WO2024048435A1 - Composition de résine, objet durci ainsi que procédé de fabrication de celui-ci, stratifié ainsi que procédé de fabrication de celui-ci, et dispositif à semi-conducteurs ainsi que procédé de fabrication de celui-ci - Google Patents

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

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Publication number
WO2024048435A1
WO2024048435A1 PCT/JP2023/030662 JP2023030662W WO2024048435A1 WO 2024048435 A1 WO2024048435 A1 WO 2024048435A1 JP 2023030662 W JP2023030662 W JP 2023030662W WO 2024048435 A1 WO2024048435 A1 WO 2024048435A1
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group
resin composition
compound
formula
compounds
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PCT/JP2023/030662
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English (en)
Japanese (ja)
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大輔 浅川
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富士フイルム株式会社
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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/12—Mountings, e.g. non-detachable insulating substrates

Definitions

  • the present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device.
  • resin materials manufactured from resin compositions containing resin are utilized in various fields.
  • cyclized resins such as polyimide have excellent heat resistance and insulation properties, and are therefore used in a variety of applications.
  • the above-mentioned uses are not particularly limited, but in the case of semiconductor devices for mounting, for example, they may be used as materials for insulating films and sealing materials, or as protective films. It is also used as a base film and coverlay for flexible substrates.
  • a cyclized resin such as polyimide is used in the form of a resin composition containing the cyclized resin or a precursor of the cyclized resin such as a polyimide precursor.
  • a resin composition is applied to a base material by coating, for example, to form a photosensitive film, and then, as necessary, exposure, development, heating, etc. are performed to form a cured product on the base material.
  • the precursor of the cyclized resin such as a polyimide precursor, is cyclized, for example, by heating, and becomes a cyclized resin such as polyimide in the cured product.
  • the resin composition can be applied by known coating methods, there is a high degree of freedom in designing the shape, size, application position, etc. of the resin composition when it is applied. It can be said that it has excellent characteristics.
  • cyclized resins such as polyimide
  • Patent Document 1 describes (A) an alkali-soluble resin, (B) a copolymer resin, (C) a photoinitiator that generates radicals and bases, (D) an epoxy resin, and (E) a black colorant.
  • the alkali-soluble resin (A) contains (A1) a carboxyl group-containing imide resin, and the content of the black colorant (E) is equal to or less than that of the curable resin composition.
  • a curable resin composition is described in which the solid content is 1.0% by mass or more based on the total mass of solids.
  • a resin composition for obtaining a cured product is required to have excellent adhesion to a substrate even after the resulting cured product is exposed to high-temperature conditions.
  • the present invention includes a resin composition that has excellent adhesion to a base material even after the obtained cured product is exposed to high temperature conditions, a cured product obtained by curing the above resin composition, and the above cured product.
  • the present invention aims to provide a laminate, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product.
  • a resin composition comprising a compound A represented by the following formula (A-1) and having a total number of carbon atoms of 3 to 30.
  • R 1 represents a monovalent organic group
  • the bonding site in R 1 with the nitrogen atom described in formula (A-1) is a carbon atom
  • R 2 is a hydrogen atom
  • R 3 represents a monovalent organic group
  • R 2 and R 3 may be combined to form a ring structure.
  • the resin composition according to ⁇ 1> which contains a compound represented by the following formula (A-2) as the compound A.
  • Ar 1 and Ar 2 each independently represent an aromatic group which may have a substituent, and at least one of the ring member of the aromatic group and the substituent has oxygen.
  • R 2 represents a hydrogen atom or a monovalent organic group.
  • ⁇ 4> The resin composition according to ⁇ 2> or ⁇ 3>, wherein at least one of Ar 1 , Ar 2 and R 2 has a heterocyclic structure.
  • ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the resin is polyimide or a polyimide precursor.
  • ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, further comprising a photopolymerization initiator and a polymerizable compound.
  • ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 8> A cured product obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 7>.
  • ⁇ 9> A laminate including two or more layers made of the cured product according to ⁇ 8>, and a metal layer between any of the layers made of the cured product.
  • a method for producing a cured product comprising a film forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 7> onto a substrate to form a film.
  • the method for producing a cured product according to ⁇ 10> including an exposure step of selectively exposing the film and a development step of developing the film using a developer to form a pattern.
  • the method for producing a cured product according to ⁇ 10> or ⁇ 11> which includes a heating step of heating the film at 50 to 450°C.
  • a method for producing a laminate including the method for producing a cured product according to any one of ⁇ 10> to ⁇ 12>.
  • ⁇ 14> A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to any one of ⁇ 10> to ⁇ 12>.
  • ⁇ 15> A semiconductor device comprising the cured product according to ⁇ 8>.
  • a resin composition that has excellent adhesion to a substrate even after the obtained cured product is exposed to high temperature conditions, a cured product obtained by curing the resin composition, and a cured product obtained by curing the resin composition.
  • a laminate including the above, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product.
  • a numerical range expressed using the symbol " ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as the lower limit and upper limit, respectively.
  • the term “step” includes not only independent steps but also steps that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.
  • substitution or unsubstitution includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • alkyl group includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • (meth)acrylate means both “acrylate” and “methacrylate”, or either “(meth)acrylate”
  • (meth)acrylic means both “acrylic” and “methacrylic”
  • (meth)acryloyl means either or both of "acryloyl” and “methacryloyl.”
  • Me in the structural formula represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the total solid content refers to the total mass of all components of the composition excluding the solvent.
  • the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
  • weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC), and are defined as polystyrene equivalent values.
  • weight average molecular weight (Mw) and number average molecular weight (Mn) are expressed using, for example, HLC-8220GPC (manufactured by Tosoh Corporation) and guard column HZ-L, TSKgel Super HZM-M, TSKgel.
  • THF tetrahydrofuran
  • NMP N-methyl-2-pyrrolidone
  • a detector with a wavelength of 254 nm of UV rays is used for detection in the GPC measurement.
  • each layer constituting a laminate when the positional relationship of each layer constituting a laminate is described as "upper” or “lower", there is another layer above or below the reference layer among the plurality of layers of interest. It would be good if there was. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other.
  • the direction in which layers are stacked relative to the base material is referred to as "top”, or if there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as "top”. , the opposite direction is called "down".
  • the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Further, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.
  • the temperature is 23° C.
  • the atmospheric pressure is 101,325 Pa (1 atm)
  • the relative humidity is 50% RH. In this specification, combinations of preferred aspects are more preferred aspects.
  • the resin composition of the present invention is represented by the following formula (A-1) and at least one resin selected from the group consisting of cyclized resins and precursors thereof, and the total carbon Compound A having 3 to 30 atoms.
  • R 1 represents a monovalent organic group
  • the bonding site in R 1 with the nitrogen atom described in formula (A-1) is a carbon atom
  • R 2 is a hydrogen atom
  • R 3 represents a monovalent organic group
  • R 2 and R 3 may be combined to form a ring structure.
  • the resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and is preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent.
  • the resin composition of the present invention can be used, for example, to form an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and can be used for forming an interlayer insulating film for a rewiring layer. preferable.
  • the resin composition of the present invention is used for forming an interlayer insulating film for a rewiring layer.
  • the resin composition of the present invention may be used to form a photosensitive film to be subjected to positive development, or may be used to form a photosensitive film to be subjected to negative development.
  • negative development refers to development in which non-exposed areas are removed by development during exposure and development
  • positive development refers to development in which exposed areas are removed by development.
  • the above-mentioned exposure method, the above-mentioned developer, and the above-mentioned development method include, for example, the exposure method explained in the exposure step in the description of the method for producing a cured product, and the developer and development method explained in the development step. is used.
  • a cured product having excellent adhesion to a substrate can be obtained even after being exposed to high-temperature conditions.
  • a substrate particularly a metal substrate, particularly a copper substrate
  • the resin composition of the present invention contains compound A having a specific structure.
  • BACKGROUND ART Conventionally, in order to improve the adhesion between a cured product formed from a resin composition and a base material, a compound having a nitrogen atom has been blended into a resin composition. Here, it is believed that the adhesion is further improved by increasing the number of nitrogen atoms in the compound.
  • the above-mentioned compounds sometimes have low thermal stability, and for example, when exposed to high temperature conditions, there are cases where adhesion cannot be maintained.
  • Patent Document 1 does not describe a precursor of a cyclized resin and a composition containing Compound A.
  • the resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof.
  • the cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in its main chain structure.
  • the "main chain” refers to the relatively longest bond chain in the resin molecule, and the “side chain” refers to other bond chains.
  • the cyclized resin include polyimide, polybenzoxazole, polyamideimide, and the like.
  • the precursor of cyclized resin refers to a resin that undergoes a chemical structure change due to external stimulation to become a cyclized resin.
  • a resin that undergoes a chemical structure change due to heat to become a cyclized resin, and that undergoes a ring-closing reaction due to heat More preferred is a resin that becomes a cyclized resin by forming a ring structure.
  • the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, a polyamideimide precursor, and the like. That is, the resin composition contains, as the specific resin, at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor. It is preferable.
  • the resin composition contains polyimide or a polyimide precursor as the specific resin. It is preferable that the specific resin has a polymerizable group, and more preferably a radically polymerizable group.
  • the resin composition of the present invention preferably contains a radical polymerization initiator, and more preferably contains a radical polymerization initiator and a radical crosslinking agent.
  • a sensitizer can be included if necessary.
  • a negative photosensitive film is formed from such a resin composition.
  • the specific resin may have a polarity converting group such as an acid-decomposable group.
  • the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive or negative photosensitive film is formed.
  • the polyimide precursor used in the present invention is not particularly limited in its type, but preferably contains a repeating unit represented by the following formula (2).
  • a 1 and A 2 each independently represent an oxygen atom or -NR z -
  • 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
  • R z represents a hydrogen atom or a monovalent organic group.
  • a 1 and A 2 in formula (2) each independently represent an oxygen atom or -NR z -, and preferably an oxygen atom.
  • Rz represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.
  • R 111 in formula (2) represents a divalent organic group.
  • divalent organic groups include groups containing straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, including straight-chain or branched aliphatic groups having 2 to 20 carbon atoms, A group consisting of a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
  • the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the above cyclic aliphatic group and aromatic group, the hydrocarbon group in the chain may be substituted with a hetero atom. may be substituted with a group containing.
  • R 111 in formula (2) include groups represented by -Ar- and -Ar-L-Ar-, with a group represented by -Ar-L-Ar- being preferred.
  • Ar is each independently an aromatic group
  • L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO -, -S-, -SO 2 -, -NHCO-, or a combination of two or more of the above.
  • R 111 is derived from a diamine.
  • diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic, and aromatic diamines.
  • One type of diamine may be used, or two or more types may be used.
  • R 111 is a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or any of these.
  • a diamine containing a combination of groups is preferable, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable.
  • the above straight chain or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom.
  • the above cyclic aliphatic group and aromatic group may have a ring member hydrocarbon group substituted with a hetero atom. may be substituted with a group containing.
  • groups containing aromatic groups include the following.
  • diamine specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane , bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodipheny
  • diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598.
  • diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 are also preferably used.
  • R 111 is preferably represented by -Ar-L-Ar-.
  • Ar is each independently an aromatic group
  • L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- , -SO 2 -, -NHCO-, or a combination of two or more of the above.
  • Ar is preferably a phenylene group
  • L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms optionally substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 - .
  • the aliphatic hydrocarbon group here is preferably an alkylene group.
  • R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61).
  • a divalent organic group represented by formula (61) is more preferable.
  • R 50 to R 57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, or a trifluoro It is a methyl group, and each * independently represents a bonding site with the nitrogen atom in formula (2).
  • the monovalent organic groups R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples include fluorinated alkyl groups.
  • R 58 and R 59 each independently represent a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2). represent.
  • Examples of the diamine giving the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'- Bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminoctafluorobiphenyl, and the like. These may be used alone or in combination of two or more.
  • R 115 in formula (2) 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.
  • * each independently represents a bonding site with another structure.
  • R 112 is a single bond or a divalent linking group, and is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a fluorine atom, -O-, A group selected from -CO-, -S-, -SO 2 -, -NHCO-, and combinations thereof is preferable, and the number of carbon atoms optionally substituted with a single bond or a fluorine atom is preferable.
  • it is a group selected from 1 to 3 alkylene groups, -O-, -CO-, -S- and -SO 2 -, including -CH 2 -, -C(CF 3 ) 2 -, - More preferably, it is a divalent group selected from the group consisting of C(CH 3 ) 2 -, -O-, -CO-, -S- and -SO 2 -.
  • R 115 include a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride.
  • the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue, or may contain two or more types of tetracarboxylic dianhydride residues as the structure corresponding to R115 .
  • the tetracarboxylic dianhydride is represented by the following formula (O).
  • R 115 represents a tetravalent organic group.
  • the preferred range of R 115 is the same as the preferred range of R 115 in formula (2).
  • tetracarboxylic dianhydride examples include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'- Diphenylsulfidetetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3' , 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2',3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,
  • preferred examples include tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598.
  • R 111 and R 115 may have an OH group. More specifically, R 111 includes a residue of a bisaminophenol derivative.
  • R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
  • the monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
  • at least one of R 113 and R 114 contains a polymerizable group, and it is more preferable that both of them contain a polymerizable group.
  • the polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, radicals, etc., and a radically polymerizable group is preferable.
  • the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. It will be done.
  • the radically polymerizable group contained in the polyimide precursor is preferably a group having an ethylenically unsaturated bond.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinyl phenyl group, etc.), and a (meth)acrylamide group.
  • (meth)acryloyloxy group a group represented by the following formula (III), and the like, with the group represented by the following formula (III) being preferred.
  • R 200 represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and preferably a hydrogen atom or a methyl group.
  • * represents a bonding site with another structure.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 -, a cycloalkylene group or a polyalkyleneoxy group.
  • R 201 examples include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1, Examples include 3-butanediyl group, -CH 2 CH (OH) CH 2 -, polyalkyleneoxy group, alkylene groups such as ethylene group and propylene group, -CH 2 CH (OH) CH 2 -, cyclohexyl group, polyalkylene group.
  • An oxy group is more preferred, and an alkylene group such as an ethylene group or a propylene group, or a polyalkyleneoxy group is even more preferred.
  • a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
  • the alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
  • the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or an arrangement having blocks. Alternatively, an arrangement having an alternating pattern or the like may be used.
  • the number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6.
  • the alkylene group may have a substituent.
  • Preferred substituents include alkyl groups, aryl groups, halogen atoms, and the like.
  • the number of alkyleneoxy groups contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
  • polyalkyleneoxy groups include polyethyleneoxy groups, polypropyleneoxy groups, polytrimethyleneoxy groups, polytetramethyleneoxy groups, or multiple ethyleneoxy groups and multiple propyleneoxy groups.
  • a group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is even more preferable.
  • the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in an alternating pattern. Preferred embodiments of the repeating number of ethyleneoxy groups, etc. in these groups are as described above.
  • R 113 is a hydrogen atom or when R 114 is a hydrogen atom, even if the polyimide precursor forms a counter salt with a tertiary amine compound having an ethylenically unsaturated bond.
  • a tertiary amine compound having such an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.
  • R 113 and R 114 may be a polarity converting group such as an acid-decomposable group.
  • the acid-decomposable group is not particularly limited as long as it decomposes under the action of an acid to produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but examples include an acetal group, a ketal group, a silyl group, and a silyl ether group. , a tertiary alkyl ester group, etc. are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.
  • acid-decomposable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group. group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
  • the polyimide precursor has a fluorine atom in its structure.
  • the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
  • the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
  • examples include embodiments in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are used as the diamine.
  • the repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one type of polyimide precursor used in the present invention is a precursor having a repeating unit represented by formula (2-A). When the polyimide precursor contains a repeating unit represented by formula (2-A), it becomes possible to further widen the exposure latitude.
  • a 1 and A 2 represent an oxygen atom
  • R 111 and R 112 each independently represent a divalent organic group
  • R 113 and R 114 each independently, It represents a hydrogen atom or a monovalent organic group
  • at least one of R 113 and R 114 is a group containing a polymerizable group, and preferably both are groups containing a polymerizable group.
  • a 1 , A 2 , R 111 , R 113 and R 114 each independently have the same meaning as A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and their preferred ranges are also the same.
  • R 112 has the same meaning as R 112 in formula (5), and the preferred ranges are also the same.
  • the polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. Furthermore, it may contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit of formula (2) above, the polyimide precursor may also contain other types of repeating units.
  • An embodiment of the polyimide precursor in the present invention includes an embodiment in which the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units.
  • the total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%.
  • the upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor excluding the terminal may be repeating units represented by formula (2).
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000.
  • the number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
  • the molecular weight dispersity of the polyimide precursor is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
  • the upper limit of the degree of molecular weight dispersion of the polyimide precursor is not particularly determined, for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
  • the molecular weight dispersity is a value calculated from weight average molecular weight/number average molecular weight.
  • the resin composition contains multiple types of polyimide precursors as the specific resin, it is preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyimide precursor are within the above ranges.
  • the weight average molecular weight, number average molecular weight, and degree of dispersion calculated from the plurality of types of polyimide precursors as one resin are each within the above ranges.
  • the polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide soluble in a developer containing an organic solvent as a main component.
  • the alkali-soluble polyimide refers to a polyimide that dissolves 0.1 g or more at 23°C in 100 g of a 2.38% by mass tetramethylammonium aqueous solution, and from the perspective of pattern formation, 0.5 g or more.
  • the polyimide is preferably a polyimide that dissolves, and more preferably a polyimide that dissolves 1.0 g or more.
  • the upper limit of the amount dissolved is not particularly limited, but is preferably 100 g or less.
  • the polyimide is preferably a polyimide having a plurality of imide structures in its main chain from the viewpoint of film strength and insulation properties of the organic film obtained.
  • the polyimide has a fluorine atom.
  • the fluorine atom is preferably included in, for example, R 132 in the repeating unit represented by formula (4) described below or R 131 in the repeating unit represented by formula (4) described later; It is more preferable that R 132 in the repeating unit represented by formula (4) or R 131 in the repeating unit represented by formula (4) described below be included as a fluorinated alkyl group.
  • the amount of fluorine atoms based on the total mass of the polyimide is preferably 5% by mass or more, and preferably 20% by mass or less.
  • the polyimide contains silicon atoms.
  • the silicon atom is preferably included in R 131 in the repeating unit represented by formula (4) described later, and is preferably included in R 131 in the repeating unit represented by formula (4) described later.
  • the silicon atom or the organically modified (poly)siloxane structure may be included in the side chain of the polyimide, but is preferably included in the main chain of the polyimide.
  • the amount of silicon atoms based on the total mass of the polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.
  • the polyimide preferably has ethylenically unsaturated bonds.
  • Polyimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but it is preferable to have it in a side chain.
  • the ethylenically unsaturated bond preferably has radical polymerizability.
  • the ethylenically unsaturated bond is preferably included in R 132 or R 131 in the repeating unit represented by formula (4) described below, and is preferably included in R 132 or R 131 as a group having an ethylenically unsaturated bond. is more preferable.
  • the ethylenically unsaturated bond is preferably included in R 131 in the repeating unit represented by formula (4) described below, and more preferably included in R 131 as a group having an ethylenically unsaturated bond.
  • groups having an ethylenically unsaturated bond include groups having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, and a vinyl phenyl group, a (meth)acrylamide group, and a (meth)acrylamide group.
  • examples include an acryloyloxy group and a group represented by the following formula (IV).
  • R 20 represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and preferably a hydrogen atom or a methyl group.
  • the alkylene group having 2 to 12 carbon atoms may be linear, branched, cyclic, or a combination thereof.
  • the alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms.
  • R 21 is preferably a group represented by any of the following formulas (R1) to (R3), and more preferably a group represented by formula (R1).
  • L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group combining two or more of these; represents an oxygen atom or a sulfur atom, * represents a bonding site with another structure, and ⁇ represents a bonding site with the oxygen atom to which R 21 in formula (IV) is bonded.
  • a preferred embodiment of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L is R 21 in formula (IV).
  • the preferred embodiments are the same as the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms.
  • X is preferably an oxygen atom.
  • * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
  • the structure represented by formula (R1) includes, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, and a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). Obtained by reaction.
  • the structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
  • the structure represented by formula (R3) can be obtained by, for example, reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate). can get.
  • * represents a bonding site with another structure, and is preferably a bonding site with the main chain of polyimide.
  • the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, more preferably 0.0005 to 0.05 mol/g.
  • the polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
  • examples of polymerizable groups other than groups having ethylenically unsaturated bonds include cyclic ether groups such as epoxy groups and oxetanyl groups, alkoxymethyl groups such as methoxymethyl groups, and methylol groups.
  • a polymerizable group other than the group having an ethylenically unsaturated bond is preferably included in R 131 in the repeating unit represented by formula (4) described below, for example.
  • the amount of polymerizable groups other than the group having an ethylenically unsaturated bond relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and preferably 0.001 to 0.05 mol/g. More preferred.
  • the polyimide may have a polarity converting group such as an acid-decomposable group.
  • the acid-decomposable group in the polyimide is the same as the acid-decomposable group explained for R 113 and R 114 in the above formula (2), and the preferred embodiments are also the same.
  • the polarity converting group is contained, for example, in R 131 and R 132 in the repeating unit represented by formula (4) described below, the terminal of polyimide, and the like.
  • the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and 70 mgKOH/g or more. It is more preferable that The acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
  • the acid value of the polyimide is preferably 1 to 35 mgKOH/g, more preferably 2 to 30 mgKOH/g.
  • the acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
  • the acid group contained in the polyimide is preferably an acid group having a pKa of 0 to 10, more preferably an acid group having a pKa of 3 to 8, from the viewpoint of achieving both storage stability and developability.
  • pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is expressed by its negative common logarithm pKa.
  • pKa is a value calculated by ACD/ChemSketch (registered trademark).
  • the acid group is a polyhydric acid such as phosphoric acid
  • the above pKa is the first dissociation constant.
  • the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably a phenolic hydroxy group.
  • the polyimide has a phenolic hydroxy group.
  • the polyimide may have a phenolic hydroxy group at the end of the main chain or at the side chain.
  • the phenolic hydroxy group is preferably included, for example, in R 132 or R 131 in the repeating unit represented by formula (4) described below.
  • the amount of phenolic hydroxyl groups based on the total mass of the polyimide is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g.
  • the polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it preferably contains a repeating unit represented by the following formula (4).
  • R 131 represents a divalent organic group
  • R 132 represents a tetravalent organic group.
  • the polymerizable group may be located at at least one of R 131 and R 132 , or may be located at the terminal end of the polyimide as shown in the following formula (4-1) or formula (4-2). It may be located in Formula (4-1)
  • R 133 is a polymerizable group, and the other groups have the same meanings as in formula (4).
  • Formula (4-2) At least one of R 134 and R 135 is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other groups have the same meanings as in formula (4).
  • R 131 represents a divalent organic group.
  • the divalent organic group include those similar to R 111 in formula (2), and the preferred ranges are also the same.
  • R 131 include diamine residues remaining after removal of the amino group of diamine. Examples of diamines include aliphatic, cycloaliphatic, and aromatic diamines. A specific example is R 111 in formula (2) of the polyimide precursor.
  • R 131 is preferably a diamine residue having at least two alkylene glycol units in its main chain in order to more effectively suppress the occurrence of warpage during firing. More preferred are diamine residues containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferred are diamine residues containing no aromatic ring among the above diamines. It is.
  • diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, and EDR.
  • 1-(2-(2-(2-aminopropoxy)ethoxy) Examples include, but are not limited to, propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, and the like.
  • R 132 represents a tetravalent organic group.
  • examples of the tetravalent organic group include those similar to R 115 in formula (2), and the preferred ranges are also the same.
  • R 132 examples include a tetracarboxylic acid residue remaining after the anhydride group is removed from the tetracarboxylic dianhydride.
  • a specific example is R 115 in formula (2) of the polyimide precursor. From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
  • R 131 and R 132 has an OH group. More specifically, as R 131 , 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2- Bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) are listed as preferred examples. As R 132 , the above (DAA-1) to (DAA-5) are mentioned as more preferable examples.
  • the polyimide has a fluorine atom in its structure.
  • the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.
  • the polyimide may be copolymerized with an aliphatic group having a siloxane structure.
  • the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.
  • the main chain end of the polyimide must be capped with a terminal capping agent such as a monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. is preferred.
  • monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7 -aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2 -Hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6- Aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzo
  • the imidization rate (also referred to as "ring closure rate") of polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of film strength, insulation properties, etc. of the organic film obtained. More preferably, it is 90% or more.
  • the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
  • the above imidization rate is measured, for example, by the following method. The infrared absorption spectrum of polyimide is measured, and the peak intensity P1 near 1377 cm ⁇ 1 , which is an absorption peak derived from the imide structure, is determined. Next, the polyimide is heat-treated at 350° C.
  • the polyimide may include repeating units represented by the above formula (4) in which all of the repeating units have the same combination of R 131 and R 132 , or two or more repeating units with different combinations of R 131 and R 132 .
  • the repeating unit represented by the above formula (4) may be included.
  • the polyimide may contain other types of repeating units.
  • Other types of repeating units include, for example, the repeating unit represented by the above formula (2).
  • Polyimide can be produced, for example, by reacting tetracarboxylic dianhydride and diamine (partly replaced with an acid anhydride) at low temperature; A method of reacting a diester with a diamine (substituted with an end-capping agent that is a compound or a monoacid chloride compound or a monoactive ester compound) with a diamine, and a diester is obtained with a tetracarboxylic dianhydride and an alcohol, and then a diamine (partly of which is a monoamine) is reacted with a diamine.
  • a diester is obtained by reacting tetracarboxylic dianhydride and alcohol in the presence of a condensing agent, and then the remaining dicarboxylic acid is converted into an acid chloride, and a diamine (some of which is substituted with a monoamine) is reacted with a condensing agent.
  • a polyimide precursor is obtained using a method such as reacting with a terminal capping agent), and this is completely imidized using a known imidization reaction method, or an imidization reaction is performed during the process. It can be synthesized by stopping the polymer and introducing a partial imide structure, or by blending a fully imidized polymer with its polyimide precursor to introduce a partial imide structure. . Further, other known polyimide synthesis methods can also be applied.
  • the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, even more preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the bending resistance of the cured film can be improved. In order to obtain an organic film with excellent mechanical properties (for example, elongation at break), the weight average molecular weight is particularly preferably 15,000 or more.
  • the number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
  • the molecular weight dispersity of the polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
  • the upper limit of the degree of dispersion of the molecular weight of polyimide is not particularly determined, for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
  • the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyimide are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated by considering the plurality of types of polyimides as one resin are each within the above ranges.
  • polybenzoxazole precursor examples include compounds described in paragraphs 0073 to 0095 of International Publication No. 2022/145355. The above description is incorporated herein.
  • polybenzoxazole examples include compounds described in paragraphs 0096 to 0103 of International Publication No. 2022/145355. The above description is incorporated herein.
  • polyamideimide precursor examples include compounds described in paragraphs 0104 to 0119 of International Publication No. 2022/145355. The above description is incorporated herein.
  • polyamideimide examples include compounds described in paragraphs 0120 to 0133 of International Publication No. 2022/145355. The above description is incorporated herein.
  • polyimide precursors can be obtained by reacting tetracarboxylic dianhydride and diamine at low temperature, by reacting tetracarboxylic dianhydride and diamine at low temperature to obtain polyamic acid, and by using a condensing agent or an alkylating agent.
  • a method of esterifying using a tetracarboxylic dianhydride and an alcohol a method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol, and then reacting it with a diamine in the presence of a condensing agent, a method of obtaining a diester with a tetracarboxylic dianhydride and an alcohol, The remaining dicarboxylic acid can then be acid-halogenated using a halogenating agent and reacted with a diamine.
  • a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid-halogenated using a halogenating agent and reacted with a diamine is more preferable.
  • the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, Examples include N'-disuccinimidyl carbonate and trifluoroacetic anhydride.
  • alkylating agent examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, triethyl orthoformate, and the like.
  • halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride, and the like.
  • an organic solvent In the method for producing polyimide precursors, etc., it is preferable to use an organic solvent during the reaction.
  • the number of organic solvents may be one or two or more.
  • the organic solvent can be determined as appropriate depending on the raw material, and examples include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, ⁇ -butyrolactone, etc. is exemplified.
  • a basic compound In the method for producing polyimide precursors, etc., it is preferable to add a basic compound during the reaction.
  • the number of basic compounds may be one or two or more.
  • the basic compound can be determined as appropriate depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-amino Examples include pyridine.
  • -Terminal sealing agent- In the production method of polyimide precursors, etc., in order to further improve storage stability, it is preferable to seal the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the end of the resin such as the polyimide precursor.
  • examples of the terminal capping agent include monoalcohol, phenol, thiol, thiophenol, monoamine, etc. From the viewpoint of properties, it is more preferable to use monoalcohols, phenols, and monoamines.
  • Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol, secondary alcohols such as 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantane alcohol.
  • primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, and isopropanol.
  • 2-butanol cyclohexyl alcohol
  • Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalen-1-ol, naphthalen-2-ol, and hydroxystyrene.
  • Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6- Aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminona
  • sealing agents for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic anhydrides, and sulfonic acid carboxylic acid anhydrides, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. preferable.
  • Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like.
  • Preferred carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexane carbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantane carbonyl chloride. , heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.
  • the method for producing a polyimide precursor or the like may include a step of precipitating a solid. Specifically, after filtering off the water-absorbed by-products of the dehydration condensation agent coexisting in the reaction solution, the obtained product is added to a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof.
  • a polyimide precursor or the like can be obtained by depositing the polymer component as a solid and drying it. In order to improve the degree of purification, operations such as redissolving the polyimide precursor, reprecipitation, drying, etc. may be repeated.
  • the method may include a step of removing ionic impurities using an ion exchange resin.
  • the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more based on the total solid content of the resin composition. It is even more preferable that the amount is 50% by mass or more. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass or less based on the total solid content of the resin composition. % or less, even more preferably 97% by mass or less, even more preferably 95% by mass or less.
  • the resin composition of the present invention may contain only one type of specific resin, or may contain two or more types of specific resin. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention contains at least two types of resin.
  • the resin composition of the present invention may contain a total of two or more types of specific resin and other resins described below, or may contain two or more types of specific resin, but may contain a specific resin. It is preferable to include two or more types.
  • the resin composition of the present invention contains two or more specific resins, for example, two or more polyimides that are polyimide precursors and have different dianhydride-derived structures (R 115 in the above formula (2))
  • a precursor is included.
  • the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter also simply referred to as "other resin").
  • Other resins include phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane resin, butyral resin, styryl resin, polyether resin, polyester resin. etc.
  • phenolic resin polyamide
  • epoxy resin polysiloxane
  • resin containing siloxane structure phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure
  • a (meth)acrylic resin by further adding a (meth)acrylic resin, a resin composition with excellent coating properties can be obtained, and a pattern (
  • a polymerizable group having a high polymerizable group value with a weight average molecular weight of 20,000 or less may be used instead of or in addition to the polymerizable compound described below.
  • a polymerizable group having a high polymerizable group value with a weight average molecular weight of 20,000 or less for example, the molar amount of polymerizable groups contained in 1 g of resin
  • a (meth)acrylic resin having a concentration of 1 ⁇ 10 ⁇ 3 mol/g or more
  • it is possible to improve the coating properties of the resin composition, the solvent resistance of the pattern (cured product), etc. can.
  • the content of the other resins is preferably 0.01% by mass or more, and 0.05% by mass or more based on the total solid content of the resin composition. It is more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more. More preferred.
  • the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass based on the total solid content of the resin composition. It is more preferably at most 60% by mass, even more preferably at most 50% by mass.
  • the content of other resins may be low.
  • the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less based on the total solid content of the resin composition. is more preferable, even more preferably 5% by mass or less, even more preferably 1% by mass or less.
  • the lower limit of the content is not particularly limited, and may be 0% by mass or more.
  • the resin composition of the present invention may contain only one type of other resin, or may contain two or more types of other resins. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention contains Compound A.
  • Compound A is represented by the following formula (A-1), and the total number of carbon atoms in formula (A-1) is 3 to 30.
  • R 1 represents a monovalent organic group
  • the bonding site in R 1 with the nitrogen atom described in formula (A-1) is a carbon atom
  • R 2 is a hydrogen atom
  • R 3 represents a monovalent organic group
  • R 2 and R 3 may be combined to form a ring structure.
  • the total number of carbon atoms in formula (A-1) is 3 to 30.
  • the total number of carbon atoms contained in formula (A-1) refers to the total number of all carbon atoms contained in the compound represented by formula (A-1).
  • the resulting cured product has excellent chemical resistance. It is thought that the copper corrosion inhibitor that could not be adsorbed to the substrate exists on the surface of the film or at intermediate depths. However, if molecules with a total number of carbon atoms exceeding 30 are present on the surface of the film as described above, the plasticity of the film increases, the solubility of the film increases, and the chemical resistance deteriorates. It is thought that this will decrease.
  • the lower limit of the number of carbon atoms is preferably 4 or more, more preferably 5 or more, and even more preferably 6 or more.
  • the upper limit of the number of carbon atoms is preferably 25 or less, more preferably 22 or less, and even more preferably 20 or less.
  • R 1 may be either an aliphatic group or an aromatic group, but is preferably an aromatic group.
  • Examples of the aliphatic group include an alkyl group.
  • aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but from the viewpoint of adhesion of the cured product after being exposed to heating conditions, aromatic A group heterocyclic group is preferred.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group.
  • R 1 is an aromatic hydrocarbon group
  • the aromatic hydrocarbon group may further have a substituent.
  • the substituent is not particularly limited, and includes an alkyl group, an alkoxy group, a hydroxy group, a dimethylphosphoryl group, and the like. Among these, it is preferable to have a substituent having at least one atom selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, and a phosphorus atom.
  • R 1 is an aromatic hydrocarbon group having a substituent
  • the substituent is bonded to a ring member adjacent to the ring member bonded to the nitrogen atom in formula (A-1) in R 1 is preferred.
  • R 1 is a phenyl group having a hydroxy group
  • heteroatom in the aromatic heterocyclic group examples include a nitrogen atom, a sulfur atom, an oxygen atom, etc., but preferably it contains at least one of a nitrogen atom and a sulfur atom, more preferably a nitrogen atom, and a nitrogen atom. It is particularly preferred that it contains two or more atoms. Furthermore, an embodiment containing a nitrogen atom and a sulfur atom is also one of the preferred embodiments of the present invention.
  • the number of heteroatoms in the aromatic heterocyclic group is not particularly limited, but is preferably from 1 to 8, more preferably from 1 to 6, and even more preferably from 2 to 4.
  • the aromatic heterocyclic group mentioned above is a group in which one hydrogen atom is removed from a 5-membered ring structure, a group in which one hydrogen atom is removed from a 6-membered ring structure, and a ring in which a 5-membered ring structure and a 6-membered ring structure are condensed.
  • a group in which one hydrogen atom is removed from a structure or a ring structure in which two six-membered ring structures are condensed is preferable.
  • Examples of the 5-membered ring structure in a group in which one hydrogen atom is removed from the 5-membered ring structure include a pyrrole ring, a pyrazole ring, an imidazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring, and a tetrazole ring. , thiazole ring, thiophene ring, oxazole ring, furan ring and the like.
  • Examples of the 6-membered ring structure in a group in which one hydrogen atom is removed from the 6-membered ring structure include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a 1,2,4-triazine ring, and a 1,3,5-triazine ring. etc.
  • Ring structures in which a 5-membered ring structure and a 6-membered ring structure are condensed in a group in which one hydrogen atom is removed from a ring structure in which a 5-membered ring structure and a 6-membered ring structure are condensed include an indole ring, an isoindole ring, Examples include an indolizine ring, an indazole ring, a benzimidazole ring, a 7-azaindole ring, a 7-azaindazole ring, a pyrazolo "1,5-a” pyrimidine ring, a purine ring, a benzothiophene ring, and a benzisothiazole ring.
  • Ring structures in which a 5-membered ring structure and a 6-membered ring structure are condensed in a group in which one hydrogen atom is removed from a ring structure in which a 5-membered ring structure and a 6-membered ring structure are condensed include a naphthalene ring, a quinoline ring, and an isoquinoline ring.
  • the aromatic heterocyclic group may further have a substituent.
  • substituents include an alkyl group, an aryl group, an alkoxy group, a hydroxy group, and a cyano group.
  • an alkyl group for example, a straight-chain alkyl group such as a methyl group or an ethyl group, or a branched alkyl group such as an isopropyl group or a 2-ethylhexyl group
  • an alkyl group for example, a straight-chain alkyl group such as a methyl group or an ethyl group, or a branched alkyl group such as an isopropyl group or a 2-ethylhexyl group
  • R 1 is not limited to the following structure.
  • * represents a bonding site with the nitrogen atom in formula (A-1).
  • R 2 represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.
  • the monovalent organic group for R 2 is not particularly limited, but includes an alkyl group, an aryl group, and the like, with an alkyl group having 1 to 4 carbon atoms or a phenyl group being preferred.
  • R 3 represents a monovalent organic group, which may be either an aliphatic group or an aromatic group, but is preferably an aromatic group. Examples of the aliphatic group include an alkyl group.
  • aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but from the viewpoint of adhesion of the cured product after being exposed to heating conditions, aromatic A group hydrocarbon group is preferred.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group.
  • the aromatic hydrocarbon group may further have a substituent.
  • the substituent is not particularly limited, and examples include an alkyl group, an alkoxy group, a hydroxy group, and a hydroxy group is preferred.
  • R 3 is an aromatic hydrocarbon group having a substituent, the substituent is bonded to a ring member adjacent to the ring member bonded to the nitrogen atom in formula (A-1) in R 1 . is preferred.
  • R 1 is a phenyl group having a hydroxy group, it is preferable that the bonding site with the nitrogen atom in formula (A-1) and the hydroxy group in the phenyl group exist in the ortho position.
  • Preferred embodiments of the aromatic heterocyclic group when R 3 is an aromatic heterocyclic group are the same as the preferred embodiments when R 1 is an aromatic heterocyclic group described above. Further, an embodiment in which R 3 is an aromatic heterocyclic group having no nitrogen atom is also one of the preferred embodiments of the present invention. Examples of the aromatic heterocyclic group in such an embodiment include a furanyl group and a thienyl group.
  • R 3 represents a bonding site with the carbon atom in formula (A-1).
  • R 2 and R 3 may be combined to form a ring structure.
  • the ring structure formed is preferably a ring structure condensed with the aromatic ring structure in R 3 described above, more preferably an aliphatic ring structure condensed with the aromatic ring structure in R 3 described above, More preferably, it is an aliphatic 5-membered ring structure condensed with the aromatic ring structure in R 3 described above.
  • Examples of structures in which R 2 and R 3 combine to form a ring structure are shown below, but the present invention is not limited thereto.
  • * represents a bonding site with the nitrogen atom in formula (A-1).
  • the carbon atom directly bonded to * through a double bond in the structure below is the carbon atom in formula (A-1).
  • the resin composition of the present invention preferably contains a compound represented by the following formula (A-2) as the compound A.
  • Ar 1 and Ar 2 each independently represent an aromatic group which may have a substituent, and at least one of the ring member of the aromatic group and the substituent has oxygen.
  • R 2 represents a hydrogen atom or a monovalent organic group.
  • a preferred embodiment of Ar 1 is the same as the preferred embodiment when R 1 in formula (A-1) described above is an aromatic group.
  • preferred embodiments of R 2 are the same as the preferred embodiments of R 2 in formula (A-1) above.
  • a preferred embodiment of Ar 2 is the same as the preferred embodiment when R 3 in formula (A-1) described above is an aromatic group.
  • At least one of the above Ar 1 , the above Ar 2 and the above R 2 has a phenolic hydroxyl group.
  • at least one of Ar 1 and Ar 2 has a phenolic hydroxyl group.
  • at least one of the above Ar 1 and the above Ar 2 is a 2-hydroxyphenyl group.
  • At least one of the above Ar 1 , the above Ar 2 and the above R 2 has a heterocyclic structure. Among these, it is preferable that at least one of Ar 1 and Ar 2 has a heterocyclic structure.
  • the heterocyclic structure an aromatic heterocyclic structure is preferable. Preferred embodiments of the aromatic heterocyclic structure are the same as the preferred embodiments in the case where R 1 or R 3 is an aromatic heterocyclic group.
  • the molecular weight of compound A is preferably 150 to 2,000, more preferably 160 to 1,000, and even more preferably 180 to 500.
  • Compound A can be synthesized, for example, by the method described in Examples below. Further, it may be synthesized using other known synthesis methods, and the synthesis method is not particularly limited.
  • compound A examples include, but are not limited to, F-1 to F-23 used in Examples.
  • the content of compound A based on the total solid content of the resin composition of the present invention is preferably 0.01 to 10% by mass.
  • the lower limit is more preferably 0.02% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more.
  • the upper limit is more preferably 8% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less.
  • One type of compound A may be used alone, or two or more types may be used in combination. When two or more types are used together, it is preferable that the total amount falls within the above range.
  • the content of compound A relative to 100 parts by mass of the specific resin is preferably 0.05 to 8 parts by mass, more preferably 0.10 to 5 parts by mass.
  • the resin composition of the present invention may contain an organometallic complex from the viewpoint of chemical resistance.
  • the organometallic complex is not particularly limited as long as it is an organic complex compound containing a metal atom, but it is preferably a complex compound containing a metal atom and an organic group, and a compound in which an organic group is coordinated to a metal atom. are more preferred, and metallocene compounds are even more preferred.
  • the metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives which may have substituents as ⁇ 5-ligands.
  • the organic group is not particularly limited, but preferably a hydrocarbon group or a group consisting of a combination of a hydrocarbon group and a heteroatom.
  • a hydrocarbon group As the heteroatom, an oxygen atom, a sulfur atom, and a nitrogen atom are preferable.
  • At least one of the above organic groups is preferably a cyclic group, and more preferably at least two are cyclic groups.
  • the cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably a 5-membered cyclic group.
  • the above-mentioned cyclic group may be a hydrocarbon ring or a heterocycle, but a hydrocarbon ring is preferable.
  • As the 5-membered cyclic group a cyclopentadienyl group is preferred.
  • the organometallic complex preferably contains 2 to 4 cyclic groups in one molecule.
  • the metal contained in the organometallic complex is not particularly limited, but it is preferably a metal that falls under Group 4 elements, and more preferably at least one metal selected from the group consisting of titanium, zirconium, and hafnium.
  • at least one metal selected from the group consisting of titanium and zirconium is more preferable, and titanium is particularly preferable.
  • the organometallic complex may contain two or more metal atoms or only one metal atom, but preferably contains only one metal atom.
  • the organometallic complex may contain two or more metal atoms, it may contain only one kind of metal atom, or it may contain two or more kinds of metal atoms.
  • the organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound, or a hafnocene compound, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, and even more preferably a titanocene compound or a zirconocene compound.
  • titanocene compounds are particularly preferred.
  • the organometallic complex has the ability to initiate photoradical polymerization.
  • having the ability to initiate photoradical polymerization means being able to generate free radicals that can initiate radical polymerization by irradiation with light. For example, when a composition containing a radical cross-linking agent and an organometallic complex is irradiated with light in a wavelength range in which the organometallic complex absorbs light and in which the radical cross-linker does not absorb light, radicals By checking whether the crosslinking agent disappears, it is possible to check whether the photoradical polymerization initiation ability exists.
  • the organometallic complex has the ability to initiate photoradical polymerization
  • the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, and preferably a titanocene compound or a zirconocene compound. are more preferred, and titanocene compounds are particularly preferred.
  • the organometallic complex contains at least one compound selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds, and hafnocene compounds.
  • the compound is a type of compound, more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds and hafnocene compounds, and at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds. More preferably, it is a species compound, and particularly preferably a titanocene compound.
  • the molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.
  • each R is independently a substituent.
  • each R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.
  • the metal atom represented by M in formula (P) is preferably an iron atom, a titanium atom, a zirconium atom, or a hafnium atom, more preferably a titanium atom, a zirconium atom, or a hafnium atom, and even more preferably a titanium atom or a zirconium atom. Atoms are particularly preferred.
  • the aromatic group for R in formula (P) includes an aromatic group having 6 to 20 carbon atoms, preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, such as a phenyl group, a 1-naphthyl group, or , 2-naphthyl group, etc.
  • the alkyl group for R in formula (P) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, ethyl group, propyl group, octyl group, isopropyl group. , t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group, and the like.
  • Examples of the halogen atom in R include F, Cl, Br, and I.
  • the alkyl group constituting the alkylsulfonyloxy group in R above is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an octyl group, Examples include isopropyl group, t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, and cyclopentyl group.
  • the above R may further have a substituent.
  • substituents include halogen atoms (F, Cl, Br, I), hydroxy groups, carboxy groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxy Examples include a carbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, and a diarylamino group.
  • halogen atoms F, Cl, Br, I
  • hydroxy groups carboxy groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxy
  • substituents include halogen atoms (F, Cl, Br, I), hydroxy groups, carboxy groups, amino groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, ary
  • organometallic complexes include, but are not limited to, tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonato)titanium, Bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, pentamethylcyclopentadienyltitanium trimethoxide, bis ( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium and the following compounds may be mentioned.
  • the content of the organometallic complex is preferably 0.1 to 30% by mass based on the total solid content of the resin composition.
  • the lower limit is more preferably 1.0% by mass or more, still more preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more.
  • the upper limit is more preferably 25% by mass or less.
  • One type or two or more types of organometallic complexes can be used. When two or more types are used, the total amount is preferably within the above range.
  • the resin composition of the present invention contains a polymerizable compound.
  • the resin composition of the present invention contains a photopolymerization initiator and a polymerizable compound, which will be described later.
  • the polymerizable compound include radical crosslinking agents and other crosslinking agents.
  • the resin composition of the present invention contains a radical crosslinking agent.
  • a radical crosslinking agent is a compound having a radically polymerizable group.
  • the radically polymerizable group a group containing an ethylenically unsaturated bond is preferable.
  • the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinyl phenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
  • (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferable, and from the viewpoint of reactivity, (meth)acryloyl group is more preferable.
  • the radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds.
  • the radical crosslinking agent may have three or more ethylenically unsaturated bonds.
  • the compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and more preferably a compound having 2 to 6 ethylenically unsaturated bonds. More preferred are compounds having the following.
  • the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above ethylenically unsaturated bonds. It is also preferable.
  • the molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
  • radical crosslinking agents include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. These are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds.
  • addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxy groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxies, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • the radical crosslinking agent is also preferably a compound having a boiling point of 100°C or higher under normal pressure.
  • Examples of the compound having a boiling point of 100° C. or higher under normal pressure include the compounds described in paragraph 0203 of International Publication No. 2021/112189. This content is incorporated herein.
  • Preferred radical crosslinking agents other than those mentioned above include radically polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021/112189. This content is incorporated herein.
  • radical crosslinking agents examples include dipentaerythritol triacrylate (commercially available product: KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available product: KAYARAD D-320 (made by Nippon Kayaku Co., Ltd.) Co., Ltd.), A-TMMT (Shin Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (Nippon Kayaku Co., Ltd.)), dipenta Erythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and these (meth)acryloyl groups are ethylene glyco
  • radical crosslinking agents include, for example, SR-494, which is a tetrafunctional acrylate with four ethyleneoxy chains, and SR-209, 231, and 239, which are difunctional methacrylates with four ethyleneoxy chains (all of which are sold by Sartomer Co., Ltd.). (manufactured by Nippon Kayaku Co., Ltd.), DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, TPA-330, a trifunctional acrylate with three isobutyleneoxy chains (manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers.
  • SR-494 which is a tetrafunctional acrylate with four ethyleneoxy chains
  • SR-209, 231, and 239 which are difunctional methacrylates with four ethyleneoxy chains (all of which are sold by Sartomer Co., Ltd.).
  • DPCA-60 a hexafunctional acrylate with six penty
  • urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765, Urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
  • radical crosslinking agent compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, can also be used. can.
  • the radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphoric acid group.
  • the radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group.
  • a radical crosslinking agent having the following is more preferable.
  • the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. It is a compound that is Commercially available products include, for example, polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.
  • the acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, more preferably 1 to 100 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, it will have excellent handling properties during production and excellent developability. Moreover, it has good polymerizability. The above acid value is measured in accordance with the description of JIS K 0070:1992.
  • bifunctional methacrylate or acrylate as the resin composition from the viewpoint of pattern resolution and film stretchability.
  • Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, and PEG 600 diacrylate.
  • PEG200 diacrylate refers to polyethylene glycol diacrylate in which the formula weight of polyethylene glycol chains is about 200.
  • a monofunctional radical crosslinking agent can preferably be used as the radical crosslinking agent from the viewpoint of suppressing warping of the pattern (cured product).
  • monofunctional radical crosslinking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, and cyclohexyl (meth)acrylate.
  • (meth)acrylate benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc.
  • Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl glycidyl ether, and the like are preferably used.
  • the monofunctional radical crosslinking agent a compound having a boiling point of 100° C. or higher at normal pressure is also preferred in order to suppress volatilization before exposure.
  • examples of the radical crosslinking agent having two or more functional groups include allyl compounds such as diallyl phthalate and triallyl trimellitate.
  • the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less based on the total solid content of the resin composition.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
  • One type of radical crosslinking agent may be used alone, or a mixture of two or more types may be used. When two or more types are used together, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention contains another crosslinking agent different from the above-mentioned radical crosslinking agent.
  • Other crosslinking agents refer to crosslinking agents other than the above-mentioned radical crosslinking agents, and the above-mentioned photoacid generators or photobase generators can be used to interact with other compounds in the composition or their reaction products.
  • the compound has a plurality of groups in its molecule that promote the reaction of forming a covalent bond between the compounds, and the reaction of forming a covalent bond with other compounds in the composition or the reaction products thereof is preferably Compounds having a plurality of groups in the molecule that are promoted by the action of acids or bases are preferred.
  • the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
  • Other crosslinking agents include compounds described in paragraphs 0179 to 0207 of International Publication No. 2022/145355. The above description is incorporated herein.
  • the resin composition of the present invention preferably contains a polymerization initiator.
  • the polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator.
  • the photopolymerization initiator is preferably a radical photopolymerization initiator.
  • the radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet to visible range is preferred. Alternatively, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.
  • the photoradical polymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 within the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). It is preferable.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g/L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • any known compound can be used.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc.
  • ketone compound examples include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
  • Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd. is also suitably used.
  • a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, the content of which is herein incorporated by reference. Incorporated.
  • ⁇ -hydroxyketone initiators examples include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DA ROCUR 1173, IRGACURE 500, IRGACURE -2959 and IRGACURE 127 (manufactured by BASF) can be used.
  • ⁇ -aminoketone initiators examples include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369. , and IRGACURE 379 (manufactured by BASF) can be used.
  • aminoacetophenone initiator the acylphosphine oxide initiator, and the metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021/112189 can also be suitably used. This content is incorporated herein.
  • photoradical polymerization initiator include oxime compounds.
  • an oxime compound By using an oxime compound, it becomes possible to improve exposure latitude more effectively.
  • Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.
  • oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A 2000-080068, compounds described in JP-A 2006-342166, J. C. S. Perkin II (1979, pp. 1653-1660); C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000-0 Compounds described in Publication No. 66385, Compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Patent No. 6065596, compounds described in International Publication No. 2015/152153, International Publication No.
  • Preferred oxime compounds include, for example, compounds with the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy( imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino)) -1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, etc.
  • an oxime compound as a photoradical polymerization initiator.
  • oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF), and ADEKA Optomer N-1919 (manufactured by ADEKA Corporation, JP-A-2012-014052).
  • Examples of the photoradical polymerization initiator include oxime compounds having a fluorene ring described in paragraphs 0169 to 0171 of International Publication No. 2021/112189, and oximes having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring.
  • Compounds, oxime compounds having a fluorine atom can also be used.
  • an oxime compound having a nitro group, an oxime compound having a benzofuran skeleton, and an oxime compound having a substituent having a hydroxy group bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of International Publication No. 2021/020359 may be used. You can also do it. Their contents are incorporated herein.
  • oxime compound OX an oxime compound having an aromatic ring group Ar OX1 (hereinafter also referred to as oxime compound OX) in which an electron-withdrawing group is introduced into the aromatic ring.
  • Examples of the electron-withdrawing group possessed by the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group,
  • An acyl group and a nitro group are preferred, an acyl group is more preferred because a film with excellent light resistance can be easily formed, and a benzoyl group is even more preferred.
  • the benzoyl group may have a substituent.
  • substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, and more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group. More preferably, it is a sulfanyl group or an amino group.
  • the oxime compound OX is preferably at least one selected from a compound represented by formula (OX1) and a compound represented by formula (OX2), and more preferably a compound represented by formula (OX2). preferable.
  • R X3 to R X14 each independently represent a hydrogen atom or a substituent. However, at least one of R X10 to R X14 is an electron-withdrawing group.
  • R X12 is preferably an electron-withdrawing group
  • R X10 , R X11 , R X13 , and R X14 are preferably hydrogen atoms.
  • oxime compound OX examples include compounds described in paragraph numbers 0083 to 0105 of Japanese Patent No. 4,600,600, the contents of which are incorporated herein.
  • Particularly preferable oxime compounds include oxime compounds having a specific substituent group as shown in JP-A No. 2007-269779, and oxime compounds having a thioaryl group as shown in JP-A No. 2009-191061. Incorporated herein.
  • photoradical polymerization initiators include trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triaryl compounds. selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.
  • Compounds such as
  • the photoradical polymerization initiator is a trihalomethyltriazine compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, an acetophenone compound, At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferred, and metallocene compounds or oxime compounds are even more preferred.
  • a difunctional, trifunctional or more functional photoradical polymerization initiator may be used as the photoradical polymerization initiator.
  • a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained.
  • the crystallinity decreases and the solubility in solvents improves, making it difficult to precipitate over time, thereby improving the stability of the resin composition over time.
  • Specific examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include those listed in Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
  • the resin composition contains a photopolymerization initiator
  • its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and 0.5% by mass based on the total solid content of the resin composition. It is more preferably from 1.0 to 10% by weight, and even more preferably from 1.0 to 10% by weight.
  • the photopolymerization initiator may contain only one type, or may contain two or more types. When containing two or more types of photopolymerization initiators, it is preferable that the total amount is within the above range. Note that since the photopolymerization initiator may also function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further promoted by heating with an oven, a hot plate, or the like.
  • the resin composition may contain a sensitizer.
  • the sensitizer absorbs specific actinic radiation and becomes electronically excited.
  • the sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and effects such as electron transfer, energy transfer, and heat generation occur.
  • the thermal radical polymerization initiator and the photo radical polymerization initiator undergo a chemical change and are decomposed to generate radicals, acids, or bases.
  • Usable sensitizers include benzophenone series, Michler's ketone series, coumarin series, pyrazole azo series, anilinoazo series, triphenylmethane series, anthraquinone series, anthracene series, anthrapyridone series, benzylidene series, oxonol series, and pyrazolotriazole azo series.
  • pyridone azo type cyanine type, phenothiazine type, pyrrolopyrazole azomethine type, xanthene type, phthalocyanine type, penzopyran type, indigo type and the like can be used.
  • sensitizer examples include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl Denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso Naphthothiazole, 1,3-
  • the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. More preferably 0.5 to 10% by mass.
  • the sensitizers may be used alone or in combination of two or more.
  • the resin composition of the present invention may contain a chain transfer agent.
  • Chain transfer agents are defined, for example, in the Polymer Dictionary, 3rd edition (edited by the Society of Polymer Science and Technology, 2005), pages 683-684.
  • Examples of chain transfer agents include compounds having -S-S-, -SO 2 -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and RAFT (Reversible Addition Fragmentation chain Transfer).
  • Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used in polymerization are used. These can generate radicals by donating hydrogen to low-activity radicals, or can generate radicals by being oxidized and then deprotonated.
  • thiol compounds can be preferably used.
  • the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, and 0.1 to 10 parts by mass based on 100 parts by mass of the total solid content of the resin composition. More preferably, 0.5 to 5 parts by mass is even more preferred.
  • the number of chain transfer agents may be one, or two or more. When there are two or more types of chain transfer agents, it is preferable that the total is within the above range.
  • the resin composition of the present invention may also contain a base generator.
  • the base generator is a compound that can generate a base by physical or chemical action.
  • Preferred base generators include thermal base generators and photobase generators.
  • the resin composition contains a base generator.
  • the resin composition contains a thermal base generator, the cyclization reaction of the precursor can be promoted by heating, for example, and the cured product has good mechanical properties and chemical resistance. The performance as an interlayer insulating film for wiring layers is improved.
  • the base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
  • the base generator is not particularly limited, and any known base generator can be used.
  • Known base generators include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amine imides. compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, ⁇ -lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like.
  • Specific examples of nonionic base generators include compounds described in paragraphs 0249 to 0275 of International Publication No. 2022/145355. The above description is incorporated herein.
  • Examples of the base generator include, but are not limited to, the following compounds.
  • the molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
  • the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
  • Specific preferred compounds of the ionic base generator include, for example, the compounds described in paragraph numbers 0148 to 0163 of International Publication No. 2018/038002.
  • ammonium salts include, but are not limited to, the following compounds.
  • iminium salts include, but are not limited to, the following compounds.
  • the content of the base generator is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the resin in the resin composition.
  • the lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
  • the upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.
  • One type or two or more types of base generators can be used. When two or more types are used, the total amount is preferably within the above range.
  • the resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent.
  • the solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
  • esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone.
  • alkyloxyacetates e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate) , methyl ethoxy acetate, ethyl ethoxy acetate, etc.
  • 3-alkyloxypropionate alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • alkyl 2-alkyloxypropionate esters e.g., methyl 2-alkyloxypropionate, 2-alkyloxypropionate
  • propyl 2-alkyloxypropionate etc.
  • Methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate for example, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
  • Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc. are preferred. It is mentioned as something.
  • ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol Suitable examples include monobutyl ether acetate
  • Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone, and the like.
  • Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.
  • Suitable examples of sulfoxides include dimethyl sulfoxide.
  • Amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, Preferred examples include 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.
  • Suitable ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.
  • Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
  • solvent selected from methyl ether acetate, levoglucosenone, and dihydrolevoglucosenone, or a mixed solvent composed of two or more types is preferable.
  • Particularly preferred is the combination of amide, ⁇ -butyrolactone and dimethyl sulfoxide, or the combination of N-methyl-2-pyrrolidone and ethyl lactate.
  • toluene is further added to the solvent used in combination in an amount of about 1 to 10% by mass based on the total mass of the solvent.
  • an embodiment containing ⁇ -valerolactone as a solvent is also one of the preferred embodiments of the present invention.
  • the content of ⁇ -valerolactone based on the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass or more. preferable.
  • the upper limit of the content is not particularly limited and may be 100% by mass. The above content may be determined in consideration of the solubility of components such as the specific resin contained in the resin composition.
  • dimethyl sulfoxide and ⁇ -valerolactone when dimethyl sulfoxide and ⁇ -valerolactone are used together, it is preferable to contain 60 to 90% by mass of ⁇ -valerolactone and 10 to 40% by mass of dimethyl sulfoxide, based on the total mass of the solvent. It is more preferable to contain ⁇ 90% by mass of ⁇ -valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and more preferably to contain 75 to 85% by mass of ⁇ -valerolactone and 15 to 25% by mass of dimethyl sulfoxide. More preferred.
  • the content of the solvent is preferably such that the total solids concentration of the resin composition of the present invention is 5 to 80% by mass, and preferably 5 to 75% by mass. More preferably, the amount is 10 to 70% by mass, and even more preferably 20 to 70% by mass.
  • the solvent content may be adjusted depending on the desired thickness of the coating and the application method. When two or more types of solvents are contained, it is preferable that the total amount is within the above range.
  • the resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used for electrodes, wiring, etc.
  • metal adhesion improvers include silane coupling agents having alkoxysilyl groups, aluminum adhesion aids, titanium adhesion aids, compounds having a sulfonamide structure and thiourea structure, phosphoric acid derivative compounds, ⁇ - Examples include ketoester compounds and amino compounds.
  • silane coupling agent examples include the compounds described in paragraph 0316 of International Publication No. 2021/112189 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573, the contents of which are not included herein. Incorporated. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group and Et represents an ethyl group. Further, the following R includes a structure derived from a blocking agent in a blocked isocyanate group.
  • the blocking agent may be selected depending on the desorption temperature, and includes alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, active methylene compounds, and the like. For example, from the viewpoint of desiring a desorption temperature of 160 to 180°C, caprolactam and the like are preferred. Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • silane coupling agents examples include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane.
  • an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent.
  • examples of such oligomer type compounds include compounds containing a repeating unit represented by the following formula (S-1).
  • R S1 represents a monovalent organic group
  • R S2 represents a hydrogen atom, a hydroxy group, or an alkoxy group
  • n represents an integer of 0 to 2.
  • R S1 preferably has a structure containing a polymerizable group.
  • Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinyl phenyl group, etc.), and a (meth)acrylamide group.
  • R S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
  • n represents an integer from 0 to 2, preferably 1.
  • n is 1 or 2 in at least one of the plurality of repeating units represented by formula (S-1) contained in the oligomer type compound, and n is 1 or 2 in at least two. More preferably, n is 2, and even more preferably n is 1 in at least two cases.
  • Commercially available products can be used as such oligomer type compounds, and examples of commercially available products include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Aluminum-based adhesion aid examples include aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.
  • the content of the metal adhesion improver is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the specific resin.
  • the content of the metal adhesion improver is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the specific resin.
  • the resin composition of the present invention further contains a migration inhibitor.
  • a migration inhibitor for example, when a resin composition is applied to a metal layer (or metal wiring) to form a film, metal ions derived from the metal layer (or metal wiring) may migrate into the film. can be effectively suppressed.
  • the compound corresponding to the above-mentioned compound A does not correspond to a migration inhibitor.
  • Migration inhibitors are not particularly limited, but include heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenol compounds , salicylic acid derivative compounds, and hydrazide derivative compounds.
  • heterocycles pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring
  • triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
  • an ion trapping agent that traps anions such as halogen ions can also be used.
  • Other migration inhibitors include the rust inhibitors described in paragraph 0094 of JP-A-2013-015701, the compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and the compounds described in JP-A-2011-059656.
  • Compounds described in paragraph 0052, compounds described in paragraphs 0114, 0116, and 0118 of JP 2012-194520, compounds described in paragraph 0166 of WO 2015/199219, etc. can be used, and the contents thereof is incorporated herein.
  • migration inhibitors include the following compounds.
  • the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, and 0.01 to 5.0% by mass based on the total solid content of the resin composition.
  • the amount is more preferably 0.05 to 2.0% by weight, and even more preferably 0.1 to 1.0% by weight.
  • Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more types of migration inhibitors, it is preferable that the total is within the above range.
  • the resin composition of the present invention contains a polymerization inhibitor.
  • the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.
  • Specific compounds of the polymerization inhibitor include the compound described in paragraph 0310 of International Publication No. 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1- Examples include oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, and the like. This content is incorporated herein.
  • the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, and 0.02 to 20% by mass based on the total solid content of the resin composition. It is more preferably 15% by mass, and even more preferably 0.05 to 10% by mass.
  • Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more types of polymerization inhibitors, it is preferable that the total is within the above range.
  • the resin composition of the present invention contains a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure.
  • Whether or not a certain compound a contained in the resin composition corresponds to a light absorber can be determined by the following method. First, a solution of compound a with the same concentration as that contained in the resin composition is prepared, and the molar extinction coefficient (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 , also referred to as “molar extinction coefficient 1”) of compound a at the wavelength of exposure light is determined. ). The above measurement is performed quickly so as to minimize the influence of changes such as a decrease in the molar extinction coefficient of compound a.
  • the solvent in the above solution when the resin composition contains a solvent, that solvent is used, and when the resin composition does not contain a solvent, N-methyl-2-pyrrolidone is used.
  • the solution of compound a is irradiated with exposure light.
  • the exposure amount is 500 mJ as an integrated amount for 1 mol of compound a.
  • the molar extinction coefficient (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 , also referred to as “molar extinction coefficient 2”) of compound a at the wavelength of the exposure light is measured.
  • Attenuation rate (%) 1 - molar extinction coefficient 2 / molar extinction coefficient 1 x 100
  • the attenuation rate is preferably 10% or more, more preferably 20% or more. Further, the lower limit of the attenuation rate is not particularly limited, and may be 0% or more.
  • the wavelength of the exposure light may be any wavelength at which the photosensitive film is exposed. Further, the wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition is sensitive.
  • a photopolymerization initiator having sensitivity to a certain wavelength means that a polymerization initiation species is generated when the photopolymerization initiator is exposed to light at a certain wavelength.
  • the wavelength of the exposure light is (1) semiconductor laser (wavelength: 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, G-line (wavelength 436nm), H-line (wavelength 405nm), I-line (wavelength 365nm), Broad (3 wavelengths of g, h, i-line), (4) Excimer laser, KrF excimer laser (wavelength 248nm), ArF excimer Laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) Extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) Electron beam, (7) YAG laser second harmonic 532 nm, third harmonic Examples include 355 nm.
  • the wavelength of the exposure light may be selected, for example, from a wavelength to which the photopolymerization initiator is sensitive, preferably the h-line (wavelength: 405 nm) or the i-line (wavelength: 365 nm), and more preferably the i-line (wavelength: 365 nm).
  • the light absorber may be a compound that generates radical polymerization initiation species upon exposure to light, but from the viewpoint of resolution and chemical resistance, it is preferably a compound that does not generate radical polymerization initiation species upon exposure. Whether the light absorber is a compound that generates radical polymerization initiating species upon exposure to light is determined by the following method. A solution containing a light absorber and a radical crosslinking agent at the same concentration as that contained in the resin composition is prepared. When the resin composition contains a radical crosslinking agent, the same compound as the radical crosslinking agent contained in the resin composition is used at the same concentration as the radical crosslinking agent in the solution.
  • the resin composition does not contain a radical crosslinker, methyl methacrylate is used at a concentration five times that of the light absorber. After that, exposure light is irradiated. The exposure amount is 500 mJ as an integrated amount.
  • the polymerization of the polymerizable compound is determined by, for example, high performance liquid chromatography, and if the ratio of the molar amount of the polymerizable compound to the total molar amount of the polymerizable compound is 10% or less, the light absorber is It is determined that the compound does not generate radical polymerization initiation species upon exposure to light.
  • the molar amount ratio is preferably 5% or less, more preferably 3% or less.
  • the lower limit of the above molar amount ratio is not particularly limited, and may be 0%.
  • the wavelength of the exposure light may be any wavelength at which the photosensitive film is exposed. Further, the wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition is sensitive.
  • Examples of the compound that generates a radical polymerization initiator upon exposure to light include the same compounds as the above-mentioned photoradical polymerization initiators.
  • the composition contains a photoradical polymerization initiator as a light absorber
  • the one having the lowest polymerization initiating ability of the generated radical species is the light absorber
  • the others are the photopolymerization initiators.
  • Examples of compounds that do not generate radical polymerization initiation species upon exposure include photoacid generators, photobase generators, and dyes whose absorption wavelength changes upon exposure.
  • the light absorber is preferably a naphthoquinone diazide compound or a dye whose absorbance changes upon exposure, and more preferably a naphthoquinone diazide compound. It is also conceivable to use, as the light absorber, a combination of, for example, a photoacid generator or a photobase generator and a compound whose absorbance at the exposure wavelength decreases depending on the pH.
  • Naphthoquinonediazide compound examples include compounds that produce indenecarboxylic acid upon exposure and have a low absorbance at the exposure wavelength, and compounds having a 1,2-naphthoquinonediazide structure are preferred.
  • the naphthoquinone diazide compound is preferably a naphthoquinone diazide sulfonic acid ester of a hydroxy compound.
  • compounds represented by any of the following formulas (H1) to (H6) are preferred.
  • R 1 and R 2 each independently represent a monovalent organic group
  • R 3 and R 4 each independently represent a hydrogen atom or a monovalent organic group
  • n1, n2, m1 and m2 are each independently an integer of 0 to 5
  • at least one of m1 and m2 is an integer of 1 to 5.
  • Z represents a tetravalent organic group
  • L 1 , L 2 , L 3 and L 4 each independently represent a single bond or a divalent organic group
  • R 5 , R 6 , R 7 and R8 each independently represent a monovalent organic group
  • n3, n4, n5 and n6 each independently represent an integer of 0 to 3
  • m3, m4, m5 and m6 each independently represent 0 ⁇ 2, and at least one of m3, m4, m5, and m6 is 1 or 2.
  • R 9 and R 10 each independently represent a hydrogen atom or a monovalent organic group
  • L 5 each independently represents a divalent organic group
  • n7 represents an integer from 3 to 8. represent.
  • L 6 represents a divalent organic group
  • L 7 and L 8 each independently represent a divalent organic group containing an aliphatic tertiary or quaternary carbon.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 each independently represent a hydrogen atom, a halogen atom or a monovalent organic represents a group
  • L 9 , L 10 and L 11 each independently represent a single bond or a divalent organic group
  • m7, m8, m9, m10 each independently represent an integer from 0 to 2, m7, At least one of m8, m9, and m10 is 1 or 2.
  • R 42 , R 43 , R 44 , and R 45 each independently represent a hydrogen atom or a monovalent organic group
  • R 46 and R 47 each independently represent a monovalent organic group.
  • n16 and n17 each independently represent an integer from 0 to 4
  • m11 and m12 each independently represent an integer from 0 to 4
  • at least one of m11 and m12 is an integer from 1 to 4. be.
  • R 1 and R 2 are each independently preferably a monovalent organic group having 1 to 60 carbon atoms, more preferably a monovalent organic group having 1 to 30 carbon atoms.
  • Examples of the monovalent organic group in R 1 and R 2 include a hydrocarbon group that may have a substituent, such as an aromatic hydrocarbon group that may have a substituent such as a hydroxy group. Can be mentioned.
  • R 3 and R 4 are each independently preferably a monovalent organic group having 1 to 60 carbon atoms, more preferably a monovalent organic group having 1 to 30 carbon atoms. .
  • Examples of the monovalent organic group in R 3 and R 4 include a hydrocarbon group that may have a substituent, such as a hydrocarbon group that may have a substituent such as a hydroxy group.
  • n1 and n2 are each independently preferably 0 or 1, and more preferably 0.
  • m1 and m2 are preferably both 1.
  • the compound represented by formula (H1) is preferably a compound represented by any one of formulas (H1-1) to (H1-5).
  • R 21 , R 22 and R 23 each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and hydrogen An atom or a group represented by the following formula (R-1) is more preferable.
  • R 29 represents a hydrogen atom, an alkyl group, or an alkoxy group
  • n13 represents an integer of 0 to 2
  • * represents a bonding site with another structure.
  • n8, n9 and n10 each independently represent an integer of 0 to 2, preferably 0 or 1.
  • R 24 represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
  • n14, n15 and n16 each independently represent an integer from 0 to 2.
  • R 30 represents a hydrogen atom or an alkyl group.
  • R 25 , R 26 , R 27 and R 28 each independently represent a monovalent organic group, and are represented by a hydrogen atom, an alkyl group, or the above formula (R-1). It is preferable that it is a group.
  • n11, n12 and n13 each independently represent an integer of 0 to 2, preferably 0 or 1.
  • the compound represented by formula (H1-1) is preferably a compound represented by any one of the following formulas (H1-1-1) to (H1-1-4).
  • the compound represented by the formula (H1-2) is preferably a compound represented by the following formula (H1-2-1) or (H1-2-2).
  • Z is preferably a tetravalent group having 1 to 20 carbon atoms, and more preferably a group represented by any of the following formulas (Z-1) to (Z-4).
  • * represents a bonding site with another structure.
  • L 1 , L 2 , L 3 and L 4 are preferably each independently a single bond or a methylene group.
  • R 5 , R 6 , R 7 and R 8 are each independently preferably an organic group having 1 to 30 carbon atoms.
  • n3, n4, n5 and n6 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.
  • m3, m4, m5 and m6 are each independently preferably 1 or 2, more preferably 1.
  • Examples of the compound represented by formula (H2) include compounds having the following structure.
  • R 9 and R 10 each independently preferably represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
  • each L 5 is preferably independently a group represented by the following formula (L-1).
  • R 30 represents a monovalent organic group having 1 to 20 carbon atoms
  • n14 represents an integer of 1 to 5
  • * represents a bonding site with another structure.
  • n7 is preferably an integer of 4 to 6. Examples of the compound represented by formula (H3) include the following compounds.
  • each n independently represents an integer of 0 to 9.
  • L 7 and L 8 are each independently preferably a divalent organic group having 2 to 20 carbon atoms. Examples of the compound represented by formula (H4) include the following compounds.
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl A group, an alkoxy group, an allyl group or an acyl group are preferred.
  • R 31 and R 32 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group
  • R 34 , R 35 , R 36 and R 37 each independently represents a hydrogen atom or an alkyl group
  • n15 is an integer of 1 to 5
  • R 38 , R 39 , R 40 and R 41 each independently represent a hydrogen atom or an alkyl group
  • Examples of the compound represented by formula (H5) include the following compounds.
  • R 42 , R 43 , R 44 , and R 45 each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. , a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
  • R 46 and R 47 are each independently preferably an alkyl group, an alkoxy group, or an aryl group, and more preferably an alkyl group.
  • n16 and n17 are each independently preferably an integer of 0 to 2, more preferably 0 or 1.
  • n16 and n17 are each independently preferably an integer of 1 to 3, more preferably 2 or 3. Examples of the compound represented by formula (H6) include the following compounds.
  • hydroxy compounds include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'- Methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,4,6,3',4'-pentahydroxybenzophenone, 2,3, 4,2',4'-pentahydroxybenzophenone, 2,3,4,2',5'-pentahydroxybenzophenone, 2,4,6,3',4',5'-hexahydroxybenzophenone, 2,3 , 4,3',4',5'-hexahydroxybenzophenone and other polyhydroxybenzophenones; Polyhydroxyphenylalkyl ketones such as 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyphenylpentyl ketone, 2,3,4-trihydroxyphenylhexyl ketone, Bis(
  • polyhydroxybiphenyls Bis(polyhydroxy) sulfides such as 4,4'-thiobis(1,3-dihydroxy)benzene, Bis(polyhydroxyphenyl) ethers such as 2,2',4,4'-tetrahydroxydiphenyl ether, Bis(polyhydroxyphenyl) sulfoxides such as 2,2',4,4'-tetrahydroxydiphenyl sulfoxide, Bis(polyhydroxyphenyl)sulfones such as 2,2',4,4'-diphenylsulfone, Tris(4-hydroxyphenyl)methane, 4,4',4''-trihydroxy-3,5,3',5'-tetramethyltriphenylmethane, 4,4',3'',4''-tetrahydroxy- 3,5,3',5'-tetramethyltriphenylmethane, 4-[bis(3,5-dimethyl-4-hydroxyphenyl)methyl]-2-methoxy-phenol, 4,
  • JP-A-4-253058 Polyhydroxy compounds described in JP-A-5-224410, such as ⁇ , ⁇ , ⁇ ′, ⁇ ′, ⁇ ′′, ⁇ ′′-hexakis-(4-hydroxyphenyl)-1,3,5-triethylbenzene, etc. JP-A-5-303200, EP-530148 of polyhydroxy compounds, 1,2,2,3-tetra(p-hydroxyphenyl)propane, 1,3,3,5-tetra(p-hydroxyphenyl)pentane, etc.
  • naphthoquinone diazide sulfonic acid examples include 6-diazo 5,6-dihydro-5-oxo-1-naphthalene sulfonic acid, 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid, and mixtures thereof. It may also be used as
  • the method for producing naphthoquinone diazide sulfonyl ester of a hydroxy compound is not particularly limited, but for example, naphthoquinone diazide sulfonic acid is converted into a sulfonyl chloride with chlorosulfonic acid or thionyl chloride, and the resulting naphthoquinone diazide sulfonyl chloride is condensed with a hydroxy compound. Obtained by reaction.
  • esterification is performed by reacting a predetermined amount of a hydroxy compound and naphthoquinonediazide sulfonyl chloride in a solvent such as dioxane, acetone, or tetrahydrofuran in the presence of a basic catalyst such as triethylamine, and the resulting product is washed with water. , can be obtained by drying.
  • a solvent such as dioxane, acetone, or tetrahydrofuran
  • a basic catalyst such as triethylamine
  • the esterification rate of the naphthoquinonediazide sulfonic acid ester is not particularly limited, but is preferably 10% or more, more preferably 20% or more. Further, the upper limit of the esterification rate is not particularly limited, and may be 100%. The esterification rate can be confirmed by 1 H-NMR or the like as the proportion of esterified groups among the hydroxy groups of the hydroxy compound.
  • the resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, etc., as long as the effects of the present invention can be obtained. Contains organic titanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g. antifoaming agents, flame retardants, etc.). You can stay there.
  • the resin composition of the present invention may also contain a urea compound, a carbodiimide compound, or an isourea compound. By appropriately containing these components, properties such as film physical properties can be adjusted.
  • the viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition.
  • it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and 2,500 mm 2 /s to 8,000 mm. 2 /s is more preferable.
  • it becomes easy to obtain a coating film with high uniformity. If it is 1,000 mm 2 /s or more, it is easy to coat with the thickness required for example as an insulating film for rewiring, and if it is 12,000 mm 2 /s or less, the coating surface quality is excellent. A coating film is obtained.
  • the water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition will improve.
  • Methods for maintaining the moisture content include adjusting the humidity during storage conditions and reducing the porosity of the storage container during storage.
  • the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, from the viewpoint of insulation.
  • metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals included as complexes of organic compounds and metals are excluded. When a plurality of metals are included, the total of these metals is preferably within the above range.
  • a method for reducing metal impurities that is unintentionally included in the resin composition of the present invention is to select a raw material with a low metal content as a raw material constituting the resin composition of the present invention.
  • Methods include filtering the raw materials constituting the product, lining the inside of the apparatus with polytetrafluoroethylene, etc., and performing distillation under conditions that suppress contamination as much as possible.
  • the resin composition of the present invention has a halogen atom content of preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably less than 200 mass ppm from the viewpoint of wiring corrosion. is even more preferable.
  • those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
  • the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atoms and bromine atoms, or the total of chlorine ions and bromine ions, is each within the above range.
  • Preferred methods for adjusting the content of halogen atoms include ion exchange treatment.
  • the storage container may be a multilayer bottle whose inner wall is made of 6 types of 6 layers of resin, or a container with 7 layers of 6 types of resin. It is also preferred to use structured bottles. Examples of such a container include the container described in JP-A No. 2015-123351.
  • a cured product of the resin composition By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.
  • the cured product of the present invention is a cured product obtained by curing a resin composition.
  • the resin composition is preferably cured by heating, and the heating temperature is more preferably 120°C to 400°C, even more preferably 140°C to 380°C, and particularly preferably 170°C to 350°C.
  • the form of the cured product of the resin composition is not particularly limited, and can be selected depending on the purpose, such as film, rod, sphere, or pellet form. In the present invention, the cured product is preferably in the form of a film.
  • the thickness of the cured product is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
  • the shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
  • the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.
  • the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
  • the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.
  • the resin composition of the present invention can be prepared by mixing the above components.
  • the mixing method is not particularly limited and can be performed by a conventionally known method. Examples of the mixing method include mixing using a stirring blade, mixing using a ball mill, and mixing using a rotating tank.
  • the temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.
  • the filter pore diameter is, for example, preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, even more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferably HDPE (high density polyethylene).
  • the filter may be washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using multiple types of filters, filters with different pore sizes or materials may be used in combination.
  • connection mode examples include a mode in which an HDPE filter with a pore diameter of 1 ⁇ m is connected in series as the first stage and an HDPE filter with a pore diameter of 0.2 ⁇ m as the second stage. Additionally, various materials may be filtered multiple times. When filtration is performed multiple times, circulation filtration may be used. Alternatively, filtration may be performed under pressure.
  • the pressure to be applied is preferably, for example, 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, still more preferably 0.05 MPa or more and 0.7 MPa or less, and 0.01 MPa or more and 0.9 MPa or less, still more preferably 0.05 MPa or more and 0.7 MPa or less, and 0.01 MPa or more and 0.9 MPa or less, for example. Even more preferably 0.05 MPa or more and 0.5 MPa or less.
  • impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined.
  • a known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtration using a filter, the resin composition filled in the bottle may be placed under reduced pressure and degassed.
  • the method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition onto a base material to form a film.
  • the method for producing a cured product includes the above film forming step, an exposure step of selectively exposing the film formed in the film forming step, and developing the film exposed in the exposure step using a developer to form a pattern. It is more preferable to include a developing step.
  • the method for producing a cured product includes the film formation step, the exposure step, the development step, a heating step of heating the pattern obtained in the development step, and a post-development exposure step of exposing the pattern obtained in the development step. It is particularly preferable to include at least one of them.
  • the method for producing a cured product includes the above-mentioned film forming step and the step of heating the above-mentioned film. The details of each step will be explained below.
  • the resin composition of the present invention can be used in a film forming step in which a film is formed by applying it on a substrate.
  • the method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition onto a base material to form a film.
  • the type of base material can be appropriately determined depending on the purpose and is not particularly limited.
  • the base material include semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposited films, magnetic films, reflective films, Ni, Cu,
  • a metal base material such as Cr or Fe (for example, a base material formed from a metal or a base material on which a metal layer is formed by, for example, plating or vapor deposition), paper, SOG (Spin On Examples include glass), TFT (thin film transistor) array substrates, mold substrates, and electrode plates for plasma display panels (PDP).
  • the base material is particularly preferably a semiconductor production base material, and more preferably a silicon base material, a Cu base material, and a mold base material. These base materials may be provided with a layer such as an adhesive layer or an oxidized layer made of hexamethyldisilazane (HMDS) or the like on the surface.
  • the shape of the base material is not particularly limited, and may be circular or rectangular. As for the size of the base material, if it is circular, the diameter is preferably 100 to 450 mm, more preferably 200 to 450 mm. If it is rectangular, the length of the short side is preferably 100 to 1000 mm, more preferably 200 to 700 mm.
  • a plate-shaped, preferably panel-shaped base material (substrate) is used as the base material.
  • the resin layer or metal layer serves as the base material.
  • Coating is preferred as a means for applying the resin composition onto the substrate.
  • the methods to be applied include dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, Examples include inkjet method. From the viewpoint of uniformity of film thickness, spin coating method, slit coating method, spray coating method, or inkjet method is preferable, and from the viewpoint of uniformity of film thickness and productivity, spin coating method and slit coating method are preferable. A coating method is more preferred. A film with a desired thickness can be obtained by adjusting the solid content concentration and application conditions of the resin composition depending on the means to be applied.
  • the coating method can be appropriately selected depending on the shape of the substrate, and for circular substrates such as wafers, spin coating, spray coating, inkjet methods, etc. are preferable, and for rectangular substrates, slit coating, spray coating, etc. method, inkjet method, etc. are preferred.
  • spin coating it can be applied, for example, at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. It is also possible to apply a method in which a coating film that has been previously formed on a temporary support by the above-mentioned application method is transferred onto a base material.
  • the transfer method the production method described in paragraphs 0023, 0036 to 0051 of JP-A No.
  • 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used. Further, a step of removing excess film may be performed at the end of the base material. Examples of such processes include edge bead rinsing (EBR), back rinsing, and the like.
  • EBR edge bead rinsing
  • a pre-wet process may be employed in which various solvents are applied to the base material before the resin composition is applied to the base material to improve the wettability of the base material, and then the resin composition is applied.
  • the film may be subjected to a step of drying the formed film (layer) (drying step) in order to remove the solvent.
  • the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.
  • the drying step is preferably performed after the film forming step and before the exposure step.
  • the drying temperature of the membrane in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C.
  • drying may be performed under reduced pressure.
  • the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.
  • the film may be subjected to an exposure process that selectively exposes the film.
  • the method for producing a cured product may include an exposure step of selectively exposing the film formed in the film forming step. Selectively exposing means exposing a portion of the film. Furthermore, by selectively exposing the film, an exposed area (exposed area) and an unexposed area (unexposed area) are formed in the film.
  • the exposure amount is not particularly limited as long as it can cure the resin composition of the present invention, but for example, it is preferably 50 to 10,000 mJ/cm 2 and more preferably 200 to 8,000 mJ/cm 2 in terms of exposure energy at a wavelength of 365 nm. preferable.
  • the exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
  • the exposure wavelength is: (1) semiconductor laser (wavelength: 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, G-line (wavelength) 436 nm), h line (wavelength 405 nm), i line (wavelength 365 nm), broad (three wavelengths of g, h, i line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc.
  • semiconductor laser wavelength: 830 nm, 532 nm, 488 nm, 405 nm, 375 nm,
  • the resin composition of the present invention exposure using a high-pressure mercury lamp is particularly preferred, and from the viewpoint of exposure sensitivity, exposure using i-line is more preferred.
  • the method of exposure is not particularly limited, and may be any method as long as at least a portion of the film made of the resin composition of the present invention is exposed to light, and examples thereof include exposure using a photomask, exposure using a laser direct imaging method, etc. .
  • the film may be subjected to a heating step after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.
  • the post-exposure heating step can be performed after the exposure step and before the development step.
  • the heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.
  • the heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
  • the temperature increase rate in the post-exposure heating step is preferably 1 to 12°C/min, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min from the temperature at the start of heating to the maximum heating temperature. Further, the temperature increase rate may be changed as appropriate during heating.
  • the heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, etc. can be used. It is also preferable that the heating be performed in an atmosphere with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon.
  • the exposed film may be subjected to a development step of developing a pattern using a developer. That is, the method for producing a cured product of the present invention may include a development step of developing the film exposed in the exposure step using a developer to form a pattern. By performing development, one of the exposed and non-exposed areas of the film is removed and a pattern is formed.
  • development in which the non-exposed portions of the film are removed in the developing step is referred to as negative development
  • development in which the exposed portions of the film are removed in the development step is referred to as positive development.
  • Examples of the developer used in the development step include an alkaline aqueous solution or a developer containing an organic solvent.
  • examples of basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
  • TMAH tetramethylammonium hydroxide
  • potassium hydroxide sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine , dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, Butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammoni
  • the compound described in paragraph 0387 of International Publication No. 2021/112189 can be used as the organic solvent.
  • alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene glycol, etc.
  • Amides include N-methylpyrrolidone, N-ethylpyrrolidone, Dimethylformamide and the like are also suitable.
  • the developer contains an organic solvent
  • one type of organic solvent or a mixture of two or more types can be used.
  • a developer containing at least one member selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred.
  • a developer containing at least one selected from the group consisting of and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.
  • the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more. is more preferable, and particularly preferably 90% by mass or more. Moreover, the said content may be 100 mass %.
  • the developer may further contain at least one of a basic compound and a base generator.
  • the developer may further contain at least one of the basic compound and the base generator in the developer permeates into the pattern, performance such as elongation at break of the pattern may be improved.
  • an organic base is preferable from the viewpoint of reliability when remaining in the cured film (adhesion to the substrate when the cured product is further heated).
  • a basic compound having an amino group is preferable, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc.
  • a primary amine, a secondary amine, a tertiary amine or an ammonium salt is preferred, a secondary amine, a tertiary amine or an ammonium salt is more preferred, a secondary amine or a tertiary amine is even more preferred, and a tertiary amine is particularly preferred.
  • the basic compound is preferably one that does not easily remain in the cured film (obtained cured product), and from the viewpoint of promoting cyclization, it can be used by vaporization etc. It is preferable that the amount remaining is not likely to decrease before heating.
  • the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and even more preferably 100°C to 230°C at normal pressure (101,325 Pa).
  • the boiling point of the basic compound is preferably higher than the boiling point of the organic solvent contained in the developer minus 20°C, and more preferably higher than the boiling point of the organic solvent contained in the developer.
  • the basic compound used preferably has a boiling point of 80°C or higher, more preferably 100°C or higher.
  • the developer may contain only one type of basic compound, or may contain two or more types of basic compounds.
  • basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N, N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N , N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diaminopentane, N-methylhexy
  • the preferred embodiments of the base generator are the same as the preferred embodiments of the base generator contained in the above-mentioned composition.
  • the base generator is preferably a thermal base generator.
  • the content of the basic compound or base generator is preferably 10% by mass or less, and 5% by mass or less based on the total mass of the developer. More preferred.
  • the lower limit of the above content is not particularly limited, but is preferably 0.1% by mass or more, for example. If the basic compound or base generator is solid in the environment in which the developer is used, the content of the basic compound or base generator should be 70 to 100% by mass based on the total solid content of the developer. is also preferable.
  • the developing solution may contain only one type of at least one of a basic compound and a base generator, or may contain two or more types. When at least one of the basic compound and the base generator is two or more types, it is preferable that the total is within the above range.
  • the developer may further contain other components.
  • other components include known surfactants and known antifoaming agents.
  • the method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and methods include immersing the base material on which the film is formed in the developer, and supplying the developer to the film formed on the base material using a nozzle.
  • a method of supplying with a spray nozzle is more preferable.
  • the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied again using the straight nozzle, the base material is spun, and the developer is applied to the base material.
  • a process of removing from above may be adopted, or this process may be repeated multiple times.
  • Methods for supplying the developer in the development process include a process in which the developer is continuously supplied to the base material, a process in which the developer is kept in a substantially stationary state on the base material, and a process in which the developer is applied to the base material using ultrasonic waves. Examples include a step of vibrating with the like, and a step of combining these.
  • the development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
  • the temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.
  • the pattern may be further cleaned (rinsed) with a rinse solution.
  • a method such as supplying a rinsing liquid before the developer in contact with the pattern is completely dried may be adopted.
  • the developing solution is an alkaline aqueous solution
  • water can be used as the rinsing solution, for example.
  • the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (e.g., water, an organic solvent different from the organic solvent contained in the developer) is used as the rinse agent. be able to.
  • Examples of the organic solvent when the rinsing liquid contains an organic solvent include the same organic solvents as those exemplified in the case where the above-mentioned developer contains an organic solvent.
  • the organic solvent contained in the rinsing liquid is preferably an organic solvent different from the organic solvent contained in the developer, and more preferably an organic solvent in which the pattern has a lower solubility than the organic solvent contained in the developer.
  • the rinsing liquid contains an organic solvent
  • the organic solvent is preferably cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and cyclohexanone or PGMEA. More preferred.
  • the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the rinsing liquid. Moreover, the organic solvent may be 100% by mass with respect to the total mass of the rinsing liquid.
  • the rinsing liquid may contain at least one of a basic compound and a base generator.
  • a basic compound and a base generator when the developer contains an organic solvent, one preferred embodiment of the present invention is an embodiment in which the rinsing solution contains an organic solvent and at least one of a basic compound and a base generator.
  • the basic compound and base generator contained in the rinsing solution include the compounds exemplified as the basic compound and base generator that may be included when the above-mentioned developer contains an organic solvent, and preferred embodiments are also included. The same is true.
  • the basic compound and base generator contained in the rinsing liquid may be selected in consideration of their solubility in the solvent in the rinsing liquid.
  • the content of the basic compound or base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the rinsing liquid. preferable.
  • the lower limit of the above content is not particularly limited, but is preferably 0.1% by mass or more, for example. If the basic compound or base generator is solid in the environment where the rinse solution is used, the content of the basic compound or base generator should be 70 to 100% by mass based on the total solid content of the rinse solution. is also preferable.
  • the rinsing liquid may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types of the basic compound and the base generator. .
  • the total is within the above range.
  • the rinse solution may further contain other components.
  • other components include known surfactants and known antifoaming agents.
  • a method of supplying the rinsing liquid using a spray nozzle is more preferable.
  • a method of supplying the rinsing liquid using a spray nozzle is more preferable.
  • the type of nozzle and examples include straight nozzles, shower nozzles, spray nozzles, and the like.
  • the rinsing step is preferably a step in which the rinsing liquid is supplied to the exposed film through a straight nozzle or continuously, and more preferably a step in which the rinsing liquid is supplied through a spray nozzle.
  • Methods for supplying the rinsing liquid in the rinsing process include a process in which the rinsing liquid is continuously supplied to the substrate, a process in which the rinsing liquid is kept almost stationary on the substrate, and a process in which the rinsing liquid is applied to the substrate by ultrasonic waves. It is possible to adopt a process of vibrating the wafer, etc., and a process of combining these.
  • the rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
  • the temperature of the rinsing liquid during rinsing is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.
  • the developing step may include a step of bringing the processing solution into contact with the pattern after processing using the developer or after cleaning the pattern with a rinse solution.
  • a method may be adopted in which the processing liquid is supplied before the developing liquid or rinsing liquid in contact with the pattern is completely dried.
  • the treatment liquid examples include a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator.
  • Preferred embodiments of the organic solvent, and at least one of the basic compound and base generator are the same as the preferred embodiments of the organic solvent, and at least one of the basic compound and base generator used in the above-mentioned rinsing liquid.
  • the method for supplying the treatment liquid to the pattern can be the same as the method for supplying the rinsing liquid described above, and the preferred embodiments are also the same.
  • the content of the basic compound or base generator in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the treatment liquid.
  • the lower limit of the content is not particularly limited, but is preferably 0.1% by mass or more, for example.
  • the content of the basic compound or base generator is 70 to 100% by mass based on the total solid content of the treatment liquid. It's also good to have one.
  • the processing liquid contains at least one of a basic compound and a base generator
  • the processing liquid may contain only one type of at least one of the basic compound and the base generator, or may contain two or more types of the basic compound and the base generator. .
  • at least one of the basic compound and the base generator is two or more types, it is preferable that the total is within the above range.
  • the pattern obtained by the development step may be subjected to a heating step of heating the pattern obtained by the development. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the developing step. Further, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing a developing step, or a film obtained by a film forming step. In the heating step, a resin such as a polyimide precursor is cyclized to become a resin such as polyimide.
  • the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, particularly 160 to 230°C. preferable.
  • the heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor within the pattern by heating and the action of a base generated from the base generator.
  • Heating in the heating step is preferably carried out at a temperature increase rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature.
  • the temperature increase rate is more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min.
  • the temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, even more preferably 25°C to 120°C.
  • the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started.
  • the temperature of the film (layer) after drying is, for example, 30°C higher than the boiling point of the solvent contained in the resin composition. It is preferable to raise the temperature from a lower temperature by ⁇ 200°C.
  • the heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
  • the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher.
  • the upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.
  • Heating may be performed in stages. As an example, the temperature is raised from 25°C to 120°C at a rate of 3°C/min, held at 120°C for 60 minutes, and the temperature is raised from 120°C to 180°C at a rate of 2°C/min, and held at 180°C for 120 minutes. , etc. may be performed. It is also preferable to perform the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such pretreatment steps can improve the properties of the film. The pretreatment step is preferably carried out for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
  • the pretreatment step may be performed in two or more steps, for example, the first pretreatment step is performed at a temperature of 100 to 150°C, and then the second pretreatment step is performed at a temperature of 150 to 200°C. Good too. Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5° C./min.
  • the heating step is preferably performed in an atmosphere with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure, from the viewpoint of preventing decomposition of the specific resin.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
  • the heating means in the heating step is not particularly limited, but includes, for example, a hot plate, an infrared oven, an electric oven, a hot air oven, an infrared oven, and the like.
  • the pattern obtained in the development process (in the case of performing a rinsing process, the pattern after rinsing) is subjected to a post-development exposure process in which the pattern after the development process is exposed to light, instead of or in addition to the above heating process. may be served.
  • the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained in the development step.
  • the method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
  • the post-development exposure step for example, a reaction in which cyclization of a polyimide precursor etc.
  • the post-development exposure step at least a portion of the pattern obtained in the development step may be exposed, but it is preferable that the entire pattern be exposed.
  • the exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , more preferably 100 to 15,000 mJ/cm 2 in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive.
  • the post-development exposure step can be performed, for example, using the light source used in the above-mentioned exposure step, and it is preferable to use broadband light.
  • the pattern obtained by the development process may be subjected to a metal layer forming process of forming a metal layer on the pattern. That is, the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on the pattern obtained in the development step (preferably one that has been subjected to at least one of a heating step and a post-development exposure step). It is preferable to include.
  • metal layer existing metal species can be used without particular limitation, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. copper and aluminum are more preferred, and copper is even more preferred.
  • the method for forming the metal layer is not particularly limited, and existing methods can be applied.
  • the methods described in JP 2007-157879, JP 2001-521288, JP 2004-214501, JP 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 are used. can do.
  • photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and a combination thereof can be used.
  • a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating can be mentioned.
  • a preferred embodiment of plating includes electrolytic plating using copper sulfate or copper cyanide plating solution.
  • the thickness of the metal layer is preferably 0.01 to 50 ⁇ m, more preferably 1 to 10 ⁇ m at the thickest part.
  • Fields to which the method for producing a cured product of the present invention or the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. Other methods include forming a pattern by etching a sealing film, a substrate material (a base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above.
  • a substrate material a base film or coverlay of a flexible printed circuit board, an interlayer insulating film
  • an insulating film for mounting purposes as described above.
  • the method for producing a cured product of the present invention or the cured product of the present invention can be used for producing plates such as offset plates or screen plates, for etching molded parts, and for use in protective lacquers and dielectric layers in electronics, particularly microelectronics. It can also be used for manufacturing.
  • the laminate of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
  • the laminate is a laminate including two or more layers made of cured material, and may be a laminate in which three or more layers are laminated. At least one of the two or more layers made of the cured product contained in the laminate is a layer made of the cured product of the present invention, and shrinkage of the cured product or deformation of the cured product due to the shrinkage, etc. From the viewpoint of suppression, it is also preferable that all the layers made of the cured product contained in the above-mentioned laminate are layers made of the cured product of the present invention.
  • the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.
  • the laminate of the present invention preferably includes two or more layers made of a cured product and includes a metal layer between any of the layers made of the cured product.
  • the metal layer is preferably formed by the metal layer forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on the layer made of the cured product during the method for producing the cured product which is performed multiple times. A preferred embodiment of the metal layer forming step is as described above.
  • the resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product have the same composition. It may be a product or a composition having a different composition.
  • the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
  • the method for manufacturing a laminate of the present invention includes a lamination step.
  • the lamination process refers to (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process and development on the surface of the pattern (resin layer) or metal layer again. This is a series of steps including performing at least one of the post-exposure steps in this order.
  • an embodiment may be adopted in which at least one of (a) the film forming step and (d) the heating step and the post-development exposure step are repeated.
  • a metal layer forming step may be included after at least one of the (d) heating step and the post-development exposure step.
  • the lamination step may further include the above-mentioned drying step and the like as appropriate.
  • a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer forming step.
  • Plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.
  • the above lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
  • the above layers may have the same composition, shape, thickness, etc., or may have different compositions, shapes, thicknesses, etc.
  • a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer.
  • the following steps are repeated in the following order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of the heating step and post-development exposure step, and (e) metal layer formation step.
  • an embodiment may be mentioned in which (a) a film forming step, (d) at least one of a heating step and a post-development exposure step, and (e) a metal layer forming step are repeated in this order.
  • the method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface activation treatment of at least a portion of the metal layer and the resin composition layer.
  • the surface activation treatment step is usually performed after the metal layer forming step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer is subjected to the surface activation treatment. After performing this step, the metal layer forming step may be performed.
  • the surface activation treatment may be performed on at least a portion of the metal layer, or may be performed on at least a portion of the resin composition layer after exposure, or the surface activation treatment may be performed on at least a portion of the metal layer and the resin composition layer after exposure.
  • the surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable that the surface activation treatment is performed on a part or all of the region of the metal layer on which the resin composition layer is to be formed.
  • the surface activation treatment is also performed on part or all of the resin composition layer (resin layer) after exposure.
  • the resin composition layer when the resin composition layer is hardened, such as when performing negative development, it is less likely to be damaged by surface treatment and adhesion is likely to be improved.
  • the surface activation treatment can be performed, for example, by the method described in paragraph 0415 of International Publication No. 2021/112189. This content is incorporated herein.
  • the present invention also discloses a semiconductor device containing the cured product or laminate of the present invention.
  • the present invention also discloses a method for manufacturing a semiconductor device, including a method for manufacturing a cured product of the present invention or a method for manufacturing a laminate.
  • a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer the descriptions in paragraphs 0213 to 0218 of JP 2016-027357A and the description in FIG. 1 can be referred to, Their contents are incorporated herein.
  • resin 2 with an Mw of 5,000, resin 2 with an Mw of 10,000, and resin 2 with an Mw of 30,000 can also be used. Synthesized.
  • the resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again.
  • the obtained resin was dried at 40° C. for one day under reduced pressure to obtain Resin 10.
  • Mw weight average molecular weight
  • P-10 1 H-NMR
  • Examples and comparative examples> In each Example, the components listed in the table below were mixed to obtain each resin composition. In addition, in a comparative example, the components listed in the table below were mixed to obtain a comparative composition. Specifically, the content (blended amount) of each component listed in the table other than the solvent was the amount (parts by mass) listed in the "parts by mass” column in each column of the table. The content (compounding amount) of the solvent is determined so that the solid content concentration of the composition is the value of "solid content concentration" (mass %) in the table, and the ratio of the content of each solvent to the total mass of the solvent (mass %) is determined. The ratio) was set to be the ratio described in the "Ratio" column in the table. The obtained resin composition and comparative composition were pressure-filtered using a polytetrafluoroethylene filter with a pore width of 0.8 ⁇ m. Furthermore, in the table, the description "-" indicates that the composition does not contain the corresponding component.
  • ⁇ I-1 to I-5 Compounds with the following structure ⁇ I-6: Omnirad 1312 (manufactured by IGM) ⁇ I-7: Omnirad TPO H (manufactured by IGM)
  • Silane coupling agent (metal adhesion improver)] - C-1 to C-3 Compounds with the following structure.
  • Et represents an ethyl group.
  • ⁇ C-4 X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent with protected isocyanate group)
  • ⁇ C-5 KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd., silane coupling agent that is an acrylic group-containing oligomer)
  • Tris-PA trade name, manufactured by Kagaku Kogyo Co., Ltd.
  • Tris-PA trade name, manufactured by Kagaku Kogyo Co., Ltd.
  • 47.49 g 0.07 mol
  • 1,2-naphthoquinonediazide-5-sulfonic acid chloride in an amount corresponding to 83.3 mol% of the OH group.
  • the flask was adjusted to 30°C in a constant temperature bath.
  • 17.9 g of triethylamine was dissolved in 18 g of acetone and charged into a dropping funnel, which was then dropped into the flask over 30 minutes.
  • F-1 to F-23 Compounds with the following structure.
  • F-1 to F-23 are compounds corresponding to the above-mentioned compound A.
  • FR-1 Compound with the following structure.
  • FR-1 is a compound that does not fall under the above-mentioned compound A.
  • a resin composition layer or a comparative composition layer having a uniform thickness was used.
  • the resin composition layer or the comparative composition layer on the copper substrate was exposed to an exposure energy of 500 mJ/ cm2 , and in the examples where "negative” was written in the "Development conditions” column of the table, a 100 ⁇ m square square shape was formed.
  • “Positive” is written in the "Development Conditions” column of the table, a photomask with a non-mask area formed thereon is used, and a photomask with a 100 ⁇ m square mask area formed thereon is used. It was exposed to light having the exposure wavelength (nm) described in the "Exposure wavelength (nm)" column.
  • TMAH aqueous solution in the table means a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.
  • the exposed resin composition layer is heated at a rate of 10°C/min in a nitrogen atmosphere using a hot plate. After reaching the temperature listed in the “Cure Temperature (° C.)” column of the table, the temperature was maintained for the time “Cure Time (min)” in the table to obtain a cured product.
  • the resin film obtained in each example was heated using an infrared lamp heating device (RTP-6, manufactured by Advance Riko Co., Ltd.).
  • the temperature was raised at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained for the “cure time (min)” in the table to obtain a cured product.
  • the obtained copper substrate with the cured product was placed in a tank at a temperature of 175° C. in the atmosphere for 192 hours.
  • Cross-sectional SEM (scanning microscope) measurement was performed to evaluate the void area ratio between the Cu wiring pattern and the cured product.
  • the void area ratio was calculated using the following formula.
  • Void area ratio (%) (area of voids observed by SEM measurement) / (total area of cured product) x 100 Based on the value of the void area ratio obtained, evaluation was performed according to the following evaluation criteria.
  • the evaluation results are listed in the column of "Adhesion after heat resistance test" in the table. It can be said that the smaller the void area ratio, the better the adhesion of the cured film after the heat resistance test, and it can be said that it is difficult for voids to form between the metal layer and the cured product even after a long period of time has passed.
  • -Evaluation criteria A: The void area ratio was 0.5% or less.
  • C The void area ratio was more than 1% and less than 2%.
  • D The void area ratio exceeded 2%.
  • composition stability The resin composition or comparative composition prepared in each Example or Comparative Example was allowed to stand at 38° C. for 3 days under light shielding conditions. After the above-mentioned standing is completed, the viscosity is measured using a viscometer (Toki Sangyo RE-85L), and compared with the initial state (before the above-mentioned standing), the viscosity change rate after the above-mentioned standing is completed is determined. It was calculated according to the following formula and evaluated according to the following evaluation criteria. The evaluation results are listed in the "composition stability" column of the table. It can be said that the smaller the viscosity change rate, the more excellent the composition stability is.
  • Viscosity change rate (%)
  • C The absolute value of the viscosity change rate was more than 5% and less than 8%.
  • D The absolute value of the viscosity change rate was more than 8% and less than 10%.
  • E The absolute value of the above viscosity change rate exceeded 10%.
  • the cured product formed from the resin composition of the present invention has excellent adhesion even after the heat resistance test.
  • the comparative composition according to Comparative Example 1 does not contain Compound A. It can be seen that such comparative compositions have poor adhesion after the heat resistance test.
  • Example 101 The resin composition used in Example 1 was applied in a layered manner by spin coating to the surface of the thin copper layer of the resin base material on which the thin copper layer was formed, and dried at 100°C for 5 minutes to determine the film thickness. After forming a 20 ⁇ m photoresist film, it was exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 ⁇ m). After the above exposure, it was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
  • NSR1505 i6 a binary mask with a 1:1 line-and-space pattern and a line width of 10 ⁇ m
  • the temperature was raised at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 180 minutes to form an interlayer insulating film for a rewiring layer.
  • This rewiring layer interlayer insulating film had excellent insulation properties. Furthermore, when a semiconductor device was manufactured using this interlayer insulating film for rewiring layer, it was confirmed that it operated without any problem.

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Abstract

L'invention concerne une composition de résine, un objet durci ainsi qu'un procédé de fabrication de celui-ci, un stratifié ainsi qu'un procédé de fabrication de celui-ci, et un dispositif à semi-conducteurs ainsi qu'un procédé de fabrication de celui-ci. Ladite composition de résine contient au moins une sorte de résine choisie dans un groupe constitué d'une résine de cyclisation et d'un précurseur de celle-ci, et un composé (A) représenté par la formule (A-1), le nombre d'atomes de carbone total appartenant à la formule (A-1) étant compris entre 3 et 30. Dans la formule (A-1), Ｒ１ représente un groupe organique monovalent, la région de liaison avec un atome d'azote mentionnée dans la formule (A-1) dans Ｒ１, consiste en un atome de carbone, Ｒ２ représente un atome d'hydrogène ou un groupe organique monovalent, Ｒ３ représente un groupe organique monovalent, et Ｒ２ et Ｒ３ peuvent être liés pour former une structure cyclique.
PCT/JP2023/030662 2022-08-30 2023-08-25 Composition de résine, objet durci ainsi que procédé de fabrication de celui-ci, stratifié ainsi que procédé de fabrication de celui-ci, et dispositif à semi-conducteurs ainsi que procédé de fabrication de celui-ci WO2024048435A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50100199A (fr) * 1973-12-26 1975-08-08
JPH0841327A (ja) * 1994-07-27 1996-02-13 Hitachi Chem Co Ltd アクティブ光導波路用組成物、これを用いたアクティブ光導波路の製造法及びアクティブ光導波路
JP2018111805A (ja) * 2016-11-30 2018-07-19 長興材料工業股▲ふん▼有限公司Ｅｔｅｒｎａｌ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． ポリイミド前駆体組成物及びその使用
WO2021157306A1 (fr) * 2020-02-05 2021-08-12 富士フイルム株式会社 Composition de résine, film durci, stratifié, procédé de fabrication de film durci et dispositif à semi-conducteur
JP2021181532A (ja) * 2020-05-19 2021-11-25 信越化学工業株式会社 ビスマレイミド樹脂組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50100199A (fr) * 1973-12-26 1975-08-08
JPH0841327A (ja) * 1994-07-27 1996-02-13 Hitachi Chem Co Ltd アクティブ光導波路用組成物、これを用いたアクティブ光導波路の製造法及びアクティブ光導波路
JP2018111805A (ja) * 2016-11-30 2018-07-19 長興材料工業股▲ふん▼有限公司Ｅｔｅｒｎａｌ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． ポリイミド前駆体組成物及びその使用
WO2021157306A1 (fr) * 2020-02-05 2021-08-12 富士フイルム株式会社 Composition de résine, film durci, stratifié, procédé de fabrication de film durci et dispositif à semi-conducteur
JP2021181532A (ja) * 2020-05-19 2021-11-25 信越化学工業株式会社 ビスマレイミド樹脂組成物

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