WO2018123836A1 - Photosensitive resin composition, cured film, laminate, method for producing cured film, method for producing laminate, and semiconductor device - Google Patents

Photosensitive resin composition, cured film, laminate, method for producing cured film, method for producing laminate, and semiconductor device Download PDF

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Publication number
WO2018123836A1
WO2018123836A1 PCT/JP2017/046051 JP2017046051W WO2018123836A1 WO 2018123836 A1 WO2018123836 A1 WO 2018123836A1 JP 2017046051 W JP2017046051 W JP 2017046051W WO 2018123836 A1 WO2018123836 A1 WO 2018123836A1
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group
formula
resin composition
photosensitive resin
cured film
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PCT/JP2017/046051
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French (fr)
Japanese (ja)
Inventor
悠 岩井
渋谷　明規
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富士フイルム株式会社
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Priority to JP2018559135A priority Critical patent/JP6751159B2/en
Publication of WO2018123836A1 publication Critical patent/WO2018123836A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a photosensitive resin composition, a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, and a semiconductor device.
  • Patent Document 1 discloses a polyimide precursor having a predetermined structure, (b) a compound that generates radicals upon irradiation with active light, and (c) a compound represented by the following general formula (4a) or (4b). And a resin composition containing (d) a solvent.
  • n is an integer of 3 or less.
  • R 101 and R 102 are each independently a hydrogen atom or a monovalent group.
  • M is an integer of 9 or less. .
  • Patent Document 2 discloses a resin composition containing a compound having an ethynyl group and an epoxy compound.
  • Patent Document 2 does not describe photoradical polymerization of a polyimide precursor and cannot form a pattern.
  • the present invention aims to solve the above-mentioned problems, and is a photosensitive resin composition capable of forming a pattern by photoradical polymerization, and the resulting cured resin has a high elongation at break. And a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, and a semiconductor device.
  • a polyimide precursor having a group having a carbon-carbon triple bond represented by the formula (2) described later is used in a system that is cured by radical polymerization.
  • a photosensitive resin composition capable of forming a pattern and having a high elongation at break of a cured film obtained can be provided.
  • the above problem has been solved by the following means ⁇ 1>, preferably ⁇ 2> to ⁇ 25>.
  • a photosensitive resin composition containing a polyimide precursor containing a repeating unit represented by the following formula (1), and a radical photopolymerization initiator;
  • a 1 and A 2 each independently represent an oxygen atom or NH
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group; provided that at least one terminal of R 111 , R 113 , R 114 and R 115 has a group represented by the following formula (2): Bound;
  • R 1 represents a hydrogen atom or a substituent, and * is a binding site with R 111 , R 113 , R 114 or R 115 .
  • a 0 represents a (l + m) -valent group
  • a 1 represents a single bond or a (n + 1) -valent group
  • R 1 represents a hydrogen atom or a substituent
  • Ar represents an (a + 1) -valent group
  • A, l, m and n each independently represents an integer of 1 to 5; provided that at least one of m and n represents an integer of 2 or more.
  • ⁇ 4> The photosensitive resin composition according to ⁇ 1>, wherein the polyimide precursor has a structure derived from a compound represented by the following formula (3b); Formula (3b) In formula (3b), A 0 represents a (l + m) -valent group; R 1 represents a hydrogen atom or a substituent; a, l, m and n each independently represents an integer of 1 to 5; At least one of m and n represents an integer of 2 or more.
  • ⁇ 6> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the polyimide precursor further includes a repeating unit represented by the formula (1-1); Formula (1-1) In formula (1-1), A 1 and A 2 each independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group; provided that the repeating unit represented by formula (1-1) does not include the group represented by formula (2).
  • R 111 in the above formula (1-1) is represented by —Ar—L—Ar—, wherein Ar is independently an aromatic group.
  • a hydrocarbon group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO 2 — or —NHCO—. And a group consisting of a combination of two or more of the above.
  • R 111 in the above formula (1-1) is a group represented by the following formula (51) or formula (61);
  • Formula (51) In formula (51), R 10 to R 17 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 10 to R 17 is a fluorine atom, a methyl group, a fluoromethyl group, A difluoromethyl group or a trifluoromethyl group;
  • R 18 and R 19 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.
  • ⁇ 9> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 8>, wherein at least one of R 113 and R 114 includes a radical polymerizable group.
  • R 113 and R 114 includes a radical polymerizable group.
  • R 115 is a tetravalent organic group containing an aromatic ring.
  • ⁇ 12> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 11>, further comprising a base generator.
  • ⁇ 13> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 12>, further comprising a solvent.
  • ⁇ 14> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 13>, which is used for negative development.
  • ⁇ 15> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 14>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 16> A cured film obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 15>.
  • ⁇ 17> A laminate having two or more cured films according to ⁇ 16>.
  • ⁇ 18> The laminate according to ⁇ 17>, having a metal layer between the cured films.
  • ⁇ 19> A method for producing a cured film, comprising using the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 15>.
  • the manufacturing method of the cured film as described in ⁇ 19> which has the image development process process which performs image development processing with respect to a composition layer.
  • ⁇ 23> The method for producing a cured film according to any one of ⁇ 19> to ⁇ 22>, wherein the cured film has a thickness of 1 to 30 ⁇ m.
  • ⁇ 24> After forming the cured film according to the method for producing a cured film according to any one of ⁇ 19> to ⁇ 23>, the photosensitive resin composition layer forming step, the exposure step, and A method for producing a laminate, wherein the development processing step is performed 2 to 5 times in the order described above.
  • a photosensitive resin composition capable of forming a pattern by radical photopolymerization, wherein the resulting cured film has a high elongation at break, and a cured film, a laminate, and a method for producing the cured film It has become possible to provide a method for manufacturing a laminate and a semiconductor device.
  • the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which 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).
  • “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams.
  • the light used for the exposure generally includes an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
  • an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • “(meth) acrylate” represents both and / or “acrylate” and “methacrylate”
  • (meth) acryl” represents both “acryl” and “methacryl”
  • (Meth) acryloyl” represents either or both of “acryloyl” and “methacryloyl”.
  • solid content concentration is the mass percentage of the other component except a solvent with respect to the gross mass of a composition. Moreover, solid content concentration says the density
  • a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel. It can be determined by using Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, the eluent is measured using THF (tetrahydrofuran). Unless otherwise specified, detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector.
  • the photosensitive resin composition of the present invention includes a polyimide precursor containing a repeating unit represented by the following formula (1), and radical photopolymerization initiation It contains an agent. By setting it as such a structure, a pattern can be formed by radical photopolymerization and the cured film with a high breaking elongation can be obtained. Furthermore, when the resin layers formed from the composition of the present invention are multilayered, the adhesion between the layers becomes a problem. Specifically, in addition to the adhesion between the resin layer and the resin layer, when a metal layer is provided between the resin layer and the resin layer, the adhesion between the resin layer and the metal layer is required.
  • the adhesiveness between these layers can also be improved by couple
  • the group represented by the formula (2) is less consumed even after exposure, and is presumed to have increased reactivity between the layers at the time of exposure and thermal curing in the case of multilayer lamination. Is done.
  • the photosensitive resin composition when used for forming a resin layer of a multilayer laminate, such a photosensitive resin composition desirably has a wide exposure latitude, but the photosensitive resin composition of the present invention also has a wide exposure latitude. can do.
  • a 1 and A 2 each independently represent an oxygen atom or NH
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group; provided that at least one terminal of R 111 , R 113 , R 114 and R 115 has a group represented by the following formula (2): Bound;
  • R 1 represents a hydrogen atom or a substituent
  • * is a binding site with R 111 , R 113 , R 114 or R 115 .
  • the polyimide precursor used by this invention contains the repeating unit represented by Formula (1). Furthermore, a repeating unit other than the repeating unit represented by the formula (1) may be included. Hereinafter, these contents will be described in detail.
  • the polyimide precursor used by this invention contains the repeating unit represented by Formula (1).
  • a 1 and A 2 each independently represent an oxygen atom or NH
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group; provided that at least one terminal of R 111 , R 113 , R 114 and R 115 has a group represented by the following formula (2): Bound;
  • R 1 represents a hydrogen atom or a substituent, and * is a binding site with R 111 , R 113 , R 114 or R 115 .
  • the group represented by the following formula (2) is bonded to at least one terminal of R 111 , R 113 , R 114, and R 115 ” means that inside the group such as R 111 , R 113 and / or R 114 itself is a group represented by the formula (2), or R 111 , R 113 , R 114 and R 115 are not included as a so-called linking group. It means that at least one of the constituent hydrogen atoms is substituted with a group represented by the formula (2). In the present invention, among R 111 , R 113 , R 114 and R 115 , it is preferable that at least the group represented by the formula (2) is bonded to the terminal of R 111 .
  • R 111, R 113, R 114 and R 115 at least, to one end of R 113 and R 114, aspects group represented by the formula (2) is bonded are also exemplified.
  • the other of R 113 and R 114 has a group represented by the formula (2) bonded to the terminal or a radical polymerizable group.
  • R 111, R 113, R 114 and R 115 at least, the end of the R 115, aspects group represented by the formula (2) is bonded are also exemplified.
  • R 115 is an aromatic hydrocarbon group having a substituent
  • the substituent of the aromatic hydrocarbon group is the group itself represented by the formula (2), or the aromatic hydrocarbon It is preferable that the substituent of the group is further substituted with a group represented by the formula (2).
  • 1 to 5 groups represented by the formula (2) are contained in one repeating unit represented by the formula (1), and 1 to 3 groups are contained. Is more preferable, and it is further preferable that one or two are included.
  • R 1 represents a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom.
  • R 1 is a substituent
  • the following substituent T is exemplified, and the formula weight (mass of the above substituent portion per mole, unit g) is preferably a substituent having a formula weight of 15 to 300. More preferred are ⁇ 100 substituents.
  • the substituent is preferably composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a sulfur atom and a nitrogen atom.
  • An alkyl group preferably an alkyl group having 1 to 30 carbon atoms
  • an alkenyl group preferably an alkenyl group having 2 to 30 carbon atoms
  • an alkynyl group preferably an alkynyl group having 2 to 30 carbon atoms
  • an aryl group preferably An aryl group having 6 to 30 carbon atoms
  • an amino group preferably an amino group having 0 to 30 carbon atoms
  • an alkoxy group preferably an alkoxy group having 1 to 30 carbon atoms
  • an aryloxy group preferably having 6 to 6 carbon atoms
  • aryloxy groups preferably acyl groups having 1 to 30 carbon atoms
  • alkoxycarbonyl groups preferably alkoxycarbonyl groups having 2 to 30 carbon atoms
  • aryloxycarbonyl groups preferably Is an aryloxycarbonyl group having 7 to 30 carbon atoms
  • an acyloxy group preferably an acyloxy group having 2 to 30 carbon atoms.
  • an acylamino group preferably an acylamino group having 2 to 30 carbon atoms
  • an alkoxycarbonylamino group preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms
  • an aryloxycarbonylamino group preferably having a carbon number of 7 to 30 aryloxycarbonylamino groups
  • sulfamoyl groups preferably sulfamoyl groups having 0 to 30 carbon atoms
  • carbamoyl groups preferably carbamoyl groups having 1 to 30 carbon atoms
  • alkylthio groups preferably having 1 to 30 carbon atoms
  • Alkylthio group arylthio group (preferably arylthio group having 6 to 30 carbon atoms), heteroarylthio group (preferably 1 to 30 carbon atoms), alkylsulfonyl group (preferably 1 to 30 carbon atoms), arylsulfonyl group ( Preferably 6-30 carbon atoms, heteroarylsulfur Nyl group (preferably 1-30 carbon atoms), alkylsulfinyl group (preferably 1-30 carbon atoms), arylsulfinyl group (preferably 6-30 carbon atoms), heteroarylsulfinyl group (preferably 1-30 carbon atoms) ), Ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (preferably having 1 to 30 carbon atoms), hydroxy group, mercapto group, halogen atom, cyano group, alkylsulfino group, arylsulfino group, A hydrazino group, an imino group,
  • the polyimide precursor used in the present invention preferably has a structure derived from a compound represented by the following formula (3).
  • Formula (3) In formula (3), A represents a (p + q) -valent group; R 1 represents a hydrogen atom or a substituent; p represents an integer of 1 to 5, and q represents an integer of 2 or more.
  • the amide group part is incorporated into the polyimide precursor by reacting with the carboxylic acid or carboxylic anhydride dianhydride which is the raw material of the polyimide precursor.
  • the NH—R 111 —NH moiety of formula (1) is preferably derived from the compound represented by formula (3).
  • the (p + q) -valent group represented by A includes a hydrocarbon group, a heterocyclic group, —O—, —S—, —NR—, —CO—, —COO—, —OCO—, A group consisting of —SO 2 — or a combination thereof is mentioned.
  • R represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom.
  • the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
  • the aliphatic hydrocarbon group may be cyclic or acyclic.
  • the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group.
  • the hydrocarbon group may have a substituent or may not have a substituent.
  • substituent include the above-described substituent T.
  • the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be a single ring or a condensed ring, but a single ring is preferable.
  • the aromatic hydrocarbon group include a benzene ring group, a naphthalene ring group, an indene ring group, an indane ring group, an anthracene ring group, and a tetralin ring group.
  • the heterocyclic group may be a single ring or a condensed ring.
  • the heterocyclic group is preferably a 5-membered ring or a 6-membered ring.
  • the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group.
  • a hetero atom which comprises a heterocyclic group a nitrogen atom, an oxygen atom, a sulfur atom, etc. are mentioned.
  • Heterocyclic groups include furan ring group, thiophene ring group, pyrrole ring group, pyran ring group, thiopyran ring group, pyridine ring group, oxazole ring group, thiazole ring group, imidazole ring group, pyrimidine ring group, triazine ring group, indole Examples thereof include a ring group, a quinoline ring group, a purine ring group, a benzimidazole ring group, a benzothiazole ring group, a quinoxaline ring group, and a carbazole ring group.
  • R represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom.
  • the (p + q) -valent group represented by A is composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a sulfur atom and a nitrogen atom, and has a formula weight (mass of A moiety per mole, unit) g) is preferably from 30 to 900, more preferably from 50 to 600.
  • p represents an integer of 1 to 5.
  • q represents an integer of 2 or more.
  • p is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
  • q is preferably an integer of 2 to 4, more preferably 2 or 3, and still more preferably 2.
  • a plurality of R 1 may be the same or different.
  • R 1 represents a hydrogen atom or a substituent.
  • a preferred range of R 1 in the formula (3) is the same as R 1 in formula (2).
  • the polyimide precursor has a structure derived from a compound represented by the following formula (3a). That is, it is more preferable that the compound represented by Formula (3) is represented by Formula (3a).
  • Formula (3a) In formula (3a), A 0 represents a (l + m) -valent group; A 1 represents a single bond or a (n + 1) -valent group; R 1 represents a hydrogen atom or a substituent; Ar represents an (a + 1) -valent group A, l, m and n each independently represents an integer of 1 to 5; provided that at least one of m and n represents an integer of 2 or more. .
  • the (l + m) -valent group represented by A 0 is a hydrocarbon group, a heterocyclic group, —O—, —S—, —NR—, —CO—, —COO—, —OCO—. , —SO 2 — or a combination thereof, such as —O—, —S—, —NR—, —CO—, —COO—, —OCO—, —SO 2 — or a combination thereof.
  • a group is more preferable, and a group consisting of —NH—, —CO— or a combination thereof is more preferable.
  • R represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom.
  • the details of the hydrocarbon group and heterocyclic group are the same as the range described for the (p + q) valent group represented by A described above, and the preferred range is also the same.
  • the (n + 1) -valent group represented by A 1 is a hydrocarbon group, a heterocyclic group, —O—, —S—, —NR—, —CO—, —COO—, —OCO—. , —SO 2 —, or a combination thereof.
  • R represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom.
  • the details of the hydrocarbon group and the heterocyclic group are the same as those described for the (p + q) -valent group represented by A described above.
  • the (n + 1) -valent group represented by A 1 is preferably a hydrocarbon group or a heterocyclic group, more preferably a hydrocarbon group, further preferably an aromatic hydrocarbon group, and a benzene ring. More preferably, it is a group.
  • R 1 represents a hydrogen atom or a substituent.
  • a preferred range of R 1 in the formula (3) is the same as R 1 in formula (2).
  • Ar is preferably an (a + 1) -valent aromatic hydrocarbon group, and more preferably a benzene ring group.
  • a, l, m and n each independently represents an integer of 1 to 5. However, at least one of m and n represents an integer of 2 or more.
  • l and m are each 2 or more, a plurality of R 1 , Ar, and A 1 may be the same or different from each other.
  • a is preferably 1 to 4, more preferably 1 to 3, further preferably 1 or 2, and still more preferably 1.
  • l is preferably 1 to 4, more preferably 1 to 3, further preferably 1 or 2, and still more preferably 1.
  • m is preferably 1 to 4, more preferably 1 to 3, further preferably 1 or 2, and still more preferably 1.
  • n is preferably 1 to 4, more preferably 2 to 4, still more preferably 2 or 3, and still more preferably 2.
  • (l + m) is preferably 2 to 6, more preferably 2 to 5, still more preferably 2 or 3, and particularly preferably 2.
  • the polyimide precursor has a structure derived from a compound represented by the following formula (3b). That is, it is more preferable that the compound represented by the formula (3) is represented by the formula (3b).
  • a 0 represents a (l + m) -valent group
  • R 1 represents a hydrogen atom or a substituent
  • a, l, m and n each independently represents an integer of 1 to 5
  • At least one of m and n represents an integer of 2 or more.
  • a 0 , R 1 , a, l, m and n are each independently synonymous with A 0 , R 1 , a, l, m and n in formula (3a), and a preferred range Is the same.
  • a 1 and A 2 in Formula (1) each independently represent an oxygen atom or NH, and preferably an oxygen atom.
  • R 111 in Formula (1) represents a divalent organic group.
  • the divalent organic group include a straight chain or branched aliphatic group, a group containing a cyclic aliphatic group and an aromatic hydrocarbon group, a straight chain aliphatic group having 2 to 20 carbon atoms, A group consisting of a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof is preferable.
  • a group consisting of the above aromatic hydrocarbon group is more preferred.
  • R 111 is preferably derived from a diamine.
  • the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine. Only one type of diamine may be used, or two or more types may be used.
  • the diamine is preferably a compound represented by the formula (3). If R 111 is not derived from the compound represented by the formula (3), R 111 is the same as R 111 in the repeating unit represented by the formula (1-1) described below, a preferred range is also the same.
  • R 115 in formula (1) represents a tetravalent organic group.
  • a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
  • R 112 represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO.
  • -, - NHCO- is preferably a group selected from these combinations, a single bond, an alkylene group which ⁇ 1 carbon atoms which may be 3-substituted by fluorine atoms, -O -, - CO- More preferably a group selected from -S- and -SO 2- , -CH 2- , -C (CF 3 ) 2- , -C (CH 3 ) 2- , -O-, -CO More preferred is a divalent group selected from the group consisting of —, —S— and —SO 2 —.
  • tetravalent organic group represented by R 115 in Formula (1) include a tetracarboxylic acid residue remaining after the acid dianhydride group is removed from the tetracarboxylic dianhydride. Only one tetracarboxylic dianhydride may be used, or two or more tetracarboxylic dianhydrides may be used.
  • the tetracarboxylic dianhydride is preferably a compound represented by the following formula (O).
  • tetracarboxylic dianhydride examples include pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′- Diphenyl sulfide tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′ , 4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 4,4′-PM
  • tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferable examples.
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R 113 and R 114 preferably contains a radical polymerizable group, and both are radicals. It preferably contains a polymerizable group.
  • the radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example includes a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like.
  • R 200 represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
  • R 201 is a linking group, preferably a group consisting of —CH 2 —, —O—, —CO— or a combination thereof.
  • R 113 or R 114 may be a monovalent organic group other than a hydrogen atom or a radical polymerizable group.
  • the description in paragraph 0087 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.
  • the polyimide precursor preferably has a fluorine atom in the structural unit.
  • the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
  • an aliphatic group having a siloxane structure may be copolymerized for the purpose of improving the adhesion to the substrate.
  • the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
  • the repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by the formula (1-A). By adopting such a structure, it becomes possible to further widen the width of the exposure latitude.
  • the group represented by the above formula (2) is bonded to at least one terminal of R 111 , R 113 , R 114 and R 112 .
  • a 1 , A 2 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (1), and the preferred ranges are also the same. is there.
  • R 112 has the same meaning as R 112 in formula (5), and the preferred range is also the same.
  • the polyimide precursor may contain only one type of repeating structural unit represented by the formula (1), or may contain two or more types. Moreover, the structural isomer of the repeating unit represented by Formula (1) may be included.
  • the polyimide precursor used in the present invention may contain a repeating unit other than the repeating unit represented by the formula (1), and preferably contains a repeating unit other than the repeating unit represented by the formula (1). More preferably, it contains a repeating unit represented by the formula (1-1).
  • Formula (1-1) In formula (1-1), A 1 and A 2 each independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group; provided that the repeating unit represented by formula (1-1) does not include the group represented by formula (2).
  • a 1 , A 2 , R 115 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 115 , R 113 and R 114 in formula (1).
  • the preferred range is also the same.
  • a 1 , A 2 , R 115 in the formula (1), R 113 and R 114 and A 1 , A 2 , R 115 , R 113 and R 114 in formula (1-1) may be the same or different, but are preferably the same. .
  • R 111 in formula (1-1) represents a divalent organic group.
  • the divalent organic group include a straight chain or branched aliphatic group, a group containing a cyclic aliphatic group and an aromatic hydrocarbon group, a straight chain aliphatic group having 2 to 20 carbon atoms, A group consisting of a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof is preferable. A group consisting of the above aromatic hydrocarbon group is more preferred.
  • R 111 is preferably derived from a diamine.
  • the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine. Only one type of diamine may be used, or two or more types may be used. Specifically, from a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof.
  • a diamine containing a group consisting of an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferred. The following are mentioned as an example of an aromatic hydrocarbon group.
  • A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C ( ⁇ O) —, —S—, —S ( ⁇ O) 2 —, —NHCO—, and a group selected from these combinations are preferable, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O— , —C ( ⁇ O) —, —S—, —SO 2 — is more preferable, and —CH 2 —, —O—, —S—, —SO 2 —, —C ( More preferably, it is a divalent group selected from the group consisting of CF 3 ) 2 — and —C (CH 3 ) 2 —.
  • diamines (DA-1) to (DA-18) shown below are also preferable.
  • a diamine having at least two alkylene glycol units in the main chain is also a preferred example.
  • Preferred is a diamine containing at least two ethylene glycol chains or propylene glycol chains in one molecule, more preferably a diamine containing no aromatic ring.
  • Specific examples include Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark).
  • x, y, and z are average values.
  • R 111 in formula (1-1) is preferably represented by —Ar—L—Ar— from the viewpoint of flexibility of the resulting cured film.
  • Ar is each independently an aromatic hydrocarbon group
  • L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, — S—, —SO 2 — or —NHCO—, and a group consisting of a combination of two or more of the above.
  • Ar is preferably a phenylene group
  • L is an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— or —SO 2 —.
  • the aliphatic hydrocarbon group here is preferably an alkylene group.
  • R 111 in formula (1-1) is preferably a group represented by the following formula (51) or formula (61) from the viewpoint of i-line transmittance.
  • the group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.
  • Formula (51) In formula (51), R 10 to R 17 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 10 to R 17 is a fluorine atom, a methyl group, a fluoromethyl group, A difluoromethyl group or a trifluoromethyl group.
  • Examples of the monovalent organic group represented by R 10 to R 17 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorine atom having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Alkyl group and the like.
  • Formula (61) In formula (61), R 18 and R 19 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.
  • Diamine compounds that give the structure of formula (51) or (61) include dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2 Examples include '-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like. One of these may be used, or two or more may be used in combination.
  • the polyimide precursor may include only one type of repeating structural unit represented by the formula (1-1) or two or more types. You may go out. Further, it may contain a structural isomer of a repeating unit represented by the formula (1-1).
  • a repeating unit represented by the formula (1) and a repeating unit represented by the formula (1) including the repeating unit represented by the formula (1-1) It is exemplified that the total of repeating units represented by the formula (1-1) occupies preferably 80% by mass or more, more preferably 90% by mass or more of all repeating units.
  • the repeating unit represented by the formula (1) the formula The molar ratio of the repeating unit represented by (1-1) is preferably 1: 0.02 to 1:50, and more preferably 1: 0.1 to 1:20.
  • the amount of the group represented by the formula (2) is preferably 0.05 to 5.0 mmol with respect to 1 g of the polyimide precursor, and 0.1 to 2.5 mmol. More preferably.
  • the ratio between the number of radical polymerizable groups contained in the photosensitive resin composition and the number of groups represented by formula (2) is the number of radical polymerizable groups: Formula (2).
  • the number of groups represented is preferably 1: 0.05 to 2.0, more preferably 1: 0.1 to 1.0.
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 10,000 to 50,000.
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and still more preferably 4000 to 25000.
  • the degree of dispersion is preferably 1.5 to 2.5.
  • the present invention is not limited to these examples.
  • the polyimide precursor shown below is a copolymer
  • the molar ratio of the left repeating unit to the right repeating unit is appropriately determined in the range of 1: 0.02 to 50.
  • the photosensitive resin composition of the present invention preferably contains 20 to 100% by mass, more preferably 50 to 99% by mass, and 60 to 98% by mass of the polyimide precursor with respect to the total solid content of the composition. More preferably, it is particularly preferably 70 to 95% by mass.
  • the polyimide precursor may contain only 1 type and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.
  • the polyimide precursor is obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting with a diamine.
  • an organic solvent is preferably used for the reaction.
  • One or more organic solvents may be used.
  • the organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
  • a terminal sealing agent such as an acid dianhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound in order to further improve storage stability.
  • a monoamine Preferred examples of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7.
  • -Aminonaphthalene 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2, -Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carbo Ci-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-amino Benzenesulfonic acid, 4-amino
  • a step of depositing a solid may be included. Specifically, solid precipitation can be achieved by precipitating the polyimide precursor in the reaction solution in water and dissolving it in a solvent in which the polyimide precursor such as tetrahydrofuran is soluble. Then, a polyimide precursor can be dried and a powdery polyimide precursor can be obtained.
  • the composition of the present invention contains a radical photopolymerization initiator.
  • a radical photopolymerization initiator which can be used by this invention, It can select suitably from well-known radical photopolymerization initiators.
  • a photo radical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
  • the radical photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm).
  • the molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
  • the composition of the present invention contains a photoradical polymerization initiator
  • the composition of the present invention is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then irradiated with light to generate radicals. Curing due to this occurs and the solubility in the light irradiation part can be reduced. Therefore, for example, by exposing the photosensitive resin composition layer through a photomask having a pattern that masks only the electrode portion, there is an advantage that regions having different solubility can be easily produced according to the electrode pattern. is there.
  • a known compound can be arbitrarily used.
  • halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc.
  • ketone compounds include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
  • Kaya Cure DETX manufactured by Nippon Kayaku Co., Ltd.
  • Nippon Kayaku Co., Ltd. is also preferably used.
  • hydroxyacetophenone compounds As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
  • hydroxyacetophenone-based initiator IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator compounds described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source of 365 nm or 405 nm can also be used.
  • the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • IRGACURE-819 and IRGACURE-TPO which are commercially available products can be used.
  • the metallocene compound include IRGACURE-784 (manufactured by BASF).
  • the photo radical polymerization initiator include oxime compounds.
  • the exposure latitude can be improved more effectively.
  • Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a photobase generator.
  • Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
  • Preferable oxime compounds include, for example, compounds having the following structures, 3-benzooxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxy Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
  • IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adekaoptomer N-1919 (manufactured by ADEKA Corporation, light described in JP2012-14052A) A radical polymerization initiator 2) is also preferably used.
  • TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
  • Adeka Arcles NCI-831 and Adeka Arcles NCI-930 can also be used.
  • DFI-091 (manufactured by Daitokemix Co., Ltd.) can be used. Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36-40 described in paragraphs 0345 to 0358 of JP 2014-500852 A, Examples thereof include compound (C-3) described in paragraph 0101 of JP2013-164471A. As the most preferred oxime compounds, there are oxime compounds having a specific substituent as disclosed in JP-A-2007-267979, oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, and the like.
  • Photoradical polymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryls from the viewpoint of exposure sensitivity. Selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. Are preferred.
  • More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, At least one compound selected from the group consisting of a trihalomethyltriazine compound, an ⁇ -aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and a metallocene compound or an oxime compound is more preferable, and an oxime compound. Is even more preferable.
  • photo radical polymerization initiators include N, N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl such as benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone) Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkyl anthraquinones, etc.
  • benzoin ether compounds such as benzoin alkyl ether
  • benzoin compounds such as benzoin and alkylbenzoin
  • benzyl derivatives such as benzyldimethyl ketal.
  • a compound represented by the following formula (I) can also be used.
  • R 50 represents an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms A phenyl group substituted with at least one of 18 alkyl groups and an alkyl group having 1 to 4 carbon atoms, or biphenylyl, and R 51 is a group represented by the formula (II) or the same as R 50
  • Each of R 52 to R 54 is independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or halogen.
  • radical photopolymerization initiator compounds described in paragraphs 0048 to 0055 of International Publication No. WO2015 / 125469 can be used.
  • the content of the photo radical polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably based on the total solid content of the composition of the present invention. It is 1 to 15% by mass, and more preferably 1 to 10% by mass.
  • the radical photopolymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more kinds of radical photopolymerization initiators are contained, the total is preferably in the above range.
  • the composition of the present invention may contain a thermal radical polymerization initiator without departing from the gist of the present invention.
  • the thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polyimide precursor can be advanced together with the cyclization of the polyimide precursor, so that higher heat resistance can be achieved.
  • Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.
  • the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably based on the total solid content of the composition of the present invention. Is 5 to 15% by mass.
  • the thermal radical polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more thermal radical polymerization initiators are contained, the total is preferably within the above range.
  • the composition of the present invention preferably contains a solvent.
  • a known solvent can be arbitrarily used as the solvent.
  • the solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
  • esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, and ⁇ -caprolactone , ⁇ -valerolactone, alkyl oxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.
  • alkyl oxyacetates for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl al
  • 3-alkyloxypropionic acid alkyl esters for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, 3-methoxypropionate)) Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)
  • 2-alkyloxypropionic acid alkyl esters for example, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 -Propyl alkyloxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)
  • ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
  • Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
  • Suitable examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
  • the sulfoxides for example, dimethyl sulfoxide is preferable.
  • Preferred examples of the amide include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like.
  • the solvent is preferably in the form of a mixture of two or more from the viewpoint of improving the properties of the coated surface.
  • a mixed solution composed of two or more selected from dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable.
  • the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
  • the content of the solvent is preferably an amount such that the total solid concentration of the composition of the present invention is 5 to 80% by mass, more preferably 5 to 70% by mass, from the viewpoint of applicability. An amount of 10 to 60% by mass is particularly preferable.
  • the solvent content may be adjusted depending on the desired thickness and coating method.
  • the solvent may contain only 1 type and may contain 2 or more types. When two or more solvents are contained, the total is preferably in the above range.
  • the composition of the present invention preferably contains a radical polymerizable compound (hereinafter also referred to as “polymerizable monomer”). By setting it as such a structure, the cured film excellent in heat resistance can be formed.
  • a radical polymerizable compound hereinafter also referred to as “polymerizable monomer”.
  • a compound having a radical polymerizable group can be used as the polymerizable monomer.
  • the radical polymerizable group include groups having an ethylenically unsaturated bond such as a styryl group, a vinyl group, a (meth) acryloyl group, and an allyl group.
  • the radical polymerizable group is preferably a (meth) acryloyl group.
  • the number of radical polymerizable groups possessed by the polymerizable monomer may be one or two or more, but the polymerizable monomer preferably has two or more radical polymerizable groups, more preferably three or more. .
  • the upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the molecular weight of the polymerizable monomer is preferably 2000 or less, more preferably 1500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more.
  • the composition of the present invention preferably contains at least one bifunctional or higher polymerizable monomer containing two or more polymerizable groups, and preferably contains at least one trifunctional or higher polymerizable monomer. Is more preferable. Further, it may be a mixture of a bifunctional polymerizable monomer and a trifunctional or higher functional polymerizable monomer.
  • the number of functional groups of the polymerizable monomer means the number of radical polymerizable groups in one molecule.
  • the polymerizable monomer examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. These are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds.
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • the description in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.
  • the polymerizable monomer is also preferably a compound having a boiling point of 100 ° C. or higher under normal pressure.
  • Examples include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
  • polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof described in JP-B 52-30490. it can. Also suitable are the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970.
  • polyfunctional (meth) acrylate etc. which are obtained by making the compound which has cyclic ether groups, such as glycidyl (meth) acrylate, and an ethylenically unsaturated group, react with polyfunctional carboxylic acid can also be mentioned.
  • preferable polymerizable monomers include groups having a fluorene ring and an ethylenically unsaturated bond described in JP2010-160418A, JP2010-129825A, Japanese Patent No. 4364216, and the like. It is also possible to use a compound having two or more or a cardo resin. Other examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493. And vinyl phosphonic acid compounds. Also, compounds containing a perfluoroalkyl group described in JP-A-61-22048 can be used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photopolymerizable monomers and oligomers, can also be used.
  • dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; Nippon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available products are KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meta) ) Acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups are linked via ethylene glycol and propylene glycol
  • Examples of commercially available polymerizable monomers include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209, manufactured by Sartomer, which is a bifunctional methacrylate having four ethyleneoxy chains, DPCA-60, a 6-functional acrylate having 6 pentyleneoxy chains, TPA-330, a 3-functional acrylate having 3 isobutyleneoxy chains, NK ester M-40G, NK ester 4G, manufactured by Nippon Kayaku Co., Ltd.
  • NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA- 306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME 00 (manufactured by NOF Co., Ltd.), and the like.
  • Polymerizable monomers include urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765.
  • Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.
  • compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used as polymerizable monomers. You can also.
  • the polymerizable monomer may be a polymerizable monomer having an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group.
  • the polymerizable monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxy group of the aliphatic polyhydroxy compound. More preferred is a polymerizable monomer.
  • the aliphatic polyhydroxy compound is pentaerythritol and / or diester. It is a compound that is pentaerythritol.
  • examples of commercially available products include M-510, M-520 and the like as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the polymerizable monomer having an acid group one kind may be used alone, or two or more kinds may be mixed and used.
  • a preferable acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
  • the acid value of the polymerizable monomer is within the above range, the production and handling properties are excellent, and further, the developability is excellent. Also, the polymerizability is good.
  • the content of the polymerizable monomer is preferably 1 to 50% by mass with respect to the total solid content of the composition of the present invention from the viewpoint of good polymerizability and heat resistance.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 30% by mass or less.
  • As the polymerizable monomer one kind may be used alone, or two or more kinds may be mixed and used.
  • the mass ratio of the polyimide precursor and the polymerizable monomer is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, and 90/10 to 50 / 50 is more preferable. If the mass ratio of a polyimide precursor and a polymerizable monomer is in the above range, a cured film that is superior in polymerizability and heat resistance can be formed.
  • a monofunctional polymerizable monomer can be preferably used from the viewpoint of warpage suppression accompanying the control of the elastic modulus of the cured film.
  • Monofunctional polymerizable monomers include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
  • N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Goods and the like are preferably used.
  • the monofunctional polymerizable monomer a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
  • composition of this invention can further contain other polymeric compounds other than the polyimide precursor mentioned above and a radically polymerizable compound.
  • Other polymerizable compounds include compounds having a hydroxymethyl group, alkoxymethyl group or acyloxymethyl group; epoxy compounds; oxetane compounds; benzoxazine compounds.
  • R 4 represents a t-valent organic group having 1 to 200 carbon atoms
  • R 5 represents a group represented by —OR 6 or —OCO—R 7.
  • R 6 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 7 represents an organic group having 1 to 10 carbon atoms.
  • the content of the compound represented by the formula (AM1) is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor. More preferably, it is 10 to 35 parts by mass. Further, the compound represented by the following formula (AM4) is contained in the total amount of other polymerizable compounds in an amount of 10 to 90% by mass, and the compound represented by the following formula (AM5) is contained in an amount of 10 to 90% by mass Is also preferable.
  • R 4 represents a divalent organic group having 1 to 200 carbon atoms
  • R 5 represents a group represented by —OR 6 or —OCO—R 7
  • R 6 represents a hydrogen atom or a carbon atom.
  • R 7 represents an organic group having 1 to 10 carbon atoms.
  • R 4 represents a u-valent organic group having 1 to 200 carbon atoms
  • R 5 represents a group represented by —OR 6 or —OCO—R 7.
  • R 6 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 7 represents an organic group having 1 to 10 carbon atoms.
  • the occurrence of cracks can be more effectively suppressed when the composition of the present invention is applied to an uneven substrate. Moreover, it is excellent in pattern workability and can form the cured film which has high heat resistance from which 5% mass reduction
  • Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML.
  • Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.).
  • Epoxy compound compound having an epoxy group
  • the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
  • the epoxy group undergoes a cross-linking reaction at 200 ° C. or less and does not cause a dehydration reaction derived from the cross-linking, so that film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective for low-temperature curing and warping of the composition.
  • the epoxy compound preferably contains a polyethylene oxide group. Thereby, an elasticity modulus falls more and also curvature can be suppressed.
  • the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
  • epoxy compounds include: bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidyl Examples include, but are not limited to, epoxy group-containing silicones such as (roxypropyl) siloxane.
  • Epicron (registered trademark) 850-S Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Rica Resin (registered trademark) ) BEO-60E (trade name, Shin Nippon Rika ( ) Made), EP-4003S, EP-4000S (trade names, and
  • an epoxy resin containing a polyethylene oxide group is preferable in terms of suppressing warpage and excellent heat resistance.
  • Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4822, and Licaredin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.
  • the content of the epoxy compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor. If the content of the epoxy compound is 5 parts by mass or more, warpage of the resulting cured film can be further suppressed, and if it is 50 parts by mass or less, pattern filling caused by reflow during curing can be further suppressed.
  • oxetane compound compound having oxetanyl group
  • examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, Examples include 3-ethyl-3- (2-ethylhexylmethyl) oxetane and 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester.
  • Aron Oxetane series for example, OXT-121, OXT-221, OXT-191, OXT-223 manufactured by Toagosei Co., Ltd. can be suitably used, and these are used alone. Or you may mix 2 or more types.
  • the content of the oxetane compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor.
  • a benzoxazine compound (compound having a benzoxazolyl group))
  • a benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur at the time of curing, and thermal contraction is further reduced to suppress warpage.
  • benzoxazine compound examples include Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type A dihydrobenzoxazine compound is mentioned. These may be used alone or in combination of two or more.
  • the content of the benzoxazine compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor.
  • the photosensitive resin composition further contains a migration inhibitor.
  • the migration inhibitor is not particularly limited, but a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, Compounds having pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and mercapto groups, hindered phenol compounds , Salicylic acid derivative compounds
  • an ion trapping agent that traps anions such as halogen ions can be used.
  • Examples of other migration inhibitors include rust inhibitors described in paragraph 0094 of JP2013-15701A, compounds described in paragraphs 0073 to 0076 of JP2009-283711A, and JP2011-95956A.
  • the compounds described in paragraph 0052 and the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A can be used.
  • the migration inhibitor include the following compounds.
  • the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the photosensitive resin composition, 0.05 to 2.0% by mass is more preferable, and 0.1 to 1.0% by mass is more preferable. Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more migration inhibitors, the total is preferably within the above range.
  • the composition of the present invention preferably contains a polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, p-benzoquinone, diphenyl-p-benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N -Phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-
  • a polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and compounds described in paragraphs 0031 to 0046 of international publication WO2015 / 125469 can also be used.
  • the following compound can be used (Me is a methyl group).
  • the content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the composition of the present invention. Only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
  • the composition of this invention contains the metal adhesive improvement agent for improving the adhesiveness with the metal material used for an electrode, wiring, etc.
  • metal adhesion improvers include silane coupling agents.
  • silane coupling agent examples include compounds described in paragraphs 0062 to 0073 of JP2014-191002, compounds described in paragraphs 0063 to 0071 of international publication WO2011 / 080992A1, and JP2014-191252A. Examples thereof include compounds described in paragraphs 0060 to 0061, compounds described in paragraphs 0045 to 0052 of JP 2014-41264 A, and compounds described in paragraph 0055 of international publication WO 2014/097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Moreover, it is also preferable to use the following compound for a silane coupling agent. In the following formula, Et represents an ethyl group.
  • the content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the polyimide precursor. Adhesiveness between the cured film and the metal layer after the curing process becomes good by setting it to 0.1 parts by mass or more, and heat resistance and mechanical properties of the cured film after the curing process are good by setting it to 30 parts by mass or less. Become. Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said range.
  • the composition used in the present invention may contain a base generator.
  • the base generator may be a thermal base generator or a photobase generator, and preferably contains at least a photobase generator.
  • the type of the thermal base generator is not particularly defined, but it is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having an pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one of the above.
  • pKa1 represents a logarithmic representation ( ⁇ Log 10 Ka) of the dissociation constant (Ka) of the first proton of the polyvalent acid.
  • the thermal base generator in the present invention is at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation. including. Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the base generated from these compounds can accelerate the cyclization reaction of the polyimide precursor, thereby cyclizing the polyimide precursor. Can be performed at low temperatures.
  • the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, more preferably 120 to 200 ° C.
  • the upper limit of the base generation temperature is preferably 190 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 165 ° C. or lower.
  • the lower limit of the base generation temperature is preferably 130 ° C or higher, and more preferably 135 ° C or higher. If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or higher, a base is unlikely to be generated during storage, and thus a polyimide precursor composition having excellent stability can be prepared.
  • the base generation temperature of the acidic compound (A1) and ammonium salt (A2) is 200 ° C. or lower, the cyclization temperature of the polyimide precursor can be lowered.
  • the base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.
  • the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since tertiary amine has high basicity, the cyclization temperature of a polyimide precursor can be lowered more.
  • the base generated by the thermal base generator preferably has a boiling point of 80 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 140 ° C. or higher.
  • the molecular weight of the generated base is preferably 80 to 2000.
  • the lower limit is more preferably 100 or more.
  • the upper limit is more preferably 500 or less.
  • the molecular weight value is a theoretical value obtained from the structural formula.
  • the acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the formula (101) or (102) described later.
  • the ammonium salt (A2) is preferably an acidic compound.
  • the ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.), or 40 ° C. or higher (preferably 120 to 200 ° C.). ) May be a compound excluding an acidic compound that generates a base when heated.
  • the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion.
  • the anion may be bonded to any part of the ammonium cation via a covalent bond, and may be outside the molecule of the ammonium cation, but may be outside the molecule of the ammonium cation. preferable.
  • numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple
  • the anion outside the molecule of the cation moiety is also referred to as a counter anion.
  • R 1 to R 6 each independently represents a hydrogen atom or a hydrocarbon group
  • R 7 represents a hydrocarbon group.
  • R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 5 and R 7 may be bonded to form a ring.
  • the ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-5).
  • R 101 represents an n-valent organic group
  • R 1 and R 7 are synonymous with R 1 and R 7 in the formula (101) or formula (102) It is.
  • Ar 101 and Ar 102 each independently represent an aryl group
  • n represents an integer of 1 or more
  • m represents an integer of 0 to 5 .
  • the ammonium salt preferably has an anion having an pKa1 of 0 to 4 and an ammonium cation.
  • the upper limit of the anion pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less.
  • the lower limit is preferably 0.5 or more, and more preferably 1.0 or more.
  • the kind of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because both the stability of the salt and the thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
  • the carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it is possible to provide a thermal base generator that can further improve the stability, curability and developability of the composition. In particular, the stability, curability and developability of the composition can be further improved by using an anion of a divalent carboxylic acid.
  • the carboxylic acid anion is preferably a carboxylic acid anion having a pKa1 of 4 or less. pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. According to this aspect, the stability of the composition can be further improved.
  • pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid, and the determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, D.H., Hafliger Ed .: Braude, EA, Nachod, FC; Academic Press, New York, 1955), and Data for Biochemical Research (author: Dawson, R. M.). al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) are used.
  • the carboxylate anion is preferably represented by the following formula (X1).
  • EWG represents an electron withdrawing group.
  • the electron withdrawing group means a group in which Hammett's substituent constant ⁇ m exhibits a positive value.
  • ⁇ m is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 631-642.
  • the electron withdrawing group in this embodiment is not limited to the substituent described in the said literature.
  • Me represents a methyl group
  • Ac represents an acetyl group
  • Ph represents a phenyl group (hereinafter the same).
  • EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
  • R x1 to R x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group Represents.
  • the carboxylate anion is preferably represented by the following formula (XA).
  • Formula (XA) In the formula (XA), L 10 represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an aromatic group, —NR X —, and a combination thereof, and R X represents a hydrogen atom Represents an alkyl group, an alkenyl group or an aryl group.
  • the carboxylate anion examples include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion.
  • the thermal base generator can be referred to the descriptions in paragraphs 0021 to 0077 of JP-A-2016-027357, the contents of which are incorporated herein. Examples of the thermal base generator include the following compounds.
  • the content of the thermal base generator in the composition is preferably 0.1 to 50% by mass with respect to the total solid content of the composition.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
  • 1 type (s) or 2 or more types can be used for a thermal base generator. When using 2 or more types, it is preferable that a total amount is the said range.
  • the photosensitive resin composition used in the present invention may contain a photobase generator.
  • a photobase generator generates a base upon exposure and does not exhibit activity under normal conditions of normal temperature and pressure.
  • the base (basic substance) ) Is not particularly limited as long as it generates. Since the base generated by the exposure works as a catalyst for curing the polyimide precursor by heating, it can be suitably used in the negative type.
  • photobase generators can be used.
  • M.M. Shirai, and M.M. Tsunooka Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, polymer processing, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A .; Sarker, and D. Neckers, Chem. Mater. 11, 170 (1999); Tachi, M .; Shirai, and M.M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K.K. Graziano, J. et al. Photopolym. Sci.
  • transition metal compound complexes those having a structure such as an ammonium salt, and those formed by salt formation of an amidine moiety with a carboxylic acid
  • transition metal compound complexes those having a structure such as an ammonium salt, and those formed by salt formation of an amidine moiety with a carboxylic acid
  • a urethane bond or oxime bond such as a carbamate derivative, an oxime ester derivative, or an acyl compound.
  • the basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
  • the generated basic substance is preferably a compound having an amino group having a higher basicity. This is because the catalytic action for the dehydration condensation reaction or the like in the imidization of the polyimide precursor is strong, and the catalytic effect in the dehydration condensation reaction or the like at a lower temperature can be expressed with a smaller amount of addition. That is, since the generated basic substance has a large catalytic effect, the apparent sensitivity of the negative photosensitive resin composition is improved. From the viewpoint of the catalytic effect, an amidine and an aliphatic amine are preferable.
  • the photobase generator used in the present invention preferably contains an aromatic ring and the generated basic substance is a compound having an amino group.
  • Examples of the photobase generator according to the present invention include a photobase generator having a cinnamic acid amide structure as disclosed in Japanese Patent Application Laid-Open Nos. 2009-80452 and 2009/123122.
  • a photobase generator having a carbamate structure as disclosed in Japanese Patent No. 189591 and Japanese Patent Application Laid-Open No. 2008-247747, an oxime structure as disclosed in Japanese Patent Application Laid-Open No. 2007-249013 and Japanese Patent Application Laid-Open No. 2008-003581 Examples include photobase generators having a carbamoyloxime structure, but are not limited thereto, and other known photobase generator structures can be used.
  • photobase generators include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, compounds described in paragraphs 0022 to 0069 of JP2013-194205, Examples include the compounds described in paragraphs 0026 to 0074 of JP2013-204019, and the compound described in paragraph 0052 of WO2010 / 064631.
  • photobase generators include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.) can also be used. Moreover, the following compound is illustrated as a photobase generator.
  • the content of the photobase generator in the composition is preferably 0.1 to 50% by mass with respect to the total solid content of the composition.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
  • 1 type (s) or 2 or more types can be used for a photobase generator. When using 2 or more types, it is preferable that a total amount is the said range.
  • the composition of the present invention may be various additives, for example, thermal acid generators, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, as necessary, as long as the effects of the present invention are not impaired.
  • Inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like can be blended.
  • the total blending amount is preferably 3% by mass or less of the solid content of the composition.
  • the composition of the present invention may contain a thermal acid generator.
  • the thermal acid generator generates an acid by heating, promotes cyclization of the polyimide precursor, and further improves the mechanical properties of the cured film.
  • Examples of the thermal acid generator include compounds described in paragraph 0059 of JP2013-167742A.
  • 0.01 mass part or more is preferable with respect to 100 mass parts of polyimide precursors, and, as for content of a thermal acid generator, 0.1 mass part or more is more preferable.
  • the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less from the viewpoint of electrical insulation of the cured film.
  • One type of thermal acid generator may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
  • the composition of the present invention may contain a sensitizing dye.
  • a sensitizing dye absorbs specific actinic radiation and enters an electronically excited state.
  • the sensitizing dye in an electronically excited state comes into contact with a thermal base generator, a thermal radical polymerization initiator, a radical polymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur.
  • a thermal base generator, a thermal radical polymerization initiator, and a radical polymerization initiator cause a chemical change and are decomposed to generate radicals, acids, or bases. Details of the sensitizing dye can be referred to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein.
  • the content of the sensitizing dye is preferably 0.01 to 20% by mass, and preferably 0.1 to 15% by mass with respect to the total solid content of the composition of the present invention. Is more preferable, and 0.5 to 10% by mass is even more preferable.
  • a sensitizing dye may be used individually by 1 type, and may use 2 or more types together.
  • the composition of the present invention may contain a chain transfer agent.
  • the chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by the Polymer Society, 2005) pages 683-684.
  • As the chain transfer agent for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can generate hydrogen by donating hydrogen to a low activity radical to generate a radical, or after being oxidized and deprotonated.
  • thiol compounds for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
  • 2-mercaptobenzimidazoles for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.
  • the content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the composition of the present invention, and 1 to 10 parts by mass. Part is more preferable, and 1 to 5 parts by mass is more preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably in the above range.
  • surfactant various kinds of surfactants may be added to the composition of the present invention from the viewpoint of further improving applicability.
  • various types of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • the following surfactants are also preferable.
  • the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0%, based on the total solid content of the composition of the present invention. 0.005 to 1.0 mass%. Only one surfactant may be used, or two or more surfactants may be used. When there are two or more surfactants, the total is preferably in the above range.
  • the composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and is unevenly distributed on the surface of the composition in the course of drying after coating. May be.
  • the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the composition of the present invention. Only one higher fatty acid derivative may be used, or two or more higher fatty acid derivatives may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
  • the water content of the composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of the coated surface properties.
  • the metal content of the composition of the present invention is preferably less than 5 ppm by weight (parts per million), more preferably less than 1 ppm by weight, and particularly preferably less than 0.5 ppm by weight from the viewpoint of insulation.
  • the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably in the above range.
  • a raw material having a low metal content is selected as a raw material constituting the composition of the present invention.
  • the raw material to be filtered may be filtered, or the inside of the apparatus may be lined with polytetrafluoroethylene or the like, and distillation may be performed under a condition in which contamination is suppressed as much as possible.
  • the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and particularly preferably less than 200 ppm by mass from the viewpoint of wiring corrosion.
  • a halogen ion is less than 5 mass ppm, More preferably, it is less than 1 mass ppm, More preferably, it is less than 0.5 mass ppm.
  • the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions is preferably in the above range.
  • the container for the composition of the present invention a conventionally known container can be used.
  • the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and the 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.
  • the composition of the present invention can be prepared by mixing the above components.
  • the mixing method is not particularly limited, and can be performed by a conventionally known method.
  • the filter pore size is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel.
  • filters having different pore diameters and / or materials may be used in combination.
  • Various materials may be filtered a plurality of times.
  • circulation filtration may be used.
  • you may pressurize and filter.
  • the pressure applied is preferably 0.05 MPa or more and 0.3 MPa or less.
  • impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
  • the adsorbent a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
  • the cured film of the present invention is formed by curing the composition of the present invention.
  • the thickness of the cured film of the present invention can be, for example, 0.5 ⁇ m or more, and can be 1 ⁇ m or more. Moreover, as an upper limit, it can be set to 100 micrometers or less, and can also be set to 30 micrometers or less.
  • a laminate may be obtained by laminating two or more cured films of the present invention.
  • the laminate having two or more cured films of the present invention preferably has a metal layer between the cured films.
  • Such a metal layer is preferably used as a metal wiring such as a rewiring layer.
  • Fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, and the like. Particularly, since the resolution is good, it can be preferably used for an interlayer insulating film for a rewiring layer in a three-dimensional mounting device.
  • the cured film in the present invention can also be used for electronic photoresists, galvanic resists, galvanic resists, etching resists, solder top resists, and the like.
  • the cured film of the present invention can also be used for the production of printing plates such as offset printing plates or screen printing plates, for use in etching molded parts, and for the production of protective lacquers and dielectric layers in electronics, particularly microelectronics.
  • the method for producing a cured film of the present invention includes using the composition of the present invention.
  • the photosensitive resin composition of the present invention is applied to a substrate to form a layer, a photosensitive resin composition layer forming step, an exposure step of exposing the photosensitive resin composition layer, and the exposed photosensitivity.
  • the manufacturing method of a cured film which has the image development process process which performs image development processing with respect to a conductive resin composition layer (resin layer) is mentioned.
  • the photosensitive resin composition of the present invention is preferably used when performing negative development.
  • the manufacturing method of the laminated body of this invention includes the manufacturing method of the cured film of this invention.
  • the photosensitive resin composition layer forming step, the exposure step, and the development processing step are performed again. It is preferable to carry out in order.
  • the photosensitive resin composition layer forming step, the exposure step, and the development processing step are preferably performed 2 to 5 times in the above order (that is, 3 to 6 times in total).
  • a laminated body can be obtained by laminating a cured film.
  • the manufacturing method of the laminated body of this invention includes the photosensitive resin composition layer formation process which applies the photosensitive resin composition to a board
  • the type of the substrate can be appropriately determined according to the application, but a semiconductor production substrate such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film , Reflective films, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, plasma display panel (PDP) electrode plates, etc. are not particularly limited.
  • a semiconductor manufacturing substrate is particularly preferable, and a silicon substrate is more preferable.
  • a resin layer or a metal layer becomes a board
  • coating is preferable. Specifically, as a means to apply, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, And an inkjet method.
  • a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferable.
  • a resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method.
  • the coating method can be appropriately selected depending on the shape of the substrate, and a spin coat method, a spray coat method, an ink jet method or the like is preferable for a circular substrate such as a wafer, and a slit coat method, a spray coat method, an ink jet method or the like for a rectangular substrate.
  • the method is preferred.
  • the spin coating method for example, it can be applied at a rotational speed of 500 to 2000 rpm for about 10 seconds to 1 minute.
  • the manufacturing method of the laminated body of this invention may include the process of drying in order to remove a solvent, after forming the photosensitive resin composition layer.
  • a preferred drying temperature is 50 to 150 ° C, more preferably 70 to 130 ° C, and further preferably 90 to 110 ° C.
  • Examples of the drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
  • the manufacturing method of the laminated body of this invention includes the exposure process which exposes the said photosensitive resin composition layer.
  • the amount of exposure is not particularly defined as long as the photosensitive resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and to irradiate 200 to 8000 mJ / cm 2 . It is more preferable.
  • the exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, and preferably 240 to 550 nm.
  • the manufacturing method of the laminated body of this invention includes the image development processing process which performs negative development processing with respect to the exposed photosensitive resin composition layer.
  • the development method is not particularly limited as long as a desired pattern can be formed.
  • development methods such as paddle, spray, immersion, and ultrasonic wave can be employed.
  • Development is performed using a developer.
  • the developer can be used without particular limitation as long as the unexposed part (non-exposed part) is removed.
  • the developer preferably contains an organic solvent.
  • organic solvent examples include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
  • esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -butyrolactone.
  • alkyl oxyacetate alkyl eg, methyl oxyoxyacetate, alkyl oxyacetate ethyl, alkyl oxyacetate butyl (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate), alkyl esters of 3-alkyloxypropionic acid (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • the development time is preferably 10 seconds to 5 minutes.
  • the temperature at the time of development is not particularly defined, but it can usually be carried out at 20 to 40 ° C.
  • rinsing may be further performed.
  • the rinsing is preferably performed with a solvent different from the developer. For example, it can rinse using the solvent contained in the photosensitive resin composition.
  • the rinse time is preferably 5 seconds to 1 minute.
  • the manufacturing method of the laminated body of this invention includes a heating process.
  • the heating step the cyclization reaction of the polyimide precursor proceeds.
  • the composition of this invention contains a radically polymerizable compound, hardening etc. of the unreacted radically polymerizable compound also advance.
  • the heating temperature is preferably 50 to 450 ° C, more preferably 140 to 400 ° C, and further preferably 160 to 350 ° C. Heating is preferably performed at a rate of temperature increase of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
  • the temperature at the start of heating is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and further preferably 25 ° C to 120 ° C.
  • the temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when the photosensitive resin composition is applied onto a substrate and then dried, the temperature after drying is, for example, gradually from the boiling point of the solvent contained in the photosensitive resin composition (30 to 200 ° C.).
  • the heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and particularly preferably 30 to 240 minutes.
  • the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between the layers of the cured film.
  • the reason is not certain, it is considered that the ethynyl group of the polyimide precursor between layers proceeds with a crosslinking reaction at this temperature.
  • Heating may be performed in stages. As an example, before raising the temperature from 25 ° C. to 180 ° C. at 3 ° C./min, placing at 180 ° C. for 60 minutes, raising the temperature from 180 ° C. to 200 ° C. at 2 ° C./min, and placing at 200 ° C. for 120 minutes. Processing steps may be performed.
  • the heating temperature as the pretreatment step is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and further preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the characteristics of the film.
  • the pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes.
  • the pretreatment may be performed in two or more steps.
  • the pretreatment step 1 may be performed in the range of 100 to 150 ° C.
  • the pretreatment step 2 may be performed in the range of 150 to 200 ° C. Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
  • the heating step is preferably performed in a low oxygen concentration atmosphere by flowing an inert gas such as nitrogen, helium, or argon in order to prevent decomposition of the polyimide precursor or the like.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
  • the manufacturing method of the laminated body of this invention includes the metal layer formation process which forms a metal layer on the surface of the photosensitive resin composition layer after image development processing.
  • the metal layer There are no particular limitations on the metal layer, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferable, and copper is more preferable. Further preferred.
  • the method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used.
  • the thickness of the metal layer is preferably 0.1 to 50 ⁇ m, more preferably 1 to 10 ⁇ m at the thickest part.
  • the production method of the present invention preferably further includes a lamination step.
  • a lamination process is a series of processes including performing the said photosensitive resin composition layer formation process, the said exposure process, and the said image development process again in the said order again. It goes without saying that the laminating step may further include the drying step and the heating step.
  • a surface activation treatment process may be further performed after the exposure process or after the metal layer formation process.
  • An example of the surface activation treatment is plasma treatment.
  • the lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
  • the resin layer / metal layer / resin layer / metal layer / resin layer / metal layer has a resin layer structure of 3 to 7 layers, more preferably 3 to 5 layers. That is, in the present invention, in particular, after the metal layer is provided, the photosensitive resin composition layer forming step, the exposure step, and the development processing step are performed in the above order so as to cover the metal layer. Is preferred.
  • the photosensitive resin composition layer (resin) and the metal layer forming step By alternately performing the laminating step of laminating the photosensitive resin composition layer (resin) and the metal layer forming step, the photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated.
  • the present invention also discloses a semiconductor device including the cured film or laminate of the present invention.
  • An embodiment of a semiconductor device in which the composition of the present invention is used for forming an interlayer insulating film for a rewiring layer will be described.
  • a semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a stacked body 101 in which a plurality of semiconductor elements (semiconductor chips) 101 a to 101 d are stacked is arranged on a wiring board 120.
  • the number of stacked semiconductor elements (semiconductor chips) is not particularly limited. It may be a layer, 8 layers, 16 layers, 32 layers, or the like. Moreover, one layer may be sufficient.
  • the plurality of semiconductor elements 101a to 101d are each made of a semiconductor wafer such as a silicon substrate.
  • the uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof.
  • the semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) provided integrally with the through electrodes are provided on both surfaces of each semiconductor element.
  • the stacked body 101 has a structure in which a semiconductor element 101a having no through electrode and flip-chip connection of semiconductor elements 101b to 101d having through electrodes 102b to 102d are connected. That is, the electrode pad of the semiconductor element 101a having no through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having the adjacent through electrode 102b are connected by the metal bump 103a such as a solder bump, The connection pad on the other side of the semiconductor element 101b having the electrode 102b is connected to the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the adjacent through electrode 102c by a metal bump 103b such as a solder bump.
  • connection pad on the other side of the semiconductor element 101c having the through electrode 102c is connected to the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the adjacent through electrode 102d by the metal bump 103c such as a solder bump.
  • An underfill layer 110 is formed in the gaps between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are stacked via the underfill layer 110.
  • the laminated body 101 is laminated on the wiring board 120.
  • the wiring substrate 120 for example, a multilayer wiring substrate using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used.
  • the wiring board 120 to which the resin board is applied include a multilayer copper-clad laminate (multilayer printed wiring board).
  • a surface electrode 120 a is provided on one surface of the wiring board 120.
  • An insulating film 115 on which a rewiring layer 105 is formed is disposed between the wiring substrate 120 and the stacked body 101, and the wiring substrate 120 and the stacked body 101 are electrically connected via the rewiring layer 105. It is connected.
  • the insulating film 115 is formed using the composition of the present invention. That is, one end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the rewiring layer 105 side through a metal bump 103d such as a solder bump.
  • the other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
  • An underfill layer 110 a is formed between the insulating film 115 and the stacked body 101.
  • an underfill layer 110 b is formed between the insulating film 115 and the wiring substrate 120.
  • the polyimide precursor was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at 45 ° C. under reduced pressure for 3 days to obtain a polyimide precursor (A-1).
  • the weight average molecular weight (Mw) as a polystyrene conversion value was 25,000.
  • the molar ratio of the following repeating units is 80:20.
  • the weight average molecular weight (Mw) was a polystyrene conversion value according to gel permeation chromatography (GPC measurement).
  • HLC-8220 manufactured by Tosoh Corporation
  • guard column HZ-L TSKgel Super HZM-M
  • TSKgel Super HZ4000 TSKgel Super HZ3000
  • TSKgel Super HZ2000 manufactured by Tosoh Corp.
  • THF tetrahydrofuran
  • a UV ray (ultraviolet) wavelength 254 nm detector was used.
  • the obtained polyimide precursor was dried at 45 ° C. under reduced pressure for 3 days to obtain a polyimide precursor (A-2).
  • the weight average molecular weight (Mw) as a polystyrene conversion value was 20,000.
  • the molar ratio of the following repeating units is 80:20.
  • the obtained polyimide precursor was dried at 45 ° C. under reduced pressure for 3 days to obtain a polyimide precursor (A-3).
  • Mw weight average molecular weight
  • the molar ratio of the following repeating units is 80:20.
  • Synthesis Example 5 [Polyimide from 4,4′-oxydiphthalic dianhydride, m-tolidine, N- (4′-ethynylphenyl) -3,5-diaminobenzamide (compound (1) -1) and 2-hydroxyethyl methacrylate] Synthesis of Precursor (A-5: Polyimide Precursor Having Radical Polymerizable Group)] The same operation as in Synthesis Example 1 was performed except that 9.403 g (46.96 mmol) of 4,4′-oxydianiline in Synthesis Example 1 was changed to 9.970 g (46.96 mmol) of m-tolidine. And a polyimide precursor (A-5) was obtained.
  • a polyimide precursor (A-8) was obtained in the same manner as in Synthesis Example 1, except that it was changed to -3- (3,5-diaminophenyl) urea.
  • Mw weight average molecular weight
  • the molar ratio of the following repeating units (left repeating unit: right repeating unit) is 80:20.
  • reaction mixture was then cooled to ⁇ 10 ° C. and 16.12 g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at ⁇ 10 ⁇ 4 ° C. After dilution with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution of 11.75 g (58.70 mmol) of 4,4′-oxydianiline dissolved in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred overnight at room temperature.
  • the polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm.
  • the polyimide precursor was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again.
  • the obtained polyimide precursor was dried at 45 ° C. under reduced pressure for 3 days to obtain a polyimide precursor (R-1) for comparative example.
  • Mw weight average molecular weight as a polystyrene conversion value was 25,000.
  • Polyimide precursor parts by mass of the polyimide precursor described in Table 1 or 2 as shown in Table 1 or Table 2
  • Photoradical polymerization initiator Table 1 or Table as the radical photopolymerization initiator described in Table 1 or 2 2 parts by mass of radically polymerizable compound: the radically polymerizable compound described in Table 1 or Table 2 is the part by weight of Table 1 or Table 2
  • Other components other than the above-mentioned components in Table 1 or Table 2 Mass parts given in Table 1 or 2
  • B-1 IRGACURE OXE 01 (manufactured by BASF)
  • B-2 IRGACURE OXE 02 (manufactured by BASF)
  • B-3 IRGACURE 369 (BASF)
  • C-1 Dipentaerythritol hexa (meth) acrylate, A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • C-2 SR-209 (Sartomer)
  • C-3 Dipentaerythritol tetraacrylate, A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • H Solvent H-1: ⁇ -butyrolactone (manufactured by Sanwa Oil Chemical Co., Ltd.)
  • H-2 Dimethyl sulfoxide (Wako Pure Chemical Industries, Ltd.)
  • H-3 N-methyl-2-pyrrolidone (manufactured by Ashland)
  • the photosensitive resin composition layer on the silicon wafer was exposed on the entire surface with an exposure energy of 500 mJ / cm 2 at an exposure wavelength of 365 nm using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin The layer was heated at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, and after reaching 250 ° C., the layer was heated for 3 hours.
  • the cured resin layer was immersed in a 4.9% by mass hydrofluoric acid solution, and the resin layer was peeled from the silicon wafer to obtain a resin layer (cured film).
  • the elongation at break of the resin layer (cured film) obtained above was determined as follows. First, the peeled resin layer (cured film) is cut into a film having a width of 10 mm and a length of 50 mm, and the length (length) of the film as a crosshead speed of 300 mm / min using a tensile tester (Tensilon). With respect to the direction and the width direction, the elongation at break was measured according to JIS-K6251 in an environment of 25 ° C. and 65% relative humidity (RH). The elongation at break in the longitudinal direction and the width direction was measured 5 times each. The average value of the elongation at break in the longitudinal direction and the width direction was defined as the elongation at break. A: It exceeded 80%. B: More than 70% and 80% or less. C: It exceeded 70% and was 70% or less. D: More than 50% and 60% or less. E: It was 50% or less.
  • Each photosensitive resin composition was pressure filtered through a filter having a pore width of 0.8 ⁇ m at a pressure of 0.3 MPa, and then the photosensitive resin composition was applied onto a silicon wafer by spin coating.
  • the silicon wafer coated with the photosensitive resin composition layer was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a thickness of 10 ⁇ m on the silicon wafer.
  • the photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C).
  • the exposure is performed with i-line, using a line-and-space photomask in 1 ⁇ m increments from 5 ⁇ m to 25 ⁇ m at each exposure energy of 200, 300, 400, 500, 600, 700, 800 mJ / cm 2 at a wavelength of 365 nm. Then, exposure was performed to obtain a resin layer.
  • the resin layer obtained above was negatively developed with cyclopentanone for 60 seconds.
  • the change in the line width is small with respect to the change in exposure energy, it indicates that the exposure latitude is wide, which is a preferable result.
  • the measurement limit is 5 ⁇ m.
  • A It was 5 to 8 ⁇ m.
  • B It was 10 micrometers or less exceeding 8 micrometers.
  • C It was 15 micrometers or less exceeding 10 micrometers.
  • D It was 20 micrometers or less exceeding 15 micrometers.
  • E It exceeded 20 micrometers.
  • F A pattern having a line width with sharp edges could not be obtained.
  • the photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ / cm 2 at an exposure wavelength of 365 nm using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer ( The resin layer) was developed with cyclopentanone for 60 seconds to form holes with a diameter of 10 ⁇ m.
  • the temperature was increased at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, and after reaching 250 ° C., heating was performed for 3 hours.
  • the photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was subjected to cyclopenta Development was carried out for 60 seconds without forming holes having a diameter of 10 ⁇ m.
  • the temperature was increased at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, and after reaching 250 ° C., heating was performed for 3 hours.
  • a thin copper layer (metal layer) having a thickness of 2 ⁇ m was formed on a part of the surface of the photosensitive resin composition layer by vapor deposition so as to cover the hole portion.
  • the same kind of photosensitive resin composition is used again on the surfaces of the metal layer and the photosensitive resin composition layer, and the patterned film is heated for 3 hours from the filtration of the photosensitive resin composition in the same manner as described above.
  • the procedure up to was performed again to produce a laminate (3) composed of resin layer / metal layer / resin layer.
  • a thin copper layer (metal layer) and a resin layer are alternately produced on the surface of the laminate (3) by the same method as that for the laminate (3), and resin layer / metal layer / resin layer / metal layer A laminate (4) composed of / resin layer / metal layer / resin layer was produced.
  • Example 100 The photosensitive resin composition of Example 1 was subjected to pressure filtration at a pressure of 0.3 MPa through a filter having a pore width of 0.8 ⁇ m, and then spin coated on a substrate on which a copper thin layer was formed ( 3500 rpm, 30 seconds).
  • the photosensitive resin composition applied to the substrate was dried at 100 ° C. for 5 minutes, and then exposed using an aligner (Karl-Suss MA150). The exposure was performed by irradiating light with a wavelength of 365 nm from a high-pressure mercury lamp. After exposure, the image was developed with cyclopentanone for 75 seconds. Subsequently, it heated at 180 degreeC for 20 minutes.

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  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

Provided are the following: a photosensitive resin composition with which a pattern can be formed by means of photo-radical polymerization, and with which a cured film exhibiting high breaking elongation cane be obtained; a cured film; a laminate; a method for producing a cured film; a method for producing a laminate; and a semiconductor device. The photosensitive resin composition contains: a polyimide precursor containing a repeating unit represented by formula (1); and a photo-radical polymerization initiator. In formula (1), A1 and A2 each denote an oxygen atom or NH, R111 denotes a divalent organic group, R115 denotes a tetravalent organic group, and R113 and R114 each denote a hydrogen atom or a monovalent organic group. A group represented by formula (2) is bonded to a terminal of at least one of R111, R113, R114 and R115. In formula (2), R1 denotes a hydrogen atom or a substituent group, and * denotes the bonding position to R111, R113, R114 or R115.

Description

感光性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、積層体の製造方法および半導体デバイスPhotosensitive resin composition, cured film, laminate, method for producing cured film, method for producing laminate, and semiconductor device
　本発明は、感光性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、積層体の製造方法および半導体デバイスに関する。 The present invention relates to a photosensitive resin composition, a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, and a semiconductor device.
　従来から、半導体素子の保護膜および層間絶縁膜には優れた耐熱性と電気特性、機械特性等を併せ持つポリイミド樹脂が用いられている。しかし、近年半導体素子の高集積化、大型化が進む中、封止樹脂パッケージの薄型化小型化の要求がありＬＯＣ（リード・オン・チップ）や半田リフロー法を用いた表面実装などの方式が取られてきている。 Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, mechanical characteristics and the like has been used for a protective film and an interlayer insulating film of a semiconductor element. However, in recent years, as semiconductor devices have been highly integrated and increased in size, there has been a demand for thinner and smaller sealing resin packages, and methods such as surface mounting using LOC (lead-on-chip) or solder reflow methods are available. Has been taken.
　このような半導体素子の作製には、ポリイミド樹脂自身に感光性を付与した感光性ポリイミド樹脂組成物が用いられてきている。感光性ポリイミド樹脂組成物を用いることにより、パターン形成工程が簡略化できるためである。例えば、特許文献１には、所定の構造を有するポリイミド前駆体と、（ｂ）活性光線照射によってラジカルを発生する化合物と、（ｃ）下記一般式（４ａ）または（４ｂ）で表される化合物と、（ｄ）溶剤とを含む樹脂組成物が開示されている。
Figure JPOXMLDOC01-appb-C000009
 （一般式（４ａ）中、ｎは３以下の整数である。一般式（４ｂ）中、Ｒ１０１およびＲ１０２は、各々独立に水素原子又は１価の基である。ｍは９以下の整数である。） For the production of such a semiconductor element, a photosensitive polyimide resin composition obtained by imparting photosensitivity to a polyimide resin itself has been used. This is because the pattern forming process can be simplified by using the photosensitive polyimide resin composition. For example, Patent Document 1 discloses a polyimide precursor having a predetermined structure, (b) a compound that generates radicals upon irradiation with active light, and (c) a compound represented by the following general formula (4a) or (4b). And a resin composition containing (d) a solvent.
Figure JPOXMLDOC01-appb-C000009
 (In General Formula (4a), n is an integer of 3 or less. In General Formula (4b), R 101 and R 102 are each independently a hydrogen atom or a monovalent group. M is an integer of 9 or less. .)
　一方、特許文献２には、エチニル基を有する化合物とエポキシ化合物を含有する樹脂組成物が開示されている。 On the other hand, Patent Document 2 discloses a resin composition containing a compound having an ethynyl group and an epoxy compound.
特開２０１４－２０１６９５号公報JP 2014-201695 A 特開２０１０－０７７１９２号公報JP 2010-079192 A
　上記特許文献１を検討したところ、特許文献１に記載の樹脂組成物を硬化してなる硬化膜は、破断伸び率が不十分であることが分かった。また、特許文献２には、ポリイミド前駆体を光ラジカル重合することについて記載がなく、パターン形成ができない。
　本発明は、上記課題を解決することを目的とするものであって、光ラジカル重合によりパターンを形成できる感光性樹脂組成物であって、得られる硬化膜の破断伸び率が高い感光性樹脂組成物、ならびに、硬化膜、積層体、硬化膜の製造方法、積層体の製造方法および半導体デバイスを提供することを目的とする。 When the said patent document 1 was examined, it turned out that the fracture | rupture elongation rate of the cured film formed by hardening | curing the resin composition of patent document 1 is inadequate. Patent Document 2 does not describe photoradical polymerization of a polyimide precursor and cannot form a pattern.
The present invention aims to solve the above-mentioned problems, and is a photosensitive resin composition capable of forming a pattern by photoradical polymerization, and the resulting cured resin has a high elongation at break. And a cured film, a laminate, a method for producing a cured film, a method for producing a laminate, and a semiconductor device.
　上記課題のもと、本発明者が鋭意検討を行った結果、ラジカル重合によって硬化する系において、後述する式（２）で表される炭素炭素三重結合を有する基を有するポリイミド前駆体を用いることにより、パターン形成が可能であり、得られる硬化膜の破断伸び率が高い感光性樹脂組成物を提供できることを見出した。
　具体的には、下記手段＜１＞により、好ましくは＜２＞～＜２５＞により、上記課題は解決された。
＜１＞下記式（１）で表される繰り返し単位を含むポリイミド前駆体、および、光ラジカル重合開始剤を含む感光性樹脂組成物；
式（１）
Figure JPOXMLDOC01-appb-C000010
 式（１）中、Ａ１およびＡ２は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ１１１は、２価の有機基を表し、Ｒ１１５は、４価の有機基を表し、Ｒ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表す；但し、Ｒ１１１、Ｒ１１３、Ｒ１１４およびＲ１１５の少なくとも１つの末端には下記式（２）で表される基が結合している；
式（２）
Figure JPOXMLDOC01-appb-C000011
 式（２）において、Ｒ１は、水素原子または置換基を表し、＊はＲ１１１、Ｒ１１３、Ｒ１１４またはＲ１１５との結合部位である。
＜２＞上記ポリイミド前駆体が下記式（３）で表される化合物由来の構造を有する、＜１＞に記載の感光性樹脂組成物；
式（３）
Figure JPOXMLDOC01-appb-C000012
 式（３）中、Ａは（ｐ＋ｑ）価の基を表す；Ｒ１は水素原子または置換基を表す；ｐは１～５の整数を表し、ｑは２以上の整数を表す。
＜３＞上記ポリイミド前駆体が下記式（３ａ）で表される化合物由来の構造を有する、＜１＞に記載の感光性樹脂組成物；
式（３ａ）
Figure JPOXMLDOC01-appb-C000013
 式（３ａ）中、Ａ０は（ｌ＋ｍ）価の基を表す；Ａ１は単結合または（ｎ＋１）価の基を表す；Ｒ１は水素原子または置換基を表す；Ａｒは（ａ＋１）価の芳香族炭化水素基または芳香族複素環基を表す；ａ、ｌ、ｍおよびｎは、それぞれ独立に１～５の整数を表す；ただし、ｍおよびｎの少なくとも一方は２以上の整数を表す。
＜４＞上記ポリイミド前駆体が下記式（３ｂ）で表される化合物由来の構造を有する、＜１＞に記載の感光性樹脂組成物；
式（３ｂ）
Figure JPOXMLDOC01-appb-C000014
 式（３ｂ）中、Ａ０は（ｌ＋ｍ）価の基を表す；Ｒ１は水素原子または置換基を表す；ａ、ｌ、ｍおよびｎはそれぞれ独立に１～５の整数を表す；ただし、ｍおよびｎの少なくとも一方は２以上の整数を表す。
＜５＞上記式（１）中、少なくともＲ１１１の末端に式（２）で表される基が結合している、＜１＞～＜４＞のいずれか１つに記載の感光性樹脂組成物。
＜６＞上記ポリイミド前駆体が、さらに、式（１－１）で表される繰り返し単位を含む、＜１＞～＜５＞のいずれか１つに記載の感光性樹脂組成物；
式（１－１）
Figure JPOXMLDOC01-appb-C000015
  式（１－１）中、Ａ１およびＡ２は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ１１１は、２価の有機基を表し、Ｒ１１５は、４価の有機基を表し、Ｒ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表す；但し、式（１－１）で表される繰り返し単位は上記式（２）で表される基を含まない。
＜７＞上記式（１－１）におけるＲ１１１は、－Ａｒ－Ｌ－Ａｒ－で表される、＜６＞に記載の感光性樹脂組成物；但し、Ａｒは、それぞれ独立に、芳香族炭化水素基であり、Ｌは、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ２－または－ＮＨＣＯ－、ならびに、上記の２つ以上の組み合わせからなる基である。
＜８＞上記式（１－１）におけるＲ１１１は、下記式（５１）または式（６１）で表される基である、＜６＞に記載の感光性樹脂組成物；
式（５１）
Figure JPOXMLDOC01-appb-C000016
 式（５１）中、Ｒ１０～Ｒ１７は、それぞれ独立に水素原子、フッ素原子または１価の有機基であり、Ｒ１０～Ｒ１７の少なくとも１つはフッ素原子、メチル基、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である；
式（６１）
Figure JPOXMLDOC01-appb-C000017
 式（６１）中、Ｒ１８およびＲ１９は、それぞれ独立にフッ素原子、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。
＜９＞上記Ｒ１１３およびＲ１１４の少なくとも一方が、ラジカル重合性基を含む、＜１＞～＜８＞のいずれか１つに記載の感光性樹脂組成物。
＜１０＞上記Ｒ１１５は、芳香環を含む４価の有機基である、＜１＞～＜９＞のいずれか１つに記載の感光性樹脂組成物。
＜１１＞さらに、ラジカル重合性化合物を含む、＜１＞～＜１０＞のいずれか１つに記載の感光性樹脂組成物。
＜１２＞さらに、塩基発生剤を含む、＜１＞～＜１１＞のいずれか１つに記載の感光性樹脂組成物。
＜１３＞さらに、溶剤を含む、＜１＞～＜１２＞のいずれか１つに記載の感光性樹脂組成物。
＜１４＞ネガ型現像に用いられる、＜１＞～＜１３＞のいずれか１つに記載の感光性樹脂組成物。
＜１５＞再配線層用層間絶縁膜の形成に用いられる、＜１＞～＜１４＞のいずれか１つに記載の感光性樹脂組成物。
＜１６＞＜１＞～＜１５＞のいずれか１つに記載の感光性樹脂組成物を硬化してなる硬化膜。
＜１７＞＜１６＞に記載の硬化膜を２層以上有する、積層体。
＜１８＞上記硬化膜の間に、金属層を有する、＜１７＞に記載の積層体。
＜１９＞＜１＞～＜１５＞のいずれか１つに記載の感光性樹脂組成物を用いることを含む、硬化膜の製造方法。
＜２０＞上記感光性樹脂組成物を基板に適用して層状にする、感光性樹脂組成物層形成工程と、上記感光性樹脂組成物層を露光する露光工程と、上記露光された感光性樹脂組成物層に対して、現像処理を行う現像処理工程とを有する、＜１９＞に記載の硬化膜の製造方法。
＜２１＞上記現像処理がネガ型現像処理である、＜２０＞に記載の硬化膜の製造方法。
＜２２＞上記現像処理工程後に、現像された感光性樹脂組成物層を５０～４５０℃の温度で加熱する工程を含む、＜２０＞または＜２１＞に記載の硬化膜の製造方法。
＜２３＞上記硬化膜の膜厚が、１～３０μｍである、＜１９＞～＜２２＞のいずれか１つに記載の硬化膜の製造方法。
＜２４＞＜１９＞～＜２３＞のいずれか１つに記載の硬化膜の製造方法に従って、硬化膜を形成後、さらに、再度、上記感光性樹脂組成物層形成工程、上記露光工程、および、上記現像処理工程を、上記順に、２～５回行う、積層体の製造方法。
＜２５＞＜１６＞に記載の硬化膜、あるいは、＜１７＞または＜１８＞に記載の積層体を有する半導体デバイス。 As a result of intensive studies by the present inventor based on the above problems, a polyimide precursor having a group having a carbon-carbon triple bond represented by the formula (2) described later is used in a system that is cured by radical polymerization. Thus, it was found that a photosensitive resin composition capable of forming a pattern and having a high elongation at break of a cured film obtained can be provided.
Specifically, the above problem has been solved by the following means <1>, preferably <2> to <25>.
<1> a photosensitive resin composition containing a polyimide precursor containing a repeating unit represented by the following formula (1), and a radical photopolymerization initiator;
Formula (1)
Figure JPOXMLDOC01-appb-C000010
 In formula (1), A 1 and A 2 each independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group; provided that at least one terminal of R 111 , R 113 , R 114 and R 115 has a group represented by the following formula (2): Bound;
Formula (2)
Figure JPOXMLDOC01-appb-C000011
 In Formula (2), R 1 represents a hydrogen atom or a substituent, and * is a binding site with R 111 , R 113 , R 114 or R 115 .
<2> The photosensitive resin composition according to <1>, wherein the polyimide precursor has a structure derived from a compound represented by the following formula (3);
Formula (3)
Figure JPOXMLDOC01-appb-C000012
 In formula (3), A represents a (p + q) -valent group; R 1 represents a hydrogen atom or a substituent; p represents an integer of 1 to 5, and q represents an integer of 2 or more.
<3> The photosensitive resin composition according to <1>, wherein the polyimide precursor has a structure derived from a compound represented by the following formula (3a);
Formula (3a)
Figure JPOXMLDOC01-appb-C000013
 In formula (3a), A 0 represents a (l + m) -valent group; A 1 represents a single bond or a (n + 1) -valent group; R 1 represents a hydrogen atom or a substituent; Ar represents an (a + 1) -valent group A, l, m and n each independently represents an integer of 1 to 5; provided that at least one of m and n represents an integer of 2 or more. .
<4> The photosensitive resin composition according to <1>, wherein the polyimide precursor has a structure derived from a compound represented by the following formula (3b);
Formula (3b)
Figure JPOXMLDOC01-appb-C000014
 In formula (3b), A 0 represents a (l + m) -valent group; R 1 represents a hydrogen atom or a substituent; a, l, m and n each independently represents an integer of 1 to 5; At least one of m and n represents an integer of 2 or more.
<5> in the formula (1), at least terminus group represented by the formula (2) by R 111 are attached, <1> to the photosensitive resin composition according to any one of <4> object.
<6> The photosensitive resin composition according to any one of <1> to <5>, wherein the polyimide precursor further includes a repeating unit represented by the formula (1-1);
Formula (1-1)
Figure JPOXMLDOC01-appb-C000015
 In formula (1-1), A 1 and A 2 each independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group; provided that the repeating unit represented by formula (1-1) does not include the group represented by formula (2).
<7> The photosensitive resin composition according to <6>, wherein R 111 in the above formula (1-1) is represented by —Ar—L—Ar—, wherein Ar is independently an aromatic group. A hydrocarbon group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO 2 — or —NHCO—. And a group consisting of a combination of two or more of the above.
<8> The photosensitive resin composition according to <6>, wherein R 111 in the above formula (1-1) is a group represented by the following formula (51) or formula (61);
Formula (51)
Figure JPOXMLDOC01-appb-C000016
 In formula (51), R 10 to R 17 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 10 to R 17 is a fluorine atom, a methyl group, a fluoromethyl group, A difluoromethyl group or a trifluoromethyl group;
Formula (61)
Figure JPOXMLDOC01-appb-C000017
 In formula (61), R 18 and R 19 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.
<9> The photosensitive resin composition according to any one of <1> to <8>, wherein at least one of R 113 and R 114 includes a radical polymerizable group.
<10> The photosensitive resin composition according to any one of <1> to <9>, wherein R 115 is a tetravalent organic group containing an aromatic ring.
<11> The photosensitive resin composition according to any one of <1> to <10>, further comprising a radical polymerizable compound.
<12> The photosensitive resin composition according to any one of <1> to <11>, further comprising a base generator.
<13> The photosensitive resin composition according to any one of <1> to <12>, further comprising a solvent.
<14> The photosensitive resin composition according to any one of <1> to <13>, which is used for negative development.
<15> The photosensitive resin composition according to any one of <1> to <14>, which is used for forming an interlayer insulating film for a rewiring layer.
<16> A cured film obtained by curing the photosensitive resin composition according to any one of <1> to <15>.
<17> A laminate having two or more cured films according to <16>.
<18> The laminate according to <17>, having a metal layer between the cured films.
<19> A method for producing a cured film, comprising using the photosensitive resin composition according to any one of <1> to <15>.
<20> A photosensitive resin composition layer forming step of applying the photosensitive resin composition to a substrate to form a layer, an exposure step of exposing the photosensitive resin composition layer, and the exposed photosensitive resin. The manufacturing method of the cured film as described in <19> which has the image development process process which performs image development processing with respect to a composition layer.
<21> The method for producing a cured film according to <20>, wherein the development treatment is a negative development treatment.
<22> The method for producing a cured film according to <20> or <21>, comprising a step of heating the developed photosensitive resin composition layer at a temperature of 50 to 450 ° C. after the development processing step.
<23> The method for producing a cured film according to any one of <19> to <22>, wherein the cured film has a thickness of 1 to 30 μm.
<24> After forming the cured film according to the method for producing a cured film according to any one of <19> to <23>, the photosensitive resin composition layer forming step, the exposure step, and A method for producing a laminate, wherein the development processing step is performed 2 to 5 times in the order described above.
<25> A semiconductor device having the cured film according to <16> or the laminate according to <17> or <18>.
　本発明により、光ラジカル重合によりパターンを形成できる感光性樹脂組成物であって、得られる硬化膜の破断伸び率が高い感光性樹脂組成物、ならびに、硬化膜、積層体、硬化膜の製造方法、積層体の製造方法および半導体デバイスを提供可能になった。 According to the present invention, a photosensitive resin composition capable of forming a pattern by radical photopolymerization, wherein the resulting cured film has a high elongation at break, and a cured film, a laminate, and a method for producing the cured film It has become possible to provide a method for manufacturing a laminate and a semiconductor device.
半導体デバイスの一実施形態の構成を示す概略図である。It is the schematic which shows the structure of one Embodiment of a semiconductor device.
　以下に記載する本発明における構成要素の説明は、本発明の代表的な実施形態に基づいてなされることがあるが、本発明はそのような実施形態に限定されるものではない。
　本明細書における基（原子団）の表記に於いて、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基（無置換アルキル基）のみならず、置換基を有するアルキル基（置換アルキル基）をも包含するものである。
　本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ光）、Ｘ線、電子線等の活性光線または放射線が挙げられる。
　本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
　本明細書において、「（メタ）アクリレート」は、「アクリレート」および「メタクリレート」の双方、または、いずれかを表し、「（メタ）アクリル」は、「アクリル」および「メタクリル」の双方、または、いずれかを表し、「（メタ）アクリロイル」は、「アクリロイル」および「メタクリロイル」の双方、または、いずれかを表す。
　本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
　本明細書において、固形分濃度とは、組成物の総質量に対する、溶剤を除く他の成分の質量百分率である。また、固形分濃度は、特に述べない限り２５℃における濃度をいう。
　本明細書において、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、特に述べない限り、ゲル浸透クロマトグラフィ（ＧＰＣ測定）に従い、ポリスチレン換算値として定義される。本明細書において、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、例えば、ＨＬＣ－８２２０（東ソー（株）製）を用い、カラムとしてガードカラムＨＺ－Ｌ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺＭ－Ｍ、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ４０００、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ３０００、ＴＳＫｇｅｌ　Ｓｕｐｅｒ　ＨＺ２０００（東ソー（株）製）を用いることによって求めることができる。溶離液は特に述べない限り、ＴＨＦ（テトラヒドロフラン）を用いて測定したものとする。また、検出は特に述べない限り、ＵＶ線（紫外線）の波長２５４ｎｍ検出器を使用したものとする。 The description of the components in the present invention described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, unless otherwise specified, “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. The light used for the exposure generally includes an active ray or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays or electron beams.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the present specification, “(meth) acrylate” represents both and / or “acrylate” and “methacrylate”, and “(meth) acryl” represents both “acryl” and “methacryl”, or “(Meth) acryloyl” represents either or both of “acryloyl” and “methacryloyl”.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
In this specification, solid content concentration is the mass percentage of the other component except a solvent with respect to the gross mass of a composition. Moreover, solid content concentration says the density | concentration in 25 degreeC unless there is particular mention.
In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion values according to gel permeation chromatography (GPC measurement) unless otherwise specified. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corporation), and guard columns HZ-L, TSKgel Super HZM-M, TSKgel. It can be determined by using Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by Tosoh Corporation). Unless otherwise stated, the eluent is measured using THF (tetrahydrofuran). Unless otherwise specified, detection is performed using a UV ray (ultraviolet) wavelength 254 nm detector.
＜感光性樹脂組成物＞
　本発明の感光性樹脂組成物（以下、単に、「本発明の組成物」ということがある）は、下記式（１）で表される繰り返し単位を含むポリイミド前駆体、および、光ラジカル重合開始剤を含むことを特徴とする。このような構成とすることにより、光ラジカル重合によりパターンを形成でき、破断伸び率の高い硬化膜を得ることができる。
　さらに、本発明の組成物から形成される樹脂層を多層積層する場合、層間の密着性が問題となる。具体的には、樹脂層と樹脂層の密着性に加え、樹脂層と樹脂層の間に金属層を設ける場合には、樹脂層と金属層の密着性が求められる。本発明では、ポリイミド前駆体に式（２）で表される基を結合させることにより、これらの層間の密着性も向上させることができる。このメカニズムは推定であるが、式（２）で表される基は、露光後でも消費されることが少なく、多層積層の際の露光時や熱硬化時に層間での反応性を高めたためと推定される。
　さらに、感光性樹脂組成物を多層積層体の樹脂層の形成に用いる場合、かかる感光性樹脂組成物は、露光ラチチュードが広いことが望ましいが、本発明の感光性樹脂組成物は露光ラチチュードも広くすることができる。
式（１）
Figure JPOXMLDOC01-appb-C000018
 式（１）中、Ａ１およびＡ２は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ１１１は、２価の有機基を表し、Ｒ１１５は、４価の有機基を表し、Ｒ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表す；但し、Ｒ１１１、Ｒ１１３、Ｒ１１４およびＲ１１５の少なくとも１つの末端には下記式（２）で表される基が結合している；
式（２）
Figure JPOXMLDOC01-appb-C000019
 式（２）において、Ｒ１は、水素原子または置換基を表し、＊はＲ１１１、Ｒ１１３、Ｒ１１４またはＲ１１５との結合部位である。 <Photosensitive resin composition>
The photosensitive resin composition of the present invention (hereinafter sometimes simply referred to as “the composition of the present invention”) includes a polyimide precursor containing a repeating unit represented by the following formula (1), and radical photopolymerization initiation It contains an agent. By setting it as such a structure, a pattern can be formed by radical photopolymerization and the cured film with a high breaking elongation can be obtained.
Furthermore, when the resin layers formed from the composition of the present invention are multilayered, the adhesion between the layers becomes a problem. Specifically, in addition to the adhesion between the resin layer and the resin layer, when a metal layer is provided between the resin layer and the resin layer, the adhesion between the resin layer and the metal layer is required. In this invention, the adhesiveness between these layers can also be improved by couple | bonding the group represented by Formula (2) with a polyimide precursor. Although this mechanism is presumed, the group represented by the formula (2) is less consumed even after exposure, and is presumed to have increased reactivity between the layers at the time of exposure and thermal curing in the case of multilayer lamination. Is done.
Furthermore, when the photosensitive resin composition is used for forming a resin layer of a multilayer laminate, such a photosensitive resin composition desirably has a wide exposure latitude, but the photosensitive resin composition of the present invention also has a wide exposure latitude. can do.
Formula (1)
Figure JPOXMLDOC01-appb-C000018
 In formula (1), A 1 and A 2 each independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group; provided that at least one terminal of R 111 , R 113 , R 114 and R 115 has a group represented by the following formula (2): Bound;
Formula (2)
Figure JPOXMLDOC01-appb-C000019
 In Formula (2), R 1 represents a hydrogen atom or a substituent, and * is a binding site with R 111 , R 113 , R 114 or R 115 .
＜＜ポリイミド前駆体＞＞
　本発明で用いるポリイミド前駆体は、式（１）で表される繰り返し単位を含む。さらに、式（１）で表される繰り返し単位以外の繰り返し単位を含んでいてもよい。以下、これらの内容について詳細に説明する。 << Polyimide precursor >>
The polyimide precursor used by this invention contains the repeating unit represented by Formula (1). Furthermore, a repeating unit other than the repeating unit represented by the formula (1) may be included. Hereinafter, these contents will be described in detail.
＜＜＜式（１）で表される繰り返し単位＞＞＞
　本発明で用いるポリイミド前駆体は、式（１）で表される繰り返し単位を含む。
式（１）
Figure JPOXMLDOC01-appb-C000020
 式（１）中、Ａ１およびＡ２は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ１１１は、２価の有機基を表し、Ｒ１１５は、４価の有機基を表し、Ｒ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表す；但し、Ｒ１１１、Ｒ１１３、Ｒ１１４およびＲ１１５の少なくとも１つの末端には下記式（２）で表される基が結合している；
式（２）
Figure JPOXMLDOC01-appb-C000021
 式（２）において、Ｒ１は、水素原子または置換基を表し、＊はＲ１１１、Ｒ１１３、Ｒ１１４またはＲ１１５との結合部位である。 <<< Repeating unit represented by Formula (1) >>>
The polyimide precursor used by this invention contains the repeating unit represented by Formula (1).
Formula (1)
Figure JPOXMLDOC01-appb-C000020
 In formula (1), A 1 and A 2 each independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group; provided that at least one terminal of R 111 , R 113 , R 114 and R 115 has a group represented by the following formula (2): Bound;
Formula (2)
Figure JPOXMLDOC01-appb-C000021
 In Formula (2), R 1 represents a hydrogen atom or a substituent, and * is a binding site with R 111 , R 113 , R 114 or R 115 .
　ここで、「Ｒ１１１、Ｒ１１３、Ｒ１１４およびＲ１１５の少なくとも１つの末端には下記式（２）で表される基が結合している」とは、Ｒ１１１等の基の内部に、いわゆる連結基のように含まれているのではなく、Ｒ１１３および／またはＲ１１４自体が式（２）で表される基であるか、あるいは、Ｒ１１１、Ｒ１１３、Ｒ１１４およびＲ１１５を構成する水素原子の少なくとも１つが式（２）で表される基で置換されていることをいう。
　本発明では、Ｒ１１１、Ｒ１１３、Ｒ１１４およびＲ１１５のうち、少なくとも、Ｒ１１１の末端に式（２）で表される基が結合していることが好ましい。
　また、Ｒ１１１、Ｒ１１３、Ｒ１１４およびＲ１１５のうち、少なくとも、Ｒ１１３およびＲ１１４の一方の末端に、式（２）で表される基が結合している態様も例示される。本形態では、Ｒ１１３およびＲ１１４の他方は、末端に、式（２）で表される基が結合しているか、ラジカル重合性基を含むことが好ましい。
　さらに、Ｒ１１１、Ｒ１１３、Ｒ１１４およびＲ１１５のうち、少なくとも、Ｒ１１５の末端に、式（２）で表される基が結合している態様も例示される。本形態では、Ｒ１１５が置換基を有する芳香族炭化水素基であり、上記芳香族炭化水素基の置換基が式（２）で表される基自体であるか、あるいは、上記芳香族炭化水素基の置換基がさらに式（２）で表される基で置換されていることが好ましい。
　本発明では、１つの式（１）で表される繰り返し単位中に、式（２）で表される基が１～５つ含まれていることが好ましく、１～３つ含まれていることがより好ましく、１つまたは２つ含まれていることがさらに好ましい。 Here, “the group represented by the following formula (2) is bonded to at least one terminal of R 111 , R 113 , R 114, and R 115 ” means that inside the group such as R 111 , R 113 and / or R 114 itself is a group represented by the formula (2), or R 111 , R 113 , R 114 and R 115 are not included as a so-called linking group. It means that at least one of the constituent hydrogen atoms is substituted with a group represented by the formula (2).
In the present invention, among R 111 , R 113 , R 114 and R 115 , it is preferable that at least the group represented by the formula (2) is bonded to the terminal of R 111 .
Further, among R 111, R 113, R 114 and R 115, at least, to one end of R 113 and R 114, aspects group represented by the formula (2) is bonded are also exemplified. In the present embodiment, it is preferable that the other of R 113 and R 114 has a group represented by the formula (2) bonded to the terminal or a radical polymerizable group.
Further, among R 111, R 113, R 114 and R 115, at least, the end of the R 115, aspects group represented by the formula (2) is bonded are also exemplified. In this embodiment, R 115 is an aromatic hydrocarbon group having a substituent, and the substituent of the aromatic hydrocarbon group is the group itself represented by the formula (2), or the aromatic hydrocarbon It is preferable that the substituent of the group is further substituted with a group represented by the formula (2).
In the present invention, it is preferable that 1 to 5 groups represented by the formula (2) are contained in one repeating unit represented by the formula (1), and 1 to 3 groups are contained. Is more preferable, and it is further preferable that one or two are included.
　Ｒ１は水素原子または置換基を表し、水素原子、アルキル基、またはアリ―ル基が好ましく、水素原子またはアルキル基がより好ましく、水素原子がさらに好ましい。
　Ｒ１が置換基の場合、下記置換基Ｔが例示され、式量（１モルあたりの上記置換基部分の質量、単位ｇ）が１５～３００の置換基であることが好ましく、式量が１５～１００の置換基であることがより好ましい。上記置換基は、炭素原子、酸素原子、水素原子、硫黄原子および窒素原子から選択される原子のみで構成されることが好ましい。 R 1 represents a hydrogen atom or a substituent, preferably a hydrogen atom, an alkyl group, or an aryl group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom.
When R 1 is a substituent, the following substituent T is exemplified, and the formula weight (mass of the above substituent portion per mole, unit g) is preferably a substituent having a formula weight of 15 to 300. More preferred are ˜100 substituents. The substituent is preferably composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a sulfur atom and a nitrogen atom.
（置換基Ｔ）
　アルキル基（好ましくは炭素数１～３０のアルキル基）、アルケニル基（好ましくは炭素数２～３０のアルケニル基）、アルキニル基（好ましくは炭素数２～３０のアルキニル基）、アリール基（好ましくは炭素数６～３０のアリール基）、アミノ基（好ましくは炭素数０～３０のアミノ基）、アルコキシ基（好ましくは炭素数１～３０のアルコキシ基）、アリールオキシ基（好ましくは炭素数６～３０のアリールオキシ基）、ヘテロアリールオキシ基、アシル基（好ましくは炭素数１～３０のアシル基）、アルコキシカルボニル基（好ましくは炭素数２～３０のアルコキシカルボニル基）、アリールオキシカルボニル基（好ましくは炭素数７～３０のアリールオキシカルボニル基）、アシルオキシ基（好ましくは炭素数２～３０のアシルオキシ基）、アシルアミノ基（好ましくは炭素数２～３０のアシルアミノ基）、アルコキシカルボニルアミノ基（好ましくは炭素数２～３０のアルコキシカルボニルアミノ基）、アリールオキシカルボニルアミノ基（好ましくは炭素数７～３０のアリールオキシカルボニルアミノ基）、スルファモイル基（好ましくは炭素数０～３０のスルファモイル基）、カルバモイル基（好ましくは炭素数１～３０のカルバモイル基）、アルキルチオ基（好ましくは炭素数１～３０のアルキルチオ基）、アリールチオ基（好ましくは炭素数６～３０のアリールチオ基）、ヘテロアリールチオ基（好ましくは炭素数１～３０）、アルキルスルホニル基（好ましくは炭素数１～３０）、アリールスルホニル基（好ましくは炭素数６～３０）、ヘテロアリールスルホニル基（好ましくは炭素数１～３０）、アルキルスルフィニル基（好ましくは炭素数１～３０）、アリールスルフィニル基（好ましくは炭素数６～３０）、ヘテロアリールスルフィニル基（好ましくは炭素数１～３０）、ウレイド基（好ましくは炭素数１～３０）、リン酸アミド基（好ましくは炭素数１～３０）、ヒドロキシ基、メルカプト基、ハロゲン原子、シアノ基、アルキルスルフィノ基、アリールスルフィノ基、ヒドラジノ基、イミノ基、ヘテロアリール基（好ましくは炭素数１～３０）、テトラヒドロフラニル基。これらの基は、さらに置換可能な基である場合、さらに置換基を有してもよい。さらなる置換基としては、上述した置換基Ｔで説明した基が挙げられる。 (Substituent T)
An alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), an alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), an alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), an aryl group (preferably An aryl group having 6 to 30 carbon atoms), an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably having 6 to 6 carbon atoms). 30 aryloxy groups), heteroaryloxy groups, acyl groups (preferably acyl groups having 1 to 30 carbon atoms), alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 30 carbon atoms), aryloxycarbonyl groups (preferably Is an aryloxycarbonyl group having 7 to 30 carbon atoms), an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms). Si group), an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably having a carbon number of 7 to 30 aryloxycarbonylamino groups), sulfamoyl groups (preferably sulfamoyl groups having 0 to 30 carbon atoms), carbamoyl groups (preferably carbamoyl groups having 1 to 30 carbon atoms), alkylthio groups (preferably having 1 to 30 carbon atoms). Alkylthio group), arylthio group (preferably arylthio group having 6 to 30 carbon atoms), heteroarylthio group (preferably 1 to 30 carbon atoms), alkylsulfonyl group (preferably 1 to 30 carbon atoms), arylsulfonyl group ( Preferably 6-30 carbon atoms, heteroarylsulfur Nyl group (preferably 1-30 carbon atoms), alkylsulfinyl group (preferably 1-30 carbon atoms), arylsulfinyl group (preferably 6-30 carbon atoms), heteroarylsulfinyl group (preferably 1-30 carbon atoms) ), Ureido group (preferably having 1 to 30 carbon atoms), phosphoric acid amide group (preferably having 1 to 30 carbon atoms), hydroxy group, mercapto group, halogen atom, cyano group, alkylsulfino group, arylsulfino group, A hydrazino group, an imino group, a heteroaryl group (preferably having a carbon number of 1 to 30), and a tetrahydrofuranyl group. When these groups are further substitutable groups, they may further have a substituent. Examples of the further substituent include the groups described for the substituent T described above.
　本発明で用いるポリイミド前駆体は、下記式（３）で表される化合物由来の構造を有することが好ましい。
式（３）
Figure JPOXMLDOC01-appb-C000022
 　式（３）中、Ａは（ｐ＋ｑ）価の基を表す；Ｒ１は水素原子または置換基を表す；ｐは１～５の整数を表し、ｑは２以上の整数を表す。
　式（３）で表される化合物は、アミド基の部分が、ポリイミド前駆体の原料であるカルボン酸または無水カルボン酸二無水物と反応して、ポリイミド前駆体に取り込まれていることが好ましい。具体的には、式（１）のＮＨ－Ｒ１１１－ＮＨの部分が式（３）で表される化合物に由来することが好ましい。 The polyimide precursor used in the present invention preferably has a structure derived from a compound represented by the following formula (3).
Formula (3)
Figure JPOXMLDOC01-appb-C000022
 In formula (3), A represents a (p + q) -valent group; R 1 represents a hydrogen atom or a substituent; p represents an integer of 1 to 5, and q represents an integer of 2 or more.
In the compound represented by the formula (3), it is preferable that the amide group part is incorporated into the polyimide precursor by reacting with the carboxylic acid or carboxylic anhydride dianhydride which is the raw material of the polyimide precursor. Specifically, the NH—R 111 —NH moiety of formula (1) is preferably derived from the compound represented by formula (3).
　式（３）において、Ａが表す（ｐ＋ｑ）価の基としては、炭化水素基、複素環基、－Ｏ－、－Ｓ－、－ＮＲ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＳＯ２－もしくはこれらの組み合わせからなる基が挙げられる。Ｒは、水素原子、アルキル基またはアリール基を表し、水素原子が好ましい。
　炭化水素基は、脂肪族炭化水素基であってもよく、芳香族炭化水素基であってもよい。また、脂肪族炭化水素基は、環状であってもよく、非環状であってもよい。また、脂肪族炭化水素基は、飽和脂肪族炭化水素基であってもよく、不飽和脂肪族炭化水素基であってもよい。炭化水素基は、置換基を有していてもよく、置換基を有していなくてもよい。置換基としては上述した置換基Ｔが挙げられる。また、環状の脂肪族炭化水素基、および、芳香族炭化水素基は、単環であってもよく、縮合環であってもよいが、単環が好ましい。芳香族炭化水素基としては、ベンゼン環基、ナフタレン環基、インデン環基、インダン環基、アントラセン環基、テトラリン環基などが挙げられる。
　複素環基は、単環であってもよく、縮合環であってもよい。複素環基としては、５員環または６員環が好ましい。複素環基は、脂肪族複素環基であっても、芳香族複素環基であってもよい。また、複素環基を構成するヘテロ原子としては、窒素原子、酸素原子、硫黄原子などが挙げられる。複素環基としてはフラン環基、チオフェン環基、ピロール環基、ピラン環基、チオピラン環基、ピリジン環基、オキサゾール環基、チアゾール環基、イミダゾール環基、ピリミジン環基、トリアジン環基、インドール環基、キノリン環基、プリン環基、ベンゾイミダゾール環基、ベンゾチアゾール環基、キノキサリン環基、およびカルバゾール環基などが挙げられる。
　（ｐ＋ｑ）価の基の具体例としては、下記の構造単位が１つまたは２以上組み合わさって構成される基（環構造を形成していてもよい）が挙げられる。Ｒは、水素原子、アルキル基またはアリール基を表し、水素原子が好ましい。 In the formula (3), the (p + q) -valent group represented by A includes a hydrocarbon group, a heterocyclic group, —O—, —S—, —NR—, —CO—, —COO—, —OCO—, A group consisting of —SO 2 — or a combination thereof is mentioned. R represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom.
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be cyclic or acyclic. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have a substituent or may not have a substituent. Examples of the substituent include the above-described substituent T. Moreover, the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be a single ring or a condensed ring, but a single ring is preferable. Examples of the aromatic hydrocarbon group include a benzene ring group, a naphthalene ring group, an indene ring group, an indane ring group, an anthracene ring group, and a tetralin ring group.
The heterocyclic group may be a single ring or a condensed ring. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Moreover, as a hetero atom which comprises a heterocyclic group, a nitrogen atom, an oxygen atom, a sulfur atom, etc. are mentioned. Heterocyclic groups include furan ring group, thiophene ring group, pyrrole ring group, pyran ring group, thiopyran ring group, pyridine ring group, oxazole ring group, thiazole ring group, imidazole ring group, pyrimidine ring group, triazine ring group, indole Examples thereof include a ring group, a quinoline ring group, a purine ring group, a benzimidazole ring group, a benzothiazole ring group, a quinoxaline ring group, and a carbazole ring group.
Specific examples of the (p + q) -valent group include a group formed by combining one or more of the following structural units (which may form a ring structure). R represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　Ａが表す（ｐ＋ｑ）価の基は、炭素原子、酸素原子、水素原子、硫黄原子および窒素原子から選択される原子のみで構成され、かつ、式量（１モルあたりのＡ部分の質量、単位ｇ）が３０～９００であることが好ましく、５０～６００であることがより好ましい。 The (p + q) -valent group represented by A is composed only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a sulfur atom and a nitrogen atom, and has a formula weight (mass of A moiety per mole, unit) g) is preferably from 30 to 900, more preferably from 50 to 600.
　式（３）において、ｐは１～５の整数を表す。ｑは２以上の整数を表す。
　ｐは、１～４の整数が好ましく、１～３の整数がより好ましく、１または２がさらに好ましく、１が一層好ましい。
　ｑは、２～４の整数が好ましく、２または３がより好ましく、２がさらに好ましい。
　ｐが２以上の場合、複数存在するＲ１はそれぞれ同じでも異なっていてもよい。 In the formula (3), p represents an integer of 1 to 5. q represents an integer of 2 or more.
p is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
q is preferably an integer of 2 to 4, more preferably 2 or 3, and still more preferably 2.
When p is 2 or more, a plurality of R 1 may be the same or different.
　式（３）において、Ｒ１は水素原子または置換基を表す。式（３）におけるＲ１の好ましい範囲は、式（２）におけるＲ１と同様である。 In Formula (3), R 1 represents a hydrogen atom or a substituent. A preferred range of R 1 in the formula (3) is the same as R 1 in formula (2).
　本発明では、ポリイミド前駆体が下記式（３ａ）で表される化合物由来の構造を有することがより好ましい。すなわち、式（３）で表される化合物が式（３ａ）で表されることがより好ましい。
　式（３ａ）
Figure JPOXMLDOC01-appb-C000024
 　式（３ａ）中、Ａ０は（ｌ＋ｍ）価の基を表す；Ａ１は単結合または（ｎ＋１）価の基を表す；Ｒ１は水素原子または置換基を表す；Ａｒは（ａ＋１）価の芳香族炭化水素基または芳香族複素環基を表す；ａ、ｌ、ｍおよびｎは、それぞれ独立に１～５の整数を表す；ただし、ｍおよびｎの少なくとも一方は２以上の整数を表す。 In the present invention, it is more preferable that the polyimide precursor has a structure derived from a compound represented by the following formula (3a). That is, it is more preferable that the compound represented by Formula (3) is represented by Formula (3a).
Formula (3a)
Figure JPOXMLDOC01-appb-C000024
 In formula (3a), A 0 represents a (l + m) -valent group; A 1 represents a single bond or a (n + 1) -valent group; R 1 represents a hydrogen atom or a substituent; Ar represents an (a + 1) -valent group A, l, m and n each independently represents an integer of 1 to 5; provided that at least one of m and n represents an integer of 2 or more. .
　式（３ａ）において、Ａ０が表す（ｌ＋ｍ）価の基としては、炭化水素基、複素環基、－Ｏ－、－Ｓ－、－ＮＲ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＳＯ２－もしくはこれらの組み合わせからなる基が挙げられ、－Ｏ－、－Ｓ－、－ＮＲ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＳＯ２－もしくはこれらの組み合わせからなる基がより好ましく、－ＮＨ－、－ＣＯ－もしくはこれらの組み合わせからなる基がさらに好ましい。Ｒは、水素原子、アルキル基またはアリール基を表し、水素原子が好ましい。
　炭化水素基、複素環基の詳細については、上述したＡが表す（ｐ＋ｑ）価の基で説明した範囲と同様であり、好ましい範囲も同様である。 In the formula (3a), the (l + m) -valent group represented by A 0 is a hydrocarbon group, a heterocyclic group, —O—, —S—, —NR—, —CO—, —COO—, —OCO—. , —SO 2 — or a combination thereof, such as —O—, —S—, —NR—, —CO—, —COO—, —OCO—, —SO 2 — or a combination thereof. A group is more preferable, and a group consisting of —NH—, —CO— or a combination thereof is more preferable. R represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom.
The details of the hydrocarbon group and heterocyclic group are the same as the range described for the (p + q) valent group represented by A described above, and the preferred range is also the same.
　式（３ａ）において、Ａ１が表す（ｎ＋１）価の基としては、炭化水素基、複素環基、－Ｏ－、－Ｓ－、－ＮＲ－、－ＣＯ－、－ＣＯＯ－、－ＯＣＯ－、－ＳＯ２－もしくはこれらの組み合わせからなる基が挙げられる。Ｒは、水素原子、アルキル基またはアリール基を表し、水素原子が好ましい。炭化水素基、複素環基の詳細については、上述したＡが表す（ｐ＋ｑ）価の基で説明した範囲と同様である。Ａ１が表す（ｎ＋１）価の基としては、炭化水素基または複素環基であることが好ましく、炭化水素基であることがより好ましく、芳香族炭化水素基であることがさらに好ましく、ベンゼン環基であることが一層好ましい。 In the formula (3a), the (n + 1) -valent group represented by A 1 is a hydrocarbon group, a heterocyclic group, —O—, —S—, —NR—, —CO—, —COO—, —OCO—. , —SO 2 —, or a combination thereof. R represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom. The details of the hydrocarbon group and the heterocyclic group are the same as those described for the (p + q) -valent group represented by A described above. The (n + 1) -valent group represented by A 1 is preferably a hydrocarbon group or a heterocyclic group, more preferably a hydrocarbon group, further preferably an aromatic hydrocarbon group, and a benzene ring. More preferably, it is a group.
　式（３）において、Ｒ１は水素原子または置換基を表す。式（３）におけるＲ１の好ましい範囲は、式（２）におけるＲ１と同様である。 In Formula (3), R 1 represents a hydrogen atom or a substituent. A preferred range of R 1 in the formula (3) is the same as R 1 in formula (2).
　式（３ａ）において、Ａｒは、（ａ＋１）価の芳香族炭化水素基であることが好ましく、ベンゼン環基であることがより好ましい。 In the formula (3a), Ar is preferably an (a + 1) -valent aromatic hydrocarbon group, and more preferably a benzene ring group.
　式（３ａ）において、ａ、ｌ、ｍおよびｎは、それぞれ独立に、１～５の整数を表す。ただし、ｍおよびｎの少なくとも一方は２以上の整数を表す。ｌ、ｍがそれぞれ２以上の場合、複数存在するＲ１、Ａｒ、およびＡ１はそれぞれ独立に、同じでも異なっていてもよい。 In the formula (3a), a, l, m and n each independently represents an integer of 1 to 5. However, at least one of m and n represents an integer of 2 or more. When l and m are each 2 or more, a plurality of R 1 , Ar, and A 1 may be the same or different from each other.
　ａは、１～４であることが好ましく、１～３であることがより好ましく、１または２であることがさらに好ましく、１であることが一層好ましい。
　ｌは、１～４であることが好ましく、１～３であることがより好ましく、１または２であることがさらに好ましく、１であることが一層好ましい。
　ｍは、１～４であることが好ましく、１～３であることがより好ましく、１または２であることがさらに好ましく、１であることが一層好ましい。
　ｎは、１～４であることが好ましく、２～４であることがより好ましく、２または３であることがさらに好ましく、２であることが一層好ましい。
　また、（ｌ＋ｍ）は２～６であることが好ましく、２～５であることが更に好ましく、２または３であることが一層好ましく、２であることが特に好ましい。 a is preferably 1 to 4, more preferably 1 to 3, further preferably 1 or 2, and still more preferably 1.
l is preferably 1 to 4, more preferably 1 to 3, further preferably 1 or 2, and still more preferably 1.
m is preferably 1 to 4, more preferably 1 to 3, further preferably 1 or 2, and still more preferably 1.
n is preferably 1 to 4, more preferably 2 to 4, still more preferably 2 or 3, and still more preferably 2.
In addition, (l + m) is preferably 2 to 6, more preferably 2 to 5, still more preferably 2 or 3, and particularly preferably 2.
　本発明では、ポリイミド前駆体が下記式（３ｂ）で表される化合物由来の構造を有することがさらに好ましい。すなわち、式（３）で表される化合物が式（３ｂ）で表されることがさらに好ましい。
式（３ｂ）
Figure JPOXMLDOC01-appb-C000025
 式（３ｂ）中、Ａ０は（ｌ＋ｍ）価の基を表す；Ｒ１は水素原子または置換基を表す；ａ、ｌ、ｍおよびｎはそれぞれ独立に１～５の整数を表す；ただし、ｍおよびｎの少なくとも一方は２以上の整数を表す。
　式（３ｂ）中、Ａ０、Ｒ１、ａ、ｌ、ｍおよびｎは、それぞれ独立に、式（３ａ）におけるＡ０、Ｒ１、ａ、ｌ、ｍおよびｎと同義であり、好ましい範囲も同様である。 In the present invention, it is more preferable that the polyimide precursor has a structure derived from a compound represented by the following formula (3b). That is, it is more preferable that the compound represented by the formula (3) is represented by the formula (3b).
Formula (3b)
Figure JPOXMLDOC01-appb-C000025
 In formula (3b), A 0 represents a (l + m) -valent group; R 1 represents a hydrogen atom or a substituent; a, l, m and n each independently represents an integer of 1 to 5; At least one of m and n represents an integer of 2 or more.
In formula (3b), A 0 , R 1 , a, l, m and n are each independently synonymous with A 0 , R 1 , a, l, m and n in formula (3a), and a preferred range Is the same.
　以下に本発明で用いられる式（３）で表される化合物を例示する。本発明がこれらに限定されるものではないことは言うまでもない。
Figure JPOXMLDOC01-appb-C000026
 The compound represented by Formula (3) used by this invention below is illustrated. Needless to say, the present invention is not limited to these examples.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　式（１）におけるＡ１およびＡ２は、それぞれ独立に酸素原子またはＮＨを表し、酸素原子が好ましい。
　式（１）におけるＲ１１１は、２価の有機基を表す。２価の有機基としては、直鎖または分岐の脂肪族基、環状の脂肪族基および芳香族炭化水素基を含む基が例示され、炭素数２～２０の直鎖の脂肪族基、炭素数３～２０の分岐の脂肪族基、炭素数３～２０の環状の脂肪族基、炭素数６～２０の芳香族炭化水素基、または、これらの組み合わせからなる基が好ましく、炭素数６～２０の芳香族炭化水素基からなる基がより好ましい。 A 1 and A 2 in Formula (1) each independently represent an oxygen atom or NH, and preferably an oxygen atom.
R 111 in Formula (1) represents a divalent organic group. Examples of the divalent organic group include a straight chain or branched aliphatic group, a group containing a cyclic aliphatic group and an aromatic hydrocarbon group, a straight chain aliphatic group having 2 to 20 carbon atoms, A group consisting of a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof is preferable. A group consisting of the above aromatic hydrocarbon group is more preferred.
　Ｒ１１１は、ジアミンから誘導されることが好ましい。ポリイミド前駆体の製造に用いられるジアミンとしては、直鎖または分岐の脂肪族、環状の脂肪族または芳香族ジアミンなどが挙げられる。ジアミンは、１種のみ用いてもよいし、２種以上用いてもよい。ジアミンは、式（３）で表される化合物が好ましい。
　Ｒ１１１が式（３）で表される化合物に由来しない場合、Ｒ１１１は後述する式（１－１）で表される繰り返し単位におけるＲ１１１と同様であり、好ましい範囲も同様である。 R 111 is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine. Only one type of diamine may be used, or two or more types may be used. The diamine is preferably a compound represented by the formula (3).
If R 111 is not derived from the compound represented by the formula (3), R 111 is the same as R 111 in the repeating unit represented by the formula (1-1) described below, a preferred range is also the same.
　式（１）におけるＲ１１５は、４価の有機基を表す。４価の有機基としては、芳香環を含む４価の有機基が好ましく、下記式（５）または式（６）で表される基がより好ましい。
式（５）
Figure JPOXMLDOC01-appb-C000030
 　式（５）中、Ｒ１１２は、単結合、または、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ２－、－ＮＨＣＯ－ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－ＣＯ－、－Ｓ－および－ＳＯ２－から選択される基であることがより好ましく、－ＣＨ２－、－Ｃ（ＣＦ３）２－、－Ｃ（ＣＨ３）２－、－Ｏ－、－ＣＯ－、－Ｓ－および－ＳＯ２－からなる群から選択される２価の基がさらに好ましい。 R 115 in formula (1) represents a tetravalent organic group. As the tetravalent organic group, a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
Formula (5)
Figure JPOXMLDOC01-appb-C000030
 In the formula (5), R 112 represents a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO. 2 -, - NHCO- and is preferably a group selected from these combinations, a single bond, an alkylene group which ~ 1 carbon atoms which may be 3-substituted by fluorine atoms, -O -, - CO- More preferably a group selected from -S- and -SO 2- , -CH 2- , -C (CF 3 ) 2- , -C (CH 3 ) 2- , -O-, -CO More preferred is a divalent group selected from the group consisting of —, —S— and —SO 2 —.
式（６）
Figure JPOXMLDOC01-appb-C000031
 Formula (6)
Figure JPOXMLDOC01-appb-C000031
　式（１）におけるＲ１１５が表す４価の有機基は、具体的には、テトラカルボン酸二無水物から酸二無水物基を除去した後に残存するテトラカルボン酸残基などが挙げられる。テトラカルボン酸二無水物は、１種のみ用いてもよいし、２種以上用いてもよい。テトラカルボン酸二無水物は、下記式（Ｏ）で表される化合物が好ましい。
式（Ｏ）
Figure JPOXMLDOC01-appb-C000032
 　式（Ｏ）中、Ｒ１１５は、４価の有機基を表す。Ｒ１１５は、式（１）のＲ１１５と同義である。 Specific examples of the tetravalent organic group represented by R 115 in Formula (1) include a tetracarboxylic acid residue remaining after the acid dianhydride group is removed from the tetracarboxylic dianhydride. Only one tetracarboxylic dianhydride may be used, or two or more tetracarboxylic dianhydrides may be used. The tetracarboxylic dianhydride is preferably a compound represented by the following formula (O).
Formula (O)
Figure JPOXMLDOC01-appb-C000032
 In formula (O), R 115 represents a tetravalent organic group. R 115 has the same meaning as R 115 in formula (1).
　テトラカルボン酸二無水物の具体例としては、ピロメリット酸二無水物（ＰＭＤＡ）、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルフィドテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルメタンテトラカルボン酸二無水物、２，２’，３，３’－ジフェニルメタンテトラカルボン酸二無水物、２，３，３’，４’－ビフェニルテトラカルボン酸二無水物、２，３，３’，４’－ベンゾフェノンテトラカルボン酸二無水物、４，４’－オキシジフタル酸二無水物、２，３，６，７－ナフタレンテトラカルボン酸二無水物、１，４，５，７－ナフタレンテトラカルボン酸二無水物、２，２－ビス（３，４－ジカルボキシフェニル）プロパン二無水物、２，２－ビス（２，３－ジカルボキシフェニル）プロパン二無水物、２，２－ビス（３，４－ジカルボキシフェニル）ヘキサフルオロプロパン二無水物、１，３－ジフェニルヘキサフルオロプロパン－３，３，４，４－テトラカルボン酸二無水物、１，４，５，６－ナフタレンテトラカルボン酸二無水物、２，２’，３，３’－ジフェニルテトラカルボン酸二無水物、３，４，９，１０－ペリレンテトラカルボン酸二無水物、１，２，４，５－ナフタレンテトラカルボン酸二無水物、１，４，５，８－ナフタレンテトラカルボン酸二無水物、１，８，９，１０－フェナントレンテトラカルボン酸二無水物、１，１－ビス（２，３－ジカルボキシフェニル）エタン二無水物、１，１－ビス（３，４－ジカルボキシフェニル）エタン二無水物、１，２，３，４－ベンゼンテトラカルボン酸二無水物、ならびに、これらの炭素数１～６のアルキル誘導体および／または炭素数１～６のアルコキシ誘導体から選ばれる少なくとも１種が例示される。 Specific examples of tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′- Diphenyl sulfide tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′ , 4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5 , Naphthalenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2 -Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 1,3-diphenylhexafluoropropane-3,3,4,4-tetracarboxylic dianhydride, 1,4,5,6- Naphthalenetetracarboxylic dianhydride, 2,2 ′, 3,3′-diphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 1,2,4,5- Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,8,9,10-phenanthrenetetracarboxylic dianhydride, 1,1-bis (2,3 Dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, and their carbon number Examples thereof include at least one selected from alkyl derivatives having 1 to 6 and / or alkoxy derivatives having 1 to 6 carbon atoms.
　また、下記に示すテトラカルボン酸二無水物（ＤＡＡ－１）～（ＤＡＡ－５）も好ましい例として挙げられる。
Figure JPOXMLDOC01-appb-C000033
 Further, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) shown below are also preferable examples.
Figure JPOXMLDOC01-appb-C000033
　式（１）中、Ｒ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表し、Ｒ１１３およびＲ１１４の少なくとも一方がラジカル重合性基を含むことが好ましく、両方がラジカル重合性基を含むことが好ましい。ラジカル重合性基としては、ラジカルの作用により、架橋反応することが可能な基であって、好ましい例として、エチレン性不飽和結合を有する基が挙げられる。
　エチレン性不飽和結合を有する基としては、ビニル基、（メタ）アリル基、下記式（ＩＩＩ）で表される基などが挙げられる。 In formula (1), R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R 113 and R 114 preferably contains a radical polymerizable group, and both are radicals. It preferably contains a polymerizable group. The radical polymerizable group is a group capable of undergoing a crosslinking reaction by the action of a radical, and a preferable example includes a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like.
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　式（ＩＩＩ）において、Ｒ２００は、水素原子またはメチル基を表し、メチル基がより好ましい。
　式（ＩＩＩ）において、Ｒ２０１は、連結基であり、－ＣＨ２－、－Ｏ－、－ＣＯ－もしくはこれらの組み合わせからなる基が好ましい。 In the formula (III), R 200 represents a hydrogen atom or a methyl group, and a methyl group is more preferable.
In the formula (III), R 201 is a linking group, preferably a group consisting of —CH 2 —, —O—, —CO— or a combination thereof.
　水性現像液への溶解度の観点からは、Ｒ１１３またはＲ１１４は、水素原子またはラジカル重合性基以外の１価の有機基であってもよい。ラジカル重合性基以外の１価の有機基については、特開２０１６－０２７３５７号公報の段落００８７の記載を参酌でき、これらの内容は本明細書に組み込まれる。 From the viewpoint of solubility in an aqueous developer, R 113 or R 114 may be a monovalent organic group other than a hydrogen atom or a radical polymerizable group. Regarding the monovalent organic group other than the radical polymerizable group, the description in paragraph 0087 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.
　また、ポリイミド前駆体は、構造単位中にフッ素原子を有することも好ましい。ポリイミド前駆体中のフッ素原子含有量は１０質量％以上が好ましく、２０質量％以下が好ましい。 The polyimide precursor preferably has a fluorine atom in the structural unit. The fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
　また、基板との密着性を向上させる目的で、シロキサン構造を有する脂肪族基を共重合してもよい。具体的には、ジアミン成分として、ビス（３－アミノプロピル）テトラメチルジシロキサン、ビス（パラアミノフェニル）オクタメチルペンタシロキサンなどが挙げられる。 Further, an aliphatic group having a siloxane structure may be copolymerized for the purpose of improving the adhesion to the substrate. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
　式（１）で表される繰り返し単位は、式（１－Ａ）で表される繰り返し単位であることが好ましい。すなわち、本発明で用いるポリイミド前駆体の少なくとも１種が、式（１－Ａ）で表される繰り返し単位を有する前駆体であることが好ましい。このような構造とすることにより、露光ラチチュードの幅をより広げることが可能になる。
式（１－Ａ）
Figure JPOXMLDOC01-appb-C000035
 　式（１－Ａ）中、Ａ１およびＡ２は、酸素原子を表し、Ｒ１１１およびＲ１１２は、それぞれ独立に、２価の有機基を表し、Ｒ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表し、Ｒ１１３およびＲ１１４の少なくとも一方は、重合性基を含む基であり、重合性基であることが好ましい。但し、Ｒ１１１、Ｒ１１３、Ｒ１１４およびＲ１１２の少なくとも１つの末端には上記式（２）で表される基が結合している。 The repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by the formula (1-A). By adopting such a structure, it becomes possible to further widen the width of the exposure latitude.
Formula (1-A)
Figure JPOXMLDOC01-appb-C000035
 In formula (1-A), A 1 and A 2 each represent an oxygen atom, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each independently represent It represents a hydrogen atom or a monovalent organic group, and at least one of R 113 and R 114 is a group containing a polymerizable group, and is preferably a polymerizable group. However, the group represented by the above formula (2) is bonded to at least one terminal of R 111 , R 113 , R 114 and R 112 .
　Ａ１、Ａ２、Ｒ１１１、Ｒ１１３およびＲ１１４は、それぞれ、独立に、式（１）におけるＡ１、Ａ２、Ｒ１１１、Ｒ１１３およびＲ１１４と同義であり、好ましい範囲も同様である。Ｒ１１２は、式（５）におけるＲ１１２と同義であり、好ましい範囲も同様である。 A 1 , A 2 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (1), and the preferred ranges are also the same. is there. R 112 has the same meaning as R 112 in formula (5), and the preferred range is also the same.
　ポリイミド前駆体は、式（１）で表される繰り返し構造単位を１種のみ含んでいてもよいし、２種以上含んでいてもよい。また、式（１）で表される繰り返し単位の構造異性体を含んでいてもよい。 The polyimide precursor may contain only one type of repeating structural unit represented by the formula (1), or may contain two or more types. Moreover, the structural isomer of the repeating unit represented by Formula (1) may be included.
＜＜＜他の繰り返し単位＞＞＞
　本発明で用いるポリイミド前駆体は、式（１）で表される繰り返し単位以外の繰り返し単位を含んでいてもよく、式（１）で表される繰り返し単位以外の繰り返し単位を含むことが好ましく、式（１－１）で表される繰り返し単位を含むことがさらに好ましい。
式（１－１）
Figure JPOXMLDOC01-appb-C000036
 式（１－１）中、Ａ１およびＡ２は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ１１１は、２価の有機基を表し、Ｒ１１５は、４価の有機基を表し、Ｒ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表す；但し、式（１－１）で表される繰り返し単位は上記式（２）で表される基を含まない。 <<< other repeating units >>>
The polyimide precursor used in the present invention may contain a repeating unit other than the repeating unit represented by the formula (1), and preferably contains a repeating unit other than the repeating unit represented by the formula (1). More preferably, it contains a repeating unit represented by the formula (1-1).
Formula (1-1)
Figure JPOXMLDOC01-appb-C000036
 In formula (1-1), A 1 and A 2 each independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group; provided that the repeating unit represented by formula (1-1) does not include the group represented by formula (2).
　式（１－１）における、Ａ１、Ａ２、Ｒ１１５、Ｒ１１３およびＲ１１４は、それぞれ独立に、式（１）におけるＡ１、Ａ２、Ｒ１１５、Ｒ１１３およびＲ１１４と同義であり、好ましい範囲も同様である。本発明で用いるポリイミド前駆体が、式（１）で表される繰り返し単位と式（１－１）で表される繰り返し単位を有する場合、式（１）におけるＡ１、Ａ２、Ｒ１１５、Ｒ１１３およびＲ１１４と、式（１－１）におけるＡ１、Ａ２、Ｒ１１５、Ｒ１１３およびＲ１１４とは、同一であっても、異なっていてもよいが、同一であることが好ましい。 In formula (1-1), A 1 , A 2 , R 115 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 115 , R 113 and R 114 in formula (1). The preferred range is also the same. When the polyimide precursor used in the present invention has a repeating unit represented by the formula (1) and a repeating unit represented by the formula (1-1), A 1 , A 2 , R 115 in the formula (1), R 113 and R 114 and A 1 , A 2 , R 115 , R 113 and R 114 in formula (1-1) may be the same or different, but are preferably the same. .
　式（１－１）におけるＲ１１１は、２価の有機基を表す。２価の有機基としては、直鎖または分岐の脂肪族基、環状の脂肪族基および芳香族炭化水素基を含む基が例示され、炭素数２～２０の直鎖の脂肪族基、炭素数３～２０の分岐の脂肪族基、炭素数３～２０の環状の脂肪族基、炭素数６～２０の芳香族炭化水素基、または、これらの組み合わせからなる基が好ましく、炭素数６～２０の芳香族炭化水素基からなる基がより好ましい。 R 111 in formula (1-1) represents a divalent organic group. Examples of the divalent organic group include a straight chain or branched aliphatic group, a group containing a cyclic aliphatic group and an aromatic hydrocarbon group, a straight chain aliphatic group having 2 to 20 carbon atoms, A group consisting of a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof is preferable. A group consisting of the above aromatic hydrocarbon group is more preferred.
　Ｒ１１１は、ジアミンから誘導されることが好ましい。ポリイミド前駆体の製造に用いられるジアミンとしては、直鎖または分岐の脂肪族、環状の脂肪族または芳香族ジアミンなどが挙げられる。ジアミンは、１種のみ用いてもよいし、２種以上用いてもよい。
　具体的には、炭素数２～２０の直鎖または分岐の脂肪族基、炭素数３～２０の環状の脂肪族基、炭素数６～２０の芳香族炭化水素基、または、これらの組み合わせからなる基を含むジアミンであることが好ましく、炭素数６～２０の芳香族炭化水素基からなる基を含むジアミンであることがより好ましい。芳香族炭化水素基の例としては、下記が挙げられる。 R 111 is preferably derived from a diamine. Examples of the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamine. Only one type of diamine may be used, or two or more types may be used.
Specifically, from a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a combination thereof. A diamine containing a group consisting of an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferred. The following are mentioned as an example of an aromatic hydrocarbon group.
Figure JPOXMLDOC01-appb-C000037
 　式中、Ａは、単結合、または、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－Ｓ（＝Ｏ）２－、－ＮＨＣＯ－ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数１～３のアルキレン基、－Ｏ－、－Ｃ（＝Ｏ）－、－Ｓ－、－ＳＯ２－から選択される基であることがより好ましく、－ＣＨ２－、－Ｏ－、－Ｓ－、－ＳＯ２－、－Ｃ（ＣＦ３）２－、および、－Ｃ（ＣＨ３）２－からなる群から選択される２価の基であることがさらに好ましい。
Figure JPOXMLDOC01-appb-C000037
 In the formula, A is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —C (═O) —, —S—, —S (═O) 2 —, —NHCO—, and a group selected from these combinations are preferable, a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, —O— , —C (═O) —, —S—, —SO 2 — is more preferable, and —CH 2 —, —O—, —S—, —SO 2 —, —C ( More preferably, it is a divalent group selected from the group consisting of CF 3 ) 2 — and —C (CH 3 ) 2 —.
　ジアミンとしては、具体的には、特開２０１６－０２７３５７号公報の段落００８３の記載を参酌でき、これらの内容は本明細書に組み込まれる。 As the diamine, specifically, the description in paragraph 0083 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.
　また、下記に示すジアミン（ＤＡ－１）～（ＤＡ－１８）も好ましい。 Further, diamines (DA-1) to (DA-18) shown below are also preferable.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　また、少なくとも２つ以上のアルキレングリコール単位を主鎖にもつジアミンも好ましい例として挙げられる。好ましくは、エチレングリコール鎖、プロピレングリコール鎖のいずれかまたは両方を一分子中にあわせて２つ以上含むジアミン、より好ましくは芳香環を含まないジアミンである。具体例としては、ジェファーミン（登録商標）ＫＨ－５１１、ジェファーミン（登録商標）ＥＤ－６００、ジェファーミン（登録商標）ＥＤ－９００、ジェファーミン（登録商標）ＥＤ－２００３、ジェファーミン（登録商標）ＥＤＲ－１４８、ジェファーミン（登録商標）ＥＤＲ－１７６、ジェファーミン（登録商標）Ｄ－２００、ジェファーミン（登録商標）Ｄ－４００、ジェファーミン（登録商標）Ｄ－２０００、ジェファーミン（登録商標）Ｄ－４０００（以上商品名、ＨＵＮＴＳＭＡＮ社製）、１－（２－（２－（２－アミノプロポキシ）エトキシ）プロポキシ）プロパン－２－アミン、１－（１－（１－（２－アミノプロポキシ）プロパン－２－イル）オキシ）プロパン－２－アミンなどが挙げられるが、これらに限定されない。
　ジェファーミン（登録商標）ＫＨ－５１１、ジェファーミン（登録商標）ＥＤ－６００、ジェファーミン（登録商標）ＥＤ－９００、ジェファーミン（登録商標）ＥＤ－２００３、ジェファーミン（登録商標）ＥＤＲ－１４８、ジェファーミン（登録商標）ＥＤＲ－１７６の構造を以下に示す。 A diamine having at least two alkylene glycol units in the main chain is also a preferred example. Preferred is a diamine containing at least two ethylene glycol chains or propylene glycol chains in one molecule, more preferably a diamine containing no aromatic ring. Specific examples include Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark). ) EDR-148, Jeffermin (registered trademark) EDR-176, Jeffermin (registered trademark) D-200, Jeffermin (registered trademark) D-400, Jeffermin (registered trademark) D-2000, Jeffermin (registered trademark) ) D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-amino) Propoxy) propan-2-yl) oxy) propan-2-amine and the like.
Jeffermin (registered trademark) KH-511, Jeffermin (registered trademark) ED-600, Jeffermin (registered trademark) ED-900, Jeffermin (registered trademark) ED-2003, Jeffermin (registered trademark) EDR-148, The structure of Jeffamine (registered trademark) EDR-176 is shown below.
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　上記において、ｘ、ｙ、ｚは平均値である。 In the above, x, y, and z are average values.
　式（１－１）におけるＲ１１１は、得られる硬化膜の柔軟性の観点から、－Ａｒ－Ｌ－Ａｒ－で表されることが好ましい。但し、Ａｒは、それぞれ独立に、芳香族炭化水素基であり、Ｌは、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ２－または－ＮＨＣＯ－、ならびに、上記の２つ以上の組み合わせからなる基である。Ａｒは、フェニレン基が好ましく、Ｌは、フッ素原子で置換されていてもよい炭素数１または２の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－または－ＳＯ２－がさらに好ましい。ここでの脂肪族炭化水素基は、アルキレン基が好ましい。 R 111 in formula (1-1) is preferably represented by —Ar—L—Ar— from the viewpoint of flexibility of the resulting cured film. However, Ar is each independently an aromatic hydrocarbon group, L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, — S—, —SO 2 — or —NHCO—, and a group consisting of a combination of two or more of the above. Ar is preferably a phenylene group, and L is an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S— or —SO 2 —. preferable. The aliphatic hydrocarbon group here is preferably an alkylene group.
　式（１－１）におけるＲ１１１は、ｉ線透過率の観点から下記式（５１）または式（６１）で表わされる基であることが好ましい。特に、ｉ線透過率、入手のし易さの観点から式（６１）で表わされる基であることがより好ましい。
　式（５１）
Figure JPOXMLDOC01-appb-C000041
 式（５１）中、Ｒ１０～Ｒ１７は、それぞれ独立に水素原子、フッ素原子または１価の有機基であり、Ｒ１０～Ｒ１７の少なくとも１つはフッ素原子、メチル基、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。
　Ｒ１０～Ｒ１７の１価の有機基として、炭素数１～１０（好ましくは炭素数１～６）の無置換のアルキル基、炭素数１～１０（好ましくは炭素数１～６）のフッ化アルキル基等が挙げられる。
　式（６１）
Figure JPOXMLDOC01-appb-C000042
 式（６１）中、Ｒ１８およびＲ１９は、それぞれ独立にフッ素原子、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。
　式（５１）または（６１）の構造を与えるジアミン化合物としては、ジメチル－４,４’－ジアミノビフェニル、２，２’－ビス（トリフルオロメチル）－４，４’－ジアミノビフェニル、２，２’－ビス（フルオロ）－４，４’－ジアミノビフェニル、４，４’－ジアミノオクタフルオロビフェニル等が挙げられる。これらの１種を用いるか、２種以上を組み合わせて用いてもよい。 R 111 in formula (1-1) is preferably a group represented by the following formula (51) or formula (61) from the viewpoint of i-line transmittance. In particular, the group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.
Formula (51)
Figure JPOXMLDOC01-appb-C000041
 In formula (51), R 10 to R 17 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 10 to R 17 is a fluorine atom, a methyl group, a fluoromethyl group, A difluoromethyl group or a trifluoromethyl group.
Examples of the monovalent organic group represented by R 10 to R 17 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorine atom having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Alkyl group and the like.
Formula (61)
Figure JPOXMLDOC01-appb-C000042
 In formula (61), R 18 and R 19 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.
Diamine compounds that give the structure of formula (51) or (61) include dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,2 Examples include '-bis (fluoro) -4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, and the like. One of these may be used, or two or more may be used in combination.
　ポリイミド前駆体が、式（１－１）で表される繰り返し構造単位を含む場合、式（１－１）で表される繰り返し構造単位を１種のみ含んでいてもよいし、２種以上含んでいてもよい。また、式（１－１）で表される繰り返し単位の構造異性体を含んでいてもよい。 When the polyimide precursor includes a repeating structural unit represented by the formula (1-1), the polyimide precursor may include only one type of repeating structural unit represented by the formula (1-1) or two or more types. You may go out. Further, it may contain a structural isomer of a repeating unit represented by the formula (1-1).
　本発明におけるポリイミド前駆体の一実施形態として、式（１）で表される繰り返し単位と、式（１－１）で表される繰り返し単位を含み、式（１）で表される繰り返し単位と式（１－１）で表される繰り返し単位の合計が、全繰り返し単位の、好ましくは８０質量％以上、より好ましくは９０質量％以上を占めることが例示される。本発明で用いるポリイミド前駆体が、式（１）で表される繰り返し単位と、式（１－１）で表される繰り返し単位を含む場合、式（１）で表される繰り返し単位と、式（１－１）で表される繰り返し単位のモル比は、１：０．０２～１：５０であることが好ましく、１：０．１～１：２０であることがより好ましい。 As one embodiment of the polyimide precursor in the present invention, a repeating unit represented by the formula (1) and a repeating unit represented by the formula (1) including the repeating unit represented by the formula (1-1): It is exemplified that the total of repeating units represented by the formula (1-1) occupies preferably 80% by mass or more, more preferably 90% by mass or more of all repeating units. When the polyimide precursor used in the present invention includes the repeating unit represented by the formula (1) and the repeating unit represented by the formula (1-1), the repeating unit represented by the formula (1), the formula The molar ratio of the repeating unit represented by (1-1) is preferably 1: 0.02 to 1:50, and more preferably 1: 0.1 to 1:20.
＜＜＜ポリイミド前駆体の特性＞＞＞
　本発明で用いるポリイミド前駆体は、式（２）で表される基の量が、ポリイミド前駆体１ｇに対し、０．０５～５．０ｍｍｏｌであることが好ましく、０．１～２．５ｍｍｏｌであることがより好ましい。
　また、本発明では、感光性樹脂組成物に含まれるラジカル重合性基の数と、式（２）で表される基の数との比が、ラジカル重合性基の数：式（２）で表される基の数＝１：０．０５～２．０であることが好ましく、１：０．１～１．０であることがより好ましい。
　ポリイミド前駆体の重量平均分子量（Ｍｗ）は、好ましくは２０００～５０００００であり、より好ましくは５０００～１０００００であり、さらに好ましくは１００００～５００００である。また、数平均分子量（Ｍｎ）は、好ましくは８００～２５００００であり、より好ましくは、２０００～５００００であり、さらに好ましくは、４０００～２５０００である。
　分散度は、１．５～２．５が好ましい。 <<< Characteristics of polyimide precursor >>>
In the polyimide precursor used in the present invention, the amount of the group represented by the formula (2) is preferably 0.05 to 5.0 mmol with respect to 1 g of the polyimide precursor, and 0.1 to 2.5 mmol. More preferably.
In the present invention, the ratio between the number of radical polymerizable groups contained in the photosensitive resin composition and the number of groups represented by formula (2) is the number of radical polymerizable groups: Formula (2). The number of groups represented is preferably 1: 0.05 to 2.0, more preferably 1: 0.1 to 1.0.
The weight average molecular weight (Mw) of the polyimide precursor is preferably from 2,000 to 500,000, more preferably from 5,000 to 100,000, and even more preferably from 10,000 to 50,000. The number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2000 to 50000, and still more preferably 4000 to 25000.
The degree of dispersion is preferably 1.5 to 2.5.
　以下に、本発明で用いることができるポリイミド前駆体の具体例を示す。本発明がこれらに限定されるものではないことは言うまでもない。下記に示すポリイミド前駆体が共重合体の場合、左側の繰り返し単位と右側の繰り返し単位のモル比は、１：０．０２～５０の範囲で適宜定められる。
Figure JPOXMLDOC01-appb-C000043
 Below, the specific example of the polyimide precursor which can be used by this invention is shown. Needless to say, the present invention is not limited to these examples. When the polyimide precursor shown below is a copolymer, the molar ratio of the left repeating unit to the right repeating unit is appropriately determined in the range of 1: 0.02 to 50.
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
　本発明の感光性樹脂組成物は、ポリイミド前駆体を、組成物の全固形分に対し２０～１００質量％含むことが好ましく、５０～９９質量％含むことがより好ましく、６０～９８質量％含むことがさらに好ましく、７０～９５質量％含むことが特に好ましい。
　ポリイミド前駆体は１種のみ含んでいてもよいし、２種以上含んでいてもよい。２種以上含む場合、合計量が上記範囲となることが好ましい。 The photosensitive resin composition of the present invention preferably contains 20 to 100% by mass, more preferably 50 to 99% by mass, and 60 to 98% by mass of the polyimide precursor with respect to the total solid content of the composition. More preferably, it is particularly preferably 70 to 95% by mass.
The polyimide precursor may contain only 1 type and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.
＜＜＜ポリイミド前駆体の製造＞＞＞
　ポリイミド前駆体は、ジカルボン酸またはジカルボン酸誘導体とジアミンを反応させて得られる。好ましくは、ジカルボン酸またはジカルボン酸誘導体を、ハロゲン化剤を用いてハロゲン化させた後、ジアミンと反応させて得られる。
　ポリイミド前駆体の製造方法では、反応に際し、有機溶剤を用いることが好ましい。有機溶剤は１種でもよいし、２種以上でもよい。
　有機溶剤としては、原料に応じて適宜定めることができるが、ピリジン、ジエチレングリコールジメチルエーテル（ジグリム）、Ｎ－メチルピロリドンおよびＮ－エチルピロリドンが例示される。 <<< Production of polyimide precursor >>>
The polyimide precursor is obtained by reacting dicarboxylic acid or a dicarboxylic acid derivative with diamine. Preferably, it is obtained by halogenating a dicarboxylic acid or a dicarboxylic acid derivative with a halogenating agent and then reacting with a diamine.
In the method for producing a polyimide precursor, an organic solvent is preferably used for the reaction. One or more organic solvents may be used.
The organic solvent can be appropriately determined according to the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
　ポリイミド前駆体の製造に際し、保存安定性をより向上させるため、酸二無水物、モノカルボン酸、モノ酸クロリド化合物、モノ活性エステル化合物などの末端封止剤で封止することが好ましい。これらのうち、モノアミンを用いることがより好ましく、モノアミンの好ましい化合物としては、アニリン、２－エチニルアニリン、３－エチニルアニリン、４－エチニルアニリン、５－アミノ－８－ヒドロキシキノリン、１－ヒドロキシ－７－アミノナフタレン、１－ヒドロキシ－６－アミノナフタレン、１－ヒドロキシ－５－アミノナフタレン、１－ヒドロキシ－４－アミノナフタレン、２－ヒドロキシ－７－アミノナフタレン、２－ヒドロキシ－６－アミノナフタレン、２－ヒドロキシ－５－アミノナフタレン、１－カルボキシ－７－アミノナフタレン、１－カルボキシ－６－アミノナフタレン、１－カルボキシ－５－アミノナフタレン、２－カルボキシ－７－アミノナフタレン、２－カルボキシ－６－アミノナフタレン、２－カルボキシ－５－アミノナフタレン、２－アミノ安息香酸、３－アミノ安息香酸、４－アミノ安息香酸、４－アミノサリチル酸、５－アミノサリチル酸、６－アミノサリチル酸、２－アミノベンゼンスルホン酸、３－アミノベンゼンスルホン酸、４－アミノベンゼンスルホン酸、３－アミノ－４，６－ジヒドロキシピリミジン、２－アミノフェノール、３－アミノフェノール、４－アミノフェノール、２－アミノチオフェノール、３－アミノチオフェノール、４－アミノチオフェノールなどが挙げられる。これらを２種以上用いてもよく、複数の末端封止剤を反応させることにより、複数の異なる末端基を導入してもよい。 In the production of a polyimide precursor, it is preferable to seal with a terminal sealing agent such as an acid dianhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound in order to further improve storage stability. Of these, it is more preferable to use a monoamine. Preferred examples of the monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7. -Aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2, -Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carbo Ci-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-amino Benzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4 -Aminothiophenol and the like. Two or more of these may be used, and a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.
　ポリイミド前駆体の製造に際し、固体を析出する工程を含んでいてもよい。具体的には、反応液中のポリイミド前駆体を、水中に沈殿させ、テトラヒドロフラン等のポリイミド前駆体が可溶な溶剤に溶解させることによって、固体析出することができる。
　その後、ポリイミド前駆体を乾燥して、粉末状のポリイミド前駆体を得ることができる。 In producing the polyimide precursor, a step of depositing a solid may be included. Specifically, solid precipitation can be achieved by precipitating the polyimide precursor in the reaction solution in water and dissolving it in a solvent in which the polyimide precursor such as tetrahydrofuran is soluble.
Then, a polyimide precursor can be dried and a powdery polyimide precursor can be obtained.
＜＜光ラジカル重合開始剤＞＞
　本発明の組成物は、光ラジカル重合開始剤を含有する。
　本発明で用いることができる光ラジカル重合開始剤としては、特に制限はなく、公知の光ラジカル重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する光ラジカル重合開始剤が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよい。
　光ラジカル重合開始剤は、約３００～８００ｎｍ（好ましくは３３０～５００ｎｍ）の範囲内に少なくとも約５０のモル吸光係数を有する化合物を、少なくとも１種含有していることが好ましい。化合物のモル吸光係数は、公知の方法を用いて測定することができる。例えば、紫外可視分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５　ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶剤を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。 << Photoradical polymerization initiator >>
The composition of the present invention contains a radical photopolymerization initiator.
There is no restriction | limiting in particular as radical photopolymerization initiator which can be used by this invention, It can select suitably from well-known radical photopolymerization initiators. For example, a photo radical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable. Further, it may be an activator that generates some active radicals by generating some action with the photoexcited sensitizer.
The radical photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 to 800 nm (preferably 330 to 500 nm). The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
　本発明の組成物が光ラジカル重合開始剤を含むことにより、本発明の組成物を半導体ウェハなどの基板に適用して感光性樹脂組成物層を形成した後、光を照射することで、ラジカルに起因する硬化が起こり、光照射部における溶解性を低下させることができる。このため、例えば、電極部のみをマスクするパターンを持つフォトマスクを介して感光性樹脂組成物層を露光することで、電極のパターンにしたがって、溶解性の異なる領域を簡便に作製できるという利点がある。 When the composition of the present invention contains a photoradical polymerization initiator, the composition of the present invention is applied to a substrate such as a semiconductor wafer to form a photosensitive resin composition layer, and then irradiated with light to generate radicals. Curing due to this occurs and the solubility in the light irradiation part can be reduced. Therefore, for example, by exposing the photosensitive resin composition layer through a photomask having a pattern that masks only the electrode portion, there is an advantage that regions having different solubility can be easily produced according to the electrode pattern. is there.
　光ラジカル重合開始剤としては、公知の化合物を任意に使用できる。例えば、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を有する化合物、オキサジアゾール骨格を有する化合物、トリハロメチル基を有する化合物など）、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、ケトオキシムエーテル、アミノアセトフェノン化合物、ヒドロキシアセトフェノン、アゾ系化合物、アジド化合物、メタロセン化合物、有機ホウ素化合物、鉄アレーン錯体などが挙げられる。これらの詳細については、特開２０１６－０２７３５７号公報の段落０１６５～０１８２の記載を参酌でき、この内容は本明細書に組み込まれる。 As the photo radical polymerization initiator, a known compound can be arbitrarily used. For example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazoles, oxime derivatives, etc. Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, iron arene complexes, etc. Can be mentioned. With respect to these details, reference can be made to the descriptions in paragraphs 0165 to 0182 of JP-A-2016-027357, the contents of which are incorporated herein.
　ケトン化合物としては、例えば、特開２０１５－０８７６１１号公報の段落００８７に記載の化合物が例示され、この内容は本明細書に組み込まれる。市販品では、カヤキュアーＤＥＴＸ（日本化薬（株）製）も好適に用いられる。 Examples of ketone compounds include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein. As a commercial product, Kaya Cure DETX (manufactured by Nippon Kayaku Co., Ltd.) is also preferably used.
　光ラジカル重合開始剤としては、ヒドロキシアセトフェノン化合物、アミノアセトフェノン化合物、および、アシルホスフィン化合物も好適に用いることができる。より具体的には、例えば、特開平１０－２９１９６９号公報に記載のアミノアセトフェノン系開始剤、特許第４２２５８９８号に記載のアシルホスフィンオキシド系開始剤も用いることができる。
　ヒドロキシアセトフェノン系開始剤としては、ＩＲＧＡＣＵＲＥ　１８４（ＩＲＧＡＣＵＲＥは登録商標）、ＤＡＲＯＣＵＲ　１１７３、ＩＲＧＡＣＵＲＥ　５００、ＩＲＧＡＣＵＲＥ－２９５９、ＩＲＧＡＣＵＲＥ　１２７（商品名：いずれもＢＡＳＦ社製）を用いることができる。
　アミノアセトフェノン系開始剤としては、市販品であるＩＲＧＡＣＵＲＥ　９０７、ＩＲＧＡＣＵＲＥ　３６９、および、ＩＲＧＡＣＵＲＥ　３７９（商品名：いずれもＢＡＳＦ社製）を用いることができる。
　アミノアセトフェノン系開始剤として、３６５ｎｍまたは４０５ｎｍ等の波長光源に吸収極大波長がマッチングされた特開２００９－１９１１７９号公報に記載の化合物も用いることができる。
　アシルホスフィン系開始剤としては、２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイドなどが挙げられる。また、市販品であるＩＲＧＡＣＵＲＥ－８１９やＩＲＧＡＣＵＲＥ－ＴＰＯ（商品名：いずれもＢＡＳＦ社製）を用いることができる。
　メタロセン化合物としては、ＩＲＧＡＣＵＲＥ－７８４（ＢＡＳＦ社製）などが例示される。 As the photoradical polymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, IRGACURE 127 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source of 365 nm or 405 nm can also be used.
Examples of the acylphosphine initiator include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) which are commercially available products can be used.
Examples of the metallocene compound include IRGACURE-784 (manufactured by BASF).
　光ラジカル重合開始剤として、より好ましくはオキシム化合物が挙げられる。オキシム化合物を用いることにより、露光ラチチュードをより効果的に向上させることが可能になる。オキシム化合物は、露光ラチチュード（露光マージン）が広く、かつ、光塩基発生剤としても働くため、特に好ましい。
　オキシム化合物の具体例としては、特開２００１－２３３８４２号公報に記載の化合物、特開２０００－８００６８号公報に記載の化合物、特開２００６－３４２１６６号公報に記載の化合物を用いることができる。
　好ましいオキシム化合物としては、例えば、下記の構造の化合物や、３－ベンゾオキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイルオキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、および２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オンなどが挙げられる。
Figure JPOXMLDOC01-appb-C000050
 　市販品ではＩＲＧＡＣＵＲＥ　ＯＸＥ　０１、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０２、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０３、ＩＲＧＡＣＵＲＥ　ＯＸＥ　０４（以上、ＢＡＳＦ社製）、アデカオプトマーＮ－１９１９（（株）ＡＤＥＫＡ製、特開２０１２－１４０５２号公報に記載の光ラジカル重合開始剤２）も好適に用いられる。また、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカアークルズＮＣＩ－８３１およびアデカアークルズＮＣＩ－９３０（（株）ＡＤＥＫＡ製）も用いることができる。また、ＤＦＩ－０９１（ダイトーケミックス株式会社製）を用いることができる。
　さらに、また、フッ素原子を有するオキシム化合物を用いることも可能である。そのようなオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報に記載されている化合物、特表２０１４－５００８５２号公報の段落０３４５～０３５８に記載されている化合物２４、３６～４０、特開２０１３－１６４４７１号公報の段落０１０１に記載されている化合物（Ｃ－３）などが挙げられる。
　最も好ましいオキシム化合物としては、特開２００７－２６９７７９号公報に示される特定置換基を有するオキシム化合物や、特開２００９－１９１０６１号公報に示されるチオアリール基を有するオキシム化合物などが挙げられる。 More preferable examples of the photo radical polymerization initiator include oxime compounds. By using the oxime compound, the exposure latitude can be improved more effectively. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as a photobase generator.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Preferable oxime compounds include, for example, compounds having the following structures, 3-benzooxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxy Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
Figure JPOXMLDOC01-appb-C000050
 Among the commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), Adekaoptomer N-1919 (manufactured by ADEKA Corporation, light described in JP2012-14052A) A radical polymerization initiator 2) is also preferably used. In addition, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (manufactured by ADEKA Corporation) can also be used. Further, DFI-091 (manufactured by Daitokemix Co., Ltd.) can be used.
Furthermore, it is also possible to use an oxime compound having a fluorine atom. Specific examples of such oxime compounds include compounds described in JP 2010-262028 A, compounds 24, 36-40 described in paragraphs 0345 to 0358 of JP 2014-500852 A, Examples thereof include compound (C-3) described in paragraph 0101 of JP2013-164471A.
As the most preferred oxime compounds, there are oxime compounds having a specific substituent as disclosed in JP-A-2007-267979, oxime compounds having a thioaryl group as disclosed in JP-A-2009-191061, and the like.
　光ラジカル重合開始剤は、露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム塩化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物およびその誘導体、シクロペンタジエン－ベンゼン－鉄錯体およびその塩、ハロメチルオキサジアゾール化合物、３－アリール置換クマリン化合物からなる群より選択される化合物が好ましい。
　さらに好ましい光ラジカル重合開始剤は、トリハロメチルトリアジン化合物、α－アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム塩化合物、ベンゾフェノン化合物、アセトフェノン化合物であり、トリハロメチルトリアジン化合物、α－アミノケトン化合物、オキシム化合物、トリアリールイミダゾールダイマー、ベンゾフェノン化合物からなる群より選ばれる少なくとも１種の化合物が一層好ましく、メタロセン化合物またはオキシム化合物を用いるのがより一層好ましく、オキシム化合物がさらに一層好ましい。
　また、光ラジカル重合開始剤は、ベンゾフェノン、Ｎ，Ｎ’－テトラメチル－４，４’－ジアミノベンゾフェノン（ミヒラーケトン）等のＮ，Ｎ’－テトラアルキル－４，４’－ジアミノベンゾフェノン、２－ベンジル－２－ジメチルアミノ－１－（４－モルホリノフェニル）－ブタノン－１、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルホリノ－プロパノン－１等の芳香族ケトン、アルキルアントラキノン等の芳香環と縮環したキノン類、ベンゾインアルキルエーテル等のベンゾインエーテル化合物、ベンゾイン、アルキルベンゾイン等のベンゾイン化合物、ベンジルジメチルケタール等のベンジル誘導体などを用いることもできる。また、下記式（Ｉ）で表される化合物を用いることもできる。
Figure JPOXMLDOC01-appb-C000051
 　式（Ｉ）中、Ｒ５０は、炭素数１～２０のアルキル基、１個以上の酸素原子によって中断された炭素数２～２０のアルキル基、炭素数１～１２のアルコキシ基、フェニル基、炭素数１～２０のアルキル基、炭素数１～１２のアルコキシ基、ハロゲン原子、シクロペンチル基、シクロヘキシル基、炭素数２～１２のアルケニル基、１個以上の酸素原子によって中断された炭素数２～１８のアルキル基および炭素数１～４のアルキル基の少なくとも１つで置換されたフェニル基、またはビフェニリルであり、Ｒ５１は、式（ＩＩ）で表される基であるか、Ｒ５０と同じ基であり、Ｒ５２～Ｒ５４は各々独立に炭素数１～１２のアルキル、炭素数１～１２のアルコキシまたはハロゲンである。
Figure JPOXMLDOC01-appb-C000052
 式中、Ｒ５５～Ｒ５７は、上記式（Ｉ）のＲ５２～Ｒ５４と同じである。 Photoradical polymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryls from the viewpoint of exposure sensitivity. Selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds. Are preferred.
More preferred photoradical polymerization initiators are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, At least one compound selected from the group consisting of a trihalomethyltriazine compound, an α-aminoketone compound, an oxime compound, a triarylimidazole dimer, and a benzophenone compound is more preferable, and a metallocene compound or an oxime compound is more preferable, and an oxime compound. Is even more preferable.
Further, photo radical polymerization initiators include N, N′-tetraalkyl-4,4′-diaminobenzophenone, 2-benzyl such as benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone) Aromatic ketones such as -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, alkyl anthraquinones, etc. It is also possible to use quinones fused with the aromatic ring, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, and benzyl derivatives such as benzyldimethyl ketal. A compound represented by the following formula (I) can also be used.
Figure JPOXMLDOC01-appb-C000051
 In the formula (I), R 50 represents an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, An alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, and 2 to 2 carbon atoms interrupted by one or more oxygen atoms A phenyl group substituted with at least one of 18 alkyl groups and an alkyl group having 1 to 4 carbon atoms, or biphenylyl, and R 51 is a group represented by the formula (II) or the same as R 50 Each of R 52 to R 54 is independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons or halogen.
Figure JPOXMLDOC01-appb-C000052
 In the formula, R 55 to R 57 are the same as R 52 to R 54 in the above formula (I).
　また、光ラジカル重合開始剤は、国際公開ＷＯ２０１５／１２５４６９号の段落００４８～００５５に記載の化合物を用いることもできる。 Further, as the radical photopolymerization initiator, compounds described in paragraphs 0048 to 0055 of International Publication No. WO2015 / 125469 can be used.
　光ラジカル重合開始剤の含有量は、本発明の組成物の全固形分に対し０．１～３０質量％であることが好ましく、より好ましくは０．１～２０質量％であり、さらに好ましくは１～１５質量％であり、一層好ましくは１～１０質量％である。光ラジカル重合開始剤は１種のみ含有していてもよいし、２種以上含有していてもよい。光ラジカル重合開始剤を２種以上含有する場合は、その合計が上記範囲であることが好ましい。 The content of the photo radical polymerization initiator is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably based on the total solid content of the composition of the present invention. It is 1 to 15% by mass, and more preferably 1 to 10% by mass. The radical photopolymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more kinds of radical photopolymerization initiators are contained, the total is preferably in the above range.
＜＜熱ラジカル重合開始剤＞＞
　本発明の組成物は、本発明の趣旨を逸脱しない範囲で熱ラジカル重合開始剤を含んでいてもよい。
　熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性を有する化合物の重合反応を開始または促進させる化合物である。熱ラジカル重合開始剤を添加することによって、ポリイミド前駆体の環化と共に、ポリイミド前駆体の重合反応を進行させることもできるので、より高度な耐熱化が達成できることとなる。
　熱ラジカル重合開始剤として、具体的には、特開２００８－６３５５４号公報の段落００７４～０１１８に記載されている化合物が挙げられる。 << Thermal radical polymerization initiator >>
The composition of the present invention may contain a thermal radical polymerization initiator without departing from the gist of the present invention.
The thermal radical polymerization initiator is a compound that generates radicals by heat energy and initiates or accelerates a polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the polyimide precursor can be advanced together with the cyclization of the polyimide precursor, so that higher heat resistance can be achieved.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-63554.
　熱ラジカル重合開始剤を含む場合、その含有量は、本発明の組成物の全固形分に対し０．１～３０質量％が好ましく、より好ましくは０．１～２０質量％であり、さらに好ましくは５～１５質量％である。熱ラジカル重合開始剤は１種のみ含有していてもよいし、２種以上含有していてもよい。熱ラジカル重合開始剤を２種以上含有する場合は、その合計が上記範囲であることが好ましい。 When the thermal radical polymerization initiator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably based on the total solid content of the composition of the present invention. Is 5 to 15% by mass. The thermal radical polymerization initiator may contain only 1 type, and may contain 2 or more types. When two or more thermal radical polymerization initiators are contained, the total is preferably within the above range.
＜＜溶剤＞＞
　本発明の組成物は、溶剤を含有することが好ましい。溶剤は、公知の溶剤を任意に使用できる。溶剤は有機溶剤が好ましい。有機溶剤としては、エステル類、エーテル類、ケトン類、芳香族炭化水素類、スルホキシド類、アミド類などの化合物が挙げられる。
　エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、酢酸イソブチル、ギ酸アミル、酢酸イソアミル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ－ブチロラクトン、ε－カプロラクトン、δ－バレロラクトン、アルキルオキシ酢酸アルキル（例えば、アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－アルキルオキシプロピオン酸アルキルエステル類（例えば、３－アルキルオキシプロピオン酸メチル、３－アルキルオキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－アルキルオキシプロピオン酸アルキルエステル類（例えば、２－アルキルオキシプロピオン酸メチル、２－アルキルオキシプロピオン酸エチル、２－アルキルオキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－アルキルオキシ－２－メチルプロピオン酸メチルおよび２－アルキルオキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等が好適なものとして挙げられる。
　エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等が好適なものとして挙げられる。
　ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２－ヘプタノン、３－ヘプタノン等が好適なものとして挙げられる。
　芳香族炭化水素類として、例えば、トルエン、キシレン、アニソール、リモネン等が好適なものとして挙げられる。
　スルホキシド類として、例えば、ジメチルスルホキシドが好適なものとして挙げられる。
　アミド類として、Ｎ－メチル－２－ピロリドン、Ｎ －エチル－２－ピロリドン、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ，Ｎ－ジメチルホルムアミド等が好適なものとして挙げられる。 << Solvent >>
The composition of the present invention preferably contains a solvent. A known solvent can be arbitrarily used as the solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, and ε-caprolactone , Δ-valerolactone, alkyl oxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc. )), 3-alkyloxypropionic acid alkyl esters (for example, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (for example, methyl 3-methoxypropionate, 3-methoxypropionate)) Ethyl acetate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-alkyloxypropionic acid alkyl esters (for example, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 -Propyl alkyloxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyl Methyl oxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate , Pyruvic acid Chill, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like as preferred.
Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Preferred examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
Suitable examples of aromatic hydrocarbons include toluene, xylene, anisole, limonene and the like.
As the sulfoxides, for example, dimethyl sulfoxide is preferable.
Preferred examples of the amide include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like.
　溶剤は、塗布面性状の改良などの観点から、２種以上を混合する形態も好ましい。なかでも、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、シクロペンタノン、γ－ブチロラクトン、ジメチルスルホキシド、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールメチルエーテル、およびプロピレングリコールメチルエーテルアセテートから選択される２種以上で構成される混合溶液が好ましい。ジメチルスルホキシドとγ－ブチロラクトンとの併用が特に好ましい。 The solvent is preferably in the form of a mixture of two or more from the viewpoint of improving the properties of the coated surface. Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone A mixed solution composed of two or more selected from dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is preferable. The combined use of dimethyl sulfoxide and γ-butyrolactone is particularly preferred.
　溶剤の含有量は、塗布性の観点から、本発明の組成物の全固形分濃度が５～８０質量％になる量とすることが好ましく、５～７０質量％となる量にすることがさらに好ましく、１０～６０質量％となる量にすることが特に好ましい。溶剤含有量は、所望の厚さと塗布方法によって調節すればよい。
　溶剤は１種のみ含有していてもよいし、２種以上含有していてもよい。溶剤を２種以上含有する場合は、その合計が上記範囲であることが好ましい。 The content of the solvent is preferably an amount such that the total solid concentration of the composition of the present invention is 5 to 80% by mass, more preferably 5 to 70% by mass, from the viewpoint of applicability. An amount of 10 to 60% by mass is particularly preferable. The solvent content may be adjusted depending on the desired thickness and coating method.
The solvent may contain only 1 type and may contain 2 or more types. When two or more solvents are contained, the total is preferably in the above range.
＜＜ラジカル重合性化合物＞＞
　本発明の組成物は、ラジカル重合性化合物（以下、「重合性モノマー」ともいう）を含むことが好ましい。このような構成とすることにより、耐熱性に優れた硬化膜を形成することができる。 << Radically polymerizable compound >>
The composition of the present invention preferably contains a radical polymerizable compound (hereinafter also referred to as “polymerizable monomer”). By setting it as such a structure, the cured film excellent in heat resistance can be formed.
　重合性モノマーは、ラジカル重合性基を有する化合物を用いることができる。ラジカル重合性基としては、スチリル基、ビニル基、（メタ）アクリロイル基およびアリル基などのエチレン性不飽和結合を有する基が挙げられる。ラジカル重合性基は、（メタ）アクリロイル基が好ましい。 As the polymerizable monomer, a compound having a radical polymerizable group can be used. Examples of the radical polymerizable group include groups having an ethylenically unsaturated bond such as a styryl group, a vinyl group, a (meth) acryloyl group, and an allyl group. The radical polymerizable group is preferably a (meth) acryloyl group.
　重合性モノマーが有するラジカル重合性基の数は、１個でもよく、２個以上でもよいが、重合性モノマーはラジカル重合性基を２個以上有することが好ましく、３個以上有することがより好ましい。上限は、１５個以下が好ましく、１０個以下がより好ましく、８個以下がさらに好ましい。 The number of radical polymerizable groups possessed by the polymerizable monomer may be one or two or more, but the polymerizable monomer preferably has two or more radical polymerizable groups, more preferably three or more. . The upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.
　重合性モノマーの分子量は、２０００以下が好ましく、１５００以下がより好ましく、９００以下がさらに好ましい。重合性モノマーの分子量の下限は、１００以上が好ましい。 The molecular weight of the polymerizable monomer is preferably 2000 or less, more preferably 1500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more.
　本発明の組成物は、現像性の観点から、重合性基を２個以上含む２官能以上の重合性モノマーを少なくとも１種含むことが好ましく、３官能以上の重合性モノマーを少なくとも１種含むことがより好ましい。また、２官能の重合性モノマーと３官能以上の重合性モノマーとの混合物であってもよい。なお、重合性モノマーの官能基数は、１分子中におけるラジカル重合性基の数を意味する。 From the viewpoint of developability, the composition of the present invention preferably contains at least one bifunctional or higher polymerizable monomer containing two or more polymerizable groups, and preferably contains at least one trifunctional or higher polymerizable monomer. Is more preferable. Further, it may be a mixture of a bifunctional polymerizable monomer and a trifunctional or higher functional polymerizable monomer. The number of functional groups of the polymerizable monomer means the number of radical polymerizable groups in one molecule.
　重合性モノマーの具体例としては、不飽和カルボン酸（例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など）やそのエステル類、アミド類が挙げられ、好ましくは、不飽和カルボン酸と多価アルコール化合物とのエステル、および不飽和カルボン酸と多価アミン化合物とのアミド類である。また、ヒドロキシ基やアミノ基、メルカプト基等の求核性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能イソシアネート類或いはエポキシ類との付加反応物や、単官能若しくは多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基やエポキシ基等の親電子性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との付加反応物、さらに、ハロゲン基やトシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との置換反応物も好適である。また、別の例として、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン等のビニルベンゼン誘導体、ビニルエーテル、アリルエーテル等に置き換えた化合物群を使用することも可能である。具体例としては、特開２０１６－０２７３５７号公報の段落０１１３～０１２２の記載を参酌でき、これらの内容は本明細書に組み込まれる。 Specific examples of the polymerizable monomer include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. These are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds. In addition, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxy group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine, or thiol, and a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a compound group in which an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like is used instead of the unsaturated carboxylic acid. As specific examples, the description in paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated in the present specification.
　また、重合性モノマーは、常圧下で１００℃以上の沸点を持つ化合物も好ましい。その例としては、ポリエチレングリコールジ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ヘキサンジオール（メタ）アクリレート、トリメチロールプロパントリ（アクリロイルオキシプロピル）エーテル、トリ（アクリロイルオキシエチル）イソシアヌレート、グリセリンやトリメチロールエタン等の多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後、（メタ）アクリレート化した化合物、特公昭４８－４１７０８号公報、特公昭５０－６０３４号公報、特開昭５１－３７１９３号各公報に記載されているようなウレタン（メタ）アクリレート類、特開昭４８－６４１８３号、特公昭４９－４３１９１号、特公昭５２－３０４９０号各公報に記載されているポリエステルアクリレート類、エポキシ樹脂と（メタ）アクリル酸との反応生成物であるエポキシアクリレート類等の多官能のアクリレートやメタクリレートおよびこれらの混合物を挙げることができる。また、特開２００８－２９２９７０号公報の段落０２５４～０２５７に記載の化合物も好適である。また、多官能カルボン酸にグリシジル（メタ）アクリレート等の環状エーテル基とエチレン性不飽和基を有する化合物を反応させて得られる多官能（メタ）アクリレートなども挙げることができる。
　また、その他の好ましい重合性モノマーとして、特開２０１０－１６０４１８号公報、特開２０１０－１２９８２５号公報、特許第４３６４２１６号等に記載される、フルオレン環を有し、エチレン性不飽和結合を有する基を２個以上有する化合物や、カルド樹脂も使用することが可能である。
　さらに、その他の例としては、特公昭４６－４３９４６号公報、特公平１－４０３３７号公報、特公平１－４０３３６号公報に記載の特定の不飽和化合物や、特開平２－２５４９３号公報に記載のビニルホスホン酸系化合物等もあげることができる。また、特開昭６１－２２０４８号公報に記載のペルフルオロアルキル基を含む化合物を用いることもできる。さらに日本接着協会誌　ｖｏｌ．２０、Ｎｏ．７、３００～３０８ページ（１９８４年）に光重合性モノマーおよびオリゴマーとして紹介されているものも使用することができる。 The polymerizable monomer is also preferably a compound having a boiling point of 100 ° C. or higher under normal pressure. Examples include polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol. Many such as penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin and trimethylolethane A compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, JP-B-48-4170 Urethane (meth) acrylates as described in JP-A Nos. 50-6034 and 51-37193, JP-A 48-64183, JP-B 49-43191, Mention may be made of polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof described in JP-B 52-30490. it can. Also suitable are the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970. Moreover, the polyfunctional (meth) acrylate etc. which are obtained by making the compound which has cyclic ether groups, such as glycidyl (meth) acrylate, and an ethylenically unsaturated group, react with polyfunctional carboxylic acid can also be mentioned.
Other preferable polymerizable monomers include groups having a fluorene ring and an ethylenically unsaturated bond described in JP2010-160418A, JP2010-129825A, Japanese Patent No. 4364216, and the like. It is also possible to use a compound having two or more or a cardo resin.
Other examples include specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and JP-A-2-25493. And vinyl phosphonic acid compounds. Also, compounds containing a perfluoroalkyl group described in JP-A-61-22048 can be used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photopolymerizable monomers and oligomers, can also be used.
　上記のほか、特開２０１５－０３４９６４号公報の段落００４８～００５１に記載の化合物も好ましく用いることができ、これらの内容は本明細書に組み込まれる。 In addition to the above, compounds described in paragraphs 0048 to 0051 of JP-A No. 2015-034964 can also be preferably used, and the contents thereof are incorporated in the present specification.
　また、特開平１０－６２９８６号公報において式（１）および式（２）としてその具体例と共に記載の、多官能アルコールにエチレンオキサイドやプロピレンオキサイドを付加させた後に（メタ）アクリレート化した化合物も、重合性モノマーとして用いることができる。 In addition, compounds described in JP-A-10-62986 as formulas (1) and (2) together with specific examples thereof, which are (meth) acrylated after adding ethylene oxide or propylene oxide to a polyfunctional alcohol, It can be used as a polymerizable monomer.
　さらに、特開２０１５－１８７２１１号公報の段落０１０４～０１３１に記載の化合物も重合性モノマーとして用いることができ、これらの内容は本明細書に組み込まれる。 Furthermore, the compounds described in paragraphs 0104 to 0131 of JP-A No. 2015-187211 can also be used as the polymerizable monomer, the contents of which are incorporated herein.
　重合性モノマーとしては、ジペンタエリスリトールトリアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３３０；日本化薬（株）製）、ジペンタエリスリトールテトラアクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３２０；日本化薬（株）製、Ａ－ＴＭＭＴ：新中村化学工業（株）製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　Ｄ－３１０；日本化薬（株）製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としては　ＫＡＹＡＲＡＤ　ＤＰＨＡ；日本化薬（株）製、Ａ－ＤＰＨ；新中村化学工業（株）製）、およびこれらの（メタ）アクリロイル基がエチレングリコール、プロピレングリコール残基を介して結合している構造が好ましい。これらのオリゴマータイプも使用できる。 As a polymerizable monomer, dipentaerythritol triacrylate (as a commercial product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; Nippon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available products are KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meta) ) Acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth) acryloyl groups are linked via ethylene glycol and propylene glycol residues. Are preferably bonded to each other. These oligomer types can also be used.
　重合性モノマーの市販品としては、例えばサートマー社製のエチレンオキシ鎖を４個有する４官能アクリレートであるＳＲ－４９４、エチレンオキシ鎖を４個有する２官能メタクリレートであるサートマー社製のＳＲ－２０９、日本化薬（株）製のペンチレンオキシ鎖を６個有する６官能アクリレートであるＤＰＣＡ－６０、イソブチレンオキシ鎖を３個有する３官能アクリレートであるＴＰＡ－３３０、ＮＫエステルＭ－４０Ｇ、ＮＫエステル４Ｇ、ＮＫエステルＭ－９３００、ＮＫエステルＡ－９３００、ＵＡ－７２００（新中村化学工業（株）製）、ＤＰＨＡ－４０Ｈ（日本化薬（株）製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、ＡＩ－６００（共栄社化学（株）製）、ブレンマーＰＭＥ４００（日油（株）製）などが挙げられる。 Examples of commercially available polymerizable monomers include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209, manufactured by Sartomer, which is a bifunctional methacrylate having four ethyleneoxy chains, DPCA-60, a 6-functional acrylate having 6 pentyleneoxy chains, TPA-330, a 3-functional acrylate having 3 isobutyleneoxy chains, NK ester M-40G, NK ester 4G, manufactured by Nippon Kayaku Co., Ltd. NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA- 306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME 00 (manufactured by NOF Co., Ltd.), and the like.
　重合性モノマーは、特公昭４８－４１７０８号公報、特開昭５１－３７１９３号公報、特公平２－３２２９３号公報、特公平２－１６７６５号公報に記載されているようなウレタンアクリレート類や、特公昭５８－４９８６０号公報、特公昭５６－１７６５４号公報、特公昭６２－３９４１７号公報、特公昭６２－３９４１８号公報に記載のエチレンオキサイド系骨格を有するウレタン化合物類も好適である。さらに、重合性モノマーとして、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、特開平１－１０５２３８号公報に記載される、分子内にアミノ構造やスルフィド構造を有する化合物を用いることもできる。 Polymerizable monomers include urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used as polymerizable monomers. You can also.
　重合性モノマーは、カルボキシル基、スルホ基、リン酸基等の酸基を有する重合性モノマーであってもよい。酸基を有する重合性モノマーは、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルが好ましく、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシ基に非芳香族カルボン酸無水物を反応させて酸基を持たせた重合性モノマーがより好ましい。特に好ましくは、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシ基に非芳香族カルボン酸無水物を反応させて酸基を持たせた重合性モノマーにおいて、脂肪族ポリヒドロキシ化合物がペンタエリスリトールおよび／またはジペンタエリスリトールである化合物である。市販品としては、例えば、東亞合成（株）製の多塩基酸変性アクリルオリゴマーとして、Ｍ－５１０、Ｍ－５２０などが挙げられる。
　酸基を有する重合性モノマーは、１種を単独で用いてもよいが、２種以上を混合して用いてもよい。また、必要に応じて酸基を有しない重合性モノマーと酸基を有する重合性モノマーを併用してもよい。
　酸基を有する重合性モノマーの好ましい酸価は、０．１～４０ｍｇＫＯＨ／ｇであり、特に好ましくは５～３０ｍｇＫＯＨ／ｇである。重合性モノマーの酸価が上記範囲であれば、製造や取扱性に優れ、さらには、現像性に優れる。また、重合性が良好である。 The polymerizable monomer may be a polymerizable monomer having an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group. The polymerizable monomer having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxy group of the aliphatic polyhydroxy compound. More preferred is a polymerizable monomer. Particularly preferably, in the polymerizable monomer in which a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxy group of the aliphatic polyhydroxy compound to give an acid group, the aliphatic polyhydroxy compound is pentaerythritol and / or diester. It is a compound that is pentaerythritol. Examples of commercially available products include M-510, M-520 and the like as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
As the polymerizable monomer having an acid group, one kind may be used alone, or two or more kinds may be mixed and used. Moreover, you may use together the polymerizable monomer which does not have an acid group, and the polymerizable monomer which has an acid group as needed.
A preferable acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable monomer is within the above range, the production and handling properties are excellent, and further, the developability is excellent. Also, the polymerizability is good.
　重合性モノマーの含有量は、良好な重合性と耐熱性の観点から、本発明の組成物の全固形分に対して、１～５０質量％が好ましい。下限は５質量％以上がより好ましい。上限は、３０質量％以下がより好ましい。重合性モノマーは１種を単独で用いてもよいが、２種以上を混合して用いてもよい。
　また、ポリイミド前駆体と重合性モノマーとの質量割合（ポリイミド前駆体／重合性モノマー）は、９８／２～１０／９０が好ましく、９５／５～３０／７０がより好ましく、９０／１０～５０／５０がさらに好ましい。ポリイミド前駆体と重合性モノマーとの質量割合が上記範囲であれば、重合性および耐熱性により優れた硬化膜を形成できる。 The content of the polymerizable monomer is preferably 1 to 50% by mass with respect to the total solid content of the composition of the present invention from the viewpoint of good polymerizability and heat resistance. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 30% by mass or less. As the polymerizable monomer, one kind may be used alone, or two or more kinds may be mixed and used.
The mass ratio of the polyimide precursor and the polymerizable monomer (polyimide precursor / polymerizable monomer) is preferably 98/2 to 10/90, more preferably 95/5 to 30/70, and 90/10 to 50 / 50 is more preferable. If the mass ratio of a polyimide precursor and a polymerizable monomer is in the above range, a cured film that is superior in polymerizability and heat resistance can be formed.
　本発明の組成物は、硬化膜の弾性率制御に伴う反り抑制の観点から、単官能重合性モノマーを好ましく用いることができる。単官能重合性モノマーとしては、ｎ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、カルビトール（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、ベンジル（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、Ｎ－メチロール（メタ）アクリルアミド、グリシジル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート等の（メタ）アクリル酸誘導体、Ｎ－ビニルピロリドン、Ｎ－ビニルカプロラクタム等のＮ－ビニル化合物類、アリルグリシジルエーテル、ジアリルフタレート、トリアリルトリメリテート等のアリル化合物類等が好ましく用いられる。単官能重合性モノマーとしては、露光前の揮発を抑制するため、常圧下で１００℃以上の沸点を持つ化合物も好ましい。 In the composition of the present invention, a monofunctional polymerizable monomer can be preferably used from the viewpoint of warpage suppression accompanying the control of the elastic modulus of the cured film. Monofunctional polymerizable monomers include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc. Allylation of acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone, N-vinylcaprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, etc. Goods and the like are preferably used. As the monofunctional polymerizable monomer, a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
＜＜他の重合性化合物＞＞
　本発明の組成物は、上述したポリイミド前駆体およびラジカル重合性化合物以外の他の重合性化合物をさらに含むことができる。他の重合性化合物としては、ヒドロキシメチル基、アルコキシメチル基またはアシルオキシメチル基を有する化合物；エポキシ化合物；オキセタン化合物；ベンゾオキサジン化合物が挙げられる。 << Other polymerizable compounds >>
The composition of this invention can further contain other polymeric compounds other than the polyimide precursor mentioned above and a radically polymerizable compound. Other polymerizable compounds include compounds having a hydroxymethyl group, alkoxymethyl group or acyloxymethyl group; epoxy compounds; oxetane compounds; benzoxazine compounds.
（ヒドロキシメチル基、アルコキシメチル基またはアシルオキシメチル基を有する化合物）
　ヒドロキシメチル基、アルコキシメチル基またはアシルオキシメチル基を有する化合物としては、下記式（ＡＭ１）で示される化合物が好ましい。 (Compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group)
As the compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, a compound represented by the following formula (AM1) is preferable.
Figure JPOXMLDOC01-appb-C000053
 （式中、ｔは、１～２０の整数を示し、Ｒ４は炭素数１～２００のｔ価の有機基を示し、Ｒ５は、－ＯＲ６または、－ＯＣＯ－Ｒ７で示される基を示し、Ｒ６は、水素原子または炭素数１～１０の有機基を示し、Ｒ７は、炭素数１～１０の有機基を示す。）
Figure JPOXMLDOC01-appb-C000053
 (Wherein t represents an integer of 1 to 20, R 4 represents a t-valent organic group having 1 to 200 carbon atoms, and R 5 represents a group represented by —OR 6 or —OCO—R 7. R 6 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R 7 represents an organic group having 1 to 10 carbon atoms.)
　ポリイミド前駆体１００質量部に対して、式（ＡＭ１）で示される化合物の含有量は、５～４０質量部であることが好ましい。さらに好ましくは、１０～３５質量部である。また、他の重合性化合物の全量中に、下記式（ＡＭ４）で表される化合物を１０～９０質量％含有し、下記式（ＡＭ５）で表される化合物を１０～９０質量％含有することも好ましい。 The content of the compound represented by the formula (AM1) is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor. More preferably, it is 10 to 35 parts by mass. Further, the compound represented by the following formula (AM4) is contained in the total amount of other polymerizable compounds in an amount of 10 to 90% by mass, and the compound represented by the following formula (AM5) is contained in an amount of 10 to 90% by mass Is also preferable.
Figure JPOXMLDOC01-appb-C000054
 （式中、Ｒ４は炭素数１～２００の２価の有機基を示し、Ｒ５は、－ＯＲ６または、－ＯＣＯ－Ｒ７で示される基を示し、Ｒ６は、水素原子または炭素数１～１０の有機基を示し、Ｒ７は、炭素数１～１０の有機基を示す。）
Figure JPOXMLDOC01-appb-C000054
 (Wherein R 4 represents a divalent organic group having 1 to 200 carbon atoms, R 5 represents a group represented by —OR 6 or —OCO—R 7 , and R 6 represents a hydrogen atom or a carbon atom. An organic group having 1 to 10 carbon atoms, and R 7 represents an organic group having 1 to 10 carbon atoms.
Figure JPOXMLDOC01-appb-C000055
 （式中ｕは３～８の整数を示し、Ｒ４は炭素数１～２００のｕ価の有機基を示し、Ｒ５は、－ＯＲ６または、－ＯＣＯ－Ｒ７で示される基を示し、Ｒ６は、水素原子または炭素数１～１０の有機基を示し、Ｒ７は、炭素数１～１０の有機基を示す。）
Figure JPOXMLDOC01-appb-C000055
 (Wherein u represents an integer of 3 to 8, R 4 represents a u-valent organic group having 1 to 200 carbon atoms, and R 5 represents a group represented by —OR 6 or —OCO—R 7. R 6 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and R 7 represents an organic group having 1 to 10 carbon atoms.)
　上述のヒドロキシメチル基等を有する化合物を用いることで、凹凸のある基板上に本発明の組成物を適用した際に、クラックの発生をより効果的に抑制できる。また、パターン加工性に優れ、５％質量減少温度が３５０℃以上、より好ましくは３８０℃以上となる高い耐熱性を有する硬化膜を形成することができる。式（ＡＭ４）で示される化合物の具体例としては、４６ＤＭＯＣ、４６ＤＭＯＥＰ（以上、商品名、旭有機材工業（株）製）、ＤＭＬ－ＭＢＰＣ、ＤＭＬ－ＭＢＯＣ、ＤＭＬ－ＯＣＨＰ、ＤＭＬ－ＰＣＨＰ、ＤＭＬ－ＰＣ、ＤＭＬ－ＰＴＢＰ、ＤＭＬ－３４Ｘ、ＤＭＬ－ＥＰ、ＤＭＬ－ＰＯＰ、ｄｉｍｅｔｈｙｌｏｌＢｉｓＯＣ－Ｐ、ＤＭＬ－ＰＦＰ、ＤＭＬ－ＰＳＢＰ、ＤＭＬ－ＭＴｒｉｓＰＣ（以上、商品名、本州化学工業（株）製）、ＮＩＫＡＬＡＣ　ＭＸ－２９０（商品名、（株）三和ケミカル製）、２，６－ｄｉｍｅｔｈｏｘｙｍｅｔｈｙｌ－４－ｔ－ｂｕｔｈｙｌｐｈｅｎｏｌ、２，６－ｄｉｍｅｔｈｏｘｙｍｅｔｈｙｌ－ｐ－ｃｒｅｓｏｌ、２，６－ｄｉａｃｅｔｈｏｘｙｍｅｔｈｙｌ－ｐ－ｃｒｅｓｏｌなどが挙げられる。 By using the above-mentioned compound having a hydroxymethyl group or the like, the occurrence of cracks can be more effectively suppressed when the composition of the present invention is applied to an uneven substrate. Moreover, it is excellent in pattern workability and can form the cured film which has high heat resistance from which 5% mass reduction | decrease temperature becomes 350 degreeC or more, More preferably, it is 380 degreeC or more. Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML. -PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), NIKACALAC MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.), 2,6-dimethylmethyl-4-t-butylphenol, 2,6-dimethylmethyl-p-cresol, 2,6-diaxymethyl-p-cresol, etc. It is done.
　また、式（ＡＭ５）で示される化合物の具体例としては、ＴｒｉＭＬ－Ｐ、ＴｒｉＭＬ－３５ＸＬ、ＴＭＬ－ＨＱ、ＴＭＬ－ＢＰ、ＴＭＬ－ｐｐ－ＢＰＦ、ＴＭＬ－ＢＰＡ、ＴＭＯＭ－ＢＰ、ＨＭＬ－ＴＰＰＨＢＡ、ＨＭＬ－ＴＰＨＡＰ、ＨＭＯＭ－ＴＰＰＨＢＡ、ＨＭＯＭ－ＴＰＨＡＰ（以上、商品名、本州化学工業（株）製）、ＴＭ－ＢＩＰ－Ａ（商品名、旭有機材工業（株）製）、ＮＩＫＡＬＡＣ　ＭＸ－２８０、ＮＩＫＡＬＡＣ　ＭＸ－２７０、ＮＩＫＡＬＡＣ　ＭＷ－１００ＬＭ（以上、商品名、（株）三和ケミカル製）が挙げられる。 Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Co., Ltd.), NIKALAC MX-280, NIKALAC MX-270, NIKALAC MW-100LM (trade name, manufactured by Sanwa Chemical Co., Ltd.).
（エポキシ化合物（エポキシ基を有する化合物））
　エポキシ化合物としては、一分子中にエポキシ基を２以上有する化合物であることが好ましい。エポキシ基は、２００℃以下で架橋反応し、かつ、架橋に由来する脱水反応が起こらないため膜収縮が起きにくい。このため、エポキシ化合物を含有することは、組成物の低温硬化および反りの抑制に効果的である。 (Epoxy compound (compound having an epoxy group))
The epoxy compound is preferably a compound having two or more epoxy groups in one molecule. The epoxy group undergoes a cross-linking reaction at 200 ° C. or less and does not cause a dehydration reaction derived from the cross-linking, so that film shrinkage hardly occurs. For this reason, containing an epoxy compound is effective for low-temperature curing and warping of the composition.
　エポキシ化合物は、ポリエチレンオキサイド基を含有することが好ましい。これにより、より弾性率が低下し、また反りを抑制することができる。ポリエチレンオキサイド基は、エチレンオキサイドの繰り返し単位数が２以上のものを意味し、繰り返し単位数が２～１５であることが好ましい。 The epoxy compound preferably contains a polyethylene oxide group. Thereby, an elasticity modulus falls more and also curvature can be suppressed. The polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
　エポキシ化合物の例としては、ビスフェノールＡ型エポキシ樹脂；ビスフェノールＦ型エポキシ樹脂；プロピレングリコールジグリシジルエーテル等のアルキレングリコール型エポキシ樹脂；ポリプロピレングリコールジグリシジルエーテル等のポリアルキレングリコール型エポキシ樹脂；ポリメチル（グリシジロキシプロピル）シロキサン等のエポキシ基含有シリコーンなどを挙げることができるが、これらに限定されない。具体的には、エピクロン（登録商標）８５０－Ｓ、エピクロン（登録商標）ＨＰ－４０３２、エピクロン（登録商標）ＨＰ－７２００、エピクロン（登録商標）ＨＰ－８２０、エピクロン（登録商標）ＨＰ－４７００、エピクロン（登録商標）ＥＸＡ－４７１０、エピクロン（登録商標）ＨＰ－４７７０、エピクロン（登録商標）ＥＸＡ－８５９ＣＲＰ、エピクロン（登録商標）ＥＸＡ－１５１４、エピクロン（登録商標）ＥＸＡ－４８８０、エピクロン（登録商標）ＥＸＡ－４８５０－１５０、エピクロンＥＸＡ－４８５０－１０００、エピクロン（登録商標）ＥＸＡ－４８１６、エピクロン（登録商標）ＥＸＡ－４８２２（以上商品名、大日本インキ化学工業（株）製）、リカレジン（登録商標）ＢＥＯ－６０Ｅ（商品名、新日本理化（株）製）、ＥＰ－４００３Ｓ、ＥＰ－４０００Ｓ（以上商品名、（株）ＡＤＥＫＡ製）などが挙げられる。この中でも、ポリエチレンオキサイド基を含有するエポキシ樹脂が、反りの抑制および耐熱性に優れる点で好ましい。例えば、エピクロン（登録商標）ＥＸＡ－４８８０、エピクロン（登録商標）ＥＸＡ－４８２２、リカレジン（登録商標）ＢＥＯ－６０Ｅは、ポリエチレンオキサイド基を含有するので好ましい。 Examples of epoxy compounds include: bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidyl Examples include, but are not limited to, epoxy group-containing silicones such as (roxypropyl) siloxane. Specifically, Epicron (registered trademark) 850-S, Epicron (registered trademark) HP-4032, Epicron (registered trademark) HP-7200, Epicron (registered trademark) HP-820, Epicron (registered trademark) HP-4700, Epicron (registered trademark) EXA-4710, Epicron (registered trademark) HP-4770, Epicron (registered trademark) EXA-859CRP, Epicron (registered trademark) EXA-1514, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Rica Resin (registered trademark) ) BEO-60E (trade name, Shin Nippon Rika ( ) Made), EP-4003S, EP-4000S (trade names, and the like (Ltd.) ADEKA). Among these, an epoxy resin containing a polyethylene oxide group is preferable in terms of suppressing warpage and excellent heat resistance. For example, Epicron (registered trademark) EXA-4880, Epicron (registered trademark) EXA-4822, and Licaredin (registered trademark) BEO-60E are preferable because they contain a polyethylene oxide group.
　エポキシ化合物の含有量は、ポリイミド前駆体１００質量部に対し、５～５０質量部が好ましく、１０～５０質量部がより好ましく、１０～４０質量部がさらに好ましい。エポキシ化合物の含有量が５質量部以上であれば、得られる硬化膜の反りをより抑制でき、５０質量部以下であれば、硬化時のリフローを原因とするパターン埋まりをより抑制できる。 The content of the epoxy compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor. If the content of the epoxy compound is 5 parts by mass or more, warpage of the resulting cured film can be further suppressed, and if it is 50 parts by mass or less, pattern filling caused by reflow during curing can be further suppressed.
（オキセタン化合物（オキセタニル基を有する化合物））
　オキセタン化合物としては、一分子中にオキセタン環を２つ以上有する化合物、３－エチル－３－ヒドロキシメチルオキセタン、１，４－ビス｛［（３－エチル－３－オキセタニル）メトキシ］メチル｝ベンゼン、３－エチル－３－（２－エチルヘキシルメチル）オキセタン、１，４－ベンゼンジカルボン酸－ビス［（３－エチル－３－オキセタニル）メチル］エステル等を挙げることができる。具体的な例としては、東亞合成（株）製のアロンオキセタンシリーズ（例えば、ＯＸＴ－１２１、ＯＸＴ－２２１、ＯＸＴ－１９１、ＯＸＴ－２２３）が好適に使用することができ、これらは単独で、あるいは２種以上混合してもよい。 (Oxetane compound (compound having oxetanyl group))
Examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, Examples include 3-ethyl-3- (2-ethylhexylmethyl) oxetane and 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester. As specific examples, Aron Oxetane series (for example, OXT-121, OXT-221, OXT-191, OXT-223) manufactured by Toagosei Co., Ltd. can be suitably used, and these are used alone. Or you may mix 2 or more types.
　オキセタン化合物の含有量は、ポリイミド前駆体１００質量部に対し、５～５０質量部が好ましく、１０～５０質量部がより好ましく、１０～４０質量部がさらに好ましい。 The content of the oxetane compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor.
（ベンゾオキサジン化合物（ベンゾオキサゾリル基を有する化合物））
　ベンゾオキサジン化合物は、開環付加反応に由来する架橋反応のため、硬化時に脱ガスが発生せず、さらに熱収縮を小さくして反りの発生が抑えられることから好ましい。 (Benzoxazine compound (compound having a benzoxazolyl group))
A benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur at the time of curing, and thermal contraction is further reduced to suppress warpage.
　ベンゾオキサジン化合物の好ましい例としては、Ｂ－ａ型ベンゾオキサジン、Ｂ－ｍ型ベンゾオキサジン（以上、商品名、四国化成工業（株）製）、ポリヒドロキシスチレン樹脂のベンゾオキサジン付加物、フェノールノボラック型ジヒドロベンゾオキサジン化合物が挙げられる。これらは単独で用いるか、あるいは２種以上混合してもよい。 Preferred examples of the benzoxazine compound include Ba type benzoxazine, Bm type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type A dihydrobenzoxazine compound is mentioned. These may be used alone or in combination of two or more.
　ベンゾオキサジン化合物の含有量は、ポリイミド前駆体１００質量部に対し、５～５０質量部が好ましく、１０～５０質量部がより好ましく、１０～４０質量部がさらに好ましい。 The content of the benzoxazine compound is preferably 5 to 50 parts by mass, more preferably 10 to 50 parts by mass, and still more preferably 10 to 40 parts by mass with respect to 100 parts by mass of the polyimide precursor.
＜＜マイグレーション抑制剤＞＞
　感光性樹脂組成物は、さらにマイグレーション抑制剤を含むことが好ましい。マイグレーション抑制剤を含むことにより、金属層（金属配線）由来の金属イオンが感光性樹脂組成物層内へ移動することを効果的に抑制可能となる。
　マイグレーション抑制剤としては、特に制限はないが、複素環（ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピラゾール環、イソオキサゾール環、イソチアゾール環、テトラゾール環、ピリジン環、ピリダジン環、ピリミジン環、ピラジン環、ピペリジン環、ピペラジン環、モルホリン環、２Ｈ－ピラン環および６Ｈ－ピラン環、トリアジン環）を有する化合物、チオ尿素類およびメルカプト基を有する化合物、ヒンダードフェノール系化合物、サリチル酸誘導体系化合物、ヒドラジド誘導体系化合物が挙げられる。特に、トリアゾール、ベンゾトリアゾール等のトリアゾール系化合物、テトラゾール、ベンゾテトラゾール等のテトラゾール系化合物が好ましく使用できる。 << Migration inhibitor >>
It is preferable that the photosensitive resin composition further contains a migration inhibitor. By including the migration inhibitor, it is possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the photosensitive resin composition layer.
The migration inhibitor is not particularly limited, but a heterocyclic ring (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, Compounds having pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and mercapto groups, hindered phenol compounds , Salicylic acid derivative compounds and hydrazide derivative compounds. In particular, triazole compounds such as triazole and benzotriazole, and tetrazole compounds such as tetrazole and benzotetrazole can be preferably used.
　また、ハロゲンイオンなどの陰イオンを捕捉するイオントラップ剤を使用することもできる。 Also, an ion trapping agent that traps anions such as halogen ions can be used.
　その他のマイグレーション抑制剤としては、特開２０１３－１５７０１号公報の段落００９４に記載の防錆剤、特開２００９－２８３７１１号公報の段落００７３～００７６に記載の化合物、特開２０１１－５９６５６号公報の段落００５２に記載の化合物、特開２０１２－１９４５２０号公報の段落０１１４、０１１６および０１１８に記載の化合物などを使用することができる。 Examples of other migration inhibitors include rust inhibitors described in paragraph 0094 of JP2013-15701A, compounds described in paragraphs 0073 to 0076 of JP2009-283711A, and JP2011-95956A. The compounds described in paragraph 0052 and the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A can be used.
　マイグレーション抑制剤の具体例としては、下記化合物を挙げることができる。
Figure JPOXMLDOC01-appb-C000056
 Specific examples of the migration inhibitor include the following compounds.
Figure JPOXMLDOC01-appb-C000056
　感光性樹脂組成物がマイグレーション抑制剤を有する場合、マイグレーション抑制剤の含有量は、感光性樹脂組成物の全固形分に対して、０．０１～５．０質量％が好ましく、０．０５～２．０質量％がより好ましく、０．１～１．０質量％がさらに好ましい。
　マイグレーション抑制剤は１種のみでもよいし、２種以上であってもよい。マイグレーション抑制剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 When the photosensitive resin composition has a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the photosensitive resin composition, 0.05 to 2.0% by mass is more preferable, and 0.1 to 1.0% by mass is more preferable.
Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more migration inhibitors, the total is preferably within the above range.
＜＜重合禁止剤＞＞
　本発明の組成物は、重合禁止剤を含むことが好ましい。
　重合禁止剤としては、例えば、ヒドロキノン、ｐ－メトキシフェノール、ジ－ｔｅｒｔ－ブチル－ｐ－クレゾール、ピロガロール、ｐ－ｔｅｒｔ－ブチルカテコール、ｐ－ベンゾキノン、ジフェニル－ｐ－ベンゾキノン、４，４’－チオビス（３－メチル－６－ｔｅｒｔ－ブチルフェノール）、２，２’－メチレンビス（４－メチル－６－ｔｅｒｔ－ブチルフェノール）、Ｎ－ニトロソ－Ｎ－フェニルヒドロキシアミンアルミニウム塩、フェノチアジン、Ｎ－ニトロソジフェニルアミン、Ｎ－フェニルナフチルアミン、エチレンジアミン四酢酸、１，２－シクロヘキサンジアミン四酢酸、グリコールエーテルジアミン四酢酸、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、５－ニトロソ－８－ヒドロキシキノリン、１－ニトロソ－２－ナフトール、２－ニトロソ－１－ナフトール、２－ニトロソ－５－（Ｎ－エチル－Ｎ－スルフォプロピルアミノ）フェノール、Ｎ－ニトロソ－Ｎ－（１－ナフチル）ヒドロキシアミンアンモニウム塩、ビス（４－ヒドロキシ－３，５－ｔｅｒｔ－ブチル）フェニルメタンなどが好適に用いられる。また、特開２０１５－１２７８１７号公報の段落００６０に記載の重合禁止剤、および、国際公開ＷＯ２０１５／１２５４６９号の段落００３１～００４６に記載の化合物を用いることもできる。
　また、下記化合物を用いることができる（Ｍｅはメチル基である）。
Figure JPOXMLDOC01-appb-C000057
 　本発明の組成物が重合禁止剤を有する場合、重合禁止剤の含有量は、本発明の組成物の全固形分に対して、０．０１～５質量％が好ましい。
　重合禁止剤は１種のみでもよいし、２種以上であってもよい。重合禁止剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 << Polymerization inhibitor >>
The composition of the present invention preferably contains a polymerization inhibitor.
Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, p-benzoquinone, diphenyl-p-benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine, N -Phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso -2 Naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, bis (4- Hydroxy-3,5-tert-butyl) phenylmethane and the like are preferably used. In addition, a polymerization inhibitor described in paragraph 0060 of JP-A-2015-127817 and compounds described in paragraphs 0031 to 0046 of international publication WO2015 / 125469 can also be used.
Moreover, the following compound can be used (Me is a methyl group).
Figure JPOXMLDOC01-appb-C000057
 When the composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the composition of the present invention.
Only one polymerization inhibitor may be used, or two or more polymerization inhibitors may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
＜＜金属接着性改良剤＞＞
　本発明の組成物は、電極や配線などに用いられる金属材料との接着性を向上させるための金属接着性改良剤を含んでいることが好ましい。金属接着性改良剤としては、シランカップリング剤などが挙げられる。 << Metal adhesion improver >>
It is preferable that the composition of this invention contains the metal adhesive improvement agent for improving the adhesiveness with the metal material used for an electrode, wiring, etc. Examples of metal adhesion improvers include silane coupling agents.
　シランカップリング剤の例としては、特開２０１４－１９１００２号公報の段落００６２～００７３に記載の化合物、国際公開ＷＯ２０１１／０８０９９２Ａ１号の段落００６３～００７１に記載の化合物、特開２０１４－１９１２５２号公報の段落００６０～００６１に記載の化合物、特開２０１４－４１２６４号公報の段落００４５～００５２に記載の化合物、国際公開ＷＯ２０１４／０９７５９４号の段落００５５に記載の化合物が挙げられる。また、特開２０１１－１２８３５８号公報の段落００５０～００５８に記載のように異なる２種以上のシランカップリング剤を用いることも好ましい。また、シランカップリング剤は、下記化合物を用いることも好ましい。以下の式中、Ｅｔはエチル基を表す。
Figure JPOXMLDOC01-appb-C000058
 Examples of the silane coupling agent include compounds described in paragraphs 0062 to 0073 of JP2014-191002, compounds described in paragraphs 0063 to 0071 of international publication WO2011 / 080992A1, and JP2014-191252A. Examples thereof include compounds described in paragraphs 0060 to 0061, compounds described in paragraphs 0045 to 0052 of JP 2014-41264 A, and compounds described in paragraph 0055 of international publication WO 2014/097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Moreover, it is also preferable to use the following compound for a silane coupling agent. In the following formula, Et represents an ethyl group.
Figure JPOXMLDOC01-appb-C000058
　また、金属接着性改良剤は、特開２０１４－１８６１８６号公報の段落００４６～００４９に記載の化合物、特開２０１３－０７２９３５号公報の段落００３２～００４３に記載のスルフィド系化合物を用いることもできる。 As the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of JP-A-2014-186186 and sulfide-based compounds described in paragraphs 0032 to 0043 of JP-A-2013-072935 can also be used.
　金属接着性改良剤の含有量はポリイミド前駆体１００質量部に対して、好ましくは０．１～３０質量部であり、より好ましくは０．５～１５質量部の範囲である。０．１質量部以上とすることで硬化工程後の硬化膜と金属層との接着性が良好となり、３０質量部以下とすることで硬化工程後の硬化膜の耐熱性、機械特性が良好となる。金属接着性改良剤は１種のみでもよいし、２種以上であってもよい。２種以上用いる場合は、その合計が上記範囲であることが好ましい。 The content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the polyimide precursor. Adhesiveness between the cured film and the metal layer after the curing process becomes good by setting it to 0.1 parts by mass or more, and heat resistance and mechanical properties of the cured film after the curing process are good by setting it to 30 parts by mass or less. Become. Only one type of metal adhesion improver may be used, or two or more types may be used. When using 2 or more types, it is preferable that the sum total is the said range.
＜＜塩基発生剤＞＞
　本発明で用いる組成物は、塩基発生剤を含んでいてもよい。塩基発生剤は、熱塩基発生剤でも光塩基発生剤でもよく、光塩基発生剤を少なくとも含むことが好ましい。 << Base generator >>
The composition used in the present invention may contain a base generator. The base generator may be a thermal base generator or a photobase generator, and preferably contains at least a photobase generator.
＜＜＜熱塩基発生剤＞＞＞
　熱塩基発生剤としては、その種類等は特に定めるものではないが、４０℃以上に加熱すると塩基を発生する酸性化合物、および、ｐＫａ１が０～４のアニオンとアンモニウムカチオンとを有するアンモニウム塩から選ばれる少なくとも一種を含む熱塩基発生剤を含むことが好ましい。ここで、ｐＫａ１とは、多価の酸の第一のプロトンの解離定数（Ｋａ）の対数表示（－Ｌｏｇ１０Ｋａ）を示す。
　このような化合物を配合することにより、ポリイミド前駆体の環化反応を低温で行うことができ、また、より安定性に優れた組成物とすることができる。また、熱塩基発生剤は、加熱しなければ塩基を発生しないので、ポリイミド前駆体と共存させても、保存中におけるポリイミド前駆体の環化を抑制でき、保存安定性に優れている。 <<< Heat base generator >>>
The type of the thermal base generator is not particularly defined, but it is selected from an acidic compound that generates a base when heated to 40 ° C. or higher, and an ammonium salt having an anion having an pKa1 of 0 to 4 and an ammonium cation. It is preferable to include a thermal base generator containing at least one of the above. Here, pKa1 represents a logarithmic representation (−Log 10 Ka) of the dissociation constant (Ka) of the first proton of the polyvalent acid.
By mix | blending such a compound, the cyclization reaction of a polyimide precursor can be performed at low temperature, and it can be set as the composition excellent in stability. In addition, since the thermal base generator does not generate a base unless it is heated, cyclization of the polyimide precursor during storage can be suppressed even if it coexists with the polyimide precursor, and is excellent in storage stability.
　本発明における熱塩基発生剤は、４０℃以上に加熱すると塩基を発生する酸性化合物（Ａ１）、および、ｐＫａ１が０～４のアニオンとアンモニウムカチオンとを有するアンモニウム塩（Ａ２）から選ばれる少なくとも一種を含む。
　上記酸性化合物（Ａ１）および上記アンモニウム塩（Ａ２）は、加熱すると塩基を発生するので、これらの化合物から発生した塩基により、ポリイミド前駆体の環化反応を促進でき、ポリイミド前駆体の環化を低温で行うことができる。また、これらの化合物は、塩基により環化して硬化するポリイミド前駆体と共存させても、加熱しなければポリイミド前駆体の環化が殆ど進行しないので、安定性に優れたポリイミド前駆体組成物を調製することができる。
　なお、本明細書において、酸性化合物とは、化合物を容器に１ｇ採取し、イオン交換水とテトラヒドロフランとの混合液（質量比は水／テトラヒドロフラン＝１／４）を５０ｍＬ加えて、室温で１時間撹拌する。その溶液をｐＨメーターを用いて、２０℃にて測定した値が７未満である化合物を意味する。 The thermal base generator in the present invention is at least one selected from an acidic compound (A1) that generates a base when heated to 40 ° C. or higher, and an ammonium salt (A2) having an anion having a pKa1 of 0 to 4 and an ammonium cation. including.
Since the acidic compound (A1) and the ammonium salt (A2) generate a base when heated, the base generated from these compounds can accelerate the cyclization reaction of the polyimide precursor, thereby cyclizing the polyimide precursor. Can be performed at low temperatures. In addition, even if these compounds coexist with a polyimide precursor that is cured by cyclization with a base, since the cyclization of the polyimide precursor hardly proceeds unless heated, a polyimide precursor composition having excellent stability can be obtained. Can be prepared.
In the present specification, an acidic compound means that 1 g of a compound is collected in a container, and 50 mL of a mixed solution of ion-exchanged water and tetrahydrofuran (mass ratio is water / tetrahydrofuran = 1/4) is added to the mixture at room temperature for 1 hour. Stir. The value of the solution measured at 20 ° C. using a pH meter is less than 7.
　本発明において、酸性化合物（Ａ１）およびアンモニウム塩（Ａ２）の塩基発生温度は、４０℃以上が好ましく、１２０～２００℃がより好ましい。塩基発生温度の上限は、１９０℃以下が好ましく、１８０℃以下がより好ましく、１６５℃以下がさらに好ましい。塩基発生温度の下限は、１３０℃以上が好ましく、１３５℃以上がより好ましい。
　酸性化合物（Ａ１）およびアンモニウム塩（Ａ２）の塩基発生温度が１２０℃以上であれば、保存中に塩基が発生しにくいので、安定性に優れたポリイミド前駆体組成物を調製することができる。酸性化合物（Ａ１）およびアンモニウム塩（Ａ２）の塩基発生温度が２００℃以下であれば、ポリイミド前駆体の環化温度を低下できる。塩基発生温度は、例えば、示差走査熱量測定を用い、化合物を耐圧カプセル中５℃／分で２５０℃まで加熱し、最も温度が低い発熱ピークのピーク温度を読み取り、ピーク温度を塩基発生温度として測定することができる。 In the present invention, the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is preferably 40 ° C. or higher, more preferably 120 to 200 ° C. The upper limit of the base generation temperature is preferably 190 ° C. or lower, more preferably 180 ° C. or lower, and further preferably 165 ° C. or lower. The lower limit of the base generation temperature is preferably 130 ° C or higher, and more preferably 135 ° C or higher.
If the base generation temperature of the acidic compound (A1) and the ammonium salt (A2) is 120 ° C. or higher, a base is unlikely to be generated during storage, and thus a polyimide precursor composition having excellent stability can be prepared. If the base generation temperature of the acidic compound (A1) and ammonium salt (A2) is 200 ° C. or lower, the cyclization temperature of the polyimide precursor can be lowered. The base generation temperature is measured, for example, by using differential scanning calorimetry, heating the compound to 250 ° C. at 5 ° C./min in a pressure capsule, reading the peak temperature of the lowest exothermic peak, and measuring the peak temperature as the base generation temperature. can do.
　本発明において、熱塩基発生剤により発生する塩基は、２級アミンまたは３級アミンが好ましく、３級アミンがより好ましい。３級アミンは、塩基性が高いので、ポリイミド前駆体の環化温度をより低下できる。また、熱塩基発生剤により発生する塩基の沸点は、８０℃以上であることが好ましく、１００℃以上であることがより好ましく、１４０℃以上であることがさらに好ましい。また、発生する塩基の分子量は、８０～２０００が好ましい。下限は１００以上がより好ましい。上限は５００以下がより好ましい。なお、分子量の値は、構造式から求めた理論値である。 In the present invention, the base generated by the thermal base generator is preferably a secondary amine or a tertiary amine, more preferably a tertiary amine. Since tertiary amine has high basicity, the cyclization temperature of a polyimide precursor can be lowered more. The base generated by the thermal base generator preferably has a boiling point of 80 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 140 ° C. or higher. The molecular weight of the generated base is preferably 80 to 2000. The lower limit is more preferably 100 or more. The upper limit is more preferably 500 or less. The molecular weight value is a theoretical value obtained from the structural formula.
　本発明において、上記酸性化合物（Ａ１）は、アンモニウム塩および後述する式（１０１）または（１０２）で表される化合物から選ばれる１種以上を含むことが好ましい。 In the present invention, the acidic compound (A1) preferably contains one or more selected from an ammonium salt and a compound represented by the formula (101) or (102) described later.
　本発明において、上記アンモニウム塩（Ａ２）は、酸性化合物であることが好ましい。なお、上記アンモニウム塩（Ａ２）は、４０℃以上（好ましくは１２０～２００℃）に加熱すると塩基を発生する酸性化合物を含む化合物であってもよいし、４０℃以上（好ましくは１２０～２００℃）に加熱すると塩基を発生する酸性化合物を除く化合物であってもよい。 In the present invention, the ammonium salt (A2) is preferably an acidic compound. The ammonium salt (A2) may be a compound containing an acidic compound that generates a base when heated to 40 ° C. or higher (preferably 120 to 200 ° C.), or 40 ° C. or higher (preferably 120 to 200 ° C.). ) May be a compound excluding an acidic compound that generates a base when heated.
＜＜＜＜アンモニウム塩＞＞＞＞
　本発明において、アンモニウム塩とは、下記式（１０１）または式（１０２）で表されるアンモニウムカチオンと、アニオンとの塩を意味する。アニオンは、アンモニウムカチオンのいずれかの一部と共有結合を介して結合していてもよく、アンモニウムカチオンの分子外に有していてもよいが、アンモニウムカチオンの分子外に有していることが好ましい。なお、アニオンが、アンモニウムカチオンの分子外に有するとは、アンモニウムカチオンとアニオンが共有結合を介して結合していない場合をいう。以下、カチオン部の分子外のアニオンを対アニオンともいう。
式（１０１）　　　　式（１０２）
Figure JPOXMLDOC01-appb-C000059
 　式中Ｒ１～Ｒ６は、それぞれ独立に、水素原子または炭化水素基を表し、Ｒ７は炭化水素基を表す。Ｒ１とＲ２、Ｒ３とＲ４、Ｒ５とＲ６、Ｒ５とＲ７はそれぞれ結合して環を形成してもよい。 <<<<< Ammonium salt >>>>
In the present invention, the ammonium salt means a salt of an ammonium cation represented by the following formula (101) or formula (102) and an anion. The anion may be bonded to any part of the ammonium cation via a covalent bond, and may be outside the molecule of the ammonium cation, but may be outside the molecule of the ammonium cation. preferable. In addition, that an anion has outside the molecule | numerator of an ammonium cation means the case where an ammonium cation and an anion are not couple | bonded through a covalent bond. Hereinafter, the anion outside the molecule of the cation moiety is also referred to as a counter anion.
Formula (101) Formula (102)
Figure JPOXMLDOC01-appb-C000059
 In the formula, R 1 to R 6 each independently represents a hydrogen atom or a hydrocarbon group, and R 7 represents a hydrocarbon group. R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 5 and R 7 may be bonded to form a ring.
　アンモニウムカチオンは、下記式（Ｙ１－１）～（Ｙ１－５）のいずれかで表されることが好ましい。
Figure JPOXMLDOC01-appb-C000060
 The ammonium cation is preferably represented by any of the following formulas (Y1-1) to (Y1-5).
Figure JPOXMLDOC01-appb-C000060
　式（Ｙ１－１）～（Ｙ１－５）において、Ｒ１０１は、ｎ価の有機基を表し、Ｒ１およびＲ７は、式（１０１）または式（１０２）におけるＲ１およびＲ７と同義である。
　式（Ｙ１－１）～（Ｙ１－４）において、Ａｒ１０１およびＡｒ１０２は、それぞれ独立に、アリール基を表し、ｎは、１以上の整数を表し、ｍは、０～５の整数を表す。 In Formula (Y1-1) ~ (Y1-5), R 101 represents an n-valent organic group, R 1 and R 7 are synonymous with R 1 and R 7 in the formula (101) or formula (102) It is.
In formulas (Y1-1) to (Y1-4), Ar 101 and Ar 102 each independently represent an aryl group, n represents an integer of 1 or more, and m represents an integer of 0 to 5 .
　本実施形態において、アンモニウム塩は、ｐＫａ１が０～４のアニオンとアンモニウムカチオンとを有することが好ましい。アニオンのｐＫａ１の上限は、３．５以下がより好ましく、３．２以下が一層好ましい。下限は、０．５以上が好ましく、１．０以上がより好ましい。アニオンのｐＫａ１が上記範囲であれば、複素環含有ポリマー前駆体をより低温で環化でき、さらには、組成物の安定性を向上できる。ｐＫａ１が４以下であれば、熱塩基発生剤の安定性が良好で、加熱なしに塩基が発生することを抑制でき、組成物の安定性が良好である。ｐＫａ１が０以上であれば、発生した塩基が中和されにくく、複素環含有ポリマー前駆体などの環化効率が良好である。
　アニオンの種類は、カルボン酸アニオン、フェノールアニオン、リン酸アニオンおよび硫酸アニオンから選ばれる１種が好ましく、塩の安定性と熱分解性を両立させられるという理由からカルボン酸アニオンがより好ましい。すなわち、アンモニウム塩は、アンモニウムカチオンとカルボン酸アニオンとの塩がより好ましい。
　カルボン酸アニオンは、２個以上のカルボキシル基を持つ２価以上のカルボン酸のアニオンが好ましく、２価のカルボン酸のアニオンがより好ましい。この態様によれば、組成物の安定性、硬化性および現像性をより向上できる熱塩基発生剤とすることができる。特に、２価のカルボン酸のアニオンを用いることで、組成物の安定性、硬化性および現像性をさらに向上できる。
　本実施形態において、カルボン酸アニオンは、ｐＫａ１が４以下のカルボン酸のアニオンであることが好ましい。ｐＫａ１は、３．５以下がより好ましく、３．２以下が一層好ましい。この態様によれば、組成物の安定性をより向上できる。
　ここでｐＫａ１とは、酸の第一のプロトンの解離定数の逆数の対数を表し、Ｄｅｔｅｒｍｉｎａｔｉｏｎ　ｏｆ　Ｏｒｇａｎｉｃ　Ｓｔｒｕｃｔｕｒｅｓ　ｂｙ　Ｐｈｙｓｉｃａｌ　Ｍｅｔｈｏｄｓ（著者：Ｂｒｏｗｎ，　Ｈ．　Ｃ．，　ＭｃＤａｎｉｅｌ，　Ｄ．　Ｈ．，　Ｈａｆｌｉｇｅｒ，　Ｏ．，　Ｎａｃｈｏｄ，　Ｆ．　Ｃ．；　編纂：Ｂｒａｕｄｅ，　Ｅ．　Ａ．，　Ｎａｃｈｏｄ，　Ｆ．　Ｃ．；　Ａｃａｄｅｍｉｃ　Ｐｒｅｓｓ，　Ｎｅｗ　Ｙｏｒｋ，　１９５５）や、Ｄａｔａ　ｆｏｒ　Ｂｉｏｃｈｅｍｉｃａｌ　Ｒｅｓｅａｒｃｈ（著者：Ｄａｗｓｏｎ，　Ｒ．Ｍ．Ｃ．ｅｔ　ａｌ；　Ｏｘｆｏｒｄ，　Ｃｌａｒｅｎｄｏｎ　Ｐｒｅｓｓ，　１９５９）に記載の値を参照することができる。これらの文献に記載の無い化合物については、ＡＣＤ／ｐＫａ（ＡＣＤ／Ｌａｂｓ製）のソフトを用いて構造式より算出した値を用いることとする。 In this embodiment, the ammonium salt preferably has an anion having an pKa1 of 0 to 4 and an ammonium cation. The upper limit of the anion pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. The lower limit is preferably 0.5 or more, and more preferably 1.0 or more. When the pKa1 of the anion is in the above range, the heterocyclic ring-containing polymer precursor can be cyclized at a lower temperature, and the stability of the composition can be improved. If pKa1 is 4 or less, the stability of the thermal base generator is good, the generation of a base without heating can be suppressed, and the stability of the composition is good. If pKa1 is 0 or more, the generated base is not easily neutralized, and the cyclization efficiency of the heterocyclic-containing polymer precursor or the like is good.
The kind of anion is preferably one selected from a carboxylate anion, a phenol anion, a phosphate anion, and a sulfate anion, and a carboxylate anion is more preferable because both the stability of the salt and the thermal decomposability can be achieved. That is, the ammonium salt is more preferably a salt of an ammonium cation and a carboxylate anion.
The carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxyl groups, and more preferably a divalent carboxylic acid anion. According to this aspect, it is possible to provide a thermal base generator that can further improve the stability, curability and developability of the composition. In particular, the stability, curability and developability of the composition can be further improved by using an anion of a divalent carboxylic acid.
In the present embodiment, the carboxylic acid anion is preferably a carboxylic acid anion having a pKa1 of 4 or less. pKa1 is more preferably 3.5 or less, and even more preferably 3.2 or less. According to this aspect, the stability of the composition can be further improved.
Here, pKa1 represents the logarithm of the reciprocal of the dissociation constant of the first proton of the acid, and the determination of Organic Structures by Physical Methods (author: Brown, HC, McDaniel, D.H., Hafliger Ed .: Braude, EA, Nachod, FC; Academic Press, New York, 1955), and Data for Biochemical Research (author: Dawson, R. M.). al; Oxford, Clarendon Press, 1959). For compounds not described in these documents, values calculated from the structural formula using software of ACD / pKa (manufactured by ACD / Labs) are used.
　カルボン酸アニオンは、下記式（Ｘ１）で表されることが好ましい。
Figure JPOXMLDOC01-appb-C000061
 　式（Ｘ１）において、ＥＷＧは、電子求引性基を表す。 The carboxylate anion is preferably represented by the following formula (X1).
Figure JPOXMLDOC01-appb-C000061
 In the formula (X1), EWG represents an electron withdrawing group.
　本実施形態において電子求引性基とは、ハメットの置換基定数σｍが正の値を示すものを意味する。ここでσｍは、都野雄甫総説、有機合成化学協会誌第２３巻第８号（１９６５）ｐ．６３１－６４２に詳しく説明されている。なお、本実施形態における電子求引性基は、上記文献に記載された置換基に限定されるものではない。
　σｍが正の値を示す置換基の例としては例えば、ＣＦ３基（σｍ＝０．４３）、ＣＦ３ＣＯ基（σｍ＝０．６３）、ＨＣ≡Ｃ基（σｍ＝０．２１）、ＣＨ２＝ＣＨ基（σｍ＝０．０６）、Ａｃ基（σｍ＝０．３８）、ＭｅＯＣＯ基（σｍ＝０．３７）、ＭｅＣＯＣＨ＝ＣＨ基（σｍ＝０．２１）、ＰｈＣＯ基（σｍ＝０．３４）、Ｈ２ＮＣＯＣＨ２基（σｍ＝０．０６）などが挙げられる。なお、Ｍｅはメチル基を表し、Ａｃはアセチル基を表し、Ｐｈはフェニル基を表す（以下、同じ）。 In the present embodiment, the electron withdrawing group means a group in which Hammett's substituent constant σm exhibits a positive value. Here, σm is a review by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 631-642. In addition, the electron withdrawing group in this embodiment is not limited to the substituent described in the said literature.
Examples of substituents in which σm has a positive value include, for example, CF 3 group (σm = 0.43), CF 3 CO group (σm = 0.63), HC≡C group (σm = 0.21), CH 2 ═CH group (σm = 0.06), Ac group (σm = 0.38), MeOCO group (σm = 0.37), MeCOCH═CH group (σm = 0.21), PhCO group (σm = 0.34), H 2 NCOCH 2 group (σm = 0.06), and the like. Me represents a methyl group, Ac represents an acetyl group, and Ph represents a phenyl group (hereinafter the same).
　ＥＷＧは、下記式（ＥＷＧ－１）～（ＥＷＧ－６）で表される基であることが好ましい。
Figure JPOXMLDOC01-appb-C000062
 　式（ＥＷＧ－１）～（ＥＷＧ－６）中、Ｒｘ１～Ｒｘ３は、それぞれ独立に、水素原子、アルキル基、アルケニル基、アリール基、ヒドロキシル基またはカルボキシル基を表し、Ａｒは芳香族基を表す。 EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
Figure JPOXMLDOC01-appb-C000062
 In formulas (EWG-1) to (EWG-6), R x1 to R x3 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxyl group or a carboxyl group, and Ar represents an aromatic group Represents.
　本実施形態において、カルボン酸アニオンは、下記式（ＸＡ）で表されることが好ましい。
式（ＸＡ）
Figure JPOXMLDOC01-appb-C000063
 　式（ＸＡ）において、Ｌ１０は、単結合、または、アルキレン基、アルケニレン基、芳香族基、－ＮＲＸ－およびこれらの組み合わせから選ばれる２価の連結基を表し、ＲＸは、水素原子、アルキル基、アルケニル基またはアリール基を表す。 In the present embodiment, the carboxylate anion is preferably represented by the following formula (XA).
Formula (XA)
Figure JPOXMLDOC01-appb-C000063
 In the formula (XA), L 10 represents a single bond or a divalent linking group selected from an alkylene group, an alkenylene group, an aromatic group, —NR X —, and a combination thereof, and R X represents a hydrogen atom Represents an alkyl group, an alkenyl group or an aryl group.
　カルボン酸アニオンの具体例としては、マレイン酸アニオン、フタル酸アニオン、Ｎ－フェニルイミノ二酢酸アニオンおよびシュウ酸アニオンが挙げられる。
　熱塩基発生剤の詳細は、特開２０１６－０２７３５７号公報の段落００２１～００７７の記載を参酌でき、これらの内容は本明細書に組み込まれる。
　熱塩基発生剤としては、以下の化合物が例示される。
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000065
 Specific examples of the carboxylate anion include a maleate anion, a phthalate anion, an N-phenyliminodiacetic acid anion, and an oxalate anion.
Details of the thermal base generator can be referred to the descriptions in paragraphs 0021 to 0077 of JP-A-2016-027357, the contents of which are incorporated herein.
Examples of the thermal base generator include the following compounds.
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000067
　熱塩基発生剤を用いる場合、組成物における熱塩基発生剤の含有量は、組成物の全固形分に対し、０．１～５０質量％が好ましい。下限は、０．５質量％以上がより好ましく、１質量％以上がさらに好ましい。上限は、３０質量％以下がより好ましく、２０質量％以下がさらに好ましい。
　熱塩基発生剤は、１種または２種以上を用いることができる。２種以上を用いる場合は、合計量が上記範囲であることが好ましい。 When a thermal base generator is used, the content of the thermal base generator in the composition is preferably 0.1 to 50% by mass with respect to the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
1 type (s) or 2 or more types can be used for a thermal base generator. When using 2 or more types, it is preferable that a total amount is the said range.
＜＜＜光塩基発生剤＞＞＞
　本発明で用いる感光性樹脂組成物は、光塩基発生剤を含んでいてもよい。光塩基発生剤とは、露光により塩基を発生するものであり、常温常圧の通常の条件下では活性を示さないが、外部刺激として電磁波の照射と加熱が行なわれると、塩基（塩基性物質）を発生するものであれば特に限定されるものではない。露光により発生した塩基はポリイミド前駆体を加熱により硬化させる際の触媒として働くため、ネガ型において好適に用いることができる。 <<< Photobase generator >>>
The photosensitive resin composition used in the present invention may contain a photobase generator. A photobase generator generates a base upon exposure and does not exhibit activity under normal conditions of normal temperature and pressure. However, when an electromagnetic wave is irradiated and heated as an external stimulus, the base (basic substance) ) Is not particularly limited as long as it generates. Since the base generated by the exposure works as a catalyst for curing the polyimide precursor by heating, it can be suitably used in the negative type.
　本発明においては、光塩基発生剤として公知のものを用いることができる。例えば、Ｍ．Ｓｈｉｒａｉ，　ａｎｄ　Ｍ．Ｔｓｕｎｏｏｋａ，　Ｐｒｏｇ．Ｐｏｌｙｍ．Ｓｃｉ．，２１，１（１９９６）；角岡正弘，高分子加工，４６，２（１９９７）；Ｃ．Ｋｕｔａｌ，Ｃｏｏｒｄ．Ｃｈｅｍ．Ｒｅｖ．，２１１，３５３（２００１）；Ｙ．Ｋａｎｅｋｏ，Ａ．Ｓａｒｋｅｒ，　ａｎｄ　Ｄ．Ｎｅｃｋｅｒｓ，Ｃｈｅｍ．Ｍａｔｅｒ．，１１，１７０（１９９９）；Ｈ．Ｔａｃｈｉ，Ｍ．Ｓｈｉｒａｉ，　ａｎｄ　Ｍ．Ｔｓｕｎｏｏｋａ，Ｊ．Ｐｈｏｔｏｐｏｌｙｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，１３，１５３（２０００）；Ｍ．Ｗｉｎｋｌｅ，　ａｎｄ　Ｋ．Ｇｒａｚｉａｎｏ，Ｊ．Ｐｈｏｔｏｐｏｌｙｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，３，４１９（１９９０）；Ｍ．Ｔｓｕｎｏｏｋａ，Ｈ．Ｔａｃｈｉ，　ａｎｄ　Ｓ．Ｙｏｓｈｉｔａｋａ，Ｊ．Ｐｈｏｔｏｐｏｌｙｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，９，１３（１９９６）；Ｋ．Ｓｕｙａｍａ，Ｈ．Ａｒａｋｉ，Ｍ．Ｓｈｉｒａｉ，Ｊ．Ｐｈｏｔｏｐｏｌｙｍ．Ｓｃｉ．Ｔｅｃｈｎｏｌ．，１９，８１（２００６）に記載されているように、遷移金属化合物錯体や、アンモニウム塩などの構造を有するものや、アミジン部分がカルボン酸と塩形成することで潜在化されたもののように、塩基成分が塩を形成することにより中和されたイオン性の化合物や、カルバメート誘導体、オキシムエステル誘導体、アシル化合物などのウレタン結合やオキシム結合などにより塩基成分が潜在化された非イオン性の化合物を挙げることができる。 In the present invention, known photobase generators can be used. For example, M.M. Shirai, and M.M. Tsunooka, Prog. Polym. Sci. , 21, 1 (1996); Masahiro Kadooka, polymer processing, 46, 2 (1997); Kutal, Coord. Chem. Rev. , 211, 353 (2001); Kaneko, A .; Sarker, and D. Neckers, Chem. Mater. 11, 170 (1999); Tachi, M .; Shirai, and M.M. Tsunooka, J. et al. Photopolym. Sci. Technol. , 13, 153 (2000); Winkle, and K.K. Graziano, J. et al. Photopolym. Sci. Technol. 3,419 (1990); Tsunooka, H .; Tachi, and S. Yoshitaka, J. et al. Photopolym. Sci. Technol. , 9, 13 (1996); Suyama, H .; Araki, M .; Shirai, J. et al. Photopolym. Sci. Technol. , 19, 81 (2006), as described in transition metal compound complexes, those having a structure such as an ammonium salt, and those formed by salt formation of an amidine moiety with a carboxylic acid, An ionic compound neutralized by forming a salt with a base component, or a nonionic compound in which the base component is made latent by a urethane bond or oxime bond such as a carbamate derivative, an oxime ester derivative, or an acyl compound. Can be mentioned.
　光塩基発生剤から発生される塩基性物質としては特に限定されないが、アミノ基を有する化合物、特にモノアミンや、ジアミンなどのポリアミン、また、アミジンなどが挙げられる。
　発生される塩基性物質は、より塩基性度の高いアミノ基を有する化合物が好ましい。ポリイミド前駆体のイミド化における脱水縮合反応等に対する触媒作用が強く、より少量の添加で、より低い温度での脱水縮合反応等における触媒効果の発現が可能となるからである。つまりは、発生した塩基性物質の触媒効果が大きいため、ネガ型感光性樹脂組成物としての見た目の感度は向上する。
　上記触媒効果の観点からアミジン、脂肪族アミンであることが好ましい。
　本発明で用いる光塩基発生剤としては、芳香環を含み、発生する塩基性物質が、アミノ基を有する化合物であることが好ましい。 The basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, particularly monoamines, polyamines such as diamines, and amidines.
The generated basic substance is preferably a compound having an amino group having a higher basicity. This is because the catalytic action for the dehydration condensation reaction or the like in the imidization of the polyimide precursor is strong, and the catalytic effect in the dehydration condensation reaction or the like at a lower temperature can be expressed with a smaller amount of addition. That is, since the generated basic substance has a large catalytic effect, the apparent sensitivity of the negative photosensitive resin composition is improved.
From the viewpoint of the catalytic effect, an amidine and an aliphatic amine are preferable.
The photobase generator used in the present invention preferably contains an aromatic ring and the generated basic substance is a compound having an amino group.
　本発明に係る光塩基発生剤としては、例えば、特開２００９－８０４５２号公報および国際公開第２００９／１２３１２２号パンフレットで開示されたような桂皮酸アミド構造を有する光塩基発生剤、特開２００６－１８９５９１号公報および特開２００８－２４７７４７号公報で開示されたようなカルバメート構造を有する光塩基発生剤、特開２００７－２４９０１３号公報および特開２００８－００３５８１号公報で開示されたようなオキシム構造、カルバモイルオキシム構造を有する光塩基発生剤等が挙げられるが、これらに限定されず、その他にも公知の光塩基発生剤の構造を用いることができる。 Examples of the photobase generator according to the present invention include a photobase generator having a cinnamic acid amide structure as disclosed in Japanese Patent Application Laid-Open Nos. 2009-80452 and 2009/123122. A photobase generator having a carbamate structure as disclosed in Japanese Patent No. 189591 and Japanese Patent Application Laid-Open No. 2008-247747, an oxime structure as disclosed in Japanese Patent Application Laid-Open No. 2007-249013 and Japanese Patent Application Laid-Open No. 2008-003581, Examples include photobase generators having a carbamoyloxime structure, but are not limited thereto, and other known photobase generator structures can be used.
　その他、光塩基発生剤としては、特開２０１２－９３７４６号公報の段落０１８５～０１８８、０１９９～０２００および０２０２に記載の化合物、特開２０１３－１９４２０５号公報の段落００２２～００６９に記載の化合物、特開２０１３－２０４０１９号公報の段落００２６～００７４に記載の化合物、ならびに国際公開ＷＯ２０１０／０６４６３１号公報の段落００５２に記載の化合物が例として挙げられる。 Other photobase generators include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of JP2012-93746A, compounds described in paragraphs 0022 to 0069 of JP2013-194205, Examples include the compounds described in paragraphs 0026 to 0074 of JP2013-204019, and the compound described in paragraph 0052 of WO2010 / 064631.
　光塩基発生剤の市販品としては、ＷＰＢＧ－２６６、ＷＰＢＧ－３００、ＷＰＧＢ－３４５、ＷＰＧＢ－１４０、ＷＰＢＧ－１６５、ＷＰＢＧ－０２７、ＰＢＧ－０１８、ＷＰＧＢ－０１５、ＷＰＢＧ－０４１、ＷＰＧＢ－１７２、ＷＰＧＢ－１７４、ＷＰＢＧ－１６６、ＷＰＧＢ－１５８、ＷＰＧＢ－０２５、ＷＰＧＢ－１６８、ＷＰＧＢ－１６７およびＷＰＢＧ－０８２（和光純薬工業（株）製）を用いることもできる。
　また、光塩基発生剤としては、下記化合物が例示される。
Figure JPOXMLDOC01-appb-C000068
 Commercially available photobase generators include WPBG-266, WPBG-300, WPGB-345, WPGB-140, WPBG-165, WPBG-027, PBG-018, WPGB-015, WPBG-041, WPGB-172, WPGB-174, WPBG-166, WPGB-158, WPGB-025, WPGB-168, WPGB-167, and WPBG-082 (manufactured by Wako Pure Chemical Industries, Ltd.) can also be used.
Moreover, the following compound is illustrated as a photobase generator.
Figure JPOXMLDOC01-appb-C000068
　光塩基発生剤を用いる場合、組成物における光塩基発生剤の含有量は、組成物の全固形分に対し、０．１～５０質量％が好ましい。下限は、０．５質量％以上がより好ましく、１質量％以上がさらに好ましい。上限は、３０質量％以下がより好ましく、２０質量％以下がさらに好ましい。
　光塩基発生剤は、１種または２種以上を用いることができる。２種以上を用いる場合は、合計量が上記範囲であることが好ましい。 When a photobase generator is used, the content of the photobase generator in the composition is preferably 0.1 to 50% by mass with respect to the total solid content of the composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
1 type (s) or 2 or more types can be used for a photobase generator. When using 2 or more types, it is preferable that a total amount is the said range.
＜＜その他の添加剤＞＞
　本発明の組成物は、本発明の効果を損なわない範囲で、必要に応じて、各種の添加物、例えば、熱酸発生剤、増感色素、連鎖移動剤、界面活性剤、高級脂肪酸誘導体、無機粒子、硬化剤、硬化触媒、充填剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を配合することができる。これらの添加剤を配合する場合、その合計配合量は組成物の固形分の３質量％以下とすることが好ましい。 << Other additives >>
The composition of the present invention may be various additives, for example, thermal acid generators, sensitizing dyes, chain transfer agents, surfactants, higher fatty acid derivatives, as necessary, as long as the effects of the present invention are not impaired. Inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the composition.
＜＜＜熱酸発生剤＞＞＞
　本発明の組成物は、熱酸発生剤を含んでいてもよい。熱酸発生剤は、加熱により酸を発生し、ポリイミド前駆体の環化を促進し硬化膜の機械特性をより向上させる。熱酸発生剤は、特開２０１３－１６７７４２号公報の段落００５９に記載の化合物などが挙げられる。 <<< thermal acid generator >>>
The composition of the present invention may contain a thermal acid generator. The thermal acid generator generates an acid by heating, promotes cyclization of the polyimide precursor, and further improves the mechanical properties of the cured film. Examples of the thermal acid generator include compounds described in paragraph 0059 of JP2013-167742A.
　熱酸発生剤の含有量は、ポリイミド前駆体１００質量部に対して０．０１質量部以上が好ましく、０．１質量部以上がより好ましい。熱酸発生剤を０．０１質量部以上含有することで、架橋反応およびポリイミド前駆体の環化が促進されるため、硬化膜の機械特性および耐薬品性をより向上させることができる。また、熱酸発生剤の含有量は、硬化膜の電気絶縁性の観点から、２０質量部以下が好ましく、１５質量部以下がより好ましく、１０質量部以下が特に好ましい。
　熱酸発生剤は、１種のみ用いても、２種以上用いてもよい。２種以上用いる場合は、合計量が上記範囲となることが好ましい。 0.01 mass part or more is preferable with respect to 100 mass parts of polyimide precursors, and, as for content of a thermal acid generator, 0.1 mass part or more is more preferable. By containing 0.01 part by mass or more of the thermal acid generator, the cross-linking reaction and the cyclization of the polyimide precursor are promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. In addition, the content of the thermal acid generator is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and particularly preferably 10 parts by mass or less from the viewpoint of electrical insulation of the cured film.
One type of thermal acid generator may be used, or two or more types may be used. When using 2 or more types, it is preferable that a total amount becomes the said range.
＜＜＜増感色素＞＞＞
　本発明の組成物は、増感色素を含んでいてもよい。増感色素は、特定の活性放射線を吸収して電子励起状態となる。電子励起状態となった増感色素は、熱塩基発生剤、熱ラジカル重合開始剤、ラジカル重合開始剤などと接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより、熱塩基発生剤、熱ラジカル重合開始剤、ラジカル重合開始剤は化学変化を起こして分解し、ラジカル、酸或いは塩基を生成する。増感色素の詳細については、特開２０１６－０２７３５７号公報の段落０１６１～０１６３の記載を参酌でき、この内容は本明細書に組み込まれる。 <<< sensitizing dye >>>
The composition of the present invention may contain a sensitizing dye. A sensitizing dye absorbs specific actinic radiation and enters an electronically excited state. The sensitizing dye in an electronically excited state comes into contact with a thermal base generator, a thermal radical polymerization initiator, a radical polymerization initiator, and the like, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a thermal base generator, a thermal radical polymerization initiator, and a radical polymerization initiator cause a chemical change and are decomposed to generate radicals, acids, or bases. Details of the sensitizing dye can be referred to the descriptions in paragraphs 0161 to 0163 of JP-A-2016-027357, the contents of which are incorporated herein.
　本発明の組成物が増感色素を含む場合、増感色素の含有量は、本発明の組成物の全固形分に対し、０．０１～２０質量％が好ましく、０．１～１５質量％がより好ましく、０．５～１０質量％がさらに好ましい。増感色素は、１種単独で用いてもよいし、２種以上を併用してもよい。 When the composition of the present invention contains a sensitizing dye, the content of the sensitizing dye is preferably 0.01 to 20% by mass, and preferably 0.1 to 15% by mass with respect to the total solid content of the composition of the present invention. Is more preferable, and 0.5 to 10% by mass is even more preferable. A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.
＜＜＜連鎖移動剤＞＞＞
　本発明の組成物は、連鎖移動剤を含有してもよい。連鎖移動剤は、例えば高分子辞典第三版（高分子学会編、２００５年）６８３－６８４頁に定義されている。連鎖移動剤としては、例えば、分子内にＳＨ、ＰＨ、ＳｉＨ、ＧｅＨを有する化合物群が用いられる。これらは、低活性のラジカルに水素を供与して、ラジカルを生成するか、もしくは、酸化された後、脱プロトンすることによりラジカルを生成しうる。特に、チオール化合物（例えば、２－メルカプトベンズイミダゾール類、２－メルカプトベンズチアゾール類、２－メルカプトベンズオキサゾール類、３－メルカプトトリアゾール類、５－メルカプトテトラゾール類等）を好ましく用いることができる。 <<< Chain transfer agent >>>
The composition of the present invention may contain a chain transfer agent. The chain transfer agent is defined, for example, in Polymer Dictionary 3rd Edition (edited by the Polymer Society, 2005) pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, SiH, GeH in the molecule is used. These can generate hydrogen by donating hydrogen to a low activity radical to generate a radical, or after being oxidized and deprotonated. In particular, thiol compounds (for example, 2-mercaptobenzimidazoles, 2-mercaptobenzthiazoles, 2-mercaptobenzoxazoles, 3-mercaptotriazoles, 5-mercaptotetrazoles, etc.) can be preferably used.
　本発明の組成物が連鎖移動剤を有する場合、連鎖移動剤の含有量は、本発明の組成物の全固形分１００質量部に対し、０．０１～２０質量部が好ましく、１～１０質量部がより好ましく、１～５質量部がさらに好ましい。連鎖移動剤は１種のみでもよいし、２種以上であってもよい。連鎖移動剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 When the composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the composition of the present invention, and 1 to 10 parts by mass. Part is more preferable, and 1 to 5 parts by mass is more preferable. Only one type of chain transfer agent may be used, or two or more types may be used. When there are two or more chain transfer agents, the total is preferably in the above range.
＜＜＜界面活性剤＞＞＞
　本発明の組成物には、塗布性をより向上させる観点から、各種類の界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種類の界面活性剤を使用できる。また、下記界面活性剤も好ましい。
Figure JPOXMLDOC01-appb-C000069
 <<< surfactant >>>
Various kinds of surfactants may be added to the composition of the present invention from the viewpoint of further improving applicability. As the surfactant, various types of surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. The following surfactants are also preferable.
Figure JPOXMLDOC01-appb-C000069
　本発明の組成物が界面活性剤を有する場合、界面活性剤の含有量は、本発明の組成物の全固形分に対して、０．００１～２．０質量％が好ましく、より好ましくは０．００５～１．０質量％である。界面活性剤は１種のみでもよいし、２種以上であってもよい。界面活性剤が２種以上の場合は、その合計が上記範囲であることが好ましい。 When the composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0%, based on the total solid content of the composition of the present invention. 0.005 to 1.0 mass%. Only one surfactant may be used, or two or more surfactants may be used. When there are two or more surfactants, the total is preferably in the above range.
＜＜＜高級脂肪酸誘導体＞＞＞
　本発明の組成物は、酸素に起因する重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体を添加して、塗布後の乾燥の過程で組成物の表面に偏在させてもよい。
　本発明の組成物が高級脂肪酸誘導体を有する場合、高級脂肪酸誘導体の含有量は、本発明の組成物の全固形分に対して、０．１～１０質量％が好ましい。高級脂肪酸誘導体は１種のみでもよいし、２種以上であってもよい。高級脂肪酸誘導体が２種以上の場合は、その合計が上記範囲であることが好ましい。 <<< Higher fatty acid derivative >>>
In order to prevent polymerization inhibition due to oxygen, the composition of the present invention is added with a higher fatty acid derivative such as behenic acid or behenic acid amide, and is unevenly distributed on the surface of the composition in the course of drying after coating. May be.
When the composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the composition of the present invention. Only one higher fatty acid derivative may be used, or two or more higher fatty acid derivatives may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
＜＜その他の含有物質についての制限＞＞
　本発明の組成物の水分含有量は、塗布面性状の観点から、５質量％未満が好ましく、１質量％未満がさらに好ましく、０．６質量％未満が特に好ましい。 << Restrictions on other contained substances >>
The water content of the composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and particularly preferably less than 0.6% by mass from the viewpoint of the coated surface properties.
　本発明の組成物の金属含有量は、絶縁性の観点から、５質量ｐｐｍ（ｐａｒｔｓ　ｐｅｒ　ｍｉｌｌｉｏｎ）未満が好ましく、１質量ｐｐｍ未満がさらに好ましく、０．５質量ｐｐｍ未満が特に好ましい。金属としては、ナトリウム、カリウム、マグネシウム、カルシウム、鉄、クロム、ニッケルなどが挙げられる。金属を複数含む場合は、これらの金属の合計が上記範囲であることが好ましい。
　また、本発明の組成物に意図せずに含まれる金属不純物を低減する方法としては、本発明の組成物を構成する原料として金属含有量が少ない原料を選択する、本発明の組成物を構成する原料に対してフィルターろ過を行う、装置内をポリテトラフロロエチレン等でライニングしてコンタミネーションを可能な限り抑制した条件下で蒸留を行う等の方法を挙げることができる。 The metal content of the composition of the present invention is preferably less than 5 ppm by weight (parts per million), more preferably less than 1 ppm by weight, and particularly preferably less than 0.5 ppm by weight from the viewpoint of insulation. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are included, the total of these metals is preferably in the above range.
Further, as a method for reducing metal impurities unintentionally contained in the composition of the present invention, a raw material having a low metal content is selected as a raw material constituting the composition of the present invention. For example, the raw material to be filtered may be filtered, or the inside of the apparatus may be lined with polytetrafluoroethylene or the like, and distillation may be performed under a condition in which contamination is suppressed as much as possible.
　本発明の組成物は、ハロゲン原子の含有量が、配線腐食性の観点から、５００質量ｐｐｍ未満が好ましく、３００質量ｐｐｍ未満がより好ましく、２００質量ｐｐｍ未満が特に好ましい。中でも、ハロゲンイオンの状態で存在するものは、５質量ｐｐｍ未満が好ましく、１質量ｐｐｍ未満がより好ましく、０．５質量ｐｐｍ未満がさらに好ましい。ハロゲン原子としては、塩素原子および臭素原子が挙げられる。塩素原子および臭素原子、あるいは塩素イオンおよび臭素イオンの合計がそれぞれ上記範囲であることが好ましい。 In the composition of the present invention, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and particularly preferably less than 200 ppm by mass from the viewpoint of wiring corrosion. Especially, what exists in the state of a halogen ion is less than 5 mass ppm, More preferably, it is less than 1 mass ppm, More preferably, it is less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. The total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions is preferably in the above range.
　本発明の組成物の収納容器としては従来公知の収納容器を用いることができる。また、収納容器としては、原材料や組成物中への不純物混入を抑制することを目的に、容器内壁を６種６層の樹脂で構成された多層ボトルや、６種の樹脂を７層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開２０１５－１２３３５１号公報に記載の容器が挙げられる。 As the container for the composition of the present invention, a conventionally known container can be used. In addition, as a storage container, for the purpose of suppressing the mixing of impurities into raw materials and compositions, the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and the 6 types of resins are made into a 7 layer structure. It is also preferred to use bottles that have been used. Examples of such a container include a container described in JP-A-2015-123351.
＜＜組成物の調製＞＞
　本発明の組成物は、上記各成分を混合して調製することができる。混合方法は特に限定はなく、従来公知の方法で行うことができる。
　また、組成物中のゴミや微粒子等の異物を除去する目的で、フィルターを用いたろ過を行うことが好ましい。フィルター孔径は、１μｍ以下が好ましく、０．５μｍ以下がより好ましく、０．１μｍ以下がさらに好ましい。フィルターの材質は、ポリテトラフロロエチレン、ポリエチレンまたはナイロンが好ましい。フィルターは、有機溶剤であらかじめ洗浄したものを用いてもよい。フィルターろ過工程では、複数種のフィルターを直列または並列に接続して用いてもよい。複数種のフィルターを使用する場合は、孔径および／または材質が異なるフィルターを組み合わせて使用してもよい。また、各種材料を複数回ろ過してもよい。複数回ろ過する場合は、循環ろ過であってもよい。また、加圧してろ過を行ってもよい。加圧してろ過を行う場合、加圧する圧力は０．０５ＭＰａ以上０．３ＭＰａ以下が好ましい。
　フィルターを用いたろ過の他、吸着材を用いた不純物の除去処理を行ってもよい。フィルターろ過と吸着材を用いた不純物除去処理とを組み合わせてもよい。吸着材としては、公知の吸着材を用いることができる。例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材が挙げられる。 << Preparation of composition >>
The composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.
Moreover, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the composition. The filter pore size is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. A filter that has been washed in advance with an organic solvent may be used. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using a plurality of types of filters, filters having different pore diameters and / or materials may be used in combination. Various materials may be filtered a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and filter. When the pressure is applied for filtration, the pressure applied is preferably 0.05 MPa or more and 0.3 MPa or less.
In addition to filtration using a filter, impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
＜硬化膜、半導体デバイス、硬化膜の製造方法、積層体の製造方法および半導体デバイスの製造方法＞
　次に、本発明の硬化膜、半導体デバイス、硬化膜の製造方法、積層体の製造方法および半導体デバイスの製造方法について説明する。
　本発明の硬化膜は、本発明の組成物を硬化してなる。本発明の硬化膜の膜厚は、例えば、０．５μｍ以上とすることができ、１μｍ以上とすることができる。また、上限値としては、１００μｍ以下とすることができ、３０μｍ以下とすることもできる。 <Curing Film, Semiconductor Device, Cured Film Manufacturing Method, Laminate Manufacturing Method, and Semiconductor Device Manufacturing Method>
Next, the cured film, the semiconductor device, the cured film manufacturing method, the laminate manufacturing method, and the semiconductor device manufacturing method of the present invention will be described.
The cured film of the present invention is formed by curing the composition of the present invention. The thickness of the cured film of the present invention can be, for example, 0.5 μm or more, and can be 1 μm or more. Moreover, as an upper limit, it can be set to 100 micrometers or less, and can also be set to 30 micrometers or less.
　本発明の硬化膜を２層以上積層して積層体としてもよい。本発明の硬化膜を２層以上有する積層体は、硬化膜の間に金属層を有する態様が好ましい。このような金属層は、再配線層などの金属配線として好ましく用いられる。 A laminate may be obtained by laminating two or more cured films of the present invention. The laminate having two or more cured films of the present invention preferably has a metal layer between the cured films. Such a metal layer is preferably used as a metal wiring such as a rewiring layer.
　本発明の硬化膜の適用可能な分野としては、半導体デバイスの絶縁膜、再配線層用層間絶縁膜などが挙げられる。特に、解像性が良好であるため、３次元実装デバイスにおける再配線層用層間絶縁膜などに好ましく用いることができる。
　また、本発明における硬化膜は、エレクトロニクス用のフォトレジスト、ガルバニック（電解）レジスト（ｇａｌｖａｎｉｃ　ｒｅｓｉｓｔ）、エッチングレジスト、ソルダートップレジスト（ｓｏｌｄｅｒ　ｔｏｐ　ｒｅｓｉｓｔ）などに用いることもできる。
　また、本発明における硬化膜は、オフセット版面またはスクリーン版面などの版面の製造、成形部品のエッチングへの使用、エレクトロニクス、特に、マイクロエレクトロニクスにおける保護ラッカーおよび誘電層の製造などにも用いることもできる。 Fields to which the cured film of the present invention can be applied include insulating films for semiconductor devices, interlayer insulating films for rewiring layers, and the like. Particularly, since the resolution is good, it can be preferably used for an interlayer insulating film for a rewiring layer in a three-dimensional mounting device.
The cured film in the present invention can also be used for electronic photoresists, galvanic resists, galvanic resists, etching resists, solder top resists, and the like.
The cured film of the present invention can also be used for the production of printing plates such as offset printing plates or screen printing plates, for use in etching molded parts, and for the production of protective lacquers and dielectric layers in electronics, particularly microelectronics.
　本発明の硬化膜の製造方法は、本発明の組成物を用いることを含む。好ましくは、本発明の感光性樹脂組成物を基板に適用して層状にする、感光性樹脂組成物層形成工程と、上記感光性樹脂組成物層を露光する露光工程と、上記露光された感光性樹脂組成物層（樹脂層）に対して、現像処理を行う現像処理工程とを有する、硬化膜の製造方法が挙げられる。本発明の感光性樹脂組成物は、ネガ型現像を行う場合に好ましく用いられる。 The method for producing a cured film of the present invention includes using the composition of the present invention. Preferably, the photosensitive resin composition of the present invention is applied to a substrate to form a layer, a photosensitive resin composition layer forming step, an exposure step of exposing the photosensitive resin composition layer, and the exposed photosensitivity. The manufacturing method of a cured film which has the image development process process which performs image development processing with respect to a conductive resin composition layer (resin layer) is mentioned. The photosensitive resin composition of the present invention is preferably used when performing negative development.
　本発明の積層体の製造方法は、本発明の硬化膜の製造方法を含む。本発明の積層体の製造方法は、本発明の硬化膜の製造方法に従って、硬化膜を形成後、さらに、再度、感光性樹脂組成物層形成工程、露光工程、および、現像処理工程を、上記順に行うことが好ましい。特に、感光性樹脂組成物層形成工程、露光工程、および、現像処理工程を、さらに、上記順に２～５回（すなわち、合計で３～６回）行うことが好ましい。このように硬化膜を積層することにより、積層体とすることができる。本発明では特に、硬化膜を設けて現像した後、現像除去された部分に金属層を設けることが好ましい。
　以下これらの詳細を説明する。 The manufacturing method of the laminated body of this invention includes the manufacturing method of the cured film of this invention. According to the method for producing a laminate of the present invention, after forming a cured film according to the method for producing a cured film of the present invention, the photosensitive resin composition layer forming step, the exposure step, and the development processing step are performed again. It is preferable to carry out in order. In particular, the photosensitive resin composition layer forming step, the exposure step, and the development processing step are preferably performed 2 to 5 times in the above order (that is, 3 to 6 times in total). Thus, a laminated body can be obtained by laminating a cured film. In the present invention, in particular, it is preferable to provide a metal layer in a portion that has been developed and removed after providing and developing a cured film.
These details will be described below.
＜＜感光性樹脂組成物層形成工程＞＞
　本発明の積層体の製造方法は、感光性樹脂組成物を基板に適用して層状にする、感光性樹脂組成物層形成工程を含む。
　基板の種類は、用途に応じて適宜定めることができるが、シリコン、窒化シリコン、ポリシリコン、酸化シリコン、アモルファスシリコンなどの半導体作製基板、石英、ガラス、光学フィルム、セラミック材料、蒸着膜、磁性膜、反射膜、Ｎｉ、Ｃｕ、Ｃｒ、Ｆｅなどの金属基板、紙、ＳＯＧ（Ｓｐｉｎ  Ｏｎ  Ｇｌａｓｓ）、ＴＦＴ（薄膜トランジスタ）アレイ基板、プラズマディスプレイパネル（ＰＤＰ）の電極板など特に制約されない。本発明では、特に、半導体作製基板が好ましく、シリコン基板がより好ましい。
　また、樹脂層の表面や金属層の表面に感光性樹脂組成物層を形成する場合は、樹脂層や金属層が基板となる。
　感光性樹脂組成物を基板に適用する手段としては、塗布が好ましい。
　具体的には、適用する手段としては、ディップコート法、エアーナイフコート法、カーテンコート法、ワイヤーバーコート法、グラビアコート法、エクストルージョンコート法、スプレーコート法、スピンコート法、スリットコート法、およびインクジェット法などが例示される。感光性樹脂組成物層の厚さの均一性の観点から、より好ましくはスピンコート法、スリットコート法、スプレーコート法、インクジェット法である。方法に応じて適切な固形分濃度や塗布条件を調整することで、所望の厚さの樹脂層を得ることができる。また、基板の形状によっても塗布方法を適宜選択でき、ウェハ等の円形基板であればスピンコート法やスプレーコート法、インクジェット法等が好ましく、矩形基板であればスリットコート法やスプレーコート法、インクジェット法等が好ましい。スピンコート法の場合は、例えば、５００～２０００ｒｐｍの回転数で、１０秒～１分程度適用することができる。 << Photosensitive resin composition layer formation process >>
The manufacturing method of the laminated body of this invention includes the photosensitive resin composition layer formation process which applies the photosensitive resin composition to a board | substrate, and makes it layered.
The type of the substrate can be appropriately determined according to the application, but a semiconductor production substrate such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, quartz, glass, optical film, ceramic material, vapor deposition film, magnetic film , Reflective films, metal substrates such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, plasma display panel (PDP) electrode plates, etc. are not particularly limited. In the present invention, a semiconductor manufacturing substrate is particularly preferable, and a silicon substrate is more preferable.
Moreover, when forming the photosensitive resin composition layer on the surface of a resin layer or the surface of a metal layer, a resin layer or a metal layer becomes a board | substrate.
As a means for applying the photosensitive resin composition to the substrate, coating is preferable.
Specifically, as a means to apply, dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, And an inkjet method. From the viewpoint of uniformity of the thickness of the photosensitive resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an ink jet method are more preferable. A resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Also, the coating method can be appropriately selected depending on the shape of the substrate, and a spin coat method, a spray coat method, an ink jet method or the like is preferable for a circular substrate such as a wafer, and a slit coat method, a spray coat method, an ink jet method or the like for a rectangular substrate. The method is preferred. In the case of the spin coating method, for example, it can be applied at a rotational speed of 500 to 2000 rpm for about 10 seconds to 1 minute.
＜＜乾燥工程＞＞
　本発明の積層体の製造方法は、感光性樹脂組成物層を形成後、溶剤を除去するために乾燥する工程を含んでいてもよい。好ましい乾燥温度は５０～１５０℃で、７０℃～１３０℃がより好ましく、９０℃～１１０℃がさらに好ましい。乾燥時間としては、３０秒～２０分が例示され、１分～１０分が好ましく、３分～７分がより好ましい。 << Drying process >>
The manufacturing method of the laminated body of this invention may include the process of drying in order to remove a solvent, after forming the photosensitive resin composition layer. A preferred drying temperature is 50 to 150 ° C, more preferably 70 to 130 ° C, and further preferably 90 to 110 ° C. Examples of the drying time include 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
＜＜露光工程＞＞
　本発明の積層体の製造方法は、上記感光性樹脂組成物層を露光する露光工程を含む。露光量は、感光性樹脂組成物を硬化できる限り特に定めるものではないが、例えば、波長３６５ｎｍでの露光エネルギー換算で１００～１００００ｍＪ／ｃｍ２照射することが好ましく、２００～８０００ｍＪ／ｃｍ２照射することがより好ましい。
　露光波長は、１９０～１０００ｎｍの範囲で適宜定めることができ、２４０～５５０ｎｍが好ましい。 << Exposure process >>
The manufacturing method of the laminated body of this invention includes the exposure process which exposes the said photosensitive resin composition layer. The amount of exposure is not particularly defined as long as the photosensitive resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and to irradiate 200 to 8000 mJ / cm 2 . It is more preferable.
The exposure wavelength can be appropriately determined in the range of 190 to 1000 nm, and preferably 240 to 550 nm.
＜＜現像処理工程＞＞
　本発明の積層体の製造方法は、露光された感光性樹脂組成物層に対して、ネガ型現像処理を行う現像処理工程を含む。ネガ型現像を行うことにより、露光されていない部分（非露光部）が除去される。現像方法は、所望のパターンを形成できれば特に制限は無く、例えば、パドル、スプレー、浸漬、超音波等の現像方法が採用可能である。
　現像は現像液を用いて行う。現像液は、露光されていない部分（非露光部）が除去されるのであれば、特に制限なく使用できる。現像液は、有機溶剤を含むことが好ましい。有機溶剤は、エステル類として、例えば、酢酸エチル、酢酸－ｎ－ブチル、ギ酸アミル、酢酸イソアミル、酢酸イソブチル、プロピオン酸ブチル、酪酸イソプロピル、酪酸エチル、酪酸ブチル、乳酸メチル、乳酸エチル、γ－ブチロラクトン、ε－カプロラクトン、δ－バレロラクトン、アルキルオキシ酢酸アルキル（例：アルキルオキシ酢酸メチル、アルキルオキシ酢酸エチル、アルキルオキシ酢酸ブチル（例えば、メトキシ酢酸メチル、メトキシ酢酸エチル、メトキシ酢酸ブチル、エトキシ酢酸メチル、エトキシ酢酸エチル等））、３－アルキルオキシプロピオン酸アルキルエステル類（例：３－アルキルオキシプロピオン酸メチル、３－アルキルオキシプロピオン酸エチル等（例えば、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル等））、２－アルキルオキシプロピオン酸アルキルエステル類（例：２－アルキルオキシプロピオン酸メチル、２－アルキルオキシプロピオン酸エチル、２－アルキルオキシプロピオン酸プロピル等（例えば、２－メトキシプロピオン酸メチル、２－メトキシプロピオン酸エチル、２－メトキシプロピオン酸プロピル、２－エトキシプロピオン酸メチル、２－エトキシプロピオン酸エチル））、２－アルキルオキシ－２－メチルプロピオン酸メチルおよび２－アルキルオキシ－２－メチルプロピオン酸エチル（例えば、２－メトキシ－２－メチルプロピオン酸メチル、２－エトキシ－２－メチルプロピオン酸エチル等）、ピルビン酸メチル、ピルビン酸エチル、ピルビン酸プロピル、アセト酢酸メチル、アセト酢酸エチル、２－オキソブタン酸メチル、２－オキソブタン酸エチル等、並びに、エーテル類として、例えば、ジエチレングリコールジメチルエーテル、テトラヒドロフラン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート等、並びに、ケトン類として、例えば、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、２－ヘプタノン、３－ヘプタノン、Ｎ－メチル－２－ピロリドン等、並びに、芳香族炭化水素類として、例えば、トルエン、キシレン、アニソール、リモネン等、スルホキシド類としてジメチルスルホキシドが好適に挙げられる。
　本発明では、特にシクロペンタノン、γ－ブチロラクトンが好ましく、シクロペンタノンがより好ましい。 << Development process >>
The manufacturing method of the laminated body of this invention includes the image development processing process which performs negative development processing with respect to the exposed photosensitive resin composition layer. By performing negative development, the unexposed part (non-exposed part) is removed. The development method is not particularly limited as long as a desired pattern can be formed. For example, development methods such as paddle, spray, immersion, and ultrasonic wave can be employed.
Development is performed using a developer. The developer can be used without particular limitation as long as the unexposed part (non-exposed part) is removed. The developer preferably contains an organic solvent. Examples of the organic solvent include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and γ-butyrolactone. , Ε-caprolactone, δ-valerolactone, alkyl oxyacetate alkyl (eg, methyl oxyoxyacetate, alkyl oxyacetate ethyl, alkyl oxyacetate butyl (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate), alkyl esters of 3-alkyloxypropionic acid (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, 3-methoxypropyl) Ethyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionic acid alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2 -Propyl alkyloxypropionate and the like (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyl Methyl oxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate , Pyruvic acid Chillyl, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like, and ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like Keto As methyls, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone and the like, and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc. A preferred example of the sulfoxide is dimethyl sulfoxide.
In the present invention, cyclopentanone and γ-butyrolactone are particularly preferable, and cyclopentanone is more preferable.
　現像時間としては、１０秒～５分が好ましい。現像時の温度は、特に定めるものではないが、通常、２０～４０℃で行うことができる。
　現像液を用いた処理の後、さらに、リンスを行ってもよい。リンスは、現像液とは異なる溶剤で行うことが好ましい。例えば、感光性樹脂組成物に含まれる溶剤を用いてリンスすることができる。リンス時間は、５秒～１分が好ましい。 The development time is preferably 10 seconds to 5 minutes. The temperature at the time of development is not particularly defined, but it can usually be carried out at 20 to 40 ° C.
After treatment with a developer, rinsing may be further performed. The rinsing is preferably performed with a solvent different from the developer. For example, it can rinse using the solvent contained in the photosensitive resin composition. The rinse time is preferably 5 seconds to 1 minute.
＜＜加熱工程＞＞
　本発明の積層体の製造方法は、加熱工程を含むことが好ましい。加熱工程では、ポリイミド前駆体の環化反応が進行する。また、本発明の組成物がラジカル重合性化合物を含む場合、未反応のラジカル重合性化合物の硬化なども進行する。加熱温度（最高加熱温度）としては、５０～４５０℃が好ましく、１４０～４００℃がより好ましく、１６０～３５０℃がさらに好ましい。
　加熱は、加熱開始時の温度から最高加熱温度まで１～１２℃／分の昇温速度で行うことが好ましく、２～１０℃／分がより好ましく、３～１０℃／分がさらに好ましい。昇温速度を２℃／分以上とすることにより、生産性を確保しつつ、アミンの過剰な揮発を防止することができ、昇温速度を１２℃／分以下とすることにより、硬化膜の残存応力を緩和することができる。
　加熱開始時の温度は、２０℃～１５０℃が好ましく、２０℃～１３０℃がより好ましく、２５℃～１２０℃がさらに好ましい。加熱開始時の温度は、最高加熱温度まで加熱する工程を開始する際の温度のことをいう。例えば、感光性樹脂組成物を基板の上に適用した後、乾燥させる場合、この乾燥後の温度であり、例えば、感光性樹脂組成物に含まれる溶剤の沸点－（３０～２００℃）から徐々に昇温させることが好ましい。
　加熱時間（最高加熱温度での加熱時間）は、１０～３６０分であることが好ましく、２０～３００分であることがさらに好ましく、３０～２４０分であることが特に好ましい。
　特に多層の積層体を形成する場合、硬化膜の層間の密着性の観点から、加熱温度は１８０℃～３２０℃で加熱することが好ましく、１８０℃～２６０℃で加熱することがより好ましい。その理由は定かではないが、この温度とすることで、層間のポリイミド前駆体のエチニル基同士が架橋反応を進行しているためと考えられる。 << Heating process >>
It is preferable that the manufacturing method of the laminated body of this invention includes a heating process. In the heating step, the cyclization reaction of the polyimide precursor proceeds. Moreover, when the composition of this invention contains a radically polymerizable compound, hardening etc. of the unreacted radically polymerizable compound also advance. The heating temperature (maximum heating temperature) is preferably 50 to 450 ° C, more preferably 140 to 400 ° C, and further preferably 160 to 350 ° C.
Heating is preferably performed at a rate of temperature increase of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min. By setting the heating rate to 2 ° C./min or more, it is possible to prevent excessive volatilization of the amine while ensuring productivity, and by setting the heating rate to 12 ° C./min or less, the cured film Residual stress can be relaxed.
The temperature at the start of heating is preferably 20 ° C to 150 ° C, more preferably 20 ° C to 130 ° C, and further preferably 25 ° C to 120 ° C. The temperature at the start of heating refers to the temperature at the start of the step of heating to the maximum heating temperature. For example, when the photosensitive resin composition is applied onto a substrate and then dried, the temperature after drying is, for example, gradually from the boiling point of the solvent contained in the photosensitive resin composition (30 to 200 ° C.). It is preferable to raise the temperature to
The heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and particularly preferably 30 to 240 minutes.
In particular, when a multilayer laminate is formed, the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between the layers of the cured film. Although the reason is not certain, it is considered that the ethynyl group of the polyimide precursor between layers proceeds with a crosslinking reaction at this temperature.
　加熱は段階的に行ってもよい。例として、２５℃～１８０℃まで３℃／分で昇温し、１８０℃にて６０分置き、１８０～２００℃まで２℃／分で昇温し、２００℃にて１２０分置く、といった前処理工程を行ってもよい。前処理工程としての加熱温度は１００～２００℃が好ましく、１１０～１９０℃であることがより好ましく、１２０～１８５℃であることがさらに好ましい。この前処理工程においては、米国特許９１５９５４７号公報に記載のように紫外線を照射しながら処理することも好ましい。このような前処理工程により膜の特性を向上させることが可能である。前処理工程は１０秒間～２時間程度の短い時間で行うとよく、１５秒～３０分間がより好ましい。前処理は２段階以上のステップとしてもよく、例えば１００～１５０℃の範囲で前処理工程１を行い、その後に１５０～２００℃の範囲で前処理工程２を行ってもよい。
　さらに、加熱後冷却してもよく、この場合の冷却速度としては、１～５℃／分であることが好ましい。 Heating may be performed in stages. As an example, before raising the temperature from 25 ° C. to 180 ° C. at 3 ° C./min, placing at 180 ° C. for 60 minutes, raising the temperature from 180 ° C. to 200 ° C. at 2 ° C./min, and placing at 200 ° C. for 120 minutes. Processing steps may be performed. The heating temperature as the pretreatment step is preferably 100 to 200 ° C, more preferably 110 to 190 ° C, and further preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the characteristics of the film. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in two or more steps. For example, the pretreatment step 1 may be performed in the range of 100 to 150 ° C., and then the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
Further, it may be cooled after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
　加熱工程は、窒素、ヘリウム、アルゴンなどの不活性ガスを流す等により、低酸素濃度の雰囲気で行うことがポリイミド前駆体等の分解を防ぐ点で好ましい。酸素濃度は、５０ｐｐｍ（体積比）以下が好ましく、２０ｐｐｍ（体積比）以下がより好ましい。 The heating step is preferably performed in a low oxygen concentration atmosphere by flowing an inert gas such as nitrogen, helium, or argon in order to prevent decomposition of the polyimide precursor or the like. The oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
＜＜金属層形成工程＞＞
　本発明の積層体の製造方法は、現像処理後の感光性樹脂組成物層の表面に金属層を形成する金属層形成工程を含んでいることが好ましい。
　金属層としては、特に限定なく、既存の金属種を使用することができ、銅、アルミニウム、ニッケル、バナジウム、チタン、クロム、コバルト、金およびタングステンが例示され、銅およびアルミニウムがより好ましく、銅がさらに好ましい。
　金属層の形成方法は、特に限定なく、既存の方法を適用することができる。例えば、特開２００７－１５７８７９号公報、特表２００１－５２１２８８号公報、特開２００４－２１４５０１号公報、特開２００４－１０１８５０号公報に記載された方法を使用することができる。例えば、フォトリソグラフィ、リフトオフ、電解メッキ、無電解メッキ、エッチング、印刷、およびこれらを組み合わせた方法などが考えられる。より具体的には、スパッタリング、フォトリソグラフィおよびエッチングを組み合わせたパターニング方法、フォトリソグラフィと電解メッキを組み合わせたパターニング方法が挙げられる。
　金属層の厚さとしては、最も厚肉部で、０．１～５０μｍが好ましく、１～１０μｍがより好ましい。 << Metal layer formation process >>
It is preferable that the manufacturing method of the laminated body of this invention includes the metal layer formation process which forms a metal layer on the surface of the photosensitive resin composition layer after image development processing.
There are no particular limitations on the metal layer, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten. Copper and aluminum are more preferable, and copper is more preferable. Further preferred.
The method for forming the metal layer is not particularly limited, and an existing method can be applied. For example, the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, and JP 2004-101850 A can be used. For example, photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a combination of these can be considered. More specifically, a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating may be mentioned.
The thickness of the metal layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm at the thickest part.
＜＜積層工程＞＞
　本発明の製造方法は、さらに、積層工程を含むことが好ましい。
　積層工程とは、再度、上記感光性樹脂組成物層形成工程、上記露光工程、および、上記現像処理工程を、上記順に行うことを含む一連の工程である。積層工程には、さらに、上記乾燥工程や加熱工程等を含んでいてもよいことは言うまでもない。
　積層工程後、さらに積層工程を行う場合には、上記露光工程後、または、上記金属層形成工程後に、さらに、表面活性化処理工程を行ってもよい。表面活性化処理としては、プラズマ処理が例示される。
　上記積層工程は、２～５回行うことが好ましく、３～５回行うことがより好ましい。
　例えば、樹脂層／金属層／樹脂層／金属層／樹脂層／金属層のような、樹脂層が３層以上７層以下の構成が好ましく、３層以上５層以下がさらに好ましい。
　すなわち、本発明では特に、金属層を設けた後、さらに、上記金属層を覆うように、上記感光性樹脂組成物層形成工程、上記露光工程、および、上記現像処理工程を、上記順に行うことが好ましい。感光性樹脂組成物層（樹脂）を積層する積層工程と、金属層形成工程を交互に行うことにより、感光性樹脂組成物層（樹脂層）と金属層を交互に積層することができる。 << Lamination process >>
The production method of the present invention preferably further includes a lamination step.
A lamination process is a series of processes including performing the said photosensitive resin composition layer formation process, the said exposure process, and the said image development process again in the said order again. It goes without saying that the laminating step may further include the drying step and the heating step.
When a lamination process is further performed after the lamination process, a surface activation treatment process may be further performed after the exposure process or after the metal layer formation process. An example of the surface activation treatment is plasma treatment.
The lamination step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
For example, the resin layer / metal layer / resin layer / metal layer / resin layer / metal layer has a resin layer structure of 3 to 7 layers, more preferably 3 to 5 layers.
That is, in the present invention, in particular, after the metal layer is provided, the photosensitive resin composition layer forming step, the exposure step, and the development processing step are performed in the above order so as to cover the metal layer. Is preferred. By alternately performing the laminating step of laminating the photosensitive resin composition layer (resin) and the metal layer forming step, the photosensitive resin composition layer (resin layer) and the metal layer can be alternately laminated.
　本発明は、本発明の硬化膜または積層体を含む半導体デバイスも開示する。本発明の組成物を再配線層用層間絶縁膜の形成に用いた半導体デバイスの一実施形態について説明する。 The present invention also discloses a semiconductor device including the cured film or laminate of the present invention. An embodiment of a semiconductor device in which the composition of the present invention is used for forming an interlayer insulating film for a rewiring layer will be described.
　図１に示す半導体デバイス１００は、いわゆる３次元実装デバイスであり、複数の半導体素子（半導体チップ）１０１ａ～１０１ｄが積層した積層体１０１が、配線基板１２０の上に配置されている。なお、この実施形態では、半導体素子（半導体チップ）の積層数が４層である場合を中心に説明するが、半導体素子（半導体チップ）の積層数は特に限定されるものではなく、例えば、２層、８層、１６層、３２層等であってもよい。また、１層であってもよい。 A semiconductor device 100 shown in FIG. 1 is a so-called three-dimensional mounting device, and a stacked body 101 in which a plurality of semiconductor elements (semiconductor chips) 101 a to 101 d are stacked is arranged on a wiring board 120. In this embodiment, the case where the number of stacked semiconductor elements (semiconductor chips) is four will be mainly described. However, the number of stacked semiconductor elements (semiconductor chips) is not particularly limited. It may be a layer, 8 layers, 16 layers, 32 layers, or the like. Moreover, one layer may be sufficient.
　複数の半導体素子１０１ａ～１０１ｄは、いずれもシリコン基板等の半導体ウェハからなる。最上段の半導体素子１０１ａは、貫通電極を有さず、その一方の面に電極パッド（図示せず）が形成されている。半導体素子１０１ｂ～１０１ｄは、貫通電極１０２ｂ～１０２ｄを有し、各半導体素子の両面には、貫通電極に一体に設けられた接続パッド（図示せず）が設けられている。 The plurality of semiconductor elements 101a to 101d are each made of a semiconductor wafer such as a silicon substrate. The uppermost semiconductor element 101a does not have a through electrode, and an electrode pad (not shown) is formed on one surface thereof. The semiconductor elements 101b to 101d have through electrodes 102b to 102d, and connection pads (not shown) provided integrally with the through electrodes are provided on both surfaces of each semiconductor element.
　積層体１０１は、貫通電極を有さない半導体素子１０１ａと、貫通電極１０２ｂ～１０２ｄを有する半導体素子１０１ｂ～１０１ｄとをフリップチップ接続した構造を有している。すなわち、貫通電極を有さない半導体素子１０１ａの電極パッドと、これに隣接する貫通電極１０２ｂを有する半導体素子１０１ｂの半導体素子１０１ａ側の接続パッドが、半田バンプ等の金属バンプ１０３ａで接続され、貫通電極１０２ｂを有する半導体素子１０１ｂの他方の側の接続パッドが、それに隣接する貫通電極１０２ｃを有する半導体素子１０１ｃの半導体素子１０１ｂ側の接続パッドと、半田バンプ等の金属バンプ１０３ｂで接続されている。同様に、貫通電極１０２ｃを有する半導体素子１０１ｃの他方の側の接続パッドが、それに隣接する貫通電極１０２ｄを有する半導体素子１０１ｄの半導体素子１０１ｃ側の接続パッドと、半田バンプ等の金属バンプ１０３ｃで接続されている。 The stacked body 101 has a structure in which a semiconductor element 101a having no through electrode and flip-chip connection of semiconductor elements 101b to 101d having through electrodes 102b to 102d are connected. That is, the electrode pad of the semiconductor element 101a having no through electrode and the connection pad on the semiconductor element 101a side of the semiconductor element 101b having the adjacent through electrode 102b are connected by the metal bump 103a such as a solder bump, The connection pad on the other side of the semiconductor element 101b having the electrode 102b is connected to the connection pad on the semiconductor element 101b side of the semiconductor element 101c having the adjacent through electrode 102c by a metal bump 103b such as a solder bump. Similarly, the connection pad on the other side of the semiconductor element 101c having the through electrode 102c is connected to the connection pad on the semiconductor element 101c side of the semiconductor element 101d having the adjacent through electrode 102d by the metal bump 103c such as a solder bump. Has been.
　各半導体素子１０１ａ～１０１ｄの間隙には、アンダーフィル層１１０が形成されており、各半導体素子１０１ａ～１０１ｄは、アンダーフィル層１１０を介して積層している。 An underfill layer 110 is formed in the gaps between the semiconductor elements 101a to 101d, and the semiconductor elements 101a to 101d are stacked via the underfill layer 110.
　積層体１０１は、配線基板１２０の上に積層されている。配線基板１２０としては、例えば樹脂基板、セラミックス基板、ガラス基板等の絶縁基板を基材として用いた多層配線基板が使用される。樹脂基板を適用した配線基板１２０としては、多層銅張積層板（多層プリント配線板）等が挙げられる。 The laminated body 101 is laminated on the wiring board 120. As the wiring substrate 120, for example, a multilayer wiring substrate using an insulating substrate such as a resin substrate, a ceramic substrate, or a glass substrate as a base material is used. Examples of the wiring board 120 to which the resin board is applied include a multilayer copper-clad laminate (multilayer printed wiring board).
　配線基板１２０の一方の面には、表面電極１２０ａが設けられている。
　配線基板１２０と積層体１０１との間には、再配線層１０５が形成された絶縁膜１１５が配置されており、配線基板１２０と積層体１０１とは、再配線層１０５を介して電気的に接続されている。絶縁膜１１５は、本発明の組成物を用いて形成してなるものである。
　すなわち、再配線層１０５の一端は、半田バンプ等の金属バンプ１０３ｄを介して、半導体素子１０１ｄの再配線層１０５側の面に形成された電極パッドに接続されている。また、再配線層１０５の他端は、配線基板の表面電極１２０ａと、半田バンプ等の金属バンプ１０３ｅを介して接続している。
　そして、絶縁膜１１５と積層体１０１との間には、アンダーフィル層１１０ａが形成されている。また、絶縁膜１１５と配線基板１２０との間には、アンダーフィル層１１０ｂが形成されている。 A surface electrode 120 a is provided on one surface of the wiring board 120.
An insulating film 115 on which a rewiring layer 105 is formed is disposed between the wiring substrate 120 and the stacked body 101, and the wiring substrate 120 and the stacked body 101 are electrically connected via the rewiring layer 105. It is connected. The insulating film 115 is formed using the composition of the present invention.
That is, one end of the rewiring layer 105 is connected to an electrode pad formed on the surface of the semiconductor element 101d on the rewiring layer 105 side through a metal bump 103d such as a solder bump. The other end of the rewiring layer 105 is connected to the surface electrode 120a of the wiring board via a metal bump 103e such as a solder bump.
An underfill layer 110 a is formed between the insulating film 115 and the stacked body 101. In addition, an underfill layer 110 b is formed between the insulating film 115 and the wiring substrate 120.
　以下に実施例を挙げて本発明をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り、適宜、変更することができる。従って、本発明の範囲は以下に示す具体例に限定されるものではない。「部」、「％」は特に述べない限り、質量基準である。 The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. “Parts” and “%” are based on mass unless otherwise specified.
（合成例１）
［４，４’－オキシジフタル酸二無水物、４，４’－オキシジアニリン（４，４’－ジアミノジフェニルエーテル）、Ｎ－（３’－エチニルフェニル）－３，５－ジアミノベンズアミド（化合物（１）－１）および２－ヒドロキシエチルメタクリレートとからのポリイミド前駆体（Ａ－1：ラジカル重合性基を有するポリイミド前駆体）の合成］
　２０．０ｇ（６４．５ミリモル）の４，４’－オキシジフタル酸二無水物（１４０℃で１２時間乾燥した）と、１８．６ｇ（１２９ミリモル）の２－ヒドロキシエチルメタクリレートと、０．０５ｇのハイドロキノンと、１０．７ｇのピリジンと、１４０ｇのジグリム（ジエチレングリコールジメチルエーテル）とを混合し、６０℃の温度で１８時間撹拌して、４，４’－オキシジフタル酸と２－ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、反応混合物を－１０℃に冷却し、温度を－１０±４℃に保ちながら１６．１２ｇ（１３５．５ミリモル）のＳＯＣｌ２を１０分かけて加えた。５０ｍｌのＮ－メチルピロリドンで希釈した後、反応混合物を室温で２時間撹拌した。次いで、１００ｍｌのＮ－メチルピロリドンに９．４０３ｇ（４６．９６ミリモル）の４，４’－オキシジアニリン、および２．９５０ｇ（１１．７４ミリモル）のＮ－（３’－エチニルフェニル）－３，５－ジアミノベンズアミドを溶解させた溶液を、２０～２３℃で２０分かけて反応混合物に滴下した。次いで、反応混合物を室温で１晩撹拌した。次いで、５リットルの水の中でポリイミド前駆体を沈殿させ、水－ポリイミド前駆体混合物を５０００ｒｐｍの速度で１５分間撹拌した。ポリイミド前駆体を濾過して除き、４リットルの水の中で再度３０分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体を減圧下で、４５℃で３日間乾燥し、ポリイミド前駆体（Ａ－１）を得た。
　このポリイミド前駆体（Ａ－１）についてＧＰＣ測定を行った結果、ポリスチレン換算値として、重量平均分子量（Ｍｗ）は、２５，０００であった。下記繰り返し単位のモル比率（左側の繰り返し単位：右側の繰り返し単位）は、８０：２０である。
Figure JPOXMLDOC01-appb-C000070
 (Synthesis Example 1)
[4,4′-oxydiphthalic dianhydride, 4,4′-oxydianiline (4,4′-diaminodiphenyl ether), N- (3′-ethynylphenyl) -3,5-diaminobenzamide (compound (1 ) -1) and 2-hydroxyethyl methacrylate to prepare a polyimide precursor (A-1: polyimide precursor having a radical polymerizable group)]
20.0 g (64.5 mmol) 4,4′-oxydiphthalic dianhydride (dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g Hydroquinone, 10.7 g of pyridine and 140 g of diglyme (diethylene glycol dimethyl ether) are mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. did. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at −10 ± 4 ° C. After dilution with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then 9.403 g (46.96 mmol) of 4,4′-oxydianiline and 2.950 g (11.74 mmol) of N- (3′-ethynylphenyl) -3 in 100 ml of N-methylpyrrolidone. , 5-Diaminobenzamide was dissolved in the reaction mixture dropwise at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at 45 ° C. under reduced pressure for 3 days to obtain a polyimide precursor (A-1).
As a result of GPC measurement of this polyimide precursor (A-1), the weight average molecular weight (Mw) as a polystyrene conversion value was 25,000. The molar ratio of the following repeating units (left repeating unit: right repeating unit) is 80:20.
Figure JPOXMLDOC01-appb-C000070
　尚、重量平均分子量（Ｍｗ）は、ゲル浸透クロマトグラフィー（ＧＰＣ測定）に従ったポリスチレン換算値とした。ＨＬＣ－８２２０（東ソー（株）製）を用い、カラムとしてガードカラムＨＺ－Ｌ、ＴＳＫｇｅｌ Ｓｕｐｅｒ　ＨＺＭ－Ｍ、ＴＳＫｇｅｌ Ｓｕｐｅｒ　ＨＺ４０００、ＴＳＫｇｅｌ Ｓｕｐｅｒ　ＨＺ３０００、ＴＳＫｇｅｌ Ｓｕｐｅｒ　ＨＺ２０００（東ソー（株）製）を用い、溶離液はＴＨＦ(テトラヒドロフラン)を用いて測定した。また、検出は、ＵＶ線（紫外線）の波長２５４ｎｍ検出器を使用した。 In addition, the weight average molecular weight (Mw) was a polystyrene conversion value according to gel permeation chromatography (GPC measurement). HLC-8220 (manufactured by Tosoh Corporation) was used, and guard column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, TSKgel Super HZ2000 (manufactured by Tosoh Corp.) was used as the column. Was measured using THF (tetrahydrofuran). For detection, a UV ray (ultraviolet) wavelength 254 nm detector was used.
（合成例２）
［ピロメリット酸二無水物、４，４’－オキシジアニリン、Ｎ－（３’－エチニルフェニル）－３，５－ジアミノベンズアミド（化合物（１）－１）および２－ヒドロキシエチルメタクリレートとからのポリイミド前駆体（Ａ－２：ラジカル重合性基を有するポリイミド前駆体）の合成］
　１４．０６ｇ（６４．５ミリモル）のピロメリット酸二無水物（１４０℃で１２時間乾燥した）と、１８．６ｇ（１２９ミリモル）の２－ヒドロキシエチルメタクリレートと、０．０５ｇのハイドロキノンと、１０．７ｇのピリジンと、１４０ｇのＮＭＰ（Ｎ－メチル－２－ピロリドン）とを混合し、６０℃の温度で１８時間撹拌して、ピロメリット酸と２－ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、反応混合物を－１０℃に冷却し、温度を－１０±４℃に保ちながら１６．１２ｇ（１３５．５ミリモル）のＳＯＣｌ２を１０分かけて加えた。５０ｍｌのＮ－メチルピロリドンで希釈した後、反応混合物を室温で２時間撹拌した。次いで、１００ｍｌのＮ－メチルピロリドンに９．４０３ｇ（４６．９６ミリモル）の４，４’－オキシジアニリン、および２．９５０ｇ（１１．７４ミリモル）のＮ－（３’－エチニルフェニル）－３，５－ジアミノベンズアミドを溶解させた溶液を、２０～２３℃で２０分かけて反応混合物に滴下した。次いで、反応混合物を室温で１晩撹拌した。次いで、５リットルの水の中でポリイミド前駆体を沈殿させ、水－ポリイミド前駆体混合物を５０００ｒｐｍの速度で１５分間撹拌した。ポリイミド前駆体を濾過して除き、４リットルの水の中で再度３０分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体を減圧下で、４５℃で３日間乾燥し、ポリイミド前駆体（Ａ－２）を得た。
　このポリイミド前駆体（Ａ－２）についてＧＰＣ測定を行った結果、ポリスチレン換算値として、重量平均分子量（Ｍｗ）は、２０，０００であった。下記繰り返し単位のモル比率（左側の繰り返し単位：右側の繰り返し単位）は、８０：２０である。
Figure JPOXMLDOC01-appb-C000071
 (Synthesis Example 2)
[From pyromellitic dianhydride, 4,4′-oxydianiline, N- (3′-ethynylphenyl) -3,5-diaminobenzamide (compound (1) -1) and 2-hydroxyethyl methacrylate Synthesis of polyimide precursor (A-2: polyimide precursor having radical polymerizable group)]
14.06 g (64.5 mmol) pyromellitic dianhydride (dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g hydroquinone, 10 0.7 g of pyridine and 140 g of NMP (N-methyl-2-pyrrolidone) were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce pyromellitic acid and 2-hydroxyethyl methacrylate diester. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at −10 ± 4 ° C. After dilution with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then 9.403 g (46.96 mmol) of 4,4′-oxydianiline and 2.950 g (11.74 mmol) of N- (3′-ethynylphenyl) -3 in 100 ml of N-methylpyrrolidone. , 5-Diaminobenzamide was dissolved in the reaction mixture dropwise at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at 45 ° C. under reduced pressure for 3 days to obtain a polyimide precursor (A-2).
As a result of GPC measurement of this polyimide precursor (A-2), the weight average molecular weight (Mw) as a polystyrene conversion value was 20,000. The molar ratio of the following repeating units (left repeating unit: right repeating unit) is 80:20.
Figure JPOXMLDOC01-appb-C000071
（合成例３）
［４，４’－オキシジフタル酸二無水物、ｐ－フェニレンジアミン、Ｎ－（３’－エチニルフェニル）－３，５－ジアミノベンズアミド（化合物（１）－１）および２－ヒドロキシエチルメタクリレートとからのポリイミド前駆体（Ａ－３：ラジカル重合性基を有するポリイミド前駆体）の合成］
　２０．０ｇ（６４．５ミリモル）の４，４’－オキシジフタル酸二無水物（１４０℃で１２時間乾燥した）と、１８．６ｇ（１２９ミリモル）の２－ヒドロキシエチルメタクリレートと、０．０５ｇのハイドロキノンと、１０．７ｇのピリジンと、１４０ｇのダイグライムとを混合し、６０℃の温度で１８時間撹拌して、４，４’－オキシジフタル酸と２－ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、反応混合物を－１０℃に冷却し、温度を－１０±４℃に保ちながら１６．１２ｇ（１３５．５ミリモル）のＳＯＣｌ２を１０分かけて加えた。５０ｍｌのＮ－メチルピロリドンで希釈した後、反応混合物を室温で２時間撹拌した。次いで、１００ｍｌのＮ－メチルピロリドンに５．０７８ｇ（４６．９６ミリモル）のp-フェニレンジアミンおよび２．９５０ｇ（１１．７４ミリモル）のＮ－（３’－エチニルフェニル）－３，５－ジアミノベンズアミドを溶解させた溶液を、２０～２３℃で２０分かけて反応混合物に滴下した。次いで、反応混合物を室温で１晩撹拌した。次いで、５リットルの水の中でポリイミド前駆体を沈殿させ、水－ポリイミド前駆体混合物を５０００ｒｐｍの速度で１５分間撹拌した。ポリイミド前駆体を濾過して除き、４リットルの水の中で再度３０分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体を減圧下で、４５℃で３日間乾燥し、ポリイミド前駆体（Ａ－３）を得た。
　このポリイミド前駆体（Ａ－３）についてＧＰＣ測定を行った結果、ポリスチレン換算値として、重量平均分子量（Ｍｗ）は、２０，０００であった。下記繰り返し単位のモル比率（左側の繰り返し単位：右側の繰り返し単位）は、８０：２０である。
Figure JPOXMLDOC01-appb-C000072
 (Synthesis Example 3)
[From 4,4′-oxydiphthalic dianhydride, p-phenylenediamine, N- (3′-ethynylphenyl) -3,5-diaminobenzamide (compound (1) -1) and 2-hydroxyethyl methacrylate Synthesis of polyimide precursor (A-3: polyimide precursor having radical polymerizable group)]
20.0 g (64.5 mmol) 4,4′-oxydiphthalic dianhydride (dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g Hydroquinone, 10.7 g of pyridine, and 140 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at −10 ± 4 ° C. After dilution with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, 5.078 g (46.96 mmol) p-phenylenediamine and 2.950 g (11.74 mmol) N- (3′-ethynylphenyl) -3,5-diaminobenzamide in 100 ml N-methylpyrrolidone. The solution in which was dissolved was added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at 45 ° C. under reduced pressure for 3 days to obtain a polyimide precursor (A-3).
As a result of GPC measurement of this polyimide precursor (A-3), the weight average molecular weight (Mw) as a polystyrene conversion value was 20,000. The molar ratio of the following repeating units (left repeating unit: right repeating unit) is 80:20.
Figure JPOXMLDOC01-appb-C000072
（合成例４）
［４，４’－オキシジフタル酸二無水物、Ｎ－（３’－エチニルフェニル）－３，５－ジアミノベンズアミド（化合物（１）－１）および２－ヒドロキシエチルメタクリレートとからのポリイミド前駆体（Ａ－４：ラジカル重合性基を有するポリイミド前駆体）の合成］
　２０．０ｇ（６４．５ミリモル）の４，４’－オキシジフタル酸二無水物（１４０℃で１２時間乾燥した）と、１８．６ｇ（１２９ミリモル）の２－ヒドロキシエチルメタクリレートと、０．０５ｇのハイドロキノンと、１０．７ｇのピリジンと、１４０ｇのジグリムとを混合し、６０℃の温度で１８時間撹拌して、４，４’－オキシジフタル酸と２－ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、反応混合物を－１０℃に冷却し、温度を－１０±４℃に保ちながら１６．１２ｇ（１３５．５ミリモル）のＳＯＣｌ２を１０分かけて加えた。５０ｍｌのＮ－メチルピロリドンで希釈した後、反応混合物を室温で２時間撹拌した。次いで、１００ｍｌのＮ－メチルピロリドンに１４．７５０ｇ（５８．７０ミリモル）のＮ－（３’－エチニルフェニル）－３，５－ジアミノベンズアミドを溶解させた溶液を、２０～２３℃で２０分かけて反応混合物に滴下した。次いで、反応混合物を室温で１晩撹拌した。次いで、５リットルの水の中でポリイミド前駆体を沈殿させ、水－ポリイミド前駆体混合物を５０００ｒｐｍの速度で１５分間撹拌した。ポリイミド前駆体を濾過して除き、４リットルの水の中で再度３０分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体を減圧下で、４５℃で３日間乾燥し、ポリイミド前駆体（Ａ－４）を得た。
　このポリイミド前駆体（Ａ－４）についてＧＰＣ測定を行った結果、ポリスチレン換算値として、重量平均分子量（Ｍｗ）は、２２，０００であった。
Figure JPOXMLDOC01-appb-C000073
 (Synthesis Example 4)
[Polyimide precursor from 4,4′-oxydiphthalic dianhydride, N- (3′-ethynylphenyl) -3,5-diaminobenzamide (compound (1) -1) and 2-hydroxyethyl methacrylate (A -4: Synthesis of polyimide precursor having radically polymerizable group]
20.0 g (64.5 mmol) 4,4′-oxydiphthalic dianhydride (dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g Hydroquinone, 10.7 g of pyridine, and 140 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at −10 ± 4 ° C. After dilution with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Next, a solution of 14.750 g (58.70 mmol) of N- (3′-ethynylphenyl) -3,5-diaminobenzamide dissolved in 100 ml of N-methylpyrrolidone was added at 20 to 23 ° C. over 20 minutes. Was added dropwise to the reaction mixture. The reaction mixture was then stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at 45 ° C. under reduced pressure for 3 days to obtain a polyimide precursor (A-4).
As a result of GPC measurement of this polyimide precursor (A-4), the weight average molecular weight (Mw) as a polystyrene conversion value was 22,000.
Figure JPOXMLDOC01-appb-C000073
（合成例５）
［４，４’－オキシジフタル酸二無水物、ｍ－トリジン、Ｎ－（４’－エチニルフェニル）－３，５－ジアミノベンズアミド（化合物（１）－１）および２－ヒドロキシエチルメタクリレートとからのポリイミド前駆体（Ａ－５：ラジカル重合性基を有するポリイミド前駆体）の合成］
　合成例１の９．４０３ｇ（４６．９６ミリモル）の４，４’－オキシジアニリンを、９．９７０ｇ（４６．９６ミリモル）のｍ－トリジンに変更した以外は、合成例１と同じ操作を行い、ポリイミド前駆体（Ａ－５）を得た。
　このポリイミド前駆体（Ａ－５）についてＧＰＣ測定を行った結果、ポリスチレン換算値として、重量平均分子量（Ｍｗ）は、２１，０００であった。下記繰り返し単位のモル比率（左側の繰り返し単位：右側の繰り返し単位）は８０：２０である。
Figure JPOXMLDOC01-appb-C000074
 (Synthesis Example 5)
[Polyimide from 4,4′-oxydiphthalic dianhydride, m-tolidine, N- (4′-ethynylphenyl) -3,5-diaminobenzamide (compound (1) -1) and 2-hydroxyethyl methacrylate] Synthesis of Precursor (A-5: Polyimide Precursor Having Radical Polymerizable Group)]
The same operation as in Synthesis Example 1 was performed except that 9.403 g (46.96 mmol) of 4,4′-oxydianiline in Synthesis Example 1 was changed to 9.970 g (46.96 mmol) of m-tolidine. And a polyimide precursor (A-5) was obtained.
As a result of GPC measurement of this polyimide precursor (A-5), the weight average molecular weight (Mw) was 21,000 as a polystyrene conversion value. The molar ratio of the following repeating units (left repeating unit: right repeating unit) is 80:20.
Figure JPOXMLDOC01-appb-C000074
（合成例６）
[４，４’－オキシジフタル酸二無水物、４，４’－オキシジアニリン、Ｎ－（４’－エチニルフェニル）－３，５－ジアミノベンズアミド（化合物（１）－２）および２－ヒドロキシエチルメタクリレートとからのポリイミド前駆体（Ａ－６：ラジカル重合性基を有するポリイミド前駆体）の合成]
　合成例１の２．９５０ｇ（１１．７４ミリモル）のＮ－（３’－エチニルフェニル）－３，５－ジアミノベンズアミドを、２．９５０ｇ（１１．７４ミリモル）のＮ－（４’－エチニルフェニル）－３，５－ジアミノベンズアミドに変更した以外は、合成例１と同じ操作を行い、ポリイミド前駆体（Ａ－６）を得た。
　このポリイミド前駆体（Ａ－６）についてＧＰＣ測定を行った結果、ポリスチレン換算値として、重量平均分子量（Ｍｗ）は、２５，０００であった。下記繰り返し単位のモル比率（左側の繰り返し単位：右側の繰り返し単位）は、８０：２０である。
Figure JPOXMLDOC01-appb-C000075
 (Synthesis Example 6)
[4,4′-oxydiphthalic dianhydride, 4,4′-oxydianiline, N- (4′-ethynylphenyl) -3,5-diaminobenzamide (compound (1) -2) and 2-hydroxyethyl Synthesis of polyimide precursor from methacrylate (A-6: polyimide precursor having radical polymerizable group)]
2.950 g (11.74 mmol) of N- (3′-ethynylphenyl) -3,5-diaminobenzamide of Synthesis Example 1 was added to 2.950 g (11.74 mmol) of N- (4′-ethynylphenyl). ) Except for changing to 3,5-diaminobenzamide, the same operation as in Synthesis Example 1 was performed to obtain a polyimide precursor (A-6).
As a result of GPC measurement of this polyimide precursor (A-6), the weight average molecular weight (Mw) as a polystyrene conversion value was 25,000. The molar ratio of the following repeating units (left repeating unit: right repeating unit) is 80:20.
Figure JPOXMLDOC01-appb-C000075
（合成例７）
[４，４’－オキシジフタル酸二無水物、４，４’－オキシジアニリン、Ｎ－（３’、５’－ジエチニルフェニル）－３，５－ジアミノベンズアミド（化合物（１）－１０）および２－ヒドロキシエチルメタクリレートとからのポリイミド前駆体（Ａ－７：ラジカル重合性基を有するポリイミド前駆体）の合成]
　合成例１の２．９５０ｇ（１１．７４ミリモル）のＮ－（３’－エチニルフェニル）－３，５－ジアミノベンズアミドを、３．２３２ｇ（１１．７４ミリモル）のＮ－（３’、５’－ジエチニルフェニル）－３，５－ジアミノベンズアミドに変更した以外は、合成例１と同じ操作を行い、ポリイミド前駆体（Ａ－７）を得た。
　このポリイミド前駆体（Ａ－７）についてＧＰＣ測定を行った結果、ポリスチレン換算値として、重量平均分子量（Ｍｗ）は、２６，０００であった。下記繰り返し単位のモル比率（左側の繰り返し単位：右側の繰り返し単位）は、８０：２０である。
Figure JPOXMLDOC01-appb-C000076
 (Synthesis Example 7)
[4,4′-oxydiphthalic dianhydride, 4,4′-oxydianiline, N- (3 ′, 5′-diethynylphenyl) -3,5-diaminobenzamide (compound (1) -10) and Synthesis of polyimide precursor from 2-hydroxyethyl methacrylate (A-7: polyimide precursor having radical polymerizable group)]
2.950 g (11.74 mmol) of N- (3′-ethynylphenyl) -3,5-diaminobenzamide of Synthesis Example 1 was added to 3.232 g (11.74 mmol) of N- (3 ′, 5 ′. Except for the change to -diethynylphenyl) -3,5-diaminobenzamide, the same operation as in Synthesis Example 1 was performed to obtain a polyimide precursor (A-7).
As a result of GPC measurement of this polyimide precursor (A-7), the weight average molecular weight (Mw) as a polystyrene conversion value was 26,000. The molar ratio of the following repeating units (left repeating unit: right repeating unit) is 80:20.
Figure JPOXMLDOC01-appb-C000076
（合成例８）
[４，４’－オキシジフタル酸二無水物、４，４’－オキシジアニリン、１－（３－エチニルフェニル）－３－（３，５－ジアミノフェニル）ウレア（化合物（１）－２４）および２－ヒドロキシエチルメタクリレートとからのポリイミド前駆体（Ａ－８：ラジカル重合性基を有するポリイミド前駆体）の合成]
　合成例１の２．９５０ｇ（１１．７４ミリモル）のＮ－（３’－エチニルフェニル）－３，５－ジアミノベンズアミドを、２．９５０ｇ（１１．７４ミリモル）の１－（３－エチニルフェニル）－３－（３，５－ジアミノフェニル）ウレアに変更した以外は、合成例１と同じ操作を行い、ポリイミド前駆体（Ａ－８）を得た。
　このポリイミド前駆体（Ａ－８）についてＧＰＣ測定を行った結果、ポリスチレン換算値として、重量平均分子量（Ｍｗ）は、１９，０００であった。下記繰り返し単位のモル比率（左側の繰り返し単位：右側の繰り返し単位）は、８０：２０である。
Figure JPOXMLDOC01-appb-C000077
 (Synthesis Example 8)
[4,4′-oxydiphthalic dianhydride, 4,4′-oxydianiline, 1- (3-ethynylphenyl) -3- (3,5-diaminophenyl) urea (compound (1) -24) and Synthesis of polyimide precursor from 2-hydroxyethyl methacrylate (A-8: polyimide precursor having radical polymerizable group)]
2.950 g (11.74 mmol) of N- (3′-ethynylphenyl) -3,5-diaminobenzamide of Synthesis Example 1 was converted to 2.950 g (11.74 mmol) of 1- (3-ethynylphenyl). A polyimide precursor (A-8) was obtained in the same manner as in Synthesis Example 1, except that it was changed to -3- (3,5-diaminophenyl) urea.
As a result of GPC measurement of this polyimide precursor (A-8), the weight average molecular weight (Mw) as a polystyrene conversion value was 19,000. The molar ratio of the following repeating units (left repeating unit: right repeating unit) is 80:20.
Figure JPOXMLDOC01-appb-C000077
（合成例９）
［４，４’－オキシジフタル酸二無水物、４，４’－オキシジアニリン、および２－ヒドロキシエチルメタクリレートとからのポリイミド前駆体（比較例用ポリマー Ｒ－１：ラジカル重合性基を有するポリイミド前駆体）の合成］
　２０．０ｇ（６４．５ミリモル）の４，４’－オキシジフタル酸二無水物（１４０℃で１２時間乾燥した）と、１８．６ｇ（１２９ミリモル）の２－ヒドロキシエチルメタクリレートと、０．０５ｇのハイドロキノンと、１０．７ｇのピリジンと、１４０ｇのジグリムとを混合し、６０℃の温度で１８時間撹拌して、４，４’－オキシジフタル酸と２－ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、反応混合物を－１０℃に冷却し、温度を－１０±４℃に保ちながら１６．１２ｇ（１３５．５ミリモル）のＳＯＣｌ２を１０分かけて加えた。５０ｍｌのＮ－メチルピロリドンで希釈した後、反応混合物を室温で２時間撹拌した。次いで、１００ｍｌのＮ－メチルピロリドンに１１．７５ｇ（５８．７０ミリモル）の４，４’－オキシジアニリンを溶解させた溶液を、２０～２３℃で２０分かけて反応混合物に滴下した。次いで、反応混合物を室温で１晩撹拌した。次いで、５リットルの水の中でポリイミド前駆体を沈殿させ、水－ポリイミド前駆体混合物を５０００ｒｐｍの速度で１５分間撹拌した。ポリイミド前駆体を濾過して除き、４リットルの水の中で再度３０分間撹拌し再び濾過した。次いで、得られたポリイミド前駆体を減圧下で、４５℃で３日間乾燥し、比較例用ポリイミド前駆体（Ｒ－１）を得た。
　このポリイミド前駆体（Ｒ－１）についてＧＰＣ測定を行った結果、ポリスチレン換算値として、重量平均分子量（Ｍｗ）は、２５，０００であった。
Figure JPOXMLDOC01-appb-C000078
 (Synthesis Example 9)
[Polyimide precursor from 4,4′-oxydiphthalic dianhydride, 4,4′-oxydianiline, and 2-hydroxyethyl methacrylate (polymer for comparative example R-1: polyimide precursor having radical polymerizable group) Body)]
20.0 g (64.5 mmol) 4,4′-oxydiphthalic dianhydride (dried at 140 ° C. for 12 hours), 18.6 g (129 mmol) 2-hydroxyethyl methacrylate, 0.05 g Hydroquinone, 10.7 g of pyridine, and 140 g of diglyme were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of 4,4′-oxydiphthalic acid and 2-hydroxyethyl methacrylate. The reaction mixture was then cooled to −10 ° C. and 16.12 g (135.5 mmol) of SOCl 2 was added over 10 minutes while maintaining the temperature at −10 ± 4 ° C. After dilution with 50 ml N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours. Then, a solution of 11.75 g (58.70 mmol) of 4,4′-oxydianiline dissolved in 100 ml of N-methylpyrrolidone was added dropwise to the reaction mixture at 20-23 ° C. over 20 minutes. The reaction mixture was then stirred overnight at room temperature. The polyimide precursor was then precipitated in 5 liters of water and the water-polyimide precursor mixture was stirred for 15 minutes at a speed of 5000 rpm. The polyimide precursor was filtered off and stirred again in 4 liters of water for 30 minutes and filtered again. Next, the obtained polyimide precursor was dried at 45 ° C. under reduced pressure for 3 days to obtain a polyimide precursor (R-1) for comparative example.
As a result of GPC measurement of this polyimide precursor (R-1), the weight average molecular weight (Mw) as a polystyrene conversion value was 25,000.
Figure JPOXMLDOC01-appb-C000078
＜実施例および比較例＞
　下記記載の成分を混合し、均一な溶液として、感光性樹脂組成物の塗布液を調製した。
＜感光性樹脂組成物の組成＞
　ポリイミド前駆体：表１または表２に記載のポリイミド前駆体を表１または表２に記載の質量部
　光ラジカル重合開始剤：表１または表２に記載の光ラジカル重合開始剤を表１または表２に記載の質量部
　ラジカル重合性化合物：表１または表２に記載のラジカル重合性化合物を表１または表２に記載の質量部
　その他の成分：表１または表２記載の上記以外の成分を表１または表２に記載の質量部 <Examples and Comparative Examples>
The following components were mixed to prepare a photosensitive resin composition coating solution as a uniform solution.
<Composition of photosensitive resin composition>
Polyimide precursor: parts by mass of the polyimide precursor described in Table 1 or 2 as shown in Table 1 or Table 2 Photoradical polymerization initiator: Table 1 or Table as the radical photopolymerization initiator described in Table 1 or 2 2 parts by mass of radically polymerizable compound: the radically polymerizable compound described in Table 1 or Table 2 is the part by weight of Table 1 or Table 2 Other components: other than the above-mentioned components in Table 1 or Table 2 Mass parts given in Table 1 or 2
Figure JPOXMLDOC01-appb-T000079
Figure JPOXMLDOC01-appb-T000079
Figure JPOXMLDOC01-appb-T000080
Figure JPOXMLDOC01-appb-T000080
（Ｂ）ラジカル重合開始剤
Ｂ－１：ＩＲＧＡＣＵＲＥ　ＯＸＥ　０１（ＢＡＳＦ社製）
Ｂ－２：ＩＲＧＡＣＵＲＥ　ＯＸＥ　０２（ＢＡＳＦ社製）
Ｂ－３：ＩＲＧＡＣＵＲＥ　３６９（ＢＡＳＦ社製） (B) Radical polymerization initiator B-1: IRGACURE OXE 01 (manufactured by BASF)
B-2: IRGACURE OXE 02 (manufactured by BASF)
B-3: IRGACURE 369 (BASF)
（Ｃ）ラジカル重合性化合物
Ｃ－１：ジペンタエリスリトールヘキサ（メタ）アクリレート、Ａ－ＤＰＨ（新中村化学工業（株）製）
Ｃ－２：ＳＲ－２０９（サートマー社製）
Figure JPOXMLDOC01-appb-C000081
 Ｃ－３：ジペンタエリスリトールテトラアクリレート、Ａ－ＴＭＭＴ（新中村化学工業（株）製） (C) Radical polymerizable compound C-1: Dipentaerythritol hexa (meth) acrylate, A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)
C-2: SR-209 (Sartomer)
Figure JPOXMLDOC01-appb-C000081
 C-3: Dipentaerythritol tetraacrylate, A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)
（Ｄ）重合禁止剤
Ｄ－１：２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール（東京化成工業（株）製）
Ｄ－２：ｐ－ベンゾキノン（東京化成工業（株）製）
Ｄ－３：ｐ－メトキシフェノール（東京化成工業（株）製）
（Ｅ）マイグレーション抑制剤
Ｅ－１：下記化合物
Ｅ－２：下記化合物
Ｅ－３：下記化合物
Ｅ－４：下記化合物 (D) Polymerization inhibitor D-1: 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
D-2: p-benzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)
D-3: p-methoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
(E) Migration inhibitor E-1: the following compound E-2: the following compound E-3: the following compound E-4: the following compound
（Ｆ）金属接着性改良剤
Ｆ－１：下記化合物
Ｆ－２：下記化合物
Ｆ－３：下記化合物  (F) Metal adhesion improver F-1: Compound F-2 below: Compound F-3 below: Compound below
Figure JPOXMLDOC01-appb-C000082
Figure JPOXMLDOC01-appb-C000082
（Ｇ）塩基発生剤
Ｇ－１（光塩基発生剤）：下記化合物
Figure JPOXMLDOC01-appb-C000083
 Ｇ－２（光塩基発生剤）：下記化合物
Figure JPOXMLDOC01-appb-C000084
 Ｇ－３（熱塩基発生剤）：下記化合物
Figure JPOXMLDOC01-appb-C000085
 (G) Base generator G-1 (photobase generator): the following compound
Figure JPOXMLDOC01-appb-C000083
 G-2 (photobase generator): the following compound
Figure JPOXMLDOC01-appb-C000084
 G-3 (thermal base generator): the following compound
Figure JPOXMLDOC01-appb-C000085
（Ｈ）溶剤
Ｈ－１：γ－ブチロラクトン（三和油化工業（株）製）
Ｈ－２：ジメチルスルホキシド（和光純薬工業（株）製）
Ｈ－３：Ｎ－メチル－２－ピロリドン（Ａｓｈｌａｎｄ社製） (H) Solvent H-1: γ-butyrolactone (manufactured by Sanwa Oil Chemical Co., Ltd.)
H-2: Dimethyl sulfoxide (Wako Pure Chemical Industries, Ltd.)
H-3: N-methyl-2-pyrrolidone (manufactured by Ashland)
＜評価＞
＜＜破断伸び率＞＞
　各感光性樹脂組成物を、細孔の幅が０．８μｍのフィルターを通して加圧濾過した後、シリコンウェハ上にスピンコート法により感光性樹脂組成物を塗布した。感光性樹脂組成物層が塗布されたシリコンウェハをホットプレート上で、１００℃で５分間乾燥し、シリコンウェハ上に２０μｍの厚さの均一な感光性樹脂組成物層を形成した。シリコンウェハ上の感光性樹脂組成物層を、ステッパー（Ｎｉｋｏｎ　ＮＳＲ　２００５　ｉ９Ｃ）を用いて、露光波長３６５ｎｍで、５００ｍＪ／ｃｍ２の露光エネルギーで全面露光し、露光した感光性樹脂組成物層（樹脂層）を、窒素雰囲気下で、１０℃／分の昇温速度で昇温し、２５０℃に達した後、３時間加熱した。硬化後の樹脂層を４．９質量％フッ化水素酸溶液に浸漬し、シリコンウェハから樹脂層を剥離し、樹脂層（硬化膜）を得た。 <Evaluation>
<< Elongation at break >>
Each photosensitive resin composition was filtered under pressure through a filter having a pore width of 0.8 μm, and then the photosensitive resin composition was applied on a silicon wafer by spin coating. The silicon wafer coated with the photosensitive resin composition layer was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a thickness of 20 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed on the entire surface with an exposure energy of 500 mJ / cm 2 at an exposure wavelength of 365 nm using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin The layer was heated at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, and after reaching 250 ° C., the layer was heated for 3 hours. The cured resin layer was immersed in a 4.9% by mass hydrofluoric acid solution, and the resin layer was peeled from the silicon wafer to obtain a resin layer (cured film).
　上記で得られた樹脂層（硬化膜）の破断伸び率を、以下の通り求めた。
　まず、上記で剥離した樹脂層（硬化膜）を幅１０ｍｍ、長さ５０ｍｍのフィルム状に切断し、引張り試験機（テンシロン）を用いてクロスヘッドスピード３００ｍｍ／分、としてフィルムの長手（長さ）方向、幅方向について、２５℃、６５％相対湿度（ＲＨ）の環境下にてＪＩＳ－Ｋ６２５１に準拠して破断伸びを測定した。長手方向、幅方向それぞれの破断伸びの測定を各５回ずつ行った。長手方向と幅方向の破断伸び率の平均値を破断伸び率とした。
Ａ：８０％を超えた。
Ｂ：７０％を超えて８０％以下であった。
Ｃ：６０％を超えて７０％以下であった。
Ｄ：５０％を超えて６０％以下であった。
Ｅ：５０％以下であった。 The elongation at break of the resin layer (cured film) obtained above was determined as follows.
First, the peeled resin layer (cured film) is cut into a film having a width of 10 mm and a length of 50 mm, and the length (length) of the film as a crosshead speed of 300 mm / min using a tensile tester (Tensilon). With respect to the direction and the width direction, the elongation at break was measured according to JIS-K6251 in an environment of 25 ° C. and 65% relative humidity (RH). The elongation at break in the longitudinal direction and the width direction was measured 5 times each. The average value of the elongation at break in the longitudinal direction and the width direction was defined as the elongation at break.
A: It exceeded 80%.
B: More than 70% and 80% or less.
C: It exceeded 70% and was 70% or less.
D: More than 50% and 60% or less.
E: It was 50% or less.
＜＜露光ラチチュード＞＞
　各感光性樹脂組成物を、細孔の幅が０．８μｍのフィルターを通して０．３ＭＰａの圧力で加圧ろ過した後、シリコンウェハ上にスピンコート法により感光性樹脂組成物を塗布した。感光性樹脂組成物層が塗布されたシリコンウェハをホットプレート上で、１００℃で５分間乾燥し、シリコンウェハ上に１０μｍの膜厚の均一な感光性樹脂組成物層を形成した。シリコンウェハ上の感光性樹脂組成物層を、ステッパー（Ｎｉｋｏｎ　ＮＳＲ　２００５　ｉ９Ｃ）を用いて露光した。露光はi線で行い、波長３６５ｎｍにおいて、２００、３００、４００、５００、６００、７００、８００ｍＪ／ｃｍ２の各露光エネルギーで、５μｍから２５μｍまで１μｍ刻みのラインアンドスペースのフォトマスクを使用して、露光を行って樹脂層を得た。 << Exposure latitude >>
Each photosensitive resin composition was pressure filtered through a filter having a pore width of 0.8 μm at a pressure of 0.3 MPa, and then the photosensitive resin composition was applied onto a silicon wafer by spin coating. The silicon wafer coated with the photosensitive resin composition layer was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a thickness of 10 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C). The exposure is performed with i-line, using a line-and-space photomask in 1 μm increments from 5 μm to 25 μm at each exposure energy of 200, 300, 400, 500, 600, 700, 800 mJ / cm 2 at a wavelength of 365 nm. Then, exposure was performed to obtain a resin layer.
　上記で得られた樹脂層を、シクロペンタノンで６０秒間ネガ型現像した。得られた樹脂層（パターン）の線幅が小さければ小さいほど光照射部と光非照射部との現像液に対する溶解性の差が大きくなっていることを表し、好ましい結果となる。また、露光エネルギーの変化に対して、線幅の変化が小さければ、露光ラチチュードが広いことを表し、好ましい結果となる。測定限界は５μｍである。
Ａ：５μｍ以上８μｍ以下であった。
Ｂ：８μｍを超えて１０μｍ以下であった。
Ｃ：１０μｍを超えて１５μｍ以下であった。
Ｄ：１５μｍを超えて２０μｍ以下であった。
Ｅ：２０μｍを超えた。
Ｆ：エッジの鋭さを持つ線幅を有するパターンが得られなかった。 The resin layer obtained above was negatively developed with cyclopentanone for 60 seconds. The smaller the line width of the obtained resin layer (pattern), the greater the difference in solubility in the developer between the light-irradiated part and the non-light-irradiated part, which is a preferable result. Further, if the change in the line width is small with respect to the change in exposure energy, it indicates that the exposure latitude is wide, which is a preferable result. The measurement limit is 5 μm.
A: It was 5 to 8 μm.
B: It was 10 micrometers or less exceeding 8 micrometers.
C: It was 15 micrometers or less exceeding 10 micrometers.
D: It was 20 micrometers or less exceeding 15 micrometers.
E: It exceeded 20 micrometers.
F: A pattern having a line width with sharp edges could not be obtained.
＜＜剥離欠陥評価（層間密着性）＞＞
＜＜＜積層体（１）の製造＞＞＞
　各感光性樹脂組成物を、細孔の幅が０．８μｍのフィルターを通して加圧濾過した後、シリコンウェハ上にスピンコート法により感光性樹脂組成物を塗布した。感光性樹脂組成物層が塗布されたシリコンウェハをホットプレート上で、１００℃で５分間乾燥し、シリコンウェハ上に１５μｍの厚さの均一な感光性樹脂組成物層を形成した。ついで、シリコンウェハ上の感光性樹脂組成物層を、ステッパー（Ｎｉｋｏｎ　ＮＳＲ　２００５　ｉ９Ｃ）を用いて、露光波長３６５ｎｍで、５００ｍＪ/ｃｍ２の露光エネルギーで露光し、露光した感光性樹脂組成物層（樹脂層）を、シクロペンタノンで６０秒間現像して、直径１０μｍのホールを形成した。次いで、窒素雰囲気下で、１０℃／分の昇温速度で昇温し、２５０℃に達した後、３時間加熱した。室温まで冷却後、樹脂層の表面に、再度、上記感光性樹脂組成物と同じ種類の感光性樹脂組成物を用いて、上記と同様に感光性樹脂組成物の濾過から、パターン化した膜の３時間加熱までの手順を再度実施して、樹脂層を２層有する積層体（１）を形成した。 << Peeling defect evaluation (interlayer adhesion) >>
<<< Manufacturing of Laminate (1) >>>
Each photosensitive resin composition was filtered under pressure through a filter having a pore width of 0.8 μm, and then the photosensitive resin composition was applied on a silicon wafer by spin coating. The silicon wafer coated with the photosensitive resin composition layer was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. Next, the photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ / cm 2 at an exposure wavelength of 365 nm using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer ( The resin layer) was developed with cyclopentanone for 60 seconds to form holes with a diameter of 10 μm. Next, the temperature was increased at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, and after reaching 250 ° C., heating was performed for 3 hours. After cooling to room temperature, again using the same type of photosensitive resin composition as the photosensitive resin composition on the surface of the resin layer, filtration of the photosensitive resin composition in the same manner as above, The procedure up to heating for 3 hours was performed again to form a laminate (1) having two resin layers.
＜＜＜積層体（２）の製造＞＞＞
　上記で得られた積層体（１）の表面に、積層体（１）の製造に用いた感光性樹脂組成物と同じ種類の感光性樹脂組成物を用いて、積層体（１）の製造と同様の手順を再度実施することで、樹脂層を４層有する積層体（２）を作製した。 <<< Production of Laminate (2) >>>
Using the same type of photosensitive resin composition as the photosensitive resin composition used for the production of the laminate (1) on the surface of the laminate (1) obtained above, the production of the laminate (1) and By repeating the same procedure again, the laminated body (2) which has four resin layers was produced.
＜＜＜積層体（３）の製造＞＞＞
　各感光性樹脂組成物を、細孔の幅が０．８μｍのフィルターを通して加圧濾過した後、シリコンウェハ上にスピンコート法により感光性樹脂組成物を塗布した。感光性樹脂組成物層が塗布されたシリコンウェハをホットプレート上で、１００℃で５分間乾燥し、シリコンウェハ上に１５μｍの厚さの均一な感光性樹脂組成物層を形成した。シリコンウェハ上の感光性樹脂組成物層を、ステッパー（Ｎｉｋｏｎ　ＮＳＲ　２００５　ｉ９Ｃ）を用いて、５００ｍＪ/ｃｍ２の露光エネルギーで露光し、露光した感光性樹脂組成物層（樹脂層）を、シクロペンタノンで６０秒間現像して、直径１０μｍのホールを形成した。次いで、窒素雰囲気下で、１０℃／分の昇温速度で昇温し、２５０℃に達した後、３時間加熱した。室温まで冷却後、上記ホール部分を覆うように、感光性樹脂組成物層の表面の一部に、蒸着法により厚さ２μｍの銅薄層（金属層）を形成した。さらに、金属層および感光性樹脂組成物層の表面に、再度、同じ種類の感光性樹脂組成物を用いて、上記と同様に感光性樹脂組成物の濾過から、パターン化した膜の３時間加熱までの手順を再度実施して、樹脂層／金属層／樹脂層からなる積層体（３）を作製した。 <<< Production of Laminate (3) >>>
Each photosensitive resin composition was filtered under pressure through a filter having a pore width of 0.8 μm, and then the photosensitive resin composition was applied on a silicon wafer by spin coating. The silicon wafer coated with the photosensitive resin composition layer was dried on a hot plate at 100 ° C. for 5 minutes to form a uniform photosensitive resin composition layer having a thickness of 15 μm on the silicon wafer. The photosensitive resin composition layer on the silicon wafer was exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed photosensitive resin composition layer (resin layer) was subjected to cyclopenta Development was carried out for 60 seconds without forming holes having a diameter of 10 μm. Next, the temperature was increased at a rate of temperature increase of 10 ° C./min in a nitrogen atmosphere, and after reaching 250 ° C., heating was performed for 3 hours. After cooling to room temperature, a thin copper layer (metal layer) having a thickness of 2 μm was formed on a part of the surface of the photosensitive resin composition layer by vapor deposition so as to cover the hole portion. Furthermore, the same kind of photosensitive resin composition is used again on the surfaces of the metal layer and the photosensitive resin composition layer, and the patterned film is heated for 3 hours from the filtration of the photosensitive resin composition in the same manner as described above. The procedure up to was performed again to produce a laminate (3) composed of resin layer / metal layer / resin layer.
＜＜＜積層体（４）の製造＞＞＞
　上記積層体（３）の表面に、さらに、積層体（３）と同様の方法により、銅薄層（金属層）と樹脂層を交互に作製し、樹脂層／金属層／樹脂層／金属層／樹脂層／金属層／樹脂層からなる積層体（４）を作製した。 <<< Manufacturing of Laminate (4) >>>
A thin copper layer (metal layer) and a resin layer are alternately produced on the surface of the laminate (3) by the same method as that for the laminate (3), and resin layer / metal layer / resin layer / metal layer A laminate (4) composed of / resin layer / metal layer / resin layer was produced.
＜＜＜剥離欠陥評価Ａ（加熱処理なし）＞＞＞
　上記で得られた各積層体の樹脂層面に対し、垂直方向に幅５ｍｍとなるように、かつ、樹脂層と樹脂層が接している部分と、金属層と樹脂層が接している部分を、それぞれ、切り出し、その断面を観察して、１つの切り出し片における、樹脂層／樹脂層間、および金属層／樹脂層間での剥がれの有無を光学顕微鏡で確認した。なお、倍率は、剥がれ箇所の大小で適宜調整した。剥がれの発生は、樹脂層/樹脂層間、金属層/樹脂層間の剥がれに関わらず全体での個数を確認し、剥がれの発生がなければ、優れた接着性を有していることを表し、好ましい結果となる。
Ａ：剥がれの発生なし
Ｂ：剥がれの発生が１～２個
Ｃ：剥がれの発生が３～５個
Ｄ：剥がれの発生が６個以上 <<< Peeling defect evaluation A (no heat treatment) >>>
With respect to the resin layer surface of each laminate obtained above, the width is 5 mm in the vertical direction, the portion where the resin layer and the resin layer are in contact, and the portion where the metal layer and the resin layer are in contact, Each was cut out and the cross section was observed, and the presence or absence of peeling between the resin layer / resin layer and the metal layer / resin layer in one cut piece was confirmed with an optical microscope. The magnification was appropriately adjusted depending on the size of the peeled portion. The occurrence of peeling confirms the total number regardless of peeling between the resin layer / resin layer and the metal layer / resin layer, and if there is no peeling, it indicates that it has excellent adhesiveness, which is preferable. Result.
A: No peeling occurred B: 1 to 2 peeling occurrences C: 3 to 5 peeling occurrences D: 6 or more peeling occurrences
＜＜＜剥離欠陥評価Ｂ（加熱処理後）＞＞＞
　上記で得られた各積層体を、窒素中３００℃で３時間加熱した。その後、各積層体の樹脂層面に対し、垂直方向に幅５ｍｍとなるように、かつ、樹脂層と樹脂層が接している部分と、金属層と樹脂層が接している部分を、それぞれ、切り出し、その断面を観察して、１つの切り出し片における、樹脂層／樹脂層間、および金属層／樹脂層間での剥がれの有無を光学顕微鏡で確認した。剥がれの発生は、樹脂層/樹脂層間、金属層/樹脂層間の剥がれに関わらず全体での個数を確認し、剥がれの発生がなければ、優れた接着性を有していることを表し、好ましい結果となる。
Ａ：剥がれの発生なし
Ｂ：剥がれの発生が１～２個
Ｃ：剥がれの発生が３～５個
Ｄ：剥がれの発生が６個以上
Figure JPOXMLDOC01-appb-T000086
 　上記表３における露光ラチチュードの２００～８００の数字は、露光エネルギー（単位：ｍＪ／ｃｍ２）を示している。  <<< Peeling defect evaluation B (after heat treatment) >>>
Each laminate obtained above was heated in nitrogen at 300 ° C. for 3 hours. After that, cut out a portion where the resin layer and the resin layer are in contact with each other, and a portion where the resin layer and the resin layer are in contact with each other, and a portion where the metal layer and the resin layer are in contact with each other. The cross section was observed, and the presence or absence of peeling between the resin layer / resin layer and the metal layer / resin layer in one cut piece was confirmed with an optical microscope. The occurrence of peeling confirms the total number regardless of peeling between the resin layer / resin layer and the metal layer / resin layer, and if there is no peeling, it indicates that it has excellent adhesiveness, which is preferable. Result.
A: No peeling occurred B: 1 to 2 peeling occurrences C: 3 to 5 peeling occurrences D: 6 or more peeling occurrences
Figure JPOXMLDOC01-appb-T000086
 The numbers from 200 to 800 of exposure latitude in Table 3 above indicate exposure energy (unit: mJ / cm 2 ).
Figure JPOXMLDOC01-appb-T000087
Figure JPOXMLDOC01-appb-T000087
Figure JPOXMLDOC01-appb-T000088
Figure JPOXMLDOC01-appb-T000088
＜実施例１００＞
　実施例１の感光性樹脂組成物を、細孔の幅が０．８μｍのフィルターを通して０．３ＭＰａの圧力で加圧ろ過した後、表面に、銅薄層が形成された基板にスピンコートした（３５００ｒｐｍ、３０秒）。基板に適用した感光性樹脂組成物を、１００℃で５分間乾燥した後、アライナー（Ｋａｒｌ－Ｓｕｓｓ　ＭＡ１５０）を用いて露光した。露光は高圧水銀ランプから波長３６５ｎｍの光を照射して行った。露光の後、シクロペンタノンで７５秒間画像を現像した。次いで、１８０℃で２０分加熱した。このようにして、再配線層用層間絶縁膜を形成した。
　この再配線層用層間絶縁膜は、絶縁性に優れていた。
　また、この再配線層用層間絶縁膜を使用して半導体デバイスを製造したところ、問題なく動作することを確認した。 <Example 100>
The photosensitive resin composition of Example 1 was subjected to pressure filtration at a pressure of 0.3 MPa through a filter having a pore width of 0.8 μm, and then spin coated on a substrate on which a copper thin layer was formed ( 3500 rpm, 30 seconds). The photosensitive resin composition applied to the substrate was dried at 100 ° C. for 5 minutes, and then exposed using an aligner (Karl-Suss MA150). The exposure was performed by irradiating light with a wavelength of 365 nm from a high-pressure mercury lamp. After exposure, the image was developed with cyclopentanone for 75 seconds. Subsequently, it heated at 180 degreeC for 20 minutes. In this way, an interlayer insulating film for a rewiring layer was formed.
This interlayer insulation film for rewiring layers was excellent in insulation.
Moreover, when a semiconductor device was manufactured using this interlayer insulating film for rewiring layer, it was confirmed that it operated without any problem.
１００：半導体デバイス
１０１ａ～１０１ｄ：半導体素子
１０１：積層体
１０２ｂ～１０２ｄ：貫通電極
１０３ａ～１０３ｅ：金属バンプ
１０５：再配線層
１１０、１１０ａ、１１０ｂ：アンダーフィル層
１１５：絶縁膜
１２０：配線基板
１２０ａ：表面電極
  100: Semiconductor devices 101a to 101d: Semiconductor element 101: Stacked bodies 102b to 102d: Through electrodes 103a to 103e: Metal bump 105: Rewiring layers 110, 110a, 110b: Underfill layer 115: Insulating film 120: Wiring substrate 120a: Surface electrode

Claims (25)

  1. 下記式（１）で表される繰り返し単位を含むポリイミド前駆体、および、光ラジカル重合開始剤を含む感光性樹脂組成物；
    式（１）
    Figure JPOXMLDOC01-appb-C000001
     式（１）中、Ａ１およびＡ２は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ１１１は、２価の有機基を表し、Ｒ１１５は、４価の有機基を表し、Ｒ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表す；但し、Ｒ１１１、Ｒ１１３、Ｒ１１４およびＲ１１５の少なくとも１つの末端には下記式（２）で表される基が結合している；
    式（２）
    Figure JPOXMLDOC01-appb-C000002
     式（２）において、Ｒ１は、水素原子または置換基を表し、＊はＲ１１１、Ｒ１１３、Ｒ１１４またはＲ１１５との結合部位である。     A photosensitive resin composition containing a polyimide precursor containing a repeating unit represented by the following formula (1), and a radical photopolymerization initiator;
    Formula (1)
    Figure JPOXMLDOC01-appb-C000001
     In formula (1), A 1 and A 2 each independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group; provided that at least one terminal of R 111 , R 113 , R 114 and R 115 has a group represented by the following formula (2): Bound;
    Formula (2)
    Figure JPOXMLDOC01-appb-C000002
     In Formula (2), R 1 represents a hydrogen atom or a substituent, and * is a binding site with R 111 , R 113 , R 114 or R 115 .
  2. 前記ポリイミド前駆体が下記式（３）で表される化合物由来の構造を有する、請求項１に記載の感光性樹脂組成物；
    式（３）
    Figure JPOXMLDOC01-appb-C000003
     式（３）中、Ａは（ｐ＋ｑ）価の基を表す；Ｒ１は水素原子または置換基を表す；ｐは１～５の整数を表し、ｑは２以上の整数を表す。     The photosensitive resin composition according to claim 1, wherein the polyimide precursor has a structure derived from a compound represented by the following formula (3);
    Formula (3)
    Figure JPOXMLDOC01-appb-C000003
     In formula (3), A represents a (p + q) -valent group; R 1 represents a hydrogen atom or a substituent; p represents an integer of 1 to 5, and q represents an integer of 2 or more.
  3. 前記ポリイミド前駆体が下記式（３ａ）で表される化合物由来の構造を有する、請求項１に記載の感光性樹脂組成物；
    式（３ａ）
    Figure JPOXMLDOC01-appb-C000004
     式（３ａ）中、Ａ０は（ｌ＋ｍ）価の基を表す；Ａ１は単結合または（ｎ＋１）価の基を表す；Ｒ１は水素原子または置換基を表す；Ａｒは（ａ＋１）価の芳香族炭化水素基または芳香族複素環基を表す；ａ、ｌ、ｍおよびｎは、それぞれ独立に１～５の整数を表す；ただし、ｍおよびｎの少なくとも一方は２以上の整数を表す。     The photosensitive resin composition according to claim 1, wherein the polyimide precursor has a structure derived from a compound represented by the following formula (3a);
    Formula (3a)
    Figure JPOXMLDOC01-appb-C000004
     In formula (3a), A 0 represents a (l + m) -valent group; A 1 represents a single bond or a (n + 1) -valent group; R 1 represents a hydrogen atom or a substituent; Ar represents an (a + 1) -valent group A, l, m and n each independently represents an integer of 1 to 5; provided that at least one of m and n represents an integer of 2 or more. .
  4. 前記ポリイミド前駆体が下記式（３ｂ）で表される化合物由来の構造を有する、請求項１に記載の感光性樹脂組成物；
    式（３ｂ）
    Figure JPOXMLDOC01-appb-C000005
     式（３ｂ）中、Ａ０は（ｌ＋ｍ）価の基を表す；Ｒ１は水素原子または置換基を表す；ａ、ｌ、ｍおよびｎはそれぞれ独立に１～５の整数を表す；ただし、ｍおよびｎの少なくとも一方は２以上の整数を表す。     The photosensitive resin composition according to claim 1, wherein the polyimide precursor has a structure derived from a compound represented by the following formula (3b);
    Formula (3b)
    Figure JPOXMLDOC01-appb-C000005
     In formula (3b), A 0 represents a (l + m) -valent group; R 1 represents a hydrogen atom or a substituent; a, l, m and n each independently represents an integer of 1 to 5; At least one of m and n represents an integer of 2 or more.
  5. 前記式（１）中、少なくともＲ１１１の末端に式（２）で表される基が結合している、請求項１～４のいずれか１項に記載の感光性樹脂組成物。 In the formula (1), it is groups bond represented by the formula (2) at the end of at least R 111, the photosensitive resin composition according to any one of claims 1 to 4.
  6. 前記ポリイミド前駆体が、さらに、式（１－１）で表される繰り返し単位を含む、請求項１～５のいずれか１項に記載の感光性樹脂組成物；
    式（１－１）
    Figure JPOXMLDOC01-appb-C000006
     式（１－１）中、Ａ１およびＡ２は、それぞれ独立に酸素原子またはＮＨを表し、Ｒ１１１は、２価の有機基を表し、Ｒ１１５は、４価の有機基を表し、Ｒ１１３およびＲ１１４は、それぞれ独立に、水素原子または１価の有機基を表す；但し、式（１－１）で表される繰り返し単位は前記式（２）で表される基を含まない。     The photosensitive resin composition according to any one of claims 1 to 5, wherein the polyimide precursor further contains a repeating unit represented by the formula (1-1);
    Formula (1-1)
    Figure JPOXMLDOC01-appb-C000006
     In formula (1-1), A 1 and A 2 each independently represent an oxygen atom or NH, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group; provided that the repeating unit represented by the formula (1-1) does not include the group represented by the formula (2).
  7. 前記式（１－１）におけるＲ１１１は、－Ａｒ－Ｌ－Ａｒ－で表される、請求項６に記載の感光性樹脂組成物；但し、Ａｒは、それぞれ独立に、芳香族炭化水素基であり、Ｌは、フッ素原子で置換されていてもよい炭素数１～１０の脂肪族炭化水素基、－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ２－または－ＮＨＣＯ－、ならびに、前記の２つ以上の組み合わせからなる基である。 The photosensitive resin composition according to claim 6, wherein R 111 in the formula (1-1) is represented by -Ar-L-Ar-; wherein Ar is independently an aromatic hydrocarbon group. L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, —CO—, —S—, —SO 2 — or —NHCO—, and It is a group consisting of a combination of two or more of the above.
  8. 前記式（１－１）におけるＲ１１１は、下記式（５１）または式（６１）で表される基である、請求項６に記載の感光性樹脂組成物；
    式（５１）
    Figure JPOXMLDOC01-appb-C000007
     式（５１）中、Ｒ１０～Ｒ１７は、それぞれ独立に水素原子、フッ素原子または１価の有機基であり、Ｒ１０～Ｒ１７の少なくとも１つはフッ素原子、メチル基、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である；
    式（６１）
    Figure JPOXMLDOC01-appb-C000008
     式（６１）中、Ｒ１８およびＲ１９は、それぞれ独立にフッ素原子、フルオロメチル基、ジフルオロメチル基、または、トリフルオロメチル基である。     The photosensitive resin composition according to claim 6, wherein R 111 in the formula (1-1) is a group represented by the following formula (51) or the formula (61);
    Formula (51)
    Figure JPOXMLDOC01-appb-C000007
     In formula (51), R 10 to R 17 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 10 to R 17 is a fluorine atom, a methyl group, a fluoromethyl group, A difluoromethyl group or a trifluoromethyl group;
    Formula (61)
    Figure JPOXMLDOC01-appb-C000008
     In formula (61), R 18 and R 19 are each independently a fluorine atom, a fluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.
  9. 前記Ｒ１１３およびＲ１１４の少なくとも一方が、ラジカル重合性基を含む、請求項１～８のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 8, wherein at least one of R 113 and R 114 contains a radical polymerizable group.
  10. 前記Ｒ１１５は、芳香環を含む４価の有機基である、請求項１～９のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 9, wherein R 115 is a tetravalent organic group containing an aromatic ring.
  11. さらに、ラジカル重合性化合物を含む、請求項１～１０のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 10, further comprising a radical polymerizable compound.
  12. さらに、塩基発生剤を含む、請求項１～１１のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 11, further comprising a base generator.
  13. さらに、溶剤を含む、請求項１～１２のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 12, further comprising a solvent.
  14. ネガ型現像に用いられる、請求項１～１３のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 13, which is used for negative development.
  15. 再配線層用層間絶縁膜の形成に用いられる、請求項１～１４のいずれか１項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 14, which is used for forming an interlayer insulating film for a rewiring layer.
  16. 請求項１～１５のいずれか１項に記載の感光性樹脂組成物を硬化してなる硬化膜。 A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 15.
  17. 請求項１６に記載の硬化膜を２層以上有する、積層体。 A laminate having two or more cured films according to claim 16.
  18. 前記硬化膜の間に、金属層を有する、請求項１７に記載の積層体。 The laminated body of Claim 17 which has a metal layer between the said cured films.
  19. 請求項１～１５のいずれか１項に記載の感光性樹脂組成物を用いることを含む、硬化膜の製造方法。 A method for producing a cured film, comprising using the photosensitive resin composition according to any one of claims 1 to 15.
  20. 前記感光性樹脂組成物を基板に適用して層状にする、感光性樹脂組成物層形成工程と、
    前記感光性樹脂組成物層を露光する露光工程と、
    前記露光された感光性樹脂組成物層に対して、現像処理を行う現像処理工程とを有する、請求項１９に記載の硬化膜の製造方法。     Applying the photosensitive resin composition to a substrate to form a layer, a photosensitive resin composition layer forming step;
    An exposure step of exposing the photosensitive resin composition layer;
    The manufacturing method of the cured film of Claim 19 which has the image development process process which performs image development processing with respect to the said exposed photosensitive resin composition layer.
  21. 前記現像処理がネガ型現像処理である、請求項２０に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 20, wherein the development treatment is a negative development treatment.
  22. 前記現像処理工程後に、現像された感光性樹脂組成物層を５０～４５０℃の温度で加熱する工程を含む、請求項２０または２１に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 20 or 21, further comprising a step of heating the developed photosensitive resin composition layer at a temperature of 50 to 450 ° C after the development processing step.
  23. 前記硬化膜の膜厚が、１～３０μｍである、請求項１９～２２のいずれか１項に記載の硬化膜の製造方法。 The method for producing a cured film according to any one of claims 19 to 22, wherein the thickness of the cured film is 1 to 30 µm.
  24. 請求項１９～２３のいずれか１項に記載の硬化膜の製造方法に従って、硬化膜を形成後、さらに、再度、前記感光性樹脂組成物層形成工程、前記露光工程、および、前記現像処理工程を、前記順に、２～５回行う、積層体の製造方法。 According to the method for producing a cured film according to any one of claims 19 to 23, after forming the cured film, again, the photosensitive resin composition layer forming step, the exposure step, and the development processing step Is performed in the order described above 2 to 5 times.
  25. 請求項１６に記載の硬化膜、あるいは、請求項１７または１８に記載の積層体を有する半導体デバイス。 A semiconductor device comprising the cured film according to claim 16 or the laminate according to claim 17 or 18.
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