WO2024048604A1 - Composition de résine, objet durci ainsi que procédé de fabrication de celui-ci, stratifié ainsi que procédé de fabrication de celui-ci, et dispositif à semi-conducteurs ainsi que procédé de fabrication de celui-ci - Google Patents

Composition de résine, objet durci ainsi que procédé de fabrication de celui-ci, stratifié ainsi que procédé de fabrication de celui-ci, et dispositif à semi-conducteurs ainsi que procédé de fabrication de celui-ci Download PDF

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Publication number
WO2024048604A1
WO2024048604A1 PCT/JP2023/031310 JP2023031310W WO2024048604A1 WO 2024048604 A1 WO2024048604 A1 WO 2024048604A1 JP 2023031310 W JP2023031310 W JP 2023031310W WO 2024048604 A1 WO2024048604 A1 WO 2024048604A1
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group
formula
resin composition
cured product
compound
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PCT/JP2023/031310
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English (en)
Japanese (ja)
Inventor
敦靖 野崎
享平 崎田
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富士フイルム株式会社
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Publication of WO2024048604A1 publication Critical patent/WO2024048604A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers

Definitions

  • the present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device.
  • resin materials manufactured from resin compositions containing resin are utilized in various fields.
  • polyimide has excellent heat resistance and insulation properties, so it is used for various purposes.
  • the above-mentioned uses are not particularly limited, but in the case of semiconductor devices for mounting, for example, they may be used as materials for insulating films and sealing materials, or as protective films. It is also used as a base film and coverlay for flexible substrates.
  • polyimide is used in the form of a resin composition containing a polyimide precursor.
  • a resin composition is applied to a base material by coating, for example, to form a photosensitive film, and then, as necessary, exposure, development, heating, etc. are performed to form a cured product on the base material. be able to.
  • the polyimide precursor is cyclized, for example, by heating, and becomes polyimide in the cured product. Since the resin composition can be applied by known coating methods, there is a high degree of freedom in designing the shape, size, application position, etc. of the resin composition when it is applied. It can be said that it has excellent characteristics. In addition to the high performance of polyimide, there are increasing expectations for the industrial application of the above-mentioned resin composition due to its excellent manufacturing adaptability.
  • Patent Document 1 contains a polyimide precursor having a polymerizable unsaturated bond, a polymerizable monomer having an aliphatic cyclic skeleton and at least two methacryloyloxy groups, a photopolymerization initiator, and a solvent.
  • a photosensitive resin composition is described.
  • Patent Document 2 describes that (A) a polyimide precursor having a polymerizable unsaturated bond, (B) a polymerizable monomer having an aliphatic cyclic skeleton, (C) a photopolymerization initiator, and (D) a thermal crosslinking agent.
  • a photosensitive resin composition containing the same is described.
  • cured products containing polyimide it is required to reduce the dielectric constant of the cured products from the viewpoint of suppressing transmission loss.
  • improvement in chemical resistance is required from the viewpoint of improving resistance to developers when laminated in multiple layers, resistance to solvents contained in resin compositions, etc.
  • the present invention relates to a resin composition from which a cured product having a low dielectric constant and excellent chemical resistance can be obtained, a cured product obtained by curing the above resin composition, a laminate containing the above cured product, and a cured product obtained from the above cured product. It is an object of the present invention to provide a manufacturing method of a semiconductor device including a manufacturing method, a method of manufacturing the laminate, a method of manufacturing the cured product, and a semiconductor device including the cured product.
  • Y 11 is a group containing a structure in which two or more hydrogen atoms are removed from the structure represented by any of the following formulas (a), (b), or (c), Or, it represents a divalent linking group, and at least one of X 11 and Y 11 has two or more hydrogen atoms removed from the structure represented by formula (a), formula (b), or formula (c).
  • R 11 and R 12 are each independently a hydrogen atom or a monovalent organic group, and at least one of R 11 and R 12 is a monovalent organic group containing a polymerizable group. be.
  • X 1 and X 2 are each independently a hydrogen atom or an alkyl group optionally substituted with a halogen atom
  • R 1 and R 2 are each independently , represents a hydrogen atom or a monovalent substituent, and R 1 and R 2 may be combined to form a ring structure.
  • Y 11 is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (a), formula (b) or formula (c), in ⁇ 1> The resin composition described.
  • R 21 and R 22 are each independently a hydrogen atom or a monovalent organic group, and out of all R 21 and R 22 contained in the polyimide precursor, 2 polymerizable groups are The proportion of R 21 and R 22 , which are monovalent organic groups containing at least one group, is 50 mol% or more.
  • X 1 and X 2 are each independently a hydrogen atom or an alkyl group optionally substituted with a halogen atom
  • R 1 and R 2 are each independently , represents a hydrogen atom or a monovalent substituent, and R 1 and R 2 may be combined to form a ring structure.
  • ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the polymerizable compound includes a compound having a ClogP value of 3.0 or more.
  • ⁇ 7> Any one of ⁇ 1> to ⁇ 6>, wherein the polymerizable compound includes a compound having a ClogP value of 3.0 or more and having an aromatic ring structure or an aliphatic ring structure having 6 or more carbon atoms.
  • the resin composition according to item 1. ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, further comprising an azole compound and a silane coupling agent.
  • ⁇ 9> The 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 including two or more layers made of the cured product according to ⁇ 10> and a metal layer between any of the layers made of the cured product.
  • ⁇ 12> A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 9> onto a substrate to form a film.
  • the method for producing a cured product according to ⁇ 12> comprising an exposure step of selectively exposing the film and a development step of developing the film using a developer to form a pattern.
  • the method for producing a cured product according to ⁇ 12> or ⁇ 13> which includes a heating step of heating the film at 50 to 450°C.
  • a method for producing a laminate including the method for producing a cured product according to any one of ⁇ 12> to ⁇ 14>.
  • ⁇ 16> A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to any one of ⁇ 12> to ⁇ 14>.
  • ⁇ 17> A semiconductor device comprising the cured product according to ⁇ 10>.
  • a resin composition capable of obtaining a cured product having a low dielectric constant and excellent chemical resistance, a cured product obtained by curing the above resin composition, a laminate containing the above cured product, and the above
  • a method for producing a cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product are provided.
  • a numerical range expressed using the symbol " ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as the lower limit and upper limit, respectively.
  • the term “step” includes not only independent steps but also steps that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.
  • substitution or unsubstitution includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • alkyl group includes not only an alkyl group without a 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, unless otherwise specified. Examples of the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • (meth)acrylate means both “acrylate” and “methacrylate”, or either “(meth)acrylate”
  • (meth)acrylic means both “acrylic” and “methacrylic”
  • (meth)acryloyl means either or both of "acryloyl” and “methacryloyl.”
  • 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 refers to the total mass of all 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.
  • weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC), and are defined as polystyrene equivalent values.
  • weight average molecular weight (Mw) and number average molecular weight (Mn) are expressed using, for example, HLC-8220GPC (manufactured by Tosoh Corporation) and guard column HZ-L, TSKgel Super HZM-M, TSKgel.
  • THF tetrahydrofuran
  • NMP N-methyl-2-pyrrolidone
  • a detector with a wavelength of 254 nm of UV rays is used for detection in the GPC measurement.
  • each layer constituting a laminate when the positional relationship of each layer constituting a laminate is described as "upper” or “lower", there is another layer above or below the reference layer among the plurality of layers of interest. It would be good if there was. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other.
  • the direction in which layers are stacked on the base material is referred to as "top”, or if there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as "top”. , the opposite direction is called "down".
  • the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Further, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.
  • the temperature is 23° C.
  • the atmospheric pressure is 101,325 Pa (1 atm)
  • the relative humidity is 50% RH. In this specification, combinations of preferred aspects are more preferred aspects.
  • the resin composition according to the first aspect of the present invention contains a repeating unit represented by formula (1-1), and contains a polymerizable group. It contains a polyimide precursor, a polymerization initiator, and a polymerizable compound having an amount of 2 mmol/g or more and an amide bond content of 1.5 mmol/g or less.
  • the resin composition according to the second aspect of the present invention (hereinafter also simply referred to as “second resin composition”) has a content of repeating units represented by formula (1-2) that is higher than that of the polyimide precursor.
  • first resin composition contains a polyimide precursor, a polymerization initiator, and a polymerizable compound that is 90% by mass or more based on the total mass and has a polymerizable group content of 2 mmol/g or more.
  • first resin composition and the second resin composition are also simply referred to as "resin composition”.
  • a polyimide precursor containing a repeating unit represented by formula (1-1) and having a polymerizable group content of 2 mmol/g or more and an amide bond content of 1.5 mmol/g or less will be referred to as " Also referred to as “first polyimide precursor.”
  • the content of the repeating unit represented by formula (1-2) is 90% by mass or more based on the total mass of the polyimide precursor, and the content of the polymerizable group is 2 mmol/g or more.
  • the polyimide precursor is also referred to as a "second polyimide precursor.”
  • polyimide precursor when it is simply described as “polyimide precursor”, it refers to both the first polyimide precursor and the second polyimide precursor.
  • the first polyimide precursor and the second polyimide precursor are also collectively referred to as a "specific resin.”
  • the resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and is preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent.
  • the resin composition of the present invention can be used, for example, to form an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and can be used for forming an interlayer insulating film for a rewiring layer. preferable.
  • the resin composition of the present invention is used for forming an interlayer insulating film for a rewiring layer.
  • the resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to negative development.
  • negative development refers to development in which non-exposed areas are removed by development during exposure and development
  • positive development refers to development in which exposed areas are removed by development.
  • the above-mentioned exposure method, the above-mentioned developer, and the above-mentioned development method include, for example, the exposure method explained in the exposure step in the description of the method for producing a cured product, and the developer and development method explained in the development step. is used.
  • the first resin composition of the present invention includes a first polyimide precursor.
  • the first polyimide precursor has an amide bond content of 1.5 mmol/g or less, and in formula (1-1), at least one of X 11 and Y 11 has a structure having a relatively large molecular weight. It includes a structure represented by any one of formulas (a) to (c). For this reason, the content ratio of imide structures in the polyimide obtained after curing becomes small. It is presumed that a cured product with a low dielectric constant can be obtained by reducing the content ratio of polarized structures such as imide structures in this way. Further, the first polyimide precursor has a polymerizable group content of 2 mmol/g or more.
  • a crosslinked structure is sufficiently formed between the polyimides or between the polyimide and the polymerizable compound, and a cured product with excellent chemical resistance is obtained. It is assumed that.
  • the content of the repeating unit represented by formula (1-2) in the second polyimide precursor is 90% by mass or more based on the total mass of the polyimide precursor, and in formula (1-2), At least one of Y 21 and Y 21 contains a structure represented by any one of formulas (a) to (c) that has a relatively large molecular weight. As a result, the content of imide structures in the polyimide obtained after curing becomes smaller.
  • the second polyimide precursor has a polymerizable group content of 2 mmol/g or more, and among all R 11 and R 12 , it is a monovalent organic group containing two or more polymerizable groups.
  • the ratio of R 21 and R 22 is 50 mol% or more. Therefore, in the cured product obtained from the second resin composition, a crosslinked structure is sufficiently formed between the polyimides or between the polyimide and the polymerizable compound, and a cured product with excellent chemical resistance is obtained. It is assumed that.
  • Patent Documents 1 and 2 do not describe a resin composition containing a specific resin.
  • the first resin composition contains a repeating unit represented by formula (1-1), has a polymerizable group content of 2 mmol/g or more, and an amide bond content of 1.5 mmol/g or less.
  • a certain polyimide precursor (first polyimide precursor) is included.
  • first polyimide precursor represents a tetravalent linking group
  • Y 11 is a group containing a structure in which two or more hydrogen atoms are removed from the structure represented by any of the following formulas (a), (b), or (c), Or, it represents a divalent linking group, and at least one of X 11 and Y 11 has two or more hydrogen atoms removed from the structure represented by formula (a), formula (b), or formula (c).
  • R 11 and R 12 are each independently a hydrogen atom or a monovalent organic group, and at least one of R 11 and R 12 is a monovalent organic group containing a polymerizable group.
  • X 1 and X 2 are each independently a hydrogen atom or an alkyl group optionally substituted with a halogen atom
  • R 1 and R 2 are each independently , represents a hydrogen atom or a monovalent substituent, and R 1 and R 2 may be combined to form a ring structure.
  • X 11 is preferably a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by any one of formula (a), formula (b), or formula (c).
  • X 1 and X 2 are preferably an alkyl group optionally substituted with a halogen atom, and preferably an alkyl group having 1 to 4 carbon atoms and optionally substituted with a halogen atom. More preferred is a methyl group or a trifluoromethyl group.
  • R 1 and R 2 are preferably each independently a hydrogen atom. When R 1 and R 2 combine to form a ring structure, the structure formed by combining R 1 and R 2 is preferably a single bond, -O- or -CR 2 -, and -O - or -CR 2 - is more preferred, and -O- is even more preferred.
  • R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.
  • X 11 is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (a)
  • X 11 is represented by the following formula (a-1) or formula (a-2).
  • a group represented by formula (a-2) is preferable, and a group represented by formula (a-2) is preferable from the viewpoint of lowering the amine value in the resin.
  • a bond that intersects with a side of a ring structure means substituting one of the hydrogen atoms in the ring structure.
  • * represents a bonding site with four carbonyl groups to which X 11 in formula (1-1) is bonded.
  • preferred embodiments of X 1 and X 2 are as described above.
  • the hydrogen atoms in these structures may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • X 11 is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (b), it is preferable that X 11 is a group represented by formula (b-1) below.
  • * represents a bonding site with four carbonyl groups to which X 11 in formula (1-1) is bonded
  • n represents an integer from 1 to 5.
  • the hydrogen atom in the structure below may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • X 11 is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (c)
  • X 11 is represented by the following formula (c-1) or formula (c-2).
  • a group represented by formula (c-2) is preferable, and a group represented by formula (c-2) is preferable from the viewpoint of lowering the dielectric constant.
  • * represents a bonding site with four carbonyl groups to which X 11 in formula (1-1) is bonded.
  • R 1 and R 2 are as described above.
  • the hydrogen atoms in these structures may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • X 11 is a group containing a structure in which two or more hydrogen atoms are removed from the structure represented by formula (a), formula (b), or formula (c), X 11 is one of the following: Preferably, it is a structure. In the following formula, * represents a bonding site with four carbonyl groups to which X 11 in formula (1-1) is bonded. Further, the hydrogen atoms in these structures may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • X 11 is a tetravalent linking group different from a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by any one of formula (a), formula (b) and formula (c)
  • X 11 is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).
  • formula (5) or formula (6) * each independently represents a bonding site with another structure.
  • R 112 is a single bond or a divalent linking group, and is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 -, -NHCO-, and a group selected from combinations thereof (excluding structures corresponding to the above formula (a)), More preferably, it is a single bond or a group selected from -O-, -CO-, -S- and -SO 2 -.
  • X 11 include tetracarboxylic acid residues remaining after removal of the anhydride group from tetracarboxylic dianhydride.
  • the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue, or may contain two or more types of tetracarboxylic dianhydride residues as the structure corresponding to X11 . It is preferable that the tetracarboxylic dianhydride is represented by the following formula (O).
  • X 11 represents a tetravalent organic group.
  • the preferred range of X 11 is the same as the preferred range of X 11 in formula (1-1).
  • tetracarboxylic dianhydride examples include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'- Diphenylsulfidetetracarboxylic 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 dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,
  • X 11 is a group containing a structure in which two or more hydrogen atoms are removed from the structure represented by formula (a), formula (b), or formula (c), tetracarboxylic dianhydride It is preferable to use the following compounds as Further, the hydrogen atoms in these structures may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • preferred examples include tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598.
  • X 11 is represented by formula (a), formula (b), or formula (c).
  • the proportion of repeating units that are groups containing a structure in which two or more hydrogen atoms are removed is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and 70 to 100 mol%. is even more preferable.
  • Y 11 is a group containing a structure in which two or more hydrogen atoms are removed from the structure represented by formula (a), formula (b), or formula (c), or 2 represents a valent linking group.
  • Y 11 is preferably a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by any one of formula (a), formula (b), or formula (c).
  • a group containing a structure in which two or more hydrogen atoms are removed from the structure represented by either formula (a) or formula (c) is particularly preferable.
  • Preferred embodiments of X 1 and X 2 in formula (a) and R 1 and R 2 in formula (c) are X 1 and X 2 in formula (a) in the above-mentioned X 11 , and The preferred embodiments of R 1 and R 2 are similar to those of R 1 and R 2 .
  • Y 11 is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (a)
  • Y 11 is represented by the following formula (a-3) or formula (a-4).
  • a group represented by formula (a-4) is preferable, and a group represented by formula (a-4) is preferable from the viewpoint of lowering the amine value in the resin.
  • * represents a bonding site with two nitrogen atoms to which Y 11 in formula (1-1) is bonded.
  • preferred embodiments of X 1 and X 2 are as described above.
  • the hydrogen atoms in these structures may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • Y 11 is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (b), Y 11 is preferably a group represented by formula (b-2) below.
  • * represents a bonding site with two nitrogen atoms to which Y 11 in formula (1-1) is bonded
  • n represents an integer from 1 to 5.
  • the hydrogen atom in the structure below may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • Y 11 is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (c)
  • Y 11 is represented by the following formula (c-3) or formula (c-4).
  • a group represented by formula (c-3) is preferable, and a group represented by formula (c-3) is preferable from the viewpoint of lowering the dielectric constant.
  • * represents a bonding site with two nitrogen atoms to which Y 11 in formula (1-1) is bonded.
  • R 1 and R 2 are as described above.
  • the hydrogen atoms in these structures may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • Y 11 is a group containing a structure in which two or more hydrogen atoms are removed from the structure represented by formula (a), formula (b), or formula (c), Y 11 is one of the following: Preferably, it is a structure. In the following formula, * represents a bonding site with two nitrogen atoms to which Y 11 in formula (1-1) is bonded. Further, the hydrogen atoms in these structures may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • a divalent organic group is preferred.
  • divalent organic groups include groups containing straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, including straight-chain or branched aliphatic groups having 2 to 20 carbon atoms, A group consisting of a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
  • the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the above cyclic aliphatic group and aromatic group, the hydrocarbon group in the chain may be substituted with a hetero atom. may be substituted with a group containing.
  • Examples of Y 11 in formula (1-1) include groups represented by -Ar- and -Ar-L-Ar-, with a group represented by -Ar-L-Ar- being preferred.
  • Ar is each independently an aromatic group
  • L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO -, -S-, -SO 2 -, -NHCO-, or a group consisting of a combination of two or more of the above (however, the structure corresponding to the above formula (a) is excluded).
  • Y 11 is derived from a diamine.
  • diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, and aromatic diamines.
  • One type of diamine may be used, or two or more types may be used.
  • Y 11 is a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or any of these.
  • a diamine containing a combination of groups is preferable, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable.
  • the above straight chain or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom.
  • the above cyclic aliphatic group and aromatic group may have a ring member hydrocarbon group substituted with a hetero atom. may be substituted with a group containing.
  • groups containing aromatic groups include the following.
  • * represents a bonding site with another structure.
  • diamine specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 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 and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodipheny
  • Y 11 is a group containing a structure in which two or more hydrogen atoms are removed from the structure represented by formula (a), formula (b), or formula (c), the following compounds may be used as the diamine. It is preferable to use Further, the hydrogen atoms in these structures may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
  • diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598.
  • diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 are also preferably used.
  • R 111 is preferably represented by -Ar-L-Ar- from the viewpoint of flexibility of the resulting organic film.
  • Ar is each independently an aromatic group
  • L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- , -SO 2 -, -NHCO-, or a combination of two or more of the above.
  • Ar is preferably a phenylene group
  • L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms optionally substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 - .
  • the aliphatic hydrocarbon group here is preferably an alkylene group.
  • R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61).
  • a divalent organic group represented by formula (61) is more preferable.
  • R 50 to R 57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, or a trifluoro It is a methyl group, and each * independently represents a bonding site with the nitrogen atom in formula (1-1).
  • the monovalent organic groups R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples include fluorinated alkyl groups.
  • R 58 and R 59 each independently represent a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bond with the nitrogen atom in formula (1-1). Represents a part.
  • Examples of the diamine giving the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'- Bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminoctafluorobiphenyl, and the like. These may be used alone or in combination of two or more.
  • Y 11 is represented by formula (a), formula (b), or formula (c).
  • the proportion of repeating units that are groups containing a structure in which two or more hydrogen atoms are removed is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and 70 to 100 mol%. is even more preferable.
  • X 11 is two or more hydrogen atoms from a structure represented by formula (a), formula (b), or formula (c).
  • R 11 and R 12 - R 11 and R 12 in formula (1-1) each independently represent a hydrogen atom or a monovalent organic group.
  • the monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
  • at least one of R 11 and R 12 is a monovalent organic group containing a polymerizable group.
  • An embodiment in which both R 11 and R 12 are monovalent organic groups containing a polymerizable group is also one of the preferred embodiments of the present invention.
  • the polymerizable group may be a cationically polymerizable group, but preferably a radically polymerizable group.
  • polymerizable groups examples include epoxy groups, oxetanyl groups, alkoxymethyl groups, acyloxymethyl groups, methylol groups, blocked isocyanate groups, and groups containing ethylenically unsaturated bonds. It is preferable that it is a group.
  • the group containing an ethylenically unsaturated bond is preferably a radically polymerizable group.
  • Groups containing ethylenically unsaturated bonds include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (for example, vinyl phenyl groups, etc.), (meth) Examples include an acrylamide group, a (meth)acryloyloxy group, a vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group, and a (meth)acrylamide group or a (meth)acryloyloxy group. More preferred.
  • the number of polymerizable groups in the monovalent organic group containing a polymerizable group in R 11 and R 12 is preferably 1 to 10.
  • the lower limit is preferably 2 or more from the viewpoint of increasing the polymerizable group value.
  • the upper limit is preferably 5 or less, more preferably 3 or less.
  • the monovalent organic group containing a polymerizable group is a monovalent organic group containing two polymerizable groups.
  • each polymerizable group may have the same structure or different structures.
  • an embodiment in which at least one of R 11 and R 12 in formula (1-1) is a monovalent organic group containing two or more polymerizable groups is also one of the preferred embodiments of the present invention.
  • the monovalent organic group containing a polymerizable group in R 11 and R 12 is preferably a group represented by the following formula (R-1).
  • L R1 represents an n1+1-valent linking group
  • R R1 represents a polymerizable group
  • n1 represents an integer from 1 to 10
  • * represents an oxygen atom in formula (1-1).
  • L R1 is selected from the group consisting of a hydrocarbon group, or a hydrocarbon group and -O-, -CO-, -S-, -SO 2 -, and -NR N -.
  • a group represented by a combination with at least one structure is preferable, and a hydrocarbon group is more preferable.
  • R N is a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or a phenyl group, and even more preferably a hydrogen atom.
  • a hydrocarbon group an aliphatic hydrocarbon group is preferable, and a saturated aliphatic hydrocarbon group is preferable.
  • the hydrocarbon group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms.
  • L R1 L R1 .
  • * has the same meaning as * in formula (R-1), and # represents the binding site with R R1 .
  • R R1 represents a polymerizable group, and preferred embodiments of the polymerizable group are as described above.
  • n1 is preferably an integer of 2 to 10, more preferably an integer of 2 to 5, and even more preferably 2 or 3. Further, the embodiment 2 is also one of the preferred embodiments of the present invention.
  • the formula weight of formula (R-1) is preferably 100 to 1,000, more preferably 150 to 800, even more preferably 200 to 500.
  • the monovalent organic group containing a polymerizable group in R 11 and R 12 may be a group represented by the following formula (III).
  • R 200 represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and preferably a hydrogen atom or a methyl group.
  • * represents a bonding site with another structure.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 -, a cycloalkylene group or a polyalkyleneoxy group.
  • R 201 examples include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1, Examples include 3-butanediyl group, -CH 2 CH(OH)CH 2 -, polyalkyleneoxy group, alkylene groups such as ethylene group and propylene group, -CH 2 CH(OH)CH 2 -, cyclohexyl group, polyalkylene group.
  • An oxy group is more preferred, and an alkylene group such as an ethylene group or a propylene group, or a polyalkyleneoxy group is even more preferred.
  • the polyalkyleneoxy group a polyethyleneoxy group or a polypropyleneoxy group is preferable, and a polyethyleneoxy group is more preferable.
  • the polyimide precursor forms a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. It's okay.
  • a tertiary amine compound having such an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.
  • the proportion of R 11 and R 12 which are monovalent organic groups containing two or more polymerizable groups, among all R 11 and R 12 in the first polyimide precursor is , is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more.
  • the upper limit is not particularly limited and may be 100 mol%.
  • the proportion of R 11 and R 12 which are monovalent organic groups containing one or more polymerizable groups, is 60 mol%. It is preferably at least 70 mol%, more preferably at least 80 mol%.
  • the upper limit is not particularly limited and may be 100 mol%.
  • R 11 and R 12 which are monovalent organic groups containing a polymerizable group in the first polyimide precursor
  • R 11 and R 12 which are monovalent organic groups containing two or more polymerizable groups The proportion is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more.
  • the upper limit is not particularly limited and may be 100 mol%.
  • the content of the repeating unit represented by formula (1-1) with respect to all repeating units contained in the first polyimide precursor is preferably 50 to 100 mol%, more preferably 60 to 100 mol%. It is preferably 70 to 100 mol%, more preferably 70 to 100 mol%.
  • the content of the repeating unit represented by formula (1-1) with respect to the total mass of the first polyimide precursor is preferably 60 to 100% by mass, more preferably 70 to 100% by mass. , more preferably 80 to 100% by mass.
  • the first polyimide precursor may include a repeating unit different from that of formula (1-1) (another repeating unit).
  • Other repeating units include a repeating unit represented by the following formula (2).
  • formula (2 ) represents a valent linking group
  • Y A is different from a group containing a structure in which two or more hydrogen atoms are removed from the structure represented by any of the above formulas (a), (b), and (c). It represents a divalent linking group
  • R A1 and R A2 are each independently a hydrogen atom or a monovalent organic group.
  • a preferred embodiment of X A is such that in formula (1-1) above, X 11 is two or more from the structure represented by any of formula (a), formula (b), and formula (c).
  • a preferred embodiment of Y A is such that X 11 in the above formula (1-1) is two or more from the structure represented by any one of formula (a), formula (b), and formula (c). This is the same as the preferred embodiment in the case where it is a divalent linking group different from a group containing a structure excluding a hydrogen atom.
  • preferred embodiments of R A1 and R A2 are the same as the preferred embodiments of R 11 and R 12 in the above-mentioned formula (1-1), respectively.
  • the structure may be such that neither R 11 nor R 12 is a monovalent organic group containing a polymerizable group.
  • the content of the repeating unit represented by formula (2) with respect to all repeating units contained in the first polyimide precursor is preferably 40 mol% or less, more preferably 30 mol% or less, and 20 mol% It is more preferable that it is the following.
  • the lower limit of the above content is not particularly limited, and may be 0 mol%.
  • the content of the repeating unit represented by formula (2) with respect to the total mass of the first polyimide precursor is preferably 40% by mass or less, more preferably 30% by mass or less, and 20% by mass. It is more preferable that it is the following.
  • the lower limit of the content is not particularly limited, and may be 0% by mass.
  • the total content of repeating units represented by formula (1-1) and repeating units represented by formula (2) with respect to all repeating units contained in the first polyimide precursor is 70 mol% or more. It is preferably at least 80 mol%, more preferably at least 90 mol%.
  • the upper limit of the content is not particularly limited, and may be 100 mol%.
  • the total content of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (2) with respect to the total mass of the first polyimide precursor may be 70% by mass or more. It is preferably 80% by mass or less, more preferably 90% by mass or less.
  • the upper limit of the content is not particularly limited, and may be 100% by mass.
  • the content of the repeating unit represented by the following formula (1-2) in the second resin composition is 90% by mass or more based on the total mass of the polyimide precursor, and the content of the polymerizable group is 2 mmol/g or more (second polyimide precursor).
  • R 21 and R 22 are each independently a hydrogen atom or a monovalent organic group, and out of all R 21 and R 22 contained in the polyimide precursor, 2 polymerizable groups are The proportion of R 21 and R 22 , which are monovalent organic groups containing at least one group, is 50 mol% or more.
  • X 1 and X 2 are each independently a hydrogen atom or an alkyl group optionally substituted with a halogen atom
  • R 1 and R 2 are each independently , represents a hydrogen atom or a monovalent substituent, and R 1 and R 2 may be combined to form a ring structure.
  • X 21 , Y 21 , R 21 and R 22 are the same as preferred embodiments of X 11 , Y 11 , R 11 and R 12 in formula (1-1). .
  • the proportion of R21 and R22 in the second polyimide precursor is 50 mol% or more, and 60 mol%. % or more, more preferably 70 mol% or more.
  • the upper limit is not particularly limited and may be 100 mol%.
  • the proportion of R 21 and R 22 in the second polyimide precursor is preferably 50 mol% or more. , more preferably 60 mol% or more, and still more preferably 80 mol% or more.
  • the upper limit is not particularly limited and may be 100 mol%.
  • R 21 and R 22 which are monovalent organic groups containing a polymerizable group in the second polyimide precursor
  • R 21 and R 22 which are monovalent organic groups containing two or more polymerizable groups The proportion is preferably 50 mol% or more, more preferably 60 mol% or more, and even more preferably 80 mol% or more.
  • the upper limit is not particularly limited and may be 100 mol%.
  • the content of the repeating unit represented by formula (1-2) with respect to all repeating units contained in the second polyimide precursor is preferably 80 to 100 mol%, more preferably 85 to 100 mol%. It is preferably 90 to 100 mol%, more preferably 90 to 100 mol%.
  • the content of the repeating unit represented by formula (1-2) with respect to the total mass of the second polyimide precursor is 90% by mass or more, preferably 92% by mass or more, and 95% by mass or more. It is even more preferable that there be.
  • the upper limit is not particularly limited and may be 100% by mass.
  • the second polyimide precursor may contain a repeating unit different from that of formula (1-2) (another repeating unit).
  • Other repeating units include the repeating unit represented by the above formula (2).
  • the content of the repeating unit represented by formula (2) with respect to all repeating units contained in the second polyimide precursor is preferably 10 mol% or less, more preferably 8 mol% or less, and 5 mol% It is more preferable that it is the following.
  • the lower limit of the above content is not particularly limited, and may be 0 mol%.
  • the content of the repeating unit represented by formula (2) with respect to the total mass of the second polyimide precursor is preferably 10% by mass or less, more preferably 8% by mass or less, and 5% by mass. It is more preferable that it is the following.
  • the lower limit of the content is not particularly limited, and may be 0% by mass.
  • the total content of the repeating unit represented by formula (1-2) and the repeating unit represented by formula (2) with respect to all repeating units contained in the second polyimide precursor is 90 mol% or more It is preferably 95 mol% or more, more preferably 98 mol% or more.
  • the upper limit of the content is not particularly limited, and may be 100 mol%.
  • the total content of the repeating unit represented by formula (1-2) and the repeating unit represented by formula (2) with respect to the total mass of the second polyimide precursor may be 90% by mass or more. It is preferably 92% by mass or less, more preferably 95% by mass or less.
  • the upper limit of the content is not particularly limited, and may be 100% by mass.
  • the content of polymerizable groups in the polyimide precursor (hereinafter also referred to as "polymerizable group value”) is 2 mmol/g or more, preferably 2.2 mmol/g or more, and 2.5 mmol/g or more. It is more preferable that there be. Although the upper limit is not particularly limited, it is preferably 4.0 mmol/g or less.
  • the content of polymerizable groups in the polyimide precursor is calculated as the ratio of the molar amount of the polymerizable groups contained in the polyimide precursor to the number average molecular weight of the polyimide precursor.
  • the content of amide bonds (hereinafter also referred to as "amide value") in the first polyimide precursor is 1.5 mmol/g or less.
  • the amide value of the second polyimide precursor is preferably 1.5 mmol/g or less.
  • the amide value of the polyimide precursor is more preferably 1.48 mmol/g or less, and even more preferably 1.46 mmol/g or less.
  • the lower limit is not particularly limited, but from the viewpoint of elongation at break, etc., it is preferably 1.0 mmol/g or more.
  • the content of amide bonds in the polyimide precursor is calculated as the ratio of the molar amount of amide bonds contained in the polyimide precursor to the number average molecular weight of the polyimide precursor.
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, even more preferably 15,000 to 40,000.
  • the number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
  • the molecular weight dispersity of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
  • the upper limit of the degree of molecular weight dispersion of the polyimide precursor is not particularly determined, for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
  • the molecular weight dispersity is a value calculated from weight average molecular weight/number average molecular weight.
  • the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyimide precursor are within the above ranges.
  • the weight average molecular weight, number average molecular weight, and degree of dispersion calculated from the plurality of types of polyimide precursors as one resin are each within the above ranges.
  • polyimide precursors can be obtained by reacting tetracarboxylic dianhydride and diamine at low temperature, by reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamic acid, and by using a condensing agent or an alkylating agent.
  • Examples of the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, Examples include N'-disuccinimidyl carbonate and trifluoroacetic anhydride.
  • Examples of the alkylating agent include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.
  • halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride, and the like.
  • an organic solvent used in the method for producing polyimide precursors, etc.
  • the number of organic solvents may be one or two or more.
  • the organic solvent can be determined as appropriate depending on the raw material, and examples include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, ⁇ -butyrolactone, etc. is exemplified.
  • a basic compound in the method for producing polyimide precursors, etc., it is preferable to add a basic compound during the reaction.
  • the number of basic compounds may be one or two or more.
  • the basic compound can be determined as appropriate depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-amino Examples include pyridine.
  • -Terminal sealing agent- In the production method of polyimide precursors, etc., in order to further improve storage stability, it is preferable to seal the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the end of the resin such as the polyimide precursor.
  • examples of the terminal capping agent include monoalcohol, phenol, thiol, thiophenol, monoamine, etc. From the viewpoint of properties, it is more preferable to use monoalcohols, phenols, and monoamines.
  • Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol, secondary alcohols such as 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantane alcohol.
  • primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, and isopropanol.
  • 2-butanol cyclohexyl alcohol
  • Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalen-1-ol, naphthalen-2-ol, and hydroxystyrene.
  • Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6- Aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminona
  • sealing agents for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic anhydrides, and sulfonic acid carboxylic acid anhydrides, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. preferable.
  • Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like.
  • Preferred carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexane carbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantane carbonyl chloride. , heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.
  • the method for producing a polyimide precursor or the like may include a step of precipitating a solid. Specifically, after filtering off the water-absorbed by-products of the dehydration condensation agent coexisting in the reaction solution, the obtained product is added to a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof.
  • a polyimide precursor or the like can be obtained by depositing the polymer component as a solid and drying it. In order to improve the degree of purification, operations such as redissolving the polyimide precursor, reprecipitation, drying, etc. may be repeated.
  • the method may include a step of removing ionic impurities using an ion exchange resin.
  • Specific examples of the specific resin include SP-1 to SP-15 in Examples described below, but the present invention is not limited thereto.
  • the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more based on the total solid content of the resin composition. It is even more preferable that the amount is 50% by mass or more. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass or less based on the total solid content of the resin composition. % or less, even more preferably 97% by mass or less, even more preferably 95% by mass or less.
  • the resin composition of the present invention may contain only one type of specific resin, or may contain two or more types of specific resin. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention contains at least two types of resin.
  • the resin composition of the present invention may contain a total of two or more types of specific resin and other resins described below, or may contain two or more types of specific resin, but may contain a specific resin. It is preferable to include two or more types.
  • the resin composition of the present invention contains two or more types of specific resins, for example, a polyimide precursor and a dianhydride-derived structure (X 11 in the above formula (1-1), formula (1-2 It is preferable that two or more types of polyimide precursors having different X 21 ) in ) are included.
  • the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter also simply referred to as "other resin").
  • Other resins include other polyimide precursors different from the specific resin, polyimides, polybenzoxazole precursors, polybenzoxazole, polyamideimide precursors, polyamideimides, aromatic polyethers, phenolic resins, polyamides, epoxy resins, Examples include polysiloxane, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins.
  • polyimide precursors include the compounds described in paragraphs 0017 to 0138 of International Publication No. 2022/145355. The above description is incorporated herein.
  • the aromatic polyether is not particularly limited, but polyphenylene ether is preferred. It is preferable that the polyphenylene ether contains a repeating unit represented by the following formula (PE).
  • R E1 represents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an amino group that may have a substituent, a nitro group, a carboxy group, etc. .
  • polyphenylene ether is a compound having a polymerizable group.
  • the above polymerizable group is preferably an epoxy group, an oxetanyl group, an oxazolyl group, a methylol group, an alkoxymethyl group, an acyloxymethyl group, a blocked isocyanate group, or a group having an ethylenically unsaturated bond. More preferable groups have the following.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinyl phenyl group, etc.), and a (meth)acrylamide group.
  • (meth)acryloyloxy group, etc. preferably vinylphenyl group, (meth)acrylamide group or (meth)acryloyloxy group, more preferably vinylphenyl group or (meth)acryloyloxy group, (meth)acryloyloxy group, etc. More preferred are groups.
  • polyphenylene ether is a compound having a polymerizable group
  • the position of the polymerizable group is not particularly limited, but, for example, a structure in which the polymerizable group is introduced at the end of the main chain is preferable.
  • the polyphenylene ether may also contain other repeating units.
  • the content of the other repeating units mentioned above is preferably 30% by mass or less, more preferably 20% by mass or less, and preferably 10% by mass or less based on the total mass of polyphenylene ether. More preferred.
  • the number average molecular weight of polyphenylene ether is not particularly limited, but is preferably from 500 to 50,000.
  • the lower limit of the number average molecular weight is preferably 800 or more, more preferably 1000 or more, and even more preferably 1500 or more.
  • the upper limit of the number average molecular weight is preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 10,000 or less.
  • polyphenylene ether examples include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), and poly(2-methyl-6-ethyl-1,4-phenylene ether).
  • PPE polyphenylene ether
  • poly(2,6-dimethyl-1,4-phenylene ether) examples include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), and poly(2-methyl-6-ethyl-1,4-phenylene ether).
  • -methyl-6-phenyl-1,4-phenylene ether poly(2,6-dichloro-1,4-phenylene ether), 2,6-dimethylphenol and other phenols (e.g.
  • polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols; , 6-dimethyl-1,4-phenylene ether), etc., with a phenol compound such as bisphenols or trisphenols in the presence of an organic peroxide in a toluene solvent, and a redistribution reaction is performed.
  • examples include polyphenylene ether having a linear structure or a branched structure, but are not limited thereto.
  • a resin composition with excellent coating properties can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained.
  • a polymerizable group having a high polymerizable group value with a weight average molecular weight of 20,000 or less may be used instead of or in addition to the polymerizable compound described below.
  • a polymerizable group having a high polymerizable group value with a weight average molecular weight of 20,000 or less for example, the molar amount of polymerizable groups contained in 1 g of resin
  • a (meth)acrylic resin having a concentration of 1 ⁇ 10 ⁇ 3 mol/g or more
  • it is possible to improve the coating properties of the resin composition, the solvent resistance of the pattern (cured product), etc. can.
  • the resin composition of the present invention preferably further contains at least one resin selected from the group consisting of polyimide, polybenzoxazole, and aromatic polyether.
  • polyimide examples include compounds described in paragraphs 0045 to 0072 of International Publication No. 2022/145355. The above description is incorporated herein. Among these, polyimides having ethylenically unsaturated bonds are particularly preferred.
  • polybenzoxazole examples include compounds described in paragraphs 0096 to 0103 of International Publication No. 2022/145355. The above description is incorporated herein.
  • the aromatic polyether is not particularly limited, but polyphenylene ether is preferred. It is preferable that the polyphenylene ether contains a repeating unit represented by the following formula (PE).
  • R E1 represents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an amino group that may have a substituent, a nitro group, a carboxy group, etc. .
  • polyphenylene ether is a compound having a polymerizable group.
  • the above polymerizable group is preferably an epoxy group, an oxetanyl group, an oxazolyl group, a methylol group, an alkoxymethyl group, an acyloxymethyl group, a blocked isocyanate group, or a group having an ethylenically unsaturated bond. More preferable groups have the following.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinyl phenyl group, etc.), and a (meth)acrylamide group.
  • (meth)acryloyloxy group, etc. preferably vinylphenyl group, (meth)acrylamide group or (meth)acryloyloxy group, more preferably vinylphenyl group or (meth)acryloyloxy group, (meth)acryloyloxy group, etc. More preferred are groups.
  • polyphenylene ether is a compound having a polymerizable group
  • the position of the polymerizable group is not particularly limited, but, for example, a structure in which the polymerizable group is introduced at the end of the main chain is preferable.
  • the polyphenylene ether may also contain other repeating units.
  • the content of the other repeating units mentioned above is preferably 30% by mass or less, more preferably 20% by mass or less, and preferably 10% by mass or less based on the total mass of polyphenylene ether. More preferred.
  • the number average molecular weight of polyphenylene ether is not particularly limited, but is preferably from 500 to 50,000.
  • the lower limit of the number average molecular weight is preferably 800 or more, more preferably 1,000 or more, and even more preferably 1,500 or more.
  • the upper limit of the number average molecular weight is preferably 30,000 or less, more preferably 20,000 or more, and even more preferably 10,000 or more.
  • polyphenylene ether examples include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), and poly(2-methyl-6-ethyl-1,4-phenylene ether).
  • PPE polyphenylene ether
  • poly(2,6-dimethyl-1,4-phenylene ether) examples include poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), and poly(2-methyl-6-ethyl-1,4-phenylene ether).
  • -methyl-6-phenyl-1,4-phenylene ether poly(2,6-dichloro-1,4-phenylene ether), 2,6-dimethylphenol and other phenols (e.g.
  • polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols; , 6-dimethyl-1,4-phenylene ether) and the like with a phenol compound such as bisphenols or trisphenols in a toluene solvent in the presence of an organic peroxide, resulting in a redistribution reaction.
  • a phenol compound such as bisphenols or trisphenols in a toluene solvent in the presence of an organic peroxide, resulting in a redistribution reaction.
  • examples include, but are not limited to, polyphenylene ether having a linear structure or a branched structure.
  • the content of the other resins is preferably 0.01% by mass or more, and 0.05% by mass or more based on the total solid content of the resin composition. It is more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more. More preferred.
  • the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass based on the total solid content of the resin composition. It is more preferably at most 60% by mass, even more preferably at most 50% by mass.
  • the content of other resins may be low.
  • the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less based on the total solid content of the resin composition. is more preferable, even more preferably 5% by mass or less, even more preferably 1% by mass or less.
  • the lower limit of the content is not particularly limited, and may be 0% by mass or more.
  • the resin composition further contains at least one resin selected from the group consisting of polyimide, polybenzoxazole, and aromatic polyether
  • the content of these resins (if it contains multiple types, or When a plurality of the same kind are included, the total content is preferably 5 to 150 parts by mass based on 100 parts by mass of the specific resin.
  • the lower limit is preferably 8 parts by mass or more, more preferably 10 parts by mass or more.
  • the upper limit is preferably 120 parts by mass or less, more preferably 100 parts by mass or less.
  • the resin composition of the present invention may contain only one type of other resin, or may contain two or more types of other resins. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention contains a polymerizable compound.
  • the polymerizable compound contains a compound having a ClogP value of 3.0 or more, and having an aromatic ring structure or carbon number. It is more preferable to include a compound having six or more aliphatic ring structures.
  • the ClogP value of a compound is defined as below.
  • the octanol-water partition coefficient (logP value) can generally be measured by the flask immersion method described in JIS Japanese Industrial Standard Z7260-107 (2000). Further, the octanol-water partition coefficient (logP value) can also be estimated by a computational chemical method or an empirical method instead of actual measurement. Calculation methods include Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)) and Viswanadhan's fragmentation method (J. Chem. Inf. Comput. Sci., 29, 16). 3 (1989)), Broto's fragmentation method (Eur. J. Med. Chem.-Chim.
  • Theor., 19, 71 (1984)), etc. are known to be used.
  • Crippen's fragmentation method J. Chem. Inf. Comput. Sci., 27, 21 (1987)
  • the ClogP value is a value obtained by calculating the common logarithm logP of the partition coefficient P between 1-octanol and water.
  • known methods and software can be used to calculate the ClogP value, unless otherwise specified, the present invention uses the ClogP program incorporated in the PCModels system of Daylight Chemical Information Systems.
  • the ClogP value is preferably 4.0 or more, more preferably 6.0 or more. Further, the upper limit of the ClogP value is not particularly limited, but is preferably 15.0 or less.
  • the aromatic ring structure may be an aromatic hydrocarbon ring or an aromatic heterocycle, but an aromatic hydrocarbon ring is preferable, and it is more preferable to include a benzene ring. Moreover, from the viewpoint of lowering the dielectric constant, a fused ring such as a fluorene ring is preferable.
  • a fused ring such as a fluorene ring is preferable.
  • an aliphatic ring structure having 6 to 30 carbon atoms is preferable, and an aliphatic ring structure having 6 to 20 carbon atoms is more preferable.
  • Examples of aliphatic ring structures having 6 or more carbon atoms include monocycles such as a cyclohexane ring, dicyclopentane rings, and double rings such as tricyclo[5.2.1.0 2,6 ]decane rings. It is preferable that there be.
  • Polymerizable compounds with a ClogP value of 3.0 or more are ethylenically unsaturated.
  • a compound containing a group having a bond is preferable, and a compound containing two or more groups having an ethylenically unsaturated bond is more preferable. Further, it is also preferable that the compound contains two groups having ethylenically unsaturated bonds.
  • polymerizable compounds having a ClogP value of 3.0 or more are described below.
  • the compound is a radical crosslinking agent.
  • polymerizable compounds having a ClogP value of 3.0 or more include, but are not limited to, the following compounds.
  • Examples of the polymerizable compound include radical crosslinking agents and other crosslinking agents.
  • the resin composition of the present invention contains a radical crosslinking agent.
  • a radical crosslinking agent is a compound having a radically polymerizable group.
  • the radically polymerizable group a group containing an ethylenically unsaturated bond is preferable.
  • the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinyl phenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
  • (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferable, and from the viewpoint of reactivity, (meth)acryloyl group is more preferable.
  • the radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds.
  • the radical crosslinking agent may have three or more ethylenically unsaturated bonds.
  • the compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and more preferably a compound having 2 to 6 ethylenically unsaturated bonds. More preferred are compounds having the following.
  • the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above ethylenically unsaturated bonds. It is also preferable.
  • the molecular weight of the radical crosslinking agent 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 radical crosslinking agent is preferably 100 or more.
  • radical crosslinking agents include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. These are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds.
  • addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxy groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxies, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • the radical crosslinking agent is also preferably a compound having a boiling point of 100°C or higher under normal pressure.
  • Examples of the compound having a boiling point of 100° C. or higher under normal pressure include the compounds described in paragraph 0203 of International Publication No. 2021/112189. This content is incorporated herein.
  • Preferred radical crosslinking agents other than those mentioned above include radically polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021/112189. This content is incorporated herein.
  • radical crosslinking agents examples include dipentaerythritol triacrylate (commercially available product: KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available product: KAYARAD D-320 (made by Nippon Kayaku Co., Ltd.) Co., Ltd.), A-TMMT (Shin Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (Nippon Kayaku Co., Ltd.)), dipenta Erythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and these (meth)acryloyl groups are ethylene glyco
  • radical crosslinking agents include, for example, SR-494, which is a tetrafunctional acrylate with four ethyleneoxy chains, and SR-209, 231, and 239, which are difunctional methacrylates with four ethyleneoxy chains (all of which are sold by Sartomer Co., Ltd.). (manufactured by Nippon Kayaku Co., Ltd.), DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, TPA-330, a trifunctional acrylate with three isobutyleneoxy chains (manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers.
  • SR-494 which is a tetrafunctional acrylate with four ethyleneoxy chains
  • SR-209, 231, and 239 which are difunctional methacrylates with four ethyleneoxy chains (all of which are sold by Sartomer Co., Ltd.).
  • DPCA-60 a hexafunctional acrylate with six penty
  • urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765, Urethane compounds having an ethylene oxide 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.
  • radical crosslinking agent compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, can also be used. can.
  • the radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphoric acid group.
  • the radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group.
  • a radical crosslinking agent having the following is more preferable.
  • the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. It is a compound that is Commercially available products include, for example, polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.
  • the acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, more preferably 1 to 100 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, it will have excellent handling properties during production and excellent developability. Moreover, it has good polymerizability. The above acid value is measured in accordance with the description of JIS K 0070:1992.
  • bifunctional methacrylate or acrylate as the resin composition from the viewpoint of pattern resolution and film stretchability.
  • Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, and PEG 600 diacrylate.
  • PEG200 diacrylate refers to polyethylene glycol diacrylate in which the formula weight of polyethylene glycol chains is about 200.
  • a monofunctional radical crosslinking agent can preferably be used as the radical crosslinking agent from the viewpoint of suppressing warpage of the pattern (cured product).
  • monofunctional radical crosslinking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, and cyclohexyl (meth)acrylate.
  • (meth)acrylate benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc.
  • Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl glycidyl ether, and the like are preferably used.
  • the monofunctional radical crosslinking agent a compound having a boiling point of 100° C. or higher at normal pressure is also preferred in order to suppress volatilization before exposure.
  • examples of the radical crosslinking agent having two or more functional groups include allyl compounds such as diallyl phthalate and triallyl trimellitate.
  • the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less based on the total solid content of the resin composition.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
  • One type of radical crosslinking agent may be used alone, or a mixture of two or more types may be used. When two or more types are used together, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention contains another crosslinking agent different from the above-mentioned radical crosslinking agent.
  • Other crosslinking agents refer to crosslinking agents other than the above-mentioned radical crosslinking agents, and the above-mentioned photoacid generators or photobase generators are photosensitive to other compounds in the composition or their reaction products.
  • the compound has a plurality of groups in its molecule that promote the reaction of forming a covalent bond between the compounds, and the reaction of forming a covalent bond with other compounds in the composition or the reaction products thereof is preferably Compounds having a plurality of groups in the molecule that are promoted by the action of acids or bases are preferred.
  • the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
  • Other crosslinking agents include compounds described in paragraphs 0179 to 0207 of International Publication No. 2022/145355. The above description is incorporated herein.
  • the resin composition of the present invention contains a polymerization initiator.
  • the polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator.
  • the photopolymerization initiator is preferably a radical photopolymerization initiator.
  • the radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet to visible range is preferred. Alternatively, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.
  • the photoradical polymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 within the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). It 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).
  • any known compound can be used.
  • halogenated hydrocarbon derivatives e.g., 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, etc.
  • ketone compound examples include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
  • Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd. is also suitably used.
  • a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used as the photoradical polymerization initiator. 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 be used, the content of which is herein incorporated by reference. Incorporated.
  • ⁇ -hydroxyketone initiators examples include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DA ROCUR 1173, IRGACURE 500, IRGACURE -2959 and IRGACURE 127 (manufactured by BASF) can be used.
  • ⁇ -aminoketone initiators examples include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369. , and IRGACURE 379 (manufactured by BASF) can be used.
  • aminoacetophenone initiator the acylphosphine oxide initiator, and the metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021/112189 can also be suitably used. This content is incorporated herein.
  • photoradical polymerization initiator include oxime compounds.
  • an oxime compound By using an oxime compound, it becomes possible to improve exposure latitude more effectively.
  • Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.
  • oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A 2000-080068, compounds described in JP-A 2006-342166, J. C. S. Perkin II (1979, pp. 1653-1660); C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000-0 Compounds described in Publication No. 66385, Compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Patent No. 6065596, compounds described in International Publication No. 2015/152153, International Publication No.
  • Preferred oxime compounds include, for example, compounds with the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy( imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino)) -1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, etc.
  • an oxime compound as a photoradical polymerization initiator.
  • oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF), ADEKA Optomer N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-open No. 2012-014052).
  • Photoradical polymerization initiator 2 described in the publication, TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), Adeka Arcles NCI-730, NCI-831, and Adeka Arcles NCI- 930 (manufactured by ADEKA Co., Ltd.), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Moreover, oxime compounds having the following structures can also be used.
  • Examples of the photoradical polymerization initiator include oxime compounds having a fluorene ring described in paragraphs 0169 to 0171 of International Publication No. 2021/112189, and oximes having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring.
  • Compounds, oxime compounds having a fluorine atom can also be used.
  • an oxime compound having a nitro group, an oxime compound having a benzofuran skeleton, and an oxime compound having a substituent having a hydroxy group bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of International Publication No. 2021/020359 may be used. You can also do it. Their contents are incorporated herein.
  • oxime compound OX an oxime compound having an aromatic ring group Ar OX1 (hereinafter also referred to as oxime compound OX) in which an electron-withdrawing group is introduced into the aromatic ring.
  • Examples of the electron-withdrawing group possessed by the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group,
  • An acyl group and a nitro group are preferred, an acyl group is more preferred because a film with excellent light resistance can be easily formed, and a benzoyl group is even more preferred.
  • the benzoyl group may have a substituent.
  • substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, and more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group. More preferably, it is a sulfanyl group or an amino group.
  • the oxime compound OX is preferably at least one selected from a compound represented by formula (OX1) and a compound represented by formula (OX2), and more preferably a compound represented by formula (OX2). preferable.
  • R X3 to R X14 each independently represent a hydrogen atom or a substituent. However, at least one of R X10 to R X14 is an electron-withdrawing group.
  • R X12 is preferably an electron-withdrawing group
  • R X10 , R X11 , R X13 , and R X14 are preferably hydrogen atoms.
  • oxime compound OX examples include compounds described in paragraph numbers 0083 to 0105 of Japanese Patent No. 4,600,600, the contents of which are incorporated herein.
  • Particularly preferable oxime compounds include oxime compounds having a specific substituent group as shown in JP-A No. 2007-269779, and oxime compounds having a thioaryl group as shown in JP-A No. 2009-191061. Incorporated herein.
  • photoradical polymerization initiators include trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triaryl compounds. selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.
  • Compounds such as
  • the photoradical polymerization initiator is a trihalomethyltriazine compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, an acetophenone compound, At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferred, and metallocene compounds or oxime compounds are even more preferred.
  • a difunctional, trifunctional or more functional photoradical polymerization initiator may be used as the photoradical polymerization initiator.
  • a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained.
  • the crystallinity decreases and the solubility in solvents improves, making it difficult to precipitate over time, thereby improving the stability of the resin composition over time.
  • Specific examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include those listed in Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
  • the resin composition contains a photopolymerization initiator
  • its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and 0.5% by mass based on the total solid content of the resin composition. It is more preferably from 1.0 to 10% by weight, and even more preferably from 1.0 to 10% by weight.
  • the photopolymerization initiator may contain only one type, or may contain two or more types. When containing two or more types of photopolymerization initiators, it is preferable that the total amount is within the above range. Note that since the photopolymerization initiator may also function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further promoted by heating with an oven, a hot plate, or the like.
  • the resin composition may contain a sensitizer.
  • the sensitizer absorbs specific actinic radiation and becomes electronically excited.
  • the sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and effects such as electron transfer, energy transfer, and heat generation occur.
  • the thermal radical polymerization initiator and the photo radical polymerization initiator undergo a chemical change and are decomposed to generate radicals, acids, or bases.
  • Usable sensitizers include benzophenone series, Michler's ketone series, coumarin series, pyrazole azo series, anilinoazo series, triphenylmethane series, anthraquinone series, anthracene series, anthrapyridone series, benzylidene series, oxonol series, and pyrazolotriazole azo series.
  • pyridone azo type cyanine type, phenothiazine type, pyrrolopyrazole azomethine type, xanthene type, phthalocyanine type, penzopyran type, indigo type and the like can be used.
  • sensitizer examples include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl Denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso Naphthothiazole, 1,3-
  • the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. More preferably 0.5 to 10% by mass.
  • the sensitizers may be used alone or in combination of two or more.
  • the 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), pages 683-684.
  • Examples of chain transfer agents include compounds having -S-S-, -SO 2 -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and RAFT (Reversible Addition Fragmentation chain Transfer).
  • Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used in polymerization are used. These can generate radicals by donating hydrogen to low-activity radicals, or can generate radicals by being oxidized and then deprotonated.
  • thiol compounds can be preferably used.
  • the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, and 0.1 to 10 parts by mass based on 100 parts by mass of the total solid content of the resin composition. More preferably, 0.5 to 5 parts by mass is even more preferred.
  • the number of chain transfer agents may be one, or two or more. When there are two or more types of chain transfer agents, it is preferable that the total is within the above range.
  • the resin composition of the present invention may also contain a base generator.
  • the base generator is a compound that can generate a base by physical or chemical action.
  • Preferred base generators include thermal base generators and photobase generators.
  • the resin composition contains a base generator.
  • the resin composition contains a thermal base generator, the cyclization reaction of the precursor can be promoted by heating, for example, and the cured product has good mechanical properties and chemical resistance. The performance as an interlayer insulating film for wiring layers is improved.
  • the base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
  • the base generator is not particularly limited, and any known base generator can be used.
  • Known base generators include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amine imides. compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, ⁇ -lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like.
  • Specific examples of nonionic base generators include compounds described in paragraphs 0249 to 0275 of International Publication No. 2022/145355. The above description is incorporated herein.
  • Examples of the base generator include, but are not limited to, the following compounds.
  • the molecular weight of the nonionic base 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.
  • Specific preferred compounds of the ionic base generator include, for example, the compounds described in paragraph numbers 0148 to 0163 of International Publication No. 2018/038002.
  • ammonium salts include, but are not limited to, the following compounds.
  • iminium salts include, but are not limited to, the following compounds.
  • the content of the base generator is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the resin in the resin composition.
  • the lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
  • the upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.
  • One type or two or more types of base generators can be used. When two or more types are used, the total amount is preferably within the above range.
  • the resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent.
  • the solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
  • esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone.
  • alkyloxyacetates e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate) , methyl ethoxy acetate, ethyl ethoxy acetate, etc.
  • 3-alkyloxypropionate alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • alkyl 2-alkyloxypropionate esters e.g., methyl 2-alkyloxypropionate, 2-alkyloxypropionate
  • propyl 2-alkyloxypropionate etc.
  • Methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
  • Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred. It is mentioned as something.
  • ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol Suitable examples include monobutyl ether acetate
  • Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone, and the like.
  • Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.
  • Suitable examples of sulfoxides include dimethyl sulfoxide.
  • Amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, Preferred examples include 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.
  • Suitable ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.
  • Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
  • solvent selected from methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more types is preferable.
  • Particularly preferred is the combination of amide, ⁇ -butyrolactone and dimethyl sulfoxide, or the combination of N-methyl-2-pyrrolidone and ethyl lactate.
  • toluene is further added to the solvent used in combination in an amount of about 1 to 10% by mass based on the total mass of the solvent.
  • an embodiment containing ⁇ -valerolactone as a solvent is also one of the preferred embodiments of the present invention.
  • the content of ⁇ -valerolactone based on the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more. preferable.
  • the upper limit of the content is not particularly limited and may be 100% by mass. The above content may be determined in consideration of the solubility of components such as the specific resin contained in the resin composition.
  • dimethyl sulfoxide and ⁇ -valerolactone when dimethyl sulfoxide and ⁇ -valerolactone are used together, it is preferable to contain 60 to 90% by mass of ⁇ -valerolactone and 10 to 40% by mass of dimethyl sulfoxide, based on the total mass of the solvent. It is more preferable to contain ⁇ 90% by mass of ⁇ -valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and more preferably to contain 75 to 85% by mass of ⁇ -valerolactone and 15 to 25% by mass of dimethyl sulfoxide. More preferred.
  • the content of the solvent is preferably such that the total solids concentration of the resin composition of the present invention is 5 to 80% by mass, and preferably 5 to 75% by mass. More preferably, the amount is 10 to 70% by mass, and even more preferably 20 to 70% by mass.
  • the solvent content may be adjusted depending on the desired thickness of the coating and the application method. When two or more types of solvents are contained, it is preferable that the total amount is within the above range.
  • the resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used for electrodes, wiring, etc.
  • metal adhesion improvers include silane coupling agents having alkoxysilyl groups, aluminum adhesion aids, titanium adhesion aids, compounds having a sulfonamide structure and thiourea structure, phosphoric acid derivative compounds, and ⁇ -keto esters. compounds, amino compounds, etc.
  • silane coupling agent examples include the compounds described in paragraph 0316 of International Publication No. 2021/112189 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573, the contents of which are not included herein. Incorporated. 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. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group and Et represents an ethyl group. Further, the following R includes a structure derived from a blocking agent in a blocked isocyanate group.
  • the blocking agent may be selected depending on the desorption temperature, and includes alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, active methylene compounds, and the like. For example, from the viewpoint of desiring a desorption temperature of 160 to 180°C, caprolactam and the like are preferred. Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • silane coupling agents examples include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane.
  • an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent.
  • examples of such oligomer type compounds include compounds containing a repeating unit represented by the following formula (S-1).
  • R S1 represents a monovalent organic group
  • R S2 represents a hydrogen atom, a hydroxy group, or an alkoxy group
  • n represents an integer of 0 to 2.
  • R S1 preferably has a structure containing a polymerizable group.
  • Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinyl phenyl group, etc.), and a (meth)acrylamide group.
  • R S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
  • n represents an integer from 0 to 2, preferably 1.
  • n is 1 or 2 in at least one of the plurality of repeating units represented by formula (S-1) contained in the oligomer type compound, and n is 1 or 2 in at least two. More preferably, n is 2, and even more preferably n is 1 in at least two cases.
  • Commercially available products can be used as such oligomer type compounds, and examples of commercially available products include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Aluminum-based adhesion aid examples include aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.
  • the content of the metal adhesion improver is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the specific resin.
  • the content of the metal adhesion improver is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the specific resin.
  • the resin composition of the present invention further contains a migration inhibitor.
  • a migration inhibitor for example, when a resin composition is applied to a metal layer (or metal wiring) to form a film, metal ions derived from the metal layer (or metal wiring) may migrate into the film. can be effectively suppressed.
  • Migration inhibitors are not particularly limited, but include heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring) , pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenol type compounds, salicylic acid derivative compounds, and hydrazide derivative compounds.
  • heterocycles pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole
  • triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
  • the resin composition of the present invention contains an azole compound.
  • An azole compound is a compound containing an azole structure, and an azole structure refers to a 5-membered ring structure containing a nitrogen atom as a ring member, and may be a 5-membered ring structure containing 2 or more nitrogen atoms as a ring member.
  • examples of the azole structure include an imidazole structure, a triazole structure, and a tetrazole structure. These structures may form a polycyclic ring by condensation with other ring structures, such as benzimidazole and benzotriazole.
  • a compound in which a group represented by the following formula (R-1) or the following formula (R-2) is directly bonded to the azole structure is also preferable.
  • R 1 represents a monovalent organic group
  • * represents a bonding site with an azole structure.
  • R-2 represents a hydrogen atom or a monovalent organic group
  • R 3 represents a monovalent organic group
  • * represents a bonding site with an azole structure.
  • a group represented by a bond with at least one group selected from the group consisting of - is preferable.
  • R N is as described above.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. Further, the total number of carbon atoms in R 1 is preferably 1 to 30, preferably 2 to 25, and more preferably 3 to 20.
  • the bonding site in R 1 with the carbonyl group in formula (R-1) is preferably a hydrocarbon group or -NR N -.
  • R 2 is preferably a hydrogen atom.
  • R 2 is a monovalent organic group
  • R N is as described above.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof.
  • R 2 when R 2 is a monovalent organic group, the total number of carbon atoms is preferably 1 to 30, preferably 2 to 25, and more preferably 3 to 20.
  • a group represented by a bond with at least one group selected from the group consisting of - is preferable.
  • R N is as described above.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. Further, when R 3 is a monovalent organic group, the total number of carbon atoms is preferably 1 to 30, preferably 2 to 25, and more preferably 3 to 20.
  • * represents a bonding site with an azole structure, and is preferably a bonding site with a carbon atom that is a ring member of the azole structure.
  • an ion trapping agent that traps anions such as halogen ions can also be used.
  • Other migration inhibitors include the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and the compounds described in JP-A-2011-059656.
  • Compounds described in paragraph 0052, compounds described in paragraphs 0114, 0116, and 0118 of JP 2012-194520, compounds described in paragraph 0166 of WO 2015/199219, etc. can be used, and the contents thereof is incorporated herein.
  • migration inhibitors include the following compounds.
  • the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, and 0.01 to 5.0% by mass based on the total solid content of the resin composition.
  • the amount is more preferably 0.05 to 2.0% by weight, and even more preferably 0.1 to 1.0% by weight.
  • Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more types of migration inhibitors, it is preferable that the total is within the above range.
  • the resin composition of the present invention preferably further contains the above-mentioned azole compound and the above-mentioned silane coupling agent from the viewpoint of improving the adhesion to the base material.
  • the adhesiveness with the base material is easily maintained even after the cured product is exposed to high temperature and high humidity conditions.
  • the resin composition of the present invention contains a polymerization inhibitor.
  • the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.
  • Specific compounds of the polymerization inhibitor include the compound described in paragraph 0310 of International Publication No. 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1- Examples include oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, and the like. This content is incorporated herein.
  • the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, and 0.02 to 20% by mass based on the total solid content of the resin composition.
  • the content is more preferably 15% by mass, and even more preferably 0.05 to 10% by mass.
  • Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more types of polymerization inhibitors, it is preferable that the total is within the above range.
  • the resin composition of the present invention contains a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure.
  • Whether or not a certain compound a contained in the resin composition corresponds to a light absorber can be determined by the following method. First, a solution of compound a with the same concentration as that contained in the resin composition is prepared, and the molar extinction coefficient (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 , also referred to as “molar extinction coefficient 1”) of compound a at the wavelength of exposure light is determined. ). The above measurement is performed quickly so as to minimize the influence of changes such as a decrease in the molar extinction coefficient of compound a.
  • the solvent in the above solution when the resin composition contains a solvent, that solvent is used, and when the resin composition does not contain a solvent, N-methyl-2-pyrrolidone is used.
  • the solution of compound a is irradiated with exposure light.
  • the exposure amount is 500 mJ as an integrated amount for 1 mol of compound a.
  • the molar extinction coefficient (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 , also referred to as “molar extinction coefficient 2”) of compound a at the wavelength of the exposure light is measured.
  • the attenuation rate is preferably 10% or more, more preferably 20% or more.
  • the lower limit of the above-mentioned attenuation rate is not particularly limited, and may be 0% or more.
  • the wavelength of the exposure light may be any wavelength at which the photosensitive film is exposed. Further, the wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition is sensitive.
  • a photopolymerization initiator having sensitivity to a certain wavelength means that a polymerization initiation species is generated when the photopolymerization initiator is exposed to light at a certain wavelength.
  • the wavelength of the exposure light is (1) semiconductor laser (wavelength: 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, G-line (wavelength 436nm), H-line (wavelength 405nm), I-line (wavelength 365nm), Broad (3 wavelengths of g, h, i-line), (4) Excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer Laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) Extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) Electron beam, (7) YAG laser second harmonic 532 nm, third harmonic Examples include 355 nm.
  • the wavelength of the exposure light may be selected, for example, from a wavelength to which the photopolymerization initiator is sensitive, preferably the h-line (wavelength: 405 nm) or the i-line (wavelength: 365 nm), and more preferably the i-line (wavelength: 365 nm).
  • the light absorber may be a compound that generates radical polymerization initiation species upon exposure to light, but from the viewpoint of resolution and chemical resistance, it is preferably a compound that does not generate radical polymerization initiation species upon exposure. Whether the light absorber is a compound that generates radical polymerization initiating species upon exposure to light is determined by the following method. A solution containing a light absorber and a radical crosslinking agent at the same concentration as that contained in the resin composition is prepared. When the resin composition contains a radical crosslinking agent, the same compound as the radical crosslinking agent contained in the resin composition is used at the same concentration as the radical crosslinking agent in the solution.
  • the resin composition does not contain a radical crosslinker, methyl methacrylate is used at a concentration five times that of the light absorber. After that, exposure light is irradiated. The exposure amount is 500 mJ as an integrated amount.
  • the polymerization of the polymerizable compound is determined by, for example, high performance liquid chromatography, and if the ratio of the molar amount of the polymerizable compound to the total molar amount of the polymerizable compound is 10% or less, the light absorber is It is determined that the compound does not generate radical polymerization initiation species upon exposure to light.
  • the molar amount ratio is preferably 5% or less, more preferably 3% or less.
  • the lower limit of the above molar amount ratio is not particularly limited, and may be 0%.
  • the wavelength of the exposure light may be any wavelength at which the photosensitive film is exposed. Further, the wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition is sensitive.
  • Examples of the compound that generates a radical polymerization initiator upon exposure to light include the same compounds as the above-mentioned photoradical polymerization initiators.
  • the composition contains a photoradical polymerization initiator as a light absorber
  • the one having the lowest polymerization initiating ability of the generated radical species is the light absorber
  • the others are the photopolymerization initiators.
  • Examples of compounds that do not generate radical polymerization initiation species upon exposure include photoacid generators, photobase generators, and dyes whose absorption wavelength changes upon exposure.
  • the light absorber is preferably a naphthoquinone diazide compound or a dye whose absorbance changes upon exposure, and more preferably a naphthoquinone diazide compound. It is also conceivable to use, as a light absorber, a combination of, for example, a photoacid generator or a photobase generator and a compound whose absorbance at the exposure wavelength decreases depending on the pH.
  • Naphthoquinonediazide compound examples include compounds that produce indenecarboxylic acid upon exposure and have a low absorbance at the exposure wavelength, and compounds having a 1,2-naphthoquinonediazide structure are preferred.
  • the naphthoquinone diazide compound is preferably a naphthoquinone diazide sulfonic acid ester of a hydroxy compound.
  • compounds represented by any of the following formulas (H1) to (H6) are preferred.
  • R 1 and R 2 each independently represent a monovalent organic group
  • R 3 and R 4 each independently represent a hydrogen atom or a monovalent organic group
  • n1, n2, m1 and m2 are each independently an integer of 0 to 5
  • at least one of m1 and m2 is an integer of 1 to 5.
  • Z represents a tetravalent organic group
  • L 1 , L 2 , L 3 and L 4 each independently represent a single bond or a divalent organic group
  • R 5 , R 6 , R 7 and R8 each independently represent a monovalent organic group
  • n3, n4, n5 and n6 each independently represent an integer of 0 to 3
  • m3, m4, m5 and m6 each independently represent 0 ⁇ 2, and at least one of m3, m4, m5, and m6 is 1 or 2.
  • R 9 and R 10 each independently represent a hydrogen atom or a monovalent organic group
  • L 5 each independently represents a divalent organic group
  • n7 represents an integer from 3 to 8. represent.
  • L 6 represents a divalent organic group
  • L 7 and L 8 each independently represent a divalent organic group containing an aliphatic tertiary or quaternary carbon.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 each independently represent a hydrogen atom, a halogen atom or a monovalent organic represents a group
  • L 9 , L 10 and L 11 each independently represent a single bond or a divalent organic group
  • m7, m8, m9, m10 each independently represent an integer from 0 to 2, m7, At least one of m8, m9, and m10 is 1 or 2.
  • R 42 , R 43 , R 44 , and R 45 each independently represent a hydrogen atom or a monovalent organic group
  • R 46 and R 47 each independently represent a monovalent organic group.
  • n16 and n17 each independently represent an integer from 0 to 4
  • m11 and m12 each independently represent an integer from 0 to 4
  • at least one of m11 and m12 is an integer from 1 to 4. be.
  • R 1 and R 2 are each independently preferably a monovalent organic group having 1 to 60 carbon atoms, more preferably a monovalent organic group having 1 to 30 carbon atoms.
  • Examples of the monovalent organic group in R 1 and R 2 include a hydrocarbon group that may have a substituent, such as an aromatic hydrocarbon group that may have a substituent such as a hydroxy group. Can be mentioned.
  • R 3 and R 4 are each independently preferably a monovalent organic group having 1 to 60 carbon atoms, more preferably a monovalent organic group having 1 to 30 carbon atoms. .
  • Examples of the monovalent organic group in R 3 and R 4 include a hydrocarbon group that may have a substituent, such as a hydrocarbon group that may have a substituent such as a hydroxy group.
  • n1 and n2 are each independently preferably 0 or 1, and more preferably 0.
  • m1 and m2 are preferably both 1.
  • the compound represented by formula (H1) is preferably a compound represented by any one of formulas (H1-1) to (H1-5).
  • R 21 , R 22 and R 23 each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and hydrogen An atom or a group represented by the following formula (R-1) is more preferable.
  • R 29 represents a hydrogen atom, an alkyl group, or an alkoxy group
  • n13 represents an integer of 0 to 2
  • * represents a bonding site with another structure.
  • n8, n9 and n10 each independently represent an integer of 0 to 2, preferably 0 or 1.
  • R 24 represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • n14, n15 and n16 each independently represent an integer from 0 to 2.
  • R 30 represents a hydrogen atom or an alkyl group.
  • R 25 , R 26 , R 27 and R 28 each independently represent a monovalent organic group, and are represented by a hydrogen atom, an alkyl group, or the above formula (R-1). It is preferable that it is a group.
  • n11, n12 and n13 each independently represent an integer of 0 to 2, preferably 0 or 1.
  • the compound represented by formula (H1-1) is preferably a compound represented by any one of the following formulas (H1-1-1) to (H1-1-4).
  • the compound represented by the formula (H1-2) is preferably a compound represented by the following formula (H1-2-1) or (H1-2-2).
  • Z is preferably a tetravalent group having 1 to 20 carbon atoms, and more preferably a group represented by any of the following formulas (Z-1) to (Z-4).
  • * represents a bonding site with another structure.
  • L 1 , L 2 , L 3 and L 4 are preferably each independently a single bond or a methylene group.
  • R 5 , R 6 , R 7 and R 8 are each independently preferably an organic group having 1 to 30 carbon atoms.
  • n3, n4, n5 and n6 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.
  • m3, m4, m5 and m6 are each independently preferably 1 or 2, more preferably 1.
  • Examples of the compound represented by formula (H2) include compounds having the following structure.
  • R 9 and R 10 each independently preferably represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • each L 5 is preferably independently a group represented by the following formula (L-1).
  • R 30 represents a monovalent organic group having 1 to 20 carbon atoms
  • n14 represents an integer of 1 to 5
  • * represents a bonding site with another structure.
  • n7 is preferably an integer of 4 to 6. Examples of the compound represented by formula (H3) include the following compounds.
  • each n independently represents an integer of 0 to 9.
  • L 7 and L 8 are each independently preferably a divalent organic group having 2 to 20 carbon atoms. Examples of the compound represented by formula (H4) include the following compounds.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl , an alkoxy group, an allyl group or an acyl group.
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group
  • R 34 , R 35 , R 36 and R 37 each independently represents a hydrogen atom or an alkyl group
  • n15 is an integer of 1 to 5
  • R 38 , R 39 , R 40 and R 41 each independently represent a hydrogen atom or an alkyl group
  • Examples of the compound represented by formula (H5) include the following compounds.
  • R 42 , R 43 , R 44 , and R 45 each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. , a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • R 46 and R 47 are each independently preferably an alkyl group, an alkoxy group, or an aryl group, and more preferably an alkyl group.
  • n16 and n17 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.
  • n16 and n17 are each independently preferably an integer of 1 to 3, more preferably 2 or 3. Examples of the compound represented by formula (H6) include the following compounds.
  • hydroxy compounds include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'- Methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,4,6,3',4'-pentahydroxybenzophenone, 2,3, 4,2',4'-pentahydroxybenzophenone, 2,3,4,2',5'-pentahydroxybenzophenone, 2,4,6,3',4',5'-hexahydroxybenzophenone, 2,3 , 4,3',4',5'-hexahydroxybenzophenone and other polyhydroxybenzophenones; Polyhydroxyphenylalkyl ketones such as 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyphenylpentyl ketone, 2,3,4-trihydroxyphenylhexyl ketone, Bis(
  • polyhydroxybiphenyls Bis(polyhydroxy) sulfides such as 4,4'-thiobis(1,3-dihydroxy)benzene, Bis(polyhydroxyphenyl) ethers such as 2,2',4,4'-tetrahydroxydiphenyl ether, Bis(polyhydroxyphenyl) sulfoxides such as 2,2',4,4'-tetrahydroxydiphenyl sulfoxide, Bis(polyhydroxyphenyl)sulfones such as 2,2',4,4'-diphenylsulfone, Tris(4-hydroxyphenyl)methane, 4,4',4''-trihydroxy-3,5,3',5'-tetramethyltriphenylmethane, 4,4',3'',4''-tetrahydroxy- 3,5,3',5'-tetramethyltriphenylmethane, 4-[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]-2-methoxy-phenol, 4,
  • JP-A-4-253058 Polyhydroxy compounds described in JP-A-5-224410, such as ⁇ , ⁇ , ⁇ ′, ⁇ ′, ⁇ ′′, ⁇ ′′-hexakis-(4-hydroxyphenyl)-1,3,5-triethylbenzene, etc. JP-A-5-303200, EP-530148 of polyhydroxy compounds, 1,2,2,3-tetra(p-hydroxyphenyl)propane, 1,3,3,5-tetra(p-hydroxyphenyl)pentane, etc.
  • naphthoquinone diazide sulfonic acid examples include 6-diazo 5,6-dihydro-5-oxo-1-naphthalene sulfonic acid, 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid, and mixtures thereof. It may also be used as
  • the method for producing naphthoquinonediazide sulfonyl ester of a hydroxy compound is not particularly limited, but for example, naphthoquinonediazide sulfonic acid is converted into a sulfonyl chloride with chlorosulfonic acid or thionyl chloride, and the resulting naphthoquinonediazide sulfonyl chloride is condensed with a hydroxy compound. Obtained by reaction.
  • esterification is performed by reacting a predetermined amount of a hydroxy compound and naphthoquinonediazide sulfonyl chloride in a solvent such as dioxane, acetone, or tetrahydrofuran in the presence of a basic catalyst such as triethylamine, and the resulting product is washed with water. , can be obtained by drying.
  • a solvent such as dioxane, acetone, or tetrahydrofuran
  • a basic catalyst such as triethylamine
  • the esterification rate of the naphthoquinonediazide sulfonic acid ester is not particularly limited, but is preferably 10% or more, more preferably 20% or more. Further, the upper limit of the esterification rate is not particularly limited, and may be 100%. The esterification rate can be confirmed by 1 H-NMR or the like as the proportion of esterified groups among the hydroxy groups of the hydroxy compound.
  • the resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, etc., as long as the effects of the present invention can be obtained.
  • additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, etc.
  • properties such as film physical properties can be adjusted.
  • inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
  • the average particle diameter of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, even more preferably 0.03 to 1.0 ⁇ m, and particularly preferably 0.04 to 0.5 ⁇ m. .
  • the above average particle diameter of the inorganic particles is a primary particle diameter and a volume average particle diameter.
  • the volume average particle diameter can be measured, for example, by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, measurement can also be performed by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method.
  • organic titanium compounds examples include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organic titanium compounds are shown in I) to VII) below:
  • I) Titanium chelate compound A titanium chelate compound having two or more alkoxy groups is more preferred because the resin composition has good storage stability and a good curing pattern can be obtained. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate).
  • Tetraalkoxytitanium compounds for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , titanium tetramethoxypropoxide, titanium tetramethyl phenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis ⁇ 2,2-(allyloxymethyl)] butoxide ⁇ ], etc.
  • Titanocene compounds for example, pentamethylcyclopentadienyl titanium trimethoxide, bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis( ⁇ 5-2, 4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.
  • Monoalkoxytitanium compounds For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and the like.
  • Titanium oxide compound For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.
  • the organic titanium compound is at least one compound selected from the group consisting of the above I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. It is preferable that there be.
  • titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H -pyrrol-1-yl)phenyl)titanium is preferred.
  • an organic titanium compound When an organic titanium compound is included, its content is preferably 0.05 to 10 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the specific resin. When the content is 0.05 parts by mass or more, the resulting cured pattern has better heat resistance and chemical resistance, and when the content is 10 parts by mass or less, the storage stability of the composition is better.
  • These other additives include compounds described in paragraphs 0316 to 0358 of WO 2022/145355. The above description is incorporated herein.
  • the viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition.
  • it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and 2,500 mm 2 /s to 8,000 mm. 2 /s is more preferable.
  • it becomes easy to obtain a coating film with high uniformity. If it is 1,000 mm 2 /s or more, it is easy to coat with the thickness required for example as an insulating film for rewiring, and if it is 12,000 mm 2 /s or less, the coating surface quality is excellent. A coating film is obtained.
  • the water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition will improve.
  • Methods for maintaining the moisture content include adjusting the humidity during storage conditions and reducing the porosity of the storage container during storage.
  • the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulation.
  • metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals included as complexes of organic compounds and metals are excluded. When a plurality of metals are included, the total of these metals is preferably within the above range.
  • a method for reducing metal impurities that is unintentionally included in the resin composition of the present invention is to select a raw material with a low metal content as a raw material constituting the resin composition of the present invention.
  • Methods include filtering the raw materials constituting the product, lining the inside of the apparatus with polytetrafluoroethylene, etc., and performing distillation under conditions that suppress contamination as much as possible.
  • the resin composition of the present invention has a halogen atom content of preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably less than 200 mass ppm from the viewpoint of wiring corrosion. is even more preferable.
  • those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
  • the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atoms and bromine atoms, or the total of chlorine ions and bromine ions, is each within the above range.
  • Preferred methods for adjusting the content of halogen atoms include ion exchange treatment.
  • the storage container may be a multilayer bottle whose inner wall is made of 6 types of 6 layers of resin, or a container with 7 layers of 6 types of resin. It is also preferred to use structured bottles. Examples of such a container include the container described in JP-A No. 2015-123351.
  • a cured product of the resin composition By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.
  • the cured product of the present invention is a cured product obtained by curing a resin composition.
  • the resin composition is preferably cured by heating, and the heating temperature is more preferably 120°C to 400°C, even more preferably 140°C to 380°C, and particularly preferably 170°C to 350°C.
  • the form of the cured product of the resin composition is not particularly limited, and can be selected depending on the purpose, such as film, rod, sphere, or pellet form. In the present invention, the cured product is preferably in the form of a film.
  • the thickness of the cured product is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
  • the shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
  • the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.
  • the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
  • the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.
  • the resin composition of the present invention can be prepared by mixing the above components.
  • the mixing method is not particularly limited and can be performed by a conventionally known method. Examples of the mixing method include mixing using a stirring blade, mixing using a ball mill, and mixing using a rotating tank.
  • the temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.
  • the filter pore diameter is, for example, preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, even 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. When the material of the filter is polyethylene, it is more preferably HDPE (high density polyethylene).
  • the filter may be washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using multiple types of filters, filters with different pore sizes or materials may be used in combination.
  • connection mode examples include a mode in which an HDPE filter with a pore diameter of 1 ⁇ m is connected in series as the first stage and an HDPE filter with a pore diameter of 0.2 ⁇ m as the second stage. Additionally, various materials may be filtered multiple times. When filtration is performed multiple times, circulation filtration may be used. Alternatively, filtration may be performed under pressure.
  • the pressure to be applied is preferably, for example, 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, still more preferably 0.05 MPa or more and 0.7 MPa or less, and 0.01 MPa or more and 0.9 MPa or less, still more preferably 0.05 MPa or more and 0.7 MPa or less, and 0.01 MPa or more and 0.9 MPa or less, for example. Even more preferably 0.05 MPa or more and 0.5 MPa or less.
  • impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined.
  • a known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtration using a filter, the resin composition filled in the bottle may be placed under reduced pressure and degassed.
  • the method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition onto a base material to form a film.
  • the method for producing a cured product includes the above film forming step, an exposure step of selectively exposing the film formed in the film forming step, and developing the film exposed in the exposure step using a developer to form a pattern. It is more preferable to include a developing step.
  • the method for producing a cured product includes the film formation step, the exposure step, the development step, a heating step of heating the pattern obtained in the development step, and a post-development exposure step of exposing the pattern obtained in the development step. It is particularly preferable to include at least one of them.
  • the method for producing a cured product includes the above-mentioned film forming step and the step of heating the above-mentioned film. The details of each step will be explained below.
  • the resin composition of the present invention can be used in a film forming step in which a film is formed by applying it on a substrate.
  • the method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition onto a base material to form a film.
  • the type of base material can be appropriately determined depending on the purpose and is not particularly limited.
  • the base material include semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposited films, magnetic films, reflective films, Ni, Cu,
  • a metal base material such as Cr or Fe (for example, a base material formed from a metal or a base material on which a metal layer is formed by, for example, plating or vapor deposition), paper, SOG (Spin On Examples include glass), TFT (thin film transistor) array substrates, mold substrates, and electrode plates for plasma display panels (PDP).
  • the base material is particularly preferably a semiconductor production base material, and more preferably a silicon base material, a Cu base material, and a mold base material. These base materials may be provided with a layer such as an adhesive layer or an oxidized layer made of hexamethyldisilazane (HMDS) or the like on the surface.
  • the shape of the base material is not particularly limited, and may be circular or rectangular. As for the size of the base material, if it is circular, the diameter is preferably 100 to 450 mm, more preferably 200 to 450 mm. If it is rectangular, the length of the short side is preferably 100 to 1000 mm, more preferably 200 to 700 mm.
  • a plate-shaped, preferably panel-shaped base material (substrate) is used as the base material.
  • the resin layer or metal layer serves as the base material.
  • Coating is preferred as a means for applying the resin composition onto the substrate.
  • the methods to be applied include dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, Examples include inkjet method. From the viewpoint of uniformity of film thickness, spin coating method, slit coating method, spray coating method, or inkjet method is preferable, and from the viewpoint of uniformity of film thickness and productivity, spin coating method and slit coating method are preferable. A coating method is more preferred. A film with a desired thickness can be obtained by adjusting the solid content concentration and application conditions of the resin composition depending on the means to be applied.
  • the coating method can be appropriately selected depending on the shape of the substrate, and for circular substrates such as wafers, spin coating, spray coating, inkjet methods, etc. are preferable, and for rectangular substrates, slit coating, spray coating, etc. method, inkjet method, etc. are preferred.
  • spin coating it can be applied, for example, at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. It is also possible to apply a method in which a coating film that has been previously formed on a temporary support by the above-mentioned application method is transferred onto a base material.
  • the transfer method the production method described in paragraphs 0023, 0036 to 0051 of JP-A No.
  • 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used. Further, a step of removing excess film may be performed at the end of the base material. Examples of such processes include edge bead rinsing (EBR), back rinsing, and the like.
  • EBR edge bead rinsing
  • a pre-wet process may be employed in which various solvents are applied to the base material before the resin composition is applied to the base material to improve the wettability of the base material, and then the resin composition is applied.
  • the film may be subjected to a step of drying the formed film (layer) (drying step) in order to remove the solvent.
  • the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.
  • the drying step is preferably performed after the film forming step and before the exposure step.
  • the drying temperature of the membrane in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C.
  • drying may be performed under reduced pressure.
  • the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.
  • the film may be subjected to an exposure process that selectively exposes the film.
  • the method for producing a cured product may include an exposure step of selectively exposing the film formed in the film forming step. Selectively exposing means exposing a portion of the film. Furthermore, by selectively exposing the film, an exposed area (exposed area) and an unexposed area (unexposed area) are formed in the film.
  • the exposure amount is not particularly limited as long as it can cure the resin composition of the present invention, but for example, it is preferably 50 to 10,000 mJ/cm 2 and more preferably 200 to 8,000 mJ/cm 2 in terms of exposure energy at a wavelength of 365 nm. preferable.
  • the exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
  • the exposure wavelength is: (1) semiconductor laser (wavelength: 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, G-line (wavelength) 436 nm), h line (wavelength 405 nm), i line (wavelength 365 nm), broad (three wavelengths of g, h, i line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc.
  • semiconductor laser wavelength: 830 nm, 532 nm, 488 nm, 405 nm, 375 nm,
  • the resin composition of the present invention exposure using a high-pressure mercury lamp is particularly preferred, and from the viewpoint of exposure sensitivity, exposure using i-line is more preferred.
  • the method of exposure is not particularly limited, and may be any method as long as at least a portion of the film made of the resin composition of the present invention is exposed to light, and examples thereof include exposure using a photomask, exposure using a laser direct imaging method, etc. .
  • the film may be subjected to a heating step after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.
  • the post-exposure heating step can be performed after the exposure step and before the development step.
  • the heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.
  • the heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
  • the temperature increase rate in the post-exposure heating step is preferably 1 to 12°C/min, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min from the temperature at the start of heating to the maximum heating temperature. Further, the temperature increase rate may be changed as appropriate during heating.
  • the heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, etc. can be used. It is also preferable that the heating be performed in an atmosphere with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon.
  • the film after exposure may be subjected to a development step of developing a pattern using a developer.
  • the method for producing a cured product of the present invention may include a development step of developing the film exposed in the exposure step using a developer to form a pattern. By performing development, one of the exposed and non-exposed areas of the film is removed and a pattern is formed.
  • development in which the non-exposed areas of the film are removed in the developing step is referred to as negative development
  • development in which the exposed areas of the film are removed in the development process is referred to as positive development.
  • Examples of the developer used in the development step include an alkaline aqueous solution or a developer containing an organic solvent.
  • basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
  • TMAH tetramethylammonium hydroxide
  • potassium hydroxide sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine , dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, Butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammoni
  • the compound described in paragraph 0387 of International Publication No. 2021/112189 can be used as the organic solvent.
  • alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene glycol, etc.
  • Amides include N-methylpyrrolidone, N-ethylpyrrolidone, Dimethylformamide and the like are also suitable.
  • the developer contains an organic solvent
  • one type of organic solvent or a mixture of two or more types can be used.
  • a developer containing at least one member selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred.
  • a developer containing at least one selected from the group consisting of and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.
  • the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more. is more preferable, and particularly preferably 90% by mass or more. Moreover, the said content may be 100 mass %.
  • the developer may further contain at least one of a basic compound and a base generator.
  • the developer may further contain at least one of the basic compound and the base generator in the developer permeates into the pattern, performance such as elongation at break of the pattern may be improved.
  • an organic base is preferable from the viewpoint of reliability when remaining in the cured film (adhesion to the substrate when the cured product is further heated).
  • a basic compound having an amino group is preferable, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc.
  • a primary amine, a secondary amine, a tertiary amine or an ammonium salt is preferred, a secondary amine, a tertiary amine or an ammonium salt is more preferred, a secondary amine or a tertiary amine is even more preferred, and a tertiary amine is particularly preferred.
  • the basic compound is preferably one that does not easily remain in the cured film (obtained cured product), and from the viewpoint of promoting cyclization, it can be used by vaporization etc. It is preferable that the amount remaining is not likely to decrease before heating.
  • the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and even more preferably 100°C to 230°C at normal pressure (101,325 Pa).
  • the boiling point of the basic compound is preferably higher than the boiling point of the organic solvent contained in the developer minus 20°C, and more preferably higher than the boiling point of the organic solvent contained in the developer.
  • the basic compound used preferably has a boiling point of 80°C or higher, more preferably 100°C or higher.
  • the developer may contain only one type of basic compound, or may contain two or more types of basic compounds.
  • basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N , N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diaminopentane, N-methylhexy
  • the preferred embodiments of the base generator are the same as the preferred embodiments of the base generator contained in the above-mentioned composition.
  • the base generator is preferably a thermal base generator.
  • the content of the basic compound or base generator is preferably 10% by mass or less, and 5% by mass or less based on the total mass of the developer. More preferred.
  • the lower limit of the above content is not particularly limited, but is preferably 0.1% by mass or more, for example. If the basic compound or base generator is solid in the environment in which the developer is used, the content of the basic compound or base generator should be 70 to 100% by mass based on the total solid content of the developer. is also preferable.
  • the developer may contain only one type of at least one of a basic compound and a base generator, or may contain two or more types. When at least one of the basic compound and the base generator is two or more types, it is preferable that the total is within the above range.
  • the developer may further contain other components.
  • other components include known surfactants and known antifoaming agents.
  • the method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and methods include immersing the base material on which the film is formed in the developer, and supplying the developer to the film formed on the base material using a nozzle.
  • a method of supplying with a spray nozzle is more preferable.
  • the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied again using the straight nozzle, the base material is spun, and the developer is applied to the base material.
  • a process of removing from above may be adopted, or this process may be repeated multiple times.
  • Methods for supplying the developer in the development process include a process in which the developer is continuously supplied to the base material, a process in which the developer is kept in a substantially stationary state on the base material, and a process in which the developer is applied to the base material using ultrasonic waves. Examples include a step of vibrating with the like, and a step of combining these.
  • the development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
  • the temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.
  • the pattern may be further cleaned (rinsed) with a rinse solution.
  • a method such as supplying a rinsing liquid before the developer in contact with the pattern is completely dried may be adopted.
  • the developing solution is an alkaline aqueous solution
  • water can be used as the rinsing solution, for example.
  • the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) is used as the rinse agent. be able to.
  • Examples of the organic solvent when the rinsing liquid contains an organic solvent include the same organic solvents as those exemplified in the case where the above-mentioned developer contains an organic solvent.
  • the organic solvent contained in the rinsing liquid is preferably an organic solvent different from the organic solvent contained in the developer, and more preferably an organic solvent in which the pattern has a lower solubility than the organic solvent contained in the developer.
  • the rinsing liquid contains an organic solvent
  • the organic solvent is preferably cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and cyclohexanone or PGMEA. More preferred.
  • the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the rinsing liquid. Moreover, the organic solvent may be 100% by mass with respect to the total mass of the rinsing liquid.
  • the rinsing liquid may contain at least one of a basic compound and a base generator.
  • a basic compound and a base generator when the developer contains an organic solvent, one preferred embodiment of the present invention is an embodiment in which the rinsing solution contains the organic solvent and at least one of a basic compound and a base generator.
  • the basic compound and base generator contained in the rinsing solution include the compounds exemplified as the basic compound and base generator that may be included when the above-mentioned developer contains an organic solvent, and preferred embodiments are also included. The same is true.
  • the basic compound and base generator contained in the rinsing liquid may be selected in consideration of their solubility in the solvent in the rinsing liquid.
  • the content of the basic compound or base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the rinsing liquid. preferable.
  • the lower limit of the above content is not particularly limited, but is preferably 0.1% by mass or more, for example. If the basic compound or base generator is solid in the environment where the rinse solution is used, the content of the basic compound or base generator should be 70 to 100% by mass based on the total solid content of the rinse solution. is also preferable.
  • the rinsing liquid may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types of the basic compound and the base generator. .
  • the total is within the above range.
  • the rinse solution may further contain other components.
  • other components include known surfactants and known antifoaming agents.
  • a method of supplying the rinsing liquid using a spray nozzle is more preferable.
  • a method of supplying the rinsing liquid using a spray nozzle is more preferable.
  • the type of nozzle and examples include straight nozzles, shower nozzles, spray nozzles, and the like.
  • the rinsing step is preferably a step in which the rinsing liquid is supplied to the exposed film through a straight nozzle or continuously, and more preferably a step in which the rinsing liquid is supplied through a spray nozzle.
  • Methods for supplying the rinsing liquid in the rinsing process include a process in which the rinsing liquid is continuously supplied to the substrate, a process in which the rinsing liquid is kept almost stationary on the substrate, and a process in which the rinsing liquid is applied to the substrate by ultrasonic waves. It is possible to adopt a process of vibrating the wafer, etc., and a process of combining these.
  • the rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
  • the temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.
  • the developing step may include a step of bringing the processing solution into contact with the pattern after processing using the developer or after cleaning the pattern with a rinse solution.
  • a method may be adopted in which the processing liquid is supplied before the developing liquid or the rinsing liquid in contact with the pattern is completely dried.
  • the treatment liquid examples include a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator.
  • Preferred embodiments of the organic solvent, and at least one of the basic compound and base generator are the same as the preferred embodiments of the organic solvent, and at least one of the basic compound and base generator used in the above-mentioned rinsing liquid.
  • the method for supplying the treatment liquid to the pattern can be the same as the method for supplying the rinsing liquid described above, and the preferred embodiments are also the same.
  • the content of the basic compound or base generator in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the treatment liquid.
  • the lower limit of the content is not particularly limited, but is preferably 0.1% by mass or more, for example.
  • the content of the basic compound or base generator is 70 to 100% by mass based on the total solid content of the treatment liquid. It's also good to have one.
  • the processing liquid contains at least one of a basic compound and a base generator
  • the processing liquid may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types of the basic compound and the base generator. .
  • at least one of the basic compound and the base generator is two or more types, it is preferable that the total is within the above range.
  • the pattern obtained by the development step may be subjected to a heating step of heating the pattern obtained by the development. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the developing step. Further, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing a developing step, or a film obtained by a film forming step. In the heating step, a resin such as a polyimide precursor is cyclized to become a resin such as polyimide.
  • the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, particularly 160 to 230°C. preferable.
  • the heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor within the pattern by heating and the action of a base generated from the base generator.
  • Heating in the heating step is preferably carried out at a temperature increase rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature.
  • the temperature increase rate is 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, 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, for example, 30°C higher than the boiling point of the solvent contained in the resin composition. It is preferable to raise the temperature from a lower temperature by ⁇ 200°C.
  • the heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
  • the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher.
  • the upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.
  • Heating may be performed in stages. As an example, the temperature is raised from 25°C to 120°C at a rate of 3°C/min, held at 120°C for 60 minutes, and the temperature is raised from 120°C to 180°C at a rate of 2°C/min, and held at 180°C for 120 minutes. , etc. may be performed. It is also preferable to perform the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such pretreatment steps can improve the properties of the film. The pretreatment step is preferably carried out for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
  • the pretreatment step may be performed in two or more steps, for example, the first pretreatment step is performed at a temperature of 100 to 150°C, and then the second pretreatment step is performed at a temperature of 150 to 200°C. Good too. Furthermore, 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 with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure, from the viewpoint of preventing decomposition of the specific resin.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
  • the heating means in the heating step is not particularly limited, but includes, for example, a hot plate, an infrared oven, an electric oven, a hot air oven, an infrared oven, and the like.
  • the pattern obtained in the development process (in the case of performing a rinsing process, the pattern after rinsing) is subjected to a post-development exposure process in which the pattern after the development process is exposed to light, instead of or in addition to the above heating process.
  • the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained in the development step.
  • the method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
  • the post-development exposure step for example, the reaction of cyclization of the polyimide precursor etc.
  • the post-development exposure step can be promoted by exposure to the photobase generator.
  • the post-development exposure step at least a portion of the pattern obtained in the development step may be exposed, but it is preferable that the entire pattern be exposed.
  • the exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , more preferably 100 to 15,000 mJ/cm 2 in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive.
  • the post-development exposure step can be performed, for example, using the light source used in the above-mentioned exposure step, and it is preferable to use broadband light.
  • the pattern obtained by the development process may be subjected to a metal layer forming process of forming a metal layer on the pattern. That is, the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on the pattern obtained in the development step (preferably one that has been subjected to at least one of a heating step and a post-development exposure step). It is preferable to include.
  • metal layer existing metal species can be used without particular limitation, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. copper and aluminum are more preferred, and copper is even more preferred.
  • the method for forming the metal layer is not particularly limited, and any existing method can be applied.
  • the methods described in JP 2007-157879, JP 2001-521288, JP 2004-214501, JP 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 are used. can do.
  • photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and a combination thereof can be used.
  • a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating can be mentioned.
  • a preferred embodiment of plating includes electrolytic plating using copper sulfate or copper cyanide plating solution.
  • the thickness of the metal layer is preferably 0.01 to 50 ⁇ m, more preferably 1 to 10 ⁇ m at the thickest part.
  • Fields to which the method for producing a cured product of the present invention or the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. Other methods include forming a pattern by etching a sealing film, a substrate material (a base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above.
  • a substrate material a base film or coverlay of a flexible printed circuit board, an interlayer insulating film
  • an insulating film for mounting purposes as described above.
  • the method for producing a cured product of the present invention or the cured product of the present invention can be used for producing plates such as offset plates or screen plates, for etching molded parts, and for use in protective lacquers and dielectric layers in electronics, particularly microelectronics. It can also be used for manufacturing.
  • the laminate of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
  • the laminate is a laminate including two or more layers made of cured material, and may be a laminate in which three or more layers are laminated. At least one of the two or more layers made of the cured product contained in the laminate is a layer made of the cured product of the present invention, and shrinkage of the cured product or deformation of the cured product due to the shrinkage, etc. From the viewpoint of suppression, it is also preferable that all the layers made of the cured product contained in the above-mentioned laminate are layers made of the cured product of the present invention.
  • the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.
  • the laminate of the present invention preferably includes two or more layers made of a cured product and includes a metal layer between any of the layers made of the cured product.
  • the metal layer is preferably formed by the metal layer forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on the layer made of the cured product during the method for producing the cured product which is performed multiple times. A preferred embodiment of the metal layer forming step is as described above.
  • the resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product have the same composition. It may be a product or 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.
  • the method for manufacturing a laminate of the present invention includes a lamination step.
  • the lamination process refers to (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process and development on the surface of the pattern (resin layer) or metal layer again. This is a series of steps including performing at least one of the post-exposure steps in this order.
  • an embodiment may be adopted in which at least one of (a) the film forming step and (d) the heating step and the post-development exposure step are repeated.
  • a metal layer forming step may be included after at least one of the (d) heating step and the post-development exposure step.
  • the lamination step may further include the above-mentioned drying step and the like as appropriate.
  • a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer forming step.
  • Plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.
  • the above lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
  • the above layers may have the same composition, shape, thickness, etc., or may have different compositions, shapes, thicknesses, etc.
  • a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer.
  • the following steps are repeated in the following order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of the heating step and post-development exposure step, and (e) metal layer formation step.
  • an embodiment may be mentioned in which (a) a film forming step, (d) at least one of a heating step and a post-development exposure step, and (e) a metal layer forming step are repeated in this order.
  • the method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface activation treatment of at least a portion of the metal layer and the resin composition layer.
  • the surface activation treatment step is usually performed after the metal layer forming step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer is subjected to the surface activation treatment. After performing this step, the metal layer forming step may be performed.
  • the surface activation treatment may be performed on at least a portion of the metal layer, or may be performed on at least a portion of the resin composition layer after exposure, or the surface activation treatment may be performed on at least a portion of the metal layer and the resin composition layer after exposure.
  • the surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable that the surface activation treatment is performed on a part or all of the region of the metal layer on which the resin composition layer is to be formed.
  • the surface activation treatment is also performed on part or all of the resin composition layer (resin layer) after exposure.
  • the resin composition layer when the resin composition layer is hardened, such as when performing negative development, it is less likely to be damaged by surface treatment and adhesion is likely to be improved.
  • the surface activation treatment can be performed, for example, by the method described in paragraph 0415 of International Publication No. 2021/112189. This content is incorporated herein.
  • the present invention also discloses a semiconductor device containing the cured product or laminate of the present invention.
  • the present invention also discloses a method for manufacturing a semiconductor device, including a method for manufacturing a cured product of the present invention or a method for manufacturing a laminate.
  • a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer the descriptions in paragraphs 0213 to 0218 of JP 2016-027357A and the description in FIG. 1 can be referred to, Their contents are incorporated herein.
  • a diester of phenoxy)bis(phthalic anhydride) and glycerol dimethacrylate was produced. Then, after cooling the mixture to -10°C, 9.53 g (79.2 lmol) of thionyl chloride was added dropwise over 90 minutes and stirred for 2 hours to obtain a white precipitate of pyridinium hydrochloride. Next, 13.47 g (32.8 mmol) of 4,4'-isopropylidenebis[(4-aminophenoxy)benzene] was dissolved in 100 mL of NMP (N-methyl-2-pyrrolidone) for 2 hours. It dripped. Then 10.0 g (217 mmol) of ethanol was added and the mixture was stirred for 2 hours.
  • NMP N-methyl-2-pyrrolidone
  • the polyimide precursor resin was then precipitated in 4 liters of water and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes.
  • the polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes, filtered again, and dried at 40° C. for 2 days. Subsequently, the resin dried above was dissolved in 200 g of tetrahydrofuran, 50 g of ion exchange resin (MB-1: manufactured by Organo) was added, and the mixture was stirred for 6 hours.
  • the polyimide precursor resin was then precipitated in 4 liters of water and the water-polyimide precursor resin mixture was stirred at a speed of 500 rpm for 15 minutes.
  • a polyimide precursor resin was obtained by filtration and dried at 45° C. for 2 days under reduced pressure to obtain a polyimide precursor (SP-1).
  • the weight average molecular weight of the obtained polyimide precursor (SP-1) was 28,500, and the number average molecular weight was 10,400. Note that the proportion of polymerizable groups was 2.96 mmol/g, and the content of amide bonds was 1.46 mmol/g.
  • the polyimide precursor (SP-1) is a resin having a repeating unit represented by the following formula (SP-1). The structure of the repeating unit was determined from the 1 H-NMR spectrum.
  • Synthesis examples SP-2 to SP-15 Synthesis of polyimide precursors (SP-2) to (SP-15)]
  • Polyimide precursors (SP-2) to (SP-148) were synthesized in the same manner as polyimide precursor (SP-1), except that the carboxylic dianhydride, alcohol, and diamine used were changed as appropriate.
  • a polyimide precursor (SP-15) was synthesized in the same manner as the comparative polyimide precursor (A-1) described below, except that the carboxylic dianhydride, alcohol, and diamine used were changed as appropriate.
  • the polyimide precursors (SP-2) to (SP-15) are resins having repeating units represented by the following formulas (SP-2) to (SP-15), respectively.
  • each repeating unit was determined from the 1 H-NMR spectrum.
  • the ratios represent the molar ratios contained in each structure. Further, the weight average molecular weight and number average molecular weight of these resins are listed in the table below.
  • acetic acid manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • 2,2,6,6-tetramethylpiperidine 1-oxyl free radical manufactured by Tokyo Chemical Industry Co., Ltd. 0.03 g was weighed out, 200 mL of isopropyl alcohol (IPA) and 30 mL of pure water were added, and the mixture was stirred.
  • IPA isopropyl alcohol
  • 16.2 g of dinitro compound (A-1) was added little by little over 1 hour, and the mixture was stirred for 30 minutes.
  • the external temperature was raised to 85°C, stirred for 2 hours, cooled to 25°C or lower, and then filtered using Celite (registered trademark).
  • the filtrate was concentrated using a rotary evaporator and dissolved in 800 mL of ethyl acetate. This was transferred to a separating funnel and washed twice with 300 mL of saturated sodium bicarbonate solution, followed by 300 mL of water and 300 mL of saturated saline solution. After separation and washing, the mixture was dried over 30 g of magnesium sulfate, concentrated using an evaporator, and dried under vacuum to obtain 11.0 g of diamine (AA-1). It was confirmed from the 1 H-NMR spectrum that it was diamine (AA-1).
  • polyimide resin (PI-1)
  • the weight average molecular weight of PI-1 was 23,200, and the number average molecular weight was 12,800.
  • Polyimide (PI-1) is a resin having a repeating unit represented by the following formula (PI-1). The structure of the repeating unit was determined from the 1 H-NMR spectrum.
  • polyimide PI-2 A polyimide precursor (PI-2) was synthesized in the same manner as polyimide (PI-1), except that the carboxylic dianhydride, alcohol, and diamine used were changed as appropriate.
  • Polyimide (PI-2) is a resin having two repeating units represented by the following formula (PI-2). The structure of each repeating unit was determined from the 1 H-NMR spectrum. The subscripts in parentheses represent the molar ratio of each repeating unit. Further, the weight average molecular weight of the polyimide (PI-2) was 20,100, and the number average molecular weight was 8,900.
  • PB-1 polybenzoxazole
  • the weight average molecular weight of PB-1 was 20,400.
  • Polybenzoxazole (PB-1) is a resin having a repeating unit represented by the following formula (PB-1). The structure of the repeating unit was determined from the 1 H-NMR spectrum.
  • the resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting 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 dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and vacuum-dried to obtain a powdered comparative polyimide precursor (A-1). Obtained.
  • the weight average molecular weight (Mw) of this comparative polyimide precursor (A-1) was measured and found to be 22,600.
  • the comparative polyimide precursor (A-1) is a resin having a repeating unit represented by the following formula (A-1). The structure of the repeating unit was determined from the 1 H-NMR spectrum. The molar ratio of each repeating unit is 1:1.
  • a comparative polyimide precursor (A-2) was synthesized in the same manner as the comparative polyimide precursor (A-1), except that the carboxylic dianhydride and diamine were changed. The weight average molecular weight (Mw) of the comparative polyimide precursor (A-2) was measured and found to be 30,400. Note that the proportion of polymerizable groups was 1.90 mmol/g, and the content of amide bonds was 1.90 mmol/g.
  • Examples and comparative examples> In each Example, the components listed in the table below were mixed to obtain each resin composition. In each comparative example, the components listed in the table below were mixed to obtain comparative compositions. Specifically, the content of each component listed in the table was the amount (parts by mass) listed in the "addition amount” column in each column of the table. The obtained resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter with a pore width of 0.5 ⁇ m. Furthermore, in the table, the description "-" indicates that the composition does not contain the corresponding component.
  • ⁇ resin ⁇ - SP-1 to SP-15 Polyimide precursors (SP-1) to (SP-15) synthesized above.
  • ⁇ A-1 to A-2 Comparative polyimide precursors (A-1) to (A-2) synthesized above ⁇ PI-1 to PI-2: Polyimide (PI-1) to polyimide (PI-2) synthesized above ⁇ PB-1: Polybenzoxazole (PB-1) synthesized above ⁇ PE-1: NORYL (registered trademark) SA9000 (manufactured by Sabic)
  • DMSO/GBL dimethyl sulfoxide
  • NMP N-methylpyrrolidone
  • ⁇ I-1 N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • ⁇ I-2 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6 Ester of ',7,7'hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid
  • I-3 Synthetic product below
  • ⁇ Other additives Synthesis of diazonaphthoquinone compound I-3> 29.72 g (70 mmol) of 4,4'-(1-(2-(4hydroxyphenyl)-2-propyl)phenyl)ethylidene)bisphenol (manufactured by Honshu Chemical Industry Co., Ltd.: Tris-PA)) was placed in a flask. was added.
  • a resin composition layer was formed by applying a resin composition or a comparative composition onto a silicon wafer by a spin coating method.
  • the silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to obtain a resin composition layer with a uniform thickness of about 15 ⁇ m on the silicon wafer.
  • the entire surface of the obtained resin composition layer was exposed to i-line using a stepper (Nikon NSR 2005 i9C) at an exposure energy of 500 mJ/cm 2 .
  • the peeled cured film was punched out using a punching machine to produce a test piece with a sample width of 3 mm and a sample length of 30 mm.
  • the obtained test piece was tested using a tensile tester (Tensilon) at a crosshead speed of 300 mm/min in an environment of 25°C and 65% RH (relative humidity) in accordance with JIS-K6251.
  • the elongation at break in the longitudinal direction was measured.
  • the evaluation was performed five times each, and the arithmetic mean value of the elongation rate when the test piece broke (elongation rate at break) was used as an index value.
  • the above index values were evaluated according to the following evaluation criteria, and the evaluation results are listed in the "Elongation at Break” column of the table. It can be said that the larger the index value is, the better the film strength (elongation at break) of the resulting cured film is.
  • evaluation criteria A: The above index value was 70% or more.
  • D The above index value was less than 50%.
  • a resin composition layer was formed by applying a resin composition or a comparative composition onto a silicon wafer by a spin coating method.
  • the silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to obtain a curable resin composition layer with a uniform thickness of about 15 ⁇ m on the silicon wafer.
  • the entire surface of the obtained curable resin composition layer was exposed to i-line using a stepper (Nikon NSR 2005 i9C). The exposure amount was 400 mJ/cm 2 .
  • the curable resin composition layer (resin layer) after the above exposure is developed using the developer listed in the "Development conditions (developer)" column of the table, and the developer listed in the "Rinse solution” column of the table. Washed using the rinsing solution. Subsequently, the temperature was raised at a rate of 10°C/min in a nitrogen atmosphere, and after reaching the temperature listed in the "Temperature” column of “Curing conditions” in the table, heating was carried out for 3 hours in the table, and 25 Cooled to °C. Heating was carried out under nitrogen using a CLH-21 manufactured by Koyo.
  • the film was immersed in the mixed solution at 75°C for 15 minutes, and the film thickness before and after immersion was compared to calculate the remaining film ratio (film thickness after immersion/film thickness before immersion).
  • Residual film rate without input into high temperature and high humidity tank / Remaining film rate with input x 100 (%, ratio of residual film rate) is less than 20%, A is 20-40%, B is 40%. Those exceeding 60% were rated C, and those exceeding 60% were rated D.
  • the evaluation results are listed in the "Moisture resistance" column of the table. It can be said that the smaller the ratio of the above-mentioned residual film ratio is, the more excellent the resulting cured film is in moisture resistance.
  • Each curable resin composition or comparative composition prepared in each Example and Comparative Example 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 with a uniform thickness of 15 ⁇ m on the silicon wafer.
  • the entire surface of the curable resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ/ cm2 , and the exposed curable resin composition layer (resin layer) was It was developed using the developer described in the column “Development conditions (developer)" in Table 1, and washed using the rinse solution described in the column “Rinse solution” in the table. Subsequently, the temperature was raised in a nitrogen atmosphere at a temperature increase rate of 10° C./min, and heated for 180 minutes at the temperature listed in the "curing conditions” column of Table 2 to form a cured layer of the curable resin composition layer. (resin layer) was obtained.
  • the obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
  • Chemical solution 90:10 (mass ratio) mixture of dimethyl sulfoxide (DMSO) and 25% by mass aqueous solution of tetramethylammonium hydroxide (TMAH)
  • Evaluation conditions Immerse the resin layer in the chemical solution at 75°C for 15 minutes before and after immersion
  • the film thicknesses were compared and the dissolution rate (nm/min) was calculated. Evaluation was performed according to the following evaluation criteria, and the evaluation results are listed in the "Chemical Resistance" column of the table. It can be said that the lower the dissolution rate, the better the chemical resistance.
  • -Evaluation criteria- A The dissolution rate was less than 200 nm/min.
  • the dissolution rate was 200 nm/min or more and less than 300 nm/min.
  • C The dissolution rate was 300 nm/min or more and less than 400 nm/min.
  • D The dissolution rate was 400 nm/min or more.
  • Each resin composition or comparative composition prepared in each Example and Comparative Example was applied onto a 12-inch silicon wafer by spin coating to form a resin composition layer.
  • the silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to form a resin composition layer with a uniform thickness of 15 ⁇ m on the silicon wafer.
  • the entire surface of the resin composition layer on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ/cm 2 , and the exposed resin composition layer (resin layer) was exposed under a nitrogen atmosphere.
  • the temperature was raised at a temperature increase rate of 10° C./min and heated for 180 minutes at the temperature listed in the "Temperature” column of “Curing conditions” in the table to obtain a cured layer (resin layer) of the resin composition layer. .
  • the cured layer (resin film) after curing was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and the cured film was peeled off from the silicon wafer.
  • the dielectric constant (Dk) and dielectric loss tangent (Df) of the film sample at 28 GHz were measured using the resonator perturbation method.
  • Example 101 The resin composition used in Example 1 was applied in a layered manner by spin coating to the surface of the thin copper layer of the resin base material on which the thin copper layer was formed, and dried at 100°C for 4 minutes to determine the film thickness. After forming a 20 ⁇ m resin composition layer, it was exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 ⁇ m). After exposure, it was heated at 100° C. for 4 minutes. After the heating, it was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
  • NSR1505 i6 manufactured by Nikon Corporation
  • the temperature was raised at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 3 hours to form an interlayer insulating film for a rewiring layer.
  • This rewiring layer interlayer insulating film had excellent insulation properties. Furthermore, when semiconductor devices were manufactured using these interlayer insulating films for rewiring layers, it was confirmed that they operated without problems.

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  • Manufacturing & Machinery (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne une composition de résine contenant: un précurseur polyimide contenant des unités répétitives représentées par la formule (1-1), dans lequel la teneur en groupes polymérisables est supérieure ou égal à 2 mmol/g et la teneur en liaisons amide est inférieure ou égale à 1,5 mmol/g; un initiateur de polymérisation; et un composé polymérisable. L'invention concerne également un objet durci ainsi qu'un procédé de fabrication de celui-ci, un stratifié ainsi qu'un procédé de fabrication de celui-ci, et un dispositif à semi-conducteurs ainsi qu'un procédé de fabrication de celui-ci.
PCT/JP2023/031310 2022-08-31 2023-08-29 Composition de résine, objet durci ainsi que procédé de fabrication de celui-ci, stratifié ainsi que procédé de fabrication de celui-ci, et dispositif à semi-conducteurs ainsi que procédé de fabrication de celui-ci WO2024048604A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0990632A (ja) * 1995-09-28 1997-04-04 Sumitomo Bakelite Co Ltd 感光性樹脂組成物及びそのパターン形成方法
JPH09329893A (ja) * 1996-06-10 1997-12-22 Sumitomo Bakelite Co Ltd 感光性樹脂組成物
JP2018165819A (ja) * 2017-03-28 2018-10-25 東レ株式会社 感光性樹脂組成物、感光性シート、ならびにそれらの硬化膜およびその製造方法
JP2020024374A (ja) * 2018-04-23 2020-02-13 旭化成株式会社 感光性樹脂組成物、硬化レリーフパターンの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0990632A (ja) * 1995-09-28 1997-04-04 Sumitomo Bakelite Co Ltd 感光性樹脂組成物及びそのパターン形成方法
JPH09329893A (ja) * 1996-06-10 1997-12-22 Sumitomo Bakelite Co Ltd 感光性樹脂組成物
JP2018165819A (ja) * 2017-03-28 2018-10-25 東レ株式会社 感光性樹脂組成物、感光性シート、ならびにそれらの硬化膜およびその製造方法
JP2020024374A (ja) * 2018-04-23 2020-02-13 旭化成株式会社 感光性樹脂組成物、硬化レリーフパターンの製造方法

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