WO2020196363A1 - Composition de résine durcissable, film durci, produit stratifié, procédé de production de film durci, et dispositif à semi-conducteurs - Google Patents

Composition de résine durcissable, film durci, produit stratifié, procédé de production de film durci, et dispositif à semi-conducteurs Download PDF

Info

Publication number
WO2020196363A1
WO2020196363A1 PCT/JP2020/012594 JP2020012594W WO2020196363A1 WO 2020196363 A1 WO2020196363 A1 WO 2020196363A1 JP 2020012594 W JP2020012594 W JP 2020012594W WO 2020196363 A1 WO2020196363 A1 WO 2020196363A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
resin composition
curable resin
preferable
Prior art date
Application number
PCT/JP2020/012594
Other languages
English (en)
Japanese (ja)
Inventor
青島　俊栄
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to JP2021509365A priority Critical patent/JP7177249B2/ja
Priority to KR1020217030851A priority patent/KR102637928B1/ko
Publication of WO2020196363A1 publication Critical patent/WO2020196363A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/72—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms
    • C07C235/76—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/84—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C08F20/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • C08F290/145—Polyamides; Polyesteramides; Polyimides
    • 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
    • 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
    • C08G73/22—Polybenzoxazoles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC

Definitions

  • the present invention relates to a curable resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.
  • a resin obtained by cyclizing and curing a polymer precursor such as a polyimide resin or a polybenzoxazole resin (hereinafter, the polyimide resin precursor and the polybenzoxazole resin precursor are collectively referred to as a "heterocycle-containing polymer precursor").
  • a polymer precursor such as a polyimide resin or a polybenzoxazole resin
  • the polyimide resin precursor and the polybenzoxazole resin precursor are collectively referred to as a "heterocycle-containing polymer precursor”
  • a semiconductor device for mounting include use as a material for an insulating film or a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.
  • the heterocycle-containing polymer precursor is used in the form of a curable resin composition containing the heterocycle-containing polymer precursor.
  • a curable resin composition is applied to a substrate by, for example, coating, and then the heterocyclic-containing polymer precursor is cyclized by heating or the like to form a cured resin on the substrate.
  • the curable resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the curable resin composition to be applied. It can be said that it has excellent adaptability.
  • industrial application development of curable resin compositions containing heterocyclic-containing polymer precursors is expected more and more.
  • Patent Document 1 describes a polyimide resin composition containing polyimide and a bisimide compound having a specific structure or a bisisoimide compound having a specific structure.
  • a curable resin composition obtained by curing a curable resin composition containing a heterocyclic-containing polymer precursor such as a polyimide precursor, for example, a curable resin composition is further applied on the cured film and cured to form a laminate.
  • the formed cured film may come into contact with the developing solution or other composition. Therefore, in the curable resin composition, for example, from the viewpoint of resistance to the developing solution or suppression of dissolution of the cured film due to contact with other compositions, the obtained cured film has excellent chemical resistance. The provision of goods is desired.
  • the present invention comprises a curable resin composition having excellent chemical resistance of the obtained cured film, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, a method for producing the cured film, and a method for producing the cured film.
  • An object of the present invention is to provide a semiconductor device including the cured film or the laminate.
  • X 1 represents -O- or -S-
  • L 1 represents a divalent linking group having a formula quantity of 1,000 or less
  • R 1 and R 2 are independent of each other. Representing a monovalent organic group, R 1 and at least one of R 2 and L 1 contain a group having an ethylenically unsaturated group.
  • ⁇ 7> The curable resin composition according to any one of ⁇ 1> to ⁇ 6>, further comprising a photoradical polymerization initiator.
  • ⁇ 8> The curable resin composition according to any one of ⁇ 1> to ⁇ 7>, which contains a polyimide precursor as the polymer precursor.
  • ⁇ 9> The curable resin composition according to ⁇ 8>, wherein the polyimide precursor has a repeating unit represented by the following formula (1); In formula (1), A 1 and A 2 independently represent -O- or -NH-, R 111 represents a divalent organic group, and R 115 represents a tetravalent organic group. R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
  • ⁇ 10> The curable resin composition according to ⁇ 9>, wherein at least one of R 113 and R 114 in the above formula (1) contains a radically polymerizable group.
  • ⁇ 11> The curable resin composition according to any one of ⁇ 1> to ⁇ 10>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 12> A cured film obtained by curing the curable resin composition according to any one of ⁇ 1> to ⁇ 11>.
  • ⁇ 13> A laminate containing two or more layers of the cured film according to ⁇ 12> and containing a metal layer between any of the cured films.
  • ⁇ 14> A method for producing a cured film, which comprises a film forming step of applying the curable resin composition according to any one of ⁇ 1> to ⁇ 11> to a substrate to form a film.
  • the method for producing a cured film according to ⁇ 14> which comprises an exposure step of exposing the film and a developing step of developing the film.
  • the method for producing a cured film according to ⁇ 14> or ⁇ 15> which comprises a heating step of heating the film at 50 to 450 ° C.
  • a semiconductor device comprising the cured film according to ⁇ 12> or the laminate according to ⁇ 13>.
  • a curable resin composition having excellent chemical resistance of the obtained cured film a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and a method for producing the cured film.
  • a semiconductor device including the cured film or the laminate is provided.
  • the present invention is not limited to the specified embodiments.
  • the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
  • the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
  • the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also exposure using particle beams such as an electron beam and an ion beam. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
  • (meth) acrylate means both “acrylate” and “methacrylate”, or either
  • (meth) acrylic means both “acrylic” and “methacrylic", or
  • (meth) acryloyl means both “acryloyl” and “methacrylic", or either.
  • Me in the structural formula represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the total solid content means the total mass of all the components of the composition excluding the solvent.
  • the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
  • GPC measurement gel permeation chromatography
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
  • the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as “upper”.
  • the opposite direction is referred to as "down”.
  • the composition may contain, as each component contained in the composition, two or more kinds of compounds corresponding to the component.
  • the content of each component in the composition means the total content of all the compounds corresponding to the component.
  • the temperature is 23 ° C. and the atmospheric pressure is 101,325 Pa (1 atm).
  • the combination of preferred embodiments is a more preferred embodiment.
  • the curable resin composition of the present invention contains at least one polymer precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and a compound represented by the following formula (1-1). .. Further, the curable resin composition of the present invention preferably further contains a photoradical polymerization initiator described later.
  • X 1 represents -O- or -S-
  • L 1 represents a divalent linking group having a formula quantity of 1,000 or less
  • R 1 and R 2 are independent of each other. Representing a monovalent organic group, R 1 and at least one of R 2 and L 1 include a group having an ethylenically unsaturated group.
  • the curable resin composition of the present invention is excellent in chemical resistance of the obtained cured film.
  • the mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
  • the formula (1-1) When the curable resin composition of the present invention or the composition containing a polymer component in which at least a part of the ethylenically unsaturated group in the curable resin composition is polymerized is heated, for example, the formula (1-1).
  • the structure represented by the following formula (1-1-1) derived from the compound represented by is considered to be cyclized to become an imide structure represented by the following formula (1-1-2).
  • X 1 has the same meaning as X 1 in the formula (1-1)
  • L A is the formula (1-1) in It is a structure derived from L 1 or L 1 of the above, and * and the wavy line portion each independently represent a binding site with another structure.
  • L A is, for example, L 1 in the formula (1-1), or represents a structure ethylenically unsaturated group in the L 1 is formed by polymerizing with other ethylenically unsaturated groups.
  • * is formed, for example, by polymerizing the binding site with R 2 in the above formula (1-1) or the ethylenically unsaturated group in the above R 2 with another ethylenically unsaturated group.
  • at least one of R 2 and L 1 contains a group having an ethylenically unsaturated group, so that the imide structure finally becomes a polymer component in the cured film. It is considered to be included.
  • the cured film obtained after heating contains a polymer component having an imide structure derived from the compound represented by the formula (1-1). Since such a polymer component having an imide structure has a strong intermolecular interaction between the polymer components, it is considered that the cured film becomes a strong film and has excellent chemical resistance. Further, according to the curable resin composition of the present invention, it is considered that a cured film having a high imidization reaction rate of the polyimide precursor and the polybenzoxazole precursor in the curing step and excellent elongation at break can be easily obtained.
  • Patent Document 1 does not describe or suggest a curable resin composition containing the compound represented by the formula (1-1). Further, in the curable resin composition in Patent Document 1, there is room for further improvement in the chemical resistance of the cured film.
  • the components contained in the curable resin composition of the present invention will be described in detail.
  • the curable resin composition of the present invention contains a heterocyclic polymer precursor.
  • the curable resin composition of the present invention contains, as the heterocyclic-containing polymer precursor, at least one precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and includes a polyimide precursor. Is preferable.
  • the polyimide precursor preferably has a repeating unit represented by the following formula (1).
  • a 1 and A 2 independently represent -O- or -NH-
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
  • -A 1 and A 2- A 1 and A 2 in the formula (1) independently represent -O- or -NH-, and -O- is preferable.
  • -R 111- R 111 in the formula (1) represents a divalent organic group.
  • the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are combined, and the number of carbon atoms is exemplified.
  • the group combined as described above is preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.
  • R 111 in formula (1) is preferably derived from diamine.
  • diamine used for producing the polyimide precursor include linear or branched-chain aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
  • the diamine is a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or these. It is preferably a diamine containing two or more combined groups, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. Examples of aromatic groups include the following.
  • diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane or isophoronediamine; meta or paraphenylenediamine, diaminotoluene, 4,4'-or 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether,
  • the diamines (DA-1) to (DA-18) shown below are also preferable.
  • a diamine having at least two alkylene glycol units in the main chain is also mentioned as a preferable example.
  • a diamine containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule is preferable, and a diamine containing no aromatic ring is preferable.
  • Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, and Jeffamine (registered trademark).
  • EDR-148 Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2)) -Aminopropoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propane-2-amine, etc., but are limited to these. Not done.
  • x, y, and z are arithmetic mean values.
  • R 111 in the formula (1) from the viewpoint of flexibility of the cured film obtained, -Ar 0 -L 0 -Ar 0 - is preferably represented by.
  • Ar 0 is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and a phenylene group is preferable.
  • the preferred range of L 0 is synonymous with A above.
  • R 111 in the formula (1) is preferably a divalent organic group represented by the following formula (51) or the formula (61).
  • a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.
  • R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, a fluoromethyl group, It is a difluoromethyl group or a trifluoromethyl group, and * independently represents a binding site with another structure.
  • the monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
  • R 58 and R 59 are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups, or trifluoromethyl groups, respectively.
  • Examples of the diamine compound giving the structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2. Examples thereof include'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. One of these may be used, or two or more thereof may be used in combination.
  • -R 115- R 115 in the formula (1) represents a tetravalent organic group.
  • a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
  • R 112 is synonymous with A and has the same preferred range. * Independently represent a binding site with another structure.
  • tetravalent organic group represented by R 115 in the formula (1) include a tetracarboxylic acid residue remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
  • the tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
  • R 115 represents a tetravalent organic group.
  • R 115 has the same meaning as R 115 in formula (1).
  • tetracarboxylic dianhydride examples include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4 , 4'-diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Dihydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxy
  • DAA-1 to DAA-5 tetracarboxylic dianhydrides
  • DAA-5 tetracarboxylic dianhydrides
  • R 113 and R 114- R 113 and R 114 in the formula (1) independently represent a hydrogen atom or a monovalent organic group. At least one of R 113 and R 114 preferably contains a radically polymerizable group, and more preferably both contain a radically polymerizable group.
  • the radically polymerizable group include a group capable of a cross-linking reaction by the action of a radical, and a preferable example thereof is a group having an ethylenically unsaturated bond.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a (meth) acryloyl group, and a group represented by the following formula (III).
  • R200 represents a hydrogen atom or a methyl group, and a methyl group is preferable.
  • R 201 is an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- or a (poly) oxyalkylene group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom).
  • ⁇ 12 is preferable, 1 to 6 is more preferable, 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, 1 to 6 is more preferable, and 1 to 3 is particularly preferable).
  • the (poly) oxyalkylene group means an oxyalkylene group or a polyoxyalkylene group.
  • R 201 examples include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH 2 CH (OH) CH 2-, and more preferably ethylene group, propylene group, trimethylene group, -CH 2 CH (OH) CH 2- .
  • R 200 is a methyl group and R 201 is an ethylene group.
  • * represents a binding site with another structure.
  • Alkyl groups and the like can be mentioned. Specific examples thereof include an aromatic group having an acid group having 6 to 20 carbon atoms and an arylalkyl group having an acid group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned.
  • the acid group is preferably a hydroxy group. That is, R 113 or R 114 is preferably a group having a hydroxy group.
  • a substituent that improves the solubility of the developing solution is preferably used.
  • R 113 or R 114 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.
  • R 113 or R 114 is preferably a monovalent organic group.
  • a monovalent organic group a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group is preferable, and an alkyl group substituted with an aromatic group is more preferable.
  • the number of carbon atoms of the alkyl group is preferably 1 to 30 (3 or more in the case of a cyclic group).
  • the alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and octadecyl group.
  • the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
  • Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
  • Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described below is preferable.
  • aromatic group examples include a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an inden ring, and azulene.
  • the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an inden ring, and azulene.
  • the cyclic structure constituting the group includes a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolin ring, an indol ring, and a benzofuran.
  • Ring benzothiophene ring, isobenzofuran ring, quinolysin ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridin ring, acredin ring, phenanthrolin ring, thiantolen ring, chromium ring , Xanthene ring, phenoxatiin ring, phenothiazine ring or phenazine ring).
  • the polyimide precursor has a fluorine atom in the repeating unit.
  • the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or more. There is no particular upper limit, but 50% by mass or less is practical.
  • an aliphatic group having a siloxane structure may be copolymerized in a repeating unit represented by the formula (1).
  • the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
  • the repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1-A) or the formula (1-B).
  • a 11 and A 12 represent -O- or -NH-
  • R 111 and R 112 each independently represent a divalent organic radical
  • R 113 and R 114 each independently represent a hydrogen atom or It represents a monovalent organic group
  • at least one of R 113 and R 114 is preferably a group containing a radically polymerizable group, and more preferably a radically polymerizable group.
  • a 11 , A 12 , R 111 , R 113 and R 114 are synonymous with the preferred ranges of A 1 , A 2 , R 111 , R 113 and R 114 in formula (1), respectively.
  • R 112 has the same meaning as R 112 in formula (5), and more preferably among others oxygen atoms.
  • the bonding position of the carbonyl group to the benzene ring in the formula is preferably 4, 5, 3', 4'in the formula (1-A). In formula (1-B), it is preferably 1, 2, 4, 5.
  • the repeating unit represented by the formula (1) may be one kind, but may be two or more kinds. Further, the structural isomer of the repeating unit represented by the formula (1) may be contained. Further, the polyimide precursor may contain other types of repeating units in addition to the repeating units of the above formula (1).
  • the polyimide precursor in the present invention 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units are the repeating units represented by the formula (1). Is exemplified. As an upper limit, 100 mol% or less is practical.
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000.
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
  • the degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
  • the degree of dispersion of the molecular weight means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).
  • the polyimide precursor is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine.
  • the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.
  • the organic solvent may be one kind or two or more kinds.
  • the organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
  • the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
  • the polybenzoxazole precursor preferably contains a repeating unit represented by the following formula (2).
  • R 121 represents a divalent organic group
  • R 122 represents a tetravalent organic group
  • R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group. Represent.
  • R 121 represents a divalent organic group.
  • the divalent organic group includes an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, 6 to 14 carbon atoms). Is more preferable, and 6 to 12 is particularly preferable).
  • the aromatic group constituting R 121 include R 111 of the above formula (1).
  • the aliphatic group a linear aliphatic group is preferable.
  • R 121 is preferably derived from 4,4'-oxydibenzoyl chloride.
  • R 122 represents a tetravalent organic group.
  • the tetravalent organic group has the same meaning as R 115 in the above formula (1), and the preferable range is also the same.
  • R 122 is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
  • R -R 123 and R 124- R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R 113 and R 114 in the above formula (1), and the preferable range is also the same.
  • the polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units of the above formula (2).
  • the polybenzoxazole precursor further contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.
  • SL diamine residue represented by the following formula (SL) as another type of repeating unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.
  • R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R 2s.
  • Is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of R 3s , R 4s , R 5s , and R 6s is aromatic.
  • a group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms
  • the rest are hydrogen atoms or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms).
  • the a structure and the b structure may be block polymerization or random polymerization.
  • the a structure is 5 to 95 mol%
  • the b structure is 95 to 5 mol%
  • a + b is 100 mol%.
  • preferred Z includes those in which R 5s and R 6s in the b structure are phenyl groups.
  • the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000.
  • the molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight in the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be lowered, and the effect of suppressing warpage and the effect of improving solubility can be achieved at the same time.
  • the tetracarboxylic dianhydride is further provided in that it improves the alkali solubility of the curable resin composition. It is preferable that the tetracarboxylic acid residue remaining after the removal of the acid dianhydride group from the product is contained as a repeating unit. Examples of such a tetracarboxylic acid residue include the example of R 115 in the formula (1).
  • the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. is there.
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
  • the degree of dispersion of the molecular weight of the polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
  • the content of the heterocycle-containing polymer precursor in the curable resin composition of the present invention is preferably 20% by mass or more, preferably 30% by mass or more, based on the total solid content of the curable resin composition. More preferably, it is more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and further preferably 70% by mass or more.
  • the content of the heterocycle-containing polymer precursor in the curable resin composition of the present invention is preferably 99.5% by mass or less, preferably 99% by mass, based on the total solid content of the curable resin composition. The following is more preferable, 98% by mass or less is further preferable, 97% by mass or less is further preferable, and 95% by mass or less is further preferable.
  • the curable resin composition of the present invention may contain only one type of heterocyclic polymer precursor, or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.
  • the curable resin composition of the present invention contains a compound represented by the following formula (1-1).
  • X 1 represents -O- or -S-
  • L 1 represents a divalent linking group having a formula quantity of 1,000 or less
  • R 1 and R 2 are independent of each other. Representing a monovalent organic group, R 1 and at least one of R 2 and L 1 include a group having an ethylenically unsaturated group.
  • the compound represented by the formula (1-1) contains a group having an ethylenically unsaturated group. That is, the compound represented by the formula (1-1) is a compound containing at least two groups having an ethylenically unsaturated group per molecule.
  • the number of groups having an ethylenically unsaturated group in the compound represented by the formula (1-1) is preferably 2 to 8, and more preferably 2 to 6. Further, the groups having the ethylenically unsaturated group in the compound represented by the formula (1-1) may be the same or different.
  • the group having an ethylenically unsaturated group is preferably at least one selected from the group consisting of an allyl group, a vinylphenyl group, a (meth) acrylamide group, and a (meth) acryloxy group, and is preferably (meth). It is more preferably an acryloxy group and even more preferably a methacryloxy group.
  • the compound represented by the formula (1-1) may contain two or more different groups as the group having an ethylenically unsaturated group, for example, a methacrylamide group and a methacryloxy group.
  • the ethylenically unsaturated group is preferably a radically polymerizable group.
  • the amount (molar amount) of the ethylenically unsaturated group in the compound represented by the formula (1-1) of 1 g is preferably 5.0 to 7.0 mmol / g, and 5.5 to 6 More preferably, it is 5.5 mmol / g.
  • X 1 represents -O- or -S-, from the viewpoint that the above-mentioned imide structure is easily formed, the stability of the compound during storage, or the reactivity with the compound having a plurality of hydroxy groups and condensable groups described later. From the viewpoint of the above and the radical polymerization reactivity in the heating step, it is preferably —O—.
  • R 1 contains a group having an ethylenically unsaturated group, and is preferably a group represented by the following formula (A-1).
  • R 12 represents a hydrogen atom or an alkyl group
  • L 11 represents a single bond or a divalent organic group
  • L 12 represents an n1 + 1 valent organic group
  • n1 is an integer of 1 or more.
  • And * represents the binding site with X 1 in the formula (1-1).
  • R 12 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group.
  • -C ( O)-)
  • a single bond, an alkylene group, an ester bond, an ether bond, a carbonyl group, or these A group in which two or more of the above are combined is more preferable.
  • the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably an alkylene group having 2 to 10 carbon atoms.
  • the arylene group is preferably an arylene group having 6 to 20 carbon atoms, and more preferably a phenylene group.
  • RN1 represents a hydrogen atom or a hydrocarbon group, preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group, and even more preferably a hydrogen atom. If R N1 is more present in the molecule, plural of R N1 may be the same or may be different.
  • L 12 is preferably a hydrocarbon group, an ester bond, an ether bond, a carbonyl group, a urethane bond, a urea bond, an amide bond, an amino group, or a group in which two or more of these are combined, preferably a saturated fat.
  • a group hydrocarbon group, an ester bond, an ether bond, or a group in which two or more of these are combined is more preferable.
  • L 12 is a saturated aliphatic hydrocarbon group, or the site to be bonded to X 1 in the formula (1-1) in L 12 is a saturated aliphatic hydrocarbon group. And at least two groups selected from the group consisting of saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, ester bonds, ether bonds, carbonyl groups, urethane bonds, urea bonds, amide bonds and amino groups. It is preferably a combined group.
  • the saturated aliphatic hydrocarbon group a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, and a saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms is more preferable.
  • n1 is preferably an integer of 1 to 10, more preferably an integer of 1 to 6, further preferably an integer of 1 to 4, and 1 or 2. Is particularly preferable, and 1 is most preferable. If n1 is 1, L 11 is a single bond, it is preferable that L 12 is an alkylene group, L 11 is a single bond, L 12 is more an alkylene group having 2 to 10 carbon atoms preferable.
  • R 2 When R 2 contains a group having an ethylenically unsaturated group, the preferred embodiment of R 2 is the same as the preferred embodiment of R 1 described above. When R 2 does not contain a group having an ethylenically unsaturated group, R 2 is preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and an alkyl group or phenyl having 1 to 12 carbon atoms. Groups are even more preferred.
  • the formula amount of R 1 is preferably 80 to 500.
  • the formula amount is more preferably 100 or more, and further preferably 110 or more. Further, the above formula amount is more preferably 450 or less, and further preferably 400 or less.
  • Formula weight of R 2 is preferably 80-500.
  • the formula amount is more preferably 100 or more, and further preferably 120 or more. Further, the above formula amount is more preferably 450 or less, and further preferably 400 or less.
  • the formula amount of R 1 and the formula amount of R 2 are both preferably 80 to 500. When both the formula amount of R 1 and the formula amount of R 2 are 80 to 500, the formula amount of R 1 and the formula amount of R 2 may be different from each other.
  • the formula amount is more preferably 100 or more, and further preferably 120 or more. Further, the above formula amount is more preferably 450 or less, and further preferably 400 or less.
  • the formula weight of R 1 (or R 2) refers to the total atomic weight of atoms contained in R 1 (or R 2).
  • L 1 The formula amount of L 1 is 1,000 or less, preferably 20 to 1,000, more preferably 20 to 900, and even more preferably 20 to 800.
  • the formula weight of L 1 refers to the total atomic weight of atoms contained in L 1.
  • Linking chain length of L 1 is preferably 1 to 4, 1, 2, 3, or more preferably 4, more preferably 2 or 3.
  • the connecting chain length of L 1, an atom contained in L 1, and the following formula (1-1 ') by two in the compound represented by the carbon atom C 1 and C 2 It is the smallest number of atoms that exist between them.
  • the following formula (1-1') describes the symbols C 1 and C 2 for the carbon atoms in the above formula (1-1), respectively, and R 1 and R in the formula (1-1').
  • 2 X 1 and L 1 are synonymous with R 1 , R 2 , X 1 and L 1 in the formula (1-1), respectively.
  • L 1 in the compound represented by the following formula (BR) is a 1,2-phenylene group, and the linking chain length is 2.
  • the atoms at the bond positions at both ends of L 1 are carbon atoms.
  • the binding positions of both ends of the L 1, in the above formula (1-1 '), the two at the binding site for the binding site and L 1 and the carbon atom C 2 of L 1 and the carbon atom C 1 Say.
  • the structure existing between the carbon atom C 1 and the carbon atom C 2 in L 1 is a part of the aromatic ring structure or is an unsaturated aliphatic group. It preferably has a hydrocarbon structure, and a part of the benzene ring structure (particularly preferably 1,2-phenylene group) or a cisvinylene group is more preferable.
  • the benzene ring structure or the cisvinylene group may further have a known substituent.
  • the known substituent may have a substituent containing a group having an ethylenically unsaturated group.
  • L 1 may further include an imide cyclization site in a site other than the structure existing between the carbon atom C 1 and the carbon atom C 2 in the above formula (1-1').
  • the imide cyclization site in the compound represented by the formula (1-1) means a site where an imide ring is formed by heating, and for example, the structure excluding L 1 in the above formula (1-1) (the following formula).
  • (1-1A) and the combination of the two structures described in the following formula (1-1B)) can be mentioned.
  • * independently represents a binding site with another structure
  • R 1A , R 2A , and X 1A are in formula (1-1), respectively.
  • R 1 , R 2 , and X 1 of the above are synonymous with R 1 , R 2 , and X 1 of the above, and the preferred embodiment is also the same.
  • the structure existing between the structure represented by the formula (1-1A) and the structure represented by the formula (1-1B) is a part of the aromatic ring structure or is unsaturated aliphatic hydrocarbon. It preferably has a hydrogen structure.
  • Linking chain length of the structure represented by Formula structures and formulas represented by (1-1A) (1-1B) in the formula L 1 is more able to be 1-4 and preferably 2 or 3 preferable.
  • the connecting chain length structure represented by Formula structures and formulas represented by (1-1A) (1-1B) in the formula L 1 an atom contained in L 1, and the formula (1-1A ) And * in the structure represented by the formula (1-1B), which is the smallest number of atoms existing between *.
  • the connecting chain length of the structure represented by the formula (1-1A) and the structure represented by the formula (1-1B) in the structure corresponding to L 1 is It is 2.
  • L 1 is preferably a group having a partial structure represented by any of the following formulas (L-1) to (L-3).
  • * 2 is.
  • L-1 it is preferable that all the wavy line portions are binding sites with hydrogen atoms.
  • An example of L 1 having a partial structure represented by the formula (L-1) is the following structure. Following structure, * 1 and * 2 have the same meanings as * 1 and * 2 in each formula (L-1).
  • the wavy line portion is a hydrogen atom, a halogen atom, a hydrocarbon group, a structure described in the above formula (1-1A), a structure described in the above formula (1-1B), or two or more of these. It is preferably a binding site with the combined group.
  • the hydrocarbon group may be substituted with a known substituent.
  • An example of L 1 having a partial structure represented by the formula (L-2) is the following structure.
  • * 1 and * 2 have the same meanings as * 1 and * 2 in each formula (L-2), in the structure in which one of Z 1 and Z 2 is represented by the formula (1-1A) *
  • the binding site with * is represented by the binding site with *, and the other is represented by the binding site with * in the structure represented by the formula (1-1B).
  • the wavy line portion is a hydrogen atom, a halogen atom, a hydrocarbon group, a structure described in the above formula (1-1A), a structure described in the above formula (1-1B), or two or more of these. It is preferably a binding site with the combined group.
  • the hydrocarbon group may be substituted with a known substituent.
  • An example of L 1 having a partial structure represented by the formula (L-3) is the following structure.
  • * 1 and * 2 have the same meanings as * 1 and * 2 in each formula (L-3), in the structure in which one of Z 1 and Z 2 is represented by the formula (1-1A) *
  • the binding site with * is represented by the binding site with *, and the other is represented by the binding site with * in the structure represented by the formula (1-1B).
  • L 1 has a structure other than the structure existing between the carbon atom C 1 and the carbon atom C 2, and the formula (1).
  • a compound having one structure represented by -1A) and one structure represented by the formula (1-1B) is also preferably mentioned.
  • One structure other than the structure in which L 1 exists between the carbon atom C 1 and the carbon atom C 2 includes a structure represented by the formula (1-1A) and a structure represented by the formula (1-1B).
  • a compound represented by the following formula (1-2) is preferably mentioned.
  • L 2 represents a tetravalent organic group
  • R 1 , R 2 and X 1 are independently similar to R 1 , R 2 and X 1 in formula (1-1).
  • a group that is a combination of at least one is preferable.
  • the hydrocarbon group in L 2 may be substituted with a known substituent such as a halogeno group.
  • L 2 preferably contains at least one selected from the group consisting of an ethylenically unsaturated bond and an aromatic ring structure.
  • Linking chain length of C 1 and C 2 in L 2 is preferably 1-4, more preferably 2 or 3.
  • the connecting chain length of C 3 and C 4 in L 2 is preferably 1 to 4, more preferably 2 or 3.
  • the connecting chain length of C 1 and C 4 in L 2 is preferably 2 or more, more preferably 3 or more, and further preferably 4 to 20.
  • the connecting chain length of C 2 and C 3 in L 2 is preferably 2 or more, more preferably 3 or more, and further preferably 4 to 20.
  • the chain length connecting A and B in L 2 is the smallest number of atoms contained in L 2 and existing between two carbon atoms A and B.
  • the formula amount of L 2 is preferably 20 to 500, and more preferably 20 to 400.
  • the formula weight of L 2 refers to the total atomic weight of atoms contained in L 2.
  • L 2 is preferably a group represented by either the following formula (1-3) or formula (1-4).
  • A1, A2 and A3 independently represent a ring structure
  • A represents a single bond or a divalent binding group
  • * 1 represents the formula (1).
  • -2) The binding site with C 1 in the formula (1-2), * 2 is the binding site with C 2 in the formula (1-2), and * 3 is the binding site with C 3 in the formula (1-2).
  • * 4 represent the binding sites with C 4 in the formula (1-2), respectively.
  • A1 preferably represents a monocyclic structure, a condensed ring structure, a crosslinked ring structure, or a spiro ring structure, more preferably a monocyclic structure, a condensed ring structure, or a crosslinked ring structure.
  • An aromatic ring structure or a monocyclic alicyclic structure is more preferable.
  • A1 may be a hydrocarbon ring or a heterocycle, but is preferably a hydrocarbon ring. Examples of the complex atom in the above-mentioned heterocycle include an oxygen atom, a nitrogen atom, a sulfur atom and the like.
  • Examples of A1 include a benzene ring, a naphthalene ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a dicyclopentane ring, a dicyclopentene ring, a cyclohexene ring, a tetrahydronaphthalene ring and the like.
  • the ring structure in A1 may be substituted with a known substituent such as an alkyl group or a halogeno group.
  • * 1 and * 2 preferably exist at adjacent positions in the ring structure, and * 3 and * 4 preferably exist at adjacent positions.
  • a and B are adjacent to the ring structure
  • A is present in an atom which is a ring member in the ring structure
  • B is a ring member adjacent to the atom in the ring structure. It means that it exists in an atom that is.
  • the ring structure is a benzene ring structure
  • the fact that A and B are present at adjacent positions means that A and B are present at the ortho position in the benzene ring structure.
  • A2 and A3 each independently preferably represent a monocyclic structure, a fused ring structure, a crosslinked ring structure, or a spiro ring structure, and a monocyclic structure, a condensed ring structure, or a crosslinked ring structure.
  • a monocyclic aromatic ring structure or a monocyclic alicyclic structure is further preferable, a monocyclic aromatic ring structure is particularly preferable, and a benzene ring structure is most preferable.
  • A2 and A3 may be independently a hydrocarbon ring or a heterocycle, but it is preferable that both are hydrocarbon rings.
  • Examples of the complex atom in the above-mentioned heterocycle include an oxygen atom, a nitrogen atom, a sulfur atom and the like.
  • the ring structure in A2 or A3 may be substituted with a known substituent such as an alkyl group or a halogeno group.
  • * 1 and * 2 are preferably present at adjacent positions in the ring structure.
  • * 3 and * 4 are preferably present at adjacent positions in the ring structure.
  • A represents a divalent linking group, a divalent hydrocarbon group, a divalent heterocyclic group, an ester bond, an ether bond, a carbonyl group, a sulfonyl group, a urethane bond, a urea bond, An amide bond or a group in which two or more of these are combined is preferable, and a hydrocarbon group, an ester bond, an ether bond, a sulfonyl group, or a group in which two or more of these are combined is more preferable.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group in which two or more of these are combined.
  • the hydrocarbon group preferably has 6 to 30 carbon atoms.
  • the hydrocarbon group is preferably an alkylene group, an alkenylene group, an alkynylene group, an arylene group, or a group in which two or more of these are combined.
  • the hydrocarbon group may be substituted with a known substituent such as a halogeno group.
  • the heterocyclic group include a heterocyclic group containing an oxygen atom, a sulfur atom or a nitrogen atom as a ring member.
  • the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group, but is preferably an aromatic heterocyclic group.
  • the heterocyclic group is preferably a group obtained by removing two hydrogen atoms from the 5-membered or 6-membered heterocycle.
  • heterocycle in the heterocyclic group examples include a thiophene ring, a furan ring, a pyridine ring, a pyrimidine ring, a pyrazole ring, a pyrazole ring, a triazole ring, an imidazole ring and the like, and a thiophene ring and a furan ring are preferable.
  • the heterocyclic group may have a known substituent.
  • the heterocycle may further form a condensed ring with another ring.
  • the other ring is not particularly limited, and may be a hydrocarbon ring or a heterocycle.
  • the structure of L 1 or L 2 may be selected in consideration of, for example, the formation efficiency of the imide structure, the solubility in an organic solvent, and the like.
  • the molecular weight of the compound represented by the formula (1-1) may be determined in consideration of, for example, cyclization temperature, volatility, etc., but is preferably 100 or more, more preferably 150 or more. It is more preferably 200 or more, and further preferably 250 or more. The upper limit is not particularly limited, but is preferably 2,000 or less.
  • the temperature (cyclization temperature) for forming the imide structure in the compound represented by the formula (1-1) is preferably 130 ° C. or higher, more preferably 140 ° C. or higher, and 150 ° C. or higher. It is more preferable that the temperature is 160 ° C. or higher.
  • the upper limit is preferably 350 ° C. or lower, more preferably 300 ° C. or lower, and even more preferably 250 ° C. or lower.
  • the cyclization temperature is determined as the peak temperature of the exothermic peak, which is the lowest temperature when the compound represented by the formula (1-1) is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule.
  • the method for synthesizing the compound represented by the formula (1-1) is not particularly limited, but for example, by adding an alcohol compound to a dicarboxylic acid anhydride and then condensing it with an amine compound in the presence of a carbodiimide compound. It is synthesized.
  • a phthalic acid monoester compound can be obtained by adding hydroxyethyl methacrylate to phthalic anhydride and heating and stirring. Subsequently, aminoethyl methacrylate hydrochloride is added in the presence of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride, and the mixture is stirred at about 10 ° C. to obtain B-2.
  • the content of the compound represented by the formula (1-1) is the total content of the curable resin composition from the viewpoint of improving the storage stability of the curable resin composition and the elongation at break of the obtained cured film. It is preferably 0.005 to 50% by mass with respect to the solid content.
  • the lower limit is more preferably 0.05% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.
  • the upper limit of the content is preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, from the viewpoint of chemical resistance and elongation at break of the cured film.
  • the curable resin composition of the present invention may contain only one type of the compound represented by the formula (1-1), or may contain two or more types. When two or more types are included, the total amount is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a compound having a plurality of groups capable of condensing with at least one group selected from the group consisting of hydroxy groups and thiol groups.
  • the structure represented by the above formula (1-1-1) has the following formula together with the structure represented by the above formula (1-1-2). It is considered that the structure represented by (1-1-3) is produced.
  • the structure represented by this formula (1-1-3) is crosslinked by a compound having a plurality of groups capable of condensing with at least one group selected from the group consisting of the hydroxy group and the thiol group. Further, it is considered that a cured film having excellent chemical resistance can be easily obtained.
  • X 1 has the same meaning as X 1 in the formula (1-1)
  • the wavy line section represents a binding site with another structure.
  • R 1 in the above formula (1-1) or the ethylenically unsaturated group in the above R 1 is polymerized with another ethylenically unsaturated group. Represents a binding site with a structure formed by
  • a compound having a plurality of groups capable of condensing with at least one group selected from the group consisting of a hydroxy group and a thiol group may have one of these groups alone, or may have two or more of these groups. You may be doing it.
  • the isocyanate group is preferably a blocked isocyanate group blocked by a known blocking agent.
  • the blocking agent is a compound having a group that undergoes an addition reaction with an isocyanate group to form a urethane bond or a urea bond.
  • an alcohol-based blocking agent such as methanol or ethanol, a phenol-based blocking agent such as phenol or cresol, or a form.
  • Oxime-based blocking agents such as aldoxime, acetoaldoxime, methylethylketoxim, methylisobutylketoxim, cyclohexanone oxime, acetoxime, diacetylmonooxime, benzophenone oxime, and acid amide-based blocking agents such as acetoanilide, ⁇ -caprolactam, and ⁇ -butyrolactam.
  • active oxime-based blocking agents such as dimethyl malonate, diethyl malonate, methyl acetoacetate, mercaptan-based blocking agents such as butyl mercaptan, imide-based blocking agents such as imide succinate and imide maleate, imidazole, 2 -Imidazole-based blocking agents such as methylimidazole, urea-based blocking agents such as urea and thiourea, carbamic acid-based blocking agents such as phenyl N-phenylcarbamate, amine-based blocking agents such as diphenylamine and aniline, and ethylene.
  • active oxime-based blocking agents such as dimethyl malonate, diethyl malonate, methyl acetoacetate
  • mercaptan-based blocking agents such as butyl mercaptan
  • imide-based blocking agents such as imide succinate and imide maleate
  • imidazole 2 -Imidazole-based blocking agents
  • imide-based blocking agents such as imine and polyethyleneimine
  • pyrazole-based blocking agents such as pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole.
  • imide-based blocking agents such as imine and polyethyleneimine
  • pyrazole-based blocking agents such as pyrazole, 3-methylpyrazole, and 3,5-dimethylpyrazole.
  • These blocking agents may be selected in consideration of the temperature at which they dissociate to generate isocyanate groups.
  • the compound having an isocyanate group (hereinafter, also referred to as an isocyanate compound) is not particularly limited as long as it is a compound having an isocyanate group or a blocked isocyanate group, but from the viewpoint of curability, two or more isocyanate groups or two or more isocyanate groups in one molecule or It is preferably a compound having a blocked isocyanate group.
  • the upper limit of the number of isocyanate groups or blocked isocyanate groups is not particularly specified, but is preferably 6 or less.
  • the skeleton of the compound having an isocyanate group is not particularly limited, and any compound having two isocyanate groups in one molecule may be used, and it may be aliphatic, alicyclic or aromatic. It may be a group polyisocyanate, and may be, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,3-trimethylene diisocyanate, 1,4.
  • TDI tolylene diisocyanate
  • MDI diphenylmethane diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • Isocyanate is preferable, and a blocked isocyanate compound in which the isocyanate group in the compound selected from the group consisting of hexamethylene diisocyanate, isophorone diisocyanate, and multimers thereof is protected by the above-mentioned blocking agent is more preferable.
  • the multimer of the isocyanate compound is not particularly limited as long as it is a dimer or more, and biuret, isocyanurate, adduct and the like can be exemplified, and biuret is preferable.
  • Examples of the compound having a plurality of hydroxymethyl groups include methylolated melamine, methylolated benzoguanamine, methylolated glycoluryl and the like.
  • As the compound having a plurality of alkoxymethyl groups alkoxymethylated melamine, alkoxymethylated benzoguanamine, alkoxymethylated glycoluril, alkoxymethylated urea and the like are preferable. These are obtained, for example, by converting the methylol group of methylolated melamine, methylolated benzoguanamine, methylolated glycoluryl, or methylolated urea into an alkoxymethyl group.
  • the type of the alkoxymethyl group is not particularly limited, and examples thereof include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group, but from the viewpoint of the amount of outgas generated, methoxy Methyl groups are particularly preferred.
  • methoxy Methyl groups are particularly preferred.
  • alkoxymethylated melamine, alkoxymethylated benzoguanamine, and alkoxymethylated glycol uryl are mentioned as preferable compounds, and alkoxymethylated glycol uryl is particularly preferable from the viewpoint of transparency.
  • Examples of the compound having two or more epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and aliphatic epoxy resin. These are available as commercial products. For example, as a compound having two or more epoxy groups in the molecule, JER152, JER157S70, JER157S65, JER806, JER828, JER1007 (manufactured by Mitsubishi Chemical Corporation), etc. Examples thereof include the listed commercial products.
  • Compounds having two or more oxetanyl groups in the molecule include 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene and 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene.
  • Ethyl-3-oxetanyl) methyl] ester and the like can be mentioned.
  • Specific examples include the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223).
  • Examples of the compound having a plurality of vinyl sulfonic acid groups include 1,3-bisvinylsulfonyl-2-propanol, 1,2-bis (vinylsulfonylacetamide) ethane, and bis (vinylsulfonyl). Methyl) ether and the like.
  • the content of the compound having a plurality of groups capable of condensing with at least one group selected from the group consisting of a hydroxy group and a thiol group improves the storage stability of the composition and the elongation at break of the obtained cured film, etc. From this point of view, it is preferably 0.005 to 50% by mass based on the total solid content of the curable resin composition.
  • the lower limit is more preferably 0.05% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.
  • the content of the compound having a plurality of groups capable of condensing with at least one group selected from the group consisting of a hydroxy group and a thiol group is based on the total mass of the compound represented by the formula (1-1). It is preferably 1% by mass to 200% by mass, and more preferably 10% by mass to 100% by mass.
  • the curable resin composition of the present invention may contain only one compound having a plurality of groups capable of condensing with at least one group selected from the group consisting of a hydroxy group and a thiol group, or two or more kinds. It may be included. When two or more types are included, the total amount is preferably in the above range.
  • the curable resin composition of the present invention preferably contains an onium salt.
  • the type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt and phosphonium salt are preferably mentioned. Among these, ammonium salt or iminium salt is preferable from the viewpoint of high thermal stability, and sulfonium salt, iodonium salt or phosphonium salt is preferable from the viewpoint of compatibility with the polymer.
  • the onium salt is a salt of a cation and an anion having an onium structure, and the cation and the anion may or may not be bonded via a covalent bond. .. That is, the onium salt may be an intermolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are separate molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the curable resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
  • an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.
  • the onium salt used in the present invention may be a thermobase generator.
  • the thermal base generator refers to a compound that generates a base by heating, and examples thereof include an acidic compound that generates a base when heated to 40 ° C. or higher.
  • ammonium salt means a salt of an ammonium cation and an anion.
  • R 1 to R 4 independently represent a hydrogen atom or a hydrocarbon group, and at least two of R 1 to R 4 may be bonded to each other to form a ring.
  • R 1 to R 4 are each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms or 6 to 6 carbon atoms. It is more preferably 12 aryl groups.
  • R 1 to R 4 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group. Examples thereof include a carbonyl group and an acyloxy group.
  • the ring may contain a hetero atom. Examples of the hetero atom include a nitrogen atom.
  • the ammonium cation is preferably represented by any of the following formulas (Y1-1) and (Y1-2).
  • R 101 represents an n-valent organic group
  • R 1 has the same meaning as R 1 in the formula (101)
  • Ar 101 and Ar 102 are each independently , Represents an aryl group
  • n represents an integer of 1 or more.
  • R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
  • n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
  • Ar 101 and Ar 102 are preferably phenyl groups or naphthyl groups, respectively, and more preferably phenyl groups.
  • the anion in the ammonium salt one selected from a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfate anion is preferable, and a carboxylic acid anion is more preferable because both salt stability and thermal decomposability can be achieved.
  • the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
  • the carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxy groups, and more preferably a divalent carboxylic acid anion.
  • the stability, curability and developability of the curable resin composition can be further improved.
  • the stability, curability and developability of the curable resin composition can be further improved.
  • the carboxylic acid anion is preferably represented by the following formula (X1).
  • EWG represents an electron-attracting group.
  • the electron-attracting group means that the substituent constant ⁇ m of Hammett shows a positive value.
  • ⁇ m is a review article by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642.
  • the EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
  • R x1 to R x3 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group or a carboxy group, and Ar is an aromatic group. Represents.
  • the carboxylic acid anion is preferably represented by the following formula (XA).
  • L 10 represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR X - represents and divalent connecting group selected from the group consisting a combination thereof, R X is , Hydrogen atom, alkyl group, alkenyl group or aryl group.
  • carboxylic acid anion examples include maleic acid anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion.
  • the onium salt in the present invention contains an ammonium cation as a cation, and the onium salt is an anion from the viewpoint that the cyclization of the specific precursor is easily performed at a low temperature and the storage stability of the curable resin composition is easily improved. It is preferable to contain an anion having a pKa (pKaH) of 2.5 or less, and more preferably to contain an anion having a pKa (pKaH) of 1.8 or less.
  • the lower limit of pKa is not particularly limited, but it is preferably -3 or more, preferably -2 or more, from the viewpoint that the generated base is not easily neutralized and the cyclization efficiency of the specific precursor or the like is improved. Is more preferable.
  • the above pKa includes Determination of Organic Strategies by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O., Nachod, FC See Nachod, F.C .; Academic Press, New York, 1955) and Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 19). Can be done. For compounds not described in these documents, the values calculated from the structural formulas using ACD / pKa (manufactured by ACD / Labs) software shall be used.
  • ammonium salt examples include the following compounds, but the present invention is not limited thereto.
  • the iminium salt means a salt of an iminium cation and an anion.
  • the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
  • a pyridinium cation is preferable.
  • a cation represented by the following formula (102) is also preferable.
  • R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group
  • R 7 represents a hydrocarbon group
  • at least two of R 5 to R 7 are bonded to each other to form a ring. It may be formed.
  • R 5 and R 6 have the same meaning as R 1 to R 4 in the above formula (101), and the preferred embodiment is also the same.
  • R 7 preferably combines with at least one of R 5 and R 6 to form a ring.
  • the ring may contain a heteroatom. Examples of the hetero atom include a nitrogen atom. Further, as the ring, a pyridine ring is preferable.
  • the iminium cation is preferably represented by any of the following formulas (Y1-3) to (Y1-5).
  • R 101 represents an n-valent organic group
  • R 5 has the same meaning as R 5 in the formula (102)
  • R 7 is R in the formula (102) Synonymous with 7
  • n represents an integer of 1 or more
  • m represents an integer of 0 to 4.
  • R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from the structure to which these are bonded, and has 2 to 30 carbon atoms.
  • n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
  • m is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
  • iminium salt examples include the following compounds, but the present invention is not limited thereto.
  • the sulfonium salt means a salt of a sulfonium cation and an anion.
  • the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
  • sulfonium cation a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable. Further, as the sulfonium cation, a cation represented by the following formula (103) is preferable.
  • R 8 to R 10 each independently represent a hydrocarbon group.
  • Each of R 8 to R 10 is preferably an alkyl group or an aryl group independently, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
  • R 8 to R 10 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group.
  • Examples thereof include a carbonyl group and an acyloxy group.
  • an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have 10 alkoxy groups.
  • R 8 to R 10 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
  • the iodonium salt means a salt of an iodonium cation and an anion.
  • the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
  • iodonium cation a diallyl iodonium cation is preferable. Further, as the iodonium cation, a cation represented by the following formula (104) is preferable.
  • R 11 and R 12 each independently represent a hydrocarbon group.
  • R 11 and R 12 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
  • R 11 and R 12 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group.
  • Examples thereof include a carbonyl group and an acyloxy group.
  • R 11 and R 12 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
  • the phosphonium salt means a salt of a phosphonium cation and an anion.
  • the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
  • a quaternary phosphonium cation is preferable, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation. Further, as the phosphonium cation, a cation represented by the following formula (105) is preferable.
  • R 13 to R 16 independently represent a hydrogen atom or a hydrocarbon group.
  • Each of R 13 to R 16 is preferably an alkyl group or an aryl group independently, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
  • R 13 to R 16 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group.
  • Examples thereof include a carbonyl group and an acyloxy group.
  • R 13 to R 16 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
  • the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention.
  • the lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
  • the onium salt one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
  • the curable resin composition of the present invention may contain a thermal base generator.
  • the thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
  • examples of other thermobase generators include nonionic thermobase generators.
  • Examples of the nonionic thermobase generator include compounds represented by the formula (B1) or the formula (B2).
  • Rb 1 , Rb 2 and Rb 3 are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. Further, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group.
  • the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.
  • Rb 1 , Rb 2 and Rb 3 contains a cyclic structure, and it is more preferable that at least two contain a cyclic structure.
  • the cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable.
  • the single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring.
  • a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.
  • Rb 1 and Rb 2 are hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), and alkenyl groups (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ⁇ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have substituents as long as the effects of the present invention are exhibited. Rb 1 and Rb 2 may be coupled to each other to form a ring.
  • Rb 1 and Rb 2 are particularly linear, branched, or cyclic alkyl groups that may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
  • a cyclohexyl group which may be used is more preferable.
  • an alkyl group preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms
  • an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6.
  • alkoxy group (2 to 24 carbon atoms are preferable, 2 to 12 is more preferable, 2 to 6 is more preferable
  • arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable).
  • an arylalkenyl group (8 to 24 carbon atoms is preferable, 8 to 20 is more preferable, 8 to 16 is more preferable), and an alkoxyl group (1 to 24 carbon atoms is preferable, 2 to 2 to 24).
  • 18 is more preferable, 3 to 12 is more preferable), an aryloxy group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), or an arylalkyloxy group (7 to 12 carbon atoms is more preferable).
  • 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable).
  • a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, further preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable.
  • Rb 3 may further have a substituent as long as the effects of the present invention are exhibited.
  • the compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
  • Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively.
  • Rb 13 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effects of the present invention are exhibited. Of these, Rb 13 is preferably an arylalkyl group.
  • Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms). , 2 to 8 are more preferable, 2 to 3 are more preferable), aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable), arylalkyl groups (7 to 7 carbon atoms are more preferable). 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is further preferable), and a hydrogen atom is preferable.
  • Rb 35 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferable), aryl group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable). , 7-12 is more preferable), and an aryl group is preferable.
  • the compound represented by the formula (B1-1) is also preferable.
  • Rb 11 and Rb 12 have the same meanings as Rb 11 and Rb 12 in the formula (B1-1).
  • Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), aryl group (6 to 22 carbon atoms are preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7).
  • Rb 17 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
  • the molecular weight of the nonionic thermobase generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
  • the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
  • the following compounds can be mentioned as specific examples of the compound which is a thermal base generator or other specific examples of the thermal base generator.
  • the content of the thermal base generator is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
  • the thermobase generator one kind or two or more kinds can be used. When two or more types are used, the total amount is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • the photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators.
  • a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable.
  • it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
  • the photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol -1 ⁇ cm -1 within the range of about 300 to 800 nm (preferably 330 to 500 nm). Is preferable.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • a known compound can be arbitrarily used as the photoradical polymerization initiator.
  • halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like.
  • paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.
  • Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated in the present specification.
  • KayaCure DETX manufactured by Nippon Kayaku Co., Ltd.
  • Nippon Kayaku Co., Ltd. is also preferably used.
  • a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be preferably used. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
  • IRGACURE 184 (IRGACURE is a registered trademark)
  • DAROCUR 1173 As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
  • the compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
  • acylphosphine-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.
  • metallocene compound examples include IRGACURE-784 (manufactured by BASF).
  • An oxime compound is more preferable as the photoradical polymerization initiator.
  • the exposure latitude can be improved more effectively.
  • the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
  • the compound described in JP-A-2001-233842 the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.
  • Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
  • an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator.
  • IRGACURE OXE 01 IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052).
  • the radical polymerization initiator 2) is also preferably used.
  • TR-PBG-304 manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.
  • Adeka Arkuru's NCI-831 and Adeka Arkuru's NCI-930 can also be used.
  • DFI-091 manufactured by Daito Chemix Corp.
  • an oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.
  • Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.
  • the photoradical polymerization initiator includes a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, and a triaryl.
  • a trihalomethyltriazine compound Selected from the group consisting of imidazole dimer, onium salt compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene-benzene-iron complex and its salt, halomethyloxaziazole compound, 3-aryl substituted coumarin compound. Compounds are preferred.
  • More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds.
  • At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more preferable.
  • the photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone).
  • 2-benzyl such as benzophenone
  • benzoin ether compounds such as benzoin alkyl ether
  • benzoin compounds such as benzoin and alkyl benzoin
  • benzyl derivatives such as benzyl dimethyl ketal.
  • a compound represented by the following formula (I) can also be used.
  • R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like.
  • R I01 is a group represented by formula (II), the same as R I00
  • the groups, R I02 to R I04, are independently alkyls having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogens, respectively.
  • R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
  • the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/1254669 can also be used.
  • the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total is preferably in the above range.
  • the curable resin composition of the present invention may contain a thermal polymerization initiator as the polymerization initiator, and may particularly contain a thermal radical polymerization initiator.
  • a thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the heterocyclic polymer precursor can be allowed to proceed as well as the cyclization of the heterocyclic polymer precursor, so that higher heat resistance can be achieved.
  • thermal radical polymerization initiator examples include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
  • the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. %, More preferably 5 to 15% by mass. Only one type of thermal radical polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal radical polymerization initiators are contained, the total is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a polymerizable compound.
  • the definition of this polymerizable compound includes a compound represented by the above formula (1-1) and a group capable of condensing with at least one group selected from the group consisting of the above-mentioned hydroxy group and thiol group. Compounds having multiple compounds shall not be included.
  • a radically polymerizable compound can be used as the polymerizable compound.
  • the radically polymerizable compound is a compound having a radically polymerizable group.
  • Examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
  • the radically polymerizable group is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.
  • the number of radically polymerizable groups contained in the radically polymerizable compound may be one or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, and preferably has three or more radically polymerizable groups. More preferred.
  • the upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the molecular weight of the radically polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more.
  • the curable resin composition of the present invention preferably contains at least one bifunctional or higher functional radical polymerizable compound containing two or more radical polymerizable groups, and is preferably a trifunctional or higher functional radical polymerizable compound. It is more preferable to contain at least one kind. Further, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound.
  • the number of functional groups of a bifunctional or higher functional polymerizable monomer means that the number of radically polymerizable groups in one molecule is two or more.
  • the radically polymerizable compound examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and preferred examples thereof.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group.
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amines or thiols, and a halogeno group.
  • Substitution reactions of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
  • a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
  • examples include polyethylene glycol di (meth) acrylate, trimethylol ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol.
  • Penta (meth) acrylate dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylpropantri (acryloxypropyl) ether, tri (acryloxyethyl) isocyanurate, glycerin, trimethylolethane, etc.
  • a compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993.
  • Urethane (meth) acrylates such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.
  • a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
  • a preferable radically polymerizable compound other than the above it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like. It is also possible to use a compound having two or more groups having the above, or a cardo resin.
  • the compound described in Japanese Patent Application Laid-Open No. 10-062986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol is also (meth) acrylated. It can be used as a radically polymerizable compound.
  • radically polymerizable compound examples include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku).
  • SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
  • SR-209 which is a bifunctional methacrylate having four ethyleneoxy chains.
  • DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS- 10, UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H ( Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.
  • Examples of the radically polymerizable compound include urethane acrylates as described in JP-A-48-041708, JP-A-51-0371993, JP-A-02-032293, and JP-A-02-016765.
  • Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
  • radically polymerizable compound compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. It can also be used.
  • the radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxy group or a phosphoric acid group.
  • the radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
  • a radically polymerizable compound having a group is more preferable.
  • the aliphatic polyhydroxy compound in a radical polymerizable compound in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, is pentaerythritol or dipenta. It is a compound that is erythritol.
  • examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
  • the acid value of the radically polymerizable compound is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizable property is good.
  • the acid value is measured according to the description of JIS K 0070: 1992.
  • a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the cured film.
  • the monofunctional radically polymerizable compound include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth).
  • Acrylate derivatives N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used.
  • the monofunctional radical polymerizable compound a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
  • the curable resin composition of the present invention can further contain a polymerizable compound other than the radically polymerizable compound described above.
  • a polymerizable compound other than the above-mentioned radically polymerizable compound include a compound having a hydroxymethyl group and an acyloxymethyl group; and a benzoxazine compound.
  • R 104 represents an organic group having a t-valence of 1 to 200 carbon atoms
  • R 105 is a group represented by -OR 106 or -OCO-R 107.
  • R 106 represents a hydrogen atom
  • R 107 represents an organic group having 1 to 10 carbon atoms.
  • R 404 represents a divalent organic group having 1 to 200 carbon atoms
  • R 405 represents a group represented by -OR 406 or -OCO-R 407
  • R 406 represents a hydrogen atom.
  • R 407 represents an organic group having 1 to 10 carbon atoms.
  • U in the formula represents an integer of 3 to 8
  • R 504 represents a u-valent organic group having 1 to 200 carbon atoms
  • R 505 represents a group represented by -OR 506 or -OCO-R 507.
  • R 506 represents a hydrogen atom
  • R 507 represents an organic group having 1 to 10 carbon atoms.
  • Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML. -PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylolBisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), etc. Can be mentioned.
  • Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, and the like.
  • Examples thereof include HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), and TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.).
  • benzoxazine compound Preferred examples of the benzoxazine compound are BA type benzoxazine, Bm type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzo.
  • Oxazine compounds can be mentioned. These may be used alone or in combination of two or more.
  • the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable resin composition of the present invention.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
  • the curable resin composition of the present invention has an embodiment in which the content of the polymerizable compound is less than 5% by mass with respect to the total mass of the curable resin composition from the viewpoint of further improving chemical resistance. You can also do it.
  • the content is preferably less than 3% by mass, more preferably less than 1% by mass.
  • the lower limit of the content is not particularly limited, and may be 0% by mass or more.
  • One type of polymerizable compound may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a solvent.
  • a solvent a known solvent can be arbitrarily used.
  • the solvent is preferably an organic solvent.
  • the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
  • esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, and ⁇ -caprolactone.
  • alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)
  • 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate
  • Etc. eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate
  • 2-alkyloxy-2-methylpropionate etc.
  • Methyl acid and ethyl 2-alkyloxy-2-methylpropionate eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
  • methyl pyruvate, ethyl pyruvate, pyruvin Suitable examples include propyl acid acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate and the like.
  • ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol.
  • Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
  • ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferable.
  • aromatic hydrocarbons for example, toluene, xylene, anisole, limonene and the like are preferable.
  • sulfoxides for example, dimethyl sulfoxide is preferable.
  • N-methyl-2-pyrrolidone N-ethyl-2-pyrrolidone
  • N, N-dimethylacetamide N, N-dimethylformamide and the like are preferable.
  • the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
  • the mixed solvent to be mixed is preferable.
  • the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
  • the content of the solvent is preferably such that the total solid content concentration of the curable resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferable that the amount is 10 to 70% by mass, and more preferably 40 to 70% by mass.
  • the solvent content may be adjusted according to the desired thickness and coating method.
  • the solvent may contain only one type, or may contain two or more types. When two or more kinds of solvents are contained, the total is preferably in the above range.
  • the curable resin composition of the present invention preferably further contains a migration inhibitor.
  • a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the curable resin composition layer.
  • the migration inhibitor is not particularly limited, but is a heterocycle (pyran ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
  • triazole-based compounds such as 1,2,4-triazole and benzotriazole
  • tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.
  • an ion trap agent that traps anions such as halogen ions can also be used.
  • Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656.
  • the compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used.
  • the migration inhibitor include the following compounds.
  • the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the curable resin composition, and is 0. It is more preferably 0.05 to 2.0% by mass, and further preferably 0.1 to 1.0% by mass.
  • the migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a polymerization inhibitor.
  • polymerization inhibitor examples include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'.
  • -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, Bis (4-hydroxy-3,5-ter
  • the content of the polymerization inhibitor shall be 0.01 to 5% by mass with respect to the total solid content of the curable resin composition of the present invention. Is more preferable, 0.02 to 3% by mass is more preferable, and 0.05 to 2.5% by mass is further preferable.
  • the polymerization inhibitor may be only one type or two or more types. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
  • a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
  • the metal adhesiveness improving agent include a silane coupling agent.
  • silane coupling agent examples include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992.
  • Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent.
  • Et represents an ethyl group.
  • the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used. ..
  • the content of the metal adhesion improver is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further, with respect to 100 parts by mass of the heterocyclic polymer precursor. It is preferably in the range of 0.5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the cured film and the metal layer after the curing step is good, and when it is at least the above upper limit value, the heat resistance and mechanical properties of the cured film after the curing step are good.
  • the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.
  • the curable resin composition of the present invention contains various additives such as a thermoacid generator, a sensitizer such as N-phenyldiethanolamine, and a chain transfer agent, if necessary, as long as the effects of the present invention are not impaired.
  • additives such as a thermoacid generator, a sensitizer such as N-phenyldiethanolamine, and a chain transfer agent, if necessary, as long as the effects of the present invention are not impaired.
  • Surfactants, higher fatty acid derivatives, inorganic particles, curing agents, curing catalysts, fillers, antioxidants, ultraviolet absorbers, antiaggregating agents and the like can be blended.
  • the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.
  • the curable resin composition of the present invention may contain a sensitizer.
  • the sensitizer absorbs specific active radiation and enters an electronically excited state.
  • the sensitizer in the electron-excited state comes into contact with the thermal curing accelerator, the thermal radical polymerization initiator, the photoradical polymerization initiator, and the like, and acts such as electron transfer, energy transfer, and heat generation occur.
  • the thermal curing accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases.
  • the sensitizer include sensitizers such as N-phenyldiethanolamine.
  • the content of the sensitizer may be 0.01 to 20% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass.
  • the sensitizer may be used alone or in combination of two or more.
  • the curable resin composition of the present invention may contain a chain transfer agent.
  • Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684.
  • As the chain transfer agent for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
  • a thiol compound can be preferably used.
  • the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition of the present invention.
  • 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable.
  • the chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.
  • Each type of surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving the coatability.
  • the surfactant various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used.
  • the following surfactants are also preferable.
  • the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit
  • the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.
  • the surfactant the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
  • the content of the surfactant is 0.001 to 2.0% by mass based on the total solid content of the curable resin composition of the present invention. It is preferably 0.005 to 1.0% by mass, more preferably 0.005 to 1.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When there are two or more types of surfactant, the total is preferably in the above range.
  • the curable resin composition of the present invention has a curable resin composition in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of an object.
  • a higher fatty acid derivative such as behenic acid or behenic acid amide
  • the content of the higher fatty acid derivative is 0.1 to 10% by mass with respect to the total solid content of the curable resin composition of the present invention. Is preferable. Only one type of higher fatty acid derivative may be used, or two or more types may be used. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.
  • the water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties.
  • the metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulating properties.
  • the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.
  • a raw material having a low metal content is selected as a raw material constituting the curable resin composition of the present invention.
  • Methods such as filtering the raw materials constituting the curable resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible can be mentioned. be able to.
  • the curable resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably 200 mass ppm from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
  • the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
  • a conventionally known storage container can be used as the storage container for the curable resin composition of the present invention.
  • a multi-layer bottle having the inner wall of the container composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a bottle having a layered structure. Examples of such a container include the container described in JP-A-2015-123351.
  • the curable resin composition of the present invention can be prepared by mixing the above components.
  • the mixing method is not particularly limited, and a conventionally known method can be used.
  • the filter pore diameter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the filter may be one that has been pre-cleaned with an organic solvent.
  • a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters or materials may be used in combination. In addition, various materials may be filtered a plurality of times.
  • circulation filtration When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
  • impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
  • adsorbent a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
  • the curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer. In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.
  • the cured film of the present invention is obtained by curing the curable resin composition of the present invention.
  • the film thickness of the cured film of the present invention can be, for example, 0.5 ⁇ m or more, and can be 1 ⁇ m or more. Further, the upper limit value can be 100 ⁇ m or less, and can be 30 ⁇ m or less.
  • the cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. It is preferable that the laminate of the present invention contains two or more cured films and includes a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferable.
  • the first cured film and the second cured film are both cured films of the present invention.
  • both the first cured film and the second cured film are curable of the present invention.
  • a preferred embodiment is a film obtained by curing the resin composition.
  • the curable resin composition of the present invention used for forming the first cured film and the curable resin composition of the present invention used for forming the second cured film have the same composition. It may be a composition having a different composition.
  • the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
  • Examples of applicable fields of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
  • a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above may be patterned by etching. For these applications, for example, Science & Technology Co., Ltd.
  • the cured film in the present invention can also be used for manufacturing a plate surface such as an offset plate surface or a screen plate surface, using it for etching molded parts, and manufacturing a protective lacquer and a dielectric layer in electronics, particularly microelectronics.
  • the method for producing a cured film of the present invention includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film.
  • the method for producing a cured film of the present invention preferably includes the film forming step, an exposure step for exposing the film, and a developing step for developing the film.
  • the method for producing a cured film of the present invention more preferably includes the film forming step and, if necessary, the developing step, and also includes a heating step of heating the film at 50 to 450 ° C. Specifically, it is also preferable to include the following steps (a) to (d).
  • A Film forming step of applying the curable resin composition to a substrate to form a film (curable resin composition layer)
  • Exposure step of exposing the film after the film forming step
  • Exposure Development step for developing the film
  • Heating step for heating the developed film at 50 to 450 ° C. By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the above-mentioned thermal base generator is decomposed to obtain sufficient curability.
  • the method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention.
  • the method for producing the laminated body of the present embodiment is the step (a), the steps (a) to (c), or (a) after the cured film is formed according to the above-mentioned method for producing the cured film. )-(D).
  • a laminated body can be obtained.
  • the production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the curable resin composition is applied to a substrate to form a film (layered).
  • the type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, There are no particular restrictions on magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe, paper, SOG (Spin On Glass), TFT (thin film) array substrates, and electrode plates of plasma display panels (PDPs).
  • a semiconductor-made base material is particularly preferable, and a silicon base material is more preferable.
  • a plate-shaped base material (board) is used as the base material.
  • the resin layer or the metal layer serves as a base material.
  • Coating is preferable as a means for applying the curable resin composition to the base material.
  • the means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method.
  • the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable.
  • a resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the substrate.
  • a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method is preferable.
  • the method, the inkjet method and the like are preferable.
  • the spin coating method for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. It is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate.
  • the transfer method the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention.
  • the production method of the present invention may include a step of forming the film (curable resin composition layer), followed by a film forming step (layer forming step), and then drying to remove the solvent.
  • the preferred drying temperature is 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C.
  • the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
  • the production method of the present invention may include an exposure step of exposing the film (curable resin composition layer).
  • the amount of exposure is not particularly determined as long as the curable resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ /. It is more preferable to irradiate with cm 2 .
  • the exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
  • the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h.
  • the curable resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays. As a result, particularly high exposure sensitivity can be obtained.
  • the production method of the present invention may include a developing step of developing the exposed film (curable resin composition layer) (developing the film). By performing the development, the unexposed portion (non-exposed portion) is removed.
  • the developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.
  • the developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
  • the developer preferably contains an organic solvent, and more preferably the developer contains 90% or more of the organic solvent.
  • the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3.
  • the ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
  • Organic solvents include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone.
  • alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl propionate ethoxyacetate, etc.)
  • alkyl esters of 3-alkyloxypropionate eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-
  • Ke Tons include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc.
  • aromatic hydrocarbons include, for example, toluene, xylene, anisole, limonene, etc.
  • Dimethyl sulfoxide is preferably mentioned as the sulfoxides.
  • cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.
  • the developing solution preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent. Further, the developing solution may be 100% by mass of an organic solvent.
  • the development time is preferably 10 seconds to 5 minutes.
  • the temperature of the developing solution at the time of development is not particularly specified, but is usually 20 to 40 ° C.
  • the rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with a solvent contained in the curable resin composition.
  • the rinsing time is preferably 5 seconds to 1 minute.
  • the production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ° C.
  • the heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step.
  • the heating step for example, the above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the heterocyclic polymer precursor proceeds.
  • the curable resin composition of the present invention may contain a radically polymerizable compound other than the heterocyclic polymer precursor, but may also cure a radically polymerizable compound other than the unreacted heterocyclic polymer precursor. It can be advanced in this step.
  • the heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable.
  • the upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.
  • the heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
  • a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
  • the temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C.
  • the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started.
  • the temperature of the film (layer) after drying is higher than, for example, the boiling point of the solvent contained in the curable resin composition. It is preferable to gradually raise the temperature from a temperature as low as 30 to 200 ° C.
  • the heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.
  • the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C. from the viewpoint of adhesion between layers of the cured film.
  • the ethynyl groups of the heterocyclic polymer precursors between the layers are undergoing a cross-linking reaction at this temperature.
  • Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed.
  • the heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547.
  • the pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
  • the pretreatment may be performed in two or more steps.
  • the pretreatment step 1 may be performed in the range of 100 to 150 ° C.
  • the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
  • cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
  • the heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the heterocyclic polymer precursor.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
  • the production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (curable resin composition layer).
  • metal layer existing metal types can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper is preferable. More preferred.
  • the method for forming the metal layer is not particularly limited, and an existing method can be applied.
  • the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used.
  • photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
  • the thickness of the metal layer is preferably 0.1 to 50 ⁇ m, more preferably 1 to 10 ⁇ m at the thickest portion.
  • the production method of the present invention preferably further includes a laminating step.
  • the laminating step means that (a) film forming step (layer forming step), (b) exposure step, (c) developing step, and (d) heating step are performed again on the surface of the cured film (resin layer) or metal layer. , A series of steps including performing in this order. However, the mode may be such that only the film forming step (a) is repeated. Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated curable resin composition layers all at once.
  • the (c) developing step may include (e) a metal layer forming step, and even if the heating is performed each time (d), the steps of (d) are collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the drying step, the heating step, and the like as appropriate.
  • the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step.
  • An example of the surface activation treatment is plasma treatment.
  • the laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
  • the resin layer is 3 or more and 7 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, and more preferably 3 or more and 5 or less.
  • a cured film (resin layer) of the curable resin composition so as to cover the metal layer after the metal layer is provided.
  • Examples thereof include an embodiment in which the steps, (b) exposure steps, (c) development steps, and (e) metal layer forming steps are repeated in this order, and (d) heating steps are collectively provided at the end or in the middle.
  • the present invention also discloses a semiconductor device containing the cured film or laminate of the present invention.
  • the semiconductor device in which the curable resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer the description in paragraphs 0213 to 0218 and the description in FIG. 1 of JP-A-2016-0273557 are taken into consideration. Yes, these contents are incorporated herein.
  • reaction mixture was cooled to room temperature and 21.43 g (270.9 mmol) of pyridine and 90 mL of N-methylpyrrolidone were added.
  • the reaction mixture was then cooled to ⁇ 10 ° C. and 16.12 g (135.5 mmol) of SOCL 2 was added over 10 minutes while keeping the temperature at ⁇ 10 ⁇ 4 ° C. Viscosity increased while SOCL 2 was added. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours.
  • the polyimide precursor was removed by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. The obtained polyimide precursor was then dried under reduced pressure at 45 ° C. for 3 days. The weight average molecular weight of this polyimide precursor was 18,000.
  • the obtained diester is chlorinated with SOCL 2 , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether by the same method as in Synthesis Example 1, and the polyimide precursor is converted into a polyimide precursor by the same method as in Synthesis Example 1. Obtained.
  • the weight average molecular weight of this polyimide precursor was 18,000.
  • ⁇ Synthesis example 4> [4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotridine) and polyimide precursor from 2-hydroxyethyl methacrylate (A-4: having a radically polymerizable group) Synthesis of polyimide precursor)] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g of hydroquinone.
  • the polybenzoxazole precursor was then precipitated in 6 liters of water and the water-polybenzoxazole precursor mixture was stirred at a rate of 5000 rpm for 15 minutes.
  • the polybenzoxazole precursor was filtered off and stirred again in 6 liters of water for 30 minutes and filtered again.
  • the resulting polybenzoxazole precursor was then dried under reduced pressure at 45 ° C. for 3 days.
  • the weight average molecular weight of this polybenzoxazole precursor was 15,000.
  • the obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate composed of a crude polymer.
  • the produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution.
  • the obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polymer A-6.
  • the weight average molecular weight (Mw) of this polymer A-6 was measured and found to be 20,000.
  • ⁇ Synthesis example 7> [3,3', 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-diaminodiphenyl ether, and polyimide precursor from 2-hydroxyethyl methacrylate (A-7: Polyimide having a radically polymerizable group) Synthesis of precursor)] Synthesis Example 6 except that 147.1 g of 3,3'4,4'-biphenyltetracarboxylic acid dianhydride was used instead of 155.1 g of 4,4'-oxydiphthalic acid dianhydride in Synthesis Example 7. The reaction was carried out in the same manner as described in 1. Polymer A-7 was obtained. The weight average molecular weight (Mw) of this polymer A-7 was measured and found to be 22,000.
  • the mixture was extracted by pouring into a solution of 150 ml of ethyl acetate and 150 ml of 3 mass% dilute hydrochloric acid water with stirring.
  • the ethyl acetate solution was dried over anhydrous sodium sulfate, 50 mg of 4-methoxyphenol was added, and ethyl acetate was distilled off under reduced pressure.
  • Examples and Comparative Examples> In each example, the components listed in Table 1 below were mixed to obtain each curable resin composition. Further, in each comparative example, the components shown in Table 1 below were mixed to obtain each comparative composition. Specifically, the content of the components listed in the columns other than "solvent” in Table 1 shall be the amount listed in "parts by mass” in Table 1, and the content of the components listed in the column “solvent” in Table 1 shall be included. The amount was such that the solid content concentration of the composition was the value shown in Table 1. Further, for example, in the description of "I-1 / I-2" and "80/20" of "solvent” in Table 1, the ratio of the contents of I-1 and I-2 is I-1: I in terms of mass ratio.
  • ⁇ Additive ⁇ ⁇ J-1 Death module BL3575 / 1 (manufactured by Covestro)
  • ⁇ J-2 N-Phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • -RB-1 for comparative example: A compound having the following structure
  • [Migration inhibitor] -G-1 to G-2 Compounds having the following structure [Metal adhesion improver] -H-1 to H-3: Compounds having the following structures ⁇ solvent ⁇
  • I-1 ⁇ -Butyrolactone (manufactured by Sanwa Yuka Co., Ltd.)
  • I-2 Dimethyl sulfoxide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • I-3 N-methyl-2-pyrrolidone (manufactured by Ashland)
  • I-4 Ethyl lactate (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • a curable resin composition or a comparative composition was applied onto a silicon wafer by a spin coating method to form a resin layer.
  • the silicon wafer on which the resin layer was formed was dried on a hot plate at 100 ° C. for 4 minutes to obtain a resin composition layer having a uniform thickness of 20 ⁇ m on the silicon wafer.
  • the resin composition layer on the silicon wafer was exposed to an exposure energy of 400 mJ / cm 2 using a broadband exposure machine (manufactured by Ushio, Inc .: UX-1000SN-EH01), and the exposed resin composition layer was exposed.
  • the temperature was raised at a heating rate of 5 ° C./min under a nitrogen atmosphere, and after reaching 180 ° C., heating was performed at this temperature for 2 hours.
  • the heated resin composition layer and the silicon wafer were immersed in a 3 mass% hydrofluoric acid aqueous solution, and the heated resin composition layer was peeled off from the silicon wafer. The peeled and heated resin composition layer was used as a cured film.
  • the dissolution rate is less than 250 nm / min.
  • B The dissolution rate is 250 nm / min or more and less than 500 nm / min.
  • C The dissolution rate is 500 nm / min or more.
  • the curable resin composition containing the heterocyclic polymer precursor and the compound represented by the formula (1-1) according to the present invention has excellent chemical resistance of the cured film. ..
  • the curable resin composition according to Comparative Examples 1 and 2 does not contain the compound represented by the formula (1-1). It can be seen that the curable resin compositions according to Comparative Examples 1 and 2 are inferior in the chemical resistance of the cured film.
  • Example 101 The curable resin composition according to Example 1 is applied in layers to the surface of a resin base material on which a thin copper layer is formed by a spin coating method, dried at 100 ° C. for 5 minutes, and has a curability of a film thickness of 20 ⁇ m. After forming the resin composition layer, it was exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm via a mask (a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m). After exposure, it was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a layer pattern.
  • NSR1505 i6 a binary mask with a pattern of 1: 1 line and space and a line width of 10 ⁇ m.
  • the interlayer insulating film for the rewiring layer was excellent in insulating properties. Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Materials For Photolithography (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

La présente invention concerne une composition de résine durcissable qui comprend un précurseur de polymère sélectionné dans le groupe constitué d'un précurseur de polyimide et d'un précurseur de polybenzoxazole et d'un composé représenté par la formule (1-1); un film durci obtenu par durcissement de la composition de résine durcissable; un produit stratifié comprenant le film durci; un procédé de production du film durci; et un dispositif à semi-conducteur comprenant le film durci ou le produit stratifié. Dans la formule (1-1), X1 représente -O- ou -S-, L1 représente un groupe de liaison divalent ayant un poids de formule de 1000 ou moins, R1 et R2 représentent chacun indépendamment un groupe organique monovalent et R1 et au moins un de R2 et L contiennent un groupe non saturé par l'éthylène.
PCT/JP2020/012594 2019-03-27 2020-03-23 Composition de résine durcissable, film durci, produit stratifié, procédé de production de film durci, et dispositif à semi-conducteurs WO2020196363A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2021509365A JP7177249B2 (ja) 2019-03-27 2020-03-23 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
KR1020217030851A KR102637928B1 (ko) 2019-03-27 2020-03-23 경화성 수지 조성물, 경화막, 적층체, 경화막의 제조 방법, 및, 반도체 디바이스

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019060798 2019-03-27
JP2019-060798 2019-03-27

Publications (1)

Publication Number Publication Date
WO2020196363A1 true WO2020196363A1 (fr) 2020-10-01

Family

ID=72610931

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/012594 WO2020196363A1 (fr) 2019-03-27 2020-03-23 Composition de résine durcissable, film durci, produit stratifié, procédé de production de film durci, et dispositif à semi-conducteurs

Country Status (4)

Country Link
JP (1) JP7177249B2 (fr)
KR (1) KR102637928B1 (fr)
TW (1) TWI836038B (fr)
WO (1) WO2020196363A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114524938A (zh) * 2021-10-28 2022-05-24 江苏三月科技股份有限公司 一种聚合物、感光树脂组合物及其制备的固化膜与电子元件
WO2023032820A1 (fr) * 2021-08-31 2023-03-09 富士フイルム株式会社 Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur, dispositif à semi-conducteur et composé
WO2023190061A1 (fr) * 2022-03-29 2023-10-05 富士フイルム株式会社 Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000515129A (ja) * 1996-06-24 2000-11-14 サイテク・テクノロジー・コーポレーシヨン 重合性尿素／ウレイド官能モノマー類
JP2003301164A (ja) * 2002-02-05 2003-10-21 Nitto Denko Corp 重合性ゲル化剤
WO2017002858A1 (fr) * 2015-06-30 2017-01-05 富士フイルム株式会社 Composition de précurseur, composition de résine photosensible, procédé de production d'une composition de précurseur, film durci, procédé de production de film durci, et dispositif à semi-conducteur

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4999318B2 (ja) 2005-11-16 2012-08-15 マナック株式会社 ビスイミド又はビスイソイミド化合物及びそれを含む樹脂組成物
JP5602448B2 (ja) * 2009-03-26 2014-10-08 富士フイルム株式会社 顔料分散液、着色硬化性組成物、カラーフィルタ、及びカラーフィルタの製造方法
WO2017169574A1 (fr) * 2016-03-30 2017-10-05 東レ株式会社 Composition adhésive photosensible, produit durci, feuille adhésive photosensible, et procédé de fabrication d'un substrat stratifié et substrat stratifié comportant un motif adhésif
JP2019026697A (ja) * 2017-07-27 2019-02-21 日立化成株式会社 重合性モノマー、並びに、それを用いたポリマー、ゲル及びゲル化方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000515129A (ja) * 1996-06-24 2000-11-14 サイテク・テクノロジー・コーポレーシヨン 重合性尿素／ウレイド官能モノマー類
JP2003301164A (ja) * 2002-02-05 2003-10-21 Nitto Denko Corp 重合性ゲル化剤
WO2017002858A1 (fr) * 2015-06-30 2017-01-05 富士フイルム株式会社 Composition de précurseur, composition de résine photosensible, procédé de production d'une composition de précurseur, film durci, procédé de production de film durci, et dispositif à semi-conducteur

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023032820A1 (fr) * 2021-08-31 2023-03-09 富士フイルム株式会社 Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur, dispositif à semi-conducteur et composé
CN114524938A (zh) * 2021-10-28 2022-05-24 江苏三月科技股份有限公司 一种聚合物、感光树脂组合物及其制备的固化膜与电子元件
CN114524938B (zh) * 2021-10-28 2024-02-09 江苏三月科技股份有限公司 一种聚合物、感光树脂组合物及其制备的固化膜与电子元件
WO2023190061A1 (fr) * 2022-03-29 2023-10-05 富士フイルム株式会社 Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur

Also Published As

Publication number Publication date
KR20210134002A (ko) 2021-11-08
JPWO2020196363A1 (ja) 2021-12-23
TWI836038B (zh) 2024-03-21
TW202102941A (zh) 2021-01-16
KR102637928B1 (ko) 2024-02-21
JP7177249B2 (ja) 2022-11-22

Similar Documents

Publication Publication Date Title
CN112639616A (zh) 感光性树脂组合物、固化膜、层叠体、固化膜的制造方法及半导体器件
JP7065120B2 (ja) 感光性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、積層体の製造方法、半導体デバイス
JP7008732B2 (ja) 感光性樹脂組成物、樹脂、硬化膜、積層体、硬化膜の製造方法、半導体デバイス
JP7237978B2 (ja) 樹脂組成物、硬化膜、積層体、硬化膜の製造方法、および半導体デバイス
JP7333383B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
JP7277572B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
JP2020154205A (ja) パターン形成方法、硬化性樹脂組成物、膜、硬化膜、積層体、及び、半導体デバイス
JP7177249B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
JP7477579B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、半導体デバイス、及び、ポリマー前駆体
WO2020189481A1 (fr) Composition de résine durcissable, film durci, corps multicouche, procédé de production de film durci et dispositif à semi-conducteur
WO2021002383A1 (fr) Composition de résine durcissable, procédé de production de composition de résine durcissable, film durci, corps multicouche, procédé de production de film durci et dispositif à semi-conducteur
WO2020255859A1 (fr) Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et polyimide ou précurseur de polyimide
JP7277573B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
JP7023379B2 (ja) 樹脂組成物、硬化膜、積層体、硬化膜の製造方法、および半導体デバイス
JP7086882B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
JP7351896B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、半導体デバイス、及び、熱塩基発生剤
WO2020246234A1 (fr) Composition durcissable négative, film durci, produit en couches, procédé de production de film durci, et dispositif à semi-conducteur
WO2020255825A1 (fr) Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et polyimide, polybenzoxazole, précurseur de polyimide ou précurseur de polybenzoxazole
JPWO2019189327A1 (ja) 感光性樹脂組成物、硬化膜、積層体およびこれらの応用
WO2020262228A1 (fr) Composition de resine durcissable, film durci, corps stratifie, procede de fabrication de film durci et dispositif a semi-conducteurs
JP7426375B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、半導体デバイス、及び、熱塩基発生剤
TWI856063B (zh) 硬化性樹脂組成物、硬化膜、積層體、硬化膜的製造方法、半導體器件及熱鹼產生劑
JP6875526B2 (ja) 熱硬化性樹脂組成物、およびその硬化膜、積層体、半導体デバイス、ならびにそれらの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20777853

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021509365

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20217030851

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20777853

Country of ref document: EP

Kind code of ref document: A1