WO2018123836A1 - Composition de résine photosensible, film durci, stratifié, procédé de fabrication de film durci, procédé de fabrication de stratifié et dispositif à semi-conducteurs - Google Patents

Composition de résine photosensible, film durci, stratifié, procédé de fabrication de film durci, procédé de fabrication de stratifié et dispositif à semi-conducteurs 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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English (en)
Japanese (ja)
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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/ja
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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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Abstract

L'invention concerne les éléments suivants : une composition de résine photosensible qui permet de former un motif au moyen d'une polymérisation photo-radicalaire et d'obtenir un film durci présentant un taux élevé d'allongement à la rupture ; un film durci ; un stratifié ; un procédé de fabrication d'un film durci ; un procédé de fabrication d'un stratifié ; un dispositif à semi-conducteurs. La composition de résine photosensible contient : un précurseur de polyimide contenant des motifs répétés représentés par la formule (1) ; un initiateur de polymérisation photo-radicalaire. Dans la formule (1), A1 et A2 représentent chacun un atome d'oxygène ou NH, R111 représente un groupe organique divalent, R115 représente un groupe organique tétravalent, et R113 et R114 représentent chacun un atome d'hydrogène ou un groupe organique monovalent. Un groupe représenté par la formule (2) est lié à une borne d'au moins un élément parmi R111, R113, R114 et R115. Dans la formule (2), R1représente un atome d'hydrogène ou un groupe substituant, et * représente la position de liaison à R111, R113, R114 ou R115.
PCT/JP2017/046051 2016-12-28 2017-12-22 Composition de résine photosensible, film durci, stratifié, procédé de fabrication de film durci, procédé de fabrication de stratifié et dispositif à semi-conducteurs WO2018123836A1 (fr)

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WO2021153608A1 (fr) * 2020-01-30 2021-08-05 旭化成株式会社 Composition de résine photosensible négative et procédé de fabrication d'un motif en relief durci
CN114341731A (zh) * 2019-08-27 2022-04-12 富士胶片株式会社 固化膜的制造方法、光固化性树脂组合物、层叠体的制造方法及半导体器件的制造方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019146378A1 (fr) * 2018-01-23 2019-08-01 Jsr株式会社 Composition pour former un film de sous-couche de réserve, film de sous-couche de réserve, procédé de formation associé et procédé de production de substrat à motifs
WO2019189111A1 (fr) * 2018-03-29 2019-10-03 富士フイルム株式会社 Composition de résine photosensible, film durci, stratifié, procédé de fabrication de ceux-ci, dispositif à semi-conducteur et générateur de base thermique utilisés dans ceux-ci
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CN114341731A (zh) * 2019-08-27 2022-04-12 富士胶片株式会社 固化膜的制造方法、光固化性树脂组合物、层叠体的制造方法及半导体器件的制造方法
EP4063953A4 (fr) * 2019-11-21 2023-05-31 FUJIFILM Corporation Procédé de formation de motif, composition de résine photodurcissable, procédé de fabrication de corps stratifié et procédé de fabrication de dispositif électronique
WO2021100768A1 (fr) * 2019-11-21 2021-05-27 富士フイルム株式会社 Procédé de formation de motif, composition de résine photodurcissable, procédé de fabrication de corps stratifié et procédé de fabrication de dispositif électronique
JPWO2021153608A1 (fr) * 2020-01-30 2021-08-05
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WO2021153608A1 (fr) * 2020-01-30 2021-08-05 旭化成株式会社 Composition de résine photosensible négative et procédé de fabrication d'un motif en relief durci

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