WO2020189481A1 - Composition de résine durcissable, film durci, corps multicouche, procédé de production de film durci et dispositif à semi-conducteur - Google Patents

Composition de résine durcissable, film durci, corps multicouche, procédé de production de film durci et dispositif à semi-conducteur Download PDF

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Publication number
WO2020189481A1
WO2020189481A1 PCT/JP2020/010733 JP2020010733W WO2020189481A1 WO 2020189481 A1 WO2020189481 A1 WO 2020189481A1 JP 2020010733 W JP2020010733 W JP 2020010733W WO 2020189481 A1 WO2020189481 A1 WO 2020189481A1
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group
formula
resin composition
curable resin
preferable
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PCT/JP2020/010733
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English (en)
Japanese (ja)
Inventor
倫弘 小川
修平 山口
悠 岩井
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富士フイルム株式会社
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Priority to JP2021507266A priority Critical patent/JP7281533B2/ja
Publication of WO2020189481A1 publication Critical patent/WO2020189481A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a curable resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.
  • 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 as 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 contains (A) a polyimide precursor and (B) a photosensitizer, and the (A) polyimide precursor is an amic acid represented by (a-1) the general formula (1).
  • a photosensitive resin composition which is a resin having a structural unit of an ester, is described.
  • Patent Document 2 describes a tetracarboxylic acid diester compound characterized by having a specific structure.
  • Patent Document 3 describes a polyamic acid characterized by containing a specific repeating unit.
  • curable resin composition containing a heterocyclic-containing polymer precursor such as a polyimide precursor, it is desired to provide a curable resin composition having an excellent elongation at break of the obtained cured product.
  • a heterocyclic-containing polymer precursor such as a polyimide precursor
  • the present invention relates to a curable resin composition having an excellent elongation at break 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 the like.
  • An object of the present invention is to provide a semiconductor device including the cured film or the laminate.
  • At least one type of branched structure selected from the group consisting of the branched structure represented by the following formula (A-1) and the branched structure represented by the following formula (A-2).
  • R 115 represents a tetravalent organic group
  • RA 21 represents a hydrogen atom or a monovalent organic group
  • * is an independent structure with another structure. Represents the binding site of.
  • ⁇ 2> The curable resin composition according to ⁇ 1>, wherein the content of the branched structure contained in the polyimide precursor is 0.01 to 10 ⁇ mol / g with respect to the total solid content of the composition.
  • ⁇ 3> The curable resin composition according to any one of ⁇ 1> or ⁇ 2>, wherein the polyimide precursor has a repeating unit represented by the following formula (1); In formula (1), A 1 and A 2 independently represent an oxygen atom or -NH-, R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, and R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, and * 1 and * 2 each independently represent a bonding site with another structure.
  • R 111 in the above formula (1) is represented by the following formula (51) or formula (61);
  • R 50 to R 57 independently represent a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom and a methyl group.
  • Fluoromethyl group, difluoromethyl group or trifluoromethyl group, R 58 and R 59 independently represent fluorine atom, fluoromethyl group, difluoromethyl group or trifluoromethyl group, and * independently represent each. Represents a site of connection with other structures.
  • the curable resin composition according to one. ⁇ 9> The curable resin composition according to any one of ⁇ 1> to ⁇ 8>, further comprising a radical polymerization initiator, a radical polymerizable compound, a silane coupling agent, and an onium salt.
  • ⁇ 10> The curable resin composition according to any one of ⁇ 1> to ⁇ 9>, which further contains another heterocyclic-containing polymer precursor different from the above-mentioned polyimide precursor.
  • ⁇ 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.
  • 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.
  • ⁇ 15> 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.
  • ⁇ 16> The method for producing a cured film according to ⁇ 14> or ⁇ 15>, which comprises a heating step of heating the film at 80 to 450 ° C.
  • a semiconductor device comprising the cured film according to ⁇ 12> or the laminate according to ⁇ 13>.
  • 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 physical property values are values under the conditions of a temperature of 23 ° C. and an atmospheric pressure of 101,325 Pa (1 atm) unless otherwise specified.
  • the combination of preferred embodiments is a more preferred embodiment.
  • the curable resin composition of the present invention (hereinafter, also simply referred to as “the composition of the present invention”) is represented by a branched structure represented by the formula (A-1) and a formula (A-2).
  • a polyimide precursor having at least one branched structure selected from the group consisting of branched structures and having a branched chain having a repeating unit as a branched chain to be bonded to the branched structure (hereinafter, Also referred to as "specific polymer precursor”).
  • the curable resin composition of the present invention preferably further contains a radical polymerization initiator described later, a radical polymerizable compound described later, a silane coupling agent described later, and an onium salt described later.
  • the curable resin composition of the present invention is excellent in the elongation at break of the obtained cured film.
  • the mechanism by which the above effect is obtained is unknown, but it is presumed as follows.
  • a polyimide precursor having a branched chain having a repeating unit as a specific branched structure and a molecular chain bonded to the branched structure
  • the entanglement of the polymer chains in the polymer formed after curing is increased. Therefore, it is presumed that the elongation at break is improved.
  • the storage stability is likely to be improved because the cyclization during storage is suppressed due to the steric hindrance effect of having the branched chain.
  • Patent Documents 1 to 3 do not describe or suggest a composition containing a specific polymer precursor. Further, the cured film obtained by curing the curable resin composition in Patent Documents 1 to 3 has a problem that the elongation at break is low.
  • 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 specific polymer precursor.
  • the specific polymer precursor has at least one branched structure selected from the group consisting of the branched structure represented by the formula (A-1) and the branched structure represented by the formula (A-2).
  • a polyimide precursor having a branched chain having a repeating unit is included as the branched chain having and bonded to the branched structure. It is preferable that * in the formulas (A-1) and (A-2) is bound to a molecular chain having a repeating unit.
  • a molecular chain having a repeating unit and having the longest molecular chain is referred to as a main chain
  • a molecular chain having a repeating unit and different from the main chain is referred to as a branched chain.
  • the main chain may have a branched structure
  • the branched chain may further have a branched structure and a branched chain.
  • the branched chain is bound to the main chain or the branched chain via the branched structure.
  • the specific polymer precursor has a branched structure represented by the following formula (A-1), a branched structure represented by the formula (A-2), and a branched structure represented by the formula (A-3). Includes a structure represented by at least one equation selected from the group consisting of branched structures.
  • R 115 represents a tetravalent organic group
  • RA 21 represents a hydrogen atom or a monovalent organic group
  • * represents an independent structure with another structure. Represents a binding site.
  • R 115 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.
  • O) 2- O
  • * Independently represent a binding site with another structure.
  • the tetravalent organic group represented by R 115 in the formula (A-1) is a tetracarboxylic acid residue (tetracarboxylic acid) that remains after the acid dianhydride group is removed from the tetracarboxylic dianhydride. (Structure in which all four of the four carboxy groups in the above are amidated) and the like. 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 (A-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
  • R 115 represents a tetravalent organic group.
  • R 115 in formula (A-2) has the same meaning as R 115 in formula (A-1), a preferable embodiment thereof is also the same.
  • R A21 represents a hydrogen atom or a monovalent organic group, the group represented by hydrogen or -X A21 -R A22 is preferable.
  • the X A21 represents an oxygen atom or ⁇ NH—, and an oxygen atom is preferable.
  • the RA22 represents a monovalent organic group, and a monovalent organic group containing a radically polymerizable group is preferable.
  • the radically polymerizable group may be any group that can undergo 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.
  • an aliphatic group, an aromatic group, an arylalkyl group or the like having one, two or three, preferably one acid group, etc. 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, RA22 is preferably a group having a hydroxy group.
  • a substituent that improves the solubility of the developing solution is preferably used.
  • RA22 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.
  • RA22 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 content of the branched structure contained in the specific polymer precursor is preferably 0.01 to 10 ⁇ mol / g with respect to the total solid content of the composition from the viewpoint of improving the elongation at break of the cured product. It is preferably 0.01 to 8 ⁇ mol / g, and more preferably 0.02 to 5 ⁇ mol / g.
  • the specific polymer precursor may have only one type of branched structure represented by the formula (A-1) or the formula (A-2) as the branched structure, or the formula (A-1) or The branched structure represented by the formula (A-2) may be provided as two or more branched structures having different structures. When the specific polymer precursor has two or more kinds of branched structures, the content of the branched structure is the branching represented by all the formulas (A-1) or (A-2) in the specific polymer precursor. The total content of the mold structure.
  • the specific polymer precursor may further have a branched structure represented by the following formula (A-3) as another branched structure.
  • RA31 represents an n-valent linking group
  • n represents an integer of 3 or more
  • * represents a binding site with another structure independently.
  • RA31 represents an n-valent linking group, which is a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, a heteroaromatic group, or these.
  • Examples of a group in which two or more are combined are a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 6 to 20 carbon atoms.
  • An aromatic group of 20 or a group in which two or more of these are combined is preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.
  • RA31 in the formula (A-3) is preferably derived from an n-valent amine compound.
  • the n-valent amine compound used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic n-valent amine compounds. Only one type of n-valent amine compound may be used, or two or more types may be used.
  • the n-valent amine compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, and an aromatic group having 6 to 20 carbon atoms.
  • it is preferably an n-valent amine compound containing a group in which two or more of these are combined, and more preferably an n-valent amine compound containing an aromatic group having 6 to 20 carbon atoms.
  • aromatic groups include the following.
  • n represents an integer of 3 or more
  • a represents an integer of 1 or more
  • b represents an integer of 1 or more
  • a + b is 3 or more
  • A is a carbon which may be substituted with a fluorine atom.
  • n is preferably an integer of 3 to 10, and more preferably an integer of 3 to 6.
  • a is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and more preferably 1 or 2.
  • b is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and more preferably 1 or 2.
  • a + b is preferably an integer of 3 to 10, and more preferably an integer of 3 to 6.
  • -It is more preferable that it is a divalent group selected from the group consisting of.
  • Each of the n * may be bonded to the same carbon atom in the formula, but it is preferably bonded to different carbon atoms.
  • Each of a * may be bonded to the same carbon atom in the formula, but it is preferably bonded to different carbon atoms.
  • Each of the b * may be bonded to the same carbon atom in the formula, but it is preferably bonded to a different carbon atom.
  • n-valent amine compound examples include compounds having the following structures.
  • n represents an integer of 3 or more, preferably an integer of 3 to 10, and more preferably an integer of 3 to 6.
  • the specific polymer precursor is selected as a repeating unit having a branched structure from a group consisting of a repeating unit represented by the following formula (B-1) and a repeating unit represented by the following formula (B-2). It is preferable to contain at least one kind. Further, the specific polymer precursor may further have a repeating unit represented by the following formula (B-3).
  • R 115 represents a tetravalent organic group
  • RA 21 represents a hydrogen atom or a monovalent organic group
  • B14 , RB21 , RB22 and RB23 independently represent a divalent linking group
  • RA31 represents an n-valent linking group
  • n represents an integer of 3 or more
  • a represents an integer of 1 to 3.
  • B represents an integer of 0 to 2
  • a + b is 3
  • * represents a coupling site with another structure independently.
  • R 115 has the same meaning as R 115 in the above formula (A-1), a preferable embodiment thereof is also the same.
  • RB11 , RB12 , RB13 and RB14 each independently represent 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 B11 , R B12 , R B13 and R B14 in the formula (B-1) are independently derived from the diamine.
  • the 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,
  • 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.
  • 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 B11 , R B12 , R B13 and R B14 in the formula (1) are independently divalent organic groups represented by the following formula (51) or the formula (61) from the viewpoint of i-ray transmittance. Is preferable. In particular, 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 has the same meaning as R 115 in the above formula (A-2), preferable embodiments thereof are also the same.
  • R A21 has the same meaning as R A21 in the above formula (A-2), preferable embodiments thereof are also the same.
  • R B21 , R B22, and R B23 are independently synonymous with R B11 , R B12 , R B13, and R B14 in the above formula (B-1), and the preferred embodiments are also the same. Is.
  • R 115 has the same meaning as R 115 in the above formula (A-1), a preferable embodiment thereof is also the same.
  • R A31 has the same meaning as R A31 in the above formula (A-3), preferable embodiments thereof are also the same.
  • n has the same meaning as n in the above formula (A-3), and the preferred embodiment is also the same.
  • a is preferably 1.
  • b is preferably 2.
  • the repeating unit represented by the formula (B-1) may be one kind, or two or more kinds. Good. Further, the structural isomer of the repeating unit represented by the formula (B-1) may be contained. Similarly, when the repeating unit represented by the formula (B-2) is included and when the repeating unit represented by the formula (B-3) is included, these repeating units may be one kind. However, it may be two or more kinds and may contain structural isomers.
  • the specific polymer precursor preferably contains a repeating unit other than the repeating unit having the above-mentioned branched structure.
  • the specific polymer precursor preferably has a repeating unit represented by the following formula (1) as the other repeating unit.
  • a 1 and A 2 independently represent an oxygen atom or -NH-
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group
  • * 1 and * 2 each independently represent a bonding site with another structure.
  • the specific polymer precursor is selected from the group consisting of a repeating unit represented by the formula (1), a repeating unit represented by the formula (B-1), and a repeating unit represented by the formula (B-2).
  • * 1 in the repeating unit represented by the formula (1) and the repeating unit represented by the formula (B-1) or the repeating unit represented by the formula (B-2) are shown. It is preferable that * in the repeating unit to be used is combined. Further, in this case, * 2 in the repeating unit represented by the formula (1) is preferably combined with * 1 in the repeating unit represented by the other formula (1).
  • the specific polymer precursor contains a repeating unit represented by the formula (1) and a repeating unit represented by the formula (B-3), * 2 in the repeating unit represented by the formula (1). And * in the repeating unit represented by the formula (B-3) are preferably combined. Further, in this case, * 1 in the repeating unit represented by the formula (1) is preferably combined with * 2 in the repeating unit represented by the other formula (1).
  • the repeating unit represented by the formula (B-1), the repeating unit represented by the formula (B-2), and the formula (B-) for all the repeating units.
  • the specific polymer precursor in which the total content of the repeating unit represented by 3) and the repeating unit represented by the formula (1) is 50 mol% or more, further 70 mol% or more, particularly 90 mol% or more. Is exemplified. As an upper limit, 100 mol% or less is practical.
  • the specific polymer precursor contains the repeating unit represented by the formula (1), the above-mentioned branched structure and the repeating unit represented by the formula (1) are bonded by any structure. May be good. That is, even when the specific polymer precursor contains the repeating unit represented by the formula (1), the structure of the specific polymer precursor is not particularly limited as long as it has the above-mentioned branched structure.
  • -A 1 and A 2- A 1 and A 2 in the formula (1) independently represent an oxygen atom or -NH-, and an oxygen atom is preferable.
  • R 111 has the same meaning as RB 11 in the above formula (B-1), and the preferred embodiment is also the same.
  • R 115 has the same meaning as R 115 in the above formula (A-1), a preferable embodiment thereof is also the same.
  • R 113 and R 114 are independently synonymous with RA 22 included in the preferred embodiment of RA 21 in the above formula (A-1), and the preferred embodiments are also the same.
  • the repeating unit represented by the formula (1) is preferably a repeating unit represented by the formula (1-A) or the formula (1-B).
  • a 11 and A 12 represent an oxygen atom or -NH-
  • R 111 and R 112 each independently represent a divalent organic radical
  • R 113 and R 114 independently represent a hydrogen atom or 1 It represents a valent organic group
  • * 1 and * 2 each independently represent a bonding site with another structure
  • at least one of R 113 and R 114 is preferably a group containing a radically polymerizable group. More preferably, it is a radically polymerizable group.
  • a 11 , A 12 , R 111 , R 113, R 114 , * 1 and * 2 are A 1 , A 2 , R 111 , R 113 , R 114 , * 1 and * 1 in equation (1), respectively. It is synonymous with the preferable range of * 2 .
  • 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 specific polymer precursor may contain other types of repeating units in addition to the repeating units of the above formula (1).
  • the branched chain of the specific polymer precursor is the same as at least one of the repeating units contained in the main chain of the specific polymer precursor.
  • the repeating units contained in the main chain only one branched chain containing the same repeating unit as at least one repeating unit may be contained in the specific polymer precursor, or two or more may be contained. ..
  • the specific polymer precursor may further have a branched chain that does not contain the same repeating unit as at least one of the repeating units contained in the main chain, but an embodiment that does not have the repeating unit is also preferable.
  • the branched chain preferably contains a repeating unit represented by the above formula (1).
  • the main chain is represented by the formula (1) and at least one selected from the group consisting of the repeating unit represented by (B-1) and the repeating unit represented by the formula (B-2). It is preferable to include a repeating unit.
  • the main chain may further contain a repeating unit represented by the formula (B-3). Further, it is preferable that both the main chain and the branched chain contain a repeating unit represented by the formula (1), and both the main chain and the branched chain are the repeating units represented by the formula (1). It is more preferable to include the same repeating unit.
  • the weight average molecular weight of the specific polymer precursor is preferably 1,000 to 100,000, more preferably 3,000 to 90,000, and even more preferably 5,000 to 75,000. ..
  • the degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.2 to 3.5, more preferably 1.5 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).
  • Specific examples of the specific polymer precursor include PA-1 to PA-4 used in Examples described later, and compounds represented by the following structural formulas.
  • two or three repeating units contained in parentheses are combined to form a resin.
  • * and the wavy line portion are combined in each repetition unit.
  • these resins may have still other repeating units as long as the effects of the present invention can be obtained.
  • the specific polymer precursor is synthesized, for example, by the synthetic method shown in the synthetic examples in Examples described later. Specifically, for example, it is obtained by reacting a polyvalent carboxylic acid or a polyvalent carboxylic acid derivative with a diamine.
  • a polyvalent carboxylic acid or the polyvalent carboxylic acid derivative at least a trivalent or higher polyvalent carboxylic acid or a trivalent or higher polyvalent carboxylic acid derivative is used, and a trivalent or tetravalent polyvalent carboxylic acid (tricarboxylic acid) is used.
  • a tetracarboxylic acid or a trivalent or tetravalent polycarboxylic acid derivative (tricarboxylic acid derivative or tetracarboxylic acid derivative).
  • a divalent carboxylic acid or a divalent carboxylic acid derivative (dicarboxylic acid derivative) is further used. May be good.
  • the polyvalent carboxylic acid or the polyvalent carboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.
  • a method of reacting a dicarboxylic acid or a dicarboxylic acid derivative with a trivalent or higher polyvalent amine can be mentioned.
  • the dicarboxylic acid or the dicarboxylic acid derivative is halogenated with a halogenating agent and then reacted with a trivalent or higher polyvalent amine.
  • 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 specific polymer precursor in the reaction solution can be precipitated in water, and the specific polymer precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
  • the content of the specific polymer precursor in the curable resin composition of the present invention is 0.001% by mass with respect to the total solid content of the curable resin composition from the viewpoint of improving the elongation at break of the obtained cured film.
  • the above is preferable, 0.01% by mass or more is more preferable, and 0.5% by mass or more is further preferable.
  • the upper limit of the content is preferably 30% by mass or less, more preferably 20% by mass or less, and 15% by mass or less from the viewpoint of improving the resolution of the curable resin composition. It is more preferably 10% by mass or less, and even more preferably 5% by mass or less.
  • the content of the specific polymer precursor is specified from the viewpoint of improving the breaking elongation of the obtained cured film. It is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and 0.05% by mass or more, based on the total amount of the polymer precursor and other heterocyclic-containing polymer precursors. It is more preferable to have.
  • the upper limit of the content is preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass or less from the viewpoint of improving the resolution of the curable resin composition. It is more preferably 25% by mass or less, and even more preferably 10% by mass or less.
  • the curable resin composition of the present invention may contain only one type of specific 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 preferably contains other heterocyclic-containing polymer precursors (hereinafter, also simply referred to as “other polymer precursors”) other than the above-mentioned specific polymer precursors.
  • the curable resin composition of the present invention preferably contains, as the other polymer precursor, at least one precursor selected from the group consisting of a polyimide precursor and a polybenzoxazole precursor, and the polyimide precursor is used. It is more preferable to include it.
  • the polyimide precursor preferably has the repeating unit represented by the formula (1) in the above-mentioned specific polymer precursor.
  • 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 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 content of the other polymer precursor in the curable resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, based on the total solid content of the curable resin composition. It is more preferably 40% by mass or more, further preferably 50% by mass or more, further preferably 60% by mass or more, and even more preferably 70% by mass or more.
  • the content of the other polymer precursor in the curable resin composition of the present invention is preferably 99.5% by mass or less, preferably 99% by mass or less, based on the total solid content of the curable resin composition. It is more preferably 98% by mass or less, further preferably 97% by mass or less, and even more preferably 95% by mass or less.
  • the curable resin composition of the present invention may contain only one type of other 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 may further contain other resins.
  • another resin for example, it has a branched structure represented by the above formula (A-1), and as a branched chain bonded to the branched structure, it has a branched chain having a repeating unit and has a branched chain.
  • examples thereof include compounds that do not form an imide structure by heating.
  • Other resins are not polyimide precursors because they do not form an imide structure when heated.
  • Specific examples thereof include a resin having a branched structure represented by the above formula (A-1) and not having a repeating unit represented by the above formula (1).
  • resins include, but are not limited to, PA-5 used in the examples, resins having the following structure, and the like.
  • the two repeating units contained in parentheses are combined to form a resin.
  • * and the wavy line portion are combined in each repetition unit.
  • these resins may have still other repeating units as long as the effects of the present invention can be obtained.
  • the content of the other resin may be more than 0% by mass and 50% by mass or less with respect to the total solid content of the curable resin composition. It is preferably more than 0% by mass and more preferably 30% by mass or less.
  • 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 R1 to R4 in the above formula (101), and the preferred embodiment is also the same.
  • R 7 preferably combines with at least one of R 5 and R 6 to form a ring.
  • the ring may contain a heteroatom. Examples of the hetero atom include a nitrogen atom. Further, as the ring, a pyridine ring is preferable.
  • the iminium cation is preferably represented by any of the following formulas (Y1-3) to (Y1-5).
  • R 101 represents an n-valent organic group
  • R 5 has the same meaning as R 5 in the formula (102)
  • R 7 is R in the formula (102) Synonymous with 7
  • n and m represent integers of 1 or more.
  • R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from 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.
  • sulfonium salt examples include the following compounds, but the present invention is not limited thereto.
  • the iodonium salt means a salt of an iodonium cation and an anion.
  • the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
  • iodonium cation a diallyl iodonium cation is preferable. Further, as the iodonium cation, a cation represented by the following formula (104) is preferable.
  • R 11 and R 12 each independently represent a hydrocarbon group.
  • R 11 and R 12 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
  • R 11 and R 12 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, and an aryloxy group.
  • Examples thereof include a carbonyl group and an acyloxy group.
  • R 11 and R 12 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
  • iodonium salt examples include the following compounds, but the present invention is not limited thereto.
  • the phosphonium salt means a salt of a phosphonium cation and an anion.
  • the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
  • a quaternary phosphonium cation is preferable, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation. Further, as the phosphonium cation, a cation represented by the following formula (105) is preferable.
  • R 13 to R 16 independently represent a hydrogen atom or a hydrocarbon group.
  • Each of R 13 to R 16 is preferably an alkyl group or an aryl group independently, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
  • R 13 to R 16 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group.
  • Examples thereof include a carbonyl group and an acyloxy group.
  • R 13 to R 16 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
  • phosphonium salt examples include the following compounds, but the present invention is not limited thereto.
  • the content of the onium salt is preferably 0.1 to 50% by mass 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. It is assumed that the other thermobase generator does not contain the compound corresponding to 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 further preferable).
  • a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable.
  • Rb 3 may further have a substituent as long as the 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 12 carbon atoms, 3 to 12 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 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 12 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 promoted together with 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.
  • a radically polymerizable compound can be used as the polymerizable compound.
  • the radically polymerizable compound is a compound having a radically polymerizable group.
  • examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
  • the radically polymerizable group is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.
  • the number of radically polymerizable groups contained in the radically polymerizable compound may be one or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, and preferably has three or more radically polymerizable groups. More preferred.
  • the upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the molecular weight of the radically polymerizable compound is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radically polymerizable compound is preferably 100 or more.
  • the curable resin composition of the present invention preferably contains at least one bifunctional or higher functional radical polymerizable compound containing two or more radical polymerizable groups, and is preferably a trifunctional or higher functional radical polymerizable compound. It is more preferable to contain at least one kind. Further, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound.
  • the number of functional groups of a bifunctional or higher functional polymerizable monomer means that the number of radically polymerizable groups in one molecule is two or more.
  • the radically polymerizable compound examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and preferred examples thereof.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group.
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amines or thiols, and a halogeno group.
  • Substitution reactions of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
  • a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
  • examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
  • a compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993.
  • Urethane (meth) acrylates such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.
  • a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
  • 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, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound.
  • R 104 represents an organic group having a t-valence of 1 to 200 carbon atoms
  • R 105 is a group represented by -OR 106 or -OCO-R 107.
  • R 106 indicates a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 107 indicates an organic group having 1 to 10 carbon atoms.
  • R 404 represents a divalent organic group having 1 to 200 carbon atoms
  • R 405 represents a group represented by -OR 406 or -OCO-R 407
  • R 406 is a hydrogen atom or carbon.
  • R 407 indicates an organic group having 1 to 10 carbon atoms.
  • U 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 or an organic group having 1 to 10 carbon atoms
  • R 507 represents an organic group having 1 to 10 carbon atoms.
  • Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML.
  • Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, and the like.
  • HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), NIKALAC MX-280, Examples thereof include NIKALAC MX-270 and NIKALAC MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).
  • the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
  • the epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the curable resin composition.
  • the epoxy compound preferably contains a polyethylene oxide group.
  • the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
  • epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidi).
  • epoxy groups include, but are not limited to, epoxy group-containing silicones such as loxypropyl) siloxane.
  • Epicron® 850-S Epicron® HP-4032, Epicron® HP-7200, Epicron® HP-820, Epicron® HP-4700, Epicron® EXA-4710, Epicron® HP-4770, Epicron® EXA-859CRP, Epicron® EXA-1514, Epicron® EXA-4880, Epicron® EXA-4850-150, Epicron EXA-4850-1000, Epicron (registered trademark) EXA-4816, Epicron (registered trademark) EXA-4822 (trade name, manufactured by DIC Co., Ltd.), Rica Resin (registered trademark) BEO-60E (Product name, Shin Nihon Rika Co., Ltd.), EP-4003S, EP-4000S (trade name, manufactured by ADEKA Co., Ltd.) and the like.
  • an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance.
  • Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain a polyethylene oxide group.
  • oxetane compound compound having an oxetanyl group
  • the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, and the like.
  • examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like.
  • the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or Two or more kinds may be mixed.
  • benzoxazine compound Preferred examples of the benzoxazine compound are BA type benzoxazine, Bm type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzo.
  • Oxazine compounds can be mentioned. These may be used alone or in combination of two or more.
  • the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable resin composition of the present invention.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
  • One type of polymerizable compound may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a solvent.
  • a solvent a known solvent can be arbitrarily used.
  • the solvent is preferably an organic solvent.
  • the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
  • esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, 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 ether diamine 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-tert
  • 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 structural units of the main chain represent the content (mol%) of each structural unit
  • the parentheses indicating the structural units of the side chain represent the number of repetitions of each structural 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 filter material 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 formed 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.
  • the compositions may be present or have different compositions, but from the viewpoint of production suitability, the compositions having the same composition are preferable.
  • Such a metal layer is preferably used as a 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. Is preferable. Further, the method for producing a cured film of the present invention further includes the film forming step, and further includes an exposure step for exposing the film and a developing step for developing the film (developing the film). Is more preferable. Further, the method for producing a cured film of the present invention further includes the film forming step (and the developing step if necessary), and further includes a heating step of heating the film at 80 to 450 ° C. preferable.
  • Exposure step of exposing the film after the film forming step (c) Exposure Development step of developing the developed film
  • 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 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 performing a developing treatment on the exposed film (curable resin composition layer). By performing the development, the unexposed portion (non-exposed portion) is removed.
  • the developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.
  • the developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
  • 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 ethoxyacetate, etc.)
  • 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • Ke As tons for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc.
  • Dimethyl sulfoxide is preferably mentioned as the sulfoxides.
  • cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.
  • the 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 heating step (heating step) of heating the developed film at 80 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 onium salt or other thermobase 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 80 ° C. or higher, more preferably 140 ° C. or higher, further preferably 150 ° C. or higher, and 160 ° C. or higher. Is particularly preferable, and 170 ° C. or higher is most preferable.
  • the upper limit is preferably 450 ° C. or lower, more preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and particularly preferably 220 ° C. or lower.
  • the heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
  • a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
  • the temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C.
  • the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started.
  • the temperature of the film (layer) after drying is higher than, for example, the boiling point of the solvent contained in the curable resin composition. It is preferable to gradually raise the temperature from a temperature as low as 30 to 200 ° C.
  • the heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.
  • the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C., from the viewpoint of adhesion between layers of the cured film.
  • the reason is not clear, but it is considered that the ethynyl groups of the heterocyclic polymer 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 film (curable resin composition layer) after the development treatment.
  • 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 (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 having 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 referred to. 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 19,000.
  • ⁇ Synthesis example 5> [4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotridin) and polyimide precursor from 2-hydroxyethyl methacrylate (A-5: 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.
  • PA-1 The weight average molecular weight of this polyimide precursor (PA-1) was 23,000. It is presumed that PA-1 is a resin in which three repeating units represented by the following formula (PA-1) are bonded. In the formula (PA-1), * and the wavy line portion are combined in each repetition unit.
  • PA-3 The weight average molecular weight of this polyimide precursor PA-3 was 23,500. It is presumed that PA-3 is a resin in which two repeating units represented by the following formula (PA-3) are bonded. In the formula (PA-3), * and the wavy line portion are combined in each repetition unit.
  • Example 1 ⁇ Examples and Comparative Examples>
  • the components shown in Table 1 below were mixed to obtain each curable resin composition and a comparative composition.
  • the obtained curable resin composition and comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 ⁇ m.
  • the numerical value in the column of "parts by mass” indicates the content (parts by mass) of each component.
  • the description of "-” indicates that the corresponding component is not contained.
  • the description in the column of "content of branched structure” indicates “content of branched structure contained in the polyimide precursor ( ⁇ mol / g) with respect to the total solid content of the composition”.
  • ⁇ D-1 A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
  • -D-2 SR-209 (manufactured by Sartmer, compound with the following structure)
  • ⁇ D-3 A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
  • ⁇ solvent ⁇ -I-1 ⁇ -Butyrolactone (manufactured by Sanwa Yuka Co., Ltd.)
  • -I-2 Dimethyl sulfoxide (manufactured by Wako Pure Chemical Industries, Ltd.)
  • -I-3 N-methyl-2-pyrrolidone (manufactured by Ashland)
  • Viscosity fluctuation rate (%) 100 ⁇ ⁇ 1- (viscosity (14 days) / viscosity (0 days)) ⁇ The viscosity was measured at 25 ° C., and the others were in accordance with JIS Z 8803: 2011. -Evaluation criteria- A: The viscosity fluctuation rate was 5% or less. B: The viscosity fluctuation rate was more than 5% and 10% or less. C: The viscosity fluctuation rate was more than 10% and 15% or less. D: Viscosity fluctuation rate exceeded 15%.
  • the curable resin composition or the comparative composition was applied in layers on a silicon wafer by a spin coating method.
  • a curable resin composition layer or a comparative composition layer was formed.
  • the film thickness (the film thickness ( ⁇ m) of the unexposed portion before development) was set to 20 ⁇ m.
  • a silicon wafer to which the obtained curable resin composition layer or comparative composition layer is applied is dried on a hot plate at 100 ° C. for 5 minutes, and a uniform curable resin composition having a thickness of 15 ⁇ m is placed on the silicon wafer. It was used as a layer or a composition layer for comparison.
  • Unexposed area residual film ratio (%) (film thickness of unexposed area after development ( ⁇ m) / film thickness of unexposed area before development ( ⁇ m)) ⁇ 100
  • each curable resin composition or comparative composition is applied in layers on a silicon wafer by a spin coating method to obtain a curable resin composition layer or a comparative composition layer. Formed. A silicon wafer to which the obtained curable resin composition layer or comparative composition layer is applied is dried on a hot plate at 100 ° C. for 5 minutes, and a uniform curable resin composition having a thickness of 20 ⁇ m is placed on the silicon wafer. It was used as a layer or a composition layer for comparison. The curable resin composition layer or the comparative composition layer on the silicon wafer was exposed to an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).
  • the exposed curable resin composition layer or comparative composition layer was heated in a nitrogen atmosphere at a heating rate of 10 ° C./min, and after reaching 180 ° C., this temperature was maintained for 3 hours. A cured resin layer was obtained. The cured resin layer was immersed in a 4.9% hydrofluoric acid solution, and the resin layer was peeled off from the silicon wafer to obtain a resin film 1.
  • the film has a longitudinal direction and a width direction of 25 ° C. and 65% relative humidity.
  • the elongation at break was measured in accordance with JIS-K6251: 2017 under the environment of (RH).
  • the curable resin composition containing the specific polymer precursor according to the present invention is excellent in the elongation at break of the obtained cured film.
  • the comparative compositions according to Comparative Examples 1 to 4 do not contain a specific polymer precursor. It can be seen that the curable resin compositions according to Comparative Examples 1 to 4 are inferior in elongation at break.
  • Example 101 The curable resin composition according to Example 1 was spun and applied to the surface of a resin base material on which a thin copper layer was formed so that the film thickness was 20 ⁇ m.
  • the curable resin composition applied to the resin substrate was dried at 100 ° C. for 2 minutes and then exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). The exposure was performed through a mask of a square pattern (a square pattern having a length of 100 ⁇ m and a width of 100 ⁇ m, a number of repetitions of 10) at a wavelength of 365 nm and an exposure amount of 400 mJ / cm2 to create a square remaining pattern.
  • 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.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne une composition de résine durcissable qui contient un précurseur de polyimide qui possède au moins une structure ramifiée qui est choisie dans le groupe constitué des structures ramifiées représentées par la formule (A-1) et des structures ramifiées représentées par la formule (A-2), et qui possède une chaîne ramifiée comportant un motif répété en tant que chaîne ramifiée qui est liée à la structure ramifiée ; un film durci qui est obtenu par durcissement de la composition de résine durcissable décrite ci-dessus ; un corps multicouche qui comprend le film durci décrit ci-dessus ; un procédé de production du film durci décrit ci-dessus ; et un dispositif à semi-conducteur qui comprend le film durci décrit ci-dessus ou le corps multicouche décrit ci-dessus. Dans la formule (A-1) et la formule (A-2), R115 représente un groupe organique tétravalent ; RA21 représente un atome d'hydrogène ou un groupe organique monovalent ; et chaque * représente indépendamment un site de liaison à une autre structure.
PCT/JP2020/010733 2019-03-19 2020-03-12 Composition de résine durcissable, film durci, corps multicouche, procédé de production de film durci et dispositif à semi-conducteur WO2020189481A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022270373A1 (fr) * 2021-06-21 2022-12-29 住友化学株式会社 Composition
WO2022270375A1 (fr) * 2021-06-21 2022-12-29 住友化学株式会社 Composition
WO2022270374A1 (fr) * 2021-06-21 2022-12-29 住友化学株式会社 Composition

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11106509A (ja) * 1997-10-07 1999-04-20 Unitika Ltd 感光性ポリイミド前駆体溶液、それから得られるポリイミド塗膜又はポリイミドフィルム、及びそれらの製造方法
JP2016200643A (ja) * 2015-04-07 2016-12-01 日立化成デュポンマイクロシステムズ株式会社 感光性樹脂組成物、パターン硬化膜の製造方法及び電子部品
WO2017043474A1 (fr) * 2015-09-11 2017-03-16 富士フイルム株式会社 Procédé de production d'un matériau précurseur de polymère contenant un hétérocycle et application associée

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11106509A (ja) * 1997-10-07 1999-04-20 Unitika Ltd 感光性ポリイミド前駆体溶液、それから得られるポリイミド塗膜又はポリイミドフィルム、及びそれらの製造方法
JP2016200643A (ja) * 2015-04-07 2016-12-01 日立化成デュポンマイクロシステムズ株式会社 感光性樹脂組成物、パターン硬化膜の製造方法及び電子部品
WO2017043474A1 (fr) * 2015-09-11 2017-03-16 富士フイルム株式会社 Procédé de production d'un matériau précurseur de polymère contenant un hétérocycle et application associée

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022270373A1 (fr) * 2021-06-21 2022-12-29 住友化学株式会社 Composition
WO2022270375A1 (fr) * 2021-06-21 2022-12-29 住友化学株式会社 Composition
WO2022270374A1 (fr) * 2021-06-21 2022-12-29 住友化学株式会社 Composition

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