WO2020262227A1 - Composition de resine durcissable, film durci, corps stratifie, procede de fabrication de film durci et dispositif a semi-conducteurs - Google Patents

Composition de resine durcissable, film durci, corps stratifie, procede de fabrication de film durci et dispositif a semi-conducteurs Download PDF

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Publication number
WO2020262227A1
WO2020262227A1 PCT/JP2020/024108 JP2020024108W WO2020262227A1 WO 2020262227 A1 WO2020262227 A1 WO 2020262227A1 JP 2020024108 W JP2020024108 W JP 2020024108W WO 2020262227 A1 WO2020262227 A1 WO 2020262227A1
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group
formula
resin composition
preferable
curable resin
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PCT/JP2020/024108
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English (en)
Japanese (ja)
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敦靖 野崎
悠 岩井
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富士フイルム株式会社
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Priority to JP2021526907A priority Critical patent/JP7194278B2/ja
Publication of WO2020262227A1 publication Critical patent/WO2020262227A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • 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
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—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 curable resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.
  • Polymer precursors such as polyimide resin, polyamideimide resin, and polybenzoxazole resin are collectively referred to as "heterocycle-containing polymer precursor”.
  • the resin obtained by cyclizing (also referred to as) is excellent in heat resistance, insulating property, and the like, and is therefore applied to various uses.
  • the above application is not particularly limited, and examples of a semiconductor device for mounting include use as a material for an insulating film or a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.
  • the heterocycle-containing polymer precursor is used in the form of a curable resin composition containing the heterocycle-containing polymer precursor.
  • a curable resin composition is applied to a base material by, for example, coating, and then the heterocyclic-containing polymer precursor is cyclized by heating or the like to form a cured resin on the base material.
  • the curable resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the curable resin composition to be applied. It can be said that it has excellent adaptability.
  • industrial application development of curable resin compositions containing heterocyclic-containing polymer precursors is expected more and more.
  • Patent Document 1 describes a polyamic acid composed of water and N-methyl-2-pyrrolidone, a mixed solvent in which the proportion of water is 10 to 90% by mass, a repeating unit having a specific structure, and imidazoles.
  • a polyimide precursor composition obtained by dissolving a basic compound selected from the group consisting of an amine compound and an amine compound is described.
  • Patent Document 2 describes a resin composition containing a heterocycle-containing polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor and an acidic compound having a pKa of 4.0 or less. a cured film thickness of 10 [mu] m, the conductivity of the cured film after heating for 60 minutes at 350 ° C.
  • Patent Document 3 describes an acidic compound that generates a base when heated to 40 ° C. or higher, a thermosetting agent containing at least one selected from an ammonium salt having an anion having pKa1 of 0 to 4 and an ammonium cation, and a thermosetting agent. A thermosetting resin composition containing this is described.
  • curable resin composition containing a heterocyclic-containing polymer precursor, it is desired to provide a curable resin composition having excellent storage stability of the composition and film strength of the obtained cured product.
  • the present invention relates to a curable resin composition having excellent storage stability of the composition and the film strength of the obtained cured film, a cured film obtained by curing the curable resin composition, and a laminate containing the cured film. It is an object of the present invention to provide a method for producing the cured film and a semiconductor device including the cured film or the laminate.
  • R 11 and R 12 each independently represent a hydrogen atom or an organic group, and R 11 and R 12 may be bonded to form a ring structure.
  • R 21 and R 22 each independently represent a hydrogen atom or an organic group, R 21 and R 22 may be bonded to form a ring structure, and * represents a bonding site with another structure.
  • ⁇ 2> The curable resin composition according to ⁇ 1>, wherein the anion has two or more structures represented by the formula (1-1) and a structure represented by the formula (1-2) in total.
  • ⁇ 3> The curable resin composition according to ⁇ 1> or ⁇ 2>, wherein the above R 11 , R 12 , R 21 and R 22 are independently aliphatic hydrocarbon groups.
  • the anion is any one of ⁇ 1> to ⁇ 3>, which is an anion represented by the following formula (1-3), the following formula (1-4), or the following formula (1-5).
  • R 31 and R 32 each independently represent a hydrogen atom or an organic group, and R 31 and R 32 are bonded and ringed.
  • the structure may be formed, where a represents an integer of 0 to 3, and when a is 2 or more, R 33 of 2 or more may be the same or different, and R 33 is a monovalent substitution.
  • R 41 , R 42 , R 43 and R 44 each independently represent a hydrogen atom or an organic group, R 41 and R 42 may be bonded to form a ring structure, and R 43 and R 44 may be bonded.
  • C represents an integer of 0 to 2, and when c is 2, the two R 45s may be the same or different, where R 45 is a monovalent substitution.
  • R 55 and R 56 each independently represent a hydrogen atom or a substituent, and when n + m is 2 or more, 2 or more R 55 and 2 or more R 56 or 2 or more.
  • R 55 and R 56 may be combined to form a ring structure, n represents an integer of 0 or more, m represents an integer of 0 or more, n + m represents an integer of 1 or more, and n + m is 1.
  • X 2 represents a monovalent substituent or hydrogen atom
  • n + m is 2 or more
  • X 2 represents a single bond or n + m valent linking group, and if n is 2 or more, 2
  • the above R 51 , R 52 and R 55 may be the same or different, and when m is 2 or more, the two or more R 53 , R 54 and R 56 may be the same or different.
  • the bonds shown with broken lines may be single bonds or double bonds independently of each other.
  • ⁇ 5> The curable resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the organic cation is an ammonium cation, an iminium cation, or a phosphonium cation.
  • the organic cation is a cation represented by the following formula (A-1), or a protonated cation of a compound represented by any of the following formulas (A-2) to (A-5).
  • each R A11 ⁇ R A14 independently represent a hydrogen atom or a substituent
  • R A21 represents a hydrogen atom or a substituent
  • R A31 is a hydrogen atom or represents a substituent
  • R A41 represents a hydrogen atom or a substituent
  • each X 1 ⁇ X 4 are independently,-N-or -CR A42 - represents
  • R A42 represents a hydrogen atom or a substituent
  • R A51 ⁇ RA55 independently represent a hydrogen atom or a substituent
  • RA61 to RA64 each independently represent a hydrogen atom or a substituent.
  • ⁇ 7> The curable resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the compound containing the anion is a thermosetting agent.
  • ⁇ 8> The curable resin composition according to any one of ⁇ 1> to ⁇ 7>, further comprising a photopolymerization initiator and a polymerizable compound.
  • ⁇ 9> The curable resin composition according to any one of ⁇ 1> to ⁇ 8>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 11> A laminate containing two or more layers of the cured film according to ⁇ 10> and containing a metal layer between any of the cured films.
  • ⁇ 12> A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of ⁇ 1> to ⁇ 9> to a substrate to form a film.
  • ⁇ 13> The method for producing a cured film according to ⁇ 12>, which comprises an exposure step of exposing the film and a developing step of developing the film.
  • the method for producing a cured film according to ⁇ 12> or ⁇ 13> which comprises a heating step of heating the film at 50 to 450 ° C.
  • a semiconductor device comprising the cured film according to ⁇ 10> or the laminate according to ⁇ 11>.
  • a thermobase generator In formula (1-3), formula (1-4) or formula (1-5), R 31 and R 32 each independently represent a hydrogen atom or an organic group, and R 31 and R 32 are bonded and ringed.
  • the structure may be formed, where a represents an integer of 0 to 3, and when a is 2 or more, R 33 of 2 or more may be the same or different, and R 33 is a monovalent substitution. represents a group, b represents an integer of 1 or more, b represents 1 and which is X 1 is a monovalent substituent or a hydrogen atom in the case, X 1 is when b is 2 or more single bond or Represents a b-valent linking group, and when b is 2 or more, R 31 , R 32 , R 33 and a of 2 or more may be the same or different, respectively.
  • R 41 , R 42 , R 43 and R 44 each independently represent a hydrogen atom or an organic group, R 41 and R 42 may be bonded to form a ring structure, and R 43 and R 44 may be bonded.
  • C represents an integer of 0 to 2, and when c is 2, the two R 45s may be the same or different, where R 45 is a monovalent substitution.
  • Represents a group R 51 , R 52 , R 53 and R 54 each independently represent a hydrogen atom or an organic group, R 51 and R 52 may be bonded to form a ring structure, and R 53 and R 54 may be bonded.
  • R 55 and R 56 each independently represent a hydrogen atom or a substituent, and when n + m is 2 or more, 2 or more R 55 and 2 or more R 56 or 2 or more.
  • R 55 and R 56 may be combined to form a ring structure, n represents an integer of 0 or more, m represents an integer of 0 or more, n + m represents an integer of 1 or more, and n + m is 1.
  • X 2 represents a monovalent substituent or hydrogen atom
  • n + m is 2 or more
  • X 2 represents a single bond or n + m valent linking group
  • n is 2 or more
  • R 51 , R 52 and R 55 may be the same or different
  • m is 2 or more
  • R 53 , R 54 and R 56 may be the same or different.
  • the bonds shown with broken lines may be single bonds or double bonds independently of each other.
  • a curable resin composition having excellent storage stability of the composition and the film strength of the obtained cured film, a cured film obtained by curing the curable resin composition, and a laminate containing the cured film.
  • a body, a method for producing the cured film, and a semiconductor device including the cured film or the laminate are provided.
  • the present invention is not limited to the specified embodiments.
  • the numerical range represented by using the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
  • the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
  • the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • 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 exposure using particle beams such as electron beams and ion beams. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
  • (meth) acrylate means both “acrylate” and “methacrylate”, or either
  • (meth) acrylic means both “acrylic” and “methacrylic", or
  • (meth) acryloyl means both “acryloyl” and “methacrylic", or either.
  • Me in the structural formula represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the total solid content means the total mass of all the components of the composition excluding the solvent.
  • the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
  • GPC measurement gel permeation chromatography
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
  • the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as “upper”.
  • the opposite direction is referred to as "down”.
  • the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component.
  • the content of each component in the composition means the total content of all the compounds corresponding to the component.
  • the temperature is 23 ° C. and the atmospheric pressure is 101,325 Pa (1 atm).
  • the combination of preferred embodiments is a more preferred embodiment.
  • the curable resin composition of the present invention comprises at least one resin selected from the group consisting of a polyimide precursor, a polyamide-imide precursor, and a polybenzoxazole precursor, the following formula (1-1) or the following formula (1). It contains an anion having a structure represented by 1-2) and an organic cation. Further, the curable resin composition of the present invention preferably further contains a photopolymerization initiator and a polymerizable compound described later.
  • R 11 and R 12 each independently represent a hydrogen atom or an organic group, and R 11 and R 12 may be bonded to form a ring structure.
  • R 21 and R 22 each independently represent a hydrogen atom or an organic group, R 21 and R 22 may be bonded to form a ring structure, and * represents a bonding site with another structure.
  • the curable resin composition of the present invention is excellent in storage stability of the composition and the film strength of the obtained cured film.
  • the mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
  • the curable resin composition of the present invention contains an anion having a structure represented by the formula (1-1) or the formula (1-2). Since the anion having the specific structure is excellent in base generation efficiency at the time of heating, for example, it is considered that the cyclization rate of the polymer precursor is increased and the film strength of the obtained cured film is improved. Further, when stored at a low temperature, the anion is stable by forming a salt with the organic cation or the like, and is therefore considered to be excellent in storage stability.
  • a curable resin composition containing a polymer precursor for example, when a curable resin composition is further applied on the cured film and cured to prepare a laminate.
  • the cured film formed earlier may come into contact with the developer or other composition. Therefore, in the curable resin composition, for example, from the viewpoint of resistance of the cured film to a developing solution or suppression of dissolution of the cured film due to contact with other compositions, the obtained cured film is cured with excellent chemical resistance. It is desired to provide a sex resin composition.
  • the curable resin composition of the present invention since the cyclization rate of the polymer precursor in the cured film is increased by the above-mentioned mechanism, it is considered that the cured film is likely to have excellent chemical resistance.
  • Patent Documents 1 to 3 do not describe or suggest a curable resin composition containing an anion having a structure represented by the formula (1-1) or the formula (1-2).
  • the components contained in the curable resin composition of the present invention will be described in detail.
  • the curable resin composition of the present invention contains a heterocyclic polymer precursor.
  • the curable resin composition of the present invention contains, as the heterocyclic-containing polymer precursor, at least one precursor selected from the group consisting of a polyimide precursor, a polyamide-imide precursor, and a polybenzoxazole precursor, and is a polyimide. It preferably contains a precursor.
  • polyimide precursor, polyamide-imide precursor From the viewpoint of the film strength of the obtained cured film, the polyimide precursor or the polyamide-imide precursor preferably has a repeating unit represented by the following 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 represent a hydrogen atom or a monovalent organic group.
  • -A 1 and A 2- A 1 and A 2 in the formula (1) independently represent an oxygen atom or -NH-, and an oxygen atom is preferable.
  • -R 111- R 111 in the formula (1) represents a divalent organic group.
  • the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are combined, and the number of carbon atoms is exemplified.
  • the group combined as described above is preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.
  • R 111 in formula (1) is preferably derived from diamine.
  • diamine used for producing the polyimide precursor or the polyamide-imide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
  • the diamine is a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or these. It is preferably a diamine containing two or more combined groups, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms.
  • aromatic groups include:
  • diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane or isophoronediamine; meta or paraphenylenediamine, diaminotoluene, 4,4'-or 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether,
  • 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 mentioned as a preferable example.
  • a diamine containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule is preferable, and a diamine containing no aromatic ring is preferable.
  • Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, and Jeffamine (registered trademark).
  • EDR-148 Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2)) -Aminopropoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propane-2-amine, etc., but are limited to these. Not done.
  • x, y, and z are arithmetic mean values.
  • R 111 in the formula (1) from the viewpoint of flexibility of the cured film obtained, -Ar 0 -L 0 -Ar 0 - is preferably represented by.
  • Ar 0 is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and a phenylene group is preferable.
  • the preferred range of L 0 is synonymous with A above.
  • R 111 in the formula (1) is preferably a divalent organic group represented by the following formula (51) or the formula (61).
  • R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, a fluoromethyl group, It is a difluoromethyl group or a trifluoromethyl group, and * independently represents a binding site with another structure.
  • the monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
  • R 58 and R 59 are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups, or trifluoromethyl groups, respectively.
  • Examples of the diamine compound giving the structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2. Examples thereof include'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. One of these may be used, or two or more thereof may be used in combination.
  • -R 115- R 115 in the 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 is synonymous with A and has the same preferred range. * Independently represent a binding site with another structure.
  • tetravalent organic group represented by R 115 in the formula (1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
  • the tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
  • R 115 represents a tetravalent organic group.
  • R 115 has the same meaning as R 115 in formula (1).
  • tetracarboxylic dianhydride examples include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4 , 4'-diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Dihydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxy
  • DAA-1 to DAA-5 tetracarboxylic dianhydrides
  • DAA-5 tetracarboxylic dianhydrides
  • R 113 and R 114- R 113 and R 114 in the formula (1) independently represent a hydrogen atom or a monovalent organic group. At least one of R 113 and R 114 preferably contains a radically polymerizable group, and more preferably both contain a radically polymerizable group.
  • the radically polymerizable group include a group capable of a cross-linking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond.
  • Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acryloyl group, and the following formula ( Examples thereof include groups represented by III).
  • R200 represents a hydrogen atom or a methyl group, and a methyl group is preferable.
  • R 201 is an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom).
  • ⁇ 12 is preferable, 1 to 6 is more preferable, 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, 1 to 6 is more preferable, and 1 to 3 is particularly preferable).
  • the (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
  • R 201 examples include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH 2 CH (OH) CH 2-, and more preferably an ethylene group, a propylene group, a trimethylene group, and -CH 2 CH (OH) CH 2- .
  • R 200 is a methyl group and R 201 is an ethylene group.
  • * represents a binding site with another structure.
  • a preferred embodiment of the polyimide or polyamideimide precursor in the present invention is an aliphatic group having 1, 2 or 3 or preferably 1 acid group as the monovalent organic group of R 113 or R 114 .
  • Examples include aromatic groups and arylalkyl groups. Specific examples thereof include an aromatic group having an acid group having 6 to 20 carbon atoms and an arylalkyl group having an acid group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned.
  • the acid group is preferably a hydroxy group. That is, R 113 or R 114 is preferably a group having a hydroxy group.
  • a substituent that improves the solubility of the developing solution is preferably used.
  • R 113 or R 114 is a hydrogen atom, a benzyl group, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group or a 4-hydroxybenzyl group from the viewpoint of solubility in an aqueous developer.
  • R 113 or R 114 is preferably a monovalent organic group.
  • a monovalent organic group a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group is preferable, and an alkyl group substituted with an aromatic group is more preferable.
  • the alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group).
  • the alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and octadecyl group.
  • the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
  • Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
  • Examples of the polycyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group.
  • an alkyl group substituted with an aromatic group a linear alkyl group substituted with an aromatic group described below is preferable.
  • aromatic group examples include a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an inden ring, and azulene.
  • the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an inden ring, and azulene.
  • the cyclic structure constituting the group includes a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolin ring, an indol ring, and a benzofuran.
  • Ring benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, aclysin ring, phenanthrene ring, thianthrene ring, chromene ring , Xanthene ring, phenoxatiin ring, phenothiazine ring or phenazine ring).
  • the polyimide precursor or the polyamide-imide precursor has a fluorine atom in the repeating unit.
  • the fluorine atom content in the polyimide precursor or the polyamide-imide precursor is preferably 10% by mass or more, more preferably 20% by mass or more. There is no particular upper limit, but 50% by mass or less is practical.
  • an aliphatic group having a siloxane structure may be copolymerized in a repeating unit represented by the formula (1).
  • 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) or the formula (1-B).
  • a 11 and A 12 represent an oxygen atom or -NH-
  • R 111 and R 112 each independently represent a divalent organic radical
  • R 113 and R 114 independently represent a hydrogen atom or 1 Representing a valent organic group
  • at least one of R 113 and R 114 is preferably a group containing a radically polymerizable group, and more preferably a radically polymerizable group.
  • a 11 , A 12 , R 111 , R 113 and R 114 are synonymous with the preferred ranges of A 1 , A 2 , R 111 , R 113 and R 114 in formula (1), respectively.
  • R 112 has the same meaning as R 112 in formula (5), and more preferably among others oxygen atoms.
  • the bonding position of the carbonyl group to the benzene ring in the formula is preferably 4, 5, 3', 4'in the formula (1-A). In formula (1-B), it is preferably 1, 2, 4, 5.
  • the repeating unit represented by the formula (1) may be one kind, or two or more kinds. Further, it may contain a structural isomer of a repeating unit represented by the formula (1). Further, the polyimide precursor or the polyamide-imide precursor may include other types of repeating units in addition to the repeating unit of the above formula (1).
  • the heterocyclic-containing polymer precursor is a polyamide-imide precursor
  • the polyamide-imide precursor may further contain a repeating unit represented by the following formula (PAI-1).
  • R 116 represents a divalent organic group and R 111 represents a divalent organic group.
  • R 116 is composed of a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or a single bond or a linking group. Examples of the linked groups are linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
  • the aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable.
  • a group in which two or more of the above are combined is more preferable.
  • the group is preferable, and —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
  • an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
  • halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
  • the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom.
  • preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
  • arylene group a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
  • R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
  • a compound having two carboxy groups is referred to as a dicarboxylic acid compound
  • a compound having two halogenated carboxy groups is referred to as a dicarboxylic acid dihalide compound.
  • the carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
  • Examples of the halogenated dicarboxylic acid compound or dicarboxylic acid dihalide compound used in the production of the polyamideimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids. Examples include aciddihalide compounds. Only one kind or two or more kinds of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used.
  • the dicarboxylic acid compound or the dicarboxylic acid dihalide compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic fat having 3 to 20 carbon atoms.
  • a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group group, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms is preferable.
  • a dicarboxylic acid compound or a dicarboxylic acid dihalide compound containing a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferable.
  • aromatic groups include the above-mentioned AR-1 to AR-10.
  • dicarboxylic acid compound examples include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-.
  • R 111 has the same meaning as R 111 in the above equation (1), a preferable embodiment thereof is also the same.
  • the polyamide-imide precursor may further contain a repeating unit represented by the following formula (PAI-2).
  • PAI-2 R 117 represents a trivalent organic group
  • R 111 represents a divalent organic group
  • a 2 represents an oxygen atom or -NH-
  • R 113 represents a hydrogen atom or monovalent. Represents an organic group of.
  • R 117 is composed of linear or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, heteroaromatic groups, or single-bonded or linked groups.
  • Examples of the above-mentioned linked groups include a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
  • the aromatic group of the above, or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or an aromatic group having 6 to 20 carbon atoms by a single bond or a linking group is preferable.
  • a group in which two or more of the above are combined is more preferable.
  • the group is preferable, and —O—, —S—, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded is more preferable.
  • an alkylene group having 1 to 20 carbon atoms is preferable, an alkylene group having 1 to 10 carbon atoms is more preferable, and an alkylene group having 1 to 4 carbon atoms is further preferable.
  • halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
  • the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom.
  • preferred halogenated alkylene groups include (ditrifluoromethyl) methylene groups and the like.
  • arylene group a phenylene group or a naphthylene group is preferable, a phenylene group is more preferable, and a 1,3-phenylene group or a 1,4-phenylene group is further preferable.
  • R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. Chlorination is preferable as the halogenation.
  • a compound having three carboxy groups is referred to as a tricarboxylic acid compound. Of the three carboxy groups of the tricarboxylic acid compound, two carboxy groups may be acid anhydrideized.
  • the halogenated tricarboxylic acid compound used in the production of the polyamide-imide precursor include branched chain aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. Only one kind of these tricarboxylic acid compounds may be used, or two or more kinds may be used.
  • the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a carbon number of carbon atoms.
  • a tricarboxylic acid compound containing 6 to 20 aromatic groups or a group in which two or more of these are combined by a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms or carbon by a single bond or a linking group is preferable.
  • a tricarboxylic acid compound containing a group in which two or more aromatic groups of several 6 to 20 are combined is more preferable. Examples of aromatic groups include the above-mentioned AR-1 to AR-10.
  • the tricarboxylic acid compound examples include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid.
  • Or phthalic acid anhydride and benzoic acid are single-bonded, with -O-, -CH 2- , -C (CH 3 ) 2- , -C (CF 3 ) 2- , -SO 2- or phenylene group. Examples thereof include linked compounds.
  • These compounds may be compounds in which two carboxy groups are anhydrated (eg, trimellitic acid anhydride) or compounds in which at least one carboxy group is halogenated (eg, trimellitic acid chloride). There may be.
  • each R 111, A 2, R 113 have the same meaning as R 111, A 2, R 113 in the above equation (1), a preferable embodiment thereof is also the same.
  • the polyimide precursor in the present invention 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units are the repeating units represented by the formula (1). Is exemplified. As an upper limit, 100 mol% or less is practical.
  • the repeating unit represented by the formula (1), the repeating unit represented by the formula (PAI-1), and the formula (PAI-2). The total content of the repeating units is 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more, and the polyamide-imide precursor is exemplified. As an upper limit, 100 mol% or less is practical.
  • the weight average molecular weight (Mw) of the polyimide precursor or the polyamide-imide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50. It is 000.
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
  • the degree of dispersion of the molecular weight of the polyimide precursor or the polyamide-imide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
  • the degree of molecular weight dispersion means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).
  • the polyimide precursor or polyamide-imide precursor is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine.
  • the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.
  • the organic solvent may be one kind or two or more kinds.
  • the organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.
  • the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
  • the polybenzoxazole precursor preferably contains a repeating unit represented by the following formula (2).
  • R 121 represents a divalent organic group
  • R 122 represents a tetravalent organic group
  • R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group. Represent.
  • R 121 represents a divalent organic group.
  • the divalent organic group includes an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, 6 to 14 carbon atoms). Is more preferable, and 6 to 12 is particularly preferable).
  • the aromatic group constituting R 121 include R 111 of the above formula (1).
  • the aliphatic group a linear aliphatic group is preferable.
  • R 121 is preferably derived from 4,4'-oxydibenzoyl chloride.
  • R 122 represents a tetravalent organic group.
  • the tetravalent organic group has the same meaning as R 115 in the above formula (1), and the preferable range is also the same.
  • R 122 is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
  • R -R 123 and R 124- R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R 113 and R 114 in the above formula (1), and the preferable range is also the same.
  • the polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units of the above formula (2).
  • the polybenzoxazole precursor further contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.
  • SL diamine residue represented by the following formula (SL) as another type of repeating unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.
  • R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R 2s.
  • Is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of R 3s , R 4s , R 5s , and R 6s is aromatic. It is a group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and the rest is a hydrogen atom or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms).
  • the a structure and the b structure may be block polymerization or random polymerization.
  • the a structure is 5 to 95 mol%
  • the b structure is 95 to 5 mol%
  • a + b is 100 mol%.
  • preferred Z includes those in which R 5s and R 6s in the b structure are phenyl groups.
  • the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000.
  • the molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight in the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be lowered, and the effect of suppressing warpage and the effect of improving solubility can be achieved at the same time.
  • the tetracarboxylic dianhydride is further provided in that it improves the alkali solubility of the curable resin composition. It is preferable that the tetracarboxylic acid residue remaining after the removal of the acid dianhydride group from the product is contained as a repeating unit. Examples of such a tetracarboxylic acid residue include the example of R 115 in the formula (1).
  • the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. is there.
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
  • the degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
  • the acid value of the heterocyclic polymer precursor is preferably 1 mmol / g or less, more preferably 0.5 mmol / g or less, and 0. More preferably, it is 3 mmol / g or less.
  • the lower limit of the acid value is not particularly limited, and may be 0 mmol / g or more.
  • the acid value of the heterocyclic polymer precursor is preferably 1 to 8 mmol / g, more preferably 1.5 to 6 mmol / g. It is more preferably 2 to 5 mmol / g.
  • the acid value of the heterocyclic polymer precursor refers to the amount (mmol) of acid groups contained in 1 g of the heterocyclic polymer precursor.
  • the acid group refers to a group that is neutralized by an alkali having a pH of 12 or higher (for example, sodium hydroxide). Further, the acid group is preferably a group having a pKa of 10 or less.
  • the acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
  • the content of the heterocycle-containing polymer precursor in the curable resin composition of the present invention is preferably 20% by mass or more, preferably 30% by mass or more, based on the total solid content of the curable resin composition. More preferably, it is more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and further preferably 70% by mass or more.
  • the content of the heterocycle-containing polymer precursor in the curable resin composition of the present invention is preferably 99.5% by mass or less, preferably 99% by mass, based on the total solid content of the curable resin composition. The following is more preferable, 98% by mass or less is further preferable, 97% by mass or less is further preferable, and 95% by mass or less is further preferable.
  • the curable resin composition of the present invention may contain only one type of heterocyclic polymer precursor, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
  • the curable resin composition of the present invention contains an anion having a structure represented by the formula (1-1) or the formula (1-2) (hereinafter, also referred to as “specific anion”).
  • the specific anion may form a salt structure with a cation such as an organic cation described later, or may be dissociated and exist in an anion state.
  • a compound which is a salt of the specific anion and the organic cation described later, or a solution of the above compound is used. It may be prepared by mixing with other components contained in the composition such as a heterocyclic ring-containing polymer.
  • the compound containing a specific anion is preferably a thermal base generator.
  • the compound containing a specific anion is a thermobase generator means that the compound containing a specific anion is a compound that generates a base by heating.
  • the compound containing a specific anion is preferably a compound having a decomposition rate of 50 mol% or more by heating at 230 ° C. for 3 hours, and a compound having a decomposition rate of 50 mol% or more by heating at 180 ° C. for 3 hours. Is more preferable.
  • the compound containing a specific anion is preferably a compound having a decomposition rate of 10 mol% or less by heating at 100 ° C.
  • the decomposition rate is measured by the following method.
  • the curable resin composition is applied onto glass and dried by heating at 100 ° C. for 1 minute to form a curable resin composition layer.
  • the amount of the curable resin composition applied is such that the film thickness after drying is 15 ⁇ m.
  • heating at 230 ° C. for 3 hours is performed.
  • the heating temperature and heating time it is possible to measure the decomposition rate by heating at a specific heating temperature and heating time.
  • the decomposition rate of the compound containing a specific anion is calculated from the following formula.
  • Decomposition rate of compound containing specific anion (mol%) Decomposition amount of compound containing specific anion (mol) / Amount of compound containing specific anion contained in the curable resin composition layer before heating (mol) ⁇ 100
  • the compound containing a specific anion is preferably a compound that generates a base by heating in a heating step described later.
  • the decomposition temperature of the compound containing the specific anion is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 120 ° C. or higher, and even more preferably 140 ° C. or higher. As the upper limit, it is more preferably 450 ° C. or lower, more preferably 350 ° C. or lower, and further preferably 250 ° C. or lower.
  • the decomposition temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when a compound containing a specific anion (salt of a specific anion and an organic cation) is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule. Examples of the device used for measuring the decomposition temperature include Q2000 (manufactured by TA Instruments) and the like.
  • the pKa of the conjugate acid of the base generated from the compound containing the specific anion is preferably 8 or more from the viewpoint of the film strength of the obtained cured film. It is more preferably 9 or more, and further preferably 10 or more.
  • the upper limit of the pKa is not particularly limited, but is preferably 14 or less.
  • the term "pKa" as used herein means a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is represented by its negative common logarithm pKa. The smaller the pKa, the stronger the acid. Unless otherwise specified, pKa is a value calculated by ACD / ChemSketch (registered trademark).
  • the pKa of the compound means the maximum value among the plurality of pKa in the compound, unless otherwise specified.
  • the specific anion preferably has two or more structures represented by the formula (1-1) and a structure represented by the formula (1-2) in total, and more preferably 2 to 6 structures. It is more preferable to have two. Further, when the specific anion has a structure represented by the formula (1-1) and a structure represented by the formula (1-2) in total, the specific anion is represented by the formula (1-1). It may have one structure and one structure represented by the formula (1-2), but it may have two or more structures represented by the formula (1-1), or it may have a structure represented by the formula (1-1). It is preferable to have two or more structures represented by 1-2).
  • the specific anion has two or more structures represented by the formula (1-1) and does not have the structure represented by the formula (1-2), or the formula. It is also possible to have two or more structures represented by (1-2) and not having a structure represented by the formula (1-1).
  • R 11 and R 12 are preferably hydrogen atoms or aliphatic hydrocarbon groups, respectively, and are preferably aliphatic hydrocarbon groups. More preferably, it is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and a branched alkyl group having 2 to 6 carbon atoms or 3 to 3 carbon atoms.
  • the cyclic alkyl group of 8 is particularly preferable, and the isopropyl group or cyclohexyl group is most preferable.
  • aliphatic hydrocarbon group when simply referred to as "aliphatic hydrocarbon group” or “alkyl group”, all of the aliphatic hydrocarbon groups or alkyl groups formed by linear, branched, cyclic or a combination thereof. Shall be included.
  • R 11 and R 12 may be combined to form a ring structure, and the ring structures formed include a pyrrolidine ring structure, an imidazolidine ring structure, a pyrazoledin ring structure, a piperidine ring structure, a piperazine ring structure, and morpholin.
  • Examples thereof include a nitrogen-containing aliphatic ring structure such as a ring structure, a pyrrol ring structure, an imidazole ring structure, a pyridine ring structure, a pyrazine ring structure, a pyrimidine ring structure, and a nitrogen-containing aromatic ring structure such as a pyridazine ring structure.
  • a nitrogen-containing aliphatic ring structure such as a ring structure, a pyrrol ring structure, an imidazole ring structure, a pyridine ring structure, a pyrazine ring structure, a pyrimidine ring structure, and a nitrogen-containing aromatic ring structure such as a pyridazine ring structure.
  • At least one of the nitrogen atoms contained in the nitrogen-containing aliphatic ring structure or the nitrogen-containing aromatic ring structure is a nitrogen atom to which R 11 and R 12 described in the formula (1-1) are bonded. ..
  • R 11 and R 12, or ring structure and R 11 and R 12 are formed by bonding, it may further have a substituent.
  • a known substituent can be used as long as the effect of the present invention can be obtained, and examples thereof include an alkyl group, an aryl group, and a halogen atom.
  • at least one of R 11 and R 12, or ring structure and R 11 and R 12 are formed by bonding may have a group having an ethylenically unsaturated bond as a substituent.
  • Examples of the group having an ethylenically unsaturated bond include a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acryloyl group, and the above formula. Examples thereof include the group represented by (III).
  • the specific anion may include a structure represented by the following formula (1-1-1) as a structure containing a structure represented by the formula (1-1). preferable.
  • R 11 and R 12 each independently represent a hydrogen atom or an organic group, and R 11 and R 12 may be bonded to form a ring structure, and R 13 to R may be formed.
  • Each of 16 independently represents a bonding site with a hydrogen atom, a substituent or another structure, and at least two of R 13 to R 16 may be bonded to form a ring structure. Further, when all of R 13 to R 16 are not binding sites for other structures, the specific anion may be an anion represented by the formula (1-1-1).
  • R 11 and R 12 each have the same meaning as R 11 and R 12 in the above formula (1-1), preferable embodiments thereof are also the same.
  • R 13 to R 16 independently represent a binding site with a hydrogen atom, a substituent or another structure, and may be a binding site with a hydrogen atom or another structure. preferable.
  • Substituents in R 13 to R 16 include a hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, an aromatic heterocyclic group having 5 to 20 ring members, and 5 to 20 ring members.
  • Aliphatic heterocyclic group heterocyclic ring having 3 to 20 carbon atoms, carboxy group, amide group, amino group, nitrile group, alkoxyl group, hydroxyl group, nitro group, methacryloyl group, acryloyl group, vinyl group, allyl group, epoxy group. And so on.
  • the aromatic heterocyclic group or the complex atom in the aliphatic heterocyclic group include O, S, N and the like.
  • the aromatic heterocyclic group or the aliphatic heterocyclic group may have a plurality of complex atoms, and the plurality of complex atoms may be the same complex atom but different complex atoms. You may.
  • R 13 ⁇ R 16, 1 single but a group represented by the following formula (R-1), and, for R 13 ⁇ R 16 is a group represented by the formula (R-1) , It is also preferable that at least one of R 13 to R 16 existing at the ortho position in the benzene ring structure described in the formula (1-1-1) is a group represented by the formula (R-2).
  • R 11 and R 12 have the same meanings as R 11 and R 12 in the above-described formula (1-1), preferable embodiments thereof are also the same.
  • * represents a binding site with the benzene ring structure described in the formula (1-1).
  • Examples of the ring structure formed by bonding at least two of R 13 to R 16 include an aromatic hydrocarbon ring structure, an aromatic heterocyclic structure, an aliphatic hydrocarbon ring structure, and an aliphatic heterocyclic structure. ..
  • the specific anion includes a structure represented by the following formula (1-1-2) as a structure containing a structure represented by the formula (1-1). Is preferable.
  • R 11 and R 12 independently represent a hydrogen atom or an organic group, and R 11 and R 12 may be bonded to form a ring structure, and R 17 and R may be formed.
  • Each of 18 independently represents a bonding site with a hydrogen atom, a substituent or another structure, and R 17 and R 18 may be bonded to form an aliphatic ring structure. Further, when neither R 17 nor R 18 is a binding site with another structure, the specific anion may be an anion represented by the formula (1-1-2).
  • R 11 and R 12 have the same meanings as R 11 and R 12 in the above formula (1-1), preferable embodiments thereof are also the same.
  • R 17 and R 18 each independently represent a binding site with a hydrogen atom, a substituent or another structure, and may be a binding site with a hydrogen atom or another structure.
  • the substituents in R 17 and R 18 include a hydrocarbon group having 1 to 10 carbon atoms, a heterocyclic ring having 3 to 20 carbon atoms, a carboxy group, an amide group, an amino group, a nitrile group, an alkoxyl group, a hydroxyl group and a nitro group. , Methacryloyl group, acryloyl group, vinyl group, allyl group, epoxy group and the like.
  • Examples of the aliphatic ring structure formed by combining R 17 and R 18 include an aliphatic hydrocarbon ring structure and an aliphatic heterocyclic structure.
  • the specific anion preferably contains a structure represented by the following formula (1-2-1) as a structure represented by the formula (1-2).
  • R 21 and R 22 each independently represent a hydrogen atom or an organic group, and R 21 and R 22 may be bonded to form a ring structure, and ring Cy is a fat.
  • the hydrogen atom which represents the group ring structure and is bonded to the ring member atom in the ring Cy may be substituted with a substituent or may be a bonding site with another structure.
  • the specific anion may be an anion represented by the formula (1-2-1).
  • R 21 and R 22 have the same meanings as R 21 and R 22 in the above formula (1-2), preferable embodiments thereof are also the same.
  • the ring Cy preferably has an aliphatic ring structure having 3 to 10 ring members, and more preferably an aliphatic hydrocarbon ring structure having 3 to 10 ring members. It is more preferable to have an aliphatic hydrocarbon ring structure having 3 to 6 ring members.
  • the hydrogen atom bonded to the ring member atom in the ring Cy may be substituted with a substituent or may be a binding site with another structure.
  • the substituent examples include a linear, branched or cyclic hydrocarbon group having a prime number of 1 to 10, a heterocyclic ring having 3 to 20 carbon atoms, a carboxy group, an amide group, an amino group, a nitrile group, an alkoxyl group, a hydroxyl group and a nitro group. Examples thereof include a group, a methacryloyl group, an acryloyl group, a vinyl group, an allyl group, an epoxy group and the like.
  • the ring Cy may have a group represented by the above formula (R-1) and a group represented by the above formula (R-2) as the substituent.
  • the ring-membered atom to which the group represented by the formula (R-1) is bonded and the ring-membered atom to which the group represented by the formula (R-2) is bonded are adjacent ring-membered atoms in the ring Cy. Is preferable. Further, the ring-membered atom to which the group represented by the above formula (R-1) is bonded and the ring-membered atom to which the group represented by the above formula (R-2) is bonded are both carbon atoms. preferable.
  • R 31 and R 32 each independently represent a hydrogen atom or an organic group, and R 31 and R 32 are bonded and ringed.
  • the structure may be formed, where a represents an integer of 0 to 3, and when a is 2 or more, R 33 of 2 or more may be the same or different, and R 33 is a monovalent substitution.
  • R 41 , R 42 , R 43 and R 44 each independently represent a hydrogen atom or an organic group, R 41 and R 42 may be bonded to form a ring structure, and R 43 and R 44 may be bonded.
  • C represents an integer of 0 to 2, and when c is 2, the two R 45s may be the same or different, where R 45 is a monovalent substitution.
  • R 55 and R 56 each independently represent a hydrogen atom or a substituent, and when n + m is 2 or more, 2 or more R 55 and 2 or more R 56 or 2 or more.
  • R 55 and R 56 may be combined to form a ring structure, n represents an integer of 0 or more, m represents an integer of 0 or more, n + m represents an integer of 1 or more, and n + m is 1.
  • X 2 represents a monovalent substituent or hydrogen atom
  • n + m is 2 or more
  • X 2 represents a single bond or n + m valent linking group, and if n is 2 or more, 2
  • the above R 51 , R 52 and R 55 may be the same or different, and when m is 2 or more, the two or more R 53 , R 54 and R 56 may be the same or different.
  • the bonds shown with broken lines may be single bonds or double bonds independently of each other.
  • R 31 and R 32 are synonymous with R 11 and R 12 in formula (1-1), respectively, and preferred embodiments are also the same.
  • R 33 represents a monovalent substituent, and examples thereof include an alkyl group, an aryl group, and a halogen atom.
  • a represents an integer of 0 to 3, preferably 0, 1 or 2, and more preferably 0.
  • b represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2. From the viewpoint of achieving both the efficiency of base generation and the solubility in a solvent, b is preferably 2.
  • X 1 represents a monovalent substituent or a hydrogen atom, and a hydrogen atom is preferable.
  • substituent include the same groups as the above-mentioned R 33 .
  • the RN is a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and more preferably a hydrogen atom or a methyl group.
  • a hydrogen atom is particularly preferable.
  • the aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms. It is more preferably a group.
  • the aliphatic hydrocarbon group may have a substituent, and examples of the substituent include an aromatic hydrocarbon group and a halogen atom.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 carbon atoms. It is more preferably a hydrogen group.
  • the aromatic hydrocarbon group may have a substituent, and examples of the substituent include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a halogen atom.
  • R 41 and R 42 are synonymous with R 11 and R 12 in formula (1-1), respectively, and preferred embodiments are also the same.
  • R 43 and R 44 are synonymous with R 11 and R 12 in formula (1-1), respectively, and preferred embodiments are also the same.
  • R 45 has the same meaning as R 33 in formula (1-3), and so does the preferred embodiment.
  • c represents an integer of 0 to 2, and is preferably 0.
  • R 51 and R 52 are synonymous with R 21 and R 22 in formula (1-2), respectively, and preferred embodiments are also the same.
  • R 53 and R 54 are synonymous with R 21 and R 22 in formula (1-2), respectively, and the preferred embodiments are also the same.
  • R 55 and R 56 each independently represent a hydrogen atom or a substituent, and are preferably hydrogen atoms.
  • substituents include an alkyl group, an aryl group, a halogen atom and the like.
  • n + m is 2 or more
  • two or more R 55 , two or more R 56, or two or more R 55 and R 56 may be combined to form a ring structure.
  • the ring structure is preferably a ring structure further containing X 2 in the formula (1-5).
  • the ring structure includes an aliphatic saturated hydrocarbon ring structure such as a cyclohexane ring, an aliphatic unsaturated hydrocarbon ring structure such as cyclohexene, and a crosslinked hydrocarbon such as a bicyclo [2.2.2] octa-7-ene ring structure. Rings and the like can be mentioned.
  • n represents an integer of 0 or more, preferably an integer of 0 to 10, more preferably an integer of 0 to 4, and further preferably 0, 1 or 2.
  • m represents an integer of 0 or more, preferably an integer of 0 to 10, more preferably an integer of 0 to 4, and further preferably 0, 1 or 2.
  • m + n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.
  • X 2 represents a monovalent substituent or a hydrogen atom, and is preferably a hydrogen atom. Examples of the substituent include groups similar to those of R 55 or R 56 described above.
  • X 2 represents a single bond or a linking group having an n + m valence, and is preferably the same group as X 1 described above.
  • X 2 may be included in the above-mentioned ring structure.
  • bonds shown with broken lines may be independently single bonds or double bonds, but are preferably single bonds.
  • the molecular weight of the specific anion is preferably 150 to 2,000, more preferably 150 to 1,000, and even more preferably 160 to 800.
  • Specific examples of the specific anion include, but are not limited to, the anion portion in the compounds represented by the formulas (BA-1) to (BA-22) described later.
  • the content of the specific anion is 0.005 to 50% by mass with respect to the total solid content of the curable resin composition from the viewpoint of improving the storage stability of the composition and the elongation at break of the obtained cured film.
  • the lower limit is more preferably 0.05% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.
  • the upper limit is more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less, from the viewpoint of corrosion resistance of a metal (for example, copper used for wiring or the like).
  • the content of the specific anion with respect to 100 parts by mass of the heterocyclic polymer precursor is 0.005 parts by mass or more from the viewpoint of improving the storage stability of the composition and the elongation at break of the obtained cured film. It is preferably 0.06 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 1 part by mass or more. From the viewpoint of corrosion resistance of metal (for example, copper used for wiring and the like), the upper limit is preferably, for example, 20 parts by mass or less, more preferably 15 parts by mass or less, and 10 parts by mass. It is more preferably less than or equal to 7.5 parts by mass or less.
  • the specific anion one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
  • the curable resin composition of the present invention contains an organic cation.
  • the organic cation is not particularly limited, but is preferably a monovalent organic cation.
  • the organic cation is preferably an ammonium cation, an iminium cation, or a phosphonium cation.
  • the organic cation is a cation represented by the following formula (A-1), a cation in which a compound represented by any of the formulas (A-2) to (A-5) is protonated, or the following. It is preferably a proton represented by the formula (A-6).
  • each R A11 ⁇ R A14 independently represent a hydrogen atom or a substituent
  • R A21 represents a hydrogen atom or a substituent
  • R A31 is a hydrogen atom or represents a substituent
  • R A41 represents a hydrogen atom or a substituent
  • each X 1 ⁇ X 4 are independently,-N-or -CR A42 - represents
  • R A42 represents a hydrogen atom or a substituent
  • R A51 ⁇ RA55 independently represent a hydrogen atom or a substituent
  • RA61 to RA64 each independently represent a hydrogen atom or a substituent.
  • RA11 to RA14 each independently represent a hydrogen atom or a substituent.
  • the cation represented by the formula (A-1) is preferably a secondary ammonium cation, a tertiary ammonium cation or a quaternary ammonium cation, and is a tertiary ammonium cation or a quaternary ammonium cation. Is more preferable.
  • RA11 to RA14 at least two are preferably substituents, and three or four are more preferably substituents.
  • the substituent in RA11 to RA14 is preferably a hydrocarbon group, more preferably an alkyl group having 1 to 10 carbon atoms, and a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a butyl group. It is more preferably a cyclohexyl group.
  • RA21 represents a hydrogen atom or a substituent, and is preferably a substituent.
  • substituent in RA21 an alkyl group, an aryl group, a dialkylamino group, or a diarylamino group is preferable, and a dialkylamino group is more preferable.
  • alkyl group in the alkyl group or the dialkylamino group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.
  • the dialkylamino group the two alkyl groups may be the same or different.
  • aryl group or the aryl group in the diarylamino group a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
  • RA31 represents a hydrogen atom or a substituent, and a hydrogen atom is preferable.
  • the substituent in RA31 is preferably a hydrocarbon group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and an alkyl group or phenyl group having 1 to 4 carbon atoms. More preferred.
  • RA41 represents a hydrogen atom or a substituent, and a hydrogen atom is preferable.
  • the substituent in RA41 is preferably a hydrocarbon group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, and an alkyl group or phenyl group having 1 to 4 carbon atoms. More preferred.
  • X 1 ⁇ X 4 are independently,-N-or -CR A42 - represents, preferably one of X 1 ⁇ X 4 ⁇ 3 one is a -N-, It is more preferable that one or two are -N-, and even more preferably one is -N-.
  • RA42 represents a hydrogen atom or a substituent, and a hydrogen atom is preferable.
  • the substituent in R A42 include the same groups as substituents in R A41 described above.
  • RA51 to RA55 independently represent a hydrogen atom or a substituent, and are preferably hydrogen atoms.
  • substituent in RA51 to RA55 include the same group as the substituent in RA41 described above.
  • RA61 to RA64 each independently represent a hydrogen atom or a substituent.
  • the cation represented by the formula (A-6) is preferably a secondary phosphonium cation, a tertiary phosphonium cation or a quaternary phosphomonium cation, and is a tertiary phosphonium cation or a quaternary phosphonium cation. Is more preferable.
  • RA61 to RA64 at least two are preferably substituents, and three or four are more preferably substituents.
  • the substituent in RA61 to RA64 is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a cyclohexyl group. ..
  • organic cation examples include, but are not limited to, the cation portion in the compounds represented by the formulas (BA-1) to (BA-22) described later.
  • organic cation an ammonium cation, an iminium cation, a phosphonium cation, an iodonium cation, or a sulfonium cation in the description of the onium salt described later can also be preferably used.
  • the content of the organic cation is not particularly limited as long as it is an amount that neutralizes the above-mentioned specific anion and makes the composition electrically neutral.
  • the total solid content of the curable resin composition It is preferably 0.005 to 50% by mass.
  • the lower limit is more preferably 0.05% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.
  • the upper limit is more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less.
  • the organic cation one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
  • the curable resin composition of the present invention may contain a compound which is a salt of a specific anion and an organic cation.
  • the compound which is a salt of the specific anion and the organic cation may be present as a salt of the specific anion and the organic cation in the curable resin composition, or may be dissociated into the specific anion and the organic cation.
  • it may be a compound that exists as a salt of a specific anion and an organic cation when stored at 20 ° C. or the like, and dissociates the specific anion and the organic cation when heated at 180 ° C. or the like.
  • the specific anion is further decomposed to generate a base during the above heating.
  • Preferred embodiments of the specific anion and the organic cation in the compound which is a salt of the specific anion and the organic cation are as described above. From the viewpoint of solvent solubility, a salt that is a combination of the specific anion and the organic cation described in any of the following (1) to (4) is preferable.
  • Specific examples of the compound which is a salt of a specific anion and an organic cation include, but are not limited to, compounds represented by the following formulas (BA-1) to (BA-22).
  • the content of the compound, which is a salt of the specific anion and the organic cation, is based on the total solid content of the curable resin composition from the viewpoint of improving the storage stability of the composition and the elongation at break of the obtained cured film. , 0.005 to 50% by mass is preferable.
  • the lower limit is more preferably 0.05% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.
  • the upper limit is more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less, from the viewpoint of corrosion resistance of a metal (for example, copper used for wiring or the like).
  • the content of the compound which is a salt of the specific anion and the organic cation with respect to 100 parts by mass of the heterocyclic-containing polymer precursor is from the viewpoint of improving the storage stability of the composition and the breaking elongation rate of the obtained cured film. , 0.005 parts by mass or more, more preferably 0.06 parts by mass or more, further preferably 0.5 parts by mass or more, and further preferably 1 part by mass or more.
  • the upper limit is preferably, for example, 20 parts by mass or less, more preferably 15 parts by mass or less, and 10 parts by mass. It is more preferably less than or equal to 7.5 parts by mass or less.
  • the compound which is a salt of a specific anion and an organic cation one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
  • the compound which is a salt of a specific anion and an organic cation can be synthesized, for example, by the synthesis method described in Examples described later.
  • an intermediate having a structure represented by the following formulas (B-1) to (B-20) is synthesized by reacting an acid anhydride with an amine compound, and then an ammonium hydroxide compound, described above. It is obtained by mixing the compound represented by any of the formulas (A-2) to (A-5), a phosphonium hydroxide compound, or the like with the above intermediate.
  • the curable resin composition of the present invention may further contain an onium salt other than the compound in which the above-mentioned specific anion and organic cation are bonded.
  • the compound in which the above-mentioned specific anion and the organic cation are bonded does not correspond to the above-mentioned onium salt in this description.
  • the content of the onium salt other than the compound in which the above-mentioned specific anion and the organic cation are bonded is substantially free from the total solid content of the curable resin composition.
  • ammonium salt, iminium salt, sulfonium salt, iodonium salt and phosphonium salt are preferably mentioned.
  • an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability, and a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.
  • the onium salt is a salt of a cation and an anion having an onium structure, and the cation and the anion may or may not be bonded via a covalent bond. .. That is, the onium salt may be an intermolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are different molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the curable resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
  • an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.
  • the onium salt used in the present invention may be a thermobase generator described later.
  • the thermal base generator refers to a compound that generates a base by heating, and examples thereof include a compound that generates a base when heated to 40 ° C. or higher.
  • ammonium salt means a salt of an ammonium cation and an anion.
  • ammonium cation As the ammonium cation, a quaternary ammonium cation is preferable.
  • the ammonium cation is preferably a cation represented by the following formula (101).
  • R 1 to R 4 each independently represent a hydrogen atom or a hydrocarbon group, and at least two of R 1 to R 4 may be bonded to each other to form a ring.
  • R 1 to R 4 are each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms or 6 to 6 carbon atoms. It is more preferably 12 aryl groups.
  • R 1 to R 4 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group. Examples thereof include a carbonyl group and an acyloxy group.
  • the ring may contain a hetero atom. Examples of the hetero atom include a nitrogen atom.
  • the ammonium cation is preferably represented by any of the following formulas (Y1-1) and (Y1-2).
  • R 101 represents an n-valent organic group
  • R 1 has the same meaning as R 1 in the formula (101)
  • Ar 101 and Ar 102 are each independently , Represents an aryl group
  • n represents an integer of 1 or more.
  • R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
  • n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
  • Ar 101 and Ar 102 are preferably phenyl groups or naphthyl groups, respectively, and more preferably phenyl groups.
  • the anion in the ammonium salt one selected from a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfate anion is preferable, and a carboxylic acid anion is more preferable because both the stability of the salt and the thermal decomposability can be achieved.
  • the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
  • the carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxy groups, and more preferably a divalent carboxylic acid anion.
  • the stability, curability and developability of the curable resin composition can be further improved.
  • the stability, curability and developability of the curable resin composition can be further improved.
  • the stability, curability and developability of the curable resin composition can be further improved.
  • the carboxylic acid anion is preferably represented by the following formula (X1).
  • EWG represents an electron-attracting group.
  • the electron-attracting group means that the substituent constant ⁇ m of Hammett shows a positive value.
  • ⁇ m is a review article by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642.
  • the EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
  • R x1 to R x3 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group or a carboxy group, and Ar is an aromatic group. Represents.
  • the carboxylic acid anion is preferably represented by the following formula (XA).
  • L 10 represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR X - represents and divalent connecting group selected from the group consisting a combination thereof, R X is , Hydrogen atom, alkyl group, alkenyl group or aryl group.
  • carboxylic acid anion examples include maleic acid anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion.
  • the onium salt in the present invention contains an ammonium cation as a cation, and the onium salt is an anion.
  • the onium salt is an anion.
  • the lower limit of pKa is not particularly limited, but it is preferably -3 or more, preferably -2 or more, from the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of the specific precursor or the like is improved. Is more preferable.
  • the above pKa includes Determination of Organic Strategies by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O., Nachod, F. See Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 19). Can be done. For compounds not described in these documents, the values calculated from the structural formulas using software of ACD / pKa (manufactured by ACD / Labs) shall be used.
  • ammonium salt examples include the following compounds, but the present invention is not limited thereto.
  • the iminium salt means a salt of an iminium cation and an anion.
  • the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
  • a pyridinium cation is preferable.
  • a cation represented by the following formula (102) is also preferable.
  • R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group
  • R 7 represents a hydrocarbon group
  • at least two of R 5 to R 7 are bonded to each other to form a ring. It may be formed.
  • R 5 and R 6 have the same meaning as R 1 to R 4 in the above formula (101), and the preferred embodiment is also the same.
  • R 7 preferably combines with at least one of R 5 and R 6 to form a ring.
  • the ring may contain a heteroatom. Examples of the hetero atom include a nitrogen atom. Further, as the ring, a pyridine ring is preferable.
  • the iminium cation is preferably represented by any of the following formulas (Y1-3) to (Y1-5).
  • R 101 represents an n-valent organic group
  • R 5 has the same meaning as R 5 in the formula (102)
  • R 7 is R in the formula (102) Synonymous with 7
  • n and m represent integers of 1 or more.
  • R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms.
  • n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
  • m is preferably 0 to 4, more preferably 1 or 2, and even more preferably 1.
  • iminium salt examples include the following compounds, but the present invention is not limited thereto.
  • the sulfonium salt means a salt of a sulfonium cation and an anion.
  • the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
  • sulfonium cation a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable. Further, as the sulfonium cation, a cation represented by the following formula (103) is preferable.
  • R 8 to R 10 each independently represent a hydrocarbon group.
  • Each of R 8 to R 10 is preferably an alkyl group or an aryl group independently, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
  • R 8 to R 10 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group.
  • Examples thereof include a carbonyl group and an acyloxy group.
  • an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have 10 alkoxy groups.
  • R 8 to R 10 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
  • sulfonium salt examples include the following compounds, but the present invention is not limited thereto.
  • the iodonium salt means a salt of an iodonium cation and an anion.
  • the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
  • iodonium cation a diallyl iodonium cation is preferable. Further, as the iodonium cation, a cation represented by the following formula (104) is preferable.
  • R 11 and R 12 each independently represent a hydrocarbon group.
  • R 11 and R 12 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
  • R 11 and R 12 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group.
  • Examples thereof include a carbonyl group and an acyloxy group.
  • R 11 and R 12 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
  • iodonium salt examples include the following compounds, but the present invention is not limited thereto.
  • the phosphonium salt means a salt of a phosphonium cation and an anion.
  • the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
  • a quaternary phosphonium cation is preferable, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation. Further, as the phosphonium cation, a cation represented by the following formula (105) is preferable.
  • R 13 to R 16 independently represent a hydrogen atom or a hydrocarbon group.
  • Each of R 13 to R 16 is preferably an alkyl group or an aryl group independently, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
  • R 13 to R 16 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group.
  • Examples thereof include a carbonyl group and an acyloxy group.
  • R 13 to R 16 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
  • phosphonium salt examples include the following compounds, but the present invention is not limited thereto.
  • the content of the onium salt is preferably 0.1 to 50% by mass based on the total solid content of the curable resin composition of the present invention.
  • the lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
  • the onium salt one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
  • the curable resin composition of the present invention may further contain a thermobase generator (also referred to as "another thermobase generator") other than the above-mentioned specific anion or a salt of the specific anion.
  • a thermobase generator also referred to as "another thermobase generator”
  • the above-mentioned specific anion or salt of the specific anion does not correspond to the thermobase generator in this description.
  • a configuration that does not substantially contain other thermobase generators can be used.
  • substantially free means that the content of the other thermosetting agent in the curable resin composition of the present invention is 5% by mass or less based on the total solid content of the curable resin composition. It means that it is preferably 3% by mass or less, and more preferably 1% by mass.
  • thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
  • thermobase generator other than the above-mentioned onium salt include nonionic thermobase generators.
  • nonionic thermobase generator include compounds represented by the formula (B1) or the formula (B2).
  • Rb 1 , Rb 2 and Rb 3 are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. Further, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group.
  • the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.
  • Rb 1 , Rb 2 and Rb 3 contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure.
  • the cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable.
  • the single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring.
  • a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.
  • Rb 1 and Rb 2 are hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and alkenyl groups (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ⁇ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have substituents as long as the effects of the present invention are exhibited. Rb 1 and Rb 2 may be coupled to each other to form a ring.
  • Rb 1 and Rb 2 are particularly linear, branched, or cyclic alkyl groups that may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
  • a cyclohexyl group which may be used is more preferable.
  • an alkyl group preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms
  • an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6.
  • alkoxy group (2 to 24 carbon atoms are preferable, 2 to 12 is more preferable, 2 to 6 is more preferable
  • arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable).
  • an arylalkenyl group (8 to 24 carbon atoms is preferable, 8 to 20 is more preferable, 8 to 16 is more preferable), and an alkoxyl group (1 to 24 carbon atoms is preferable, 2 to 2 to 24).
  • 18 is more preferable, 3 to 12 is more preferable), an aryloxy group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), or an arylalkyloxy group (7 to 12 carbon atoms is more preferable).
  • 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable).
  • a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable.
  • Rb 3 may further have a substituent as long as the effect of the present invention is exhibited.
  • the compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
  • Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively.
  • Rb 13 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effects of the present invention are exhibited. Of these, Rb 13 is preferably an arylalkyl group.
  • Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms). , 2 to 8 are more preferable, 2 to 3 are more preferable), aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable), arylalkyl groups (7 to 7 carbon atoms are more preferable). 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is further preferable), and a hydrogen atom is preferable.
  • Rb 35 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferable), aryl group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable). , 7-12 is more preferable), and an aryl group is preferable.
  • the compound represented by the formula (B1-1) is also preferable.
  • Rb 11 and Rb 12 have the same meanings as Rb 11 and Rb 12 in the formula (B1-1).
  • Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), aryl group (6 to 22 carbon atoms are preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7).
  • Rb 17 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
  • the molecular weight of the nonionic thermobase generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
  • the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
  • thermo base generators or specific examples of thermal base generators other than the above-mentioned onium salts include the following compounds.
  • the content of the other thermosetting agent is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention.
  • 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, further preferably 20% by mass or less.
  • the thermobase generator one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • the photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators.
  • a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable.
  • it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
  • the photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol -1 ⁇ cm -1 within the range of about 300 to 800 nm (preferably 330 to 500 nm). Is preferable.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • 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, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like.
  • Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned.
  • paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.
  • ketone compound for example, the compound described in paragraph 0087 of JP2015-087611A is exemplified, and the content thereof is incorporated in the present specification.
  • KayaCure DETX manufactured by Nippon Kayaku Co., Ltd.
  • Nippon Kayaku Co., Ltd. is also preferably used.
  • a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
  • IRGACURE 184 (IRGACURE is a registered trademark)
  • DAROCUR 1173 As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE 907, IRGACURE 369, IRGACURE 379 (trade name: all manufactured by BASF), Omnirad 907, Omnirad 369, and Omnirad 379 (all manufactured by IGM Resin). ) Can be used.
  • the compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
  • acylphosphine-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • commercially available products such as IRGACURE-819, IRGACURE-TPO (trade name: all manufactured by BASF), Omnirad 819 and Omnirad TPO (all manufactured by IGM Resins) can be used.
  • metallocene compound examples include IRGACURE-784 (manufactured by BASF).
  • An oxime compound is more preferable as the photoradical polymerization initiator.
  • the exposure latitude can be improved more effectively.
  • the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
  • the compound described in JP-A-2001-233842 the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.
  • Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
  • an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator.
  • IRGACURE OXE 01 IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052).
  • the radical polymerization initiator 2) is also preferably used.
  • TR-PBG-304 manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.
  • Adeka Arkuru's NCI-831 and Adeka Arkuru's NCI-930 can also be used.
  • DFI-091 manufactured by Daito Chemix Corp.
  • an oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.
  • Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.
  • the photoradical polymerization initiator includes a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, and a triaryl.
  • a trihalomethyltriazine compound Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.
  • More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds.
  • At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more preferable.
  • the photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone).
  • 2-benzyl such as benzophenone
  • -2-morpholino-aromatic ketones such as propanol-1, alkylanthraquinone, etc.
  • benzoin ether compounds such as benzoin alkyl ether
  • benzoin compounds such as benzoin and alkyl benzoin
  • benzyl derivatives such as benzyl dimethyl ketal.
  • a compound represented by the following formula (I) can also be used.
  • R I00 is 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, and the like.
  • R I01 is a group represented by formula (II), the same as R I00
  • the groups, R I02 to R I04, are independently alkyls having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogens, respectively.
  • R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
  • the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/1254669 can also be used.
  • the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total is preferably in the above range.
  • the curable resin composition of the present invention may contain a thermal polymerization initiator as the polymerization initiator, and may particularly contain a thermal radical polymerization initiator.
  • a thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the heterocyclic polymer precursor can be allowed to proceed as well as the cyclization of the heterocyclic polymer precursor, so that higher heat resistance can be achieved.
  • thermal radical polymerization initiator examples include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
  • thermosetting polymerization initiator When the thermosetting polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. %, More preferably 5 to 15% by mass. Only one type of thermal radical polymerization initiator may be contained, or two or more types may be contained. When two or more kinds of thermal radical polymerization initiators are contained, the total is preferably in the above range.
  • the curable resin composition of the present invention preferably further contains a polymerizable compound.
  • a radically polymerizable compound can be used as the polymerizable compound.
  • the radically polymerizable compound is a compound having a radically polymerizable group.
  • examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
  • the radically polymerizable group is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.
  • the number of radically polymerizable groups contained in the radically polymerizable compound may be one or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, and preferably has three or more radically polymerizable groups. More preferred.
  • 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 radically polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more.
  • the curable resin composition of the present invention preferably contains at least one bifunctional or higher functional radical polymerizable compound containing two or more radical polymerizable groups, and is preferably a trifunctional or higher functional radical polymerizable compound. It is more preferable to contain at least one kind. Further, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound.
  • the number of functional groups of a bifunctional or higher-functional polymerizable monomer means that the number of radically polymerizable groups in one molecule is two or more.
  • the radically polymerizable compound examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and preferred examples thereof.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group.
  • 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 a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amines or thiols, and a halogeno group.
  • Substitution reactions of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
  • a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
  • examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
  • a compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993.
  • Urethane (meth) acrylates such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.
  • a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
  • radically polymerizable compounds other than the above those described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like have a fluorene ring and have an ethylenically unsaturated bond. It is also possible to use a compound having two or more groups having the above, or a cardo resin.
  • the compound described in Japanese Patent Application Laid-Open No. 10-062986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol is also (meth) acrylated. It can be used as a radically polymerizable compound.
  • radically polymerizable compound examples include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku).
  • SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
  • SR-209 which is a bifunctional methacrylate having four ethyleneoxy chains.
  • DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS- 10, UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H ( Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.
  • Examples of the radically polymerizable compound include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765.
  • Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
  • radically polymerizable compound 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-01-105238 are used. It can also be used.
  • the radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxy group or a phosphoric acid group.
  • the radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
  • a radically polymerizable compound having a group is more preferable.
  • the aliphatic polyhydroxy compound in a radical polymerizable compound in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, is pentaerythritol or dipenta. It is a compound that is erythritol.
  • examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
  • the acid value of the radically polymerizable compound is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizable property is good.
  • the acid value is measured according to the description of JIS K 0070: 1992.
  • a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the cured film.
  • the monofunctional radically polymerizable compound include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth).
  • Acrylate derivatives N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used.
  • the monofunctional radical polymerizable compound a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
  • the curable resin composition of the present invention can further contain a polymerizable compound other than the radically polymerizable compound described above.
  • a polymerizable compound other than the above-mentioned radically polymerizable compound include a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound.
  • R 104 represents an organic group having a t-valence of 1 to 200 carbon atoms
  • R 105 is a group represented by -OR 106 or -OCO-R 107.
  • R 106 indicates a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 107 indicates an organic group having 1 to 10 carbon atoms.
  • R 404 represents a divalent organic group having 1 to 200 carbon atoms
  • R 405 represents a group represented by -OR 406 or -OCO-R 407
  • R 406 is a hydrogen atom or carbon.
  • R 407 indicates an organic group having 1 to 10 carbon atoms.
  • u represents an integer of 3 to 8
  • R 504 represents a u-valent organic group having 1 to 200 carbon atoms
  • R 505 indicates a group represented by -OR 506 or -OCO-R 507.
  • R 506 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 507 represents an organic group having 1 to 10 carbon atoms.
  • Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Industry 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, and the like.
  • HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), NIKALAC MX-280, Examples thereof include NIKALAC MX-270 and NIKALAC MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).
  • 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 lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the curable resin composition.
  • the epoxy compound preferably contains a polyethylene oxide group.
  • 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 (glycidi).
  • epoxy groups include, but are not limited to, epoxy group-containing silicones such as loxypropyl) siloxane.
  • an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance.
  • an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance.
  • Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain polyethylene oxide groups.
  • oxetane compound compound having an oxetanyl group
  • 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, and the like.
  • examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like.
  • the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone. Alternatively, two or more types may be mixed.
  • benzoxazine compound Preferred examples of the benzoxazine compound are BA type benzoxazine, Bm type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzo.
  • Oxazine compounds can be mentioned. These may be used alone or in combination of two or more.
  • the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable resin composition of the present invention.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
  • One type of polymerizable compound may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a solvent.
  • a solvent a known solvent can be arbitrarily used.
  • the solvent is preferably an organic solvent.
  • 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, ⁇ -caprolactone.
  • alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)
  • 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate
  • Etc. eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate
  • 2-alkyloxy-2-methylpropionate etc.
  • Methyl acid and ethyl 2-alkyloxy-2-methylpropionate eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
  • methyl pyruvate, ethyl pyruvate, pyruvin Propyl acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate and the like are preferred.
  • 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, and propylene glycol.
  • Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
  • ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferable.
  • aromatic hydrocarbons for example, toluene, xylene, anisole, limonene and the like are preferable.
  • sulfoxides for example, dimethyl sulfoxide is preferable.
  • N-methyl-2-pyrrolidone N-ethyl-2-pyrrolidone
  • N, N-dimethylacetamide N, N-dimethylformamide and the like are preferable.
  • the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
  • the mixed solvent to be mixed is preferable.
  • the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
  • the content of the solvent is preferably such that the total solid content concentration of the curable resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferable that the amount is 10 to 70% by mass, and more preferably 40 to 70% by mass.
  • the solvent content may be adjusted according to the desired thickness and coating method.
  • the solvent may contain only one type or two or more types. When two or more kinds of solvents are contained, the total is preferably in the above range.
  • the curable resin composition of the present invention preferably further contains a migration inhibitor.
  • a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the curable resin composition layer.
  • the migration inhibitor is not particularly limited, but heterocycles (pyrazole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
  • triazole-based compounds such as 1,2,4-triazole and benzotriazole
  • tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.
  • an ion trap agent that traps anions such as halogen ions can also be used.
  • Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656.
  • the compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like 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 curable resin composition, and is 0. It is more preferably 0.05 to 2.0% by mass, and further preferably 0.1 to 1.0% by mass.
  • the migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a polymerization inhibitor.
  • polymerization inhibitor examples include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-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, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, Bis (4-hydroxy-3,5-ter
  • the content of the polymerization inhibitor shall be 0.01 to 5% by mass with respect to the total solid content of the curable resin composition of the present invention. Is more preferable, 0.02 to 3% by mass is more preferable, and 0.05 to 2.5% by mass is further preferable.
  • the polymerization inhibitor may be only one type or two or more types. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
  • a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
  • the metal adhesiveness improving agent include a silane coupling agent.
  • silane coupling agent examples include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992.
  • Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. Further, it is also preferable to use the following compounds as the silane coupling agent.
  • Et represents an ethyl group.
  • the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used. ..
  • 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, and further, with respect to 100 parts by mass of the heterocyclic polymer precursor. It is preferably in the range of 0.5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are good.
  • the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.
  • the curable resin composition of the present invention can be used with various additives such as a thermoacid generator, a sensitizer such as N-phenyldiethanolamine, and a chain transfer agent, if necessary, as long as the effects of the present invention can be obtained.
  • additives such as a thermoacid generator, a sensitizer such as N-phenyldiethanolamine, and a chain transfer agent, if necessary, as long as the effects of the present invention can be obtained.
  • Surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, antiaggregating agents and the like can be blended.
  • the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.
  • the curable resin composition of the present invention may contain a sensitizer.
  • the sensitizer absorbs specific active radiation and becomes an electron-excited state.
  • the sensitizer in the electron-excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur.
  • the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases.
  • the sensitizer include sensitizers such as N-phenyldiethanolamine.
  • sensitizing dye As a sensitizer, you may use a sensitizing dye as a sensitizer.
  • the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.
  • the content of the sensitizer may be 0.01 to 20% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass.
  • the sensitizer may be used alone or in combination of two or more.
  • the curable resin composition of the present invention may contain a chain transfer agent.
  • Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684.
  • As the chain transfer agent for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
  • a thiol compound can be preferably used.
  • the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition of the present invention.
  • 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable.
  • the chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.
  • Each type of surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving the coatability.
  • the surfactant various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used.
  • the following surfactants are also preferable.
  • the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit
  • the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.
  • the surfactant the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
  • the content of the surfactant is 0.001 to 2.0% by mass based on the total solid content of the curable resin composition of the present invention. It is preferably 0.005 to 1.0% by mass, more preferably 0.005 to 1.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When there are two or more types of surfactant, the total is preferably in the above range.
  • the curable resin composition of the present invention has a curable resin composition in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of an object.
  • a higher fatty acid derivative such as behenic acid or behenic acid amide
  • the content of the higher fatty acid derivative is 0.1 to 10% by mass with respect to the total solid content of the curable resin composition of the present invention. Is preferable.
  • the higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.
  • the water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties.
  • the metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, still more preferably less than 0.5 mass ppm, from the viewpoint of insulating properties.
  • the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.
  • a raw material having a low metal content is selected as a raw material constituting the curable resin composition of the present invention.
  • Methods such as filtering the raw materials constituting the curable resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible can be mentioned. be able to.
  • the curable resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably 200 mass ppm from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
  • the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
  • a conventionally known storage container can be used as the storage container for the curable resin composition of the present invention.
  • a multi-layer bottle having the inner wall of the container composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a bottle having a layered structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
  • the curable resin composition of the present invention can be prepared by mixing each of the above components.
  • the mixing method is not particularly limited, and a conventionally known method can be used.
  • the filter pore diameter 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.
  • the filter may be one that has been pre-cleaned with an organic solvent.
  • a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times.
  • circulation filtration When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure 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.
  • 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 curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer. In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.
  • the cured film of the present invention is obtained by curing the curable resin composition of the present invention.
  • the film 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. Further, the upper limit value can be 100 ⁇ m or less, and can be 30 ⁇ m or less.
  • the cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. It is preferable that the laminate of the present invention contains two or more cured films and includes a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferable.
  • the first cured film and the second cured film are both cured films of the present invention.
  • both the first cured film and the second cured film are curable of the present invention.
  • An embodiment in which the resin composition is a cured film is preferable.
  • the curable resin composition of the present invention used for forming the first cured film and the curable resin composition of the present invention used for forming the second cured film have the same composition. It may be present, or it may be a composition having a different composition.
  • the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
  • Examples of the applicable field of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
  • a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above may be patterned by etching. For these applications, for example, Science & Technology Co., Ltd.
  • the cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially microelectronics.
  • the method for producing a cured film of the present invention includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film.
  • the method for producing a cured film of the present invention preferably includes the film forming step, an exposure step for exposing the film, and a developing step for developing the film.
  • the method for producing a cured film of the present invention more preferably includes the film forming step and, if necessary, the developing step, and also includes a heating step of heating the film at 50 to 450 ° C. Specifically, it is also preferable to include the following steps (a) to (d).
  • A Film forming step of applying the curable resin composition to a substrate to form a film (curable resin composition layer)
  • Exposure step of exposing the film after the film forming step
  • Exposure Development step for developing the film
  • Heating step for heating the developed film at 50 to 450 ° C. By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the above-mentioned thermal base generator is decomposed to obtain sufficient curability.
  • the method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention.
  • the method for producing the laminated body of the present embodiment is the step (a), the steps (a) to (c), or (a) after forming the cured film according to the above-mentioned method for producing the cured film. )-(D).
  • a laminated body can be obtained.
  • the production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the curable resin composition is applied to a substrate to form a film (layered).
  • the type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film transistor. There are no particular restrictions on magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, and plasma display panel (PDP) electrode plates. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material is more preferable. Further, as the base material, for example, a plate-shaped base material (board) is used.
  • the resin layer or the metal layer serves as a base material.
  • Coating is preferable as a means for applying the curable resin composition to the base material.
  • the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet 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. Further, the coating method can be appropriately selected depending on the shape of the base material.
  • a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular base material, a slit coating method or a spray coating method is used.
  • the method, the inkjet method and the like are preferable.
  • the spin coating method for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute.
  • the transfer method the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention.
  • the production method of the present invention may include a step of forming the film (curable resin composition layer), followed by a film forming step (layer forming step), and then drying to remove the solvent.
  • the preferred drying temperature is 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C.
  • the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
  • the production method of the present invention may include an exposure step of exposing the film (curable resin composition layer).
  • the amount of exposure is not particularly determined as long as the curable 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 200 to 8,000 mJ /. It is more preferable to irradiate with cm 2 .
  • the exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
  • the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h.
  • the curable resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays. As a result, particularly high exposure sensitivity can be obtained.
  • the production method of the present invention may include a developing step of developing (developing the above film) the exposed film (curable resin composition layer). By performing the development, the unexposed portion (non-exposed portion) is removed.
  • the developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.
  • the developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
  • alkaline development the case where an alkaline developer is used as the developer
  • solvent development the case where a developer containing 50% by mass or more of an organic solvent is used as the developer.
  • the developer is preferably a developer in which the content of the organic solvent is 10% by mass or less with respect to the total mass of the developer.
  • the content is more preferably 5% by mass or less, further preferably 1% by mass or less, and particularly preferably not containing an organic solvent.
  • the developing solution in alkaline development is more preferably an aqueous solution having a pH of 10 to 14.
  • Examples of the alkaline compound contained in the developing solution in alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicate. Examples include potassium silicate, ammonia or amine.
  • amines examples include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, and tetramethylammonium hydroxide.
  • TMAH tetraethylammonium hydroxide
  • tetrabutylammonium hydroxide and the like can be mentioned.
  • metal-free alkaline compounds are preferable, and amines are more preferable.
  • the alkaline compound may be only one kind or two or more kinds. When there are two or more alkaline compounds, the total is preferably in the above range.
  • the developer used in solvent development preferably has 60% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and 90% by mass or more of an organic solvent with respect to the total mass of the developer. It is more preferably a solvent. Further, the developing solution may be 100% by mass of an organic solvent with respect to the total mass of the developing solution.
  • the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
  • Organic solvents include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone.
  • alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl propionate ethoxyacetate, etc.)
  • alkyl esters of 3-alkyloxypropionate eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-
  • Ke As tons for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc.
  • Dimethyl sulfoxide is preferably mentioned as the sulfoxides.
  • cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.
  • the development time is preferably 10 seconds to 5 minutes.
  • the temperature of the developing solution at the time of development is not particularly specified, but is usually 20 to 40 ° C.
  • the rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with a solvent contained in the curable resin composition.
  • the rinsing time is preferably 5 seconds to 1 minute.
  • the production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ° C.
  • the heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step.
  • the heating step for example, the above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the heterocyclic polymer precursor proceeds.
  • the curable resin composition of the present invention may contain a radically polymerizable compound other than the heterocyclic polymer precursor, but may also cure a radically polymerizable compound other than the unreacted heterocyclic polymer precursor. It can be advanced in this step.
  • the heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable.
  • the upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.
  • the heating is preferably performed at a heating rate 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.
  • a heating rate 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 even more preferably 25 ° C. to 120 ° C.
  • the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started.
  • the temperature of the film (layer) after drying is higher than, for example, the boiling point of the solvent contained in the curable resin composition. It is preferable to gradually raise the temperature from a temperature as low as 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 even more 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 layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the heterocyclic polymer precursor between the layers are undergoing a cross-linking reaction at this temperature.
  • Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed.
  • the heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to carry out the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547.
  • the pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, 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.
  • cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
  • the heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the heterocyclic polymer precursor.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
  • the production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (curable resin composition layer).
  • metal layer existing metal types can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper is preferable. More preferred.
  • the method for forming the metal layer is not particularly limited, and an existing method can be applied.
  • the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used.
  • photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
  • the thickness of the metal layer is preferably 0.1 to 50 ⁇ m, more preferably 1 to 10 ⁇ m at the thickest portion.
  • the production method of the present invention preferably further includes a laminating step.
  • the laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step are performed again on the surface of the cured film (resin layer) or the metal layer. , A series of steps including performing in this order. However, the mode may be such that only the film forming step (a) is repeated. Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated curable resin composition layers all at once.
  • the (c) developing step may be followed by the (e) metal layer forming step, and even if the heating is performed each time (d), the steps of (d) are collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step, and the like as appropriate.
  • the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step.
  • An example of the surface activation treatment is plasma treatment.
  • the laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
  • the resin layer is 3 or more and 7 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and 3 or more and 5 or less are more preferable.
  • a cured film (resin layer) of the curable resin composition so as to cover the metal layer after the metal layer is provided.
  • Examples thereof include an embodiment in which the steps, (b) exposure steps, (c) development steps, and (e) metal layer forming steps are repeated in this order, and (d) heating steps are collectively provided at the end or in the middle.
  • the present invention also discloses a semiconductor device containing the cured film or laminate of the present invention.
  • the semiconductor device in which the curable resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer the description in paragraphs 0213 to 0218 and the description in FIG. 1 of JP-A-2016-0273557 are taken into consideration. Yes, these contents are incorporated herein.
  • thermobase generator of the present invention comprises an anion represented by the above formula (1-3), the above formula (1-4) or the above formula (1-5), and an ammonium cation, an iminium cation, or a phosphonium cation. It is preferably a thermobase generator that is a salt with a certain organic cation. Preferred embodiments of the anion represented by the above formula (1-3), the above formula (1-4) or the above formula (1-5), and the organic cation which is an ammonium cation, an iminium cation, or a phosphonium cation are described. Each is as described above.
  • thermosetting agent of the present invention is not particularly limited, but for example, a curable resin composition can be formed by using it in combination with the above-mentioned heterocyclic polymer precursor. Further, it is considered that it is excellent to use the thermobase generator of the present invention. Therefore, in various applications in which a known thermobase generator is used, the thermobase generator of the present invention is used in place of the conventional thermobase generator or in combination with the conventional thermobase generator. Is considered to be useful.
  • reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added.
  • the reaction mixture was then cooled to ⁇ 10 ° C. and 16.12 g (135.5 mmol) of SOCL 2 was added over 10 minutes while keeping the temperature at ⁇ 10 ⁇ 4 ° C. Viscosity increased while SOCL 2 was added. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours.
  • the polyimide precursor was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. The obtained polyimide precursor was then dried under reduced pressure at 45 ° C. for 3 days. The weight average molecular weight of this polyimide precursor was 22,000.
  • the obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate composed of a crude polymer.
  • the produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution.
  • the obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polymer A-7.
  • the weight average molecular weight (Mw) of this polymer A-7 was measured and found to be 20,000.
  • reaction solution was transferred to a separate funnel, 1 L of ethyl acetate was added, diluted, and then washed 3 times with 300 mL of 1 mol / L hydrochloric acid water, washed twice with 100 mL of water, and washed with 300 mL of saturated brine.
  • the solvent of the liquid transferred to the eggplant flask was distilled off under reduced pressure at 30 ° C., 100 mL of ethyl acetate was added, and recrystallization was performed. This was filtered to obtain 6.5 g of the target product (BA-2). It was confirmed from the 1 H-NMR spectrum that it was the target product (BA-2). The target product (BA-2) was analyzed by 1 1 H-NMR. The results are shown below.
  • Examples and Comparative Examples> In each example, the components shown in Table 1 or Table 2 below were mixed to obtain each curable resin composition. Further, in each comparative example, the components shown in Table 2 below were mixed to obtain each comparative composition. The content of the component shown in Table 1 or Table 2 was the amount shown in "Mass parts” of Table 1 or Table 2. Further, in Table 1 or Table 2, the description of "-" indicates that the composition does not contain the corresponding component.
  • the obtained curable resin composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 ⁇ m.
  • Heterocycle-containing polymer precursor] -A-1 to A-8 A-1 to A-8 synthesized above In Example 26, 16.9 parts by mass of A-7 and 16.9 parts by mass of A-8 were used.
  • BA-1 to BA-21 BA-1 to BA-21 synthesized above BG-12: A compound having the following structure.
  • BA-2 and BG-12 were used at 50:50 (molar ratio) in a total of 1 part by mass.
  • -RB-1 to RB-3 Compounds having the following structures. None of RB-1 to RB-3 has a structure represented by the formula (1-1) or the formula (1-2), and does not correspond to a compound containing a specific anion.
  • OXE-01 IRGACURE OXE 01 (manufactured by BASF)
  • OXE-02 IRGACURE OXE 02 (manufactured by BASF)
  • OXE-03 IRGACURE 369 (manufactured by BASF)
  • ⁇ solvent ⁇ -DMSO dimethyl sulfoxide-GBL: ⁇ -butyrolactone-ethyl lactate-NMP: N-methylpyrrolidone
  • GBL 20: 80 (mass ratio). It shows that it was mixed in the ratio of.
  • [Metal adhesion improver] -G-1 The following compound-G-2: The following compound-G-3: The following compound-G-4: The following compound Et represents an ethyl group.
  • a curable resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a curable resin composition layer.
  • the silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform curable resin composition layer having a thickness of about 15 ⁇ m on the silicon wafer.
  • the entire surface of the obtained curable resin composition layer was exposed to i-rays with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).
  • the curable resin composition layer (resin layer) after the above exposure is heated at a heating rate of 10 ° C./min under a nitrogen atmosphere, and is displayed in the “Curing temperature (° C.)” column of Table 1 or Table 2. After reaching the stated temperature, it was heated for 3 hours.
  • the cured resin layer (cured film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured film was peeled off from the silicon wafer. The peeled cured film was punched out using a punching machine to prepare a test piece having a sample width of 3 mm and a sample length of 30 mm.
  • the obtained test piece was subjected to a film in accordance with JIS-K6251 using a tensile tester (Tencilon) at a crosshead speed of 300 mm / min and in an environment of 25 ° C. and 65% RH (relative humidity).
  • the elongation at break in the longitudinal direction was measured.
  • the evaluation was carried out 5 times each, and the arithmetic mean value of the elongation rate (break elongation rate) when the film was broken was used as an index value.
  • the above index values were evaluated according to the following evaluation criteria, and the evaluation results were described in the “Film strength” column of Table 1 or Table 2. It can be said that the larger the index value is, the better the film strength (break elongation) of the obtained cured film is.
  • a curable resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a curable resin composition layer.
  • the silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a curable resin composition layer having a uniform thickness of about 15 ⁇ m on the silicon wafer.
  • the film thickness of the curable resin composition layer on the silicon wafer was measured, and this value was taken as the pre-aging film thickness.
  • the film thickness was determined as an arithmetic mean value obtained by measuring the film thickness at 10 points on the coated surface with an ellipsometer (KT-22 manufactured by Foothill).
  • the curable resin composition or the comparative composition was placed in a glass container, sealed, and allowed to stand in a light-shielded environment at 25 ° C. for 14 days, and then the pre-aging film thickness was determined.
  • a curable resin composition layer was formed by applying it on a silicon wafer by a spin coating method using the same rotation speed as in the case of.
  • the silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a curable resin composition layer having a uniform thickness on the silicon wafer.
  • the film thickness of the obtained curable resin composition layer was measured by the same method as the film thickness measuring method in the above-mentioned pre-aging film thickness measuring method, and this value was taken as the post-aging film thickness.
  • Film thickness change rate (%)
  • the calculated film thickness change rate was evaluated according to the following evaluation criteria, and the evaluation results are listed in the "Storage stability" column of Table 1 or Table 2. It can be said that the smaller the rate of change in film thickness, the better the storage stability of the curable resin composition.
  • a curable resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a curable resin composition layer.
  • the silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to form a curable resin composition layer having a uniform thickness of 15 ⁇ m on the silicon wafer.
  • the curable resin composition layer on the silicon wafer was i-line-exposed with an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed curable resin composition layer (resin layer) was subjected to i-line exposure.
  • a cured layer (resin layer) of a curable resin composition layer was obtained by heating in a nitrogen atmosphere at a heating rate of 10 ° C./min and heating at the temperatures shown in Table 1 or 2 for 3 hours. ..
  • the obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
  • Chemical solution A mixture of dimethyl sulfoxide (DMSO) and a 25 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 90:10 (mass ratio)
  • DMSO dimethyl sulfoxide
  • TMAH tetramethylammonium hydroxide
  • Evaluation conditions The resin layer is immersed in the above chemical solution at 75 ° C. for 15 minutes before and after. The film thicknesses were compared and the dissolution rate (nm / min) was calculated.
  • the film thickness was determined as an arithmetic mean value obtained by measuring the film thickness at 10 points on the coated surface with an ellipsometer (KT-22 manufactured by Foothill).
  • the evaluation was performed according to the following evaluation criteria, and the evaluation results are described in the "Chemical resistance" column of Table 1 or Table 2. It can be said that the smaller the value of the dissolution rate, the better the chemical resistance of the obtained cured film (resin layer).
  • the heterocyclic polymer precursor and the curable resin composition containing the specific anion according to the present invention are excellent in the film strength of the cured film and the storage stability of the composition.
  • the curable resin composition according to Comparative Examples 1 to 7 does not contain a specific anion. It can be seen that the curable resin compositions according to Comparative Examples 1 to 7 are inferior to at least one of the film strength of the cured film and the storage stability of the composition.
  • Example 101 The curable resin composition used in Example 1 was applied in layers to the surface of the copper thin layer of the resin base material having the copper thin layer formed on the surface by a spin coating method, and dried at 100 ° C. for 5 minutes. After forming a curable resin composition layer having a thickness of 20 ⁇ m, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m). After exposure, it was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a layer pattern.
  • NSR1505 i6 a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m
  • the interlayer insulating film for the rewiring layer was excellent in insulating property. Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

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Abstract

L'invention concerne une composition de résine durcissable qui contient: au moins une sorte de résine choisie dans un groupe constitué d'un précurseur de polyimide, un précurseur de polyamide-imide, et un précurseur de polybenzoxazole; un anion possédant une structure représentée par la formule (1-1) ou la formule (1-2); ainsi qu'un cation organique. L'invention concerne également un film durci obtenu par durcissement de ladite composition de résine durcissable, un corps stratifié contenant ledit film durci, un procédé de fabrication dudit film durci, et un dispositif à semi-conducteurs contenant ledit film durci ou ledit corps stratifié.
PCT/JP2020/024108 2019-06-26 2020-06-19 Composition de resine durcissable, film durci, corps stratifie, procede de fabrication de film durci et dispositif a semi-conducteurs WO2020262227A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013204019A (ja) * 2012-03-29 2013-10-07 Dainippon Printing Co Ltd 塩基発生剤、感光性樹脂組成物、当該感光性樹脂組成物からなるパターン形成用材料、当該感光性樹脂組成物を用いたレリーフパターンの製造方法、及び物品
JP2013222020A (ja) * 2012-04-16 2013-10-28 Fujifilm Corp 感光性樹脂組成物、硬化膜の製造方法、硬化膜、有機ｅｌ表示装置および液晶表示装置
JP2014055114A (ja) * 2012-09-11 2014-03-27 Jsr Corp 新規化合物、硬化膜形成用組成物及び硬化膜
US20180327534A1 (en) * 2015-11-19 2018-11-15 Basf Se Catalyst for the preparation of polyurethanes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013204019A (ja) * 2012-03-29 2013-10-07 Dainippon Printing Co Ltd 塩基発生剤、感光性樹脂組成物、当該感光性樹脂組成物からなるパターン形成用材料、当該感光性樹脂組成物を用いたレリーフパターンの製造方法、及び物品
JP2013222020A (ja) * 2012-04-16 2013-10-28 Fujifilm Corp 感光性樹脂組成物、硬化膜の製造方法、硬化膜、有機ｅｌ表示装置および液晶表示装置
JP2014055114A (ja) * 2012-09-11 2014-03-27 Jsr Corp 新規化合物、硬化膜形成用組成物及び硬化膜
US20180327534A1 (en) * 2015-11-19 2018-11-15 Basf Se Catalyst for the preparation of polyurethanes

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