Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
  • C08F290/145—Polyamides; Polyesteramides; Polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
• • 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
  • C08K5/54—Silicon-containing compounds
  • C08K5/544—Silicon-containing compounds containing nitrogen
• • 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
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/16—Coating processes; Apparatus therefor
  • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/68—Organic materials, e.g. photoresists
  • H10P14/683—Organic materials, e.g. photoresists carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/69—Inorganic materials
  • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
  • H10P14/6921—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon
  • H10P14/6922—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses containing silicon the material containing Si, O and at least one of H, N, C, F or other non-metal elements, e.g. SiOC, SiOC:H or SiONC

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 produced from resin compositions containing resins are being used in various fields.
• cyclized resins such as polyimide are used in various applications because of their excellent heat resistance and insulating properties.
• the applications are not particularly limited, but for example, in the case of semiconductor devices for mounting, they can be used as insulating films, sealing materials, or protective films. They are also used as base films or coverlays for flexible substrates.
• the cyclized resin such as a polyimide
• a resin composition that includes the cyclized resin or a precursor of the cyclized resin, such as a polyimide precursor.
• a resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate.
• the precursor of the cyclized resin, such as a polyimide precursor is cyclized, for example, by heating, and becomes a cyclized resin, such as a polyimide, in the cured product.
• the resin composition can be applied by a known coating method, etc., it can be said to have excellent adaptability in manufacturing, for example, high degree of freedom in designing the shape, size, application position, etc. of the resin composition when applied.
• cyclized resins such as polyimide
• industrial application development of the above-mentioned resin composition is expected to continue.
• resin materials are required to have excellent adhesion to substrates, and various methods for improving adhesion to substrates have been investigated.
• Patent Document 1 describes a curable resin composition containing at least one resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor, and a photobase generator having an alkoxysilyl group.
• Patent Document 2 describes a negative type photosensitive resin composition containing the following components: (A) a polyimide precursor; (B) a photopolymerization initiator; (C) a silane coupling agent having a specific structure; and (D) an organic solvent containing at least one selected from the group consisting of ⁇ -butyrolactone, dimethyl sulfoxide, tetrahydrofurfuryl alcohol, ethyl acetoacetate, dimethyl succinate, dimethyl malonate, and ⁇ -caprolactone.
• the present invention aims to provide a resin composition that can give a cured product that has excellent adhesion to a substrate, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product.
• R 1 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and when there is a plurality of R 1 , they may be the same or different
• R 2 is a hydrogen atom or any organic group not corresponding to the above-mentioned R 1 , and when there is a plurality of R 2 , they may be the same or different, at least two of R 1 and R 2 may be bonded to form a ring structure
• n represents an integer of 1 to 3
• m represents an integer of 1 or more
• R 3 represents an m-valent organic group.
• R 1 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and when there is a plurality of R 1 , they may be the same or different
• R 2 is a hydrogen atom or any organic group not corresponding to the above-mentioned R 1 , and when there is a plurality of R 2 , they may be the same or different
• at least two of R 1 and R 2 may be bonded to form a ring structure
• n represents an integer of 1 to 3
• L represents a divalent linking group
• R 4 represents a hydrogen atom or a monovalent organic group.
• R 3 in the above formula (A1-1) is a group represented by the following formula (R3-1):
• L 31 each independently represents a divalent linking group
• R 31 each independently represents an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or a group represented by *-C( ⁇ O)R 32 -#
• * represents a bonding site to the nitrogen atom in formula (R3-1)
• # represents a bonding site to L 32 in formula (R3-1)
• R 32 represents an organic group
• m represents an integer of 1 or more, when m is 1, L 32 represents a hydrogen atom or a substituent, and when m is 2 or more, L 32 represents a single bond or an m-valent linking group
• * represents a bonding site to the silicon
• R 21 is an organic group having an HSP value of 17.0 to 27.0 MPa 1/2 , and when there is a plurality of R 21 , they may be the same or different
• R 22 is a hydrogen atom or any organic group not corresponding to the above R 21 , and when there is a plurality of R 22 , they may be the same or different, at least two of R 21 and R 22 may be bonded to form a ring structure
• n represents an integer of 1 to 3
• m represents an integer of 1 or more
• R 23 represents an m-valent organic group.
• ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the resin is a polyimide or a polyimide precursor.
• ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the resin is a polyimide.
• ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, further comprising a photopolymerization initiator.
• ⁇ 9> The resin composition according to ⁇ 8>, further comprising a sensitizer.
• ⁇ 10> The resin composition according to any one of ⁇ 1> to ⁇ 9>, further comprising a compound having a urea bond.
• ⁇ 11> The resin composition according to any one of ⁇ 1> to ⁇ 10>, further comprising a polymerizable compound having at least one of a urea bond and a urethane bond.
• ⁇ 12> The resin composition according to any one of ⁇ 1> to ⁇ 11>, further comprising a solvent having at least one of an amide bond or a hydroxyl group.
• ⁇ 13> The resin composition according to any one of ⁇ 1> to ⁇ 12>, which is used for forming an interlayer insulating film for a redistribution layer.
• ⁇ 14> A cured product obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 13>.
• ⁇ 15> A laminate comprising two or more layers made of the cured product according to ⁇ 14>, and a metal layer between any two adjacent layers made of the cured product.
• ⁇ 16> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 13> onto a substrate to form a film.
• the method for producing a cured product according to ⁇ 16> comprising: an exposure step of selectively exposing the film to light; and a development step of developing the film with a developer to form a pattern.
• a method for producing a cured product according to ⁇ 16> or ⁇ 17> 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 ⁇ 16> to ⁇ 18>.
• a method for producing a semiconductor device comprising the method for producing a cured product according to any one of ⁇ 16> to ⁇ 18>.
• a semiconductor device comprising the cured product according to ⁇ 14>.
• the present invention provides a resin composition that can produce a cured product that has excellent adhesion to a substrate, a cured product obtained by curing the resin composition, a laminate that includes the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device that includes the method for producing the cured product, and a semiconductor device that includes the cured product.
• a numerical range expressed using the symbol "to” means a range that includes the numerical values before and after "to” as the lower limit and upper limit, respectively.
• the term “process” includes not only an independent process but also a process that cannot be clearly distinguished from other processes, so long as the process can achieve its intended effect.
• groups (atomic groups) when there is no indication of whether they are substituted or unsubstituted, the term encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups).
• an "alkyl group” encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
• exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation.
• (meth)acrylate means both or either of “acrylate” and “methacrylate”
• (meth)acrylic means both or either of “acrylic” and “methacrylic”
• (meth)acryloyl means both or either of “acryloyl” and “methacryloyl”.
• Me represents a methyl group
• Et represents an ethyl group
• Bu represents a butyl group
• Ph represents a phenyl group.
• the total solid content refers to the total mass of all components of the composition excluding the solvent
• the solid content concentration refers to the mass percentage of the other components excluding the solvent with respect to the total mass of the composition.
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) method, and are defined as polystyrene equivalent values, unless otherwise specified.
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series as columns.
• these molecular weights are measured using THF (tetrahydrofuran) as an eluent.
• THF tetrahydrofuran
• NMP N-methyl-2-pyrrolidone
• detection in GPC measurement is performed using a UV (ultraviolet) light detector with a wavelength of 254 nm.
• a third layer or element may be interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer.
• the direction in which the layers are stacked on the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as “upper”, and the opposite direction is referred to as "lower”. Note that such a vertical direction is set for the convenience of this specification, and in an actual embodiment, the "upper” direction in this specification may be different from the vertical upward direction.
• the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component.
• 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.
• combinations of preferred aspects are more preferred aspects.
• the resin composition according to the first aspect of the present invention contains at least one resin selected from the group consisting of cyclized resins and precursors thereof, and a compound A represented by formula (A1-1).
• the resin composition according to the second aspect of the present invention (hereinafter, also simply referred to as the “second resin composition”) comprises at least one resin selected from the group consisting of cyclized resins and precursors thereof, It contains a compound A represented by formula (A2-1).
• the first resin composition and the second resin composition will be collectively referred to simply as the "resin composition”.
• the compound A contained in the first resin composition and represented by formula (A1-1) will also be referred to as the "first compound A”.
• the compound A contained in the second resin composition and represented by formula (A2-1) is also referred to as the "second compound A”.
• compound A when simply described as “compound A”, it refers to both the first compound A and the second compound A.
• the resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and is preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent.
• the resin composition of the present invention can be used, for example, to form an insulating film for a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer.
• the resin composition of the present invention may be used to form a photosensitive film to be subjected to positive development, or may be used to form a photosensitive film to be subjected to negative development.
• negative development refers to a development in which the non-exposed areas are removed by development during exposure and development
• positive development refers to a development in which the exposed areas are removed by development.
• the exposure method, the developer, and the development method for example, the exposure method described in the exposure step and the developer and development method described in the development step in the description of the production method of the cured product described later can be used.
• a cured product having excellent adhesion to a substrate can be obtained.
• the mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.
• Silane coupling agents have been used in resin compositions for the purpose of improving adhesion to substrates, etc. These silane coupling agents have a simple unsubstituted trialkoxysilyl structure such as a trimethoxysilyl group.
• at least one alkoxy group in the trialkoxysilyl structure is substituted with an organic group having at least one atom selected from oxygen atom, nitrogen atom and sulfur atom.It has been found that this improves the adhesion of the cured film to the substrate after heat resistance test compared with the case of using the conventional product.
• the mechanism by which the above effect is obtained is not clear, but is presumed to be as follows.
• the introduction of a highly polar heteroatom into the hydrophobic alkoxysilyl group improves the interaction between the silane coupling agent and the metal substrate, and it is believed that the silane coupling agent is unevenly distributed near the substrate when the film is cured. As a result, the sol-gel reaction proceeds more efficiently on the substrate surface than with conventional products, which is believed to improve the adhesion of the cured film to the substrate.
• at least one alkoxy group in the trialkoxysilyl structure is substituted with an organic group having an HSP value of 17.0 to 27.0 MPa 1/2 . This has been found to improve the adhesion of the cured film to the substrate after heat resistance testing compared to the case where a conventional product is used.
• Patent Documents 1 and 2 do not describe the first compound A and the second compound A.
• the resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof.
• the cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in the main chain structure.
• the term "main chain” refers to the relatively longest bonding chain in a resin molecule, and the term “side chain” refers to any other bonding chain.
• the cyclized resin include polyimide, polybenzoxazole, and polyamideimide.
• the precursor of a cyclized resin refers to a resin that undergoes a change in chemical structure due to an external stimulus to become a cyclized resin.
• a resin that undergoes a change in chemical structure due to heat to become a cyclized resin is preferred, and a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a cyclized resin is more preferred.
• the precursor of the cyclized resin include a polyimide precursor, a polybenzoxazole precursor, and a polyamideimide precursor. That is, the resin composition preferably contains, as the specific resin, at least one resin selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole precursor, polyamideimide, and polyamideimide precursor.
• the resin composition preferably contains a polyimide or a polyimide precursor as the specific resin, and more preferably contains a polyimide.
• 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, more preferably contains a radical polymerization initiator and a radical crosslinking agent. If necessary, it can further contain a sensitizer.
• a negative photosensitive film is formed from such a resin composition.
• the specific resin may also have a polarity conversion group such as an acid-decomposable group.
• the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive or negative photosensitive film is formed.
• the polyimide precursor used in the present invention is not particularly limited in type, but preferably contains a repeating unit represented by the following formula (2).
• A1 and A2 each independently represent an oxygen atom or -NRz-
• R111 represents a divalent organic group
• R115 represents a tetravalent organic group
• R113 and R114 each independently represent a hydrogen atom or a monovalent organic group
• Rz represents a hydrogen atom or a monovalent organic group.
• a 1 and A 2 each independently represent an oxygen atom or —NR z —, and preferably an oxygen atom.
• Rz represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.
• R 111 in formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group.
• 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 preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred.
• the linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom.
• R 111 in formula (2) examples include groups represented by -Ar- and -Ar-L-Ar-, and a group represented by -Ar-L-Ar- is preferred.
• Ar is each independently an aromatic group
• L is a single bond, 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.
• the preferred ranges of these are as described above.
• R 111 is preferably derived from a diamine.
• the diamine used in the production of the polyimide precursor 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.
• R 111 is preferably a diamine containing 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, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms.
• the linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom
• the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a hetero atom.
• groups containing an aromatic group include the following.
• * represents a bonding site with other structures.
• diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodiphen
• diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017/038598.
• diamines having two or more alkylene glycol units in the main chain are also preferably used.
• diamines having two or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of WO 2017/038598.
• R 111 is preferably represented by -Ar-L-Ar-.
• each Ar is 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 which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 -.
• the aliphatic hydrocarbon group here is preferably an alkylene group.
• R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoints of i-line transmittance and ease of availability, R 111 is more preferably a divalent organic group represented by formula (61). Equation (51) In formula (51), R 50 to R 57 each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group, at least one of R 50 to R 57 represents a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2).
• Examples of the monovalent organic group for R 50 to R 57 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).
• R 58 and R 59 each independently represent a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in formula (2).
• Examples of diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.
• R 111 is also preferably a group represented by the following formula (71): In the above embodiment, R 111 is more preferably a group represented by the following formula (72).
• a 1 to A 3 each independently represent a single bond or a divalent linking group
• * represents a bonding site with the nitrogen atom in formula (2)
• each of the four benzene rings described in formula (71) may have a hydrogen atom substituted by a substituent.
• a bond that crosses an edge of a ring structure is meant to replace any of the hydrogen atoms in that ring structure.
• * represents a bonding site with the nitrogen atom in formula (2).
• a 1 to A 3 are preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C( ⁇ O)-, -S-, -S( ⁇ O) 2 -, -NHC( ⁇ O)-, or a group consisting of a combination of two or more of these, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C( ⁇ O)-, or a group consisting of a combination of two or more of these, and further preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O-.
• a 1 and A 3 are preferably —O—.
• A2 is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom.
• a 1 and A 3 are —O— and A 2 is —C(CH 3 ) 2 — is also one of the preferred embodiments of the present invention.
• the number of carbon atoms in the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 4.
• aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom include -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 - and the like, with -C(CH 3 ) 2 - being preferred.
• substituents on the four benzene rings shown in formula (71) include a fluorine atom and a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom.
• An embodiment in which all of the four benzene rings in formula (71) are unsubstituted is also one of the preferred embodiments of the present invention.
• R 111 is also preferably a group represented by the following formula (81): In the above embodiment, R 111 is more preferably a group represented by the following formula (82).
• A1 and A2 each independently represent a single bond or a divalent linking group, * represents a bonding site with the nitrogen atom in formula (2), and each of the three benzene rings depicted in formula (81) may have a hydrogen atom substituted with a substituent.
• * represents a bonding site with the nitrogen atom in formula (2).
• a 1 and A 2 are each preferably independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C( ⁇ O)-, -S-, -S( ⁇ O) 2 -, -NHC( ⁇ O)-, or a group consisting of a combination of two or more of these, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C( ⁇ O)-, or a group consisting of a combination of two or more of these, further preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O-, and particularly preferably -C(CH 3 ) 2 -.
• R 115 represents a tetravalent organic group.
• a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
• each * independently represents a bonding site to another structure.
• R 112 is a single bond or a divalent linking group and is preferably a single bond, or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 -, -NHCO-, and a combination thereof, more preferably a single bond, or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO 2 -, and still more preferably a divalent group selected from the group consisting of -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -O-, -CO-, -S-, and -SO 2 -.
• R 115 is also preferably a group represented by the following formula (7): In the above embodiment, R 115 is more preferably a group represented by the following formula (7-2).
• a 1 to A 3 each independently represent a single bond or a divalent linking group
• * represents a bonding site with the carbonyl group in formula (2)
• each of the four benzene rings described in formula (7) may have a hydrogen atom substituted by a substituent.
• * represents a bonding site with the carbonyl group in formula (2).
• preferred embodiments of A 1 to A 3 and the substituent on the benzene ring are the same as the preferred embodiments of A 1 to A 3 and the substituent on the benzene ring in formula (7-1) described above.
• R 115 include tetracarboxylic acid residues remaining after removal of anhydride groups from tetracarboxylic dianhydride.
• the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue or two or more types of tetracarboxylic dianhydride residues as the structure corresponding to R 115 .
• 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 the same as that of R 115 in formula (2), and the preferred range is also the same.
• tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl methane tetracarboxylic dianhydride, 2 ,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxy
• tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.
• R 111 and R 115 may have an OH group. More specifically, R 111 may be a residue of a bisaminophenol derivative.
• R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
• the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
• the polymerizable group is a group capable of crosslinking by the action of heat, radicals, etc., and is preferably a radical 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.
• a group having an ethylenically unsaturated bond is preferable.
• Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.
• R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
• * represents a bonding site with another structure.
• R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
• R 201 examples include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-butanediyl group, -CH 2 CH(OH)CH 2 -, and polyalkyleneoxy groups, of which alkylene groups such as ethylene group and propylene group, -CH 2 CH(OH)CH 2 -, cyclohexyl group, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene group and propylene group, or polyalkyleneoxy groups are even more preferred.
• alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-but
• the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
• the alkylene groups in the multiple 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, an arrangement having blocks, or an arrangement having a pattern such as alternating.
• the number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent, when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.
• the alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom.
• the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.
• the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group.
• the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating. The preferred embodiment of the number of repetitions of the ethyleneoxy group in these groups is 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 counter salt with a tertiary amine compound having an ethylenically unsaturated bond.
• a tertiary amine compound having an ethylenically unsaturated bond is 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 carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred.
• the acid-decomposable group examples include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
• the polyimide precursor has fluorine atoms in its structure.
• the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and 20% by mass or less.
• the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
• Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. 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 of the polyimide precursors 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 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 represent 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 it is preferable that both are groups containing a polymerizable group.
• a 1 , A 2 , R 111 , R 113 and R 114 each independently have the same meaning as A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and the preferred range is also the same.
• R 112 has the same meaning 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), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2).
• the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).
• One embodiment of the polyimide precursor of the present invention is one in which the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units.
• the total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%.
• the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000.
• the number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
• the polyimide precursor has a molecular weight dispersity 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 molecular weight dispersity of the polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
• the dispersity of molecular weight is a value calculated by weight average molecular weight/number average molecular weight.
• the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide precursor are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as one resin are each within the above ranges.
• the polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide that is soluble in a developer containing an organic solvent as a main component.
• the alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C., and from the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferable, and a polyimide that dissolves at 1.0 g or more is more preferable.
• the upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less.
• the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.
• the polyimide contains fluorine atoms.
• the fluorine atom is preferably contained, for example, in R 132 in the repeating unit represented by formula (4) described later or in R 131 in the repeating unit represented by formula (4) described later, and more preferably contained as a fluorinated alkyl group in R 132 in the repeating unit represented by formula (4) described later or in R 131 in the repeating unit represented by formula (4) described later.
• the amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and 20% by mass or less.
• the polyimide contains a silicon atom.
• the silicon atom is preferably contained in R 131 in the repeating unit represented by formula (4) described later, and more preferably contained in R 131 in the repeating unit represented by formula (4) described later as an organically modified (poly)siloxane structure described later.
• the silicon atom or the organic modified (poly)siloxane structure may be contained in a 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 the polyimide is preferably 1 mass % or more and 20 mass % or less.
• the polyimide preferably has an ethylenically unsaturated bond.
• the polyimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but preferably in the side chain.
• the ethylenically unsaturated bond is preferably radically polymerizable.
• the ethylenically unsaturated bond is preferably contained in R 132 or R 131 in the repeating unit represented by formula (4) described below, and more preferably contained in R 132 or R 131 as a group having an ethylenically unsaturated bond.
• the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by formula (4) described below, and more preferably contained in R 131 as a group having an ethylenically unsaturated bond.
• the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).
• R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
• R 21 represents 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 in the alkyleneoxy group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group consisting of a combination of two or more of these.
• the alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, and alkylene groups represented by a combination thereof.
• the alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.
• R 21 is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1).
• L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together;
• X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and ⁇ represents a bonding site with the oxygen atom to which R21 in formula (IV) is bonded.
• formulas (R1) to (R3) preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L are the same as the preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as R 21 in formula (IV).
• 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) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).
• 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 (for example, 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 (for example, glycidyl methacrylate, etc.).
• * represents a bonding site with another structure, and is preferably a bonding site with the main chain of the polyimide.
• the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.0005 to 0.05 mol/g.
• the polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
• the polymerizable group other than the group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
• the polymerizable group other than the group having an ethylenically unsaturated bond is preferably included in, for example, R 131 in the repeating unit represented by formula (4) described below.
• the amount of polymerizable groups other than groups having ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.
• 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 in R 113 and R 114 in the above formula (2), and preferred embodiments are also the same.
• the polarity conversion group is contained, for example, in R 131 and R 132 in the repeating unit represented by formula (4) described later, or at the terminal of the polyimide.
• the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more.
• the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
• the acid value of the polyimide is preferably from 1 to 35 mgKOH/g, more preferably from 2 to 30 mgKOH/g, and even more preferably from 5 to 20 mgKOH/g.
• the acid value is measured by a known method, for example, the method described in JIS K 0070:1992.
• the acid group contained in the polyimide is preferably an acid group having a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of achieving both storage stability and developability.
• pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm pKa.
• pKa is a value calculated using ACD/ChemSketch (registered trademark) unless otherwise specified.
• ACD/ChemSketch registered trademark
• pKa the value listed in "Revised 5th Edition Chemistry Handbook: Basics" compiled by the Chemical Society of Japan may be referred to.
• the acid group is a polyacid, such as phosphoric acid
• the pKa is the first dissociation constant.
• the polyimide preferably contains at least one type selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.
• the polyimide preferably has a phenolic hydroxy group.
• the polyimide may have a phenolic hydroxy group at the end of the main chain or on a side chain.
• the phenolic hydroxy group is preferably contained in, for example, R 132 or R 131 in the repeating unit represented by formula (4) described below.
• the amount of the phenolic hydroxy group relative to the total mass of the polyimide is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.
• the polyimide used in the present invention is not particularly limited as long as it is a polymeric compound having an imide structure, but it is preferable that the polyimide contains a repeating unit represented by the following formula (4).
• R 131 represents a divalent organic group
• R 132 represents a tetravalent organic group.
• the polymerizable group may be located at least one of R 131 and R 132 , or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2).
• Formula (4-2) In 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 include the same as those of R 111 in formula (2), and the preferred range is also the same.
• R 131 may be a diamine residue remaining after removal of the amino group of the diamine.
• the diamine may be an aliphatic, cycloaliphatic or aromatic diamine. Specific examples include the example of R 111 in the formula (2) of the polyimide precursor.
• R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain in order to more effectively suppress the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue of the above diamine that does not contain an aromatic ring.
• Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.
• R 132 represents a tetravalent organic group.
• examples of the tetravalent organic group include the same as those of R 115 in formula (2), and the preferred range is also the same.
• the four bonds of the tetravalent organic group exemplified as R 115 bond to the four —C( ⁇ O)— portions in formula (4) to form a condensed ring.
• R 132 may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride.
• a specific example is R 115 in the formula (2) of the polyimide precursor. From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
• R 131 and R 132 has an OH group. More specifically, preferred examples of R 131 include 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), and more preferred examples of R 132 include the above (DAA-1) to (DAA-5).
• the polyimide has fluorine atoms 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.
• diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.
• the main chain ends of the polyimide are blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
• a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
• 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-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-amino
• the imidization rate of the polyimide (also referred to as the "ring closure rate") is preferably 70% or more, and more preferably 80% or more. It is more preferable that the content is 90% or more. There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less.
• the imidization rate is measured, for example, by the following method. The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 at about 1377 cm ⁇ 1 , which is an absorption peak derived from the imide structure. Next, the polyimide is heat-treated at 350° C.
• the polyimide may contain repeating units represented by the above formula (4) in which all of the repeating units have the same combination of R 131 and R 132 , or may contain repeating units represented by the above formula (4) containing two or more different combinations of R 131 and R 132.
• the polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Examples of other types of repeating units include the repeating units represented by the above formula (2).
• Polyimides can be synthesized, for example, by reacting tetracarboxylic dianhydride with diamine (partially substituted with a terminal blocking agent that is a monoamine) at low temperature, by reacting tetracarboxylic dianhydride (partially substituted with a terminal blocking agent that is an acid anhydride, monoacid chloride compound, or monoactive ester compound) with diamine at low temperature, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine) in the presence of a condensing agent, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine), or by using a method in which a polyimide precursor is obtained and then completely
• the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties (e.g., breaking elongation), the weight average molecular weight is particularly preferably 15,000 or more.
• the number average molecular weight (Mn) of the polyimide is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and even more preferably from 4,000 to 20,000.
• the polyimide preferably has a molecular weight dispersity of 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 dispersity is not particularly limited, but is, for example, 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 dispersity of at least one polyimide are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimides as one resin are each within the above ranges.
• polybenzoxazole precursor includes the compounds described in paragraphs 0073 to 0095 of WO 2022/145355. The above descriptions are incorporated herein by reference.
• polybenzoxazole examples include compounds described in paragraphs 0096 to 0103 of WO 2022/145355. The above descriptions are incorporated herein by reference.
• polyamide-imide precursor examples include compounds described in paragraphs 0104 to 0119 of WO 2022/145355. The above descriptions are incorporated herein by reference.
• polyamide-imide examples include the compounds described in paragraphs 0120 to 0133 of WO 2022/145355. The above descriptions are incorporated herein by reference.
• polyimide precursor or the like is produced, for example, by the method described in paragraphs 0134 to 0136 of WO 2022/145355. The above description is incorporated herein by reference.
• 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, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition.
• 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, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition.
• the resin composition of the present invention may contain only one specific resin, or may contain two or more specific resins. When two or more specific resins are contained, the total amount is preferably within the above range.
• the resin composition of the present invention contains at least two types of resins.
• the resin composition of the present invention may contain a total of two or more types of the specific resin and the other resins described below, or may contain two or more types of specific resins, but it is preferable that the resin composition contains two or more types of specific resins.
• the resin composition of the present invention contains two or more specific resins, it preferably contains, for example, two or more polyimide precursors having different dianhydride-derived structures (R 115 in the above formula (2)).
• the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, simply referred to as "another resin").
• other resins include phenol resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins.
• phenol resins polyamides
• epoxy resins polysiloxanes
• resins containing a siloxane structure resins containing a siloxane structure
• (meth)acrylic resins eth)acrylamide resins
• urethane resins urethane resins
• butyral resins ethyral resins
• styryl resins polyether resins
• polyester resins polyester resins.
• the coatability of the resin composition and the solvent resistance of the pattern (cured product) can be improved.
• the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the resin composition.
• the content of the other resins is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, even more preferably 60 mass% or less, and even more preferably 50 mass% or less, based on the total solid content of the resin composition.
• the content of the other resin may be low.
• the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition.
• the lower limit of the content is not particularly limited, and may be 0% by mass or more.
• the resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.
• the first resin composition of the present invention contains a first compound A.
• the first compound A is a compound represented by formula (A1-1).
• R 1 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and when there is a plurality of R 1 , they may be the same or different
• R 2 is a hydrogen atom or any organic group not corresponding to the above-mentioned R 1 , and when there is a plurality of R 2 , they may be the same or different, at least two of R 1 and R 2 may be bonded to form a ring structure
• n represents an integer of 1 to 3
• m represents an integer of 1 or more
• R 3 represents an m-valent organic group.
• R 1 is preferably an organic group having at least one atom selected from an oxygen atom and a nitrogen atom.
• R 1 has an oxygen atom and a nitrogen atom is also one of the preferred embodiments of the present invention.
• R 1 preferably contains an amino group or an ester bond.
• the above R N represents a hydrogen atom or a hydrocarbon group in which the hydrogen atom may be substituted with a substituent.
• the above substituent includes a hydroxy group, an alkoxy group, a halogen atom, etc., and is preferably a hydroxy group.
• the above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
• the saturated aliphatic hydrocarbon group is preferably a hydrocarbon group having 2 to 10 carbon atoms, and more preferably a hydrocarbon group having 2 to 4 carbon atoms.
• substituent include a hydroxy group, an alkoxy group, a halogen atom, a polymerizable group, and the like, and a hydroxy group is preferred.
• Examples of the polymerizable group include a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, and the like.
• the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 carbon atoms.
• examples of the substituent include an alkyl group, a hydroxy group, an alkoxy group, a halogen atom, a polymerizable group, etc., and a hydroxy group is preferred.
• Examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, etc.
• the orientation of the ester bond is not particularly limited, but it is preferable that the carbon atom included in the ester bond faces the silicon atom in formula (A1-1).
• the substituent in the substituted amino group may be an alkyl group in which the hydrogen atom may be substituted with a substituent, or an aryl group in which the hydrogen atom may be substituted with a substituent.
• the substituent in the alkyl group in which the hydrogen atom is substituted may be a hydroxyl group, an alkoxyl group, a halogen atom, etc., and preferably a hydroxyl group.
• the substituent in the aryl group in which the hydrogen atom is substituted may be a hydroxyl group, an alkoxyl group, a halogen atom, etc.
• R 1 is preferably a group represented by the following formula (R-1), formula (R-2) or formula (R-3).
• L 5 R1 represents a hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O-
• R 5 R1 and R 5 R2 each independently represent a hydrocarbon group in which a hydrogen atom may be substituted with a substituent
• * represents a bonding site with the oxygen atom in formula (A1-1).
• L R1 represents a hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O-
• R R3 represents a hydrogen atom or a hydrocarbon group in which the hydrogen atom may be substituted with a substituent
• * represents the bonding site with the oxygen atom in formula (A1-1).
• L 1 R1 represents a hydrocarbon group or a group represented by a combination of a hydrocarbon group and -O-
• R 4 R4 and R 5 represent hydrogen atoms or hydrocarbon groups in which the hydrogen atoms may be substituted with substituents
• R 6 represents a hydrocarbon group in which the hydrogen atoms may be substituted with substituents
• * represents the bonding site with the oxygen atom in formula (A1-1).
• L 1 R1 is preferably an alkylene group or an alkyleneoxyalkylene group, more preferably an alkylene group.
• the number of carbon atoms in the hydrocarbon group (preferably an alkylene group) in L 1 R1 is preferably 2 to 10, more preferably 2 to 4, and even more preferably 2 or 3.
• R 1 R1 and R 2 R2 each independently represent an alkyl group in which a hydrogen atom may be substituted with a substituent, or an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
• the alkyl group is preferably an alkyl group having 2 to 10 carbon atoms, and more preferably an alkyl group having 2 to 4 carbon atoms.
• examples of the substituent include a hydroxy group, an alkoxy group, a halogen atom, etc., and a hydroxy group is preferred.
• examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, etc.
• the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably a phenyl group.
• examples of the substituent include an alkyl group, a hydroxy group, an alkoxy group, a halogen atom, a polymerizable group, etc., and a hydroxy group is preferred.
• examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, a trialkoxysilyl group, etc.
• R 1 R1 is a hydroxyalkyl group and R 2 R2 is an aromatic hydrocarbon group is also one of the preferred embodiments of the present invention.
• R 1 R1 is a hydroxyethyl group and R 2 R2 is a phenyl group.
• L 3 R1 preferred embodiments of L 3 R1 are the same as the preferred embodiments of L 3 R1 in formula (R-1) described above.
• R 1 R3 when R 1 R3 is a hydrocarbon group in which a hydrogen atom may be substituted with a substituent, the preferred embodiments are the same as the preferred embodiments of R 1 R1 in formula (R-1) described above.
• an embodiment in which L 1 R1 is an alkylene group and R 1 R3 is a hydrogen atom or an unsubstituted alkyl group is also one of the preferred embodiments of the present invention.
• L 1 R1 is a trimethylene group and R 1 R3 is a hydrogen atom, a methyl group or an ethyl group.
• R 1 R4 and R 1 R5 are preferably a hydrogen atom or an alkyl group whose hydrogen atom may be substituted with a substituent.
• the number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 2 to 4.
• substituent include a hydroxy group, an alkoxy group, and a halogen atom, and a hydroxy group is preferred.
• R 1 and R 6 are preferably an alkyl group in which the hydrogen atom may be substituted with a substituent.
• the number of carbon atoms in the alkyl group is preferably 1 to 10, and more preferably 2 to 4.
• substituent include a hydroxy group, an alkoxy group, and a halogen atom, and a hydroxy group is preferred.
• Examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, and a trialkoxysilyl group.
• L 1 R1 is an alkylene group or an alkyleneoxyalkylene group
• R 1 R4 is a hydrogen atom or a hydroxyalkyl group
• R 5 is a hydrogen atom
• R 6 is an alkyl group in which a hydrogen atom is substituted with a polymerizable group is also one of the preferred embodiments of the present invention.
• L 1 R1 is an ethylene group or an ethyleneoxyethylene group
• R 1 R4 is a hydrogen atom or a hydroxyethyl group
• R 5 is a hydrogen atom
• R 6 is a (meth)acryloyloxyethyl group
• R 1 in formula (A1-1) Specific examples of R 1 in formula (A1-1) are described below, but the present invention is not limited thereto.
• * represents a bonding site with an oxygen atom in formula (A1-1).
• HSP value described below (the total HSP value described below when * is replaced with a hydrogen atom) is described as HSP.
• R 2 is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group or an isopropyl group, and still more preferably a methyl group or an ethyl group.
• HSP values described below total HSP values described below when * is replaced with a hydrogen atom
• the ring structure formed by combining at least two of R 1 and R 2 is preferably a ring structure containing a nitrogen atom as a ring member. Specifically, it is preferably a ring structure containing a structure represented by the following formula (R-4) or formula (R-5).
• R-4 L1R2 and L1R3 each independently represent a hydrocarbon group in which a hydrogen atom may be substituted with a substituent
• R2R7 represents a hydrocarbon group in which a hydrogen atom may be substituted with a substituent
• L1R4 and L1R5 each independently represent a hydrocarbon group in which a hydrogen atom may be substituted with a substituent
• R1R8 represents a hydrogen atom or a hydrocarbon group in which a hydrogen atom may be substituted with a substituent
• R1R9 represents a hydrocarbon group in which a hydrogen atom may be substituted with a substituent
• * each represents a bonding site to the oxygen atom in formula (A1-1).
• L 1 R2 and L 1 R3 are each preferably independently an alkylene group.
• the alkylene group is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, and further preferably an ethylene group.
• preferred embodiments of R 1 R7 are the same as the preferred embodiments of R 1 R1 in formula (R-1) above.
• it is preferable that each * is bonded to the oxygen atom in formula (A1-1) via a single bond without a linking group.
• preferred embodiments of L 1 R4 and L 1 R5 are the same as the preferred embodiments of L 1 R2 and L 1 R3 in formula (R-4) above, respectively.
• preferred embodiments of R 1 R8 are the same as preferred embodiments of R 1 R5 in formula (R-3) above.
• preferred embodiments of R 1 R9 are the same as preferred embodiments of R 1 R6 in formula (R-3) above.
• each * is bonded to the oxygen atom in formula (A1-1) via a single bond without a linking group.
• n is preferably 1 or 2.
• an embodiment in which n is 1 is also one of the preferred embodiments of the present invention.
• m is preferably an integer of 1 to 3, and more preferably 1 or 2.
• m is also one of the preferred embodiments of the present invention.
• R3 represents an m-valent organic group.
• R N represents a hydrogen atom or a hydrocarbon group in which the hydrogen atom may be substituted with a substituent, preferably a hydrogen atom. Examples of the substituent include a hydroxyl group, an alkoxy group, and a halogen atom.
• the above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
• the saturated aliphatic hydrocarbon group is preferably a hydrocarbon group having 2 to 10 carbon atoms, and more preferably a hydrocarbon group having 2 to 4 carbon atoms.
• substituent include a hydroxy group, an alkoxy group, a halogen atom, and a polymerizable group.
• Examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, and a trialkoxysilyl group.
• the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 carbon atoms.
• examples of the substituent include a carboxy group, an alkyl group, a hydroxy group, an alkoxy group, a halogen atom, and a polymerizable group.
• Examples of the polymerizable group include a vinyl group, a (meth)acryloyloxy group, a (meth)acryloylamide group, a vinylphenyl ether group, a glycidyl ether group, and a trialkoxysilyl group.
• R 3 is preferably a group represented by the following formula (R3-1).
• L 31 each independently represents a divalent linking group
• R 31 each independently represents a divalent linking group
• m represents an integer of 1 or more, when m is 1
• L 32 represents a hydrogen atom or a substituent, when m is 2 or more
• L 32 represents an m-valent linking group
• * represents a bonding site to the silicon atom in formula (A1-1).
• L31 is preferably an alkylene group which may be substituted with a hydrogen atom.
• the number of carbon atoms in the alkylene group is preferably 2 to 10, and more preferably 2 to 4.
• the hydrocarbon group represented by R31 is preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or an aliphatic unsaturated hydrocarbon group in which a hydrogen atom may be substituted with a substituent, and more preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
• the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms in which a hydrogen atom may be substituted with a substituent, and more preferably a phenylene group in which a hydrogen atom may be substituted with a substituent.
• Examples of the substituent in the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent include a carboxy group, a hydroxy group, an alkyl group, an alkoxy group, a halogen atom, etc., and a carboxy group is preferred.
• Examples of the aliphatic unsaturated hydrocarbon group in which a hydrogen atom may be substituted with a substituent include an ethylene group.
• R32 represents an organic group, and is preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent. Preferred aspects of this aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent are the same as the preferred aspects of the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent when R31 is a hydrocarbon group.
• n is the same number as m in formula (A1-1).
• L 32 represents a hydrogen atom or a substituent, preferably a hydrogen atom or a carboxy group.
• substituents may be used within the range in which the effects of the present invention can be obtained.
• R3 in formula (A1-1) Specific examples of R3 in formula (A1-1) are shown below, but the present invention is not limited to these.
• * represents the bonding site to the silicon atom in formula (A1-1).
• the first compound A is preferably a compound represented by the following formula (A1-2).
• R 1 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, and when there is a plurality of R 1 , they may be the same or different
• R 2 is a hydrogen atom or any organic group not corresponding to the above-mentioned R 1 , and when there is a plurality of R 2 , they may be the same or different, at least two of R 1 and R 2 may be bonded to form a ring structure
• n represents an integer of 1 to 3
• L represents a divalent linking group
• R 4 represents a hydrogen atom or a monovalent organic group.
• R 1 , R 2 and n are the same as the preferred embodiments of R 1 , R 2 and n in formula (A1-1) described above.
• L is preferably an alkylene group which may be substituted with a hydrogen atom.
• the number of carbon atoms in the alkylene group is preferably 2 to 10, and more preferably 2 to 4.
• the hydrocarbon group represented by R 4 is preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent, or an aliphatic unsaturated hydrocarbon group in which a hydrogen atom may be substituted with a substituent, and more preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
• the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms in which a hydrogen atom may be substituted with a substituent, and more preferably a phenylene group in which a hydrogen atom may be substituted with a substituent.
• Examples of the substituent in the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent include a carboxy group, a hydroxy group, an alkyl group, an alkoxy group, a halogen atom, etc., and a carboxy group is preferred.
• Examples of the aliphatic unsaturated hydrocarbon group in which a hydrogen atom may be substituted with a substituent include an ethylene group.
• R33 represents an organic group, and is preferably an aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent.
• Preferred aspects of this aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent are the same as the preferred aspects of the aromatic hydrocarbon group in which a hydrogen atom may be substituted with a substituent when R4 is a hydrocarbon group.
• the second resin composition of the present invention contains a second compound A.
• the second compound A is a compound represented by formula (A2-1).
• R 21 is an organic group having an HSP value of 17.0 to 27.0 MPa 1/2 , and when there is a plurality of R 21 , they may be the same or different, R 22 is a hydrogen atom or any organic group not corresponding to the above R 21 , and when there is a plurality of R 22 , they may be the same or different, at least two of R 21 and R 22 may be bonded to form a ring structure, n represents an integer of 1 to 3, m represents an integer of 1 or more, and R 23 represents an m-valent organic group.
• R 21 is preferably an organic group having an HSP value of 17.0 to 25.0 MPa 1/2 , and more preferably an organic group having an HSP value of 17.5 to 24.5 MPa 1/2 .
• the SP values of R21 and R22 described later were calculated by calculating three components (dD, dP, dH) using the calculation software HSPiP (version 4.1.07) for a structure in which the bond with oxygen of R21 or R22 was replaced with hydrogen, and the total HSP derived by the following formula was used as the HSP value.
• totalHSP(MPa 1/2 ) (dD 2 +dP 2 +dH 2 ) 1/2
• R 22 is a hydrogen atom or any organic group other than the above R 21 , and is preferably any organic group other than the above R 21 .
• the arbitrary organic group not corresponding to R 21 is an organic group having an HSP value of less than 17.0 MPa 1/2 or an HSP value of more than 27.0 MPa 1/2 , and preferably an HSP value of less than 17.0 MPa 1/2 .
• the second compound A is preferably a compound represented by the following formula (A2-2).
• R 21 is an organic group having an HSP value of 17.0 to 27.0 MPa 1/2
• R 21 is an organic group having at least one atom selected from an oxygen atom, a nitrogen atom, and a sulfur atom, when there is a plurality of R 21 , they may be the same or different
• R 22 is a hydrogen atom or any organic group not corresponding to the above R 21 , when there is a plurality of R 22 , they may be the same or different
• at least two of R 21 and R 22 may be bonded to form a ring structure
• n represents an integer of 1 to 3
• L represents a divalent linking group
• R 24 represents a hydrogen atom or a monovalent organic group.
• R 21 and R 22 are the same as the preferred embodiments of R 21 and R 22 in formula (1-2).
• the preferred embodiments of n, L and R 24 are the same as the preferred embodiments of n, L and R 24 in formula (1-2).
• the molecular weight of compound A is preferably 300-1,500, more preferably 320-1,000, and even more preferably 350-800.
• Compound A is synthesized, for example, by reacting a corresponding alcohol compound with a trialkoxysilyl compound under anhydrous conditions and in the presence of a strong acid such as hydrochloric acid to carry out an alkoxy exchange reaction.
• a strong acid such as hydrochloric acid
• compound A may be synthesized using other known synthesis methods, and the synthesis method is not particularly limited.
• Specific examples of compound A include, but are not limited to, the compounds used in the examples described below.
• the content of compound A relative to the total solid content of the resin composition of the present invention is preferably 0.02 to 10 mass%.
• the lower limit is more preferably 0.05 mass% or more, even more preferably 0.10 mass% or more, and particularly preferably 0.20 mass% or more.
• the upper limit is more preferably 8 mass% or less, even more preferably 4 mass% or less, and particularly preferably 2 mass% or less.
• an embodiment in which the content is 0.5 mass% or less is also one of the preferred embodiments of the present invention.
• Compound A may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.
• the resin composition of the present invention may contain compound X1.
• Compound X1 is a compound having at least one structure selected from the group consisting of a 1,3-dicarbonyl structure and a ⁇ -hydroxycarbonyl structure, and having a molecular weight of 1,000 or less.
• the 1,3-dicarbonyl structure refers to a structure represented by the following formula (DC-1)
• the ⁇ -hydroxycarbonyl structure refers to a structure represented by the following formula (HC-1).
• * and # each represent a bonding site with another structure.
• * is preferably a bonding site with a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom.
• # is preferably a bonding site with a hydrogen atom or a carbon atom.
• the structure represented by the above formula (DC-1) may be an enol type as represented by the following formula (DC-2).
• the structure represented by the above formula (HC-1) may be an enol type as represented by the following formula (HC-2).
• * and # each represent a bonding site with another structure. * is preferably a bonding site with a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom.
• # is preferably a bonding site with a hydrogen atom or a carbon atom.
• compound X1 does not contain a metal atom in the structure.
• the metal atom in this case does not include a metalloid atom such as silica.
• the compound X1 is not coordinated to a metal atom in the resin composition.
• the molecular weight of compound X1 is 1,000 or less, preferably 100 to 500, more preferably 100 to 400, even more preferably 100 to 350, particularly preferably 100 to 300, and even more preferably 100 to 250.
• Specific examples of compound X1 include, but are not limited to, compounds having the following structures:
• the content of compound X1 relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 30 mass%.
• the lower limit is more preferably 0.02 mass% or more, even more preferably 0.05 mass% or more, and particularly preferably 0.10 mass% or more.
• the upper limit is more preferably 20 mass% or less, even more preferably 10 mass% or less, and particularly preferably 5 mass% or less.
• an embodiment in which the content is 1 mass% or less is also one of the preferred embodiments of the present invention.
• Compound X1 may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.
• Compound X2 is a compound represented by the following formula (B-1).
• R B1 represents a tertiary alkyl group
• R B2 each independently represents a hydrogen atom or an organic group.
• R B1 represents a tertiary alkyl group and is preferably a group represented by the following formula (B1-1), and more preferably a t-butyl group.
• R B3 each independently represents an alkyl group, and * represents a bonding site to the benzene ring in formula (B-1).
• R B3 are each independently preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, still more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.
• the alkyl group is preferably a linear alkyl group.
• R B2 when R B2 is an organic group, R B2 is preferably a hydrocarbon group or a group represented by a combination of a hydrocarbon group and a ring structure.
• the hydrocarbon group is preferably an aliphatic saturated hydrocarbon group or a group represented by a combination of an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
• the ring structure may be either an aromatic ring structure or an aliphatic ring structure, but is preferably an aliphatic ring structure, and more preferably an isocyanuric ring structure.
• the molecular weight of compound X2 is preferably 100 to 2000, more preferably 150 to 1000, and even more preferably 200 to 800.
• the compound represented by formula (B-1) include, but are not limited to, 2,6-di-tert-butyl-4-methylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N, N'-Hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, ethylene bis(oxyethylene)bis[3-(oxy
• the content of compound X2 relative to the total solid content of the resin composition of the present invention is preferably 0.1 to 5 mass %.
• the lower limit is more preferably 0.2 mass % or more, and even more preferably 0.3 mass % or more.
• the upper limit is more preferably 3 mass % or less, and even more preferably 1 mass % or less.
• Compound X2 may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.
• the resin composition of the present invention preferably contains a compound represented by the following formula (X-3).
• R 1 X1 represents a hydrogen atom or an alkyl group
• n is an integer of 1 to 10.
• R X1 is preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, still more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom, a methyl group, or an ethyl group.
• compound X3 include 4-hydroxybutyric acid, methyl 4-hydroxybutyrate, ethyl 4-hydroxybutyrate, propyl 4-hydroxybutyrate, isopropyl 4-hydroxybutyrate, butyl 4-hydroxybutyrate, pentyl 4-hydroxybutyrate, hexyl 4-hydroxybutyrate, heptyl 4-hydroxybutyrate, octyl 4-hydroxybutyrate, nonyl 4-hydroxybutyrate, and decyl 4-hydroxybutyrate.
• the content of compound X3 is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the specific resin.
• the resin composition of the present invention may contain a compound containing a Group 4 element.
• the compound containing a Group 4 element is preferably a compound containing titanium, zirconium or hafnium, and more preferably a compound containing titanium.
• the compound containing a Group 4 element is preferably an organometallic complex, and more preferably an organotitanium complex.
• titanium-containing compounds are shown below in I) to VII):
• I) Titanium chelate compounds include 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 ⁇ ], etc.
• Titanocene compounds For example, pentamethylcyclopentadienyltitanium trimethoxide, bis( ⁇ 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis( ⁇ 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.
• Monoalkoxytitanium compounds For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.
• Titanium oxide compounds For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.
• Titanium tetraacetylacetonate compounds For example, titanium tetraacetylacetonate, etc.
• Titanate coupling agents For example, isopropyl tridodecylbenzenesulfonyl titanate, etc.
• the titanium-containing compound is preferably at least one compound selected from the group consisting of the above I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of exhibiting better chemical resistance.
• titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis( ⁇ 5 -2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.
• the content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin.
• the content is 0.05 parts by mass or more, the heat resistance and chemical resistance are improved, and when it is 10 parts by mass or less, the storage stability is improved.
• the resin composition of the present invention preferably contains a polymerizable compound.
• the resin composition of the present invention preferably further contains a polymerizable compound having at least one of a urea bond and a urethane bond.
• the resin composition of the present invention preferably further contains a radical crosslinking agent having at least one of a urea bond and a urethane bond, which will be described later, as the polymerizable compound having at least one of a urea bond and a urethane bond.
• the polymerizable compound may include a radical crosslinking agent or other crosslinking agents.
• the resin composition of the present invention preferably contains a radical crosslinking agent.
• the radical crosslinking agent is a compound having a radical polymerizable group.
• the radical polymerizable group is preferably a group containing an ethylenically unsaturated bond.
• Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
• a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.
• the radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds.
• the radical crosslinking agent may have three or more ethylenically unsaturated bonds.
• a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 ethylenically unsaturated bonds is even more preferable.
• the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the above-mentioned compound having three or more ethylenically unsaturated bonds.
• the molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
• the lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
• radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds.
• unsaturated carboxylic acids e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
• esters and amides preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds
• amides of unsaturated carboxylic acids and polyvalent amine compounds amides of unsaturated carboxylic acids and polyvalent amine compounds.
• addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sul
• 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 substitution reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable.
• the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure.
• Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021/112189, the contents of which are incorporated herein by reference.
• radical crosslinking agents other than those mentioned above include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021/112189, the contents of which are incorporated herein by reference.
• the radical crosslinking agent is preferably dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), or a
• radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates with four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, TPA-330, a trifunctional acrylate with three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers.
• SR-494 a tetrafunctional acrylate with four ethyleneoxy chains
• SR-209, 231, and 239 which are difunctional methacrylates with four ethyleneoxy chains (all manufactured by Sartomer Corporation)
• DPCA-60 a hexafunctional acrylate with six pentyleneoxy chains
• TPA-330 a trifunctional acrylate with three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.)
• Examples include UAS-10 and UAB-140 (all manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corp.).
• radical crosslinking agents urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and 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.
• radical crosslinking agents compounds having an amino structure or sulfide structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, can also be used.
• the radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group.
• the radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride.
• a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol.
• 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 crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, more preferably 1 to 100 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, the agent has excellent handling properties during manufacturing and developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.
• the radical crosslinking agent a radical crosslinking agent having at least one bond selected from the group consisting of a urea bond and a urethane bond (hereinafter, also referred to as "crosslinking agent U") is also preferred.
• a urethane bond is a bond represented by *--O--C(.dbd.O)-- NR.sub.N --*, where R.sub.N represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom.
• R.sub.N represents a hydrogen atom or a monovalent organic group
• * represents a bonding site with a carbon atom.
• the crosslinking agent U may have only one urea bond or one urethane bond, may have one or more urea bonds and one or more urethane bonds, may have no urethane bonds but two or more urea bonds, or may have no urea bonds but two or more urethane bonds.
• the total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
• the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
• the number of urethane bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
• the radical polymerizable group in the crosslinking agent U is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. Of these, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred.
• the crosslinking agent U has two or more radically polymerizable groups, the structures of the respective radically polymerizable groups may be the same or different.
• the number of radical polymerizable groups in the crosslinking agent U may be only one or may be two or more, and is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.
• the radically polymerizable group value (mass of compound per mole of radically polymerizable group) in the crosslinking agent U is preferably 150 to 400 g/mol.
• the lower limit of the radically polymerizable group value is more preferably 200 g/mol or more, even more preferably 210 g/mol or more, still more preferably 220 g/mol or more, even more preferably 230 g/mol or more, still more preferably 240 g/mol or more, and particularly preferably 250 g/mol or more.
• the upper limit of the radically polymerizable group value is more preferably 350 g/mol or less, further preferably 330 g/mol or less, and particularly preferably 300 g/mol or less.
• the polymerizable group value of the crosslinking agent U is preferably from 210 to 400 g/mol, and more preferably from 220 to 400 g/mol.
• the crosslinking agent U preferably has a structure represented 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 radical 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, and more preferably a hydrogen atom.
• R 3 N is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
• the above-mentioned hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms.
• the above-mentioned hydrocarbon group includes a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
• R N represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.
• the hydrocarbon group includes the same as those exemplified for ZU1 , and preferred embodiments are also the same.
• X is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group.
• 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, further preferably 1 or 2, and particularly preferably 1.
• m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.
• the cross-linking agent U has at least one of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group.
• the hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group, but is preferably an alcoholic hydroxy group.
• 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, even more preferably an alkyleneoxy group having 2 to 4 carbon atoms, still more preferably an ethyleneoxy group or a propyleneoxy group, and particularly preferably an ethylene group.
• the alkyleneoxy group may be contained as a polyalkyleneoxy group in the crosslinking agent U. In this case, the number of repetitions of the alkyleneoxy group is preferably 2 to 10, and more preferably 2 to 6.
• R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group.
• the crosslinking agent U may have, in the molecule, two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (when a polyalkyleneoxy group is formed, the group is a polyalkyleneoxy group), an amide group, and a cyano group.
• the hydroxy group, alkyleneoxy group, amide group and cyano group may be present at any position of the crosslinking agent U. From the viewpoint of chemical resistance, however, it is also preferable that the crosslinking agent U is such that at least one selected from the group consisting of the hydroxy group, alkyleneoxy group, amide group and cyano group and at least one radical polymerizable group contained in the crosslinking agent U are linked via a linking group containing a urea bond or a urethane bond (hereinafter, also referred to as "linking group L2-1").
• the crosslinking agent U contains only one radically polymerizable group
• the radically polymerizable group contained in the crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group are linked via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2").
• the crosslinking agent U contains an alkyleneoxy group (however, when a polyalkyleneoxy group is constituted, a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2
• the structure bonded to the side of the alkyleneoxy group (however, when a polyalkyleneoxy group is constituted, a polyalkyleneoxy group) opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof.
• 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.
• hydrocarbon group a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond thereof can be mentioned.
• a preferred embodiment of the radically polymerizable group is the same as the preferred embodiment of the radically polymerizable group in the crosslinking agent U described above.
• the structure bonded to the side of the amide group opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof.
• the hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms.
• examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by bonds thereof.
• a preferred embodiment of the radically polymerizable group is the same as the preferred embodiment of the radically polymerizable group in the crosslinking 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 bonded to the linking group L2-1 or the linking group L2-2.
• the crosslinking agent U has a hydroxy group.
• the crosslinking agent U preferably contains an aromatic group.
• the aromatic group is preferably directly bonded to a urea bond or a urethane bond contained in the crosslinking agent U.
• the crosslinking 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 or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably an aromatic hydrocarbon group.
• the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring structure.
• the aromatic heterocyclic group is preferably a 5-membered or 6-membered aromatic heterocyclic group.
• aromatic heterocyclic ring in such an aromatic heterocyclic group examples include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings may be further condensed with other rings, such as indole and benzimidazole.
• the heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
• the aromatic group is preferably contained in a linking group that links two or more radically polymerizable groups and contains a urea bond or a urethane bond, or a linking group that links at least one selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, amide group, and cyano group to at least one radically polymerizable group contained in the crosslinking agent U.
• the number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10.
• the crosslinking agent U contains two or more urea bonds or urethane bonds in total, 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 (linking chain length) between the urea bond or urethane bond and the radically polymerizable group may be within the above range.
• the "number of atoms (linking chain length) between a urea bond or a urethane bond and a polymerizable group” refers to the chain of atoms on the path connecting two atoms or groups of atoms to be linked that links these objects with the shortest length (minimum number of atoms).
• the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.
• the crosslinking agent U is a compound having a structure that does not have an axis of symmetry.
• the fact that the crosslinking agent U does not have an axis of symmetry means that the compound is a bilaterally asymmetric compound that does not have an axis that would produce an identical molecule to the original molecule by rotating the entire compound.
• the structural formula of the crosslinking agent U is written on paper, the fact that the crosslinking agent U does not have an axis of symmetry means that the structural formula of the crosslinking agent U cannot be written in a form that has an axis of symmetry. It is believed that since the crosslinking agent U does not have an axis of symmetry, aggregation of the crosslinking agents U within the composition film is suppressed.
• the molecular weight of the crosslinking agent U is preferably 100-2,000, more preferably 150-1500, and even more preferably 200-900.
• the method for producing the crosslinking agent U is not particularly limited, but it can be obtained, for example, by reacting a compound having a radical polymerizable compound and an isocyanate group with a compound having at least one of a hydroxy group or an amino group.
• crosslinking agent U Specific examples of the crosslinking agent U are shown below, but the crosslinking agent U is not limited thereto.
• a difunctional methacrylate or acrylate for the resin composition.
• the compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexyl 1,5-dimethylphenyl ...
• PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 for the polyethylene glycol chain.
• a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent.
• the monofunctional radical crosslinking agent a compound having a boiling point of 100° C. or more under normal pressure is also preferred in order to suppress volatilization before exposure.
• the difunctional or higher radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.
• the content of the radical crosslinking agent is preferably more than 0 mass% and not more than 60 mass% based on the total solid content of the resin composition.
• the lower limit is more preferably 5 mass% or more.
• the upper limit is more preferably 50 mass% or less, and even more preferably 30 mass% or less.
• the radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total amount is within the above range.
• the resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.
• the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by the above-mentioned photoacid generator or photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote, by the action of an acid or a base, a reaction to form a covalent bond with another compound in the composition or a reaction product thereof.
• the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
• Other cross-linking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022/145355, the disclosures of which are incorporated herein by reference.
• the resin composition of the present invention preferably contains a polymerization initiator.
• the polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator.
• the photopolymerization initiator is preferably a photoradical polymerization initiator.
• the photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet to visible regions is preferable. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.
• the photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 in a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm).
• the molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.
• 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 oxides, hexaarylbiimidazoles
• oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, ⁇ -aminoketone compounds such as aminoacetophenones, ⁇ -hydroxyketone compounds such as hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc.
• ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference.
• Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd.
• Nippon Kayaku Co., Ltd. is also preferably used.
• hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. 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, the contents of which are incorporated herein by reference.
• ⁇ -Hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).
• Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.
• aminoacetophenone initiator acylphosphine oxide initiator, and metallocene compound
• aminoacetophenone initiator acylphosphine oxide initiator, and metallocene compound
• the compounds described in paragraphs 0161 to 0163 of WO 2021/112189 can also be suitably used.
• the contents of this specification are incorporated herein.
• an oxime compound is more preferably used as a photoradical polymerization initiator.
• an oxime compound By using an oxime compound, it becomes possible to more effectively improve the exposure latitude.
• Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.
• oxime compounds include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, the compounds described in JP-A-2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.
• Preferred oxime compounds include, for example, compounds having the following structure, 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.
• an oxime compound as a photoradical polymerization initiator.
• oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemistry Co., Ltd.), and SpeedCure PDO (SARTOMER Also usable are oxime compounds having the following structure:
• an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of WO 2021/112189 an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, or an oxime compound having a fluorine atom can be used.
• oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl group-containing substituent bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of WO 2021/020359 can also be used. The contents of these compounds are incorporated herein by reference.
• an oxime compound having an aromatic ring group Ar OX1 in which an electron-withdrawing group is introduced into an aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used.
• the electron-withdrawing group of the aromatic ring group Ar OX1 includes 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.
• the benzoyl group may have a substituent.
• the substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, 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, and further preferably an alkoxy group, an alkyl
• 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), and more preferably the compound represented by the formula (OX2).
• R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl 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 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl
• R X12 is an electron-withdrawing group
• R X10 , R X11 , R X13 and R X14 are each a hydrogen atom.
• oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.
• oxime compounds include oxime compounds having specific substituents as disclosed in JP 2007-269779 A and oxime compounds having thioaryl groups as disclosed in JP 2009-191061 A, the contents of which are incorporated herein by reference.
• the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole 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.
• the photoradical polymerization initiator is a trihalomethyltriazine compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound.
• At least one compound selected from the group consisting of a trihalomethyltriazine compound, an ⁇ -aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, or a benzophenone compound is more preferred, and a metallocene compound or an oxime compound is even more preferred.
• a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photoradical polymerization initiator.
• two or more radicals are generated from one molecule of the photoradical polymerization initiator, resulting in good sensitivity.
• crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time, and improving the stability of the resin composition over time.
• bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-2015/004565, WO-2016-532675, paragraphs 0407 to 0412, and WO-2017/033680, paragraphs 0039 to 0055; compound (E) and compound (G) described in WO-T-2013-522445; Examples of such initiators include Cmpd1 to 7 described in Japanese Patent Publication No.
• the content is preferably 0.1 to 30 mass% based on the total solid content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of 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 caused by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.
• the resin composition may contain a sensitizer.
• the sensitizer absorbs specific active radiation and becomes electronically excited.
• the sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur.
• the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and are decomposed to generate a radical, an acid, or a base.
• Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based compounds, and the like.
• sensitizer examples include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, and p-dimethylaminobenzylidene indanone.
• the content of the sensitizer is preferably 0.01 to 20 mass % relative to the total solid content of the resin composition, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %.
• the sensitizer may be used alone or in combination of two or more types.
• the resin composition of the present invention may contain a chain transfer agent.
• the chain transfer agent is defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684.
• Examples of the chain transfer agent include compounds having -S-S-, -SO 2 -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization.
• RAFT Reversible Addition Fragmentation Chain Transfer
• chain transfer agent may be the compound described in paragraphs 0152 to 0153 of WO 2015/199219, the contents of which are incorporated herein by reference.
• the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total solid content of the resin composition.
• the chain transfer agent may be one type or two or more types. When there are two or more types of chain transfer agents, the total is preferably within the above range.
• the resin composition of the present invention contains two or more types of polymerization initiators.
• the resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described below, or contains the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.
• the content of the thermal polymerization initiator is preferably 20 to 70 mass%, and more preferably 30 to 60 mass%, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.
• the content of the photoacid generator is preferably 20 to 70 mass%, and more preferably 30 to 60 mass%, relative to the total content of the photopolymerization initiator and the photoacid generator.
• thermal polymerization initiator examples include a thermal radical polymerization initiator.
• a thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes a 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 promoted, so that the solvent resistance can be further improved.
• thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A, the contents of which are incorporated herein by reference.
• thermal polymerization initiator When a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%.
• the resin composition may contain only one type of thermal polymerization initiator, or may contain two or more types. When two or more types of thermal polymerization initiators are included, it is preferable that the total amount is within the above range.
• the resin composition of the present invention may contain a base generator.
• the base generator is a compound that can generate a base by physical or chemical action.
• Preferred base generators include thermal base generators and photobase generators.
• the resin composition preferably contains a base generator.
• the thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, and the performance as an interlayer insulating film for a rewiring layer contained in a semiconductor package can be improved.
• the base generator may be an ionic base generator or a nonionic base generator.
• Examples of the base generated from the base generator include secondary amines and tertiary amines.
• the base generator is not particularly limited, and a known base generator can be used.
• Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, ⁇ -lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds.
• Specific examples of the non-ionic base generator include the compounds described in paragraphs 0249 to 0275 of WO 2022/145355. The above descriptions are incorporated herein by
• Base generators include, but are not limited to, the following compounds:
• the molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
• the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
• Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018/038002.
• ammonium salts include, but are not limited to, the following compounds:
• iminium salts include, but are not limited to, the following compounds:
• the base generator is preferably an amine in which the amino group is protected by a t-butoxycarbonyl group, from the viewpoints of storage stability and generating a base by deprotection during curing.
• Amine compounds protected by a t-butoxycarbonyl group include, for example, ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, Diol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-
• the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition.
• the lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
• the upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.
• the base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.
• the resin composition of the present invention preferably contains a solvent.
• the resin composition of the present invention preferably contains a solvent having at least one of an amide bond or a hydroxyl group as a solvent. Such a solvent has excellent solubility for compound A and can suppress aggregation of these compounds.
• the solvent may be any known solvent.
• the solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
• Esters for example, 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, ⁇ -valerolactone, alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (for example,
• alkyloxypropionic acid alkyl esters include alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc.
• Suitable examples of 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 monobutyl ether acetate, di
• ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.
• cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.
• dimethyl sulfoxide is preferred.
• amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.
• ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.
• Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.
• An embodiment in which toluene is further added to these combined solvents in an amount of about 1 to 10% by mass based on the total mass of the solvent is also one of the preferred embodiments of the present invention.
• an embodiment containing ⁇ -valerolactone as a solvent is one of the preferred embodiments of the present invention.
• the content of ⁇ -valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more.
• the upper limit of the content is not particularly limited and may be 100% by mass.
• the content may be determined taking into consideration the solubility of components such as a specific resin contained in the resin composition, and the like.
• the solvent preferably contains 60 to 90% by mass of ⁇ -valerolactone and 10 to 40% by mass of dimethyl sulfoxide, more preferably 70 to 90% by mass of ⁇ -valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of ⁇ -valerolactone and 15 to 25% by mass of dimethyl sulfoxide, relative to the total mass of the solvent.
• the content of the solvent is preferably an amount that results in a total solids concentration of the resin composition of the present invention of 5 to 80 mass%, more preferably an amount that results in a total solids concentration of 5 to 75 mass%, even more preferably an amount that results in a total solids concentration of 10 to 70 mass%, and even more preferably an amount that results in a total solids concentration of 20 to 70 mass%.
• the content of the solvent may be adjusted according to the desired thickness of the coating film and the coating method. When two or more types of solvents are contained, the total amount is preferably within the above range.
• the resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc.
• the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a ⁇ -ketoester compound, and an amino compound.
• the compound corresponding to the above-mentioned compound A does not correspond to the metal adhesion improver and the silane coupling agent referred to here.
• silane coupling agent examples include the compounds described in paragraph 0316 of International Publication No. 2021/112189 and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group. In addition, the following R includes a structure derived from a blocking agent in a blocked isocyanate group.
• the blocking agent may be selected according to the desorption temperature, and examples thereof include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds.
• examples thereof include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds.
• caprolactam and the like are preferred.
• Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).
• silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-
• the silane include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(a
• an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent.
• examples of such oligomer-type compounds include compounds containing a repeating unit represented by the following formula (S-1).
• R 1 S1 represents a monovalent organic group
• R 1 S2 represents a hydrogen atom, a hydroxyl group or an alkoxy group
• n represents an integer of 0 to 2.
• R S1 is preferably a structure containing a polymerizable group.
• Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group.
• Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group.
• R S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
• n represents an integer of 0 to 2, and is preferably 1.
• n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and further preferably that n is 1 in at least two.
• oligomer type compounds commercially available products can be used, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).
• Aluminum-based adhesion promoter examples include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.
• metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A, the contents of which are incorporated herein by reference.
• 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 even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By making the content equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer will be good, and by making the content equal to or less than the above upper limit, the heat resistance and mechanical properties of the pattern will be good. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total is within the above range.
• the resin composition of the present invention preferably further contains a migration inhibitor.
• a migration inhibitor for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively suppressed.
• the migration inhibitor referred to here does not include compounds corresponding to the above-mentioned compound X1 or compound X2.
• the migration inhibitor examples include compounds having a heterocycle (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), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds.
• a heterocycle pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring
• triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole
• tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferably used.
• Ion trapping agents that capture anions such as halogen ions can also be used as migration inhibitors.
• Other migration inhibitors that can be used include the rust inhibitors described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, the compounds described in paragraph 0052 of JP 2011-059656 A, the compounds described in paragraphs 0114, 0116, and 0118 of JP 2012-194520 A, and the compounds described in paragraph 0166 of WO 2015/199219 A, the contents of which are incorporated herein by reference.
• migration inhibitors include the following compounds:
• the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass %, based on the total solid content of the resin composition.
• the migration inhibitor may be one type or two or more types. When two or more types of migration inhibitors are used, it is preferable that the total is within the above range.
• the resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.
• a polymerization inhibitor such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.
• the polymerization inhibitor referred to here does not include compounds corresponding to the above-mentioned compound X1 or compound X2.
• polymerization inhibitor examples include the compounds described in paragraph 0310 of WO 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc.
• the contents of this document are incorporated herein by reference.
• the content of the polymerization inhibitor is preferably 0.01 to 20 mass % relative to the total solid content of the resin composition, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %.
• the polymerization inhibitor may be one type or two or more types. When two or more types of polymerization inhibitors are used, it is preferable that the total is within the above range.
• the resin composition of the present invention may contain at least one compound selected from the group consisting of a compound having a urea bond (urea compound), a compound having a carbodiimide structure (carbodiimide compound), and a compound having an isourea bond (isourea compound) (hereinafter also referred to as a "urea compound, etc.”).
• urea compound a compound having a urea bond
• carbodiimide compound a compound having a carbodiimide structure
• isourea compound hereinafter also referred to as a "urea compound, etc.”
• the resin composition of the present invention further contains a compound having a urea bond.
• the urea compounds and the like referred to here do not include the above-mentioned compound A, the above-mentioned polymerizable compounds, and compounds corresponding to silane coupling agents.
• Examples of the urea compound include the compound represented by the following formula (UR-1), examples of the carbodiimide compound include the compound represented by the following formula (UR-2), and examples of the isourea compound include the compound represented by the following formula (UR-3).
• R 11 and R 12 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent
• R 21 and R 22 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent
• R 31 and R 32 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent
• R 33 represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
• R 11 and R 12 each independently represent preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having at least one substituent selected from the group consisting of a primary amine salt structure, a secondary amine salt structure, a tertiary amino group, a tertiary amine salt structure, and a quaternary ammonium group, as a substituent, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.
• 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, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 2 to 7 carbon atoms, and still more preferably an ethyl group, an isopropyl group, a t-butyl group, or a cyclohexyl group.
• R 11 and R 12 may each independently be an aliphatic hydrocarbon group having 2 to 7 carbon atoms and having at least one substituent selected from the group consisting of a hydroxy group, an alkoxy group, a thiol group, and an alkylthio group.
• the aliphatic hydrocarbon group having 2 to 7 carbon atoms may have two or more of the above-mentioned substituents, but it is also preferable that the aliphatic hydrocarbon group has only one of the above-mentioned substituents.
• R 21 and R 22 each independently represent an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent.
• R 21 and R 22 are preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having an amino group or a quaternary ammonium group as a substituent, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.
• R 21 and R 22 preferred embodiments of the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in R 21 and R 22 are the same as those described above for R 11 and R 12 , respectively.
• R 31 and R 32 are preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, or an aliphatic hydrocarbon group having 1 to 7 carbon atoms and having an amino group or a quaternary ammonium group as a substituent, and more preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms.
• preferred embodiments of the unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms or the substituted aliphatic hydrocarbon group having 1 to 7 carbon atoms in R 31 and R 32 are the same as those described above for R 11 and R 12 , respectively.
• R 33 represents an aliphatic hydrocarbon group having 1 to 7 carbon atoms which may have a substituent, and is preferably an unsubstituted aliphatic hydrocarbon group having 1 to 7 carbon atoms, more preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 7 carbon atoms, and even more preferably an unsubstituted saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms.
• R 33 is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group or a t-butyl group, and more preferably an ethyl group.
• urea compounds include, but are not limited to, dicyclohexylurea, diisopropylurea, dicyclohexylcarbodiimide, diisopropylcarbodiimide, dicyclohexylisourea, and diisopropylisourea.
• the total content of the 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 even more preferably 1.0 to 6.0 parts by mass, per 100 parts by mass of the specific resin.
• the urea compounds and the like may be used alone or in combination of two or more. When two or more bases are used in combination in the base-containing treatment liquid, it is preferable that the total content thereof is within the above range.
• the resin composition of the present invention also preferably contains a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure.
• a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure.
• the light absorber include the compounds described in paragraphs 0159 to 0183 of WO 2022/202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of which are incorporated herein by reference.
• the content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%.
• the resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, photoacid generators, aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope in which the effects of the present invention can be obtained.
• additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, photoacid generators, aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope in which the effects of the present invention can be obtained.
• auxiliaries e.g., defoamers, flame retardants, etc.
• the viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the 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 even more preferably 2,500 mm 2 /s to 8,000 mm 2 /s. If it is within the above range, it is easy to obtain a coating film with high uniformity.
• 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 the water content is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.
• the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
• metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, it is preferable that the total of these metals is within the above range.
• methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention, lining the inside of the apparatus with polytetrafluoroethylene or the like and performing distillation under conditions that suppress contamination as much as possible, etc.
• the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosion.
• those present in the form of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
• Halogen atoms include chlorine atoms and bromine atoms.It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range.
• a preferred method for adjusting the content of halogen atoms is ion exchange treatment.
• a conventionally known container can be used as the container for the resin composition of the present invention.
• the container it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six layers of resin, or a bottle with a seven-layer structure of six types of resin, in order to prevent impurities from being mixed into the raw materials or the resin composition of the present invention.
• An example of such a container is the container described in JP 2015-123351 A.
• a cured product of the resin composition By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.
• the cured product of the present invention is a cured product obtained by curing a resin composition.
• the resin composition is preferably cured by heating, and the heating temperature is more preferably 120°C to 400°C, further preferably 140°C to 380°C, and particularly preferably 170°C to 350°C.
• the form of the cured product of the resin composition is not particularly limited, and can be selected according to the application, such as a film, a rod, a sphere, or a pellet.
• the cured product is preferably a film.
• the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming a via hole for conduction, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function.
• 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 percentage of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
• the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.
• the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
• the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.
• the resin composition of the present invention can be prepared by mixing the above-mentioned components.
• the resin composition can be prepared, for example, by the method described in paragraphs 0283 to 0284 of WO 2022/210532. The descriptions therein are incorporated herein by reference.
• the method for producing a cured product of the present invention preferably includes a film formation step of applying the resin composition onto a substrate to form a film. It is more preferable that the method for producing a cured product includes the above-mentioned film formation step, an exposure step of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern.
• the method for producing a cured product includes the above-mentioned film-forming step, the above-mentioned exposure step, the above-mentioned development step, and at least one of a heating step of heating the pattern obtained by the development step and a post-development exposure step of exposing the pattern obtained by the development step.
• the method for producing a cured product preferably includes the film-forming step and a step of heating the film (heating step).
• the heating step is preferably a heating step in which the film is heated at 50 to 450°C.
• the method for producing a cured product of the present invention may further include the steps described in WO 2022/210532, such as a drying step, a post-exposure heating step, a post-development exposure step, and a metal layer forming step.
• a drying step such as a drying step, a post-exposure heating step, a post-development exposure step, and a metal layer forming step.
• Each step in the method for producing a cured product of the present invention can be carried out in the same manner as each step described in paragraphs 0285 to 0325 of WO 2022/210532. These descriptions are incorporated herein by reference.
• Examples of the field of application of the method for producing the cured product of the present invention or the cured product include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc.
• Other examples include etching patterns of sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or insulating films for mounting applications such as those described above.
• the method for producing the cured product of the present invention or the cured product of the present invention can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, and for producing protective lacquers and dielectric layers in electronics, especially microelectronics.
• the laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention.
• the laminate is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers.
• at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of 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 preferably includes two or more layers made of a cured product, and includes a metal layer between any two of the layers made of the cured product.
• the metal layer is preferably formed by the metal layer forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer made of a cured product between the steps for producing a cured product which are performed multiple times.
• a preferred embodiment of the metal layer forming step is as described above.
• a laminate including at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order can be mentioned as a preferred example.
• the layer made of the first cured product and the layer made of the second cured product are preferably layers made of the cured product of the present invention.
• the resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions.
• the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
• the method for producing the laminate of the present invention preferably includes a lamination step.
• the lamination process is a series of processes including performing at least one of (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) a heating process and a post-development exposure process again on the surface of the pattern (resin layer) or metal layer in this order.
• at least one of (a) the film formation process and (d) the heating process and the post-development exposure process may be repeated.
• a metal layer formation process may be included. It goes without saying that the lamination process may further include the above-mentioned drying process and the like as appropriate.
• a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step.
• An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.
• the lamination step is preferably carried out 2 to 20 times, and more preferably 2 to 9 times.
• a structure of 2 to 20 resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a structure of 2 to 9 resin layers is more preferred.
• the layers may be the same or different in composition, shape, film thickness, etc.
• a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.
• a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.
• the following may be repeated in this order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step; or (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step.
• the method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment.
• the surface activation treatment step is usually carried out after the metal layer formation step, but after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be subjected to a surface activation treatment step before the metal layer formation step is carried out.
• the surface activation treatment may be performed on at least a part of the metal layer, or on at least a part of the resin composition layer after exposure, or on at least a part of both the metal layer and the resin composition layer after exposure.
• the surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the area of the metal layer on which the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) provided on the surface can be improved. It is preferable to perform the surface activation treatment on a part or the whole of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion with the metal layer or the resin layer provided on the surface that has been surface-activated.
• the resin composition layer when performing negative development, etc., when the resin composition layer is cured, it is less likely to be damaged by the surface treatment, and the adhesion is likely to be improved.
• the surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of WO 2021/112189, the contents of which are incorporated herein by reference.
• the present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention.
• the present invention also discloses a method for producing a semiconductor device, which includes the method for producing the cured product or the method for producing the laminate of the present invention.
• semiconductor devices using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer the descriptions in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-027357 can be referred to, and the contents of these are incorporated herein by reference.
• Resin 2A was a structure represented by the following formula (P-2):
• the molecular weight of Resin 2A was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 20,000.
• the Mw of resin 3 was 20,000
• the Mw of resin 4 was 20,000
• the Mw of resin 5 was 20,000
• the Mw of resin 6 was 20,000
• the Mw of resin 7 was 20,000
• the Mw of resin 8 was 20,000
• the Mw of resin 9 was 20,000
• the Mw of resin 12 was 20,000
• the Mw of resin 13 was 20,000
• the Mw of resin 14 was 20,000
• the Mw of resin 15 was 20,000. It was confirmed by 1 H-NMR that the structures of resins 3 to 9 and resins 12 to 15 were structures represented by the following formulas (P-3) to (P-9) and formulas (P-12) to (P-15), respectively.
• Synthesis Example 10 Synthesis of polyimide (resin 10) In a flask equipped with a condenser and a stirrer, 18.0 g (40.5 mmol) of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 80.0 g of N-methylpyrrolidone (NMP) while removing moisture. Then, 7.95 g (39.7 mmol) of 4,4'-diaminodiphenyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25°C for 3 hours, and further stirred at 45°C for 3 hours.
• NMP N-methylpyrrolidone
• the molecular weight of resin 10 was measured by gel permeation chromatography (standard polystyrene equivalent), and the weight average molecular weight (Mw) was 20,000. It was confirmed by 1 H-NMR that the structure of resin 10 was a structure represented by the following formula (P-10).
• Examples and Comparative Examples> In each of the examples, the components shown in the following table were mixed to obtain a resin composition. In each of the comparative examples, the components shown in the following table were mixed to obtain a comparative composition. Specifically, the content (blended amount) of each component shown in the table other than the solvent is the amount (parts by mass) shown in the "parts by mass” column of each column in the table. The contents (amounts) of the solvents were set so that the solids concentration of the composition was the value (mass %) of "Solids concentration” in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvents was the ratio shown in the "Ratio" column in the table. The obtained resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter having a pore width of 0.8 ⁇ m. In the table, "-" indicates that the composition does not contain the corresponding component.
• Resins 1 to 15 Resins 1 to 15 obtained by the above synthesis examples
• C-1 to C-23 Compounds having the following structure: C-1 to C-23 are compounds corresponding to compound A (wherein, in the structural formula, Me represents a methyl group, and Et represents an ethyl group).
• CR-1 A compound having the following structure. CR-1 is a compound that does not fall under Compound A (however, in the structural formula, Et represents an ethyl group).
• CX-1 to CX-4 Compounds having the following structures. CX-1 to CX-4 are compounds that do not fall under compound A (however, in the structural formulas, Me represents a methyl group and Et represents an ethyl group).
• E-1 to E-6, E-9, E-11 to E-19 Compounds having the following structures
• E-7 Ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid
• E-8 The following synthetic product
• NMP N-methyl-2-pyrrolidone
• EL Ethyl lactate
• DMSO Dimethyl sulfoxide
• GBL ⁇ -butyrolactone
• GVL ⁇ -valerolactone
• MDMPA 3-methoxy-N,N-dimethylpropanamide
• Toluene Toluene
• the resin composition layer or the comparative composition layer on the copper substrate was exposed to light with an exposure wavelength (nm) shown in the "Exposure wavelength (nm)" column of the table using a stepper as a light source and an exposure energy of 500 mJ/ cm2 , and using a photomask with a 100 ⁇ m square unmasked portion formed therein in the examples marked with "CP” in the “Developer” column of the table, and using a photomask with a 100 ⁇ m square masked portion formed therein in the examples marked with "T” in the "Developer” column of the table.
• the resin composition layer or the comparative composition layer on the copper substrate was subjected to laser direct imaging exposure in an area of 100 ⁇ m square with light of the exposure wavelength (nm) shown in the "Exposure wavelength (nm)” column in the table, using a direct exposure device (Adtec DE-6UH III) as a light source with an exposure energy of 500 mJ/cm2, without using a photomask. Thereafter, the resin layer was developed for 60 seconds with the developer shown in the "Developer” column in the table.
• "CP” in the table means cyclopentanone
• "T” in the table means a 2.38% by mass aqueous solution of tetramethylammonium hydroxide.
• the temperature was increased at a rate of 10°C/min in a nitrogen atmosphere, and after reaching the temperature given in the "Cure temperature (°C)” column in the table, the above temperature was maintained for the time given in the "Cure time (min)” column in the table to obtain a cured product.
• the resin film obtained in each Example was heated at a heating rate of 10°C/min in a nitrogen atmosphere using an infrared lamp heating device (Advance Riko Co., Ltd., RTP-6).
• the cured product formed from the resin composition of the present invention which contains a compound corresponding to compound A, has excellent substrate adhesion after high-temperature storage tests.
• the comparative composition according to Comparative Example 1 does not contain a compound corresponding to compound A. It is clear that the cured product formed from such a comparative composition has poor substrate adhesion after a high-temperature storage test.
• Example 201 The resin composition used in Example 1 was applied in a layer form by spin coating on the surface of the thin copper layer of the resin substrate on which the thin copper layer was formed, and dried at 100° C. for 5 minutes to form a photosensitive film with a thickness of 20 ⁇ m, which was then exposed using a stepper (Nikon Corporation, NSR1505 i6). The 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 exposure, the layer was developed with cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
• the temperature was increased at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 180 minutes to form an interlayer insulating film for a rewiring layer.
• This interlayer insulating film for a rewiring layer had excellent insulating properties. Furthermore, when a semiconductor device was manufactured using this interlayer insulating film for redistribution layers, it was confirmed that the device operated without any problems.

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