Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur

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 are being utilized by using resin compositions containing resins.
• cyclized resins such as polyimide are used in various applications because of their excellent heat resistance and insulating properties.
• the above applications are not particularly limited, but in the case of a semiconductor device for mounting, use as a material for an insulating film or a sealing material, or as a protective film can be mentioned. It is also used as a base film or coverlay for flexible substrates.
• the cyclized resin such as polyimide is used in the form of a resin composition containing a precursor of the cyclized resin such as a polyimide precursor.
• a resin composition is applied to a substrate, for example, by coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate.
• a 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 a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the resin composition to be applied. It can be said that it is excellent in sex.
• cyclized resins such as polyimide, from the viewpoint of such excellent manufacturing adaptability, industrial application and development of the above-mentioned resin compositions are increasingly expected.
• Patent Document 1 discloses a phenol compound with a specific structure, a titanocene compound with a specific structure, a 3-aminopropyltrialkoxysilane with a specific structure, a polyamic acid, and carbon carbon that can be dimerized or polymerized by actinic radiation.
• a light-sensitive material containing a compound having a double bond and an amino group or a quaternized salt thereof is disclosed.
• the viscosity does not easily change even under a yellow light and that it is easy to work under a yellow light.
• a resin composition whose viscosity does not easily change even under a yellow light and which is easy to work under a yellow light is also referred to as a "resin composition excellent in working stability under a yellow light”.
• the present invention provides a resin composition excellent in working stability under a yellow light, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and the laminate It aims at providing the semiconductor device manufacturing method including the manufacturing method, the manufacturing method of the said laminated body, and the semiconductor device containing the said hardened
• ⁇ 1> Resin, and containing a metallocene compound,
• the metallocene compound has a metal atom, an optionally substituted cyclopentadienyl ligand, and an aromatic ring directly linked to the metal atom,
• the aromatic ring has an electron-withdrawing group different from a halogen atom as a substituent directly connected to the aromatic ring,
• the resin composition, wherein the metallocene compound has a molar absorption coefficient at 500 nm of 330 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less.
• the metallocene compound has a metal atom, an optionally substituted cyclopentadienyl ligand, and an aromatic ring directly linked to the metal atom, and the aromatic ring is a substituent directly linked to the aromatic ring.
• a resin composition having a halogen atom as a group and an electron-withdrawing group different from the halogen atom.
• ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the resin is a polyimide or a polyimide precursor.
• ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, further comprising a polymerizable compound.
• ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the metallocene compound is a titanocene compound.
• ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, further comprising a photopolymerization initiator different from the metallocene compound.
• R 2 is a fluorine atom
• R 3 each independently represents a hydrogen atom or a halogen atom
• R 4 represents an electron-withdrawing group different from a halogen atom
• R 5 each independently represents a hydrogen atom or a fluorine atom
• one of R 5 is a fluorine atom
• each R 6 independently represents a hydrogen atom or a halogen atom
• R 7 represents an electron-withdrawing group different from the halogen atom.
• each M independently represents a titanium atom, a zirconium atom or a hafnium atom
• each R 8 independently represents a hydrogen atom or a methyl group
• each R 9 independently represents a hydrogen atom or represents a fluorine atom
• one of R 9 is a fluorine atom
• R 10 each independently represents a hydrogen atom or a halogen atom
• R 11 represents an electron-withdrawing group different from a halogen atom
• R 12 Each independently represents a hydrogen atom or a fluorine atom
• one of R 12 is a fluorine atom
• each R 13 independently represents a hydrogen atom or a halogen atom
• R 14 has an electron-withdrawing property different from that of a halogen atom.
• R 15 and R 16 each independently represent a hydrogen atom or a substituent
• A represents an oxygen atom or a sulfur atom.
• R 4 and R 7 in the above formula (1-1) are each independently a trifluoromethyl group or a nitro group
• R 11 and R 14 in the above formula (1-2) are each independently a trifluoromethyl group.
• the resin composition according to ⁇ 8> which is a fluoromethyl group or a nitro group.
• ⁇ 11> A cured product obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 10>.
• ⁇ 12> A laminate comprising two or more layers made of the cured product according to ⁇ 11> and a metal layer between any of the layers made of the cured product.
• ⁇ 13> A method for producing a cured product, comprising a film forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 10> onto a substrate to form a film.
• the method for producing a cured product according to ⁇ 13> comprising an exposure step of selectively exposing the film and a development step of developing the film with a developer to form a pattern.
• ⁇ 15> The method for producing a cured product according to ⁇ 13> or ⁇ 14>, comprising a heating step of heating the film at 50 to 450°C.
• a method for producing a laminate comprising the method for producing a cured product according to any one of ⁇ 13> to ⁇ 15>.
• a method for producing a semiconductor device comprising the method for producing a cured product according to any one of ⁇ 13> to ⁇ 15> or the method for producing a laminate according to ⁇ 16>.
• ⁇ 18> A semiconductor device comprising the cured product according to ⁇ 11> or the laminate according to ⁇ 12>.
• a resin composition excellent in working stability under a yellow light a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for producing the cured product, and the laminate
• a semiconductor device manufacturing method including a method for manufacturing a body, a method for manufacturing a laminate, and a semiconductor device including the cured product or the laminate are provided.
• a numerical range represented by the symbol "to” means a range including the numerical values before and after "to” as lower and upper limits, respectively.
• the term "process” is meant to include not only independent processes, but also processes that are indistinguishable from other processes as long as the desired effects of the process can be achieved.
• a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent.
• alkyl group includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
• exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified.
• Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
• (meth)acrylate means both or either of “acrylate” and “methacrylate”
• (meth)acrylic means both “acrylic” and “methacrylic”
• (meth)acryloyl means either or both of “acryloyl” and “methacryloyl”.
• Me in the structural formulas represents a methyl group
• Et represents an ethyl group
• Bu represents a butyl group
• Ph represents a phenyl group.
• 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.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, unless otherwise specified, and are defined as polystyrene conversion values.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, HLC-8220GPC (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel It can be obtained by connecting Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) in series. Unless otherwise stated, their molecular weights were determined using THF (tetrahydrofuran) as an eluent.
• THF tetrahydrofuran
• NMP N-methyl-2-pyrrolidone
• detection in GPC measurement uses a UV ray (ultraviolet) wavelength detector of 254 nm.
• UV ray ultraviolet
• a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other.
• the direction in which the layers are stacked with respect to the base material is referred to as "upper", or when there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as “upper”. and the opposite direction is called “down”.
• the composition may contain two or more compounds corresponding to each component contained in the composition.
• 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 pressure is 101,325 Pa (1 atm)
• the relative humidity is 50% RH, unless otherwise stated. Combinations of preferred aspects are more preferred aspects herein.
• a resin composition according to a first aspect of the present invention comprises a resin and a metallocene compound, wherein the metallocene compound comprises a metal atom, an optionally substituted cyclopentadienyl ligand, and the It has an aromatic ring directly connected to a metal atom, the aromatic ring has an electron-withdrawing group different from a halogen atom as a substituent directly connected to the aromatic ring, and the metallocene compound has a molar extinction coefficient at 500 nm of It is 330 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less.
• two atoms or structures are directly connected means that two atoms or structures are bonded without a linking group or the like between them.
• an aromatic ring directly linked to a metal atom means that the metal atom and the aromatic ring are linked without a linking group between the metal atom and the aromatic ring.
• a resin composition according to a second aspect of the present invention comprises a resin and a metallocene compound, wherein the metallocene compound comprises a metal atom, an optionally substituted cyclopentadienyl ligand, and the It has an aromatic ring directly linked to a metal atom, and the aromatic ring has a halogen atom as a substituent directly linked to the aromatic ring and an electron-withdrawing group different from the halogen atom.
• the resin composition according to the first aspect of the present invention and the resin composition according to the second aspect of the present invention are collectively referred to as "the resin composition of the present invention".
• the resin composition according to the first aspect of the present invention having a metal atom, an optionally substituted cyclopentadienyl ligand, and an aromatic ring directly connected to the metal atom,
• the aromatic ring has an electron-withdrawing group different from a halogen atom as a substituent directly connected to the aromatic ring, and a metallocene compound having a molar extinction coefficient at 500 nm of 330 mol ⁇ 1 L cm ⁇ 1 or less. Also referred to as "the first specific metallocene compound”.
• a metallocene compound having a halogen atom as a substituent directly bonded to the aromatic ring and an electron-withdrawing group different from the halogen atom is also referred to as a “second specific metallocene compound”.
• a metallocene compound corresponding to at least one of the first specific metallocene compound and the second specific metallocene compound is also simply referred to as the "specific metallocene compound”.
• the resin composition of the present invention is preferably used for forming a photosensitive film subjected to exposure and development, and is preferably used for forming a film subjected to exposure and development using a developer containing an organic solvent.
• a developer containing an organic solvent preferable.
• the resin composition of the present invention can be used, for example, to form an insulating film for semiconductor devices, an interlayer insulating film for rewiring layers, a stress buffer film, and the like, and can be used to form an interlayer insulating film for rewiring layers. preferable.
• the resin composition of the present invention contains a cyclized resin or a precursor thereof as a resin and is used for forming an interlayer insulating film for rewiring layers.
• the resin composition of the present invention may be used for forming a photosensitive film for positive development, or may be used for forming a photosensitive film for negative development.
• negative development refers to development in which non-exposed areas are removed by development in exposure and development
• positive development refers to development in which exposed areas are removed by development.
• the exposure method, the developer, and the development method include, for example, the exposure method described in the exposure step, the developer and the development method described in the development step in the description of the method for producing a cured product described later. is used.
• the resin composition of the present invention is excellent in working stability under yellow light. Although the mechanism by which the above effects are obtained is unknown, it is presumed as follows.
• an operation of curing a resin composition to obtain a cured product has been performed.
• an operation of forming a composition film from a resin composition and exposing and heating it to obtain a cured product can be mentioned.
• the glass transition temperature (Tg) of the cured product is improved by using a metallocene compound together with the resin in the resin composition.
• a titanocene compound is used as a polymerization initiator in combination with an acrylic monomer and polyamic acid.
• the dark polymerization includes polymerization of a resin and a metallocene compound, polymerization of resins, polymerization of a resin and an optionally contained polymerizable compound, polymerization of polymerizable compounds, and the like.
• the specific metallocene compounds in the first aspect and the second aspect of the present invention have a structure in which an electron-withdrawing group different from a halogen atom is directly linked to an aromatic ring. By having an electron-withdrawing group other than a halogen atom, the wavelength of the absorption spectrum of the specific metallocene compound is shortened, and dark polymerization under a yellow light can be suppressed.
• the resin composition of the present invention containing the metallocene compound of the present invention is considered to have excellent working stability under yellow light.
• the specific metallocene compound in the first aspect of the present invention has a molar extinction coefficient at 500 nm of 330 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less. According to such a mode, since the photosensitivity under a yellow light is suppressed, it is considered that the working stability under a yellow light is excellent.
• the metallocene compound in the second aspect of the invention further has a halogen atom directly attached to the aromatic ring.
• the degree of polarization of the metallocene compound is increased, and the stability of the metallocene compound in the resin composition is considered to be improved.
• the working stability under yellow light is further excellent.
• the titanocene compound described in Patent Document 1 is a metallocene compound in which the substituent on the aromatic ring is a halogen atom, an alkoxy group, or a heterocyclic group, and the aromatic ring has an electron-withdrawing group other than halogen. is neither mentioned nor suggested.
• the composition film formed from the resin composition of the present invention also suppresses dark polymerization under a yellow light. That is, even when a composition film formed from the resin composition of the present invention is handled under a yellow light, dark polymerization is suppressed, and, for example, fine patterns are likely to be obtained in pattern formation.
• Patent Document 1 does not describe a resin composition containing a specific metallocene compound.
• the resin composition of the present invention contains a resin.
• the resin is not particularly limited, and includes, for example, resins used in conventional pattern-forming compositions. It preferably contains, and more preferably contains a precursor of the cyclized resin.
• the acid value of the resin is preferably 0 to 0.8 mmol/g, more preferably 0.03 to 0.5 mmol/g, More preferably 0.1 to 0.3 mmol/g. Since the specific metallocene compound in the present invention has high stability, it is presumed that even when it is used together with a resin having such an acid value, it has excellent working stability under a yellow light.
• 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 resin preferably has a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of both storage stability and developability.
• the pKa is expressed by the negative common logarithm pKa of the equilibrium constant Ka.
• pKa is a value calculated by ACD/ChemSketch (registered trademark).
• ACD/ChemSketch registered trademark
• the values listed in the Chemical Society of Japan, Revised 5th Edition, Basics of Chemistry may be referred to.
• the acid group is a polyvalent acid such as phosphoric acid
• the above pKa is the first dissociation constant.
• the resin preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, more preferably a carboxy group or a phenolic hydroxy group.
• 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 represents the relatively longest connecting chain in the resin molecule.
• cyclized resins include polyimide, polybenzoxazole, and polyamideimide.
• a precursor of a cyclized resin is a resin that undergoes a change in chemical structure by an external stimulus to become a cyclized resin, preferably a resin that undergoes a change in chemical structure by heat to become a cyclized resin.
• a resin that becomes a cyclized resin by forming a ring structure is more preferable.
• Precursors of the cyclized resin include polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, and the like. That is, the resin composition of the present invention contains, as a specific resin, at least one selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, polyamideimides, and polyamideimide precursors. It preferably contains a resin (specific resin).
• the resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin.
• the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
• the resin composition of the present invention preferably contains a radical polymerization initiator described later, and contains a radical polymerization initiator described later and a radical cross-linking agent described later. is more preferred. Further, if necessary, a sensitizer described later can be included. For example, a negative photosensitive film is formed from the resin composition of the present invention.
• the specific resin may have a polarity conversion group such as an acid-decomposable group.
• the resin composition of the present invention preferably contains a photoacid generator, which will be described later. From such a resin composition of the present invention, for example, a chemically amplified positive photosensitive film or negative photosensitive film is formed.
• polyimide precursor Although the type of the polyimide precursor used in the present invention is not particularly limited, it preferably contains a repeating unit represented by the following formula (2).
• a 1 and A 2 each independently represent an oxygen atom or -NH-
• R 111 represents a divalent organic group
• R 115 represents a tetravalent organic group
• R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
• a 1 and A 2 in formula (2) each independently represent an oxygen atom or —NH—, preferably an oxygen atom.
• R 111 in formula (2) represents a divalent organic group.
• divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, linear or branched aliphatic groups 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 a group consisting of 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 cyclic aliphatic group and the aromatic group, the ring member hydrocarbon group is a hetero atom.
• may be substituted with a group containing Groups represented by -Ar- and -Ar-L-Ar- are exemplified as preferred embodiments of the present invention, and groups represented by -Ar-L-Ar- are particularly preferred.
• Ar is each independently an aromatic group
• L is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, -O-, -CO -, -S-, -SO 2 - or -NHCO-, or a group consisting of a combination of two or more of the above. Preferred ranges for these are as described above.
• R 111 is preferably derived from a diamine.
• Diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, 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 a group consisting of a combination thereof is preferably a diamine containing, more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. In the straight-chain or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom. may be substituted with a group containing Examples of groups containing aromatic groups include:
• * represents a binding site with other structures.
• diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane; ,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4- aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4′-diamino-3,3′-dimethylcyclohexylmethane or isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4′- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3, 3,3
• 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 preferably used.
• R 111 is preferably represented by -Ar-L-Ar- from the viewpoint of the flexibility of the resulting organic film.
• Ar is each independently an aromatic group
• L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- , —SO 2 — or —NHCO—, or a group consisting of 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 (61).
• a divalent organic group represented by Formula (61) is more preferable.
• Equation (51) In formula (51), 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 binding site to the nitrogen atom in formula (2).
• the monovalent organic groups represented by R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.
• R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is each independently a binding site to the nitrogen atom in formula (2) represent.
• Diamines that give the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′-bis (Fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl 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 (6) is more preferable.
• each * independently represents a binding site to another structure.
• R 112 is a single bond or a divalent linking group, 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 -, and -NHCO-, and preferably a group selected from combinations thereof, having 1 to 1 carbon atoms optionally substituted by a single bond or a fluorine atom 3 alkylene group, -O-, -CO-, -S- and -SO 2 -, and -CH 2 -, -C(CF 3 ) 2 -, -C( It is more preferably a divalent group selected from the group consisting of CH 3 ) 2 -, -O-, -CO-, -S- and -SO 2 -.
• R 115 specifically includes 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 thereof, as the structure corresponding to R115 .
• the tetracarboxylic dianhydride is preferably represented by the following formula (O).
• R 115 represents a tetravalent organic group.
• the preferred range of R 115 is synonymous with R 115 in formula (2), and the preferred range is also the same.
• tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′- Diphenyl sulfide tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′ ,4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2′,3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride,
• tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.
• R 111 and R 115 has an OH group. More specifically, R 111 includes residues of bisaminophenol derivatives.
• 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 preferably contains a polymerizable group, more preferably both contain a polymerizable group. It is also preferred that at least one of R 113 and R 114 contains two or more polymerizable groups.
• the polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, or the like, and is preferably a radically polymerizable group.
• 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. be done.
• a group having an ethylenically unsaturated bond is preferred.
• Groups 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 (e.g., vinylphenyl group), and a (meth)acrylamide group.
• a (meth)acryloyloxy group a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
• R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
• * represents a binding 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 ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2 —, cyclohexyl group, polyalkylene An oxy group is more preferred, and an alkylene group such as an ethylene group, a propylene group, or a polyalkyleneoxy group is even more preferred.
• alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2
• 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 a block arrangement. Alternatively, it may be arranged in a pattern such as an alternating pattern.
• the number of carbon atoms in the alkylene group is preferably 2 or more, more preferably 2 to 10, and 2 to 6. is more preferred, 2 to 5 is more preferred, 2 to 4 is even more preferred, 2 or 3 is particularly preferred, and 2 is most preferred.
• the said alkylene group may have a substituent.
• Preferred substituents include alkyl groups, aryl groups, and halogen atoms.
• 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.
• a group to which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable.
• the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in a pattern such as alternately. Preferred embodiments of the number of repetitions of ethyleneoxy groups and the like in these groups are as described above.
• the polyimide precursor when R 113 is a hydrogen atom, or when R 114 is a hydrogen atom, the polyimide precursor may form a tertiary amine compound having an ethylenically unsaturated bond and a counter salt. good.
• tertiary amine compounds having ethylenically unsaturated bonds include N,N-dimethylaminopropyl methacrylate.
• R 113 and R 114 may be a polarity conversion group such as an acid-decomposable group.
• the acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxyl group. , a tertiary alkyl ester group and the like 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, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, and tert-butoxycarbonylmethyl. groups, trimethylsilyl ether groups, and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
• the polyimide precursor preferably has a fluorine atom in its structure.
• the content of fluorine atoms 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.
• an aliphatic group having a siloxane structure there is an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.
• the repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one polyimide precursor used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of 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 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 both are preferably groups containing a polymerizable group.
• a 1 , A 2 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same.
• R 112 has the same definition as R 112 in formula (5), and the preferred range is also the same.
• the polyimide precursor may contain one type of repeating unit represented by formula (2), but may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may also contain other types of repeating units in addition to the repeating units of formula (2) above.
• 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 terminals 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, still more preferably 15,000 to 40,000. Also, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
• the polyimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyimide precursor's molecular weight dispersity is not particularly defined, 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 by weight average molecular weight/number average molecular weight.
• the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the multiple types of polyimide precursors as one resin are within the ranges described above.
• the polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer containing an organic solvent as a main component.
• the alkali-soluble polyimide refers to a polyimide that dissolves at 23° C. in an amount of 0.1 g or more in 100 g of a 2.38% by mass tetramethylammonium aqueous solution. It is preferably a polyimide that dissolves, and more preferably a polyimide that dissolves 1.0 g or more. Although the upper limit of the dissolved amount is not particularly limited, it 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 the film strength and insulating properties of the resulting organic film.
• the term "main chain” refers to the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin, and the term “side chain” refers to the other linking chain.
• the polyimide preferably has a fluorine atom.
• a fluorine atom is preferably included in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later, and the formula ( It is more preferably contained as a fluorinated alkyl group in R 132 in the repeating unit represented by 4) or R 131 in the repeating unit represented by formula (4) described later.
• the amount of fluorine atoms relative to the total mass of polyimide is preferably 5% by mass or more and preferably 20% by mass or less.
• the polyimide preferably has a silicon atom.
• a silicon atom for example, is preferably contained in R 131 in a repeating unit represented by formula (4) described later, and R 131 in a repeating unit represented by formula (4) described later is an organic modified (poly ) is more preferably contained as a siloxane structure.
• the silicon atom or the organically modified (poly)siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
• the amount of silicon atoms relative to the total mass of polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.
• the polyimide preferably has an ethylenically unsaturated bond.
• the polyimide may have an ethylenically unsaturated bond at the end of its main chain or in a side chain, preferably in a side chain.
• the ethylenically unsaturated bond preferably has radical polymerizability.
• the ethylenically unsaturated bond is preferably contained in R 132 in a repeating unit represented by the formula (4) described later, or R 131 in a repeating unit represented by the formula (4) described later.
• the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by formula (4) described later, and ethylene It is more preferably included as a group having a polyunsaturated bond.
• the group having an ethylenically unsaturated bond includes a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acrylamide group, a (meth) 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, preferably a hydrogen atom or a methyl group.
• R 21 is an alkylene group having 2 to 12 carbon atoms, —O—CH 2 CH(OH)CH 2 —, —C( ⁇ O)O—, —O(C ⁇ O)NH— , a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, 1 to 6 are more preferable, and 1 to 3 are particularly preferable), or a group in which two or more of these are combined.
• the alkylene group having 2 to 12 carbon atoms may be a linear, branched, cyclic, or a combination of these alkylene groups.
• an alkylene group having 2 to 8 carbon atoms is preferable, and an alkylene group having 2 to 4 carbon atoms is more preferable.
• R 21 is preferably a group represented by any one of the following formulas (R1) to (R3), 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 in which two or more of these are combined
• X represents an oxygen atom or a sulfur atom
• * represents a bonding site with another structure
• ⁇ represents a bonding site with the oxygen atom to which R 21 in formula (IV) bonds.
• a preferred embodiment of an alkylene group having 2 to 12 carbon atoms or a (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the above-mentioned R 21 having 2 to 12 carbon atoms. It is the same as the preferred embodiment of the 12 alkylene group 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) is, 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 (e.g., 2-isocyanatoethyl methacrylate, etc.). Obtained by reaction.
• the structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (eg, 2-hydroxyethyl methacrylate, etc.).
• the structure represented by formula (R3) can be obtained, for example, by 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 (e.g., glycidyl methacrylate, etc.) can get.
• a polyimide having a hydroxy group such as a phenolic hydroxy group
• a compound having a glycidyl group and an ethylenically unsaturated bond e.g., glycidyl methacrylate, etc.
• * represents a binding site with another structure, preferably a binding site with the main chain of polyimide.
• the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001-0.1 mol/g, more preferably 0.0005-0.05 mol/g.
• Polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
• Polymerizable groups other than groups having an ethylenically unsaturated bond include cyclic ether groups such as an epoxy group and an oxetanyl group, alkoxymethyl groups such as a methoxymethyl group, and methylol groups.
• a polymerizable group other than a group having an ethylenically unsaturated bond is preferably included, for example, in R 131 in a repeating unit represented by formula (4) described below.
• the amount of the polymerizable group other than the group having an ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. more preferred.
• the polyimide may have a polarity conversion group such as an acid-decomposable group.
• the acid-decomposable group in the polyimide is the same as the acid-decomposable group described for R 113 and R 114 in formula (2) above, and preferred embodiments are also the same.
• Polar conversion groups are included, for example, at R 131 and R 132 in the repeating unit represented by formula (4) described later, the terminal of polyimide, and the like.
• the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more, from the viewpoint of improving developability. is more preferable. Also, 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. Further, when the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development” described later), the acid value of the polyimide is preferably 1 to 35 mgKOH/g, and 2 to 30 mgKOH.
• the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, more preferably a phenolic hydroxy group.
• the polyimide preferably has a phenolic hydroxy group from the viewpoint of making the development speed with an alkaline developer appropriate.
• the polyimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
• a phenolic hydroxy group is preferably contained in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later.
• the amount of phenolic hydroxy groups relative to the total weight of the polyimide is preferably 0.1-30 mol/g, more preferably 1-20 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 and R 132 represents a tetravalent organic group.
• the polymerizable group may be located on at least one of R 131 and R 132 , and the terminal of the polyimide as shown in the following formula (4-1) or (4-2) may be located in Formula (4-1)
• R 133 is a polymerizable group, and other groups are the same as in formula (4).
• Formula (4-2) At least one of R 134 and R 135 is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups are as defined in formula (4).
• R 131 represents a divalent organic group.
• the divalent organic group are the same as those of R 111 in formula (2), and the preferred range is also the same.
• R 131 also includes a diamine residue remaining after removal of the amino group of the diamine. Diamines include aliphatic, cycloaliphatic or aromatic diamines. A specific example is the example of 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 from the viewpoint of more effectively suppressing warping during baking. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and more preferably the above diamine, which does not contain an aromatic ring. 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. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy) 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 are the same as those for R 115 in formula (2), and the preferred range is also the same.
• four bonds of a tetravalent organic group exemplified as R 115 combine with four —C( ⁇ O)— moieties in the above formula (4) to form a condensed ring.
• R 132 includes, for example, a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride.
• a specific example is the example of R 115 in formula (2) of the polyimide precursor.
• 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, R 131 is 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 preferred examples. and more preferred examples of R 132 are the above (DAA-1) to (DAA-5).
• the polyimide preferably 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 is blocked with a terminal blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound. preferably.
• a terminal blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound.
• monoamines it is more preferable to use monoamines, and 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-
• the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. 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 imidization rate is measured, for example, by the method described below. The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm ⁇ 1 , which is the absorption peak derived from the imide structure, is obtained. Next, after heat-treating the polyimide at 350° C.
• the polyimide may contain repeating units represented by the above formula (4 ) that all contain one type of R 131 or R 132 , and the above formula ( 4) may contain a repeating unit. Moreover, the polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Other types of repeating units include, for example, repeating units represented by formula (2) above.
• polyimide for example, a method of reacting a tetracarboxylic dianhydride and a diamine (partially replaced with a monoamine terminal blocker) at a low temperature, a method of reacting a tetracarboxylic dianhydride (partially with an acid anhydride) at a low temperature a monoacid chloride compound or a monoactive ester compound) and a diamine, a diester is obtained by a tetracarboxylic dianhydride and an alcohol, and then a diamine (a part of which is a monoamine A method of reacting in the presence of a condensing agent) with a condensing agent, a diester is obtained by tetracarboxylic acid dianhydride and alcohol, then the remaining dicarboxylic acid is acid chloride, diamine (part of which is a monoamine Using a method such as a method of reacting with a terminal blocking agent) to obtain a polyimide precursor
• the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. A weight-average molecular weight of 15,000 or more is particularly preferable in order to obtain an organic film having excellent mechanical properties (e.g., elongation at break).
• the number average molecular weight (Mn) of polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
• the polyimide has a molecular weight distribution of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
• the upper limit of the polyimide molecular weight dispersion is not particularly defined, 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 preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated using the above plural kinds of polyimides as one resin are within the ranges described above.
• polybenzoxazole precursor used in the present invention is not particularly defined for its structure and the like, but includes, for example, compounds described in paragraphs 0049 to 0074 of International Publication No. 2021/172420, and these descriptions are herein. incorporated into the book.
• Polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but it is preferably a compound represented by the following formula (X), and a compound represented by the following formula (X) and more preferably a compound having a polymerizable group.
• a radically polymerizable group is preferred.
• it may be a compound represented by the following formula (X) and having a polarity conversion group such as an acid-decomposable group.
• R 133 represents a divalent organic group and R 134 represents a tetravalent organic group.
• the polar conversion group such as a polymerizable group or an acid-decomposable group
• the polar conversion group may be positioned at least one of R 133 and R 134 . It may be positioned at the end of the polybenzoxazole as shown in formula (X-1) or formula (X-2).
• R 137 is a polar conversion group such as a polymerizable group or an acid-decomposable group, the others are substituents, and the other groups are the same as in formula (X).
• the polarity conversion group such as a polymerizable group or an acid-decomposable group is synonymous with the polymerizable group described above for the polymerizable group possessed by the polyimide precursor.
• R 133 represents a divalent organic group.
• Divalent organic groups include aliphatic groups and aromatic groups.
• a specific example is the example of R 121 in formula (3) of the polybenzoxazole precursor. Preferred examples thereof are the same as those of R121 .
• R 134 represents a tetravalent organic group.
• Tetravalent organic groups include examples of R 122 in the polybenzoxazole precursor formula (3). Moreover, the preferred examples thereof are the same as those of R122 .
• four bonds of a tetravalent organic group exemplified as R 122 combine with the nitrogen atom and oxygen atom in the above formula (X) to form a condensed ring.
• R 134 when R 134 is the following organic group, it forms the structure below. In the structures below, each * represents a bonding site with a nitrogen atom or an oxygen atom in formula (X).
• Polybenzoxazole preferably has an oxazole conversion rate of 85% or more, more preferably 90% or more.
• the upper limit is not particularly limited, and may be 100%.
• the oxazolization rate is measured, for example, by the method described below.
• An infrared absorption spectrum of polybenzoxazole is measured to obtain a peak intensity Q1 near 1650 cm ⁇ 1 which is an absorption peak derived from the amide structure of the precursor.
• the polybenzoxazole may contain repeating units of the above formula (X) that all contain one type of R 131 or R 132 , or may contain repeating units of the above formula (X) that contain two or more different types of R 131 or R 132 . ) repeating units.
• the polybenzoxazole may also contain other types of repeating units in addition to the repeating units of formula (X) above.
• Polybenzoxazole is obtained by, for example, reacting a bisaminophenol derivative with a dicarboxylic acid containing R 133 or a compound selected from dicarboxylic acid dichlorides and dicarboxylic acid derivatives of the above dicarboxylic acid to obtain a polybenzoxazole precursor. , which is obtained by oxazolating it using a known oxazolating reaction method.
• dicarboxylic acid in order to increase the reaction yield, etc., an active ester type dicarboxylic acid derivative pre-reacted with 1-hydroxy-1,2,3-benzotriazole or the like may be used.
• the weight average molecular weight (Mw) of polybenzoxazole is preferably from 5,000 to 70,000, more preferably from 8,000 to 50,000, even more preferably from 10,000 to 30,000.
• the weight average molecular weight is particularly preferably 20,000 or more.
• the weight average molecular weight of at least one kind of polybenzoxazole is within the above range.
• the number average molecular weight (Mn) of polybenzoxazole is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200. be.
• the polybenzoxazole has a molecular weight dispersity of preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more.
• the upper limit of the polybenzoxazole molecular weight dispersity is not particularly defined, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and even more preferably 2.3 or less.
• 2.2 or less is even more preferable.
• the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polybenzoxazole are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polybenzoxazole as one resin are within the ranges described above.
• Polyamideimide precursors are not particularly defined for their structure and the like, but include, for example, compounds described in paragraphs 0075 to 0093 of WO 2021/172420, and these descriptions are incorporated herein.
• the polyamideimide used in the present invention may be an alkali-soluble polyamideimide or a polyamideimide soluble in a developer containing an organic solvent as a main component.
• the alkali-soluble polyamideimide refers to a polyamideimide that dissolves at 23° C. in an amount of 0.1 g or more in 100 g of a 2.38 mass % tetramethylammonium aqueous solution.
• a polyamideimide that dissolves 5 g or more is preferable, and a polyamideimide that dissolves 1.0 g or more is more preferable.
• the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
• the polyamideimide is preferably a polyamideimide having a plurality of amide bonds and a plurality of imide structures in the main chain from the viewpoint of the film strength and insulating properties of the organic film to be obtained.
• the polyamideimide preferably has a fluorine atom.
• a fluorine atom is preferably contained in, for example, R 117 or R 111 in a repeating unit represented by formula (PAI-3) described later, and is preferably contained in a repeating unit represented by formula (PAI-3) described later It is more preferably contained in R 117 or R 111 as a fluorinated alkyl group.
• the amount of fluorine atoms is preferably 5% by mass or more and preferably 20% by mass or less with respect to the total mass of polyamideimide.
• the polyamideimide may have an ethylenically unsaturated bond.
• the polyamideimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, preferably in the side chain.
• the ethylenically unsaturated bond preferably has radical polymerizability.
• the ethylenically unsaturated bond is preferably contained in R 117 or R 111 in the repeating unit represented by formula (PAI-3) described later, and the repeating unit represented by formula (PAI-3) described later.
• R 117 or R 111 It is more preferably contained as a group having an ethylenically unsaturated bond in R 117 or R 111 in .
• Preferred embodiments of the group having an ethylenically unsaturated bond are the same as the preferred embodiments of the group having an ethylenically unsaturated bond in the polyimide described above.
• the amount of ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.0001 to 0.1 mol/g, more preferably 0.001 to 0.05 mol/g.
• Polyamideimide may have a polymerizable group other than the ethylenically unsaturated bond.
• the polymerizable groups other than the ethylenically unsaturated bond in the polyamideimide include the same groups as the polymerizable groups other than the ethylenically unsaturated bond in the polyimide described above.
• a polymerizable group other than an ethylenically unsaturated bond is preferably included in R 111 in a repeating unit represented by formula (PAI-3) described later, for example.
• the amount of polymerizable groups other than ethylenically unsaturated bonds relative to the total mass of polyamideimide is preferably 0.05 to 10 mol/g, more preferably 0.1 to 5 mol/g.
• -Polarity conversion group- Polyamideimide may have a polarity converting group such as an acid-decomposable group.
• the acid-decomposable group in polyamideimide is the same as the acid-decomposable group described for R 113 and R 114 in formula (2) above, and preferred embodiments are also the same.
• the acid value of the polyamideimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g, from the viewpoint of improving developability. g or more is more preferable. Also, 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 polyamideimide is preferably 2 to 35 mgKOH/g, 3 ⁇ 30 mg KOH/g is more preferred, and 5 to 20 mg KOH/g is even more preferred.
• 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 polyamideimide the same groups as the acid group in the polyimide described above can be mentioned, and the preferred embodiments are also the same.
• the polyamideimide preferably has a phenolic hydroxy group.
• Polyamideimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
• a phenolic hydroxy group is preferably included in, for example, R 117 or R 111 in a repeating unit represented by formula (PAI-3) described later.
• the amount of phenolic hydroxy groups relative to the total mass of polyamideimide is preferably 0.1 to 30 mol/g, more preferably 1 to 20 mol/g.
• the polyamideimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure and an amide bond, but it preferably contains a repeating unit represented by the following formula (PAI-3).
• R 111 and R 117 have the same definitions as R 111 and R 117 in formula (PAI-2), and preferred embodiments are also the same.
• the polymerizable group may be located at least one of R 111 and R 117 , or may be located at the end of the polyamideimide.
• the main chain end of the polyamideimide is blocked with a terminal blocker such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
• a terminal blocker such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
• Preferred aspects of the terminal blocker are the same as the preferred aspects of the terminal blocker in the polyimide described above.
• the imidization rate (also referred to as "ring closure rate") of polyamideimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. , more preferably 90% or more.
• the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
• the imidization rate is measured by the same method as the ring closure rate of the polyimide described above.
• Polyamideimide may contain repeating units represented by the above formula (PAI-3), all of which contain one type of R 111 or R 117 , and two or more different types of R 131 or R 132 . It may contain a repeating unit represented by the above formula (PAI-3). Moreover, the polyamideimide may contain other types of repeating units in addition to the repeating units represented by the above formula (PAI-3). Other types of repeating units include repeating units represented by the above formula (PAI-1) or formula (PAI-2).
• Polyamideimide is, for example, a method of obtaining a polyamideimide precursor by a known method and completely imidizing it using a known imidization reaction method, or stopping the imidization reaction in the middle and partially imidizing the imide structure and a method of partially introducing an imide structure by blending a completely imidized polymer with its polyamideimide precursor.
• the weight average molecular weight (Mw) of polyamideimide is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, even more preferably 10,000 to 30,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. In order to obtain an organic film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. Further, the number average molecular weight (Mn) of the polyamideimide is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000. .
• the polyamidoimide has a molecular weight distribution of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
• the upper limit of the polyamidoimide molecular weight dispersity is not particularly defined, 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 polyamideimide are preferably within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated from the plurality of types of polyamideimide as one resin are within the above ranges.
• Polyimide precursors and the like for example, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature to obtain a polyamic acid, a condensing agent or an alkylating agent A method of esterification using a tetracarboxylic dianhydride and an alcohol to obtain a diester, then a method of reacting in the presence of a diamine and a condensing agent, a method of reacting a tetracarboxylic dianhydride and an alcohol to obtain a diester, After that, the remaining dicarboxylic acid can be acid-halogenated using a halogenating agent and reacted with a diamine.
• the method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and reacting it with a diamine is more preferred.
• the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, trifluoroacetic anhydride and the like can be mentioned.
• alkylating agent examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate and triethyl orthoformate.
• halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.
• organic solvent In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. One type of organic solvent may be used, or two or more types may be used.
• the organic solvent can be appropriately determined according to the raw material, but pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, ⁇ -butyrolactone, and the like. are exemplified.
• pyridine diethylene glycol dimethyl ether (diglyme)
• N-methylpyrrolidone N-ethylpyrrolidone
• ethyl propionate dimethylacetamide
• dimethylformamide dimethylformamide
• tetrahydrofuran ⁇ -butyrolactone, and the like.
• the basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-amino Pyridine and the like are exemplified.
• terminal blocking agents include monoalcohols, phenols, thiols, thiophenols, monoamines, and the like. It is more preferable to use monoalcohols, phenols and monoamines from the viewpoint of their properties.
• Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol and 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantane alcohol.
• Preferable phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-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-amin
• Preferred capping agents for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromide, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides, etc., more preferably carboxylic acid anhydrides and carboxylic acid chlorides. 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. are mentioned.
• Preferred compounds of carboxylic acid chlorides include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantanecarbonyl 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 depositing a solid. Specifically, after filtering off the water absorption by-products of the dehydration condensation agent coexisting in the reaction solution as necessary, water, aliphatic lower alcohol, or a poor solvent such as a mixture thereof, the obtained A polyimide precursor or the like can be obtained by adding a polymer component and depositing the polymer component to precipitate it as a solid and drying it. In order to improve the degree of purification, operations such as redissolution, reprecipitation, drying, etc. of the polyimide precursor may be repeated. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.
• 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 with respect to the total solid content of the resin composition. is more preferable, and 50% by mass or more is even more preferable. 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, more preferably 98% by mass, based on the total solid content of the resin composition. % or less, more preferably 97 mass % or less, and even more preferably 95 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. When two or more types are included, the total amount is preferably within the above range.
• the resin composition of the present invention preferably contains at least two resins.
• the resin composition of the present invention may contain a total of two or more of the specific resin and other resins described later, or may contain two or more of the specific resins. It is preferable to include two or more kinds.
• 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)) It preferably contains a precursor.
• the resin composition of the present invention may contain other resins (hereinafter simply referred to as "other resins") different from the specific resins in addition to or instead of the specific resins described above. good.
• Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. etc.
• a (meth)acrylic resin by further adding a (meth)acrylic resin, a resin composition having excellent applicability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
• a high polymerizable group value having a weight average molecular weight of 20,000 or less for example, the molar amount of the polymerizable group in 1 g of the resin is 1 ⁇ 10 ⁇ 3 mol/g or more
• the coating properties of the resin composition and the solvent resistance of the pattern (cured product) can be improved. can.
• the content of the other resins is preferably 0.01% by mass or more, and 0.05% by mass or more, relative to the total solid content of the resin composition. More preferably, 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 further 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, based on the total solid content of the resin composition. It is more preferably 60% by mass or less, even more preferably 50% by mass or less.
• 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 with respect to the total solid content of the resin composition. is more preferable, 5% by mass or less is even more preferable, and 1% by mass or less is even more preferable.
• the lower limit of the content is not particularly limited as long as it is 0% by mass or more.
• the resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.
• the resin composition of the present invention contains a specific metallocene compound.
• the specific metallocene compound (first specific metallocene compound) contained in the resin composition according to the first aspect of the present invention comprises a metal atom, an optionally substituted cyclopentadienyl ligand, and the above It has an aromatic ring directly connected to a metal atom, the aromatic ring has an electron-withdrawing group different from a halogen atom as a substituent directly connected to the aromatic ring, and the molar extinction coefficient at 500 nm is 330 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less.
• the specific metallocene compound (second specific metallocene compound) contained in the resin composition according to the second aspect of the present invention comprises a metal atom, an optionally substituted cyclopentadienyl ligand, and the above It has an aromatic ring directly linked to a metal atom, and the aromatic ring has a halogen atom as a substituent directly linked to the aromatic ring and an electron-withdrawing group different from the halogen atom.
• the type of the metal atom contained in the specific metallocene compound is not particularly limited, but is preferably a Group 4 metal atom, more preferably a titanium atom, a zirconium atom, or a hafnium atom, from the viewpoint of stability in the composition. is more preferably a titanium atom. It is presumed that this is because the titanium atom has a small atomic radius, which improves the stability of the compound.
• the specific metallocene compound of the present invention is preferably a metallocene compound containing a Group 4 metal atom, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, and even more preferably a titanocene compound.
• the number of metal atoms contained in the specific metallocene compound is not particularly limited, but may be 1 or more, more preferably 1 to 4, further preferably 1 or 2, and 1 is particularly preferred.
• the specific metallocene compound contains two or more of the above metal atoms, the types of the above metal atoms may be the same or different.
• the specific metallocene compound may contain two titanium atoms, or may contain a titanium atom and a zirconium atom.
• the specific metallocene compound has an optionally substituted cyclopentadienyl ligand. That is, the specific metallocene compound is a cyclopentadienyl complex.
• the cyclopentadienyl ligand preferably coordinates to the metal atom in a ⁇ 5 -type coordination mode.
• the substituent in the cyclopentadienyl ligand is not particularly limited as long as the effects of the present invention can be obtained, and examples thereof include alkyl groups having 1 to 10 carbon atoms.
• the specific metallocene compound may have only one cyclopentadienyl ligand, or may have two or more cyclopentadienyl ligands, but preferably has two.
• the specific metallocene compound has two or more cyclopentadienyl ligands, their structures may be the same or different.
• the aromatic ring directly linked to a metal atom may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but an aromatic hydrocarbon ring is preferred.
• the aromatic hydrocarbon ring is preferably an aromatic ring having 6 to 20 carbon atoms, more preferably a benzene ring or a naphthalene ring, and still more preferably a benzene ring.
• As the aromatic heterocyclic ring a ring structure represented by a 5-membered ring, a 6-membered ring, or a combination thereof is preferable.
• aromatic heterocycles include pyridine ring, imidazole ring, thiophene ring, pyrazine ring, pyrrole ring, azepine ring, thiepine ring, pyrazole ring, oxazole ring, thiazole ring, imidazoline ring, thiazine ring, indole ring, iso Indole ring, benzimidazole ring, purine ring, quinoline ring, isoquinoline ring, quinoxaline ring, cinnoline ring, pteridine ring, benzofuran ring, pyrimidine ring, pyridazine ring, etc., but not limited thereto.
• the specific metallocene compound may have one or more aromatic rings directly connected to the metal atom, but preferably has one or two, more preferably two. .
• the specific metallocene compound has two or more aromatic rings directly connected to the metal atom, their structures and substituent structures may be the same or different.
• the aromatic ring has an electron-withdrawing group different from a halogen atom as a substituent directly bonded to the aromatic ring.
• the electron-withdrawing group include -CF 3 , -NO 2 , -CCl 3 , -CN, -CHO, -COCH 3 , -COOC 2 H 5 , -COOH, -SO 2 CH 3 , -SO 3 H etc., and -CF 3 or -NO 2 is preferred.
• the aromatic ring may further have a substituent in addition to the electron-withdrawing group. Examples of such substituents include halogen atoms and alkyl groups.
• the aromatic ring may have two or more electron-withdrawing groups, having only one is also one of the preferred embodiments of the present invention.
• the electron-withdrawing groups may have the same or different structures.
• the aromatic ring is a benzene ring
• the benzene ring preferably has the electron-withdrawing group at the para-position with respect to the bonding site with the metal atom in the benzene ring.
• the aromatic ring preferably further has a halogen atom as a substituent in addition to the electron-withdrawing group described above.
• the aromatic ring further has a halogen atom as a substituent in addition to the electron-withdrawing group described above.
• the halogen atom in these specific metallocene compounds include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred.
• the aromatic ring in these specific metallocene compounds is a benzene ring and further has the halogen atom as a substituent
• the benzene ring is positioned ortho to the bonding site with the metal atom in the benzene ring, or It preferably has the halogen atoms at the ortho-position and the meta-position, and more preferably has the halogen atom at the ortho-position and does not have the halogen atom at the meta-position.
• the benzene ring may have the halogen atom at both of the two ortho positions.
• the benzene ring preferably has the above halogen atom only on one side.
• the benzene ring has the halogen atoms at the ortho and meta positions with respect to the bonding site with the metal atom on the benzene ring, the benzene ring has the above at both the two ortho positions and the two meta positions, respectively.
• it may have a halogen atom, it is preferable to have the above halogen atom only at one of the two ortho positions and only at one of the two meta positions.
• the specific metallocene compound may further have other structures.
• the first specific metallocene compound may further include an unsubstituted aromatic ring.
• Preferred embodiments of the aromatic ring are the same as the preferred embodiments of the aromatic ring in the aromatic ring having a substituent.
• the molar extinction coefficient at 500 nm of the first specific metallocene compound is 330 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less, preferably 300 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less, and 250 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less, more preferably 200 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less, and particularly preferably 150 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less.
• the molar extinction coefficient at 500 nm of the second specific metallocene compound is preferably 330 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less, more preferably 300 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less, and 250 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less is more preferable, 200 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less is particularly preferable, and 150 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or less is most preferable.
• the lower limit of the molar extinction coefficient is not particularly limited, and may be 0 mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 or more.
• the molar extinction coefficient can be measured by the method described in Examples.
• a specific metallocene compound having photopolymerization initiation ability can also be used. In the present invention, even when such a specific metallocene compound is used, dark polymerization is likely to be suppressed, and it is considered that the working stability under a yellow light is excellent. Specifically, for example, a compound having photoradical polymerization initiation ability can be used as the specific metallocene compound.
• the specific metallocene compound is preferably a compound represented by the following formula (1-1) or (1-2).
• M represents a titanium atom, a zirconium atom or a hafnium atom, each R 1 independently represents a hydrogen atom or a methyl group, and each R 2 independently represents a hydrogen atom or a fluorine atom.
• R 2 is a fluorine atom
• R 3 each independently represents a hydrogen atom or a halogen atom
• R 4 represents an electron-withdrawing group different from a halogen atom
• R 5 each independently represents a hydrogen atom or a fluorine atom
• one of R 5 is a fluorine atom
• each R 6 independently represents a hydrogen atom or a halogen atom
• R 7 represents an electron-withdrawing group different from the halogen atom.
• each M independently represents a titanium atom, a zirconium atom or a hafnium atom
• each R 8 independently represents a hydrogen atom or a methyl group
• each R 9 independently represents a hydrogen atom or represents a fluorine atom
• one of R 9 is a fluorine atom
• R 10 each independently represents a hydrogen atom or a halogen atom
• R 11 represents an electron-withdrawing group different from a halogen atom
• R 12 Each independently represents a hydrogen atom or a fluorine atom
• one of R 12 is a fluorine atom
• each R 13 independently represents a hydrogen atom or a halogen atom
• R 14 has an electron-withdrawing property different from that of a halogen atom.
• group, R 15 and R 16 each independently represent a hydrogen atom or a substituent
• A represents an oxygen atom or a sulfur atom.
• M is preferably a titanium atom.
• each R 1 is preferably a hydrogen atom.
• one of R 2 is preferably a fluorine atom and the other is preferably a hydrogen atom.
• each R 3 is preferably a hydrogen atom.
• the halogen atom for R 3 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred.
• Preferred embodiments of the electron-withdrawing group different from the halogen atom in R 4 in formula (1-1) are the same as the preferred embodiments of the electron-withdrawing group described above.
• Preferred embodiments of R 5 , R 6 and R 7 in formula (1-1) are the same as preferred embodiments of R 2 , R 3 and R 4 in formula (1-1).
• both M are titanium atoms, both are zirconium atoms, or both are preferably hafnium atoms, and both are more preferably titanium atoms.
• Preferred embodiments of R 8 in formula (1-2) are the same as preferred embodiments of R 1 in formula (1-1).
• Preferred embodiments of R 9 in formula (1-2) are the same as preferred embodiments of R 2 in formula (1-1).
• Preferred embodiments of R 10 in formula (1-2) are the same as preferred embodiments of R 3 in formula (1-1).
• Preferred embodiments of R 11 in formula (1-2) are the same as preferred embodiments of R 4 in formula (1-1).
• Preferred embodiments of R 12 in formula (1-2) are the same as preferred embodiments of R 5 in formula (1-1).
• R 13 in formula (1-2) are the same as preferred embodiments of R 6 in formula (1-1).
• Preferred embodiments of R 14 in formula (1-2) are the same as preferred embodiments of R 7 in formula (1-1).
• R 15 and R 16 are each independently a cyclopentadienyl ligand optionally having a substituent as described above, an aromatic ring directly linked to the metal atom described above, or Other structures are preferred. Preferred aspects and specific examples of these structures are respectively as described above.
• A is preferably an oxygen atom.
• R 4 and R 7 in the above formula (1-1) are each independently a trifluoromethyl group or a nitro group
• R 11 and R 14 in the above formula (1-2) are each independently A trifluoromethyl group or a nitro group is preferred.
• the absorption wavelength of the specific metallocene compound can be made shorter, and it is considered that the working stability under a yellow light is more likely to be improved.
• the molecular weight of the specific metallocene compound is preferably 200 to 2,000, more preferably 300 to 1,500, even more preferably 400 to 1,000.
• the specific metallocene compound can be synthesized, for example, by reacting an aryl halide with n-BuLi and further reacting it with titanocene dichloride. Moreover, it may be synthesized using other known synthesis methods, and the synthesis method is not particularly limited.
• titanocene compounds are generally synthesized by the following method. The following reactions are carried out under a nitrogen atmosphere. A 1.6 M (mol/L) hexane solution of n-BuLi (50 mmol, 31 mL) is slowly added dropwise to a THF (100 mL) solution of aryl bromide (50 mmol) at -78°C.
• a specific metallocene compound can be synthesized by using a halogenated aryl compound having a structure in which an electron-withdrawing group is directly linked to an aromatic ring as the "aryl bromide”. Synthesis conditions, solvents and the like may be changed as appropriate.
• Specific examples of the specific metallocene compound are not particularly limited, but include A-1 to A-21 used in the examples.
• the content of the specific metallocene compound with respect to the total solid content of the resin composition of the present invention is preferably 0.1 to 20% by mass.
• the lower limit is more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.
• the upper limit is more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less.
• One of the specific metallocene compounds may be used alone, or two or more thereof may be used in combination. When two or more are used in combination, the total amount is preferably within the above range.
• the resin composition of the present invention contains a specific metallocene compound and a radical polymerization initiator described later (radical polymerization initiator different from the specific metallocene compound), the specific metallocene compound and the radical polymerization initiator (specific metallocene compound
• the total content of the radical polymerization initiator different from the above) is preferably 0.1 to 20% by mass.
• the lower limit is more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1% by mass or more.
• the upper limit is more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less.
• the resin composition of the present invention may contain an organometallic complex from the viewpoint of chemical resistance.
• the organometallic complex referred to here does not include compounds corresponding to the above-mentioned specific metallocene compounds.
• the organometallic complex may be an organic complex compound containing a metal atom, but is preferably a complex compound containing a metal atom and an organic group, and is preferably a compound in which an organic group is coordinated to a metal atom. More preferably, it is a metallocene compound.
• the metallocene compound refers to an organometallic complex having two optionally substituted cyclopentadienyl anion derivatives as ⁇ 5-ligands.
• the organic group is not particularly limited, a hydrocarbon group or a group composed of a combination of a hydrocarbon group and a hetero atom is preferable.
• Preferred heteroatoms are oxygen, sulfur and nitrogen atoms.
• at least one of the organic groups is preferably a cyclic group, 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, more preferably a 5-membered cyclic group.
• the cyclic group may be either a hydrocarbon ring or a heterocyclic ring, but is preferably a hydrocarbon ring.
• As the five-membered cyclic group a cyclopentadienyl group is preferred.
• the organometallic complex used in the present invention preferably contains 2 to 4 cyclic groups in one molecule.
• the metal contained in the organometallic complex is not particularly limited, but is preferably a metal corresponding to a Group 4 element, and at least one metal selected from the group consisting of titanium, zirconium and hafnium. More preferably, it is at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.
• the organometallic complex may contain two or more metal atoms or may contain only one metal atom, but preferably contains only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one kind of metal atom, or 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.
• an embodiment in which the organometallic complex has photoradical polymerization initiation ability is also one of preferred embodiments of the present invention.
• having the ability to initiate radical photopolymerization means being able to generate free radicals capable of initiating radical polymerization upon exposure to light.
• radicals capable of initiating radical polymerization upon exposure to light.
• the organometallic complex has photoradical polymerization initiation ability
• the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, and a titanocene compound or a zirconocene compound. is more preferred, and a titanocene compound is particularly preferred.
• the organometallic complex is at least one selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds and hafnocene compounds. 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 preferred are compounds of the species, and particularly preferred are titanocene compounds.
• the molecular weight of the organometallic complex is preferably 50 to 2,000, more preferably 100 to 1,000.
• Preferred examples of the organometallic complex include compounds represented by the following formula (P).
• M is a metal atom
• each R is independently a substituent. It is preferable that 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 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, still more preferably a titanium atom or a zirconium atom, and titanium 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, a phenyl group, a 1-naphthyl group, or , 2-naphthyl group and the like.
• 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, and is a methyl group, an ethyl group, a propyl group, an octyl group, and an isopropyl group. , t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
• Halogen atoms for 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, a methyl group, an ethyl group, a propyl group, an octyl group, isopropyl group, t-butyl group, isopentyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclopentyl group and the like.
• 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 carbonyl group, acyloxy group, monoalkylamino group, dialkylamino group, monoarylamino group, diarylamino group and the like.
• organometallic complex examples include, but are not limited to, tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetoacetate)titanium, and diisopropoxybis(acetylacetoacetate).
• nath)titanium bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, pentamethylcyclopentadienyltitanium tri
• methoxide bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, and the following compounds.
• the content of the organometallic complex is preferably 0.1 to 30% by mass based on the total solid content of the resin composition of the present invention.
• 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. 1 type(s) or 2 or more types can be used for an organometallic complex. When two or more kinds are used, the total amount is preferably within the above range.
• the resin composition of the present invention preferably contains a polymerizable compound.
• Polymerizable compounds include radical cross-linking agents or other cross-linking agents.
• the resin composition of the present invention preferably contains a radical cross-linking agent.
• a radical cross-linking agent is a compound having a radically polymerizable group.
• the radically polymerizable group a group containing an ethylenically unsaturated bond is preferred.
• Examples of the group containing an ethylenically unsaturated bond include groups containing an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
• the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and more preferably a (meth)acryloyl group from the viewpoint of reactivity.
• the radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more.
• the radical cross-linking agent may have 3 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 2 to 6.
• the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferred to include
• the molecular weight of the radical cross-linking 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 cross-linking agent is preferably 100 or more.
• radical cross-linking agent examples include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. They 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 a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or monofunctional or polyfunctional is also preferably used.
• addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and halogeno groups
• substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols.
• paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.
• the radical cross-linking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure.
• Compounds having a boiling point of 100° C. or higher under normal pressure include compounds described in paragraph 0203 of International Publication No. 2021/112189. The contents of which are incorporated herein.
• Preferred radical cross-linking agents other than those described above include radically polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021/112189. The contents of which are incorporated herein.
• dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (Nippon Kayaku ( Ltd.), A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by 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 Co., Ltd.)), and their (meth)acryloyl groups are ethylene glycol,
• radical cross-linking agents examples include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209, a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer. 231, 239, Nippon Kayaku Co., Ltd.
• DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10 , UAB-140 (manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Japan Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blenmer PME400 (manufactured by NOF Corporation) etc.
• radical cross-linking agents examples include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable.
• compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. can also
• the radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group.
• a radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. is more preferable.
• the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol is a compound.
• Examples of commercially available products include polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. such as M-510 and M-520.
• the acid value of the radical cross-linking agent having an acid group is preferably 0.1-300 mgKOH/g, particularly preferably 1-100 mgKOH/g. If the acid value of the radical cross-linking agent is within the above range, the handleability in production is excellent, and furthermore the developability is excellent. Moreover, the polymerizability is good. The acid value is measured according to JIS K 0070:1992.
• a radical cross-linking agent having at least one selected from the group consisting of a urea bond and a urethane bond (hereinafter also referred to as "crosslinking agent U") is also preferable.
• the cross-linking agent U may have only one urea bond or urethane bond, may have one or more urea bonds and one or more urethane bonds, or may have two or more urea bonds without urethane bonds.
• the total number of urea bonds and urethane bonds in the cross-linking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, even more preferably 1 or 2.
• the number of urea bonds in the cross-linking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, 1 or 2 It is even more preferable to have Further, when the cross-linking agent U does not have a urea bond, the number of urethane bonds in the cross-linking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, 1 or 2 It is even more preferable to have
• the radically polymerizable group in the cross-linking agent U is not particularly limited, but includes a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, a maleimide group, and the like.
• a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferable, and a (meth)acryloxy group is more preferable.
• the cross-linking agent U has two or more radically polymerizable groups, the structure of each radically polymerizable group may be the same or different.
• the number of radically polymerizable groups in the cross-linking agent U may be only one, or may be two or more, preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.
• the radically polymerizable group value (mass of compound per mol of radically polymerizable group) in the cross-linking agent U is preferably 150 to 400 g/mol.
• the lower limit of the radical polymerizable group value is more preferably 200 g/mol or more, still more preferably 210 g/mol or more, still more preferably 220 g/mol or more, and 230 g/mol or more. is more preferred, 240 g/mol or more is particularly preferred, and 250 g/mol or more is most preferred.
• the upper limit of the radically polymerizable group value is more preferably 350 g/mol or less, still more preferably 330 g/mol or less, and particularly preferably 300 g/mol or less.
• the radical polymerizable group value is at least the lower limit, the cured product tends to have good chemical resistance, and when it is at most the upper limit, the developability tends to be good.
• the polymerizable group value of the cross-linking agent U is preferably 210 to 400 g/mol, more preferably 220 to 400 g/mol.
• the cross-linking agent U preferably has a structure represented, for example, by the following formula (U-1).
• R U1 is a hydrogen atom or a monovalent organic group
• A is —O— or —NR N —
• R N is a hydrogen atom or a monovalent organic group
• Z U1 is an m-valent organic group
• Z U2 is an n+1-valent organic group
• X is a radically polymerizable group
• n is an integer of 1 or more
• m is an integer of 1 or more.
• R U1 is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom.
• R 3 N is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom.
• hydrocarbon group a hydrocarbon group having 20 or less carbon atoms is preferable, a hydrocarbon group having 18 or less carbon atoms is more preferable, and a hydrocarbon group having 16 or less carbon atoms is even more preferable.
• examples of the hydrocarbon group include a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
• RN represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, even more preferably a hydrogen atom or a methyl group.
• hydrocarbon group a hydrocarbon group having 20 or less carbon atoms is preferable, a hydrocarbon group having 18 or less carbon atoms is more preferable, and a hydrocarbon group having 16 or less carbon atoms is even more preferable.
• examples of the hydrocarbon group include a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
• X is not particularly limited, but includes vinyl group, allyl group, (meth)acryloyl group, (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, maleimide group, etc.
• a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferable, and a (meth)acryloxy group is more preferable.
• n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably 1 or 2, particularly preferably 1 .
• m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably 1 or 2.
• the crosslinker U also preferably has at least one of a hydroxy group, an alkyleneoxy group, an amide group and a cyano group.
• the hydroxy group may be either an alcoholic hydroxy group or a phenolic hydroxy group, but an alcoholic hydroxy group is preferred.
• the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, and an alkyleneoxy group having 2 to 4 carbon atoms.
• An oxy group is more preferred, an ethylene group or a propylene group is even more preferred, and an ethylene group is particularly preferred.
• the alkyleneoxy group may be included in the crosslinker U as a polyalkyleneoxy group.
• the repeating number of the alkyleneoxy group is preferably 2-10, more preferably 2-6.
• RN is as described above.
• R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group.
• the cross-linking agent U has two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (however, when constituting a polyalkyleneoxy group, a polyalkyleneoxy group), an amide group and a cyano group. Although it may have it, the aspect which has only one in a molecule is also one of the preferable aspects of this invention.
• the hydroxy group, alkyleneoxy group, amide group and cyano group may be present at any position of the cross-linking agent U, but from the viewpoint of chemical resistance, the cross-linking agent U should be At least one selected from the group consisting of an amide group and a cyano group and at least one radically polymerizable group contained in the cross-linking agent U are a linking group containing a urea bond or a urethane bond (hereinafter referred to as "linking group L2-1 Also referred to as ".”) is also one of the preferred aspects of the present invention.
• the cross-linking agent U contains only one radically polymerizable group, at least one selected from the group consisting of the radically polymerizable group contained in the cross-linking agent U and a hydroxy group, an alkyleneoxy group, an amide group and a cyano group It is preferable that the two are linked by a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2").
• the cross-linking agent U contains an alkyleneoxy group (however, a polyalkyleneoxy group when constituting a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2, the alkyleneoxy group (However, when constituting a polyalkyleneoxy group, the polyalkyleneoxy group)
• the structure bonded to the side opposite to the connecting group L2-1 or the connecting group L2-2 is not particularly limited, but a hydrocarbon group, Groups represented by radically polymerizable groups or combinations thereof are preferred.
• hydrocarbon group a hydrocarbon group having 20 or less carbon atoms is preferable, a hydrocarbon group having 18 or less carbon atoms is more preferable, and a hydrocarbon group having 16 or less carbon atoms is even more preferable.
• examples of the hydrocarbon group include a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
• preferred aspects of the radically polymerizable group are the same as the preferred aspects of the radically polymerizable group in the cross-linking agent U described above.
• the cross-linking agent U contains an amide group and has the linking group L2-1 or the linking group L2-2, the amide group binds to the side opposite to the linking group L2-1 or the linking group L2-2.
• a group represented by a hydrocarbon group, a radically polymerizable group, or a combination thereof is preferred.
• a hydrocarbon group having 20 or less carbon atoms is preferable, a hydrocarbon group having 18 or less carbon atoms is more preferable, and a hydrocarbon group having 16 or less carbon atoms is even more preferable.
• examples of the hydrocarbon group include a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
• preferred aspects of the radically polymerizable group are the same as the preferred aspects of the radically polymerizable group in the cross-linking agent U described above.
• the carbon atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2, or the nitrogen atom side of the amide group may be linked to the linking group L2-1 or the linking group L2-2.
• the cross-linking agent U preferably has a hydroxy group from the viewpoint of adhesion to the substrate, chemical resistance, and suppression of Cu voids.
• the cross-linking agent U preferably contains an aromatic group from the viewpoint of compatibility with the specific resin.
• the above aromatic group preferably bonds directly to the urea bond or urethane bond contained in the cross-linking agent U.
• the cross-linking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group.
• the aromatic group may be an aromatic hydrocarbon group, an aromatic heterocyclic group, or a condensed ring structure, but is preferably an aromatic hydrocarbon group.
• aromatic hydrocarbon group an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, and an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, and two or more hydrogen atoms are removed from the benzene ring structure. groups are more preferred.
• aromatic heterocyclic group a 5- or 6-membered aromatic heterocyclic group is preferable.
• Aromatic heterocycles in such aromatic heterocyclic groups include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine and the like. .
• the heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
• the aromatic group connects two or more radically polymerizable groups and is selected from the group consisting of a linking group containing a urea bond or a urethane bond, or the above-described hydroxy group, alkyleneoxy group, amide group and cyano group. and at least one radically polymerizable group contained in the cross-linking agent U.
• the number of atoms (linked chain length) between the urea bond or urethane bond and the radically polymerizable group in the cross-linking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, It is more preferably 2-10.
• the cross-linking agent U contains a total of two or more urea bonds or urethane bonds, when it contains two or more radically polymerizable groups, or when it contains two or more urea bonds or urethane bonds and two or more radically polymerizable groups.
• the minimum number of atoms (linkage chain length) between the urea bond or urethane bond and the radically polymerizable group may be within the above range.
• the term “the number of atoms (linked chain length) between the urea bond or urethane bond and the polymerizable group” refers to the number of atoms on the route connecting the two atoms or groups of atoms to be linked. , the shortest (minimum number of atoms) connecting these concatenated objects.
• the number of atoms (linkage chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.
• the cross-linking agent U is a compound having a structure that does not have an axis of symmetry.
• the fact that the cross-linking agent U does not have an axis of symmetry means that it is a bilaterally asymmetric compound that does not have an axis that produces the same molecule as the original molecule by rotating the entire compound.
• the expression that the cross-linking agent U does not have an axis of symmetry means that the structural formula of the cross-linking agent U cannot be written in a form having an axis of symmetry. . Since the cross-linking agent U does not have an axis of symmetry, aggregation of the cross-linking agents U is suppressed in the composition film.
• the molecular weight of the cross-linking agent U is preferably 100-2,000, preferably 150-1500, more preferably 200-900.
• the method for producing the cross-linking agent U is not particularly limited, but for example, it can be obtained by reacting a compound having a radically polymerizable compound and an isocyanate group with a compound having at least one of a hydroxy group and an amino group.
• cross-linking agent U Specific examples of the cross-linking agent U are shown below, but the cross-linking agent U is not limited thereto.
• the resin composition preferably uses a bifunctional methacrylate or acrylate.
• Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 diacrylate.
• PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula weight of about 200.
• a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the elastic modulus control of the pattern (cured product).
• Monofunctional radical cross-linking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, ) 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.
• N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam
• allyl glycidyl ether are preferably used.
• the monofunctional radical cross-linking agent a compound having a boiling point of 100° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
• Other di- or higher functional radical cross-linking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.
• a radical cross-linking agent When a radical cross-linking agent is contained, its content is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention. More preferably, the lower limit is 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.
• a single radical cross-linking agent may be used alone, or a mixture of two or more may be used. When two or more are used in combination, the total amount is preferably within the above range.
• the resin composition of the present invention contains another cross-linking agent different from the radical cross-linking agent described above.
• the other cross-linking agent refers to a cross-linking agent other than the above-described radical cross-linking agent, and the above-described photoacid generator or photobase generator reacts with other compounds in the composition or reacts with them.
• the compound has a plurality of groups in the molecule that promote the reaction forming covalent bonds with the product, and covalent bonds are formed with other compounds or reaction products thereof in the composition. Compounds having a plurality of groups in the molecule, the reaction of which is promoted by the action of an acid or base, 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.
• a photoacid generator or a photobase generator in the exposure step.
• cross-linking agents compounds having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group and an alkoxymethyl group are preferred.
• a compound having a structure in which at least one group selected from the group consisting of groups is directly bonded to a nitrogen atom is more preferred.
• cross-linking agents include, for example, amino group-containing compounds such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, which are reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atoms of the amino groups are converted into acyloxymethyl groups, methylol groups,
• a compound having a structure substituted with an ethylol group or an alkoxymethyl group can be mentioned.
• the method for producing these compounds is not particularly limited as long as they have the same structure as the compounds produced by the above methods. Oligomers formed by self-condensation of methylol groups of these compounds may also be used.
• a melamine-based crosslinking agent is a melamine-based crosslinking agent
• a glycoluril, urea or alkyleneurea-based crosslinking agent is a urea-based crosslinking agent
• an alkyleneurea-based crosslinking agent is an alkyleneurea-based crosslinking agent.
• a cross-linking agent using benzoguanamine is called a benzoguanamine-based cross-linking agent.
• the resin composition of the present invention preferably contains at least one compound selected from the group consisting of urea-based cross-linking agents and melamine-based cross-linking agents. More preferably, it contains at least one compound selected from the group consisting of agents.
• an alkoxymethyl group or an acyloxymethyl group is directly substituted on the nitrogen atom of an aromatic group or the following urea structure, or on a triazine.
• the alkoxymethyl group or acyloxymethyl group of the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
• the total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6.
• the molecular weight of the compound is preferably 1500 or less, preferably 180-1200.
• R 100 represents an alkyl group or an acyl group.
• R 101 and R 102 each independently represent a monovalent organic group and may combine with each other to form a ring.
• Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted by an aromatic group include compounds represented by the following general formula.
• X represents a single bond or a divalent organic group
• each R 104 independently represents an alkyl group or an acyl group
• R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group , or a group that decomposes under the action of an acid to produce an alkali-soluble group (e.g., a group that leaves under the action of an acid, a group represented by —C(R 4 ) 2 COOR 5 (R 4 is independently It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that leaves under the action of an acid.)).
• R 105 each independently represents an alkyl group or alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3 , a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.
• R 5 in the group represented by —C(R 4 ) 2 COOR 5 a group that is decomposed by the action of an acid to produce an alkali-soluble group, a group that is eliminated by the action of an acid, and —C(R 36 )(R 37 )(R 38 ), —C(R 36 )(R 37 )(OR 39 ), —C(R 01 )(R 02 )(OR 39 ), and the like.
• R 36 to R 39 each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group.
• R 36 and R 37 may combine with each other to form a ring.
• alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
• the alkyl group may be linear or branched.
• a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
• the cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.
• the aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group.
• an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
• the aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above.
• the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms. Moreover, these groups may further have a known substituent within the range in which the effects of the present invention can be obtained.
• R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
• the group that is decomposed by the action of an acid to form an alkali-soluble group or the group that is eliminated by the action of an acid is preferably a tertiary alkyl ester group, an acetal group, a cumyl ester group, an enol ester group, or the like. More preferred are tertiary alkyl ester groups and acetal groups.
• the compound having at least one group selected from the group consisting of acyloxymethyl group, methylol group, ethylol group and alkoxymethyl group includes at least one group selected from the group consisting of urea bond and urethane bond.
• compounds having A preferred embodiment of the above compound is the above-described crosslinking except that the polymerizable group is not a radically polymerizable group but at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group and an alkoxymethyl group. It is the same as the preferred embodiment of agent U.
• Specific examples of compounds having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group and an ethylol group include the following structures.
• Examples of the compound having an acyloxymethyl group include compounds obtained by changing the alkoxymethyl group of the following compounds to an acyloxymethyl group.
• Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
• the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group a commercially available one or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.
• melamine-based cross-linking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.
• urea-based cross-linking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, and dimethoxymethylated glycol.
• Uril trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril , dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril glycoluril-based crosslinkers such as uril; urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated
• benzoguanamine-based cross-linking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
• tetramethoxymethylated benzoguanamine monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetra propoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine, and the like.
• the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group includes at least one group selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
• Compounds to which a seed group is directly attached are also preferably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate.
• suitable commercial products include 46DMOC, 46DMOEP (manufactured by Asahi Organic Chemicals Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP.
• DML-34X DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (Honshu Chemical Industry Co., Ltd.), Nikalac (registered
• the resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds as another cross-linking agent.
• Epoxy compound (compound having an epoxy group) -
• the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
• the epoxy group undergoes a cross-linking reaction at 200° C. or less and does not undergo a dehydration reaction resulting from the cross-linking, so film shrinkage does not easily occur. Therefore, containing an epoxy compound is effective for low-temperature curing and suppression of warpage of the resin composition of the present invention.
• the epoxy compound preferably contains a polyethylene oxide group.
• the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2-15.
• epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether.
• alkylene glycol type epoxy resins such as trimethylolpropane triglycidyl ether or polyhydric alcohol hydrocarbon type epoxy resins
• polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether
• epoxy groups such as polymethyl (glycidyloxypropyl) siloxane Examples include, but are not limited to, containing silicones and the like.
• Epiclon (registered trademark) 850-S Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP-S, Epiclon (registered trademark) N-740 (trade name, manufactured by DIC Corporation), Ricaresin (registered trademark) BEO-20E, Jamaicaresin (registered trademark) BEO-60E, Ricaresin (registered trademark) ) HBE-100, Ricaresin (registered trademark) DME-100, Ricaresin (registered trademark)
• n is an integer of 1-5 and m is an integer of 1-20.
• n 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and elongation improvement.
• oxetane compound compound having an oxetanyl group
• the oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester and the like can be mentioned.
• Aron oxetane series manufactured by Toagosei Co., Ltd. eg, OXT-121, OXT-221
• OXT-121, OXT-221 can be suitably used, and these can be used alone or in combination of two or more. good.
• a benzoxazine compound (compound having a benzoxazolyl group)-
• a benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and thermal shrinkage is reduced to suppress the occurrence of warping.
• benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (these are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, phenol novolac-type dihydrobenzoxazines, oxazine compounds. These may be used alone or in combination of two or more.
• the content of the other cross-linking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. It is more preferably 5 to 15% by mass, particularly preferably 1.0 to 10% by mass.
• Other cross-linking agents may be contained alone, or may be contained in two or more. When two or more other cross-linking agents are contained, the total is preferably within the above range.
• the resin composition of the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat. In particular, it preferably contains a photopolymerization initiator.
• the photopolymerization initiator as used herein does not include compounds corresponding to the above-mentioned specific metallocene compounds.
• the photopolymerization initiator is preferably a photoradical polymerization 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 having photosensitivity to light in the ultraviolet region to the visible region is preferred. It may also be an activator that produces an active radical by producing some action with a photoexcited sensitizer.
• the radical photopolymerization initiator contains at least one compound having a molar extinction 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). is preferred.
• the molar extinction coefficient of a compound can be measured using known methods. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
• any known compound can be used as the photoradical polymerization initiator.
• 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 compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the content of which is 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 radical photopolymerization initiator. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used. incorporated.
• ⁇ - ⁇ Omnirad 184 ⁇ Omnirad 1173 ⁇ Omnirad 2959 ⁇ Omnirad 127( ⁇ IGM Resins B.V. ⁇ ) ⁇ IRGACURE 184(IRGACURE ⁇ ) ⁇ DAROCUR 1173 ⁇ IRGACURE 500 ⁇ IRGACURE -2959 and IRGACURE 127 (trade names: both manufactured by BASF) can be used.
• ⁇ -Aminoketone initiators include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all BASF company) can be used.
• acylphosphine oxide-based initiators for example, compounds described in paragraphs 0161 to 0163 of WO2021/112189 can also be preferably used. The contents of which are incorporated herein.
• the photoradical polymerization initiator is more preferably an oxime compound.
• an oxime compound By using an oxime compound, the exposure latitude can be improved more effectively.
• Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.
• oxime compound examples include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in 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), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-019766, compounds described in Patent No.
• Preferred oxime compounds include, for example, compounds having 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 an oxime-based radical photopolymerization initiator
• DFI-091 manufactured by Daito Chemix Co., Ltd.
• SpeedCure PDO manufactured by SARTOMER ARKEMA
• an oxime compound having the following structure can be used.
• photoradical polymerization initiators examples 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 fluorine atoms can also be used. The contents of which are incorporated herein.
• an oxime compound having a nitro group an oxime compound having a benzofuran skeleton, and a substituent having a hydroxy group on the carbazole skeleton described in paragraphs 0208 to 0210 of International Publication No. 2021/020359 are used. Bound oxime compounds can also be used. The contents of which are incorporated herein.
• an oxime compound having an aromatic ring group Ar 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used.
• the electron-withdrawing group of 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.
• a 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, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group.
• a sulfanyl group or an amino group is more preferred.
• the oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.
• R X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group
• R X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group,
• R X12 is 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 paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.
• oxime compounds having specific substituents shown in JP-A-2007-269779 and oxime compounds having a thioaryl group shown in JP-A-2009-191061. incorporated herein.
• photoradical polymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl 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; are preferred.
• More preferred radical photopolymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds.
• At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferred, and metallocene compounds or oxime compounds are even more preferred. .
• radical photopolymerization initiator compounds described in paragraphs 0175 to 0179 of International Publication No. 2021/020359 can be used. The contents of which are incorporated herein.
• radical photopolymerization initiator a difunctional or trifunctional or higher radical photopolymerization initiator may be used.
• a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained.
• the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation becomes difficult over time, and the stability over time of the resin composition can be improved.
• Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
• a photopolymerization initiator When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , more preferably 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further advanced by heating with an oven, a hot plate, or the like.
• the resin composition may contain a sensitizer.
• a sensitizer absorbs specific actinic radiation and enters an electronically excited state.
• the sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes electron transfer, energy transfer, heat generation, or the like.
• the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids or bases.
• Usable sensitizers include benzophenones, Michler's ketones, coumarins, pyrazole azos, anilinoazos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, and pyrazolotriazole azos. , pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo compounds.
• Sensitizers include, for example, 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,
• the content of the sensitizer is preferably 0.01 to 20% by mass, 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 singly or in combination of two or more.
• the resin composition of the present invention may contain a chain transfer agent.
• the chain transfer agent is defined, for example, in Kobunshi Dictionary, 3rd edition (edited by Kobunshi Gakkai, 2005), pp. 683-684.
• Chain transfer agents include, for example, a group of compounds having —S—S—, —SO 2 —S—, —NO—, SH, PH, SiH, and GeH in the molecule, RAFT (Reversible Addition Fragmentation Chain Transfer )
• Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used for polymerization are used. They can either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
• thiol compounds can be preferably used.
• chain transfer agent can also use the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, the contents of which are incorporated herein.
• the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. 1 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is even more preferable.
• One type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total is preferably within the above range.
• the resin composition of the present invention may contain a base generator.
• the base generator is a compound capable of generating a base by physical or chemical action.
• Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
• the resin composition when the resin composition contains a cyclized resin precursor, the resin composition preferably contains a base generator.
• the base generator may be an ionic base generator or a non-ionic base generator.
• bases generated from base generators include secondary amines and tertiary amines. There are no particular restrictions on the base generator used in the present invention, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amine imides.
• nonionic base generators include compounds represented by formula (B1) or formula (B2) described in paragraphs 0275 to 0285 of WO2021/112189, and WO2020/066416.
• the compound represented by formula (N1) described in paragraphs 0102 to 00162 of No. 1 or the base generator is preferably a thermal base generator described in paragraphs 0013 to 0041 of WO 2020/054226. The contents of which are incorporated herein.
• base generators include the following, but the present invention should not be construed as being limited thereto.
• 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, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.
• ammonium salts include the following compounds, but the present invention is not limited thereto.
• iminium salts include the following compounds, but the present invention is not limited thereto.
• the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention.
• 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, still more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
• One or two or more base generators can be used. When two or more kinds 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.
• Organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas and alcohols.
• Esters such as 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 , ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
• 3-alkyloxypropionic acid alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
• 2-alkyloxypropionate alkyl esters e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)
• 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
• 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 Preferred 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 sulfoxides include, for example, dimethyl sulfoxide.
• Suitable ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.
• Alcohols such as 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, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol and the like.
• a combination of dimethyl sulfoxide and ⁇ -butyrolactone or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly
• the content of the solvent is preferably an amount such that the total solid concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass. More preferably, the amount is from 10 to 70% by mass, and even more preferably from 20 to 70% by mass.
• the solvent content may be adjusted according to the desired thickness of the coating and the method of application.
• the resin composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more solvents are contained, the total is preferably within the above range.
• the resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, and the like.
• metal adhesion improvers include alkoxysilyl group-containing silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, and ⁇ -ketoesters. compounds, amino compounds, and the like.
• silane coupling agent examples include compounds described in paragraph 0316 of International Publication No. 2021/112189 and compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are herein described. 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. Moreover, it is also preferable to use the following compound as a silane coupling agent. In the following formulas, Me represents a methyl group and Et represents an ethyl group.
• silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid.
• xypropyltrimethoxysilane 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2 -(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimeth
• Aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.
• the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the specific resin. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the pattern and the metal layer is improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the pattern are improved.
• One type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.
• the resin composition of the present invention preferably further contains a migration inhibitor.
• a migration inhibitor By including the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.
• Migration inhibitors are not particularly limited, but heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenolic compounds , salicylic acid derivative-based compounds, and hydrazide derivative-based compounds.
• heterocyclic rings pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole 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 be used.
• migration inhibitors include the following compounds.
• the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the resin composition of the present invention. , more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.
• migration inhibitor Only one type of migration inhibitor may be used, or two or more types may be used. When two or more migration inhibitors are used, the total is preferably within the above range.
• the resin composition of the present invention preferably contains a polymerization inhibitor.
• Polymerization inhibitors include phenol compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, metal compounds and the like.
• Specific compounds of the polymerization inhibitor include compounds described in paragraph 0310 of International Publication No. 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1- Oxyl free radical, phenoxazine, and the like. The contents of which are incorporated herein.
• the content of the polymerization inhibitor is preferably 0.01 to 20% by mass with respect to the total solid content of the resin composition of the present invention. It is more preferably from 0.02 to 15% by mass, and even more preferably from 0.05 to 10% by mass.
• polymerization inhibitor Only one type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
• the resin composition of the present invention contains at least one compound selected from the group consisting of urea compounds, carbodiimide compounds and isourea compounds (hereinafter referred to as " (also referred to as "urea compounds, etc.”).
• the urea compound is a compound represented by the following formula (UR-1)
• the carbodiimide compound is a compound represented by the following formula (UR-2)
• the isourea compound is a compound represented by the following formula (UR-3).
• R 11 and R 12 are each independently an optionally substituted aliphatic hydrocarbon having 1 to 7 carbon atoms group
• R 21 and R 22 each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms
• R 31 and R 32 each independently represent a substituted group
• R 33 represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
• R 11 and R 12 are each independently an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or a primary amine salt structure or secondary amine salt as a substituent.
• unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms are more preferable.
• the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms for R 11 and R 12 is preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, and an unsubstituted A saturated aliphatic hydrocarbon group is more preferred, and an ethyl group, isopropyl group, t-butyl group or cyclohexyl group is more preferred.
• R 11 and R 12 each independently have 2 to 2 carbon atoms having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group.
• 7 may be an aliphatic hydrocarbon group. Although the aliphatic hydrocarbon group having 2 to 7 carbon atoms may have two or more substituents, an embodiment having only one substituent is also one of preferred embodiments of the present invention.
• R 21 and R 22 each independently represent an optionally substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.
• R 21 and R 22 are unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms, or 1 to 7 carbon atoms having an amino group or a quaternary ammonium group as a substituent. is preferred, and an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferred.
• the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in R 21 and R 22 or the aliphatic hydrocarbon group having 1 to 7 carbon atoms having the substituent is preferable. Aspects are similar to those shown in the description of R 11 and R 12 respectively.
• R 31 and R 32 are unsubstituted aliphatic hydrocarbon groups having 1 to 7 carbon atoms, or 1 to 7 carbon atoms having an amino group or a quaternary ammonium group as a substituent. is preferred, and an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferred.
• R 31 and R 32 are preferably the above unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the above substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms. Aspects are similar to those shown in the description of R 11 and R 12 respectively.
• R 33 represents an optionally substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms and is an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms. is preferred, an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms is more preferred, and a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferred.
• R 33 is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a t-butyl group, more preferably an ethyl group.
• urea compounds include, but are not limited to, dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, and diisopropylisourea.
• the total content of urea compounds and the like is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 8.0 parts by mass, and 1.0 to 6.0 parts by mass with respect to 100 parts by mass of the specific resin. Part is more preferred.
• the urea compounds and the like may be used singly or in combination of two or more. When two or more are used in combination, the total content thereof is preferably within the above range.
• 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, as long as the effects of the present invention can be obtained.
• additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, as long as the effects of the present invention can be obtained.
• Organic titanium compounds, antioxidants, anti-agglomerating agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (for example, antifoaming agents, flame retardants, etc.) can be blended. Properties such as film physical properties can be adjusted by appropriately containing these components. These components are described, for example, from paragraph number 0183 of JP-A-2012-003225 (paragraph number 0237 of corresponding US Patent Application Publication No.
• the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
• surfactant various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used.
• the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
• the liquid properties (especially fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving are further improved. can do. That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved. , the coatability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with little unevenness in thickness.
• Fluorinated surfactants include compounds described in paragraph 0328 of WO2021/112189. The contents of which are incorporated herein.
• the fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta)
• a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
• the weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
• a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as a fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, the contents of which are incorporated herein.
• Commercially available products include Megafac RS-101, RS-102 and RS-718K manufactured by DIC Corporation.
• the fluorine content in the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass.
• a fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and saving liquid, and has good solubility in the composition.
• Silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants are described in paragraphs 0329 to 0334 of WO 2021/112189, respectively. compound. The contents of which are incorporated herein.
• the surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
• a higher fatty acid derivative such as behenic acid or behenic acid amide is added in order to prevent polymerization inhibition caused by oxygen. may be unevenly distributed on the surface of the resin composition of the present invention
• the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types thereof may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
• the resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator.
• a thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be advanced, so that the solvent resistance can be further improved.
• the photopolymerization initiator described above may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
• thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.
• thermal polymerization initiator When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , more preferably 0.5 to 15% by mass.
• One type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.
• the resin composition of the present invention may contain inorganic particles.
• inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
• the average particle diameter of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, still more preferably 0.03 to 1.0 ⁇ m, and 0.04 to 0.5 ⁇ m. Especially preferred.
• the average particle size of the inorganic particles is the primary particle size and the volume average particle size.
• the volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, the centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method can be used.
• the composition of the present invention may contain an ultraviolet absorber.
• an ultraviolet absorber As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used. Specific examples of UV absorbers include compounds described in paragraphs 0341 to 0342 of WO2021/112189. The contents of which are incorporated herein.
• the above various ultraviolet absorbers may be used singly or in combination of two or more.
• the composition of the present invention may or may not contain an ultraviolet absorber, but when it does, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid mass of the composition of the present invention. It is preferably at least 1% by mass, more preferably at least 0.01% by mass and not more than 0.1% by mass.
• the resin composition of this embodiment may contain an organic titanium compound.
• an organic titanium compound By containing the organic titanium compound in the resin composition, it is possible to form a resin layer having excellent chemical resistance even when cured at a low temperature.
• Organotitanium compounds that can be used include those in which organic groups are attached to titanium atoms through covalent or ionic bonds. Specific examples of organotitanium compounds are shown below in I) to VII): I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the resin composition is good and a good curing pattern can be obtained.
• titanium bis(triethanolamine) diisopropoxide titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate ), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.
• Tetraalkoxytitanium compounds for example titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide.
• titanium tetramethoxypropoxide titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis ⁇ 2,2-(allyloxymethyl) butoxide ⁇ ] and the like.
• Titanocene compounds for example, pentamethylcyclopentadienyltitanium trimethoxide, bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis( ⁇ 5-2, 4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.
• Monoalkoxy titanium compounds for example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide and the like.
• Titanium oxide compounds for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.
• the organotitanium compound at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds provides better chemical resistance. It is preferable from the viewpoint of performance.
• titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide) and bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H) -pyrrol-1-yl)phenyl)titanium is preferred.
• the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin.
• the amount is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance more effectively. Excellent.
• compositions of the present invention may contain antioxidants.
• an antioxidant as an additive, it is possible to improve the elongation properties of the cured film and the adhesion to metal materials.
• Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Specific examples of antioxidants include compounds described in paragraphs 0348 to 0357 of WO2021/112189. The contents of which are incorporated herein.
• the amount of antioxidant to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin.
• the addition amount 0.1 parts by mass or more By making the addition amount 0.1 parts by mass or more, the effect of improving elongation characteristics and adhesion to metal materials can be easily obtained even in a high-temperature and high-humidity environment.
• the interaction with the agent improves the sensitivity of the resin composition.
• Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
• the resin composition of the present embodiment may contain an anti-aggregation agent as necessary.
• Anti-aggregation agents include sodium polyacrylate and the like.
• the aggregation inhibitor may be used alone or in combination of two or more.
• the composition of the present invention may or may not contain an anti-aggregating agent, but when it is included, the content of the anti-aggregating agent is 0.01% by mass relative to the total solid mass of the composition of the present invention. It is preferably at least 10% by mass, more preferably at least 0.02% by mass and not more than 5% by mass.
• the resin composition of the present embodiment may contain a phenolic compound as necessary.
• phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylene tris-FR-CR, BisRS-26X (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F (these are trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) and the like.
• one type of phenolic compound may be used alone, or two or more types may be used in combination.
• the composition of the present invention may or may not contain a phenolic compound, but if it does, the content of the phenolic compound is 0.01% by mass relative to the total solid mass of the composition of the present invention. It is preferably at least 30% by mass, more preferably at least 0.02% by mass and not more than 20% by mass.
• Other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolac resins, resole resins, polyhydroxystyrene resins, and copolymers thereof.
• Other polymer compounds may be modified products into which cross-linking groups such as methylol groups, alkoxymethyl groups and epoxy groups have been introduced.
• composition of the present invention may or may not contain other polymer compounds, but when it does, the content of the other polymer compound is 0 relative to the total solid mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less.
• the viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 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 preferred. If it is the said range, it will become easy to obtain a coating film with high uniformity. If it is 1,000 mm 2 /s or more, it is easy to apply the film with a film thickness required, for example, as an insulating film for rewiring . A coating 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 is improved. Methods for maintaining the moisture content include adjusting the humidity in the 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.
• metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are included, the total of these metals is preferably within the above range.
• a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention.
• Examples include a method of performing filter filtration on the raw material constituting the product, and performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.
• the resin composition of the present invention preferably has a halogen atom content of less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass from the viewpoint of wiring corrosion. is more preferred.
• 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.
• Halogen atoms include chlorine and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges.
• ion exchange treatment and the like are preferably mentioned.
• a conventionally known container can be used as the container for the resin composition of the present invention.
• the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resin are used. It is also preferred to use bottles with a seven-layer structure. Examples of such a container include the container described in JP-A-2015-123351.
• the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
• Curing of the resin composition is preferably by heating, and the heating temperature is more preferably in the range of 120°C to 400°C, further preferably in the range of 140°C to 380°C, and 170°C. It is particularly preferred to be in the range of -350°C.
• the form of the cured product of the resin composition is not particularly limited, and may be selected from film, rod, sphere, pellet, etc. according to the application. In the present invention, the cured product is preferably in the form of a film.
• pattern processing of the resin composition can be used to form protective films on walls, form via holes for conduction, adjust impedance, capacitance or internal stress, and impart heat dissipation functions. You can also choose the shape.
• the film thickness of the cured product (film made of the cured product) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
• the shrinkage ratio 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 higher, more preferably 80% or higher, and even more preferably 90% or higher. If it is 70% or more, a cured product having excellent mechanical properties may be obtained.
• 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 components described above.
• the mixing method is not particularly limited, and conventionally known methods can be used. Mixing can be performed by mixing with a stirring blade, mixing with a ball mill, mixing by rotating the tank itself, or the like.
• the temperature during mixing is preferably 10-30°C, more preferably 15-25°C.
• the filter pore size is, for example, 5 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
• the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. HDPE (high density polyethylene) is more preferable when the material of the filter is polyethylene.
• a filter that has been pre-washed with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel for use.
• filters with different pore sizes or materials may be used in combination.
• a connection mode for example, a mode in which an HDPE filter with a pore size of 1 ⁇ m is connected in series as a first stage and an HDPE filter with a pore size of 0.2 ⁇ m as a second stage are connected in series.
• various materials may be filtered multiple times.
• circulation filtration may be used.
• you may filter by pressurizing.
• the pressure to be applied is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less.
• impurities may be removed using an adsorbent.
• You may combine filter filtration and the impurity removal process using an adsorbent.
• a known adsorbent can be used as the adsorbent. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
• the resin composition filled in the bottle may be subjected to a degassing step under reduced pressure.
• the method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition onto a substrate to form a film. Further, the method for producing a cured product of the present invention includes the 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. It is more preferable to include a developing step of forming a pattern by The method for producing a cured product of the present invention includes the film forming step, the exposing step, the developing step, and a heating step of heating the pattern obtained by the developing step, and after development of exposing the pattern obtained by the developing step. It is particularly preferred to include at least one of the exposure steps. Moreover, the manufacturing method of the present invention preferably includes the film forming step and the step of heating the film. Details of each step will be described 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 onto 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 substrate to form a film.
• the type of base material can be appropriately determined according to the application, and includes semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, A magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, Fe (for example, a substrate formed of a metal, or a substrate having a metal layer formed by plating, vapor deposition, etc.) ), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, plasma display panel (PDP) electrode plates, etc., and are not particularly limited.
• semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, A magnetic film, a reflective film, a metal substrate such as Ni, Cu, Cr, Fe (for example, a substrate formed of a metal, or a substrate having
• a semiconductor fabrication substrate is particularly preferable, and a silicon substrate, a Cu substrate and a mold substrate are more preferable.
• these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
• HMDS hexamethyldisilazane
• the shape of the substrate is not particularly limited, and may be circular or rectangular.
• the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm.
• the short side length is, for example, 100 to 1000 mm, preferably 200 to 700 mm.
• the base material for example, a plate-like base material (substrate), preferably a panel-like base material (substrate) is used.
• the resin layer or metal layer serves as the base material.
• Specific means to be applied include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, An inkjet method and the like are exemplified. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet method is more preferable, and spin coating from the viewpoint of uniformity of film thickness and productivity. and slit coating methods are preferred.
• a film having a desired thickness can be obtained by adjusting the solid content concentration and application conditions of the resin composition according to the method.
• the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, inkjet method, etc.
• slit coating and spray coating are preferable for rectangular substrates.
• method, inkjet method, and the like are preferred.
• spin coating for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
• a method of transferring a coating film, which is formed on a temporary support in advance by the above application method, onto a base material can also be applied.
• the transfer method the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can also be preferably used in the present invention.
• a step of removing excess film at the edge of the substrate may be performed.
• processes include edge bead rinsing (EBR), back rinsing, and the like.
• EBR edge bead rinsing
• a pre-wetting step may also be employed in which the base material is coated with various solvents before applying the resin composition 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) to remove the solvent (drying step) after the film forming step (layer forming step). That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step. Moreover, the drying step is preferably performed after the film formation step and before the exposure step.
• the drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. Moreover, you may dry by pressure reduction.
• the drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 2 minutes to 7 minutes.
• the film may be subjected to an exposure step that selectively exposes the film. That is, the method for producing a cured product of the present invention 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. Also, by selectively exposing, the film is formed with exposed regions (exposed portions) and non-exposed regions (non-exposed portions). The amount of exposure is not particularly defined as long as the resin composition of the present invention can be cured . is more preferred.
• the exposure wavelength can be appropriately determined in the range of 190-1,000 nm, preferably 240-550 nm.
• the exposure wavelength is as follows: (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; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc.
• the resin composition of the present invention exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, particularly high exposure sensitivity can be obtained.
• the method of exposure is not particularly limited as long as at least a part of the film made of the resin composition of the present invention is exposed. mentioned.
• the film may be subjected to a step of heating 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 exposed film 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 heating rate in the post-exposure heating step is preferably 1 to 12° C./min, more preferably 2 to 10° C./min, still more preferably 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature. Also, the rate of temperature increase may be appropriately changed during heating.
• the heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters and the like can be used. Moreover, it is also preferable to carry out the heating in an atmosphere of low oxygen concentration by, for example, flowing an inert gas such as nitrogen, helium or argon.
• the film after exposure may be subjected to a development step in which the film is developed using a developer to form a pattern.
• the method for producing a cured product of the present invention may include a development step of developing a film exposed in the exposure step with a developer to form a pattern. By performing development, one of the exposed and non-exposed portions of the film is removed to form a pattern.
• development in which the unexposed portion of the film is removed by the development process is called negative development
• development in which the exposed portion of the film is removed by the development process is called positive development.
• Examples of the developer used in the development step include a developer containing an alkaline aqueous solution or an organic solvent.
• basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
• TMAH tetramethylammonium hydroxide
• potassium hydroxide sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine , dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, Butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammoni
• the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, based on the total mass of the developer. is more preferred.
• the compound described in paragraph 0387 of International Publication No. 2021/112189 can be used as the organic solvent.
• Alcohols such as methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, and triethylene glycol, and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, Dimethylformamide and the like are also suitable.
• the organic solvent can be used singly or in combination of two or more.
• a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, and cyclopentanone and ⁇ -butyrolactone. and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.
• the content of the organic solvent relative to the total weight 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 90% by mass or more is particularly preferable. Moreover, the content may be 100% by mass.
• the developer may further contain other components.
• Other components include, for example, 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.
• the type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned. From the viewpoint of permeability of the developer, removability of the non-image area, and efficiency in production, a method of supplying the developer with a straight nozzle or a method of continuously supplying the developer with a spray nozzle is preferable.
• the method of supplying with a spray nozzle is more preferable.
• the substrate is spun to remove the developer from the substrate.
• a step of removing from above may be employed, and this step may be repeated multiple times.
• the method of supplying the developer in the development process includes a process in which the developer is continuously supplied to the base material, a process in which the developer is kept substantially stationary on the base material, and a process in which the developer exceeds the developer on the base material.
• a process of vibrating with sound waves or the like and a process of combining them can be employed.
• 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 washed (rinsed) with a rinse.
• a method of supplying the rinse liquid before the developer in contact with the pattern is completely dried may be employed.
• Rinse liquid When the developer is an alkaline aqueous solution, water, for example, can be used as the rinse.
• the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) is used as the rinse liquid. be able to.
• the organic solvent when the rinse liquid contains an organic solvent examples include the same organic solvents as those exemplified when the developer contains an organic solvent.
• the organic solvent contained in the rinse liquid is preferably an organic solvent different from the organic solvent contained in the developer, and more preferably an organic solvent having a lower pattern solubility than the organic solvent contained in the developer.
• the organic solvent can be used singly or in combination of two or more.
• the organic solvent can be used singly or in combination of two or more.
• cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA and PGME are particularly preferred, cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, PGMEA and PGME are more preferred, and cyclohexanone and PGMEA are more preferred. More preferred.
• the rinse liquid contains an organic solvent
• the rinse liquid is preferably 50% by mass or more of the organic solvent, more preferably 70% by mass or more of the organic solvent, and 90% by mass or more of the organic solvent. is more preferred. Further, 100% by mass of the rinse liquid may be an organic solvent.
• the rinse liquid may contain at least one of a basic compound and a base generator.
• a basic compound an organic base is preferable from the viewpoint of reliability when it remains in the film after curing (adhesion to the substrate when the cured product is further heated).
• a basic compound having an amino group is preferable, and primary amine, secondary amine, tertiary amine, ammonium salt, tertiary amide, etc. are preferable.
• the basic compound is preferably one that hardly remains in the cured film (obtained cured product). It is preferable that the remaining amount is not easily reduced before heating. Therefore, the boiling point of the basic compound is preferably 30° C. to 350° C., more preferably 80° C. to 270° C., even more preferably 100° C. to 230° C.
• 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 boiling point of the organic solvent is 100° C.
• the boiling point of the basic compound used is preferably 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.
• 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 base generator is the same as the preferred embodiments of the base generator contained in the composition described above.
• the base generator is preferably a thermal base generator.
• the basic compound and base generator contained in the rinse solution may be selected in consideration of the solubility in the solvent in the rinse solution.
• the content of the compound corresponding to at least one of the basic compound and the base generator is 10% by mass or less with respect to the total mass of the rinse solution. is preferable, and it is more preferably 5% by mass or less. Although the lower limit of the content is not particularly limited, it is preferably 0.1% by mass or more, for example.
• the content of the compound corresponding to at least one of the basic compound and the base generator is equal to the total solid content of the rinse liquid. It is also preferable that it is 70 to 100% by mass.
• the rinse solution may contain only one kind of at least one of the basic compound and the base generator, or may contain two or more kinds. .
• the total is preferably within the above range.
• the rinse solution may further contain other components.
• Other components include, for example, known surfactants and known antifoaming agents.
• the method of supplying the rinse solution is not particularly limited as long as the desired pattern can be formed, and includes a method of immersing the base material in the rinse solution, a method of supplying the rinse solution to the base material by piling up the base material, and a method of supplying the rinse solution to the base material by showering. and a method of continuously supplying the rinsing liquid onto the substrate by means of a straight nozzle or the like.
• the permeability of the rinse liquid From the viewpoint of the permeability of the rinse liquid, the removability of the non-image areas, and the efficiency in manufacturing, there are methods of supplying the rinse liquid using a shower nozzle, a straight nozzle, a spray nozzle, etc., and a continuous supply method using a spray nozzle is preferable. From the viewpoint of the permeability of the rinsing liquid to the image area, the method of supplying the rinsing liquid with a spray nozzle is more preferable.
• the type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned.
• the rinsing step is preferably a step of supplying the rinse liquid to the film after exposure through a straight nozzle or a step of continuously supplying the same, and more preferably a step of supplying the rinse liquid through a spray nozzle.
• the method of supplying the rinse liquid in the rinse step includes a process in which the rinse liquid is continuously supplied to the base material, a process in which the rinse liquid is kept substantially stationary on the base material, and a process in which the rinse liquid is kept on the base material in a substantially stationary state. A process of vibrating with sound waves or the like and a process of combining them can be adopted.
• the rinse 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 specified, but is preferably 10 to 45°C, more preferably 18 to 30°C.
• the development step may include a step of bringing the pattern into contact with the processing solution after processing with the developer or after washing the pattern with the rinse solution.
• a method of supplying the processing liquid before the developing liquid or rinsing liquid in contact with the pattern is completely dried may be adopted.
• 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 the base generator are the same as the preferred embodiments of the organic solvent and at least one of the basic compound and the base generator used in the rinse solution described above. .
• the method of supplying the treatment liquid to the pattern the same method as the above-described method of supplying the rinsing liquid can be used, and the preferred embodiments are also the same.
• the content of the compound corresponding to at least one of the basic compound and the base generator in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, relative to the total mass of the treatment liquid. preferable. Although the lower limit of the content is not particularly limited, it is preferably 0.1% by mass or more, for example. Further, when at least one of the basic compound and the base generator is solid in the environment where the treatment liquid is used, the content of the compound corresponding to at least one of the basic compound and the base generator is the total solid content of the treatment liquid. It is also preferable that it is 70 to 100% by mass.
• the treatment liquid may contain at least one of a basic compound and a base generator, or may contain two or more of them. .
• the total is preferably within the above range.
• the pattern obtained by the development process may be subjected to a heating process for 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 by the developing step. Moreover, 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 the developing step or a film obtained by the film forming step. In the heating step, a resin such as a polyimide precursor is cyclized into 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, still 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 in the pattern by the action of the base generated from the base generator by heating.
• Heating in the heating step is preferably carried out at a temperature rising rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature.
• the rate of temperature increase is more preferably 2 to 10°C/min, still more preferably 3 to 10°C/min.
• By setting the temperature increase rate to 1°C/min or more it is possible to prevent excessive volatilization of the acid or solvent while ensuring productivity.
• the residual stress of the object can be relaxed.
• the temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C.
• the temperature at the start of heating refers to the temperature at which the process of heating up to the maximum heating temperature is started.
• the temperature of the film (layer) after drying is, for example, the boiling point of the solvent contained in the resin composition of the present invention.
• the heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, even more preferably 15 to 240 minutes.
• the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, further preferably 100° C. or higher, from the viewpoint of adhesion between layers. 120° C. or higher is particularly preferred.
• 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 done in stages. As an example, the temperature is raised from 25° C. to 120° C. at 3° C./min, held at 120° C. for 60 minutes, heated from 120° C. to 180° C. at 2° C./min, and held at 180° C. for 120 minutes. , may be performed. It is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film.
• the pretreatment step is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
• the pretreatment may be performed in two or more steps.
• the first pretreatment step may be performed in the range of 100 to 150°C, and then the second pretreatment step may be performed in the range of 150 to 200°C. good. Further, 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 carried out in an atmosphere of low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium or argon, or under reduced pressure, in order to prevent decomposition of the specific resin.
• the oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
• a heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, a hot air oven, an infrared oven and the like.
• the pattern obtained by the development step (the pattern after rinsing when the rinsing step is performed) is subjected to a post-development exposure step of exposing the pattern after the development step instead of or in addition to the heating step.
• 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 or the like proceeds by exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group proceeds by exposure of a photoacid generator is promoted. can do.
• the post-development exposure step at least part 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. preferable.
• the post-development exposure step can be performed using, for example, the light source used in the exposure step described above, and broadband light is preferably used.
• the pattern obtained by the development step may be subjected to a metal layer forming step 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 by the developing step (preferably subjected to at least one of the heating step and the post-development exposure step). is preferred.
• the metal layer is not particularly limited, and existing metal species can be used. 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 of forming the metal layer is not particularly limited, and existing methods can be applied.
• use the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Patent No. 7888181B2, US Patent No. 9177926B2 can do.
• photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lift-off, electroplating, electroless plating, etching, printing, and a combination thereof can be considered.
• a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be used.
• a preferred embodiment of plating is electroplating using a 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 cured product of the present invention can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, and stress buffer films.
• pattern formation by etching of 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 can be used.
• the method for producing the cured product of the present invention or the cured product of the present invention can also be used for the production of plates such as offset plates or screen plates, for etching molded parts, for protective lacquers and dielectrics in electronics, especially microelectronics. It can also be used for the production of layers and the like.
• 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 of the present invention is a laminate containing two or more layers made of a cured product, and may be a laminate in which three or more layers are laminated. Of the two or more layers of the cured product contained in the laminate, at least one is a layer made of the cured product of the present invention, and the shrinkage of the cured product, or the 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 laminate are layers made of the cured product of the present invention.
• the method for producing the laminate of the present invention preferably includes the method for producing the cured product of the present invention, and more preferably includes repeating the method for producing the cured product of the present invention multiple times.
• the laminate of the present invention includes two or more layers made of the cured material and a metal layer between any of the layers made of the cured material.
• the metal layer is preferably formed by the metal layer forming step. That is, it is preferable that the method for producing a laminate of the present invention further includes a metal layer forming step of forming a metal layer on the layer made of the cured product between the methods for producing the cured product performed multiple times. Preferred aspects of the metal layer forming step are as described above.
• the laminate for example, a laminate containing at least a layer structure in which three layers of a layer made of the first cured product, a metal layer, and a layer made of the second cured product are laminated in this order is preferable. be done.
• both the layer comprising the first cured product and the layer comprising the second cured product are layers comprising the cured product of the present invention.
• the resin composition of the present invention used for forming the layer comprising the first cured product and the resin composition of the present invention used for forming the layer comprising 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 a metal wiring such as a rewiring layer.
• the method for manufacturing the laminate of the present invention includes a lamination step.
• the lamination step means that the surface of the pattern (resin layer) or metal layer is again subjected to (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step and development It is a series of steps including performing at least one of the post-exposure steps in this order. However, at least one of (a) the film forming step and (d) the heating step and the post-development exposure step may be repeated. Moreover, after at least one of the (d) heating step and the post-development exposure step, (e) a metal layer forming step may be included. Needless to say, the lamination step may further include the drying step and the like as appropriate.
• a surface activation treatment process may be further performed.
• a plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.
• the lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
• Each of the layers described above may have the same composition, shape, film thickness, etc., or may differ from each other.
• a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after providing the metal layer.
• the film forming step, (b) the exposure step, (c) the developing step, (d) at least one of the heating step and the post-development exposure step, and (e) the metal layer forming step are repeated in this order.
• the film forming step, (d) at least one of the heating step and the post-development exposure step, and (e) the 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 subjecting at least part of the metal layer and the resin composition layer to surface activation treatment.
• the surface activation treatment step is usually performed after the metal layer formation 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 surface activation treatment.
• the metal layer forming step may be performed.
• the surface activation treatment may be performed only on at least part of the metal layer, may be performed only on at least part of the resin composition layer after exposure, or may be performed on the metal layer and the resin composition layer after exposure. Both may be done at least partially, respectively.
• the surface activation treatment is preferably performed on at least part of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the area of the metal layer on which the resin composition layer is formed.
• the surface of the metal layer By subjecting the surface of the metal layer to the surface activation treatment in this manner, the adhesiveness to the resin composition layer (film) provided on the surface can be improved.
• the present invention also discloses a semiconductor device comprising the cured product of the present invention or the laminate of the present invention. Moreover, this invention also discloses the manufacturing method of the semiconductor device containing the manufacturing method of the hardened
• Specific examples of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer can refer to the description of paragraphs 0213 to 0218 of JP-A-2016-027357 and the description of FIG. The contents of which are incorporated herein.
• Resin 2 is presumed to be a structure represented by the following formula (P-2).
• P-2 weight average molecular weight
• resin 2 with Mw of 5,000, resin 2 with Mw of 10,000, and resin 2 with Mw of 30,000 can also be obtained by appropriately adjusting the equivalent of 4,4′-diaminodiphenyl ether. Synthesized.
• a precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.
• the resulting reaction solution was added to 8 liters of ethyl alcohol to form a precipitate consisting of crude polymer.
• the resulting crude polymer was separated by filtration and dissolved in 5.0 liters of tetrahydrofuran to obtain a crude polymer solution.
• the resulting crude polymer solution was dropped into 60 liters of water to precipitate the polymer, and the resulting precipitate was separated by filtration and vacuum dried to obtain a powdery polymer (resin 9).
• the molecular weight of Resin 9 was measured by gel permeation chromatography (converted to standard polystyrene), the weight average molecular weight (Mw) was 25,000.
• each resin composition was obtained by mixing the components shown in the table below.
• the components shown in the table below were mixed to obtain comparative compositions.
• the content (compounding amount) of each component described in the table other than the solvent was the amount (parts by mass) described in the "parts by mass” column of each column of the table.
• the content (blending amount) of the solvent is such that the solid content concentration of the composition is the value (% by mass) of "solid content concentration” in the table, and the ratio of the content of each solvent to the total mass of the solvent (mass The ratio) was set to the ratio described in the "ratio" column in the table.
• the resulting resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter with a pore width of 0.8 ⁇ m.
• the description of "-" indicates that the composition does not contain the corresponding component.
• the acid value of each resin was measured by the method described above, and the measurement results are shown in the table.
• Resins 1 to 12 obtained by the above synthesis examples
• [Polymerizable compound] ⁇ M-1 to M-3 compounds having the following structures, the subscripts in parentheses represent the number of repetitions.
• - U-1 to U-3 compounds having the following structures.
• A-1 to A-21 Compounds having the following structures. All of A-1 to A-21 are compounds corresponding to the specific metallocene compounds described above. • AR-1: a compound having the following structure. AR-1 is a compound that does not correspond to the specific metallocene compounds described above.
• Viscosity change rate (%)
• composition -Working stability (composition)-
• the composition was placed in a transparent bottle under yellow light at 23° C. for 12 hours, and the change in viscosity was measured.
• the yellow lamp HITACHI, model number: FHF32Y-F, Toshiba Lighting & Technology Co., Ltd., model number: LEEM-40403YY-01, or NEC, model number: FHF32Y-F/LSI is used, and the composition is extracted from the yellow lamp.
• the distance to the transparent bottle containing the sample was about 1 m.
• composition film was left under a yellow light for 12 hours, and the pattern shape was evaluated.
• the details of the evaluation method are as follows.
• the composition was applied on a silicon wafer by spin coating, dried on a hot plate at 100 ° C. for 5 minutes, and coated on the silicon wafer in the column "Thickness ( ⁇ m)" of the table. A composition film having the thickness described in 1 was formed.
• the composition film on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C).
• the exposure wavelength is the wavelength described in the "Exposure wavelength (nm)" column of the table, and the exposure energy is 200, 300, 400, 500, 600, 700, 800 mJ/cm 2 , and the exposure energy is 5 to 25 ⁇ m in increments of 1 ⁇ m. Exposure was performed using a photomask on which a 1:1 line-and-space pattern was formed. In the examples described as “D” in the "Exposure conditions” column of the table, the composition film on the silicon wafer was exposed using a direct exposure apparatus (ADTEC DE-6UH III).
• ADTEC DE-6UH III direct exposure apparatus
• the exposure wavelength is the wavelength described in the “Exposure wavelength (nm)” column of the table, and the exposure energy is 200, 300, 400, 500, 600, 700, 800 mJ / cm 2 , and the laser direct imaging exposure is 5 to 5.
• a 1:1 line-and-space pattern was exposed at intervals of 1 ⁇ m up to 25 ⁇ m.
• the exposed composition film was developed for 60 seconds using the developer described in the "developer” column of the table, and the line width of the resulting pattern was evaluated. A small change in line width with respect to a change in exposure energy indicates a wide exposure latitude, which is a favorable result.
• the measurement limit is 5 ⁇ m, and evaluation was performed according to the following evaluation criteria. The evaluation results are described in the column of "working stability (composition film)" in the table. ⁇ Evaluation Criteria>> A: Less than 10 ⁇ m B: 10 ⁇ m or more and less than 20 ⁇ m C: 20 ⁇ m or more
• the prepared resin composition or comparative composition was applied onto a silicon wafer by spin coating.
• the silicon wafer is dried on a hot plate at 100° C. for 5 minutes, and a resin composition layer having a uniform thickness and having the thickness described in the “Thickness ( ⁇ m)” column of the table is formed on the silicon wafer. formed.
• the exposure condition was described as "M”
• the resin composition layer on the silicon wafer was exposed using a stepper.
• the entire surface of the photosensitive film was exposed without using a photomask using light having a wavelength indicated in "Exposure Wavelength (nm)" in the table.
• the exposure amount was 500 mJ/cm 2 .
• the resin film obtained in each example was cured using an infrared lamp heating device (RTP-6, manufactured by Advance Riko Co., Ltd.). In a nitrogen atmosphere, the temperature was raised at a temperature elevation rate of 10°C/min, and after reaching 230°C, the temperature was maintained for the time described in "curing time (min)” to form a cured film. The obtained cured film was immersed in the following chemicals under the following conditions, and the dissolution rate was calculated.
• RTP-6 infrared lamp heating device
• the resin composition of the present invention is excellent in working stability under yellow light.
• the comparative composition according to Comparative Example 1 does not contain a specific metallocene compound. It can be seen that the comparative composition has poor working stability under a yellow light.
• Example 101 The resin composition used in Example 1 was left under a yellow light for 12 hours, and then applied in a layered form by spin coating to the surface of the thin copper layer of the resin substrate having the thin copper layer formed on the surface. , and dried at 100° C. for 5 minutes to form a photosensitive film having a thickness of 20 ⁇ m, which was then 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, the film was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
• NSR1505 i6 manufactured by Nikon Corporation
• the temperature was raised at a rate of 10° C./min, reaching 230° C., and then maintained at 230° C. for 180 minutes to form an interlayer insulating film for rewiring layers.
• This interlayer insulating film for rewiring layer was excellent in insulating properties.
• a semiconductor device was manufactured using these interlayer insulating films for rewiring layers, it was confirmed that the device operated without any problem.

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• 2023
  • 2023-02-16 WO PCT/JP2023/005417 patent/WO2023157911A1/ja not_active Ceased
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