが好ましく、１～１００質量部であることがより好ましく、５～６０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。 <(D) Crosslinking agent>
The photosensitive resin composition of the present invention may contain a crosslinking agent. The crosslinking agent is a compound containing at least two crosslinking groups in the molecule, and the crosslinking group means a group that reacts with the crosslinking group / benzene ring / hydroxy group of the polybenzoxazole precursor by heat. To do. As the crosslinking group, a methylol group, an epoxy group, an oxetanyl group, an alkoxymethyl group, a blocked isocyanate group, a methacryloyl group and an acryloyl group are preferable, and a methylol group, an epoxy group, an alkoxymethyl group, a blocked isocyanate group, a methacryloyl group and an acryloyl group are preferable. More preferred.
The number of cross-linking groups in one molecule of the cross-linking agent is preferably 3 or more, and more preferably 4 or more.
The cross-linking group may have two or more of the same type of cross-linking group in the molecule, or may have two or more different types of cross-linking groups in the molecule.
These crosslinking agents react with (A) a polybenzoxazole precursor (particularly, a benzene ring and / or a phenolic hydroxyl group in the precursor) to form a crosslinked structure between (A) the polybenzoxazole precursor, The cured film obtained by the photosensitive resin composition of the present invention can be made a stronger film.
The molecular weight of the crosslinking agent used in the present invention is preferably 150 to 30000, and more preferably 200 to 10000. By setting it as such a range, the effect of this invention is exhibited more effectively.
The content of the crosslinking agent in the photosensitive resin composition of the present invention is preferably 0.01 to 200 parts by mass with respect to a total of 100 parts by mass of the component (A) when the crosslinking agent is blended. The amount is more preferably 1 to 100 parts by mass, and further preferably 5 to 60 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.
　本発明の組成物は、架橋剤を実質的に含まない構成とすることもできる。実施的に含まない構成とは、架橋剤が組成物の固形分の、例えば、１質量％以下であることをいう。 The composition of the present invention can be configured to be substantially free of a crosslinking agent. The configuration not actually included means that the cross-linking agent is, for example, 1% by mass or less of the solid content of the composition.
＜＜分子内に２個以上のエポキシ基を有する化合物＞＞
　本発明の感光性樹脂組成物では、架橋剤として、分子内に２個以上のエポキシ基を有する化合物を用いることができる。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、エポキシ基含有構成単位有するアクリル樹脂等を挙げることができる。 << Compound having two or more epoxy groups in the molecule >>
In the photosensitive resin composition of the present invention, a compound having two or more epoxy groups in the molecule can be used as a crosslinking agent. 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 epoxy group containing An acrylic resin having a structural unit can be given.
　これらは市販品として入手できる。例えば、ＪＥＲ１５２、ＪＥＲ１５７Ｓ７０、ＪＥＲ１５７Ｓ６５、ＪＥＲ８０６、ＪＥＲ８２８、ＪＥＲ１００７（（株）三菱ケミカルホールディングス製）など、特開２０１１－２２１４９４号公報の段落番号０１８９に記載の市販品などが挙げられ、その他にも、デナコールＥＸ－６１１、ＥＸ－６１２、ＥＸ－６１４、ＥＸ－６１４Ｂ、ＥＸ－６２２、ＥＸ－５１２、ＥＸ－５２１、ＥＸ－４１１、ＥＸ－４２１、ＥＸ－３１３、ＥＸ－３１４、ＥＸ－３２１、ＥＸ－３２１Ｌ、ＥＸ－２１１、ＥＸ－２１２、ＥＸ－８１０、ＥＸ－８１１、ＥＸ－８５０、ＥＸ－８５１、ＥＸ－８２１、ＥＸ－８３０、ＥＸ－８３２、ＥＸ－８４１、ＥＸ－９１１、ＥＸ－９４１、ＥＸ－９２０、ＥＸ－９３１、ＥＸ－２１２Ｌ、ＥＸ－２１４Ｌ、ＥＸ－２１６Ｌ、ＥＸ－３２１Ｌ、ＥＸ－８５０Ｌ、ＤＬＣ－２０１、ＤＬＣ－２０３、ＤＬＣ－２０４、ＤＬＣ－２０５、ＤＬＣ－２０６、ＤＬＣ－３０１、ＤＬＣ－４０２（以上ナガセケムテック製）、ＹＨ－３００、ＹＨ－３０１、ＹＨ－３０２、ＹＨ－３１５、ＹＨ－３２４、ＹＨ－３２５（以上新日鐵化学製）、セロキサイド ２０２１Ｐ、セロキサイド ２０８１、ＥＨＰＥ３１５０、ＥＨＰＥ３１５０ＣＥ（以上ダイセル）などが挙げられる。これらは１種単独または２種以上を組み合わせて使用することができる。
　これらの中でも、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂および脂肪族エポキシ樹脂がより好ましく挙げられ、ビスフェノールＡ型エポキシ樹脂が特に好ましく挙げられる。 These are available as commercial products. For example, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like are commercially available products described in paragraph No. 0189 of JP2011-221494, etc. EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX-411, EX-421, EX-313, EX-314, EX-321, EX- 321L, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212L, EX-214L, X-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402 (manufactured by Nagase Chemtech), YH-300 YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel Chemical Co., Ltd.), Celoxide 2021P, Celoxide 2081, EHPE3150, EHPE3150CE (Daicel). These can be used alone or in combination of two or more.
Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and bisphenol A type epoxy resin is particularly preferable.
＜＜分子内に２個以上のアルコキシメチル基またはメチロール基を含有する架橋剤＞＞
　本発明の感光性樹脂組成物では、架橋剤として、アルコキシメチル基またはメチロール基を含有する架橋剤を用いることができる。分子内に２個以上のアルコキシメチル基またはメチロール基を含有する架橋剤としては、下記一般式（１）または一般式（２）で表される構造を分子内に２個以上有する架橋剤であり、アルコキシメチル基とメチロール基のいずれか一方または両方を合計で２個以上分子内に含有する。
－ＣＨ2ＯＲ1　（１）
（式中、Ｒ1は炭素原子数１～８のアルキル基を表し、炭素数１～４のアルキル基が好ましく、メチル基がより好ましい。）
－ＣＨ2ＯＨ　（２） << Crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule >>
In the photosensitive resin composition of the present invention, a crosslinking agent containing an alkoxymethyl group or a methylol group can be used as the crosslinking agent. The crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule is a crosslinking agent having two or more structures represented by the following general formula (1) or general formula (2) in the molecule. , One or both of an alkoxymethyl group and a methylol group are contained in the molecule in a total of two or more.
-CH 2 OR 1 (1)
(In the formula, R 1 represents an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.)
—CH 2 OH (2)
　アルコキシメチル基またはメチロール基は、窒素原子または芳香族環を形成する炭素原子に結合していることが好ましい。 The alkoxymethyl group or methylol group is preferably bonded to a nitrogen atom or a carbon atom forming an aromatic ring.
　アルコキシメチル基またはメチロール基が、窒素原子に結合している架橋剤としては、アルコキシメチル化メラミン、メチロール化メラミン、アルコキシメチル化ベンゾグアナミン、メチロール化ベンゾグアナミン、アルコキシメチル化グリコールウリル、メチロール化グリコールウリル、アルコキシメチル化尿素およびメチロール化尿素等が好ましい。アルコキシメチル化メラミン、アルコキシメチル化ベンゾグアナミン、アルコキシメチル化グリコールウリル、アルコキシメチル化尿素は、それぞれメチロール化メラミン、メチロール化ベンゾグアナミン、メチロール化グリコールウリル、または、メチロール化尿素のメチロール基をアルコキシメチル基に変換することにより得られる。このアルコキシメチル基の種類については、メトキシメチル基、エトキシメチル基、プロポキシメチル基、ブトキシメチル基等を挙げることができるが、アウトガスの発生量の観点から、メトキシメチル基が特に好ましい。
　これらの架橋性化合物のうち、アルコキシメチル化メラミン、メチロール化メラミン、アルコキシメチル化ベンゾグアナミン、メチロール化ベンゾグアナミン、アルコキシメチル化グリコールウリル、メチロール化グリコールウリルが好ましい架橋性化合物として挙げられ、透明性の観点から、アルコキシメチル化グリコールウリルおよびメチロール化グリコールウリルが特に好ましい。
　本発明では、特開２０１２－８２２３号公報の段落番号０１０７に記載のアルコキシメチル基含有架橋剤、を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。 Examples of the crosslinking agent in which an alkoxymethyl group or a methylol group is bonded to a nitrogen atom include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril, alkoxy Methylated urea and methylolated urea are preferred. Alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, and alkoxymethylated urea convert methylolated melamine, methylolated benzoguanamine, methylolated glycoluril, or methylol group of methylolated urea to alkoxymethyl group, respectively. Can be obtained. Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group, and the methoxymethyl group is particularly preferable from the viewpoint of outgas generation amount.
Among these crosslinkable compounds, alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluril, methylolated glycoluril are mentioned as preferred crosslinkable compounds, from the viewpoint of transparency Alkoxymethylated glycoluril and methylolated glycoluril are particularly preferred.
In the present invention, the alkoxymethyl group-containing crosslinking agent described in paragraph No. 0107 of JP2012-8223A can be preferably used, and the contents thereof are incorporated in the present specification.
　分子内に２個以上のアルコキシメチル基またはメチロール基を含有する架橋剤の好ましい構造として、下記式（８－１）～（８－４）で示される化合物及を挙げることができる。
Figure JPOXMLDOC01-appb-C000040
 （上記式（８－１）～（８－４）中、Ｒ7およびＲはそれぞれ独立して水素原子または炭素数１～８のアルキル基を表し、Ｒ8～Ｒ11はそれぞれ独立して、水素原子、水酸基、アルキル基またはアルコキシル基を表し、Ｘ2は、単結合、メチレン基または酸素原子を表す。） Preferred structures of the crosslinking agent containing two or more alkoxymethyl groups or methylol groups in the molecule include compounds represented by the following formulas (8-1) to (8-4).
Figure JPOXMLDOC01-appb-C000040
 (In the above formulas (8-1) to (8-4), R 7 and R each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R 8 to R 11 each independently represents Represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxyl group, and X 2 represents a single bond, a methylene group or an oxygen atom.)
　Ｒ7およびＲが表すアルキル基は、炭素数１～８であり、炭素数１～４がより好ましく、例えばメチル基、エチル基、プロピル基が挙げられる。Ｒ8～Ｒ11が表すアルキル基は、炭素数１～８が好ましく、炭素数１～４がより好ましく、例えば、メチル基、エチル基、プロピル基が挙げられる。Ｒ8～Ｒ11が表すアルコキシル基は、炭素数１～８が好ましく、炭素数１～４がより好ましく、例えばメトキシ基、エトキシ基、プロポキシ基が挙げられる。Ｘ2は単結合またはメチレン基であるのが好ましい。Ｒ7～Ｒ11、Ｘ2は、メチル基、エチル基等のアルキル基、ハロゲン原子などで置換されていてもよい。複数個のＲ7、Ｒ、Ｒ8～Ｒ11は、各々同一でも異なっていてもよい。 The alkyl group represented by R 7 and R has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The alkyl group represented by R 8 to R 11 preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The alkoxyl group represented by R 8 to R 11 preferably has 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a propoxy group. X 2 is preferably a single bond or a methylene group. R 7 to R 11 and X 2 may be substituted with an alkyl group such as a methyl group or an ethyl group, or a halogen atom. A plurality of R 7 , R, and R 8 to R 11 may be the same or different.
　式（８－１）で表される化合物として具体的には、例えば、以下に示される化合物等を挙げることができる。
Figure JPOXMLDOC01-appb-C000041
 Specific examples of the compound represented by the formula (8-1) include the compounds shown below.
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
　式（８－２）で表される化合物として具体的には、例えば、Ｎ，Ｎ，Ｎ，Ｎ－テトラメチロールグリコールウリル、Ｎ，Ｎ，Ｎ，Ｎ－テトラメチロールグリコールウリルのメチロール基が１～４個のメトキシメチル化した化合物、Ｎ，Ｎ，Ｎ，Ｎ－テトラメチロールグリコールウリルのメチロール基が１～４個のエトキシメチル化した化合物、Ｎ，Ｎ，Ｎ，Ｎ－テトラメチロールグリコールウリルのメチロール基が1～4個のｎ－プロポキシメチル化した化合物、Ｎ，Ｎ，Ｎ，Ｎ－テトラメチロールグリコールウリルのメチロール基が１～４個のイソプロポキシメチル化した化合物、Ｎ，Ｎ，Ｎ，Ｎ－テトラメチロールグリコールウリルのメチロール基が１～４個のｎ－ブトキシメチル化した化合物、Ｎ，Ｎ，Ｎ，Ｎ－テトラメチロールグリコールウリルのメチロール基が１～４個のｔｅｒｔ－ブトキシメチル化した化合物等を挙げることができる。この中で、特に、Ｎ，Ｎ，Ｎ，Ｎ－テトラメチロールグリコールウリルのメチロール基が１～４個のメトキシメチル化した化合物が好ましい。 Specific examples of the compound represented by the formula (8-2) include N, N, N, N-tetramethylolglycoluril, N, N, N, N-tetramethylolglycoluril having 1 to 1 methylol groups. 4 methoxymethylated compounds, N, N, N, N-tetramethylolglycoluril methylol group having 1 to 4 ethoxymethylated compounds, N, N, N, N-tetramethylolglycoluril methylol N-propoxymethylated compounds having 1 to 4 groups, isopropoxymethylated compounds having 1 to 4 methylol groups in N, N, N, N-tetramethylolglycoluril, N, N, N, N -N-butoxymethylated compound having 1 to 4 methylol groups of tetramethylol glycoluril, N, N, N, N-tetramethylolglycol Methylol groups Ruuriru can be exemplified such as 1-4 tert- butoxy methylated compound. Of these, compounds having 1 to 4 methoxymethylated methylol groups of N, N, N, N-tetramethylolglycoluril are particularly preferred.
　式（８－３）で表される化合物として具体的には、例えば、以下に示される化合物等を挙げることができる。
Figure JPOXMLDOC01-appb-C000043
 Specific examples of the compound represented by the formula (8-3) include the compounds shown below.
Figure JPOXMLDOC01-appb-C000043
　式（８－４）で表される化合物として具体的には、例えば、Ｎ，Ｎ，Ｎ，Ｎ，Ｎ，Ｎ－ヘキサメチロールメラミン、Ｎ，Ｎ，Ｎ，Ｎ，Ｎ，Ｎ－ヘキサメチロールメラミンのメチロール基が1～6個メトキシメチル化した化合物、Ｎ，Ｎ，Ｎ，Ｎ，Ｎ，Ｎ－ヘキサメチロールメラミンのメチロール基が１～６個エトキシメチル化した化合物、Ｎ，Ｎ，Ｎ，Ｎ，Ｎ，Ｎ－ヘキサメチロールメラミンのメチロール基が１～６個ｎ－プロポキシメチル化した化合物、Ｎ，Ｎ，Ｎ，Ｎ，Ｎ，Ｎ－ヘキサメチロールメラミンのメチロール基が１～６個イソプロポキシメチル化した化合物、、Ｎ，Ｎ，Ｎ，Ｎ，Ｎ，Ｎ－ヘキサメチロールメラミンのメチロール基が１～６個ｎ－ブトキシメチル化した化合物、Ｎ，Ｎ，Ｎ，Ｎ，Ｎ，Ｎ－ヘキサメチロールメラミンのメチロール基が１～６個ｔｅｒｔ－ブトキシメチル化した化合物等を挙げることができる。この中で特に、Ｎ，Ｎ，Ｎ，Ｎ，Ｎ，Ｎ－ヘキサ（メトキシメチル）メラミンが好ましい。 Specific examples of the compound represented by the formula (8-4) include N, N, N, N, N, N-hexamethylol melamine, N, N, N, N, N, N-hexamethylol melamine. 1-6 methoxymethylated methylol groups, 1-6 methoxymethylated methylol groups of N, N, N, N, N, N-hexamethylolmelamine, N, N, N, N , N, N-hexamethylolmelamine 1-6 methylol groups n-propoxymethylated, N, N, N, N, N, N-hexamethylolmelamine 1-6 methylol groups isopropoxymethyl Compound, N, N, N, N, N, N-hexamethylol compound in which 1 to 6 methylol groups of melamine are n-butoxymethylated, N, N, N, N, N, N-hexamethylol Mela Methylol groups of the emission can be cited 1-6 tert- butoxy methylated compounds were like. Among these, N, N, N, N, N, N-hexa (methoxymethyl) melamine is particularly preferable.
　アルコキシメチル基またはメチロール基が、芳香族環を形成する炭素原子に結合している架橋剤の例として、例えば下記一般式（４）～（５）で表されるものを挙げることができる。 Examples of the crosslinking agent in which an alkoxymethyl group or a methylol group is bonded to a carbon atom that forms an aromatic ring include those represented by the following general formulas (4) to (5).
Figure JPOXMLDOC01-appb-C000044
 （式（４）中、Ｘは単結合または１～４価の有機基を表し、Ｒ11、Ｒ12は各々独立に水素原子または一価の有機基を表し、ｎは１～４の整数であり、ｐおよびｑは各々独立に０～４の整数である。）
Figure JPOXMLDOC01-appb-C000044
 (In the formula (4), X represents a single bond or a monovalent to tetravalent organic group, R 11 and R 12 each independently represents a hydrogen atom or a monovalent organic group, and n is an integer of 1 to 4. And p and q are each independently an integer of 0 to 4.)
Figure JPOXMLDOC01-appb-C000045
 （式（５）中、２つのＹは各々独立に水素原子または炭素原子数１～１０のアルキル基で酸素原子、フッ素原子を含んでいてもよく、Ｒ13～Ｒ16は各々独立に水素原子または一価の有機基を示し、ｍおよびｎは各々独立に１～３の整数であり、ｐおよびｑは各々独立に０～４の整数である。）
Figure JPOXMLDOC01-appb-C000045
 (In the formula (5), two Y's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms and may contain an oxygen atom or a fluorine atom, and R 13 to R 16 are each independently a hydrogen atom. Or a monovalent organic group, m and n are each independently an integer of 1 to 3, and p and q are each independently an integer of 0 to 4.)
　一般式（４）～（５）で表される具体的化合物として、例えば以下に示すものを挙げることができる。Ｍｅはメチル基を表す。
Figure JPOXMLDOC01-appb-C000046
 Specific examples of the compounds represented by the general formulas (4) to (5) include those shown below. Me represents a methyl group.
Figure JPOXMLDOC01-appb-C000046
　これらの分子内に２個以上のアルコキシメチル基またはメチロール基を含有する架橋剤は、市販品としても入手可能であり、例えば、サイメル３００、３０１、３０３、３７０、３２５、３２７、７０１、２６６、２６７、２３８、１１４１、２７２、２０２、１１５６、１１５８、１１２３、１１７０、１１７４、ＵＦＲ６５、３００（以上、三井サイアナミッド（株）製）、ニカラックＭＸ－７５０、－０３２、－７０６、－７０８、－４０、－３１、－２７０、－２８０、－２９０、－７５０ＬＭ、ニカラックＭＳ－１１、ニカラックＭＷ－３０ＨＭ、－１００ＬＭ、－３９０、（以上、（株）三和ケミカル製）などを好ましく使用することができる。これらは１種単独または２種以上を組み合わせて使用することができる。 Crosslinking agents containing two or more alkoxymethyl groups or methylol groups in these molecules are also available as commercial products, for example, Cymel 300, 301, 303, 370, 325, 327, 701, 266, 267, 238, 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (above, manufactured by Mitsui Cyanamid Co., Ltd.), Nicarax MX-750, -032, -706, -708, -40 , -31, -270, -280, -290, -750LM, Nicarak MS-11, Nicarak MW-30HM, -100LM, -390, (manufactured by Sanwa Chemical Co., Ltd.), etc. are preferably used. it can. These can be used alone or in combination of two or more.
＜＜分子内に２個以上のブロックイソシアネート基を含有する化合物＞＞
　本発明の感光性樹脂組成物では、架橋剤として、分子内に２個以上のブロックイソシアネート基を含有する化合物を用いることができる。
　本発明におけるブロックイソシアネート基とは、熱によりイソシアネート基を生成することが可能な基であり、例えば、ブロック剤とイソシアネート基とを反応させイソシアネート基を保護した基が好ましく例示できる。また、上記ブロックイソシアネート基は、９０℃～２５０℃の熱によりイソシアネート基を生成することが可能な基であることが好ましい。
　また、ブロックイソシアネート化合物としては、その骨格は特に限定されるものではなく、１分子中にイソシアネート基を２個以上有するものであればどのようなものでもよく、脂肪族、脂環族または芳香族のポリイソシアネートであってよいが、例えば２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、イソホロンジイソシアネート、１，６－ヘキサメチレンジイソシアネート、１，３－トリメチレンジイソシアネート、１，４－テトラメチレンジイソシアネート、２，２，４－トリメチルヘキサメチレンジイソシアネート、２，４，４－トリメチルヘキサメチレンジイソシアネート、１，９－ノナメチレンジイソシアネート、１，１０－デカメチレンジイソシアネート、１，４－シクロヘキサンジイソシアネート、２，２'－ジエチルエーテルジイソシアネート、ジフェニルメタン－４，４'－ジイソシアネート、ｏ－キシレンジイソシアネート、ｍ－キシレンジイソシアネート、ｐ－キシレンジイソシアネート、メチレンビス（シクロヘキシルイソシアネート）、シクロヘキサン－１，３－ジメチレンジイソシアネート、シクロヘキサン－１，４－ジメチレレンジイソシアネート、１，５－ナフタレンジイソシアネート、ｐ－フェニレンジイソシアネート、３，３'－メチレンジトリレン－４，４'－ジイソシアネート、４，４'－ジフェニルエーテルジイソシアネート、テトラクロロフェニレンジイソシアネート、ノルボルナンジイソシアネート、水素化１，３－キシリレンジイソシアネート、水素化１，４－キシリレンジイソシアネート等のイソシアネート化合物およびこれらの化合物から派生するプレポリマー型の骨格の化合物を好適に用いることができる。これらの中でも、トリレンジイソシアネート（ＴＤＩ）やジフェニルメタンジイソシアネート（ＭＤＩ）、ヘキサメチレンジイソシアネート（ＨＤＩ）、イソホロンジイソシアネート（ＩＰＤＩ）が特に好ましい。
　本発明の感光性樹脂組成物におけるブロックイソシアネート化合物の母構造としては、ビウレット型、イソシアヌレート型、アダクト型、２官能プレポリマー型等を挙げることができる。
　上記ブロックイソシアネート化合物のブロック構造を形成するブロック剤としては、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物、メルカプタン化合物、イミダゾール系化合物、イミド系化合物等を挙げることができる。これらの中でも、オキシム化合物、ラクタム化合物、フェノール化合物、アルコール化合物、アミン化合物、活性メチレン化合物、ピラゾール化合物から選ばれるブロック剤が特に好ましい。 << Compound containing two or more blocked isocyanate groups in the molecule >>
In the photosensitive resin composition of the present invention, a compound containing two or more blocked isocyanate groups in the molecule can be used as a crosslinking agent.
The blocked isocyanate group in the present invention is a group capable of generating an isocyanate group by heat. For example, a group obtained by reacting a blocking agent with an isocyanate group to protect the isocyanate group can be preferably exemplified. 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 any skeleton having two or more isocyanate groups in one molecule may be used, and may be aliphatic, alicyclic or aromatic. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4-tetraisocyanate Methylene 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, Isocyanates such as norbornane diisocyanate, hydrogenated 1,3-xylylene diisocyanate, hydrogenated 1,4-xylylene diisocyanate And prepolymer type skeleton compounds derived from these compounds can be suitably used. Among these, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and isophorone diisocyanate (IPDI) are particularly preferable.
Examples of the matrix structure of the blocked isocyanate compound in the photosensitive resin composition of the present invention include biuret type, isocyanurate type, adduct type, and bifunctional prepolymer type.
Examples of the blocking agent that forms the block structure of the blocked isocyanate compound include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds. be able to. Among these, a blocking agent selected from oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, and pyrazole compounds is particularly preferable.
　上記オキシム化合物としては、オキシム、および、ケトオキシムが挙げられ、具体的には、アセトキシム、ホルムアルドキシム、シクロヘキサンオキシム、メチルエチルケトンオキシム、シクロヘキサノンオキシム、ベンゾフェノンオキシム、アセトキシム等が例示できる。
　上記ラクタム化合物としてはε－カプロラクタム、γ－ブチロラクタム等が例示できる。
　上記フェノール化合物としては、フェノール、ナフトール、クレゾール、キシレノール、ハロゲン置換フェノール等が例示できる。
　上記アルコール化合物としては、メタノール、エタノール、プロパノール、ブタノール、シクロヘキサノール、エチレングリコールモノアルキルエーテル、プロピレングリコールモノアルキルエーテル、乳酸アルキル等が例示できる。
　上記アミン化合物としては、１級アミンおよび２級アミンが上げられ、芳香族アミン、脂肪族アミン、脂環族アミンいずれでもよく、アニリン、ジフェニルアミン、エチレンイミン、ポリエチレンイミン等が例示できる。
　上記活性メチレン化合物としては、マロン酸ジエチル、マロン酸ジメチル、アセト酢酸エチル、アセト酢酸メチル等が例示できる。
　上記ピラゾール化合物としては、ピラゾール、メチルピラゾール、ジメチルピラゾール等が例示できる。
　上記メルカプタン化合物としては、アルキルメルカプタン、アリールメルカプタン等が例示できる。 Examples of the oxime compound include oxime and ketoxime, and specific examples include acetoxime, formaldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and acetoxime.
Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.
Examples of the phenol compound include phenol, naphthol, cresol, xylenol, and halogen-substituted phenol.
Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.
Examples of the amine compound include primary amines and secondary amines, which may be aromatic amines, aliphatic amines, and alicyclic amines, and examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.
Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, methyl acetoacetate and the like.
Examples of the pyrazole compound include pyrazole, methylpyrazole, dimethylpyrazole and the like.
Examples of the mercaptan compound include alkyl mercaptans and aryl mercaptans.
　本発明の感光性樹脂組成物に使用できるブロックイソシアネート化合物は、市販品として入手可能であり、例えば、コロネートＡＰステーブルＭ、コロネート２５０３、２５１５、２５０７、２５１３、２５５５、ミリオネートＭＳ－５０（以上、日本ポリウレタン工業（株）製）、タケネートＢ－８３０、Ｂ－８１５Ｎ、Ｂ－８２０ＮＳＵ、Ｂ－８４２Ｎ、Ｂ－８４６Ｎ、Ｂ－８７０Ｎ、Ｂ－８７４Ｎ、Ｂ－８８２Ｎ（以上、三井化学（株）製）、デュラネート１７Ｂ－６０ＰＸ、１７Ｂ－６０Ｐ、ＴＰＡ－Ｂ８０Ｘ、ＴＰＡ－Ｂ８０Ｅ、ＭＦ－Ｂ６０Ｘ、ＭＦ－Ｂ６０Ｂ、ＭＦ－Ｋ６０Ｘ、ＭＦ－Ｋ６０Ｂ、Ｅ４０２－Ｂ８０Ｂ、ＳＢＮ－７０Ｄ、ＳＢＢ－７０Ｐ、Ｋ６０００（以上、旭化成ケミカルズ（株）製）、デスモジュールＢＬ１１００、ＢＬ１２６５　ＭＰＡ／Ｘ、ＢＬ３５７５／１、ＢＬ３２７２ＭＰＡ、ＢＬ３３７０ＭＰＡ、ＢＬ３４７５ＢＡ／ＳＮ、ＢＬ５３７５ＭＰＡ、ＶＰＬＳ２０７８／２、ＢＬ４２６５ＳＮ、ＰＬ３４０、ＰＬ３５０、スミジュールＢＬ３１７５（以上、住化バイエルウレタン（株）製）等を好ましく使用することができる。 The blocked isocyanate compound that can be used in the photosensitive resin composition of the present invention is commercially available. For example, Coronate AP Stable M, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (or more, Nippon Polyurethane Industry Co., Ltd.), Takenate B-830, B-815N, B-820NSU, B-842N, B-84N, B-870N, B-874N, B-882N (above, manufactured by Mitsui Chemicals, Inc.) ), Duranate 17B-60PX, 17B-60P, TPA-B80X, TPA-B80E, MF-B60X, MF-B60B, MF-K60X, MF-K60B, E402-B80B, SBN-70D, SBB-70P, K6000 (above , Manufactured by Asahi Kasei Chemicals Corporation, Death Module B 1100, BL1265 MPA / X, BL3575 / 1, BL3272MPA, BL3370MPA, BL3475BA / SN, BL5375MPA, VPLS2078 / 2, BL4265SN, PL340, PL350, Sumidur BL3175 (above, manufactured by Sumika Bayer Urethane Co., Ltd.) etc. are preferably used can do.
＜＜分子内に２個以上のメタクリロイル基またはアクリロイル基を含む化合物＞＞
　本発明の感光性樹脂組成物は、架橋剤として、メタクリロイル基またはアクリロイル基を含む化合物を使用してもよい。メタクリロイル基またはアクリロイル基を含む化合物とは、アクリル酸エステル、メタクリル酸エステルからなる群から選択される化合物である。アクリロイル基、メタクリロイル基は１分子中に２個以上、さらに好ましくは３官能以上ある化合物であることが好ましい。 << Compound containing two or more methacryloyl groups or acryloyl groups in the molecule >>
In the photosensitive resin composition of the present invention, a compound containing a methacryloyl group or an acryloyl group may be used as a crosslinking agent. The compound containing a methacryloyl group or an acryloyl group is a compound selected from the group consisting of acrylic acid esters and methacrylic acid esters. It is preferable that the acryloyl group and the methacryloyl group are compounds having two or more, more preferably trifunctional or more in one molecule.
　２官能（メタ）アクリレートとしては、例えば、エチレングリコール（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、ビスフェノキシエタノールフルオレンジアクリレート、ビスフェノキシエタノールフルオレンジアクリレートなどが挙げられる。
　３官能以上の（メタ）アクリレートとしては、例えば、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリ（（メタ）アクリロイロキシエチル）フォスフェート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレートなどが挙げられる。
　好ましい市販品としては、日本化薬社製　ＫＡＹＡＲＡＤ　ＤＰＨＡ、新中村化学工業社製　ＮＫエステルシリーズで、二官能のＡ－２００、Ａ－４００、Ａ－６００、Ａ－１０００、ＡＢＥ－３００、Ａ－ＢＰＥ－４、Ａ－ＢＰＥ－１０、Ａ－ＢＰＥ－２０、Ａ－ＢＰＥ－３０、Ａ－ＢＰＰ－３、Ａ－ＤＯＤ、Ａ－ＤＣＰ、Ａ－ＩＢＤ－２Ｅ、Ａ－ＮＰＧ、７０１Ａ、Ａ－Ｂ１２０６ＰＥ、Ａ－ＨＤ－Ｎ、Ａ－ＮＯＤ－Ｎ、ＡＰＧ－１００、ＡＰＧ－２００、ＡＰＧ－４００、ＡＰＧ－７００、１Ｇ、２Ｇ、３Ｇ、４Ｇ、９Ｇ、１４Ｇ、２３Ｇ、ＢＧ、ＢＤ、ＨＤ－Ｎ、ＮＯＤ、ＩＮＤ、ＢＰＥ－１００、ＢＰＥ－２００、ＢＰＥ－３００、ＢＰＥ－５００、ＢＰＥ－９００、ＢＰＥ－１３００Ｎ、ＮＰＧ、ＤＣＰ、１２０６ＰＥ、７０１、３ＰＧ、９ＰＧ、３官能のＡ－９３００、ＡＴ－３０Ｅ、Ａ－ＴＭＰＴ－３ＥＯ、Ａ－ＴＭＰＴ－９ＥＯ、Ａ－ＴＭＰＴ－３ＰＯ、Ａ－ＴＭＭ－３、Ａ－ＴＭＭ－３Ｌ、Ａ－ＴＭＭ－３ＬＭ－Ｎ、ＴＭＰＴ、ＴＭＰＴ－９ＥＯ、４官能以上のＡＴＭ－３５Ｅ、ＡＴＭ－４Ｅ、ＡＤ－ＴＭＰ、ＡＤ－ＴＭＰ－Ｌ、ＡＴＭ－４Ｐ、Ａ－ＴＭＭＴ、Ａ－ＤＰＨ等を挙げることができる。 Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate, Examples include tetraethylene glycol di (meth) acrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange acrylate.
Examples of the tri- or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri ((meth) acryloyloxyethyl) phosphate, and pentaerythritol tetra (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
Preferable commercially available products are KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., NK ester series manufactured by Shin-Nakamura Chemical Co., Ltd., bifunctional A-200, A-400, A-600, A-1000, ABE-300, A- BPE-4, A-BPE-10, A-BPE-20, A-BPE-30, A-BPP-3, A-DOD, A-DCP, A-IBD-2E, A-NPG, 701A, A- B1206PE, A-HD-N, A-NOD-N, APG-100, APG-200, APG-400, APG-700, 1G, 2G, 3G, 4G, 9G, 14G, 23G, BG, BD, HD- N, NOD, IND, BPE-100, BPE-200, BPE-300, BPE-500, BPE-900, BPE-1300N, NPG, DCP, 1206PE, 701, 3 G, 9PG, trifunctional A-9300, AT-30E, A-TMPT-3EO, A-TMPT-9EO, A-TMPT-3PO, A-TMM-3, A-TMM-3L, A-TMM-3LM -N, TMPT, TMPT-9EO, tetra- or higher functional ATM-35E, ATM-4E, AD-TMP, AD-TMP-L, ATM-4P, A-TMMT, A-DPH and the like can be mentioned.
＜＜分子内に２個以上のオキセタン基を含む化合物＞＞
　本発明の感光性樹脂組成物は、架橋剤として、オキセタン基を含む化合物を使用してもよい。オキセタン基は分子内に２個以上あることが好ましい。分子内に２個以上のオキセタニル基を有する化合物としては、特開２００８－２２４９７０号公報の段落０１３４～０１４５記載の化合物が挙げられ、その内容は本明細書に組み込まれる。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。 << Compound containing two or more oxetane groups in the molecule >>
The photosensitive resin composition of the present invention may use a compound containing an oxetane group as a crosslinking agent. It is preferable that there are two or more oxetane groups in the molecule. Examples of the compound having two or more oxetanyl groups in the molecule include the compounds described in paragraphs 0134 to 0145 of JP-A-2008-224970, the contents of which are incorporated herein. As specific examples, Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX (above, manufactured by Toagosei Co., Ltd.) can be used.
＜（Ｅ）溶解抑止剤＞
　本発明の感光性樹脂組成物は、酸基の少なくとも一部が酸分解性基で保護された化合物（以下、「溶解抑止剤」、「（Ｅ）化合物」ともいう）を含有していてもよい。（Ｅ）化合物は、より具体的には、酸基を有し酸基の少なくとも一部が保護基で保護されていて、酸の作用により保護基が脱離してアルカリ溶解性が増大する化合物である。（Ｅ）化合物は非露光部のアルカリ溶解性を減少させ、露光部のアルカリ溶解性を増大させる役目を担う。酸基としては、カルボキシ基またはフェノール性水酸基が好ましい。
　酸分解性基としては、酸の作用で分解する基であれば特に制限はなく、例えば、アセタール基、ケタール基、シリル基、シリルエーテル基、３級アルキルエステル基等を挙げることができ、感度の観点からアセタール基が好ましい。保護基の具体例としては、ｔｅｒｔ－ブトキシカルボニル基、イソプロポキシカルボニル基、テトラヒドロピラニル基、テトラヒドロフラニル基、エトキシエチル基、メトキシエチル基、エトキシメチル基、トリメチルシリル基、ｔｅｒｔ－ブトキシカルボニルメチル基、トリメチルシリルエーテル基などが挙げられる。感度の観点からエトキシエチル基、テトラヒドロフラニル基が好ましい。 <(E) Dissolution inhibitor>
The photosensitive resin composition of the present invention may contain a compound in which at least a part of the acid group is protected with an acid-decomposable group (hereinafter also referred to as “dissolution inhibitor” or “(E) compound”). Good. More specifically, the compound (E) is a compound that has an acid group and at least a part of the acid group is protected by a protecting group, and the protecting group is removed by the action of the acid to increase alkali solubility. is there. The compound (E) plays a role of decreasing the alkali solubility in the non-exposed area and increasing the alkali solubility in the exposed area. As the acid group, a carboxy group or a phenolic hydroxyl group is preferable.
The acid-decomposable group is not particularly limited as long as it is a group that decomposes by the action of an acid, and examples thereof include an acetal group, a ketal group, a silyl group, a silyl ether group, and a tertiary alkyl ester group. In view of the above, an acetal group is preferable. Specific examples of the protecting group include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group, And trimethylsilyl ether group. From the viewpoint of sensitivity, an ethoxyethyl group and a tetrahydrofuranyl group are preferred.
　（Ｅ）化合物は、高分子（例えば、分子量が５０００を超える、さらには、１００００を超える）であっても、低分子（例えば、５０００以下）であってもよいが、低分子が好ましく、分子量が３０００以下が好ましく、１０００以下がより好ましい。分子量はポリマーの場合にはポリスチレン換算により求めた数平均分子量である。分子量の下限値としては、１５０以上が好ましく、３００以上がより好ましい。
　また、（Ｅ）化合物は、溶解抑止能力向上の観点から、芳香環、複素環および脂環構造のいずれかを含むことが好ましい。 The compound (E) may be a polymer (for example, a molecular weight exceeding 5000 or even exceeding 10,000) or a low molecule (for example, 5000 or less). Is preferably 3000 or less, and more preferably 1000 or less. In the case of a polymer, the molecular weight is a number average molecular weight determined by polystyrene conversion. As a lower limit of molecular weight, 150 or more are preferred and 300 or more are more preferred.
Moreover, it is preferable that a compound (E) contains either an aromatic ring, a heterocyclic ring, and an alicyclic structure from a viewpoint of a dissolution inhibitory ability improvement.
　（Ｅ）化合物は、感度向上の観点から、分子内に保護された酸基を２以上有することが好ましい。
　また、（Ｅ）化合物は、（Ａ）成分との相溶性向上の観点から、芳香環および／または複素環を含むことが好ましい。また、（Ａ）成分との相溶性向上の観点から、Ｃ、Ｈ、Ｏ、Ｎ原子以外を含まないことが好ましい。
　以下、（Ｅ）化合物の好ましい態様について説明する。 The compound (E) preferably has two or more acid groups protected in the molecule from the viewpoint of improving sensitivity.
Moreover, it is preferable that a (E) compound contains an aromatic ring and / or a heterocyclic ring from a viewpoint of a compatibility improvement with (A) component. Moreover, it is preferable not to contain other than C, H, O, and N atom from a viewpoint of compatibility improvement with (A) component.
Hereinafter, preferred embodiments of the compound (E) will be described.
　（Ｅ）化合物は、下記一般式（Ｅ－１－１）で表される化合物であることが好ましい。
一般式（Ｅ－１－１）
Figure JPOXMLDOC01-appb-C000047
 （一般式（Ｅ－１－１）中、Ｒは分子量が２０００以下の１～６価の有機基を表し、Ｒ1およびＲ2は、それぞれ独立に水素原子、アルキル基、またはアリール基を表し、Ｒ1およびＲ2のいずれか一方はアルキル基、またはアリール基である。Ｒ3は、アルキル基、またはアリール基を表し、Ｒ1またはＲ2と結合して環状エーテルを形成していてもよい。ｎ１は１～６の整数を表す。） The compound (E) is preferably a compound represented by the following general formula (E-1-1).
Formula (E-1-1)
Figure JPOXMLDOC01-appb-C000047
 (In the general formula (E-1-1), R represents a monovalent to hexavalent organic group having a molecular weight of 2000 or less, and R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, or an aryl group. , R 1 and R 2 are an alkyl group or an aryl group, and R 3 represents an alkyl group or an aryl group, and may combine with R 1 or R 2 to form a cyclic ether. N1 represents an integer of 1 to 6.)
　Ｒ1およびＲ2は、それぞれ独立に水素原子、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る。
　アルキル基としては、炭素数１～１０のアルキル基が好ましく、炭素数１～８のアルキル基がより好ましく、炭素数１～６のアルキル基がさらに好ましく、炭素数１～４のアルキル基が特に好ましい。アルキル基は、置換基を有していてもよい。また、アルキル基は、直鎖、分岐、環状のいずれであってもよいが、直鎖のアルキル基が好ましい。アルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ｔ－ブチル基、ペンチル基、ヘキシル基、シクロヘキシル基等が挙げられる。
　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、炭素数６～１４のアリール基がより好ましく、炭素数６～１０のアリール基がさらに好ましい。アリール基は、置換基を有していてもよい。アリール基としては、例えば、フェニル基、ナフチル基、アントラセニル基等が挙げられ、中でもフェニル基が好ましい。 R 1 and R 2 each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R 1 and R 2 is an alkyl group or an aryl group.
As the alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable. preferable. The alkyl group may have a substituent. The alkyl group may be linear, branched or cyclic, but is preferably a linear alkyl group. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. The aryl group may have a substituent. As an aryl group, a phenyl group, a naphthyl group, an anthracenyl group etc. are mentioned, for example, A phenyl group is especially preferable.
　Ｒ3は、アルキル基、またはアリール基を表し、Ｒ1またはＲ2と結合して環状エーテルを形成していてもよい。アルキル基としては、炭素数１～１６のアルキル基が好ましく、炭素数１～１０のアルキル基がより好ましく、炭素数１～６のアルキル基がさらに好ましく、炭素数１～４のアルキル基がさらに好ましい。具体的なアルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ｔ－ブチル基、ペンチル基、ネオペンチル基、ヘキシル基などが挙げられる。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、炭素数６～１４のアリール基がより好ましく、炭素数６～１０のアリール基がさらに好ましい。具体的にアリール基としては、フェニル基、トルイル基、メシチル基、ナフチル基などが挙げられる。 R 3 represents an alkyl group or an aryl group, and may combine with R 1 or R 2 to form a cyclic ether. The alkyl group is preferably an alkyl group having 1 to 16 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and further an alkyl group having 1 to 4 carbon atoms. preferable. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a neopentyl group, and a hexyl group. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group.
　Ｒ3は、Ｒ1またはＲ2と連結して環状エーテルを形成してもよい。Ｒ1またはＲ2と連結して形成される環状エーテルとしては、３～６員環の環状エーテルが好ましく、５～６員環の環状エーテルがより好ましい。 R 3 may be linked to R 1 or R 2 to form a cyclic ether. The cyclic ether formed by linking to R 1 or R 2 is preferably a 3- to 6-membered cyclic ether, more preferably a 5- to 6-membered cyclic ether.
　Ｒ1およびＲ2は、水素原子または炭素数１～４のアルキル基であることが好ましい。また、Ｒ3は、炭素数１～４のアルキル基、Ｒ1またはＲ2と結合してテトラヒドロフラニル基を形成していることが好ましい。 R 1 and R 2 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 3 is preferably bonded to an alkyl group having 1 to 4 carbon atoms, R 1 or R 2 to form a tetrahydrofuranyl group.
　Ｒ1～Ｒ3は置換基を有していても良い。置換基としては炭素数１～６のアルキル基、ハロゲン原子（フッ素原子、塩素原子、臭素原子、およびヨウ素原子）などが挙げられ、これら置換基はさらに置換基を有していてもよい。 R 1 to R 3 may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms and a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and these substituents may further have a substituent.
　Ｒは、分子量が２０００以下の１～６価の有機基を表す。Ｒが表わす有機基は、分子量が２０００以下の１～６価の有機基であり、分子量が１５００以下の１～６価の有機基が好ましく、分子量が１０００以下の１～６価の有機基がより好ましい。Ｒが表わす有機基は、芳香環または複素環を含み、Ｃ、Ｈ、Ｏ、Ｎ原子以外を含まない有機基であることが好ましく、環状構造、および／またはカルボニル基を含む有機基であることがより好ましく、芳香族基、環状脂肪族基、カルボニル基、アルキレン基、フェニレン基、および酸素原子との組み合わせからなる基であることがさらに好ましい。 R represents a monovalent to hexavalent organic group having a molecular weight of 2000 or less. The organic group represented by R is a 1 to 6 valent organic group having a molecular weight of 2000 or less, preferably a 1 to 6 valent organic group having a molecular weight of 1500 or less, and a 1 to 6 valent organic group having a molecular weight of 1000 or less. More preferred. The organic group represented by R is preferably an organic group containing an aromatic ring or a heterocyclic ring and containing no atoms other than C, H, O, and N atoms, and is an organic group containing a cyclic structure and / or a carbonyl group. Are more preferable, and a group composed of a combination of an aromatic group, a cycloaliphatic group, a carbonyl group, an alkylene group, a phenylene group, and an oxygen atom is more preferable.
　具体的に、Ｒとしては、酸基がフェノール性ヒドロキシ基の場合、以下の有機基であることが好ましい。式中、波線は、酸素原子との結合部位を表し、Ｒ1およびＲ2は、それぞれ独立に水素原子、炭素数１～１０のアルキル基を表し、ｍおよびｎはそれぞれ独立に０～４の整数を表す。
Figure JPOXMLDOC01-appb-C000048
 Specifically, R is preferably the following organic group when the acid group is a phenolic hydroxy group. In the formula, a wavy line represents a bonding site with an oxygen atom, R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m and n each independently represents 0 to 4 Represents an integer.
Figure JPOXMLDOC01-appb-C000048
　具体的に、Ｒとしては、酸基がカルボキシ基の場合、以下の有機基であることが好ましい。式中、波線は、酸素原子との結合部位を表し、Ｒ1およびＲ2は、それぞれ独立に水素原子、炭素数１～１０のアルキル基（好ましくは炭素数１～８のアルキル基）を表し、ｍおよびｎはそれぞれ独立に０～４の整数（好ましくは０）を表す。
Figure JPOXMLDOC01-appb-C000049
 Specifically, R is preferably the following organic group when the acid group is a carboxy group. In the formula, a wavy line represents a bonding site with an oxygen atom, and R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 8 carbon atoms). , M and n each independently represents an integer of 0 to 4 (preferably 0).
Figure JPOXMLDOC01-appb-C000049
　一般式（Ｅ－１－１）で表される化合物の具体例としては、以下のような化合物が挙げられるが、本発明では特にこれに限定されない。
Figure JPOXMLDOC01-appb-C000050
 Specific examples of the compound represented by the general formula (E-1-1) include the following compounds, but the present invention is not particularly limited thereto.
Figure JPOXMLDOC01-appb-C000050
　（Ｅ）化合物は、下記一般式（Ｅ－１－２）で表される化合物であることが好ましい。
一般式（Ｅ－１－２）
Figure JPOXMLDOC01-appb-C000051
 （一般式（Ｅ－１－２）中、Ｒ1は、ｎ１価の有機基を表す。Ａｒは、置換されていてもよいアリール基を表す。ａは０以上の整数を表す。ｎ１は２以上の整数を表す。但し、ｎ１－ａは１以上の整数である。） The compound (E) is preferably a compound represented by the following general formula (E-1-2).
Formula (E-1-2)
Figure JPOXMLDOC01-appb-C000051
 (In general formula (E-1-2), R 1 represents an n1-valent organic group, Ar represents an optionally substituted aryl group, a represents an integer of 0 or more, and n1 represents 2) (An integer greater than or equal to 1 is shown, where n1-a is an integer greater than or equal to 1.)
　Ｒ1は、ｎ１価の有機基を表し、好ましくは２～８価、より好ましくは２～６価の有機基である。また、Ｒ1は、炭素数２～１５の炭化水素基、あるいはこの炭化水素基中に酸素原子１～２個がエーテル結合を形成している炭化水素基を主構造とする基が好ましい。具体的には、Ｒ1は、脂肪族炭化水素構造（例えば直鎖状アルキレン構造、分岐状アルキレン構造、シクロアルキレン構造、ノルボルナン構造、ノルボルネン構造、ノルボルナン骨格あるいはノルボルネン骨格とシクロアルキレン骨格が縮合した構造）、芳香族炭化水素構造（例えばベンゼン構造等）、アラルキル構造、あるいは、これらの構造が複数結合した構造、これらの構造がエーテル結合を介して複数結合した構造、その他テトラヒドロピラン構造等を含有する構造を挙げることができる。Ｒ1としては、特に基本骨格として、アルキレン構造、脂環式構造、エーテル構造、アラルキル構造、あるいはこれらを組み合わせたものが好ましい。 R 1 represents an n1-valent organic group, preferably a 2- to 8-valent organic group, more preferably a 2- to 6-valent organic group. R 1 is preferably a hydrocarbon group having 2 to 15 carbon atoms, or a group mainly having a hydrocarbon group in which 1 to 2 oxygen atoms form an ether bond in the hydrocarbon group. Specifically, R 1 represents an aliphatic hydrocarbon structure (for example, a linear alkylene structure, a branched alkylene structure, a cycloalkylene structure, a norbornane structure, a norbornene structure, a norbornane skeleton, or a structure in which a norbornene skeleton and a cycloalkylene skeleton are condensed). ), Aromatic hydrocarbon structures (eg, benzene structures), aralkyl structures, structures in which these structures are combined, structures in which these structures are combined through ether bonds, and other tetrahydropyran structures The structure can be mentioned. As R 1 , an alkylene structure, an alicyclic structure, an ether structure, an aralkyl structure, or a combination of these is particularly preferable as a basic skeleton.
　Ａｒは、置換されていてもよいアリール基を表す。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、炭素数６～１４のアリール基がより好ましく、炭素数６～１０のアリール基がさらに好ましい。具体的にアリール基としては、フェニル基、トルイル基、メシチル基、ナフチル基などが挙げられる。 Ar represents an optionally substituted aryl group. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, an aryl group having 6 to 14 carbon atoms is more preferable, and an aryl group having 6 to 10 carbon atoms is further preferable. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group.
　ａは０以上の整数を表し、０～３の整数が好ましく、０がさらに好ましい。ｎは２以上の整数を表し、２～８の整数が好ましく、２～６の整数が好ましく、２がより好ましい。
　一般式（Ｅ－１－２）で表される化合物の合成段階で、ａが０～ｎまでの分布を有する混合物として得られることもあるが、混合物のまま好適に用いることができる。そしてｎ－ａは１以上、好ましくは１～７の整数である。また、Ａｒは置換されていてもよいアリール基を表し、具体的にはフェニル基、ナフチル基等が挙げられ、その置換基としては塩素原子等のハロゲン原子；メチル基、ｔｅｒｔ－ブチル基等のアルキル基；メトキシ基等のアルコキシ基等を好ましく挙げられる。 a represents an integer of 0 or more, preferably an integer of 0 to 3, and more preferably 0. n represents an integer of 2 or more, preferably an integer of 2 to 8, more preferably an integer of 2 to 6, and more preferably 2.
In the synthesis step of the compound represented by the general formula (E-1-2), a mixture having a distribution of 0 to n may be obtained, but the mixture can be preferably used as it is. Na is an integer of 1 or more, preferably 1-7. Ar represents an optionally substituted aryl group, and specific examples thereof include a phenyl group and a naphthyl group. Examples of the substituent include a halogen atom such as a chlorine atom; a methyl group, a tert-butyl group and the like. Preferred examples include alkyl groups; alkoxy groups such as methoxy groups.
　一般式（Ｅ－１－２）で表される化合物としては、（Ａ）成分との相溶性向上の観点から、Ｃ、Ｈ、Ｏ、Ｎ原子以外を含まないことが好ましい。 The compound represented by the general formula (E-1-2) preferably contains no atoms other than C, H, O, and N atoms from the viewpoint of improving compatibility with the component (A).
　一般式（Ｅ－１－２）で表される化合物の具体例として、下記のものを挙げることができるが、これらに制限されるものではない。
Figure JPOXMLDOC01-appb-C000052
 Specific examples of the compound represented by the general formula (E-1-2) include the following, but are not limited thereto.
Figure JPOXMLDOC01-appb-C000052
　一般式（Ｅ－１－２）で表される化合物の具体例としては、この他、特開２００１－８３７０９号公報の段落００１８～段落００２５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。 In addition, specific examples of the compound represented by the general formula (E-1-2) include compounds described in paragraphs 0018 to 0025 of JP-A-2001-83709. It is incorporated herein.
　（Ｅ）化合物が高分子である場合、下記一般式（Ｅ－１－３）で表される繰り返し単位を有する化合物であることが好ましい。
一般式（Ｅ－１－３）
Figure JPOXMLDOC01-appb-C000053
 （一般式（Ｅ－１－３）中、Ｒ1およびＲ2は、それぞれ独立に水素原子、アルキル基、またはアリール基を表し、Ｒ1およびＲ2のいずれか一方はアルキル基、またはアリール基である。Ｒ3は、アルキル基、またはアリール基を表し、Ｒ1またはＲ2と結合して環状エーテルを形成していてもよい。Ｒ4は水素原子またはメチル基を表す。Ｘは、２価の有機基を表す。） When the compound (E) is a polymer, it is preferably a compound having a repeating unit represented by the following general formula (E-1-3).
General formula (E-1-3)
Figure JPOXMLDOC01-appb-C000053
 (In the general formula (E-1-3), R 1 and R 2 each independently represents a hydrogen atom, an alkyl group, or an aryl group, and one of R 1 and R 2 is an alkyl group or an aryl group. R 3 represents an alkyl group or an aryl group, and may combine with R 1 or R 2 to form a cyclic ether, R 4 represents a hydrogen atom or a methyl group, and X represents 2 Represents a valent organic group.)
　Ｒ1およびＲ2は、一般式（Ｅ－１－１）におけるＲ1およびＲ2と同義であり、好ましい範囲も同様である。
　Ｒ3は、一般式（Ｅ－１－１）におけるＲ3と同義であり、好ましい範囲も同様である。 R 1 and R 2 has the same meaning as R 1 and R 2 in the general formula (E-1-1), and preferred ranges are also the same.
R 3 has the same meaning as R 3 in formula (E-1-1), and the preferred range is also the same.
　Ｘは、２価の有機基を表す。Ｘが表わす２価の有機基としては、フェニレン基、カルボニル基、またはｐ－フェニレンカルボニル基などが挙げられる。 X represents a divalent organic group. Examples of the divalent organic group represented by X include a phenylene group, a carbonyl group, and a p-phenylenecarbonyl group.
　一般式（Ｅ－１－３）で表される繰り返し単位を有する化合物の好ましい具体例として、下記いずれかの構成単位を有する重合体を挙げることができる。Ｒ4は水素原子、またはメチル基を表す。
Figure JPOXMLDOC01-appb-C000054
 Preferable specific examples of the compound having a repeating unit represented by the general formula (E-1-3) include a polymer having any one of the following structural units. R 4 represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000054
　一般式（Ｅ－１－３）で表される繰り返し単位を有する化合物の重量平均分子量としては、２０００～５００００が好ましく、３０００～２００００がより好ましい。ここで、重量平均分子量は、ゲルパーミエーションクロマトグラフィーのポリスチレン換算値をもって定義される。 The weight average molecular weight of the compound having a repeating unit represented by the general formula (E-1-3) is preferably 2000 to 50000, more preferably 3000 to 20000. Here, the weight average molecular weight is defined by a polystyrene conversion value of gel permeation chromatography.
　（Ｅ）化合物として一般式（Ｅ－１－３）で表される繰り返し単位を有する化合物を用いる場合、（Ａ）成分との相溶性や現像性の観点から、その他成分を共重合させることが好ましい。その他成分としては、一般式（Ｅ－１－３）で表される繰り返し単位を有する化合物と共重合できるものであれば特に限定されない。 When a compound having a repeating unit represented by the general formula (E-1-3) is used as the compound (E), other components may be copolymerized from the viewpoint of compatibility with the component (A) and developability. preferable. Other components are not particularly limited as long as they can be copolymerized with a compound having a repeating unit represented by formula (E-1-3).
　その他成分としては、下記一般式（Ｅ－１－４）で表される繰り返し単位を有する化合物であることが好ましい。
一般式（Ｅ－１－４）
Figure JPOXMLDOC01-appb-C000055
 （一般式（Ｅ－１－４）中、Ｒ41は水素原子またはメチル基を表し、Ｘは、単結合、または２価の有機基を表し、Ｒ42は置換基を有していてもよいアリール基、またはヒドロキシル基を表す。） The other component is preferably a compound having a repeating unit represented by the following general formula (E-1-4).
General formula (E-1-4)
Figure JPOXMLDOC01-appb-C000055
 (In the general formula (E-1-4), R 41 represents a hydrogen atom or a methyl group, X represents a single bond or a divalent organic group, and R 42 may have a substituent. Represents an aryl group or a hydroxyl group.)
　Ｘは、単結合、または２価の有機基を表し、Ｘが表わす２価の有機基としては、フェニレン基、カルボニル基、カルボキシル基、またはｐ－フェニレンカルボニル基などが挙げられる。 X represents a single bond or a divalent organic group, and examples of the divalent organic group represented by X include a phenylene group, a carbonyl group, a carboxyl group, and a p-phenylenecarbonyl group.
　Ｒ42は置換基を有していてもよいアリール基、またはヒドロキシル基を表し、置換基を有していてもよいアリール基としては、一般式（Ｅ－１－１）におけるＲ1が表わすアリール基と同義であり、好ましい範囲も同様である。アリール基は置換基を有していてもよい。置換基としては炭素数１～６のアルキル基、ハロゲン原子（フッ素原子、塩素原子、臭素原子、およびヨウ素原子）、ヒドロキシル基などが挙げられ、これら置換基はさらに置換基を有していてもよい。 R 42 represents an aryl group which may have a substituent or a hydroxyl group, and the aryl group which may have a substituent includes an aryl represented by R 1 in formula (E-1-1) It is synonymous with group, and its preferable range is also the same. The aryl group may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a hydroxyl group, and the like, and these substituents may further have a substituent. Good.
　一般式（Ｅ－１－４）で表される繰り返し単位を有する化合物の好ましい具体例として、下記いずれかの構成単位を有する重合体を挙げることができる。Ｒ4は水素原子、またはメチル基を表す。
Figure JPOXMLDOC01-appb-C000056
 Preferable specific examples of the compound having a repeating unit represented by the general formula (E-1-4) include a polymer having any one of the following structural units. R 4 represents a hydrogen atom or a methyl group.
Figure JPOXMLDOC01-appb-C000056
　一般式（Ｅ－１－４）で表される繰り返し単位を有する化合物としては、（Ａ）成分との相溶性の観点から（１）～（３）の化合物を用いることが好ましく、現像性の観点から（４）～（５）の酸基を有する化合物を用いることが好ましい。 As the compound having a repeating unit represented by the general formula (E-1-4), the compounds (1) to (3) are preferably used from the viewpoint of compatibility with the component (A). From the viewpoint, it is preferable to use the compounds (4) to (5) having an acid group.
　一般式（Ｅ－１－３）で表される繰り返し単位を有する化合物とその他の成分との比（質量％）は、（Ｅ－１－３）成分／その他の成分＝３０/７０～１００/０が好ましく、４０/６０～８０/２０が好ましい。その他の成分は複数を併用しても良い。 The ratio (% by mass) of the compound having the repeating unit represented by the general formula (E-1-3) and other components is (E-1-3) component / other components = 30/70 to 100 / 0 is preferable, and 40/60 to 80/20 is preferable. A plurality of other components may be used in combination.
　（Ｅ）化合物の含有量は、配合する場合、（Ａ）ポリベンゾオキサゾール前駆体１００質量部に対して、５～５０質量部であり、１０～４０質量部であることがより好ましい。含有量を５～５０質量部とすることで、膜物性、感度を向上させることができる。また、（Ｅ）化合物は２種以上用いることができ、２種以上用いる場合は、その合計量が上記範囲となる。
　また、本発明では、（Ａ）ポリベンゾオキサゾール前駆体が酸分解性基を含むため、（Ｅ）化合物を本発明の組成物の全固形分の１質量％以下とすることもできる。 When blended, the content of the compound (E) is 5 to 50 parts by mass, and more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the (A) polybenzoxazole precursor. By setting the content to 5 to 50 parts by mass, film physical properties and sensitivity can be improved. Moreover, 2 or more types of (E) compounds can be used, and when using 2 or more types, the total amount becomes the said range.
Moreover, in this invention, since (A) polybenzoxazole precursor contains an acid-decomposable group, (E) compound can also be made into 1 mass% or less of the total solid of the composition of this invention.
＜その他の成分＞
　本発明の感光性樹脂組成物には、上記成分に加えて、必要に応じて、増感剤、アルコキシシラン化合物、塩基性化合物、界面活性剤、酸化防止剤を好ましく加えることができる。さらに本発明の感光性樹脂組成物には、酸増殖剤、現像促進剤、可塑剤、熱ラジカル発生剤、熱酸発生剤、紫外線吸収剤、増粘剤、および、有機または無機の沈殿防止剤などの公知の添加剤を加えることができる。また、これらの化合物としては、例えば特開２０１２－８８４５９号公報の段落番号０２０１～０２２４の記載の化合物を使用することができ、これらの内容は本願明細書に組み込まれる。 <Other ingredients>
In addition to the above components, a sensitizer, an alkoxysilane compound, a basic compound, a surfactant, and an antioxidant can be preferably added to the photosensitive resin composition of the present invention as necessary. Furthermore, the photosensitive resin composition of the present invention includes an acid proliferation agent, a development accelerator, a plasticizer, a thermal radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor. Known additives such as can be added. Further, as these compounds, for example, compounds described in paragraph numbers 0201 to 0224 of JP2012-8859A can be used, and the contents thereof are incorporated in the present specification.
＜＜増感剤＞＞
　本発明の感光性樹脂組成物は、光酸発生剤との組み合わせにおいて、その分解を促進させるために、増感剤を含有することが好ましい。増感剤は、活性光線を吸収して電子励起状態となる。電子励起状態となった増感剤は、光酸発生剤と接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより光酸発生剤は化学変化を起こして分解し、酸を生成する。好ましい増感剤の例としては、以下の化合物類に属しており、かつ３５０ｎｍから４５０ｎｍの波長域のいずれかに吸収波長を有する化合物を挙げることができる。 << Sensitizer >>
The photosensitive resin composition of the present invention preferably contains a sensitizer in order to promote the decomposition in combination with the photoacid generator. The sensitizer absorbs actinic rays and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid. Examples of preferred sensitizers include compounds belonging to the following compounds and having an absorption wavelength in any of the wavelength ranges from 350 nm to 450 nm.
　多核芳香族類（例えば、ピレン、ペリレン、トリフェニレン、アントラセン、９，１０－ジブトキシアントラセン、９，１０－ジエトキシアントラセン，３，７－ジメトキシアントラセン、９，１０－ジプロピルオキシアントラセン）、キサンテン類（例えば、フルオレッセイン、エオシン、エリスロシン、ローダミンＢ、ローズベンガル）、キサントン類（例えば、キサントン、チオキサントン、ジメチルチオキサントン、ジエチルチオキサントン）、シアニン類（例えばチアカルボシアニン、オキサカルボシアニン）、メロシアニン類（例えば、メロシアニン、カルボメロシアニン）、ローダシアニン類、オキソノール類、チアジン類（例えば、チオニン、メチレンブルー、トルイジンブルー）、アクリジン類（例えば、アクリジンオレンジ、クロロフラビン、アクリフラビン）、アクリドン類（例えば、アクリドン、１０－ブチル－２－クロロアクリドン）、アントラキノン類（例えば、アントラキノン）、スクアリウム類（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が増感剤を含有する場合、増感剤の含有量は、感光性樹脂組成物中の全固形成分１００質量部に対し、０.００１～１００質量部であることが好ましく、０．１～５０質量部であることがより好ましく、０．５～２０質量部であることがさらに好ましい。増感剤は、２種以上を併用することもできる。２種類以上の増感剤を用いる場合は、その合計量が上記範囲となる。 When the photosensitive resin composition of the present invention contains a sensitizer, the content of the sensitizer is 0.001 to 100 parts by mass with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. It is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 20 parts by mass. Two or more sensitizers can be used in combination. When two or more kinds of sensitizers are used, the total amount is within the above range.
＜＜アルコキシシラン化合物＞＞
　本発明の感光性樹脂組成物は、密着改良剤（密着助剤）としてアルコキシシラン化合物を含有してもよい。アルコキシシラン化合物を用いると、本発明の感光性樹脂組成物により形成された膜と基板との密着性を向上できたり、本発明の感光性樹脂組成物により形成された膜の性質を調整することができる。本発明の感光性樹脂組成物に用いることができるアルコキシシラン化合物は、基材となる無機物、例えば、シリコン、酸化シリコン、窒化シリコン等のシリコン化合物、金、銅、モリブデン、チタン、アルミニウム等の金属と絶縁膜との密着性を向上させる化合物であることが好ましい。具体的には、公知のシランカップリング剤等も有効である。
　シランカップリング剤としては、例えば、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、３－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリメトキシシランなどの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ジアルコキシシラン、３－メタクリロキシプロピルメチルジメトキシシランなどのγ－メタクリロキシプロピルトリアルコキシシラン、γ－メタクリロキシプロピルジアルコキシシラン、γ－クロロプロピルトリアルコキシシラン、γ－メルカプトプロピルトリアルコキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリアルコキシシラン、ビニルトリアルコキシシランが挙げられる。これらのうち、γ－グリシドキシプロピルトリアルコキシシランやγ－メタクリロキシプロピルトリアルコキシシランがより好ましく、γ－グリシドキシプロピルトリアルコキシシランがさらに好ましく、γ－グリシドキシプロピルトリメトキシシランがよりさらに好ましい。これらは１種単独または２種以上を組み合わせて使用することができる。 << alkoxysilane compound >>
The photosensitive resin composition of the present invention may contain an alkoxysilane compound as an adhesion improver (adhesion aid). When an alkoxysilane compound is used, the adhesion between the film formed from the photosensitive resin composition of the present invention and the substrate can be improved, or the properties of the film formed from the photosensitive resin composition of the present invention can be adjusted. Can do. The alkoxysilane compound that can be used in the photosensitive resin composition of the present invention is a base material, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium, or aluminum. Preferably, the compound improves the adhesion between the insulating film and the insulating film. Specifically, a known silane coupling agent or the like is also effective.
Examples of silane coupling agents include γ-glycid such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. Γ-methacryloxypropyltrialkoxysilane such as xylpropyltrialkoxysilane, γ-glycidoxypropyl dialkoxysilane, 3-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyl dialkoxysilane, γ-chloropropyltrialkoxy Examples thereof include silane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, and vinyltrialkoxysilane. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and γ-glycidoxypropyltrimethoxysilane is more preferable. Further preferred. These can be used alone or in combination of two or more.
　アルコキシシラン化合物は、特にこれらに限定することなく、公知のものを使用することができる。
　本発明の感光性樹脂組成物がアルコキシシラン化合物を含む場合、アルコキシシラン化合物の含有量は、感光性樹脂組成物中の全固形分１００質量部に対して、０．１～３０質量部が好ましく、０．５～２０質量部がより好ましい。アルコキシシラン化合物は、１種単独で使用しても、２種以上を併用してもよい。２種類以上のアルコキシシラン化合物を用いる場合は、その合計量が上記範囲となる。 A well-known thing can be used for an alkoxysilane compound, without specifically limiting to these.
When the photosensitive resin composition of the present invention contains an alkoxysilane compound, the content of the alkoxysilane compound is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total solid content in the photosensitive resin composition. 0.5 to 20 parts by mass is more preferable. An alkoxysilane compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of alkoxysilane compounds, the total amount becomes the said range.
＜＜塩基性化合物＞＞
　本発明の感光性樹脂組成物は、塩基性化合物を含有してもよい。塩基性化合物としては、化学増幅レジストで用いられるものの中から任意に選択して使用することができる。例えば、脂肪族アミン、芳香族アミン、複素環式アミン、第四級アンモニウムヒドロキシド、カルボン酸の第四級アンモニウム塩等が挙げられる。これらの具体例としては、特開２０１１－２２１４９４号公報の段落番号０２０４～０２０７に記載の化合物、特開２０１２－１３３０９１号公報の段落番号０１４１～０１４５に記載の化合物が挙げられ、これらの内容は本願明細書に組み込まれる。 << basic compound >>
The photosensitive resin composition of the present invention may contain a basic compound. The basic compound can be arbitrarily selected from those used in chemically amplified resists. Examples include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in paragraph numbers 0204 to 0207 of JP2011-221494A and compounds described in paragraph numbers 0141 to 0145 of JP2012-133301A. It is incorporated herein.
　具体的には、脂肪族アミンとしては、例えば、トリメチルアミン、ジエチルアミン、トリエチルアミン、ジ－ｎ－プロピルアミン、トリ－ｎ－プロピルアミン、ジ－ｎ－ペンチルアミン、トリ－ｎ－ペンチルアミン、ジエタノールアミン、トリエタノールアミン、ジシクロヘキシルアミン、ジシクロヘキシルメチルアミンなどが挙げられる。
　芳香族アミンとしては、例えば、アニリン、ベンジルアミン、Ｎ，Ｎ－ジメチルアニリン、ジフェニルアミンなどが挙げられる。
　複素環式アミンとしては、例えば、ピリジン、２－メチルピリジン、４－メチルピリジン、２－エチルピリジン、４－エチルピリジン、２－フェニルピリジン、４－フェニルピリジン、Ｎ－メチル－４－フェニルピリジン、４－ジメチルアミノピリジン、イミダゾール、ベンズイミダゾール、４－メチルイミダゾール、２－フェニルベンズイミダゾール、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、１，８－ジアザビシクロ［５．４．０］－７－ウンデセンなどが挙げられる。
　第四級アンモニウムヒドロキシドとしては、例えば、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラ－ｎ－ブチルアンモニウムヒドロキシド、テトラ－ｎ－ヘキシルアンモニウムヒドロキシドなどが挙げられる。
　カルボン酸の第四級アンモニウム塩としては、例えば、テトラメチルアンモニウムアセテート、テトラメチルアンモニウムベンゾエート、テトラ－ｎ－ブチルアンモニウムアセテート、テトラ－ｎ－ブチルアンモニウムベンゾエートなどが挙げられる。
　本発明に用いることができる塩基性化合物は、１種単独で使用しても、２種以上を併用してもよい。 Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 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-di And azabicyclo [5.3.0] -7-undecene and 1,8-diazabicyclo [5.4.0] -7-undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, tetra-n-hexylammonium hydroxide, and the like.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, tetra-n-butylammonium benzoate and the like.
The basic compounds that can be used in the present invention may be used singly or in combination of two or more.
　本発明の感光性樹脂組成物が塩基性化合物を含有する場合、塩基性化合物の含有量は、感光性樹脂組成物中の全固形成分１００質量部に対し、０．００１～３質量部であることが好ましく、０．００５～１質量部であることがより好ましい。２種類以上の塩基性化合物を用いる場合は、その合計量が上記範囲となる。 When the photosensitive resin composition of the present invention contains a basic compound, the content of the basic compound is 0.001 to 3 parts by mass with respect to 100 parts by mass of the total solid component in the photosensitive resin composition. The amount is preferably 0.005 to 1 part by mass. When using 2 or more types of basic compounds, the total amount becomes the said range.
＜＜界面活性剤＞＞
　本発明の感光性樹脂組成物は、界面活性剤を含有することが好ましい。界面活性剤としては、アニオン系、カチオン系、ノニオン系、または、両性のいずれでも使用することができるが、好ましい界面活性剤はノニオン界面活性剤である。本発明の組成物に用いられる界面活性剤としては、例えば、特開２０１２－８８４５９号公報の段落番号０２０１～０２０５に記載のものや、特開２０１１－２１５５８０号公報の段落番号０１８５～０１８８に記載のものを用いることができ、これらの記載は本願明細書に組み込まれる。
　ノニオン系界面活性剤の例としては、ポリオキシエチレン高級アルキルエーテル類、ポリオキシエチレン高級アルキルフェニルエーテル類、ポリオキシエチレングリコールの高級脂肪酸ジエステル類、シリコーン系、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－３４１、Ｘ－２２－８２２（信越化学工業（株）製）、ポリフローＮｏ．９９Ｃ（共栄社化学（株）製）、エフトップ（三菱マテリアル化成社製）、メガファック（ＤＩＣ（株）製）、フロラードノベックＦＣ－４４３０（住友スリーエム（株）製）、サーフロンＳ－２４２（ＡＧＣセイミケミカル社製）、ＰｏｌｙＦｏｘＰＦ－６３２０（ＯＭＮＯＶＡ社製）、ＳＨ－８４００（東レ・ダウコーニングシリコーン）、フタージェントＦＴＸ－２１８、ＦＴＸ－２１８Ｇ（ネオス社製）等を挙げることができる。
　また、界面活性剤として、下記一般式（Ｉ－１－１）で表される構成単位Ａおよび構成単位Ｂを含み、テトラヒドロフラン（ＴＨＦ）を溶媒とした場合のゲルパーミエーションクロマトグラフィーで測定されるポリスチレン換算の重量平均分子量（Ｍｗ）が１，０００以上１０，０００以下である共重合体を好ましい例として挙げることができる。 << Surfactant >>
The photosensitive resin composition of the present invention preferably contains a surfactant. As the surfactant, any of anionic, cationic, nonionic, or amphoteric can be used, but a preferred surfactant is a nonionic surfactant. Examples of the surfactant used in the composition of the present invention include those described in paragraph Nos. 0201 to 0205 in JP2012-88459A, and paragraphs 0185 to 0188 in JP2011-215580A. Can be used and these descriptions are incorporated herein.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . The following trade names are KP-341, X-22-822 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by Mitsubishi Materials Kasei Co., Ltd.), MegaFac (manufactured by DIC Corporation), Florard Novec FC-4430 (manufactured by Sumitomo 3M Co., Ltd.), Surflon S-242 (Manufactured by AGC Seimi Chemical Co., Ltd.), PolyFox PF-6320 (manufactured by OMNOVA), SH-8400 (Toray Dow Corning Silicone), Footgent FTX-218, FTX-218G (manufactured by Neos), and the like.
Further, the surfactant is measured by gel permeation chromatography using the structural unit A and the structural unit B represented by the following general formula (I-1-1) and using tetrahydrofuran (THF) as a solvent. A preferred example is a copolymer having a polystyrene-reduced weight average molecular weight (Mw) of 1,000 or more and 10,000 or less.
一般式（Ｉ－１－１）
Figure JPOXMLDOC01-appb-C000057
 （式（Ｉ－１－１）中、Ｒ401およびＲ403はそれぞれ独立に、水素原子またはメチル基を表し、Ｒ402は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ404は水素原子または炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐおよびｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｓは１以上１０以下の整数を表す。） Formula (I-1-1)
Figure JPOXMLDOC01-appb-C000057
 (In the formula (I-1-1), R 401 and R 403 each independently represent a hydrogen atom or a methyl group, R 402 represents a linear alkylene group having 1 to 4 carbon atoms, and R 404 represents hydrogen. Represents an atom or an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is 10 mass% to 80 mass%. The following numerical values are represented, q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and s represents an integer of 1 to 10.
　上記Ｌは、下記一般式（Ｉ－１－２）で表される分岐アルキレン基であることが好ましい。一般式（Ｉ－１－２）におけるＲ405は、炭素数１以上４以下のアルキル基を表し、相溶性と被塗布面に対する濡れ性の点で、炭素数１以上３以下のアルキル基が好ましく、炭素数２または３のアルキル基がより好ましい。ｐとｑとの和（ｐ＋ｑ）は、ｐ＋ｑ＝１００、すなわち、１００質量％であることが好ましい。 L is preferably a branched alkylene group represented by the following general formula (I-1-2). R 405 in formula (I-1-2) represents an alkyl group having 1 to 4 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. And an alkyl group having 2 or 3 carbon atoms is more preferred. The sum (p + q) of p and q is preferably p + q = 100, that is, 100% by mass.
一般式（Ｉ－１－２）
Figure JPOXMLDOC01-appb-C000058
 Formula (I-1-2)
Figure JPOXMLDOC01-appb-C000058
　上記共重合体の重量平均分子量（Ｍｗ）は、１，５００以上５，０００以下がより好ましい。
　これらの界面活性剤は、１種単独でまたは２種以上を混合して使用することができる。
　本発明の感光性樹脂組成物が界面活性剤を含有する場合、界面活性剤の含有量は、感光性樹脂組成物中の全固形成分１００質量部に対し、１０質量部以下であることが好ましく、０．００１～１０質量部であることがより好ましく、０．０１～３質量部であることがさらに好ましい。界面活性剤は、１種単独で使用しても、２種以上を併用してもよい。２種類以上の界面活性剤を用いる場合は、その合計量が上記範囲となる。 The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.
These surfactants can be used individually by 1 type or in mixture of 2 or more types.
When the photosensitive resin composition of the present invention contains a surfactant, the content of the surfactant is preferably 10 parts by mass or less with respect to 100 parts by mass of the total solid components in the photosensitive resin composition. 0.001 to 10 parts by mass is more preferable, and 0.01 to 3 parts by mass is even more preferable. Surfactant may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of surfactant, the total amount becomes the said range.
＜＜酸増殖剤＞＞
　本発明の感光性樹脂組成物は、感度向上を目的に、酸増殖剤を用いることができる。
　本発明に用いることができる酸増殖剤は、酸触媒反応によってさらに酸を発生して反応系内の酸濃度を上昇させることができる化合物であり、酸が存在しない状態では安定に存在する化合物である。
　このような酸増殖剤の具体例としては、特開２０１１－２２１４９４の段落番号０２２６～０２２８に記載の酸増殖剤が挙げられ、この内容は本願明細書に組み込まれる。 << Acid Proliferator >>
In the photosensitive resin composition of the present invention, an acid proliferating agent can be used for the purpose of improving sensitivity.
The acid proliferating agent that can be used in the present invention is a compound that can further generate an acid by an acid-catalyzed reaction to increase the acid concentration in the reaction system, and is a compound that exists stably in the absence of an acid. is there.
Specific examples of such an acid proliferating agent include acid proliferating agents described in paragraph numbers 0226 to 0228 of JP2011-221494A, the contents of which are incorporated herein.
　本発明の組成物が酸増殖剤を含有する場合、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。酸増殖剤は、１種単独で使用しても、２種以上を併用してもよい。２種類以上の酸増殖剤を用いる場合は、その合計量が上記範囲となる。 When the composition of the present invention contains an acid proliferating agent, the content of the acid proliferating agent in the photosensitive composition should be 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 part and the unexposed part, it is preferably 20 to 500 parts by mass. The acid proliferating agent may be used alone or in combination of two or more. When two or more kinds of acid proliferating agents are used, the total amount is within the above range.
＜＜現像促進剤＞＞
　本発明の感光性樹脂組成物は、現像促進剤を含有することができる。
　現像促進剤としては、特開２０１２－０４２８３７号公報の段落番号０１７１～０１７２に記載されているものを参酌でき、この内容は本願明細書に組み込まれる。
　現像促進剤は、１種を単独で用いてもよいし、２種以上を併用することも可能である。
　本発明の感光性樹脂組成物が現像促進剤を含有する場合、現像促進剤の含有量は、感度と残膜率の観点から、感光性樹脂組成物の全固形分１００質量部に対し、０～３０質量部が好ましく、０．１～２０質量部がより好ましく、０．５～１０質量部であることが最も好ましい。２種類以上の現像促進剤を用いる場合は、その合計量が上記範囲となる。 << Development accelerator >>
The photosensitive resin composition of the present invention can contain a development accelerator.
As the development accelerator, those described in paragraphs 0171 to 0172 of JP2012-042837A can be referred to, and the contents thereof are incorporated in the present specification.
A development accelerator may be used individually by 1 type, and can also use 2 or more types together.
When the photosensitive resin composition of the present invention contains a development accelerator, the content of the development accelerator is 0 with respect to 100 parts by mass of the total solid content of the photosensitive resin composition from the viewpoint of sensitivity and residual film ratio. Is preferably 30 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass. When two or more types of development accelerators are used, the total amount is within the above range.
＜＜酸化防止剤＞＞
　本発明の感光性樹脂組成物は、酸化防止剤を含有してもよい。酸化防止剤としては、公知の酸化防止剤を含有することができる。酸化防止剤を含有することにより、硬化膜の着色を防止できる、または、光や熱による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。
　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、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、光や熱による硬化膜の着色、膜厚減少の観点からフェノール系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤が好ましく、フェノール系酸化防止剤がより好ましい。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。２種以上を併用する場合は、特に限定はされないが、光や熱による硬化膜の着色、膜厚減少の観点から、フェノール系酸化防止剤とイオウ系酸化防止剤の併用が好ましい。
　好ましい市販品として、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－３３０、アデカスタブＡＯ－４１２Ｓ、アデカスタブＡＯ－５０３、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（以上、（株）ＡＤＥＫＡ製）を挙げることができる。
　本発明の感光性樹脂組成物が酸化防止剤を有する場合、酸化防止剤の含有量は、感光性樹脂組成物の全固形成分１００質量部に対し、０．１～１０質量部であることが好ましく、０．２～５質量部であることがより好ましく、０．５～４質量部であることが特に好ましい。２種類以上の酸化防止剤を用いる場合は、その合計量が上記範囲となる。
　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。 << Antioxidant >>
The photosensitive resin composition of the present invention may contain an antioxidant. As an antioxidant, a well-known antioxidant can be contained. By containing the antioxidant, there is an advantage that coloring of the cured film can be prevented, or the film thickness reduction due to decomposition by light or heat can be reduced, and the heat-resistant transparency is excellent.
Examples of the antioxidant include phosphorus antioxidants, amides, hydrazides, sulfur antioxidants, phenolic antioxidants, ascorbic acids, zinc sulfate, saccharides, nitrites, sulfites, thiosulfates, Examples include hydroxylamine derivatives. Among these, a phenolic antioxidant, a phosphorus antioxidant, and a sulfur antioxidant are preferable, and a phenolic antioxidant is more preferable from the viewpoints of coloring the cured film by light and heat and reducing the film thickness. These may be used individually by 1 type and may mix 2 or more types. When two or more kinds are used in combination, there is no particular limitation, but from the viewpoint of coloring the cured film by light or heat and reducing the film thickness, the combined use of a phenol-based antioxidant and a sulfur-based antioxidant is preferable.
Preferred commercial products 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, ADK STAB AO-50, ADK STAB AO-51, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-330, ADK STAB AO-412S, ADK STAB AO-503, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB PEP-8W, ADK STAB PEP-24G, ADK STAB PEP-36, Examples include ADK STAB PEP-36Z and ADK STAB HP-10 (above, manufactured by ADEKA Corporation).
When the photosensitive resin composition of the present invention has an antioxidant, the content of the antioxidant is 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid components of the photosensitive resin composition. The amount is preferably 0.2 to 5 parts by mass, and particularly preferably 0.5 to 4 parts by mass. When using 2 or more types of antioxidant, the total amount becomes the said range.
In addition, as other additives, thermal radical generators described in paragraphs 0120 to 0121 of JP2012-8223A, nitrogen-containing compounds and thermal acid generators described in WO2011-133604A1, can be used. Is incorporated herein by reference.
＜感光性樹脂組成物の調製方法＞
　各成分を所定の割合でかつ任意の方法で混合し、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.
　本発明の組成物の２５℃における固形分濃度は、１～６０質量％が好ましく、３～４０質量％がより好ましく、５～３０質量％がさらに好ましく、５～１７質量％が特に好ましい。
　本発明の組成物の２５℃における粘度は、１～１００ｍＰａ・ｓが好ましく、２～６０ｍＰａ・ｓがより好ましく、３～４０ｍＰａ・ｓが最も好ましい。固形分濃度、粘度を上記範囲とすることで、高品位な塗布が可能となる。粘度は、例えば、東機産業製　粘度計　ＲＥ８５Ｌ（ローター：１°３４’×Ｒ２４測定範囲０．６～１２００ｍＰａ・ｓ）を使用し、２５℃に温度調整を施した状態で測定することができる。 The solid content concentration of the composition of the present invention at 25 ° C. is preferably 1 to 60% by mass, more preferably 3 to 40% by mass, further preferably 5 to 30% by mass, and particularly preferably 5 to 17% by mass.
The viscosity at 25 ° C. of the composition of the present invention is preferably 1 to 100 mPa · s, more preferably 2 to 60 mPa · s, and most preferably 3 to 40 mPa · s. By setting the solid content concentration and viscosity within the above ranges, high-quality coating can be achieved. The viscosity can be measured, for example, using a viscometer RE85L (rotor: 1 ° 34 ′ × R24 measurement range 0.6 to 1200 mPa · s) manufactured by Toki Sangyo Co., Ltd., with the temperature adjusted to 25 ° C. .
（硬化膜の製造方法）
　本発明の硬化膜の製造方法は、以下の（１）～（５）の工程を含むことが好ましい。
（１）本発明の感光性樹脂組成物を基板の少なくとも一方の面に塗布する工程、
（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、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、
を含む硬化膜の製造方法。
　以下に各工程を順に説明する。 (Method for producing cured film)
The method for producing a cured film of the present invention preferably includes the following steps (1) to (5).
(1) A step of applying the photosensitive resin composition of the present invention to at least one surface of 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 rays,
(4) a step of developing the exposed photosensitive resin composition with an aqueous developer, and (5) a post-baking step of thermosetting the developed photosensitive resin composition,
The manufacturing method of the cured film containing this.
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。
　感光性樹脂組成物は、スリット塗布、スピン塗布、インクジェット塗布等の公知の塗布方法により、基板上に塗布することができる。中でもスリット塗布が好ましい。スリットコートは大型基板に効率よく塗布できるため、生産性が高い。大型基板とは、３０００００ｍｍ2以上１２００００００ｍｍ2以下の面積の基板をいう。スリット塗布する際には基板とスリットダイとの相対移動速度を２０～１８０ｍｍ／ｓｅｃとすることが好ましい。なお、スリット塗布した後にスピン塗布を組み合わせることもできる。
　塗布膜厚（乾燥膜厚）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 And the like.
These substrates are rarely used in the above-described form, and usually a multilayer laminated structure such as a TFT element is formed depending on the form of the final product.
The photosensitive resin composition can be applied onto the substrate by a known coating method such as slit coating, spin coating, or inkjet coating. Of these, slit coating is preferred. Since the slit coat can be efficiently applied to a large substrate, the productivity is high. And large-sized substrate refers to a substrate area of 300000Mm 2 more 12000000Mm 2 or less. When applying the slit, the relative movement speed of the substrate and the slit die is preferably 20 to 180 mm / sec. It is also possible to combine spin coating after slit coating.
The coating film thickness (dry film thickness) is not particularly limited, and can be applied with a film thickness according to the application, but 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／または加熱等により、溶剤を除去して基板上に乾燥塗膜を形成させる。溶剤除去工程の加熱条件は、好ましくは７０～１３０℃で３０～３００秒間程度である。温度と時間が上記範囲である場合、パターンの密着性がより良好で、且つ残渣もより低減できる傾向にある。 (2) In the solvent removal step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry coating film on the substrate. The heating conditions for the solvent removal step are preferably 70 to 130 ° C. and about 30 to 300 seconds. When the temperature and time are in the above ranges, the pattern adhesiveness is better and the residue tends to be further reduced.
　（３）の露光工程では、塗膜を設けた基板に所定のパターンの活性光線を照射する。この工程では、光酸発生剤が分解し酸が発生する。発生した酸の触媒作用により、塗膜成分中に含まれる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、ｉ線（３６５ｎｍ）、ｈ線（４０５ｎｍ）、ｇ線（４３６ｎｍ）などの波長３００ｎｍ以上４５０ｎｍ以下の波長を有する活性光線が好ましく使用できる。また、必要に応じて長波長カットフィルター、短波長カットフィルター、バンドパスフィルターのような分光フィルターを通して照射光を調整することもできる。露光量は好ましくは１～５００ｍＪ／ｃｍ2である。
　露光装置としては、ミラープロジェクションアライナー、ステッパー、スキャナー、プロキシミティ、コンタクト、マイクロレンズアレイ、レンズスキャナ、レーザー露光、液浸露光など各種方式の露光機を用いることができる。 In the exposure step (3), the substrate provided with the coating film is irradiated with an actinic ray having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. Due to the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to generate a carboxyl group or a phenolic hydroxyl group.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, an LED light source, an excimer laser generator, and the like can be used, and i-line (365 nm), h-line (405 nm), Actinic rays having a wavelength of 300 nm to 450 nm, such as 436 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed. The exposure amount is preferably 1 to 500 mJ / cm 2 .
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, a lens scanner, laser exposure, and immersion exposure can be used.
　また、所謂超解像技術を用いた露光をすることもできる。超解像技術としては、複数回露光する多重露光や、位相シフトマスクを用いる方法、輪帯照明法などが挙げられる。これら超解像技術を用いることでより高精細なパターン形成が可能となり、好ましい。 Also, exposure using so-called super-resolution technology can be performed. Examples of the super-resolution technique include multiple exposure in which exposure is performed a plurality of times, a method using a phase shift mask, and an annular illumination method. By using these super-resolution techniques, it is possible to form a higher definition pattern, which is preferable.
　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。 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 in order to accelerate the hydrolysis reaction. 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.
　（４）の現像工程では、遊離したカルボキシル基またはフェノール性水酸基を有する共重合体を、アルカリ性現像液を用いて現像する。アルカリ性現像液に溶解しやすいカルボキシル基またはフェノール性水酸基を有する樹脂組成物を含む露光部領域を除去することにより、ポジ画像が形成する。
　現像工程で使用する現像液には、塩基性化合物の水溶液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、炭酸セシウムなどのアルカリ金属炭酸塩類；重炭酸ナトリウム、重炭酸カリウムなどのアルカリ金属重炭酸塩類；テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、ジエチルジメチルアンモニウムヒドロキシド等のテトラアルキルアンモニウムヒドロキシド類：コリン等の（ヒドロキシアルキル）トリアルキル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ケイ酸塩類；エチルアミン、プロピルアミン、ジエチルアミン、トリエチルアミン等のアルキルアミン類；ジメチルエタノールアミン、トリエタノールアミン等のアルコールアミン類；１，８－ジアザビシクロ‐［５．４．０］－７-ウンデセン、１，５－ジアザビシクロ－［４．３．０］－５－ノネン等の脂環式アミン類を使用することができる。
　これらのうち、水酸化ナトリウム、水酸化カリウム、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、テトラプロピルアンモニウムヒドロキシド、テトラブチルアンモニウムヒドロキシド、コリン（２－ヒドロキシエチルトリメチルアンモニウムヒドロキシド）が好ましい。
　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。
　現像液のｐＨは、好ましくは１０．０～１４．０である。
　現像時間は、好ましくは３０～５００秒間であり、また、現像の手法は液盛り法（パドル法）、シャワー法、ディップ法等の何れでもよい。
　現像の後に、リンス工程を行うこともできる。リンス工程では、現像後の基板を純水などで洗うことで、付着している現像液除去、現像残渣除去を行う。リンス方法は公知の方法を用いることができる。例えばシャワーリンスやディップリンスなどを挙げる事ができる。 In the developing step (4), a copolymer having a liberated carboxyl group or phenolic hydroxyl group is developed using an alkaline developer. A positive image is formed by removing an exposed area containing a resin composition having a carboxyl group or a phenolic hydroxyl group that is easily dissolved in an alkaline developer.
The developer used in the development step preferably contains an aqueous solution of a basic compound. Examples of basic compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as sodium carbonate, potassium carbonate, and cesium carbonate; sodium bicarbonate, potassium bicarbonate Alkali metal bicarbonates such as: tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, diethyldimethylammonium hydroxide, and other tetraalkylammonium hydroxides: Alkyl) trialkylammonium hydroxides; silicates such as sodium silicate and sodium metasilicate; ethylamine, propylamine, diethylamine, triethylammonium Alkylamines such as diamine; Alcoholamines such as dimethylethanolamine and triethanolamine; 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0 ] Cycloaliphatic amines such as -5-nonene can be used.
Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium hydroxide) are preferable.
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.
The pH of the developer is preferably 10.0 to 14.0.
The development time is preferably 30 to 500 seconds, and the development method may be any of a liquid piling method (paddle method), a shower method, a dipping method, and the like.
A rinsing step can also be performed after development. In the rinsing step, the developed substrate and the development residue are removed by washing the developed substrate with pure water or the like. A known method can be used as the rinsing method. For example, shower rinse and dip rinse can be mentioned.
　（５）のポストベーク工程では、得られたポジ画像を加熱することにより、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、架橋性基、架橋剤等を架橋させ、および／または環化ＰＢＯ化を促進させることで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１８０～４００℃で所定の時間、例えばホットプレート上なら５～１２０分間、オーブンならば３０～３６０分間、加熱処理をすることが好ましい。このように架橋反応、環化反応を進行させることにより、耐熱性、硬度等により優れた保護膜や層間絶縁膜を形成することができる。また、加熱処理を行う際は窒素雰囲気下で行うことにより、透明性をより向上させることもできる。
　ポストベークの前に、比較的低温でベークを行った後にポストベークすることもできる（ミドルベーク工程の追加）。ミドルベークを行う場合は、９０～１５０℃で１～６０分加熱した後に、２００℃以上の高温でポストベークすることが好ましい。また、ミドルベーク、ポストベークを３段階以上の多段階に分けて加熱する事もできる。このようなミドルベーク、ポストベークの工夫により、パターンのテーパー角を調整することができる。これらの加熱は、ホットプレート、オーブン、赤外線ヒーターなど、公知の加熱方法を使用することができる。
　なお、ポストベークに先立ち、パターンを形成した基板に活性光線により全面再露光（ポスト露光）した後、ポストベークすることにより未露光部分に存在する光酸発生剤から酸を発生させ、架橋工程を促進する触媒として機能させることができ、膜の硬化反応を促進することができる。ポスト露光工程を含む場合の好ましい露光量としては、１００～３，０００ｍＪ／ｃｍ2が好ましく、１００～５００ｍＪ／ｃｍ2が特に好ましい。 In the post-baking step of (5), the obtained positive image is heated to thermally decompose the acid-decomposable group to generate a carboxyl group or a phenolic hydroxyl group, to crosslink the crosslinkable group, the crosslinking agent, and the like. A cured film can be formed by promoting cyclized PBO. This heating is performed using a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 400 ° C. for a predetermined time, for example, 5 to 120 minutes on a hot plate, 30 to 360 minutes for an oven. It is preferable to By proceeding with the crosslinking reaction and the cyclization reaction in this way, a protective film and an interlayer insulating film that are superior in heat resistance, hardness and the like can be formed. In addition, when the heat treatment is performed in a nitrogen atmosphere, the transparency can be further improved.
Prior to post-baking, post-baking can be performed after baking at a relatively low temperature (addition of a middle baking process). When middle baking is performed, it is preferable to post-bake at a high temperature of 200 ° C. or higher after heating at 90 to 150 ° C. for 1 to 60 minutes. Moreover, middle baking and post-baking can be heated in three or more stages. The taper angle of the pattern can be adjusted by devising such middle baking and post baking. These heating methods can use well-known heating methods, such as a hotplate, oven, and an infrared heater.
Prior to post-baking, the entire surface of the patterned substrate was re-exposed with actinic rays (post-exposure), and then post-baked to generate an acid from the photoacid generator present in the unexposed portion, thereby performing a crosslinking step. It can function as a catalyst to promote, and can accelerate the curing reaction of the film. The preferred exposure amount in the case of including a post-exposure step, preferably 100 ~ 3,000mJ / cm 2, particularly preferably 100 ~ 500mJ / cm 2.
　さらに、本発明の感光性樹脂組成物より得られた硬化膜は、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 an etching resist. In the case where a cured film obtained by thermal curing in a post-baking process is used as a dry etching resist, dry etching processes such as ashing, plasma etching, and ozone etching can be performed as the etching process.
（硬化膜）
　本発明の硬化膜は、上述した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、上述した本発明の硬化膜の形成方法により得られた硬化膜であることが好ましい。
　本発明の感光性樹脂組成物により、絶縁性に優れ、高温でベークされた場合においても高い透明性を有する層間絶縁膜が得られる。本発明の感光性樹脂組成物を用いてなる層間絶縁膜は、高い透明性を有し、硬化膜物性に優れるため、液晶表示装置や有機ＥＬ表示装置の用途に有用である。 (Cured film)
The cured film of the present invention is a cured film obtained by curing the above-described photosensitive resin composition.
The cured film of the present invention can be suitably used as an interlayer insulating film. Moreover, it is preferable that the cured film of this invention is a cured film obtained by the formation method of the cured film of this invention mentioned above.
With the photosensitive resin composition of the present invention, an interlayer insulating film having excellent insulation and high transparency even when baked at high temperatures can be obtained. Since the interlayer insulating film using the photosensitive resin composition of the present invention has high transparency and excellent cured film properties, it is useful for liquid crystal display devices and organic EL display devices.
　本発明の硬化膜における波長４００ｎｍにおける透過率は、８５～１００％であることが好ましく、９０～１００％であることがより好ましく、９５～１００％であることがさらに好ましい。波長４００ｎｍにおける透過率は、例えば、分光光度計（Ｕ－３０００：（株）日立製作所製）で測定することができる。 The transmittance of the cured film of the present invention at a wavelength of 400 nm is preferably 85 to 100%, more preferably 90 to 100%, and still more preferably 95 to 100%. The transmittance at a wavelength of 400 nm can be measured, for example, with a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.).
（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。
　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保護膜や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、カラーフィルターの保護膜や、液晶表示装置における液晶層の厚みを一定に保持するためのスペーサーや固体撮像素子においてカラーフィルター上に設けられるマイクロレンズ等に好適に用いることができる。
　図１は、アクティブマトリックス方式の液晶表示装置１０の一例を示す概念的断面図である。このカラー液晶表示装置１０は、背面にバックライトユニット１２を有する液晶パネルであって、液晶パネルは、偏光フィルムが貼り付けられた２枚のガラス基板１４，１５の間に配置されたすべての画素に対応するＴＦＴ１６の素子が配置されている。ガラス基板上に形成された各素子には、硬化膜１７中に形成されたコンタクトホール１８を通して、画素電極を形成するＩＴＯ透明電極１９が配線されている。ＩＴＯ透明電極１９の上には、液晶２０の層とブラックマトリックスを配置したＲＧＢカラーフィルター２２が設けられている。
　バックライトの光源としては、特に限定されず公知の光源を用いることができる。例えば白色ＬＥＤ、青色・赤色・緑色などの多色ＬＥＤ、蛍光灯（冷陰極管）、有機ＥＬなどを挙げる事ができる。
　また、液晶表示装置は、３Ｄ（立体視）型のものとしたり、タッチパネル型のものとしたりすることも可能である。さらにフレキシブル型にすることも可能であり、特開２０１１－１４５６８６号公報に記載の第２層間絶縁膜（４８）や、特開２００９－２５８７５８号公報に記載の層間絶縁膜（５２０）として用いることができる。
　さらに、スタティック駆動方式の液晶表示装置でも、本発明を適用することで意匠性の高いパターンを表示させることも可能である。例として、特開２００１－１２５０８６号公報に記載されているようなポリマーネットワーク型液晶の絶縁膜として本発明を適用することができる。 (Liquid crystal display device)
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 protective film, a planarizing film, and an interlayer insulating film formed using the photosensitive resin composition of the present invention, and is known in various structures. The liquid crystal display device can be mentioned.
For example, specific examples of TFT (Thin-Film Transistor) included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low-temperature polysilicon-TFT, oxide semiconductor TFT, and the like. Since the cured film of the present invention is excellent in electrical characteristics, it can be preferably used in combination with these TFTs.
In addition, as a liquid crystal driving method that can be adopted by the liquid crystal display device of the present invention, a TN (Twisted Nematic) method, a VA (Virtual Alignment) method, an IPS (In-Place-Switching) method, an FFS (Frings Field Switching) method, an OCB (Optical) method. Compensated Bend) method and the like.
In the panel configuration, the cured film of the present invention can also be used in a COA (Color Filter on Array) type liquid crystal display device. For example, the organic insulating film (115) of JP-A-2005-284291, -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, it can be suitably used for a color filter protective film, a spacer for keeping the thickness of a liquid crystal layer in a liquid crystal display device constant, a microlens provided on a color filter in a solid-state imaging device, or the like.
FIG. 1 is a conceptual cross-sectional view showing an example of an active matrix liquid crystal display device 10. The color liquid crystal display device 10 is a liquid crystal panel having a backlight unit 12 on the back surface, and the liquid crystal panel includes all pixels disposed between two glass substrates 14 and 15 having a polarizing film attached thereto. The elements of the TFT 16 corresponding to are arranged. Each element formed on the glass substrate is wired with an ITO transparent electrode 19 that forms a pixel electrode through a contact hole 18 formed in the cured film 17. On the ITO transparent electrode 19, an RGB color filter 22 in which a liquid crystal 20 layer and a black matrix are arranged is provided.
The light source of the backlight is not particularly limited, and a known light source can be used. For example, a white LED, a multicolor LED such as blue, red, and green, a fluorescent lamp (cold cathode tube), and an organic EL can be used.
Further, the liquid crystal display device can be a 3D (stereoscopic) type or a touch panel type. Further, it can be made flexible, and used as the second interlayer insulating film (48) described in Japanese Patent Application Laid-Open No. 2011-145686 and the interlayer insulating film (520) described in Japanese Patent Application Laid-Open No. 2009-258758. Can do.
Further, even in a static drive type liquid crystal display device, a pattern with high designability can be displayed by applying the present invention. As an example, the present invention can be applied as an insulating film of a polymer network type liquid crystal as described in JP-A-2001-125086.
（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。
　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 includes 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。この他、液晶表示装置における液晶層の厚みを一定に保持するためのスペーサーや、ファクシミリ、電子複写機、固体撮像素子等のオンチップカラーフィルターの結像光学系あるいは光ファイバコネクタのマイクロレンズにも好適に用いることができる。 Since the photosensitive resin composition of the present invention is excellent in flatness and transparency, for example, the bank layer (16) and the planarization film (57) described in FIG. 2 of JP-A-2011-107476, JP-A-2010- The partition wall (12) and the planarization film (102) described in FIG. 4 (a) of Japanese Patent No. 9793, the bank layer (221) and the third interlayer insulating film (216b) described in FIG. 10 of Japanese Patent Application Laid-Open No. 2010-27591. ), The second interlayer insulating film (125) and the third interlayer insulating film (126) described in FIG. 4A of JP-A-2009-128577, and the flatness described in FIG. 3 of JP-A-2010-182638. It can also be used to form a chemical film (12) and a pixel isolation insulating film (14). In addition, spacers for maintaining the thickness of the liquid crystal layer in liquid crystal display devices, imaging optical systems for on-chip color filters such as facsimiles, electronic copying machines, solid-state image sensors, and micro lenses for optical fiber connectors are also used. It can be used suitably.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。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.
合成例Ａ－１：樹脂Ａ－１の合成
　温度計、攪拌器、窒素導入管を備えた３つ口フラスコに、２９３ｇ（０.８ｍｏｌ）のヘキサフルオロ－２,２－ビス（３－アミノ－４－ヒドロキシフェニル）プロパン（日本化薬（株）製）、１５８．２ｇ（２．０ｍｏｌ）のピリジンおよび１.２ｋｇのＮ－メチル－２－ピロリドン（ＮＭＰ）を添加した。これを室温で撹拌、次いでドライアイス／アセトンバスで－２５℃まで冷却した。この溶液に、反応温度を－２０℃～－３０℃で維持しながら、７３.９ｇ（０.３６４ｍｏｌ）のイソフタロイルクロライド（東京化成（株）製）、１０７.４ｇ（０.３６４ｍｏｌ）の４,４’－オキシビスベンゾイルクロライド（４，４’－オキシビス安息香酸（Ａｌｄｒｉｃｈ製）を定法にて酸クロリドに変換して得た。）、ＮＭＰ（１－メチル－２－ピロリドン）７００ｇの混合溶液を滴下した。滴下が完了した後、得られる混合物を室温で１６時間撹拌した。
　次に、この反応液を氷／メタノールバスで－５℃以下まで冷却し、反応温度を－０℃以下で維持しながらアセチルクロライド１７．０ｇ（０．２１７ｍｏｌ）を滴下した。滴下が完了した後、さらに１６時間撹拌した。
　この反応液をアセトン２Ｌで希釈し、激しく攪拌した２０Ｌの脱イオン水中に投入し、析出した白色粉体を濾過によって回収し、そして脱イオン水および水／メタノール（５０／５０質量比）混合物によって洗浄した。真空下でポリマーを４０℃において２４時間乾燥させ、樹脂Ａ－１を得た。 Synthesis Example A-1: Synthesis of Resin A-1 In a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 293 g (0.8 mol) of hexafluoro-2,2-bis (3-amino- 4-Hydroxyphenyl) propane (Nippon Kayaku Co., Ltd.), 158.2 g (2.0 mol) of pyridine and 1.2 kg of N-methyl-2-pyrrolidone (NMP) were added. This was stirred at room temperature and then cooled to −25 ° C. with a dry ice / acetone bath. To this solution, while maintaining the reaction temperature at −20 ° C. to −30 ° C., 73.9 g (0.364 mol) of isophthaloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 107.4 g (0.364 mol) of Mixing of 4,4′-oxybisbenzoyl chloride (obtained by converting 4,4′-oxybisbenzoic acid (manufactured by Aldrich) to acid chloride by a conventional method) and 700 g of NMP (1-methyl-2-pyrrolidone) The solution was added dropwise. After the addition was complete, the resulting mixture was stirred at room temperature for 16 hours.
Next, the reaction solution was cooled to −5 ° C. or lower with an ice / methanol bath, and 17.0 g (0.217 mol) of acetyl chloride was added dropwise while maintaining the reaction temperature at −0 ° C. or lower. After completion of the dropwise addition, the mixture was further stirred for 16 hours.
The reaction solution is diluted with 2 L of acetone, poured into 20 L of deionized water with vigorous stirring, the precipitated white powder is recovered by filtration, and deionized water and a water / methanol (50/50 mass ratio) mixture. Washed. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin A-1.
合成例Ａ－２～Ａ－１４：樹脂Ａ－２～１４の合成
　樹脂Ａ－２～Ａ－１４についても樹脂Ａ－１と同様の操作で合成を行った。これらの合成で使用した装置およびピリジン量、溶媒量、ポリマーの取り出し方法等はすべて合成例Ａ－１と同等装置、同量の条件である。いずれも酸ジクロライドは全てを混合し、滴下液側に入れた。使用したモノマーの量および、得られたポリマーの分子量を以下の表に示す。 Synthesis Examples A-2 to A-14: Synthesis of Resins A-2 to 14 Resins A-2 to A-14 were synthesized in the same manner as Resin A-1. The apparatus used in these syntheses, the amount of pyridine, the amount of solvent, the method for taking out the polymer, etc. are all the same apparatus and conditions as in Synthesis Example A-1. In all cases, all of the acid dichloride was mixed and placed on the dropping liquid side. The amount of monomer used and the molecular weight of the resulting polymer are shown in the table below.
＜末端がアセチル基で封止されたポリベンゾオキサゾール前駆体＞
Figure JPOXMLDOC01-appb-T000059
 <Polybenzoxazole precursor whose end is sealed with an acetyl group>
Figure JPOXMLDOC01-appb-T000059
　表中、bis-APAFは、ヘキサフルオロ－２,２－ビス（３－アミノ－４－ヒドロキシフェニル）プロパンを表し、ODCは４,４’－オキシビスベンゾイルクロライド、ICは、イソフタル酸クロライドを表し、Seb-Cは、セバシン酸ジクロライド（ALDRICH製）を表し、Adi-Cは、アジピン酸ジクロライド（ALDRICH製）を表し、CHD-Cは、１，４－シクロヘキサンジカルボン酸ジクロリド（東京化成製 １，４－シクロヘキサンジカルボン酸を定法により酸塩化物化したもの）を表し、AcClは、アセチルクロライド（東京化成製）を表す。
　分子量（ＧＰＣ）は、表中の数値×１０００を表す。分子量は、ゲルパーミエーションクロマトグラフィーのポリスチレン換算値をもって測定したＭｗ値であり、表中の数値×１０００を表す（以下、樹脂の分子量について同じ）。
Figure JPOXMLDOC01-appb-C000060
 In the table, bis-APAF represents hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane, ODC represents 4,4′-oxybisbenzoyl chloride, and IC represents isophthalic acid chloride. Seb-C represents sebacic acid dichloride (manufactured by ALDRICH), Adi-C represents adipic acid dichloride (manufactured by ALDRICH), and CHD-C represents 1,4-cyclohexanedicarboxylic acid dichloride (manufactured by Tokyo Chemical Industry 1, 4-cyclohexanedicarboxylic acid obtained by acidification by a conventional method), and AcCl represents acetyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.).
A molecular weight (GPC) represents the numerical value x1000 in a table | surface. The molecular weight is an Mw value measured by gel permeation chromatography in terms of polystyrene, and represents a numerical value x 1000 in the table (hereinafter the same as the molecular weight of the resin).
Figure JPOXMLDOC01-appb-C000060
合成例Ｂ－１０１：樹脂Ｂ－１０１の合成
　温度計、攪拌器、窒素導入管を備えた３つ口フラスコに、合成例Ａ－１で得られた樹脂Ａ－１１５０ｇを加え、プロピレングリコール－１－モノメチルエーテル－２－アセタート（ＰＧＭＥＡ）を１．５Ｌ加え、トリエチルアミン１７．０５ｇ（０．１６８ｍｍｏｌ）、エピクロロヒドリン１０．３９ｇ（０．１１２ｍｏｌ）を添加し、室温で３時間攪拌した。
　この反応液をアセトン１．５Ｌで希釈し、激しく攪拌した２０Ｌのヘキサン中に投入し、析出した白色粉体を濾過によって回収した。真空下でポリマーを４０℃において４時間乾燥させ、このポリマーのうち１２０ｇを２Ｌのアセトンに溶解させ、激しく攪拌した１０Ｌの水中に投入し、そして脱イオン水および水／メタノール（５０／５０質量比）混合物によって洗浄した。真空下でポリマーを４０℃において２４時間乾燥させ、樹脂Ｂ－１０１を得た。 Synthesis Example B-101: Synthesis of Resin B-101 To a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube is added 150 g of the resin A-1 obtained in Synthesis Example A-1, and propylene glycol-1 -1.5 L of monomethyl ether-2-acetate (PGMEA) was added, 17.05 g (0.168 mmol) of triethylamine and 10.39 g (0.112 mol) of epichlorohydrin were added, and the mixture was stirred at room temperature for 3 hours.
The reaction solution was diluted with 1.5 L of acetone, poured into 20 L of hexane that was vigorously stirred, and the precipitated white powder was collected by filtration. The polymer was dried under vacuum at 40 ° C. for 4 hours, 120 g of this polymer was dissolved in 2 L acetone, poured into 10 L of vigorously stirred water, and deionized water and water / methanol (50/50 mass ratio) ) Washed with the mixture. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin B-101.
合成例Ｂ－１０２～Ｂ－１１４：樹脂Ｂ－１０２～Ｂ－１１４の合成
　樹脂Ｂ－１０２～Ｂ－１１４についても樹脂Ｂ－１０１と同様の操作で合成を行った。これらの合成で使用した装置および、溶媒量、ポリマーの取り出し方法等はすべて合成例Ｂ－１０１と同じ条件である。使用したモノマーの量および得られたポリマーの分子量を以下の表に示す。 Synthesis Examples B-102 to B-114: Synthesis of Resins B-102 to B-114 Resins B-102 to B-114 were synthesized in the same manner as Resin B-101. The equipment used in these syntheses, the amount of solvent, the method for taking out the polymer, etc. are all the same as in Synthesis Example B-101. The amount of monomer used and the molecular weight of the resulting polymer are shown in the table below.
＜末端がアセチル基で封止され、主鎖に架橋性基が導入されたポリベンゾオキサゾール前駆体＞
Figure JPOXMLDOC01-appb-T000061
 <Polybenzoxazole precursor whose end is sealed with an acetyl group and a crosslinkable group is introduced into the main chain>
Figure JPOXMLDOC01-appb-T000061
　表中、ＥＣＨ、はエピクロロヒドリンを表し、ＮＥｔ3はトリエチルアミンを表す。分子量は、表中の数値×１０００を表す。ここで導入率とは、酸分解性基（架橋性基）導入前のポリベンゾオキサゾール前駆体における全水酸基（モル量）に対して、ＯＨ基の酸分解性基（架橋性基）が反応したモル量を意味する（以下同じ）。 In the table, ECH represents epichlorohydrin, and NEt 3 represents triethylamine. The molecular weight represents a numerical value x 1000 in the table. Here, the introduction rate means that the acid-decomposable group (crosslinkable group) of the OH group reacted with the total hydroxyl groups (molar amount) in the polybenzoxazole precursor before introducing the acid-decomposable group (crosslinkable group). It means molar amount (the same applies hereinafter).
中間体Ｃの合成
　温度計、攪拌器、窒素導入管を備えた３つ口フラスコに、３－エチル－３－オキセタンメタノール（１１８．５ｇ、１．０２ｍｏｌ）、３－クロロプロピルイソシアネート（１１９．６ｇ、１．０ｍｏｌ）、ネオスタンＵ－６００（日東化成）０．２ｇを加え、室温で３時間攪拌した。反応液に酢酸エチル２５０ｍｌおよび水２５０ｍｌを加え攪拌し、分液ロートで有機層を抽出した。得られた有機層を３回水洗し、硫酸ナトリウムを加え、乾燥させた後、十分な濃縮を行い、下記構造の中間体Ｃを２２１．６ｇ（収率９４％）得た。
Figure JPOXMLDOC01-appb-C000062
 Synthesis of Intermediate C 3-ethyl-3-oxetanemethanol (118.5 g, 1.02 mol), 3-chloropropyl isocyanate (119.6 g) were added to a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube. 1.0 mol) and 0.2 g of Neostan U-600 (Nitto Kasei) were added and stirred at room temperature for 3 hours. To the reaction solution, 250 ml of ethyl acetate and 250 ml of water were added and stirred, and the organic layer was extracted with a separatory funnel. The obtained organic layer was washed with water three times, sodium sulfate was added and dried, followed by sufficient concentration to obtain 221.6 g (yield 94%) of Intermediate C having the following structure.
Figure JPOXMLDOC01-appb-C000062
合成例Ｃ－１０１：樹脂Ｃ－１０１の合成
　温度計、攪拌器、窒素導入管を備えた３つ口フラスコに、樹脂Ａ－１（１５０ｇ）を加え、１－メチル－２－ピロリドン（ＮＭＰ）を１．５Ｌ加え、トリエチルアミン（１７．０５ｇ、０．１６８ｍｏｌ）、中間体Ｃ（２６．４８ｇ、０．１１２ｍｏｌ）、ヨウ化カリウム（３３．２ｇ、０．２０ｍｏｌ）を添加し、室温で３時間攪拌した。
　この反応液をアセトン１．５Ｌで希釈し、激しく攪拌した２０Ｌのヘキサン中に投入し、析出した白色粉体を濾過によって回収した。真空下でポリマーを４０℃において４時間乾燥させ、このポリマーのうち１２０ｇを２Ｌのアセトンに溶解させ、激しく攪拌した１０Ｌの水中に投入し、そして脱イオン水および水／メタノール（５０／５０質量比）混合物によって洗浄した。真空下でポリマーを４０℃において２４時間乾燥させ、樹脂Ｃ－１０１を得た。 Synthesis Example C-101: Synthesis of Resin C-101 Resin A-1 (150 g) was added to a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, and 1-methyl-2-pyrrolidone (NMP) was added. 1.5 L, triethylamine (17.05 g, 0.168 mol), intermediate C (26.48 g, 0.112 mol), potassium iodide (33.2 g, 0.20 mol) were added, and 3 hours at room temperature. Stir.
The reaction solution was diluted with 1.5 L of acetone, poured into 20 L of hexane that was vigorously stirred, and the precipitated white powder was collected by filtration. The polymer was dried under vacuum at 40 ° C. for 4 hours, 120 g of this polymer was dissolved in 2 L acetone, poured into 10 L of vigorously stirred water, and deionized water and water / methanol (50/50 mass ratio) ) Washed with the mixture. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin C-101.
合成例Ｃ－１０２～Ｃ－１１４：樹脂Ｃ－１０２～Ｃ－１１４の合成
　樹脂Ｃ－１０２～Ｃ－１１４についても樹脂Ｃ－１０１と同様の操作で合成を行った。これらの合成で使用した装置および、ヨウ化カリウム量、溶媒量、ポリマーの取り出し方法等はすべて合成例Ｃ－１０１と同じの条件である。使用したモノマーの量および得られたポリマーの分子量を以下の表に示す。 Synthesis Examples C-102 to C-114: Synthesis of Resins C-102 to C-114 Resins C-102 to C-114 were synthesized in the same manner as Resin C-101. The apparatus used in these syntheses, the amount of potassium iodide, the amount of solvent, the method for taking out the polymer, etc. are all the same conditions as in Synthesis Example C-101. The amount of monomer used and the molecular weight of the resulting polymer are shown in the table below.
Figure JPOXMLDOC01-appb-T000063
Figure JPOXMLDOC01-appb-T000063
　表中、ＮＥｔ3はトリエチルアミンを表す。 In the table, NEt 3 represents triethylamine.
中間体Ｄの合成
　温度計、攪拌器、窒素導入管を備えた３つ口フラスコに、２－ブタノンオキシム　８７．９９ｇ（１．０１ｍｏｌ）、３－クロロプロピルイソシアネート１１９．５５ｇ（１．００ｍｏｌ）、ネオスタンＵ－６００（日東化成製）０．２ｇを加え、室温で３時間攪拌した。反応液に酢酸エチル２５０ｍｌ、水２５０ｍｌを加え攪拌し、分液ロートで有機層を抽出した。得られた有機層を３回水洗し、硫酸ナトリウムを加え、乾燥させた後、十分な濃縮を行い、下記構造の中間体Ｄを１９６．３ｇ（収率９５％）得た。
Figure JPOXMLDOC01-appb-C000064
 Synthesis of Intermediate D To a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, 87.99 g (1.01 mol) of 2-butanone oxime, 119.55 g (1.00 mol) of 3-chloropropyl isocyanate, 0.2 g of Neostan U-600 (manufactured by Nitto Kasei) was added and stirred at room temperature for 3 hours. To the reaction solution, 250 ml of ethyl acetate and 250 ml of water were added and stirred, and the organic layer was extracted with a separatory funnel. The obtained organic layer was washed with water three times, sodium sulfate was added and dried, followed by sufficient concentration to obtain 196.3 g (yield 95%) of Intermediate D having the following structure.
Figure JPOXMLDOC01-appb-C000064
合成例Ｄ－１０１：樹脂Ｄ－１０１の合成
　温度計、攪拌器、窒素導入管を備えた３つ口フラスコに、樹脂Ａ－１（１５０ｇ）を加え、１－メチル－２－ピロリドン（ＮＭＰ）を１．５Ｌ加え、トリエチルアミン（１７．０５ｇ、０．１６８ｍｏｌ）、中間体Ｄ（２３．２２ｇ、０．１１２ｍｏｌ）、ヨウ化カリウム（３３．２ｇ、０．２０ｍｏｌ）を添加し、室温で３時間攪拌した。
　この反応液をアセトン１．５Ｌで希釈し、激しく攪拌した２０Ｌのヘキサン中に投入し、析出した白色粉体を濾過によって回収した。真空下でポリマーを４０℃において４時間乾燥させ、このポリマーのうち１２０ｇを２Ｌのアセトンに溶解させ、激しく攪拌した１０Ｌの水中に投入し、そして脱イオン水および水／メタノール（５０／５０質量比）混合物によって洗浄した。真空下でポリマーを４０℃において２４時間乾燥させ、樹脂Ｄ－１０１を得た。 Synthesis Example D-101: Synthesis of Resin D-101 Resin A-1 (150 g) was added to a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, and 1-methyl-2-pyrrolidone (NMP) was added. 1.5 L, triethylamine (17.05 g, 0.168 mol), intermediate D (23.22 g, 0.112 mol) and potassium iodide (33.2 g, 0.20 mol) were added, and 3 hours at room temperature. Stir.
The reaction solution was diluted with 1.5 L of acetone, poured into 20 L of hexane that was vigorously stirred, and the precipitated white powder was collected by filtration. The polymer was dried under vacuum at 40 ° C. for 4 hours, 120 g of this polymer was dissolved in 2 L acetone, poured into 10 L of vigorously stirred water, and deionized water and water / methanol (50/50 mass ratio) ) Washed with the mixture. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin D-101.
合成例Ｄ－１０２～Ｄ－１１４：樹脂Ｄ－１０２～Ｄ－１１４の合成
　樹脂Ｄ－１０２～Ｄ－１１４についても樹脂Ｄ－１０１と同様の操作で合成を行った。これらの合成で使用した装置および、ヨウ化カリウム量、溶媒量、ポリマーの取り出し方法等はすべて樹脂Ｄ－１０１の合成と同じ条件である。使用したモノマーの量および得られたポリマーの分子量を以下の表に示す。 Synthesis Examples D-102 to D-114: Synthesis of Resins D-102 to D-114 Resins D-102 to D-114 were synthesized in the same manner as Resin D-101. The apparatus used in these syntheses, the amount of potassium iodide, the amount of solvent, the method for taking out the polymer, etc. are all the same conditions as in the synthesis of Resin D-101. The amount of monomer used and the molecular weight of the resulting polymer are shown in the table below.
Figure JPOXMLDOC01-appb-T000065
Figure JPOXMLDOC01-appb-T000065
　表中、ＮＥｔ3はトリエチルアミンを表す。分子量は、表中の数値×１０００を表す。 In the table, NEt 3 represents triethylamine. The molecular weight represents a numerical value x 1000 in the table.
合成例Ｂ－２０１ａ：樹脂Ｂ－２０１ａの合成
　３つ口フラスコに、樹脂Ｂ－１０１（１００ｇ）を加え、プロピレングリコール－１－モノメチルエーテル－２－アセタート（ＰＧＭＥＡ）を１．６Ｌ加え、内容物が０．９ｋｇになるまで濃縮した。温度計、攪拌器、窒素導入管を使用し、カンファースルホン酸（３質量％ＰＧＭＥＡ溶液）を９．１６ｇ（１．１８ｍｍｏｌ）、２，３－ジヒドロフラン６．８４ｇ（０．０９８ｍｏｌ）を加え、室温で４時間攪拌した。次に、トリエチルアミン（１０質量％ＰＧＭＥＡ溶液）２．９９ｇ（２．９５ｍｍｏｌ）を加えて反応を停止した。
　この反応液をアセトン１．０Ｌで希釈し、激しく攪拌した１２Ｌのヘキサン中に投入し、析出した白色粉体を濾過によって回収した。真空下でポリマーを４０℃において４時間乾燥させた。このポリマーのうち８０ｇを１．３Ｌのアセトンに溶解させ、激しく攪拌した１０Ｌの水中に投入し、そして脱イオン水および水／メタノール（５０／５０質量比）混合物によって洗浄した。真空下でポリマーを４０℃において２４時間乾燥させ、樹脂Ｂ－２０１ａを得た。 Synthesis Example B-201a: Synthesis of Resin B-201a Resin B-101 (100 g) was added to a three-necked flask and 1.6 L of propylene glycol-1-monomethyl ether-2-acetate (PGMEA) was added. Was concentrated to 0.9 kg. Using a thermometer, a stirrer, and a nitrogen introduction tube, 9.16 g (1.18 mmol) of camphorsulfonic acid (3 mass% PGMEA solution) and 6.84 g (0.098 mol) of 2,3-dihydrofuran were added, Stir at room temperature for 4 hours. Next, 2.99 g (2.95 mmol) of triethylamine (10 mass% PGMEA solution) was added to stop the reaction.
The reaction solution was diluted with 1.0 L of acetone, poured into 12 L of hexane that was vigorously stirred, and the precipitated white powder was collected by filtration. The polymer was dried at 40 ° C. for 4 hours under vacuum. 80 g of this polymer was dissolved in 1.3 L of acetone, poured into 10 L of vigorously stirred water and washed with deionized water and a water / methanol (50/50 mass ratio) mixture. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin B-201a.
合成例Ｂ－２０１ｂ～Ｂ－２１４ａ：樹脂Ｂ－２０１ｂ～Ｂ－２１４ａの合成
　樹脂Ｂ－２０１ｂ～Ｄ－２１４ａについても樹脂Ｂ－２０１ａと同様の操作で合成を行った。これらの合成で使用した装置、溶媒量、およびポリマーの取り出し方法等はすべて合成例Ｂ－２０１ａと同等装置、同量の条件である。使用したモノマーの量および、得られたポリマーの分子量を以下の表に示す。 Synthesis Examples B-201b to B-214a: Synthesis of Resins B-201b to B-214a Resins B-201b to D-214a were synthesized in the same manner as Resin B-201a. The equipment used in these syntheses, the amount of solvent, the method for extracting the polymer, etc. are all the same equipment and conditions as in Synthesis Example B-201a. The amount of monomer used and the molecular weight of the resulting polymer are shown in the table below.
＜主鎖に架橋性基が導入され、かつ、酸分解性基が導入されたポリベンゾオキサゾール前駆体＞
Figure JPOXMLDOC01-appb-T000066
 <Polybenzoxazole precursor with a crosslinkable group introduced into the main chain and an acid-decomposable group introduced>
Figure JPOXMLDOC01-appb-T000066
　表中、ＤＨＦは２，３－ジヒドロフランを表し、３％ＣＳＡはカンファースルホン酸（３質量％ＰＧＭＥＡ溶液）を表し、１０％ＮＥｔ3はトリエチルアミンの１０質量％ＰＧＭＥＡ溶液を表す。ＯＨ基保護率は、酸分解性基および架橋性基を導入する前のポリベンゾオキサゾール前駆体における全水酸基（モル量）に対して、酸分解性基が反応したモル比率％を意味する（以下同じ）。 In the table, DHF represents 2,3-dihydrofuran, 3% CSA represents camphorsulfonic acid (3% by mass PGMEA solution), and 10% NEt 3 represents a 10% by mass PGMEA solution of triethylamine. The OH group protection rate means the molar ratio% in which the acid-decomposable group has reacted with respect to the total hydroxyl groups (molar amount) in the polybenzoxazole precursor before the introduction of the acid-decomposable group and the crosslinkable group (hereinafter referred to as the following) the same).
Figure JPOXMLDOC01-appb-T000067
Figure JPOXMLDOC01-appb-T000067
　表中、ＤＨＦは２，３－ジヒドロフランを表し、３％ＣＳＡはカンファースルホン酸（３質量％ＰＧＭＥＡ溶液）を表し、１０％ＮＥｔ3はトリエチルアミンの１０質量％ＰＧＭＥＡ溶液を表す。 In the table, DHF represents 2,3-dihydrofuran, 3% CSA represents camphorsulfonic acid (3% by mass PGMEA solution), and 10% NEt 3 represents a 10% by mass PGMEA solution of triethylamine.
　合成例Ｂ－３０１ａ、Ｃ－３０１ａ、Ｄ－３０１ａ：樹脂Ｂ－３０１ａ、Ｃ－３０１ａ、Ｄ－３０１ａの合成
　樹脂Ｂ－３０１ａ、Ｃ－３０１ａ、Ｄ－３０１ａについては、使用するビニルエーテルを２，３－ジヒドロフランからエチルビニルエーテルに変更した以外は、樹脂Ｂ－２０１aと同様の操作で合成を行った。これらの合成で使用した装置及び、溶媒量、ポリマーの取り出し方法等はすべて合成例Ｂ－２０１ａと同等装置、同量の条件である。使用したモノマーの量及び、得られたポリマーの分子量を以下の表に示す。
Figure JPOXMLDOC01-appb-T000068
 　表中、ＥＶＥは、エチルビニルエーテルを表し、３％ＣＳＡはカンファースルホン酸（３質量％ＰＧＭＥＡ溶液）を表し、１０％ＮＥｔ3はトリエチルアミン（１０質量％ＰＧＭＥＡ溶液）を表す。 Synthesis Examples B-301a, C-301a, D-301a: Synthesis of Resins B-301a, C-301a, D-301a For Resins B-301a, C-301a, D-301a, 2 or 3 vinyl ethers were used. Synthesis was performed in the same manner as for Resin B-201a except that dihydrofuran was changed to ethyl vinyl ether. The equipment used in these syntheses, the amount of solvent, the method for extracting the polymer, etc. are all the same equipment and conditions as in Synthesis Example B-201a. The amount of monomer used and the molecular weight of the resulting polymer are shown in the table below.
Figure JPOXMLDOC01-appb-T000068
 In the table, EVE represents ethyl vinyl ether, 3% CSA represents camphorsulfonic acid (3% by mass PGMEA solution), and 10% NEt 3 represents triethylamine (10% by mass PGMEA solution).
合成例Ｅ－１：樹脂Ｅ－１の合成
　温度計、攪拌器、窒素導入管を備えた３つ口フラスコに、２９３ｇ（０.８ｍｏｌ）のヘキサフルオロ－２,２－ビス（３－アミノ－４－ヒドロキシフェニル）プロパン（日本化薬（株）製）、１５８．２ｇ（２．０ｍｏｌ）のピリジン、および１.２ｋｇのＮ－メチル－２－ピロリドン（ＮＭＰ）を添加した。これを室温で撹拌、次いでドライアイス／アセトンバスで－２５℃まで冷却した。この溶液に、反応温度を－２０℃～－３０℃で維持しながら、７３.９ｇ（０.３６４ｍｏｌ）のイソフタロイルクロライド（東京化成（株）製）、１０７.４ｇ（０.３６４ｍｏｌ）の４,４’－オキシビスベンゾイルクロライド（４，４’－オキシビス安息香酸（Ａｌｄｒｉｃｈ製）を定法にて酸クロリドに変換して得た。）、ＮＭＰ　７００ｇの混合溶液を滴下した。滴下が完了した後、得られる混合物を室温で１６時間撹拌した。
　次に、室温のままこの反応液へ５－ノルボルネン－２，３－ジカルボン酸無水物(分子量１６４．１６)３５．６ｇ（０．２１７ｍｏｌ）を添加した。その後さらに６０℃で５時間撹拌し、室温まで冷却した。
　この反応液をアセトン２Ｌで希釈し、激しく攪拌した２０Ｌの脱イオン水中に投入し、析出した白色粉体を濾過によって回収し、そして脱イオン水および水／メタノール（５０／５０質量比）混合物によって洗浄した。真空下でポリマーを４０℃において２４時間乾燥させ、樹脂Ｅ－１を得た。
　樹脂Ｅ－１の数平均分子量は、ポリスチレン換算で６．４×１０3、分散度２．２であった。1Ｈ－ＮＭＲより５－ノルボルネン－２，３－ジカルボン酸無水物の導入率がほぼ定量的であったことを確認した。 Synthesis Example E-1: Synthesis of Resin E-1 In a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 293 g (0.8 mol) of hexafluoro-2,2-bis (3-amino- 4-Hydroxyphenyl) propane (Nippon Kayaku Co., Ltd.), 158.2 g (2.0 mol) of pyridine, and 1.2 kg of N-methyl-2-pyrrolidone (NMP) were added. This was stirred at room temperature and then cooled to −25 ° C. with a dry ice / acetone bath. To this solution, while maintaining the reaction temperature at −20 ° C. to −30 ° C., 73.9 g (0.364 mol) of isophthaloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 107.4 g (0.364 mol) of A mixed solution of 4,4′-oxybisbenzoyl chloride (obtained by converting 4,4′-oxybisbenzoic acid (manufactured by Aldrich) into acid chloride by a conventional method) and 700 g of NMP were added dropwise. After the addition was complete, the resulting mixture was stirred at room temperature for 16 hours.
Next, 35.6 g (0.217 mol) of 5-norbornene-2,3-dicarboxylic anhydride (molecular weight 164.16) was added to the reaction solution at room temperature. Thereafter, the mixture was further stirred at 60 ° C. for 5 hours and cooled to room temperature.
The reaction solution is diluted with 2 L of acetone, poured into 20 L of deionized water with vigorous stirring, the precipitated white powder is recovered by filtration, and deionized water and a water / methanol (50/50 mass ratio) mixture. Washed. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin E-1.
The number average molecular weight of the resin E-1 was 6.4 × 10 3 in terms of polystyrene, and the degree of dispersion was 2.2. From 1 H-NMR, it was confirmed that the introduction rate of 5-norbornene-2,3-dicarboxylic anhydride was almost quantitative.
合成例Ｅ－１０１ａ：樹脂Ｅ－１０１ａの合成
　３つ口フラスコに、合成例Ｅ－１で得られたポリマー（Ｅ－１）１００ｇを加え、プロピレングリコール－１－モノメチルエーテル－２－アセタート（ＰＧＭＥＡ）を１．６Ｌ加え、内容物が０．９ｋｇになるまで濃縮した。温度計、攪拌器、窒素導入管を使用し、カンファースルホン酸（３質量％ＰＧＭＥＡ溶液）を９．１６ｇ（１．１８ｍｍｏｌ）、２，３－ジヒドロフラン９．０７ｇ（０．１２９ｍｏｌ）を加え、室温で４時間攪拌した。次に、トリエチルアミン（１０質量％ＰＧＭＥＡ溶液）２．９９ｇ（２．９５ｍｍｏｌ）を加えて反応を停止した。
　この反応液をアセトン１．０Ｌで希釈し、激しく攪拌した１２Ｌのヘキサン中に投入し、析出した白色粉体を濾過によって回収した。真空下でポリマーを４０℃において４時間乾燥させた。このポリマーのうち８０ｇを１．３Ｌのアセトンに溶解させ、激しく攪拌した１０Ｌの水中に投入し、そして脱イオン水および水／メタノール（５０／５０質量比）混合物によって洗浄した。真空下でポリマーを４０℃において２４時間乾燥させ、樹脂Ｅ－１０１ａを得た。
　樹脂Ｅ－１０１ａの数平均分子量は、ポリスチレン換算で６．９×１０3、分散度２．４であった。1Ｈ－ＮＭＲより原料樹脂Ｅ－１の全水酸基に対して、酸分解性基の導入率が３０ｍｏｌ％であることを確認した。 Synthesis Example E-101a: Synthesis of Resin E-101a To a three-necked flask, 100 g of the polymer (E-1) obtained in Synthesis Example E-1 was added, and propylene glycol-1-monomethyl ether-2-acetate (PGMEA 1.6 L) and concentrated until the content was 0.9 kg. Using a thermometer, a stirrer and a nitrogen introduction tube, 9.16 g (1.18 mmol) of camphorsulfonic acid (3 mass% PGMEA solution) and 9.07 g (0.129 mol) of 2,3-dihydrofuran were added, Stir at room temperature for 4 hours. Next, 2.99 g (2.95 mmol) of triethylamine (10 mass% PGMEA solution) was added to stop the reaction.
The reaction solution was diluted with 1.0 L of acetone, poured into 12 L of hexane that was vigorously stirred, and the precipitated white powder was collected by filtration. The polymer was dried at 40 ° C. for 4 hours under vacuum. 80 g of this polymer was dissolved in 1.3 L of acetone, poured into 10 L of vigorously stirred water and washed with deionized water and a water / methanol (50/50 mass ratio) mixture. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin E-101a.
The number average molecular weight of Resin E-101a was 6.9 × 10 3 in terms of polystyrene, and the degree of dispersion was 2.4. From 1 H-NMR, it was confirmed that the introduction rate of acid-decomposable groups was 30 mol% with respect to all the hydroxyl groups of the raw material resin E-1.
合成例Ｆ－１：樹脂Ｆ－１の合成
　温度計、攪拌器、窒素導入管を備えた３つ口フラスコに、合成例Ｅ－１で得られたポリマー（Ｅ－１）１５０ｇを加え、プロピレングリコール－１－モノメチルエーテル－２－アセタート（ＰＧＭＥＡ）を１．５Ｌ加え、トリエチルアミン１７．９１ｇ（０．１７７ｍｍｏｌ）、エピクロロヒドリン１０．８８ｇ（０．１１８ｍｏｌ）を添加し、室温で３時間攪拌した。
　この反応液をアセトン１．５Ｌで希釈し、激しく攪拌した２０Ｌのヘキサン中に投入し、析出した白色粉体を濾過によって回収した。真空下でポリマーを４０℃において４時間乾燥させ、このポリマーのうち１２０ｇを２Ｌのアセトンに溶解させ、激しく攪拌した１０Ｌの水中に投入し、そして脱イオン水および水／メタノール（５０／５０質量比）混合物によって洗浄した。真空下でポリマーを４０℃において２４時間乾燥させ、樹脂Ｆ－１を得た。
　樹脂Ｆ－１の数平均分子量は、ポリスチレン換算で６．９×１０3、分散度２．３であった。1Ｈ－ＮＭＲより水酸基へのエポキシ基導入率が１９ｍｏｌ％であることを確認した。 Synthesis Example F-1: Synthesis of Resin F-1 To a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 150 g of the polymer (E-1) obtained in Synthesis Example E-1 was added, and propylene was added. 1.5 L of glycol-1-monomethyl ether-2-acetate (PGMEA) was added, 17.91 g (0.177 mmol) of triethylamine and 10.88 g (0.118 mol) of epichlorohydrin were added, and the mixture was stirred at room temperature for 3 hours. did.
The reaction solution was diluted with 1.5 L of acetone, poured into 20 L of hexane that was vigorously stirred, and the precipitated white powder was collected by filtration. The polymer was dried under vacuum at 40 ° C. for 4 hours, 120 g of this polymer was dissolved in 2 L acetone, poured into 10 L of vigorously stirred water, and deionized water and water / methanol (50/50 mass ratio) ) Washed with the mixture. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin F-1.
The number average molecular weight of the resin F-1 was 6.9 × 10 3 in terms of polystyrene, and the degree of dispersion was 2.3. From 1 H-NMR, it was confirmed that the epoxy group introduction rate into the hydroxyl group was 19 mol%.
合成例Ｆ－１０１ａ：樹脂Ｆ－１０１ａの合成
　３つ口フラスコに、合成例Ｆ－１で得られたポリマー（Ｆ－１）１００ｇを加え、プロピレングリコール－１－モノメチルエーテル－２－アセタート（ＰＧＭＥＡ）を１．６Ｌ加え、内容物が０．９ｋｇになるまで濃縮した。温度計、攪拌器、窒素導入管を使用し、カンファースルホン酸（３質量％ＰＧＭＥＡ溶液）を９．１６ｇ（１．１８ｍｍｏｌ）、２，３－ジヒドロフラン８．６５ｇ（０．１２３ｍｏｌ）を加え、室温で４時間攪拌した。次に、トリエチルアミン（１０質量％ＰＧＭＥＡ溶液）２．９９ｇ（２．９５ｍｍｏｌ）を加えて反応を停止した。
　この反応液をアセトン１．０Ｌで希釈し、激しく攪拌した１２Ｌのヘキサン中に投入し、析出した白色粉体を濾過によって回収した。真空下でポリマーを４０℃において４時間乾燥させた。このポリマーのうち８０ｇを１．３Ｌのアセトンに溶解させ、激しく攪拌した１０Ｌの水中に投入し、そして脱イオン水および水／メタノール（５０／５０質量比）混合物によって洗浄した。真空下でポリマーを４０℃において２４時間乾燥させ、樹脂Ｆ－１０１ａを得た。
　樹脂Ｆ－１０１ａの数平均分子量は、ポリスチレン換算で７．０×１０3、分散度２．４であった。1Ｈ－ＮＭＲより原料樹脂Ｅ－１の全水酸基に対して、酸分解性基の導入率が３１ｍｏｌ％であることを確認した。 Synthesis Example F-101a: Synthesis of Resin F-101a To a three-necked flask, 100 g of the polymer (F-1) obtained in Synthesis Example F-1 was added, and propylene glycol-1-monomethyl ether-2-acetate (PGMEA 1.6 L) and concentrated until the content was 0.9 kg. Using a thermometer, a stirrer, and a nitrogen introduction tube, 9.16 g (1.18 mmol) of camphorsulfonic acid (3 mass% PGMEA solution) and 8.65 g (0.123 mol) of 2,3-dihydrofuran were added, Stir at room temperature for 4 hours. Next, 2.99 g (2.95 mmol) of triethylamine (10 mass% PGMEA solution) was added to stop the reaction.
The reaction solution was diluted with 1.0 L of acetone, poured into 12 L of hexane that was vigorously stirred, and the precipitated white powder was collected by filtration. The polymer was dried at 40 ° C. for 4 hours under vacuum. 80 g of this polymer was dissolved in 1.3 L of acetone, poured into 10 L of vigorously stirred water and washed with deionized water and a water / methanol (50/50 mass ratio) mixture. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin F-101a.
The number average molecular weight of the resin F-101a was 7.0 × 10 3 in terms of polystyrene, and the degree of dispersion was 2.4. From 1 H-NMR, it was confirmed that the introduction rate of acid-decomposable groups was 31 mol% with respect to all the hydroxyl groups of the raw material resin E-1.
合成例Ｆ－１０１ｂ：樹脂Ｆ－１０１ｂの合成
　Ｆ－１０１ａの合成において、２，３－ジヒドロフランの量を６．５８ｇ（０．０９４ｍｏｌ）に変えた以外はＦ－１０１ａの合成と同様の操作を行うことで、酸分解性基の導入量が異なるＦ１０１ｂを得た。
　樹脂Ｆ－１０１ｂの数平均分子量は、ポリスチレン換算で６．９×１０3、分散度２．３であった。1ＨＮＭＲより原料樹脂Ｅ－１の全水酸基に対して、酸分解性基の導入率が２３ｍｏｌ％であることを確認した。 Synthesis Example F-101b: Synthesis of Resin F-101b The same operation as in the synthesis of F-101a, except that the amount of 2,3-dihydrofuran was changed to 6.58 g (0.094 mol) in the synthesis of F-101a. As a result, F101b having different introduction amounts of acid-decomposable groups was obtained.
The number average molecular weight of Resin F-101b was 6.9 × 10 3 in terms of polystyrene, and the dispersity was 2.3. From 1 HNMR, it was confirmed that the introduction rate of acid-decomposable groups was 23 mol% with respect to all the hydroxyl groups of the raw material resin E-1.
合成例Ｇ－１：樹脂Ｇ－１の合成
　温度計、攪拌器、窒素導入管を備えた３つ口フラスコに、２９３ｇ（０．８ｍｏｌ）のヘキサフルオロ－２，２－ビス（３－アミノ－４－ヒドロキシフェニル）プロパン（日本化薬（株）製）、１２６．６ｇ（１６ｍｏｌ）のピリジンおよび１．２ｋｇのＮ－メチル－２－ピロリドン（ＮＭＰ）を添加した。これを室温で撹拌、次いでドライアイス／アセトンバスで－２５℃まで冷却した。この溶液に、反応温度を－２０℃～－３０℃で維持しながら、７３．９ｇ（０．３６４ｍｏｌ）のイソフタロイルクロライド（東京化成（株）製）、１０７．４ｇ（０．３６４ｍｏｌ）の４，４’－オキシビスベンゾイルクロライド（４，４’－オキシビス安息香酸（Ａｌｄｒｉｃｈ製）を定法にて酸クロリドに変換して得た。）、ＮＭＰ　７００ｇの混合溶液を滴下した。滴下が完了した後、得られる混合物を室温で１６時間撹拌した。
　この反応液をアセトン２Ｌで希釈し、激しく攪拌した２０Ｌの脱イオン水中に投入し、析出した白色粉体を濾過によって回収し、そして脱イオン水および水／メタノール（５０／５０質量比）混合物によって洗浄した。真空下でポリマーを４０℃において２４時間乾燥させ、樹脂Ｇ－１を得た。樹脂Ｇ－１の数平均分子量は、ポリスチレン換算で６．４×１０3、分散度２．１であった。 Synthesis Example G-1: Synthesis of Resin G-1 In a three-necked flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 293 g (0.8 mol) of hexafluoro-2,2-bis (3-amino- 4-Hydroxyphenyl) propane (Nippon Kayaku Co., Ltd.), 126.6 g (16 mol) of pyridine and 1.2 kg of N-methyl-2-pyrrolidone (NMP) were added. This was stirred at room temperature and then cooled to −25 ° C. with a dry ice / acetone bath. To this solution, while maintaining the reaction temperature at −20 ° C. to −30 ° C., 73.9 g (0.364 mol) of isophthaloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.), 107.4 g (0.364 mol) of A mixed solution of 4,4′-oxybisbenzoyl chloride (obtained by converting 4,4′-oxybisbenzoic acid (manufactured by Aldrich) into acid chloride by a conventional method) and 700 g of NMP were added dropwise. After the addition was complete, the resulting mixture was stirred at room temperature for 16 hours.
The reaction solution is diluted with 2 L of acetone, poured into 20 L of deionized water with vigorous stirring, the precipitated white powder is recovered by filtration, and deionized water and a water / methanol (50/50 mass ratio) mixture. Washed. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin G-1. The number average molecular weight of the resin G-1 was 6.4 × 10 3 in terms of polystyrene, and the degree of dispersion was 2.1.
合成例Ｇ－２：樹脂Ｇ－２の合成
　樹脂Ｇ－１　４００ｇをＰＧＭＥＡに溶解し１５％溶液とし、これにクロロ蟻酸アリル（東京化成製）２１ｇおよびピリジン１６ｇを添加し、室温で３時間攪拌した。得られた反応液を水洗した後、トルエン２００ｇを加え、共沸脱水により系中の水分を除くため５０℃で溶媒を留去し、固形分濃度１５％の溶液とした。系中の水分は０．０１％であった。エチルビニルエーテル１５ｇおよびｐ－トルエンスルホン酸０．１ｇを添加、室温で３時間撹拌した。さらに、エチルビニルエーテル１５ｇおよびｐ－トルエンスルホン酸０．１ｇを添加、室温で３時間撹拌した。得られた溶液にトリエチルアミン２０ｇを加え、反応液を３回水洗し、ＰＧＭＥＡ　１Ｌを加えていったん希釈した後、反応液をアセトン２Ｌで希釈し、激しく攪拌した２０Ｌの脱イオン水中に投入し、析出した白色粉体を濾過によって回収し、そして脱イオン水および水／メタノール（５０／５０質量比）混合物によって洗浄した。真空下でポリマーを４０℃において２４時間乾燥させ、樹脂Ｇ－２を得た。樹脂Ｇ－２の数平均分子量は、ポリスチレン換算で６．６×１０3、分散度２．２であった。1Ｈ－ＮＭＲよりクロロ蟻酸アリルの導入率が定量的であったこと、水酸基のエチルアセタール基保護率が２１ｍｏｌ％であることを確認した。 Synthesis Example G-2: Synthesis of Resin G-2 Resin G-1 (400 g) was dissolved in PGMEA to give a 15% solution. To this, 21 g of allyl chloroformate (manufactured by Tokyo Chemical Industry) and 16 g of pyridine were added and stirred at room temperature for 3 hours. did. The obtained reaction solution was washed with water, 200 g of toluene was added, and the solvent was distilled off at 50 ° C. to remove water in the system by azeotropic dehydration to obtain a solution having a solid content concentration of 15%. The water content in the system was 0.01%. 15 g of ethyl vinyl ether and 0.1 g of p-toluenesulfonic acid were added and stirred at room temperature for 3 hours. Further, 15 g of ethyl vinyl ether and 0.1 g of p-toluenesulfonic acid were added and stirred at room temperature for 3 hours. 20 g of triethylamine was added to the resulting solution, the reaction solution was washed with water three times, and once diluted with 1 L of PGMEA, the reaction solution was diluted with 2 L of acetone, poured into 20 L of deionized water with vigorous stirring, and precipitated. The white powder was collected by filtration and washed with deionized water and a water / methanol (50/50 weight ratio) mixture. The polymer was dried under vacuum at 40 ° C. for 24 hours to obtain Resin G-2. The number average molecular weight of the resin G-2 was 6.6 × 10 3 in terms of polystyrene, and the degree of dispersion was 2.2. From 1 H-NMR, it was confirmed that the introduction rate of allyl chloroformate was quantitative and that the hydroxyl acetal group protection rate of the hydroxyl group was 21 mol%.
＜感光性樹脂組成物の調製＞
　下記表に記載の固形分比となるように各成分を秤量し、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。表中の特に単位を付していない数値は質量部である。 <Preparation of photosensitive resin composition>
Each component was weighed so as to have a solid content ratio described in the following table, and filtered through a polytetrafluoroethylene filter having a diameter of 0.2 μm to obtain photosensitive resin compositions of various examples and comparative examples. The numerical value which does not attach | subject especially the unit 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。
Ａ.樹脂
Ｍ－１：下記に示す構造（特開２０１１－２０９６８１号公報段落０２１２～０２１７に記載の重合体（Ａ－１））
Figure JPOXMLDOC01-appb-C000069
 The details of the abbreviations indicating the compounds used in Examples and Comparative Examples are as follows.
A. Resin M-1: Structure shown below (Polymer (A-1) described in paragraphs 0212 to 0217 of JP2011-209681A)
Figure JPOXMLDOC01-appb-C000069
Ｂ.光酸発生剤
Ｂ－１：下記に示す構造（ＰＡＧ－１０３、ＢＡＳＦ社製）
Figure JPOXMLDOC01-appb-C000070
 B. Photoacid generator B-1: Structure shown below (PAG-103, manufactured by BASF)
Figure JPOXMLDOC01-appb-C000070
Ｂ－２：下記に示す構造（ＰＡＩ－１０１、みどり化学社製）Ｍｅはメチル基を表す。
Figure JPOXMLDOC01-appb-C000071
 B-2: Structure shown below (PAI-101, manufactured by Midori Chemical Co.) Me represents a methyl group.
Figure JPOXMLDOC01-appb-C000071
Ｂ－３：下記に示す構造（合成例を後述する。）
Figure JPOXMLDOC01-appb-C000072
 B-3: Structure shown below (Synthesis examples will be described later)
Figure JPOXMLDOC01-appb-C000072
Ｂ－４：下記に示す構造（合成例を後述する）Ｔｓはトシル基を表す。
Figure JPOXMLDOC01-appb-C000073
 B-4: Structure shown below (synthesis examples will be described later) Ts represents a tosyl group.
Figure JPOXMLDOC01-appb-C000073
Ｂ－５：下記に示す構造（合成例を後述する）
Figure JPOXMLDOC01-appb-C000074
 B-5: Structure shown below (synthesis example will be described later)
Figure JPOXMLDOC01-appb-C000074
Ｂ－６：下記に示す構造（ＧＳＩＤ－２６－１、トリアリールスルホニウム塩、ＢＡＳＦ社製）
Figure JPOXMLDOC01-appb-C000075
 B-6: Structure shown below (GSID-26-1, triarylsulfonium salt, manufactured by BASF)
Figure JPOXMLDOC01-appb-C000075
Ｂ－７：下記に示す構造
Figure JPOXMLDOC01-appb-C000076
 B-7: Structure shown below
Figure JPOXMLDOC01-appb-C000076
Ｃ．溶剤
ＭＥＤＧ：ジエチレングリコールエチルメチルエーテル、（ハイソルブＥＤＭ、東邦化学工業社製）
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート（昭和電工社製）
ＧＢＬ：ガンマブチロラクトン（三菱化学社製） C. Solvent MEDG: Diethylene glycol ethyl methyl ether, (Hisolv EDM, manufactured by Toho Chemical Industry Co., Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate (Showa Denko)
GBL: Gamma butyrolactone (Mitsubishi Chemical Corporation)
塩基性化合物
Ｈ－１：ＤＢＵ（１，８－ジアザビシクロ［５．４．０］－７－ウンデセン）
Ｈ－２：下記構造の化合物
Figure JPOXMLDOC01-appb-C000077
 Basic compound H-1: DBU (1,8-diazabicyclo [5.4.0] -7-undecene)
H-2: Compound having the following structure
Figure JPOXMLDOC01-appb-C000077
密着助剤
ＫＢＭ－４０３：γ－グリシドキシプロピルトリメトキシシラン（ＫＢＭ－４０３:信越化学社製） Adhesion aid KBM-403: γ-glycidoxypropyltrimethoxysilane (KBM-403: manufactured by Shin-Etsu Chemical Co., Ltd.)
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-C000078
 Surfactant W-1: Perfluoroalkyl group-containing nonionic surfactant represented by the following structural formula (F-554, manufactured by DIC)
Figure JPOXMLDOC01-appb-C000078
増感剤
ＤＢＡ：９，１０－ジブトキシアントラセン（川崎化成社製）
架橋性基を有する化合物
Ｎ－１：下記構造のエポキシ化合物（特開２００８―２２４９７０号公報段落０２７３に記載のオキセタン添加剤（Ｏ－３））
Figure JPOXMLDOC01-appb-C000079
 Sensitizer DBA: 9,10-dibutoxyanthracene (manufactured by Kawasaki Kasei Co., Ltd.)
Compound N-1 having a crosslinkable group: epoxy compound having the following structure (oxetane additive (O-3) described in paragraph 0273 of JP-A-2008-224970)
Figure JPOXMLDOC01-appb-C000079
＜＜Ｂ－３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－３（２．３ｇ）を得た。
　なお、Ｂ－３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-3 >>
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-3 (2.3 g).
The 1 H-NMR spectrum (300 MHz, CDCl 3 ) of B-3 is 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).
＜＜Ｂ－４の合成＞＞
　１－アミノ－２－ナフトール塩酸塩（東京化成製）４．０ｇをＮ－メチルピロリドン（和光純薬精）１６ｇに懸濁させ、炭酸水素ナトリウム（和光純薬製）３．４ｇを添加後、４，４－ジメチル－３－オキソ吉草酸メチル（和光純薬製）４．９ｇを滴下し、窒素雰囲気下１２０℃で２時間加熱した。放冷後、反応混合液に水、酢酸エチルを添加して分液し、有機相を硫酸マグネシウムで乾燥し、ろ過、濃縮して粗Ｂ－１－２Ａを得た。粗Ｂ－１－２Ａをシリカゲルカラムクロマトグラフィー精製して、中間体Ｂ－１－２Ａを１．７ｇ得た。
　Ｂ－１－２Ａ（１．７ｇ）とｐ－キシレン（６ｍＬ）を混合し、ｐ－トルエンスルホン酸一水和物（和光純薬製）０．２３ｇを添加して１４０℃で２時間加熱した。放冷後、反応混合液に水、酢酸エチルを添加して分液し、有機相を硫酸マグネシウムで乾燥後、ろ過、濃縮して粗Ｂ－１－２Ｂを得た。
　ＴＨＦ（２ｍＬ）と粗Ｂ－１－２Ｂ全量を混合し、氷冷下２Ｍ塩酸/ＴＨＦ溶液６．０ｍＬ、次いで亜硝酸イソペンチル（和光純薬製）（０．８４ｇ）を滴下し、室温まで昇温後２時間攪拌した。得られた反応混合物に水、酢酸エチルを添加して分液し、有機層を水で洗浄後、硫酸マグネシウムで乾燥し、ろ過、濃縮して中間体粗Ｂ－１－２Ｃを得た。
　中間体粗Ｂ－１－２Ｃ全量をアセトン（１０ｍＬ）と混合し、氷冷下でトリエチルアミン（和光純薬製）（１．２ｇ）、ｐ－トルエンスルホニルクロリド（東京化成製）（１．４ｇ）を添加後、室温まで昇温して１時間攪拌した。得られた反応混合液に水、酢酸エチルを添加して分液し、有機相を硫酸マグネシウムで乾燥後、ろ過、濃縮して粗Ｂ－４を得た。粗Ｂ－４を冷メタノールでリスラリー後、ろ過、乾燥してＢ－４（１．２ｇ）を得た。
　なお、Ｂ－４の1Ｈ－ＮＭＲスペクトル（３００ＭＨｚ、ＣＤＣｌ3）は、δ＝８．５－８．４（ｍ，１Ｈ），８．０－７．９（ｍ，４Ｈ），７．７－７．６（ｍ，２Ｈ），７．６－７．５（ｍ，１Ｈ），７．４（ｄ．２Ｈ），２．４（ｓ，３Ｈ），１．４（ｓ，９Ｈ）であった。 << Synthesis of B-4 >>
After 4.0 g of 1-amino-2-naphthol hydrochloride (manufactured by Tokyo Kasei) is suspended in 16 g of N-methylpyrrolidone (Wako Pure Chemical Industries), 3.4 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries) is added, 4.9 g of methyl 4,4-dimethyl-3-oxovalerate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise and heated at 120 ° C. for 2 hours in a nitrogen atmosphere. After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-1-2A. Crude B-1-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate B-1-2A.
B-1-2A (1.7 g) and p-xylene (6 mL) were mixed, 0.23 g of p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated at 140 ° C. for 2 hours. . After allowing to cool, water and ethyl acetate were added to the reaction mixture and the phases were separated. The organic phase was dried over magnesium sulfate, filtered and concentrated to give crude B-1-2B.
THF (2 mL) and the entire amount of crude B-1-2B were mixed, and 2 mL hydrochloric acid / THF solution 6.0 mL was added dropwise under ice cooling, and then isopentyl nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) (0.84 g) was added dropwise. The mixture was stirred for 2 hours after warming. Water and ethyl acetate were added to the obtained reaction mixture for liquid separation, and the organic layer was washed with water, dried over magnesium sulfate, filtered and concentrated to obtain Intermediate Intermediate B-1-2C.
The whole amount of intermediate crude B-1-2C was mixed with acetone (10 mL), and triethylamine (Wako Pure Chemical Industries, Ltd.) (1.2 g) and p-toluenesulfonyl chloride (Tokyo Kasei Co., Ltd.) (1.4 g) were cooled with ice. Then, the mixture was warmed to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the obtained reaction mixture to separate it, and the organic phase was dried over magnesium sulfate, filtered and concentrated to obtain crude B-4. Crude B-4 was reslurried with cold methanol, filtered and dried to obtain B-4 (1.2 g).
The 1 H-NMR spectrum (300 MHz, CDCl 3 ) of B-4 is δ = 8.5-8.4 (m, 1H), 8.0-7.9 (m, 4H), 7.7. -7.6 (m, 2H), 7.6-7.5 (m, 1H), 7.4 (d. 2H), 2.4 (s, 3H), 1.4 (s, 9H) there were.
＜＜Ｂ－５の合成＞＞
　攪拌器および温度計を装着したセパラブルフラスコにＮ―ヒドロキシナフタルイミドナトリウム塩 ３３．６ｇ、４―ジメチルアミノピリジンを０．７２ｇ、テトラヒドロフランを３００ｍｌ入れ、室温２５℃下で攪拌し溶解させた。次いで、（＋）１０―カンファースルホニルクロライド（４２ｇ）を加えて３時間攪拌した後、トリエチルアミン１５ｇを加え、室温下で１０時間攪拌した。次いで、蒸留水３００ｍｌ中に反応溶液を入れ、析出した沈殿をろ別した。この沈殿をアセトンとヘキサンを用いて再沈殿処理を数回繰り返し、Ｎ―カンファースルホニルオキシ－１，８－ナフタルイミド（１２ｇ）を得た。 << Synthesis of B-5 >>
A separable flask equipped with a stirrer and a thermometer was charged with 33.6 g of N-hydroxynaphthalimide sodium salt, 0.72 g of 4-dimethylaminopyridine and 300 ml of tetrahydrofuran, and the mixture was stirred and dissolved at room temperature of 25 ° C. Next, (+) 10-camphorsulfonyl chloride (42 g) was added and stirred for 3 hours, and then 15 g of triethylamine was added and stirred at room temperature for 10 hours. Subsequently, the reaction solution was put into 300 ml of distilled water, and the deposited precipitate was separated by filtration. This precipitation was repeated several times with acetone and hexane to obtain N-camphorsulfonyloxy-1,8-naphthalimide (12 g).
Figure JPOXMLDOC01-appb-T000080
Figure JPOXMLDOC01-appb-T000080
＜感度の評価＞
　ヘキサメチルジシラザン蒸気で１分間表面処理をしたガラス基板（コーニング１７３７、０．７ｍｍ厚（コーニング社製））上に、各感光性樹脂組成物をスリット塗布した後、９０℃／１２０秒ホットプレート上でプリベークして溶剤を揮発させ、膜厚３．０μｍの感光性樹脂組成物層を形成した。
　次に、得られた感光性樹脂組成物層を、キヤノン（株）製ＰＬＡ－５０１Ｆ露光機（超高圧水銀ランプ）を用いて、６．０μｍホールパターンに露光した。その後、９０℃、９０秒ホットプレート上で加熱した。
　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）で現像し（２４℃、６０秒）、超純水で２０秒リンスした。これにより下底の径が６．０μｍのホールパターンが形成される露光量を感度とした。必要露光量が少ないほど（高感度であるほど）好ましく、Ａ～Ｂが実用範囲である。
　　Ａ：１００ｍＪ／ｃｍ2未満
　　Ｂ：１００ｍＪ／ｃｍ2以上２００ｍＪ／ｃｍ2未満
　　Ｃ：２００ｍＪ／ｃｍ2以上３００ｍＪ／ｃｍ2未満
　　Ｄ：３００ｍＪ／ｃｍ2以上 <Evaluation of sensitivity>
Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thickness (manufactured by Corning)) that has been surface-treated with hexamethyldisilazane vapor for 1 minute, and then heated at 90 ° C. for 120 seconds. Pre-baking was performed to volatilize the solvent, and a photosensitive resin composition layer having a thickness of 3.0 μm was formed.
Next, the obtained photosensitive resin composition layer was exposed to a 6.0 μm hole pattern using a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Inc. Then, it heated on a 90 degreeC and 90 second hotplate.
Development was performed with an alkali developer (0.4 mass% tetramethylammonium hydroxide aqueous solution) (24 ° C., 60 seconds), and rinsed with ultrapure water for 20 seconds. Thus, the exposure amount at which a hole pattern with a diameter of the lower base of 6.0 μm was formed was defined as sensitivity. The smaller the required exposure amount (the higher the sensitivity), the more preferable, and A to B are practical ranges.
A: Less than 100 mJ / cm 2 B: 100 mJ / cm 2 or more and less than 200 mJ / cm 2 C: 200 mJ / cm 2 or more and less than 300 mJ / cm 2 D: 300 mJ / cm 2 or more
＜透過率の評価＞
　ガラス基板（ＯＡ－１０（日本電気硝子社製））を、ヘキサメチルジシラザン（ＨＭＤＳ）蒸気下に３０秒曝し、各感光性樹脂組成物をスリット塗布した後、バキュームドライで溶剤を揮発させた後、１２０℃／１２０秒ホットプレート上でプリベークし、膜厚２．０μｍの感光性樹脂組成物層を形成した。続いて超高圧水銀灯を用いて積算照射量が３００ｍＪ／ｃｍ2（エネルギー強度：２０ｍＷ／ｃｍ2）となるように露光し、この基板をオーブンにて窒素雰囲気下で３００℃／６０分間加熱した。この硬化膜の透過率を、分光光度計（Ｕ－３０００：（株）日立製作所製）を用いて、波長４００ｎｍで測定した。単位は％で示した。Ａ、ＢおよびＣが実用レベルである。
　Ａ：９５％以上
　Ｂ：９０％以上９５％未満
　Ｃ：８５％以上９０％未満
　Ｄ：８５％未満 <Evaluation of transmittance>
A glass substrate (OA-10 (manufactured by Nippon Electric Glass Co., Ltd.)) was exposed to hexamethyldisilazane (HMDS) vapor for 30 seconds, and each photosensitive resin composition was slit coated, and then the solvent was volatilized by vacuum drying. Then, it prebaked on a 120 degreeC / 120 second hotplate, and formed the photosensitive resin composition layer with a film thickness of 2.0 micrometers. Subsequently, exposure was performed using an ultra-high pressure mercury lamp so that the integrated irradiation amount was 300 mJ / cm 2 (energy intensity: 20 mW / cm 2 ), and the substrate was heated in an oven at 300 ° C./60 minutes in a nitrogen atmosphere. The transmittance of the cured film was measured at a wavelength of 400 nm using a spectrophotometer (U-3000: manufactured by Hitachi, Ltd.). The unit is expressed in%. A, B and C are practical levels.
A: 95% or more B: 90% or more and less than 95% C: 85% or more and less than 90% D: Less than 85%
＜鉛筆硬度の評価＞
　ヘキサメチルジシラザン蒸気で１分間表面処理をしたガラス基板（コーニング１７３７、０．７ｍｍ厚（コーニング社製））上に、各感光性樹脂組成物をスリット塗布した後、９０℃／１２０秒ホットプレート上でプリベークして溶剤を揮発させ、膜厚３．０μｍの感光性樹脂組成物層を形成した。
　次に、得られた感光性樹脂組成物層を、窒素気流下３００度で２時間ベークし、得られた硬化膜を鉛筆硬度試験機にて評価した。硬度が硬いほど好ましく、Ａ～Ｃが実用範囲である。
Ａ：６Ｈ以上
Ｂ：４～５Ｈ
Ｃ：３Ｈ
Ｄ：２Ｈ
Ｅ：ＨＢ～Ｈ
Ｆ：Ｂより柔らかい <Evaluation of pencil hardness>
Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thickness (manufactured by Corning)) that has been surface-treated with hexamethyldisilazane vapor for 1 minute, and then heated at 90 ° C. for 120 seconds. Pre-baking was performed to volatilize the solvent, and a photosensitive resin composition layer having a thickness of 3.0 μm was formed.
Next, the obtained photosensitive resin composition layer was baked at 300 ° C. for 2 hours under a nitrogen stream, and the obtained cured film was evaluated with a pencil hardness tester. The higher the hardness, the more preferable, and A to C are practical ranges.
A: 6H or more B: 4-5H
C: 3H
D: 2H
E: HB ~ H
F: Softer than B
＜高湿処理後の電気特性＞
ヘキサメチルジシラザン蒸気で１分間表面処理をしたガラス基板（コーニング１７３７、０．７ｍｍ厚（コーニング社製））上に、各感光性樹脂組成物をスリット塗布した後、９０℃／１２０秒ホットプレート上でプリベークして溶剤を揮発させ、膜厚３．０μｍの感光性樹脂組成物層を形成した。
　次に、得られた感光性樹脂組成物層を、窒素気流下３００度で２時間ベークし、得られた硬化膜を８０℃８０％の条件に２４時間暴露し、試験前後に１ＭＨｚでの膜の誘電率を測定し、以下の基準で評価した（Ａが実用範囲である）。
Ａ：暴露前後の誘電率変動が３０％未満、かつ暴露後も誘電率が３．３未満
Ｂ：暴露前後の誘電率変動が３０％未満だが、暴露後の誘電率は３．３以上が観測される
Ｃ：暴露前後の誘電率変動が３０％以上または暴露前後でのどちらかの誘電率で３．３以上が観測される。 <Electrical characteristics after high humidity treatment>
Each photosensitive resin composition is slit-coated on a glass substrate (Corning 1737, 0.7 mm thickness (manufactured by Corning)) that has been surface-treated with hexamethyldisilazane vapor for 1 minute, and then heated at 90 ° C. for 120 seconds. Pre-baking was performed to volatilize the solvent, and a photosensitive resin composition layer having a thickness of 3.0 μm was formed.
Next, the obtained photosensitive resin composition layer was baked at 300 ° C. for 2 hours under a nitrogen stream, and the obtained cured film was exposed to 80 ° C. and 80% for 24 hours, and a film at 1 MHz before and after the test. The dielectric constant was measured and evaluated according to the following criteria (A is a practical range).
A: Dielectric constant variation before and after exposure is less than 30%, and dielectric constant after exposure is less than 3.3 B: Dielectric constant variation before and after exposure is less than 30%, but dielectric constant after exposure is observed to be 3.3 or higher C: Dielectric constant variation before and after exposure is 30% or more, or 3.3 or more is observed in either dielectric constant before and after exposure.
Figure JPOXMLDOC01-appb-T000081
Figure JPOXMLDOC01-appb-T000081
　上記表から、本発明の感光性樹脂組成物を用いた実施例１～３２は、感度、透過率、鉛筆硬度、および高湿処理後の電気特性の全てが良好であることが分かった。一方、本発明の要件を満たさない比較例１～１３は、感度、透過率、鉛筆硬度、および高湿処理後の電気特性のいずれかが、実施例よりも劣ることが分かった。具体的に、比較例１～７、１３のように主鎖に架橋性基を有さない場合、鉛筆硬度および高湿処理後の電気特性が実施例１～３２よりも著しく劣ることが分かった。比較例８～１１のように酸分解性基を有さないと、感度、鉛筆硬度、および高湿処理後の電気特性のいずれかが実施例１～３２よりも劣ることが分かった。比較例１２のようにアクリル樹脂を用いると、高湿処理後の電気特性が実施例１～３２よりも著しく劣ることが分かった。 From the above table, it was found that Examples 1 to 32 using the photosensitive resin composition of the present invention were all good in sensitivity, transmittance, pencil hardness, and electrical properties after high humidity treatment. On the other hand, Comparative Examples 1 to 13 that do not satisfy the requirements of the present invention were found to be inferior to the Examples in terms of sensitivity, transmittance, pencil hardness, and electrical properties after high humidity treatment. Specifically, it was found that when there is no crosslinkable group in the main chain as in Comparative Examples 1 to 7 and 13, the pencil hardness and the electrical properties after high humidity treatment are significantly inferior to those of Examples 1 to 32. . When no acid-decomposable group was present as in Comparative Examples 8 to 11, it was found that any of sensitivity, pencil hardness, and electrical properties after high humidity treatment was inferior to Examples 1-32. It was found that when an acrylic resin was used as in Comparative Example 12, the electrical characteristics after the high-humidity treatment were significantly inferior to Examples 1-32.
３５５ｎｍレーザ露光
　さらに、実施例１～実施例３２の感光性樹脂組成物について、上記感度の評価において露光を以下のように変更した以外は上記感度の評価と同様にして、パターン形成を行った。即ち、塗膜から１５０μｍの間隔を介して、所定のフォトマスクをセットし、波長３５５ｎｍのレーザを照射した。尚、レーザ装置は、株式会社ブイテクノロジー社製の「ＡＥＧＩＳ」を使用した（波長３５５ｎｍ、パルス幅６ｎｓｅｃ）。
　いずれの実施例においても、３５５ｎｍレーザ露光でも超高圧水銀灯と同様にパターン形成可能であることがわかった。 355 nm laser exposure Further, the photosensitive resin compositions of Examples 1 to 32 were subjected to pattern formation in the same manner as the sensitivity evaluation except that the exposure was changed as follows in the sensitivity evaluation. That is, a predetermined photomask was set through a 150 μm interval from the coating film, and a laser having a wavelength of 355 nm was irradiated. The laser device used was “AEGIS” manufactured by Buoy Technology Co., Ltd. (wavelength 355 nm, pulse width 6 nsec).
In any of the examples, it was found that a pattern could be formed even by 355 nm laser exposure as in the case of an ultrahigh pressure mercury lamp.
（ＵＶ－ＬＥＤ露光）
　さらに、実施例１～実施例３２の感光性樹脂組成物について、露光をＵＶ－ＬＥＤ光源露光機に変更した以外は、上記感度の評価（ＰＥＢ無し）と同様の評価を実施したところ、いずれもパターン形成可能であることが分かった。 (UV-LED exposure)
Further, the photosensitive resin compositions of Examples 1 to 32 were evaluated in the same manner as the sensitivity evaluation (without PEB) except that the exposure was changed to a UV-LED light source exposure machine. It was found that pattern formation was possible.
＜表示装置の作製＞
（実施例１００）
　薄膜トランジスタ（ＴＦＴ）を用いた有機ＥＬ表示装置を以下の方法で作製した（図１参照）。
　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、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。 <Production of display device>
(Example 100)
An organic EL display device using a thin film transistor (TFT) was produced by the following method (see FIG. 1).
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, after forming a contact hole in the insulating film 3, a wiring 2 (height of 1.0 μm) connected to the TFT 1 through the contact hole was formed on the insulating film 3.
　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２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℃×２分）した後、マスク上から高圧水銀灯を用いてｉ線（３６５ｎｍ）を感度評価で測定した感度分の露光量を照射し、８０℃のホットプレート上で６０秒加熱した後、アルカリ水溶液にて現像してパターンを形成し、３００℃で６０分間の加熱処理を行った。感光性樹脂組成物を塗布する際の塗布性は良好で、露光、現像、焼成の後に得られた硬化膜には、しわやクラックの発生は認められなかった。さらに、配線２の平均段差は５００ｎｍ、作製した平坦化膜４の膜厚は２．０００ｎｍであった。 Further, in order to flatten the unevenness due to the formation of the wiring 2, a planarizing film 4 was formed on the insulating film 3 in a state where the unevenness due to the wiring 2 was embedded. The planarizing film 4 is formed on the insulating film 3 by spin-coating the photosensitive resin composition of Example 2 on a substrate, pre-baking on a hot plate (90 ° C. × 2 minutes), and then applying high pressure from above the mask. A mercury lamp is used to irradiate i-line (365 nm) with an exposure amount corresponding to the sensitivity measured by sensitivity evaluation, heated on an 80 ° C. hot plate for 60 seconds, and then developed with an aqueous alkaline solution to form a pattern. A heat treatment was performed at 60 ° C. for 60 minutes. The applicability when applying the photosensitive resin composition was good, and no wrinkles or cracks were observed in the cured film obtained after exposure, development and baking. Furthermore, the average level difference 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は、実施例２の感光性樹脂組成物を用い、上記と同様の方法で形成した。 Next, an insulating film 8 having a shape covering the periphery of the first electrode 5 was formed. The insulating film 8 was formed using the photosensitive resin composition of Example 2 by the same method as described above.
　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.
（実施例１０１）
　実施例２の感光性樹脂組成物を実施例６の感光性樹脂組成物に変更した以外は、実施例１００と同様にして有機ＥＬ表示装置を作製した。得られた有機ＥＬ表示装置は、良好な表示特性を示し、信頼性の高い有機ＥＬ表示装置であることが分かった。 (Example 101)
An organic EL display device was produced in the same manner as in Example 100 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 6. The obtained organic EL display device showed good display characteristics and was found to be a highly reliable organic EL display device.
（実施例１０２）
　実施例２の感光性樹脂組成物を実施例９の感光性樹脂組成物に変更した以外は、実施例１００と同様にして有機ＥＬ表示装置を作製した。得られた有機ＥＬ表示装置は、良好な表示特性を示し、信頼性の高い有機ＥＬ表示装置であることが分かった。 (Example 102)
An organic EL display device was produced in the same manner as in Example 100 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 9. The obtained organic EL display device showed good display characteristics and was found to be a highly reliable organic EL display device.
（実施例１０３）
　実施例２の感光性樹脂組成物を実施例１２の感光性樹脂組成物に変更した以外は、実施例１００と同様にして有機ＥＬ表示装置を作製した。得られた有機ＥＬ表示装置は、良好な表示特性を示し、信頼性の高い有機ＥＬ表示装置であることが分かった。 (Example 103)
An organic EL display device was produced in the same manner as in Example 100 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 12. The obtained organic EL display device showed good display characteristics and was found to be a highly reliable organic EL display device.
（実施例１０４）
　特許第３３２１００３号公報の図１および図２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１０４の液晶表示装置を得た。
　すなわち、実施例２の感光性樹脂組成物を用い、上記実施例１００における有機ＥＬ表示装置の平坦化膜４の形成方法と同様の方法で、層間絶縁膜として硬化膜１７を形成した。 (Example 104)
In the active matrix liquid crystal display device described in FIG. 1 and FIG. 2 of Japanese Patent No. 332003, a cured film 17 was formed as an interlayer insulating film as follows, and a liquid crystal display device of Example 104 was obtained.
That is, using the photosensitive resin composition of Example 2, the cured film 17 was formed as an interlayer insulating film by the same method as the method for forming the planarizing film 4 of the organic EL display device in Example 100.
　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わかった。 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１０５）
　実施例２の感光性樹脂組成物を実施例１４の感光性樹脂組成物に変更した以外は、実施例１０４と同様にして液晶表示装置を作製した。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ることが分かった。 (Example 105)
A liquid crystal display device was produced in the same manner as in Example 104 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 14. The obtained liquid crystal display device showed good display characteristics and was found to be a highly reliable liquid crystal display device.
（実施例１０６）
　実施例２の感光性樹脂組成物を実施例２４の感光性樹脂組成物に変更した以外は、実施例１０４と同様にして液晶表示装置を作製した。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ることが分かった。 (Example 106)
A liquid crystal display device was produced in the same manner as in Example 104 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 24. The obtained liquid crystal display device showed good display characteristics and was found to be a highly reliable liquid crystal display device.
（実施例１０７）
　実施例２の感光性樹脂組成物を実施例２８の感光性樹脂組成物に変更した以外は、実施例１０４と同様にして液晶表示装置を作製した。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ることが分かった。 (Example 107)
A liquid crystal display device was produced in the same manner as in Example 104 except that the photosensitive resin composition of Example 2 was changed to the photosensitive resin composition of Example 28. The obtained liquid crystal display device showed good display characteristics and was found to be a highly reliable liquid crystal display device.
　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 (14)

  1. 一般式（１）で表される繰り返し単位を含み、下記１および２の少なくとも一方を満たすを満たす、ポリベンゾオキサゾール前駆体、
    光酸発生剤、および
    溶剤
    を含む、感光性樹脂組成物；
    １：一般式（１）で表される繰り返し単位であって、Ｒ1およびＲ2の少なくとも一方が酸分解性基である繰り返し単位ａ－１、および、一般式（１）で表される繰り返し単位であって、Ｒ1およびＲ2の少なくとも一方が架橋性基である繰り返し単位ａ－２を含む；
    ２：一般式（１）で表される繰り返し単位であって、Ｒ1およびＲ2の一方が、酸分解性基を含み、他方が架橋性基である繰り返し単位ａ－３を含む；
    一般式（１）
    Figure JPOXMLDOC01-appb-C000001
     一般式（１）中、Ｘは４価の有機基を表し、Ｙは２価の有機基を表す；Ｒ1およびＲ2はそれぞれ独立に水素原子、架橋性基、アルキル基、酸分解性基、または、－ＣＯＲｃを表す；Ｒｃは、アルキル基またはアリール基を表す。     A polybenzoxazole precursor containing a repeating unit represented by the general formula (1) and satisfying at least one of the following 1 and 2:
    A photosensitive resin composition comprising a photoacid generator and a solvent;
    1: a repeating unit represented by the general formula (1), wherein at least one of R 1 and R 2 is an acid-decomposable group, and a repeating unit represented by the general formula (1) A unit comprising a repeating unit a-2 in which at least one of R 1 and R 2 is a crosslinkable group;
    2: A repeating unit represented by the general formula (1), wherein one of R 1 and R 2 includes a repeating unit a-3 containing an acid-decomposable group and the other being a crosslinkable group;
    General formula (1)
    Figure JPOXMLDOC01-appb-C000001
     In general formula (1), X represents a tetravalent organic group, Y represents a divalent organic group; R 1 and R 2 each independently represents a hydrogen atom, a crosslinkable group, an alkyl group, or an acid-decomposable group. Or represents —CORc; Rc represents an alkyl group or an aryl group.
  2. ポリベンゾオキサゾール前駆体の末端に、架橋性基を含む、請求項１に記載の感光性樹脂組成物。 The photosensitive resin composition of Claim 1 which contains a crosslinkable group at the terminal of a polybenzoxazole precursor.
  3. ポリベンゾオキサゾール前駆体の末端が、一般式（Ｘ）で表される基である、請求項１に記載の感光性樹脂組成物；
    一般式（Ｘ）
    Figure JPOXMLDOC01-appb-C000002
     一般式（Ｘ）中、Ｚは単結合、炭素原子または硫黄原子を表し、Ｒ11は１価の有機基を表す；ｎは０または１を表し、Ｚが単結合の場合、ａは０であり、Ｚが炭素原子の場合、ａは１であり、Ｚが硫黄原子の場合、ａは２である；ｎが０の場合、２つのＲ11は、互いに結合し環を形成していてもよい。     The photosensitive resin composition of Claim 1 whose terminal of a polybenzoxazole precursor is group represented by general formula (X);
    Formula (X)
    Figure JPOXMLDOC01-appb-C000002
     In the general formula (X), Z represents a single bond, a carbon atom or a sulfur atom, R 11 represents a monovalent organic group; n represents 0 or 1, and when Z is a single bond, a is 0. Yes, when Z is a carbon atom, a is 1, and when Z is a sulfur atom, a is 2, and when n is 0, two R 11 may be bonded to each other to form a ring. Good.
  4. ポリベンゾオキサゾール前駆体が、ｍ個の一般式（１）で表される繰り返し単位とｎ個の一般式（３）で表される繰り返し単位を含み、ｍは３～１０００を表し、ｎは０～１０００を表し、ｍ＋ｎは３～１０００である、請求項１～３のいずれか１項に記載の感光性樹脂組成物；
    一般式（３）
    Figure JPOXMLDOC01-appb-C000003
     一般式（３）中、Ｙ1は、それぞれ独立にアリーレン基、２価の環状脂肪族基、２価の複素環基、または、これらと、－ＣＨ2－、酸素原子、硫黄原子、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、および－Ｃ（ＣＦ3）2－の少なくとも１種との組み合わせからなる基を表し、Ｘ2は、アリーレン基、２価の複素環基、２価の環状脂肪族基、または、これらと、－ＣＨ2－、酸素原子、硫黄原子、－ＳＯ2－、－ＣＯ－、－ＮＨＣＯ－、および－Ｃ（ＣＦ3）2－の少なくとも１種との組み合わせからなる基を表す。     The polybenzoxazole precursor includes m repeating units represented by the general formula (1) and n repeating units represented by the general formula (3), m represents 3 to 1000, and n represents 0 The photosensitive resin composition according to any one of Claims 1 to 3, wherein m + n is 3 to 1000;
    General formula (3)
    Figure JPOXMLDOC01-appb-C000003
     In the general formula (3), Y 1 each independently represents an arylene group, a divalent cycloaliphatic group, a divalent heterocyclic group, or these, —CH 2 —, an oxygen atom, a sulfur atom, —SO 2 represents a group consisting of a combination with at least one of —, —CO—, —NHCO—, and —C (CF 3 ) 2 —, and X 2 represents an arylene group, a divalent heterocyclic group, a divalent group A cyclic aliphatic group or a combination thereof with at least one of —CH 2 —, oxygen atom, sulfur atom, —SO 2 —, —CO—, —NHCO—, and —C (CF 3 ) 2 —. Represents a group consisting of
  5. 架橋性基が、エポキシ基、オキセタニル基、炭素炭素不飽和結合基およびブロックイソシアネート基から選択される、請求項１～４のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 4, wherein the crosslinkable group is selected from an epoxy group, an oxetanyl group, a carbon-carbon unsaturated bond group, and a blocked isocyanate group.
  6. 酸分解性基が、酸の作用により脱離する基である、請求項１～５のいずれか１項に記載の感光性樹脂組成物；ただし、Ｒ5は、それぞれ独立に水素原子、または炭素数１～４のアルキル基を表し、Ｒ4は、酸の作用により脱離する基を表す。 The photosensitive resin composition according to any one of claims 1 to 5, wherein the acid-decomposable group is a group capable of leaving by the action of an acid; provided that each R 5 is independently a hydrogen atom or carbon Represents an alkyl group of formulas 1 to 4, and R 4 represents a group capable of leaving by the action of an acid.
  7. 酸の作用により脱離する基が、ビニルエーテル系の置換基である、請求項６に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 6, wherein the group capable of leaving by the action of an acid is a vinyl ether-based substituent.
  8. 酸の作用により脱離する基が、アルコキシカルボニル基、アルコキシアルキル基、アルキルシリル基、アセタールを構成する基、またはケタールを構成する基である、請求項６または７に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 6 or 7, wherein the group leaving by the action of an acid is an alkoxycarbonyl group, an alkoxyalkyl group, an alkylsilyl group, a group constituting an acetal, or a group constituting a ketal. .
  9. 請求項１～８のいずれか１項に記載の感光性樹脂組成物を基板の少なくとも一方の面に塗布する工程、
    塗布された感光性樹脂組成物から溶剤を除去する工程、
    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、
    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
    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、
    を含む硬化膜の製造方法。     Applying the photosensitive resin composition according to any one of claims 1 to 8 to at least one surface of a substrate;
    Removing the solvent from the applied photosensitive resin composition;
    Exposing the photosensitive resin composition from which the solvent has been removed with actinic rays,
    A step of developing the exposed photosensitive resin composition with an aqueous developer, and a post-baking step of thermosetting the developed photosensitive resin composition;
    The manufacturing method of the cured film containing this.
  10. 前記現像する工程後、前記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９に記載の硬化膜の製造方法。 The manufacturing method of the cured film of Claim 9 including the process of exposing the developed photosensitive resin composition to the whole surface after the said image development process and before the said post-baking process.
  11. 請求項１～８のいずれか１項に記載の感光性樹脂組成物を硬化してなる硬化膜または請求項９または１０に記載の方法により形成された硬化膜。 A cured film formed by curing the photosensitive resin composition according to any one of claims 1 to 8, or a cured film formed by the method according to claim 9 or 10.
  12. 層間絶縁膜である、請求項１１に記載の硬化膜。 The cured film according to claim 11, which is an interlayer insulating film.
  13. 請求項１１または１２に記載の硬化膜を有する液晶表示装置。 A liquid crystal display device having the cured film according to claim 11.
  14. 請求項１１または１２に記載の硬化膜を有する有機ＥＬ表示装置。 An organic EL display device having the cured film according to claim 11.
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JP2009036863A (en) * 2007-07-31 2009-02-19 Fujifilm Corp Photosensitive resin composition, and cured relief pattern production method using the same and semiconductor device

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* Cited by examiner, † Cited by third party
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CN108388082A (en) * 2017-02-03 2018-08-10 信越化学工业株式会社 Photosensitive polymer combination, photosensitive dry film, photosensitive resin coating and pattern forming method
CN108388082B (en) * 2017-02-03 2023-01-13 信越化学工业株式会社 Photosensitive resin composition, photosensitive dry film, photosensitive resin coating and pattern forming method
WO2019164162A1 (en) * 2018-02-23 2019-08-29 동우화인켐 주식회사 Photosensitive resin composition and dielectric film formed therefrom

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