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WO2015087832A1 - Composition de résine photosensible, procédé de production d'un film durci, film durci, dispositif d'affichage à cristaux liquides et dispositif d'affichage électroluminescent organique - Google Patents

Composition de résine photosensible, procédé de production d'un film durci, film durci, dispositif d'affichage à cristaux liquides et dispositif d'affichage électroluminescent organique 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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Japanese (ja)
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雨宮　拓馬
豪 安藤
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Fujifilm Corp
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Fujifilm Corp
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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

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Abstract

La présente invention concerne : une composition de résine photosensible qui a une excellente sensibilité, un excellent facteur de transmission, une excellente dureté à un stylet et d'excellentes caractéristiques électriques après un traitement à forte humidité ; un procédé de production d'un film durci ; un film durci ; un dispositif d'affichage à cristaux liquides ; et un dispositif d'affichage électroluminescent organique. Une composition de résine photosensible qui contient (A) un précurseur polybenzoxazole contenant une unité de répétition représentée par une formule générale (1) et satisfaisant l'exigence (1) et/ou (2) ci-dessous, (B) un générateur photoacide et (C) un solvant. (1) Le précurseur polybenzoxazole contient (a-1) une unité de répétition qui est représentée par la formule générale (1) dans laquelle R1 et/ou R2 est un groupe décomposable en milieu acide, et (a-2) une unité de répétition qui est représentée par la formule générale (1) dans laquelle R1 et/ou R2 est un groupe réticulable. (2) Le précurseur polybenzoxazole contient (a-3) une unité de répétition qui est représentée par la formule générale (1) dans laquelle R1 et R2 contient un groupe décomposable en milieu acide et l'autre est un groupe réticulable.
PCT/JP2014/082414 2013-12-11 2014-12-08 Composition de résine photosensible, procédé de production d'un film durci, film durci, dispositif d'affichage à cristaux liquides et dispositif d'affichage électroluminescent organique Ceased WO2015087832A1 (fr)

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Cited By (2)

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CN108388082A (zh) * 2017-02-03 2018-08-10 信越化学工业株式会社 感光性树脂组合物、感光性干膜、感光性树脂涂层和图案形成方法
WO2019164162A1 (fr) * 2018-02-23 2019-08-29 동우화인켐 주식회사 Composition de résine photosensible et film diélectrique formé à partir de celle-ci

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CN108388082A (zh) * 2017-02-03 2018-08-10 信越化学工业株式会社 感光性树脂组合物、感光性干膜、感光性树脂涂层和图案形成方法
CN108388082B (zh) * 2017-02-03 2023-01-13 信越化学工业株式会社 感光性树脂组合物、感光性干膜、感光性树脂涂层和图案形成方法
WO2019164162A1 (fr) * 2018-02-23 2019-08-29 동우화인켐 주식회사 Composition de résine photosensible et film diélectrique formé à partir de celle-ci

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