Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

• the present invention relates to a photosensitive 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.
• heterocycle-containing polymers such as polyimides are used in various applications due to their excellent heat resistance and insulating properties.
• the applications include, but are not limited to, materials for insulating films and sealing materials, or protective films for semiconductor devices for mounting. They are also used as base films and coverlays for flexible substrates.
• a heterocycle-containing polymer such as polyimide is used in the form of a photosensitive resin composition containing the heterocycle-containing polymer.
• a photosensitive resin composition is applied to a substrate, for example by coating, to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate.
• the photosensitive 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 photosensitive resin composition to be applied.
• the industrial application development of the above-mentioned photosensitive resin composition is expected to continue.
• Patent Document 1 describes a resin composition containing the following components (a) and (b): (a) a polyimide precursor having a specific structural unit, and (b) a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric ring structure.
• the resulting cured product has a small thermal expansion coefficient.
• a small thermal expansion coefficient provides various advantages, such as improved reliability of the operation of semiconductor devices under high and low temperature conditions.
• reliability refers to the property of easily maintaining adhesion between a cured product and a layer in contact with the cured product, such as a metal or silicon wafer, even when the temperature environment changes, such as under high temperature conditions or low temperature conditions.
• the present invention aims to provide a photosensitive resin composition that produces a cured product with a small thermal expansion coefficient, a cured product obtained by curing the photosensitive 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.
• a polyimide having a polymerizable group A polymerizable compound A having a nitrogen-containing heterocycle, and a photopolymerization initiator, Photosensitive resin composition.
• a polymerizable compound A having a nitrogen-containing heterocycle, and a photopolymerization initiator, Photosensitive resin composition.
• ⁇ 4> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the polymerizable compound A is a trifunctional polymerizable compound containing a (meth)acryloxy group.
• ⁇ 5> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 4>, in which the molecular weight of the polymerizable compound A is 2,000 or less.
• ⁇ 6> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the polymerizable group in the polyimide is a group having an ethylenically unsaturated bond.
• ⁇ 7> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the polyimide has a polymerizable group value of 0.5 to 2.5 mmol/g. ⁇ 8> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the imidization rate of the polyimide is 70% or more.
• ⁇ 9> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 8>, wherein the polyimide contains a repeating unit represented by the following formula (1-1):
• X1 represents an organic group having 4 or more carbon atoms
• Y1 represents an organic group having 4 or more carbon atoms
• each R1 independently represents a group containing a polymerizable group
• m and n independently represent an integer of 0 to 4
• either one of m and n is an integer of 1 or more.
• R 1 in the formula (1-1) is an organic group having an aromatic group.
• X 1 in formula (1-1) includes a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (V-2)
• Y 1 in formula (1-1) includes a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulas (V-1) to (V-4):
• R 1 and X1 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
• R 1 X2 and R 1 X3 each independently represent a hydrogen atom or a substituent, and R 1 X2 and R 1 X3 may be bonded to form a ring structure.
• a polymerizable compound B which is a polymerizable compound not corresponding to the polymerizable compound A.
• the polymerizable compound B contains an alkylene group having 8 or more carbon atoms.
• ⁇ 14> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 13>, in which a total mass of the polymerizable compounds contained in the photosensitive resin composition is 10 to 50 parts by mass per 100 parts by mass of polyimide.
• ⁇ 15> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 14>, further comprising a titanium compound.
• ⁇ 17> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 16>, in which the content of the polymerizable compound A is 5 parts by mass or more relative to 100 parts by mass of the polyimide.
• ⁇ 18> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 17>, which is used for forming an interlayer insulating film for a redistribution layer.
• ⁇ 19> A cured product obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 18>.
• ⁇ 20> A laminate comprising two or more layers made of the cured product according to ⁇ 19>, and a metal layer between any two adjacent layers made of the cured product.
• ⁇ 21> A method for producing a cured product, comprising a film-forming step of applying the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 18> onto a substrate to form a film.
• the method for producing a cured product according to ⁇ 21> 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.
• ⁇ 23> A method for producing a cured product according to ⁇ 21> or ⁇ 22>, comprising a heating step of heating the film at 50 to 450° C.
• ⁇ 24> A method for producing a laminate, comprising the method for producing a cured product according to any one of ⁇ 21> to ⁇ 23>.
• ⁇ 25> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of ⁇ 21> to ⁇ 23>.
• ⁇ 26> A semiconductor device comprising the cured product according to ⁇ 19>.
• the present invention provides a photosensitive resin composition that produces a cured product with a small thermal expansion coefficient, a cured product obtained by curing the photosensitive 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.
• 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, ion beams, etc. 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 a 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 the 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 photosensitive resin composition of the present invention (hereinafter also simply referred to as "resin composition") contains a polyimide having a polymerizable group, a polymerizable compound A having a nitrogen-containing heterocycle, and a photopolymerization initiator.
• the photosensitive resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to exposure and development, and is preferably used for forming a film to be subjected to exposure and development using a developer containing an organic solvent.
• the photosensitive 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 photosensitive resin composition of the present invention is preferably used for forming 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 a small thermal expansion coefficient can be obtained.
• the mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.
• the nitrogen-containing structure in the nitrogen-containing heterocyclic structure contained in the polymer of polymerizable compound A interacts with the imide group structure of the polymer through hydrogen bonding, suppressing the movement of the polyimide, and thus it is believed that the thermal expansion coefficient is reduced. Furthermore, since polyimide has a polymerizable group, the polyimide is incorporated into the polymer contained in the cured product, and the movement of the polyimide is suppressed, which is thought to result in a small thermal expansion coefficient.
• Patent Document 1 does not mention the use of a combination of a polyimide having a polymerizable group and polymerizable compound A.
• the photosensitive resin composition of the present invention contains a polyimide having a polymerizable group.
• the polyimide having a polymerizable group is also referred to as a "specific resin”.
• polyimide refers to a resin having a repeating unit containing an imide structure in the molecular chain, and is preferably a resin having a repeating unit containing an imide ring structure in the molecular chain.
• the polyimide is preferably a resin having a repeating unit containing an imide structure in the main chain, and more preferably a resin having a repeating unit containing an imide ring structure in the main chain.
• 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 imide ring structure refers to a ring structure containing two carbon atoms and all of the nitrogen atoms in the imide structure as ring members.
• the imide ring structure is preferably a five-membered ring.
• the imide ring structure may be condensed with another ring structure such as a benzene ring structure.
• the specific resin has a polymerizable group.
• the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, and a benzoxazolyl group, and the group having an ethylenically unsaturated bond is preferred.
• the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloxy group, a maleimide group, and a (meth)acrylamide group.
• (meth)acryloxy group (meth)acrylamide group, vinylphenyl group or maleimide group is preferred, and from the viewpoint of reactivity, (meth)acryloxy group is more preferred. Also, from the viewpoint of decreasing the dielectric loss tangent of the obtained cured product, vinylphenyl group or maleimide group is preferred.
• the polymerizable group value of the specific resin is preferably 0.2 to 5.0 mmol/g, more preferably 0.25 to 4.0 mmol/g, even more preferably 0.3 to 3.0 mmol/g, and particularly preferably 0.5 to 2.5 mmol/g.
• the polymerizable group value of the resin is calculated as the number of polymerizable groups in one resin molecule/number average molecular weight of the resin.
• the specific resin preferably contains a repeating unit represented by the following formula (1-1).
• X1 represents an organic group having 4 or more carbon atoms
• Y1 represents an organic group having 4 or more carbon atoms
• each R1 independently represents a group containing a polymerizable group
• n and m each independently represent an integer of 0 to 4, and either m or n is an integer of 1 or more.
• -X1- X1 has 4 or more carbon atoms, preferably 4 to 50 carbon atoms, and more preferably 4 to 40 carbon atoms.
• X1 preferably represents an organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-9) below.
• the organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-9) improves the chemical resistance and flatness of the cured product.
• X1 is an organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-4)
• effects such as suppression of development residues, lowering of the dielectric constant of the cured product, and reduction of the thermal expansion coefficient can be obtained.
• V-5 is an organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-5) to (V-9)
• effects such as an improvement in transmittance to ultraviolet light, which makes it difficult for a pattern of a cured product to become tapered, and a wide tolerance for the amount of exposure light.
• R 1 and X1 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
• R 1 X2 and R 1 X3 each independently represent a hydrogen atom or a substituent, and R 1 X2 and R 1 X3 may be bonded to form a ring structure.
• R 1 and X5 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
• R X1 are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group or a trifluoromethyl group.
• the halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom is substituted with a halogen atom. As the halogen atom, F or Cl is preferable, and F is more preferable.
• R 1 X2 and R 1 X3 each independently represent a hydrogen atom.
• R X2 and R X3 are bonded to form a ring structure
• the structure formed by bonding R X2 and R X3 is preferably a single bond, -O- or -C(R) 2 -, more preferably -O- or -C(R) 2 -, and even more preferably -O-.
• R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.
• R X5 are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group or a trifluoromethyl group.
• the halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom is substituted with a halogen atom. As the halogen atom, F or Cl is preferable, and F is more preferable.
• X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-1)
• X 1 is preferably a group represented by the following formula (V-1-1).
• * represents a bonding site to the four carbonyl groups to which X 1 in formula (1-1) is bonded
• n1 represents an integer of 0 to 5, and is also preferably an integer of 1 to 5.
• the hydrogen atoms in the following structure may be further substituted with known substituents such as a hydrocarbon group.
• X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-2), X 1 is preferably a group represented by formula (V-2-1) or formula (V-2-2) below, and from the viewpoint of lowering the amine value in the resin, it is preferably a group represented by formula (V-2-2).
• a bond crossing a side of a ring structure means substituting any of the hydrogen atoms in the ring structure.
• L X1 represents a single bond or -O-
• * represents a bonding site with the four carbonyl groups to which X 1 in formula (1-1) is bonded.
• R X1 are as described above.
• the hydrogen atoms in these structures may be further substituted with known substituents such as hydrocarbon groups.
• X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-3)
• X 1 is preferably a group represented by formula (V-3-1) or formula (V-3-2) below, and from the viewpoint of lowering the dielectric constant of the cured product, it is preferably a group represented by formula (V-3-2).
• * represents a bonding site with the four carbonyl groups to which X 1 in formula (1-1) is bonded.
• R X2 and R X3 are as described above.
• the hydrogen atoms may be further substituted with known substituents such as hydrocarbon groups.
• X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-4)
• X 1 is preferably a group represented by formula (V-4-1) below.
• * represents a bonding site to the four carbonyl groups to which X 1 in formula (1-1) is bonded
• n1 represents an integer of 0 to 5.
• the hydrogen atoms in the structure below may be further substituted with a known substituent such as a hydrocarbon group. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-4-1) is substituted.
• X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-5)
• X 1 is preferably a group represented by the following formula (V-5-1).
• * represents a bonding site with the four carbonyl groups to which X 1 in formula (1-1) is bonded.
• the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
• X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-6), X 1 is preferably a group represented by the following formula (V-6-1).
• * represents a bonding site with the four carbonyl groups to which X 1 in formula (1-1) is bonded.
• the hydrogen atoms in the following structure may be further substituted with known substituents such as a hydrocarbon group.
• X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-7)
• X 1 is preferably a group represented by the following formula (V-7-1).
• * represents a bonding site with the four carbonyl groups to which X 1 in formula (1-1) is bonded.
• the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
• X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-8)
• X1 is preferably a group represented by the following formula (V-8-1).
• * represents a bonding site with the four carbonyl groups to which X1 in formula (1-1) is bonded.
• the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
• X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-9)
• X1 is preferably a group represented by the following formula (V-9-1).
• * represents a bonding site with the four carbonyl groups to which X1 in formula (1-1) is bonded.
• the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
• X1 may be a tetracarboxylic acid residue remaining after removing an anhydride group from a tetracarboxylic dianhydride described in paragraphs 0055 to 0057 of JP-A No. 2023-003421.
• X1 does not contain an imide bond in the structure. Furthermore, it is preferable that X1 does not contain a urethane bond, a urea bond or an amide bond in the structure.
• R N 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.
• X 1 does not contain an imide bond, a urethane bond, a urea bond, or an amide bond, and it is more preferable that X 1 does not contain an imide bond, a urethane bond, a urea bond, an amide bond, or an ester bond.
• X1 may be a structure represented by the following formula (X-2), or a structure in which a hydrogen atom of a group represented by X2 or a hydrogen atom of a group represented by L3 in the structure represented by (X- 2 ) is substituted with a group represented by R1 in formula (1-1).
• X2 each independently represents a trivalent linking group
• L3 represents a divalent linking group
• * represents a bonding site to another structure.
• X2 is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, or a group in which two or more of these are linked by a single bond or a linking group.
• a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferred.
• the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
• the halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms.
• examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.
• the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms.
• preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group.
• the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a 1,3-phenylene group or a 1,4-phenylene group.
• X2 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated.
• the halogenation is preferably chlorination.
• a compound having three carboxy groups is called a tricarboxylic acid compound.
• two of the carboxy groups may be converted into acid anhydrides.
• the tricarboxylic acid compound which may be halogenated include branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.
• X2 does not contain an imide structure in the structure. Furthermore, it is preferable that X2 does not contain a urethane bond, a urea bond or an amide bond in the structure. Furthermore, it is preferable that X2 does not contain an ester bond in the structure. Among these, X2 preferably does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and more preferably does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.
• tricarboxylic acid compounds containing a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group combining two or more of these groups with a single bond or a linking group are preferred, and tricarboxylic acid compounds containing an aromatic group having 6 to 20 carbon atoms, or a group combining two or more aromatic groups having 6 to 20 carbon atoms with a single bond or a linking group are more preferred.
• tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and compounds in which phthalic acid (or phthalic anhydride) and benzoic acid are linked via a single bond, -O-, -CH2- , -C( CH3 ) 2- , -C( CF3 ) 2- , -SO2- , or a phenylene group.
• These compounds may be compounds in which two carboxy groups are anhydridized (e.g., trimellitic anhydride) or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride).
• L 3 is exemplified by a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, or a group in which two or more of these are linked by a single bond or a linking group.
• a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined by a single bond or a linking group is preferred, and an aromatic group having 6 to 20 carbon atoms, or a group in which two or more aromatic groups having 6 to 20 carbon atoms are combined by a single bond or a linking group is more preferred.
• the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
• the halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 4 carbon atoms.
• examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred.
• the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms are substituted with halogen atoms.
• preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group.
• the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and further preferably a 1,3-phenylene group or a 1,4-phenylene group.
• X1 may be a structure represented by the following formula (X-3), or a structure in which a hydrogen atom of a group represented by X2 or a hydrogen atom of a group represented by L3 in the structure represented by (X-3) is substituted with a group represented by R1 in formula (1-1).
• X2 's each independently represent a trivalent linking group
• L3 represents a divalent linking group
• * represents a bonding site to another structure.
• preferred embodiments of X2 and L3 are the same as those of X2 and L3 in formula (X-2).
• Y 1 may be a group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the above formulas (V-1) to (V-9).
• the organic group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-9) improves the chemical resistance and flatness of the cured product.
• Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-1)
• Y1 is preferably a group represented by the following formula (V-1-2).
• * represents the bonding site to the two nitrogen atoms to which Y1 in formula (1-1) is bonded
• n1 represents an integer of 1 to 5.
• the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
• Y 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-2), Y 1 is preferably a group represented by formula (V-2-3) or formula (V-2-4) below, and from the viewpoint of decreasing the dielectric constant of the cured product, a group represented by formula (V-2-4) is preferable.
• L X1 represents a single bond or -O-, and * represents a bonding site with the two nitrogen atoms to which Y 1 is bonded in formula (1-1).
• R X1 are as described above.
• the hydrogen atoms may be further substituted with known substituents such as hydrocarbon groups.
• Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-3)
• Y1 is preferably a group represented by formula (V-3-3) or formula (V-3-4) below, and from the viewpoint of decreasing the dielectric constant of the cured product, a group represented by formula (V-3-3) is preferable.
• * represents the bonding site with the two nitrogen atoms to which Y1 in formula (1-1) is bonded.
• the hydrogen atoms in these structures may be further substituted with known substituents such as hydrocarbon groups.
• Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-4)
• Y1 is preferably a group represented by the following formula (V-4-2) or (V-4-3).
• * represents a bonding site to the two nitrogen atoms to which Y1 in formula (1-1) is bonded
• n1 represents an integer of 0 to 5.
• An embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention.
• the hydrogen atoms in the following structures may be further substituted with known substituents such as a hydrocarbon group.
• Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-5)
• Y1 is preferably a group represented by the following formula (V-5-2).
• * represents the bonding site with the two nitrogen atoms to which Y1 in formula (1-1) is bonded.
• the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
• Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-6), Y1 is preferably a group represented by the following formula (V-6-2).
• * represents the bonding site with the two nitrogen atoms to which Y1 in formula (1-1) is bonded.
• the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
• Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-7)
• Y1 is preferably a group represented by the following formula (V-7-2).
• * represents the bonding site with the two nitrogen atoms to which Y1 in formula (1-1) is bonded.
• the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
• Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-8)
• Y1 is preferably a group represented by the following formula (V-8-2).
• * represents the bonding site with the two nitrogen atoms to which Y1 is bonded in formula (1-1).
• the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
• Y1 is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (V-9)
• Y1 is preferably a group represented by the following formula (V-9-2).
• * represents the bonding site with the two nitrogen atoms to which Y1 is bonded in formula (1-1).
• the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
• Y 1 may be a group described in paragraphs 0042 to 0053 of JP-A No. 2023-003421.
• Y1 does not contain an imide bond in the structure. It is also preferred that Y1 does not contain a urethane bond, a urea bond or an amide bond in the structure. Furthermore, it is preferable that Y1 does not contain an ester bond in the structure.
• Y1 does not contain an imide bond, a urethane bond, a urea bond, or an amide bond, and it is more preferable that Y1 does not contain an imide bond, a urethane bond, a urea bond, an amide bond, or an ester bond.
• X 1 and Y 1 in formula (1-1) are each an organic group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the above formulas (V-1) to (V-4), and it is more preferable that X 1 in formula (1-1) contains a structure obtained by removing two or more hydrogen atoms from a structure represented by the above formula (V-2), and Y 1 in formula (1-1) contains a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the above formulas (V-2) to (V-4).
• the preferred aspects of these groups are as described above.
• R 1 in formula (1-1) is a group containing a polymerizable group. Preferred embodiments of the polymerizable group are as described above. Furthermore, R 1 is preferably a group having an aromatic group, and more preferably Z 1 in formula (R-1) described later is a group which is an aromatic group.
• the aromatic group may be either an aromatic hydrocarbon group or a heteroaromatic ring group, but is preferably an aromatic hydrocarbon ring group or a heteroaromatic ring group containing a nitrogen atom as a ring member.
• the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group is preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and even more preferably a benzene ring.
• heteroaromatic ring in the heteroaromatic ring group examples include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, an oxazole ring, a pyridine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an indazole ring, a benzimidazole ring, and a purine ring.
• Examples of the aliphatic ring in the cyclic aliphatic group include an aliphatic hydrocarbon ring having 5 to 20 carbon atoms, a pyrrolidine ring, a pyrroline ring, a pyrazolidine ring, an imidazolidine ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a piperidine ring, a piperazine ring, a tetrahydropyran ring, a dioxane ring, and a morpholine ring.
• Z1 is preferably a benzene ring, a cyclohexane ring or an adamantane ring, and more preferably a benzene ring.
• R 1 in formula (1-1) is preferably a structure represented by the following formula (R-1).
• L1 represents a linking group having a valence of a2+1
• Z1 represents an aromatic group or a cyclic aliphatic group
• A1 represents a polymerizable group
• a1 represents an integer of 1 or more and not exceeding the maximum number of substituents of Z1
• a2 represents an integer of 1 or more
• * represents a bonding site with X1 or Y1 in formula (1-1).
• L1 is preferably a group represented by the following formula (L-1).
• Lx2 represents a linking group having a valence of a2+1, a2 represents an integer of 1 or more, * represents a bonding site with Y1 in formula (1-1), and # represents a bonding site with Z1 in formula (R-1).
• L x2 is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, further preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group.
• the preferred embodiments of a2 in formula (L-1) are the same as the preferred embodiments of a2 in formula (R-1).
• Z1 in formula (R-1) is more preferably an aromatic group.
• Preferred embodiments of the aromatic group are as described above.
• a 1 in formula (R-1) is preferably a methacryloxy group, an acryloxy group, a vinyl group or a vinyl ether group, more preferably a vinyl group or a vinyl ether group, and even more preferably a vinyl group.
• a1 is preferably an integer of 1 to 4, and more preferably an integer of 1 or 2. Moreover, an embodiment in which a1 is 1 is also one of the preferred embodiments of the present invention.
• a2 represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.
• the number of ester bonds contained in formula (R-1) is preferably 1 or 0.
• R 1 in formula (1-1) contains a maleimide group.
• R 1 is preferably a group represented by the following formula (A-1).
• A-1 L A1 represents a single bond or a linking group having a valence of m+1, R R1 each independently represents a hydrogen atom or an organic group, two R R1 may be linked together, m represents an integer of 1 or more, and * represents a bonding site to another atom.
• L A1 preferably contains an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms.
• the aromatic group or the aliphatic saturated hydrocarbon group having 4 or more carbon atoms is preferably bonded to the maleimide group (that is, the nitrogen atom in formula (A-1)) via a single bond without a linking group.
• the aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred.
• the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and more preferably an aromatic hydrocarbon group having 6 carbon atoms. Examples of the heteroatom in the aromatic heterocyclic group include an oxygen atom, a nitrogen atom, and a sulfur atom.
• the number of heteroatoms in the aromatic heterocyclic group is preferably 1 or 2.
• the aromatic heterocyclic group is preferably a 5-membered or 6-membered ring group containing the above-mentioned heteroatom.
• the aromatic heterocyclic group may be condensed with another aromatic heterocyclic group or another aromatic hydrocarbon ring group.
• the aliphatic saturated hydrocarbon group having 4 or more carbon atoms may be any of a straight-chain, branched-chain, or cyclic structure, or a structure represented by a combination thereof.
• the aliphatic saturated hydrocarbon group having 4 or more carbon atoms preferably has 4 to 20 carbon atoms, and more preferably has 5 to 10 carbon atoms.
• L A1 is also preferably represented by the following formula (A-1-1) or formula (A-2-2).
• Z1 represents -O- or -NR N -;
• R N represents a hydrogen atom or a monovalent organic group;
• R A1 represents an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms;
• m represents an integer of 1 or more; * has the same meaning as * in formula (A-1); and # represents a bonding site with the nitrogen atom in formula (A-1).
• Z2 represents -O- or -NR N -;
• R N represents a hydrogen atom or a monovalent organic group;
• R A2 represents an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms;
• m represents an integer of 1 or more; * has the same meaning as * in formula (A-1); and
• # represents a bonding site with the nitrogen atom in formula (A-1).
• Z 1 is preferably —O—.
• R N 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.
• R A1 represents an aromatic group or an aliphatic saturated hydrocarbon group having 4 or more carbon atoms, and preferred embodiments of these groups are as described above.
• m has the same meaning as m in formula (A-1), and the preferred embodiments are also the same.
• Z 2 is preferably —O—.
• Z 2 when Z 2 is —NR N —, the preferred embodiments of R N are as described above.
• the preferred embodiments of R A2 are the same as the preferred embodiments of R A1 in formula (A-1-1).
• m has the same meaning as m in formula (A-1), and the preferred embodiments are also the same.
• R and R1 each independently represent preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, further preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
• examples of the ring structure formed by combining two R 1 and R 2 include a cyclohexene ring.
• m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably an integer of 1 to 3, and particularly preferably 1 or 2.
• m is 1 is also one of the preferred embodiments of the present invention.
• n is preferably 1 or 2, and more preferably 2.
• the specific resin may contain a repeating unit represented by formula (4).
• the repeating unit represented by formula (1-1) does not fall under the repeating unit represented by formula (4).
• R 131 represents a divalent organic group
• R 132 represents a tetravalent organic group.
• R 131 represents a divalent organic group.
• R 131 include the group represented by Y 1 in the above formula (1-1) or the groups described in paragraphs 0042 to 0053 of JP-A-2023-003421. These descriptions are incorporated herein by reference.
• R 132 represents a tetravalent organic group.
• R 132 include the group represented by X 1 in the above formula (1-1) and the compounds described in paragraphs 0055 to 0057 of JP-A-2023-003421. These descriptions are incorporated herein by reference.
• the content of the repeating unit represented by formula (1-1) relative to the total mass of the specific resin is preferably 15% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and particularly preferably 70% by mass or more.
• the upper limit of the content is not particularly limited, and may be 100% by mass.
• the total content of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (4) relative to the total mass of the specific resin is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
• the upper limit of the content is not particularly limited, and may be 100% by mass.
• the specific resin when the specific resin contains a repeating unit represented by formula (1-1), it may contain two or more repeating units represented by formula (1-1) having different structures. In that case, it is preferable that the total amount is within the above range.
• the specific resin when the specific resin contains a repeating unit represented by formula (4), it may contain two or more repeating units represented by formula (4) having different structures. In that case, it is preferable that the total amount is within the above range.
• the weight average molecular weight (Mw) of the specific resin is preferably 3,000 to 100,000.
• the lower limit of the Mw is preferably 5,000 or more, more preferably 6,000 or more, and even more preferably 8,000 or more.
• the upper limit of the Mw is preferably 80,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less.
• the number average molecular weight (Mn) of the specific resin is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000, and even more preferably from 5,000 to 20,000.
• the molecular weight dispersity of the specific resin is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
• the upper limit of the molecular weight dispersity is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, even more preferably 6.0 or less, still more preferably 4.5 or less, and particularly preferably 3.0 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 of the resins 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 plurality of resins as one resin are each within the above ranges.
• the imidization rate (also referred to as "ring closure rate") of the specific resin is preferably 10% or more, more preferably 35% or more, even more preferably 50% or more, still more preferably 70% or more, even more preferably 80% or more, particularly preferably 90% or more, and most preferably 95% or more.
• the upper limit of the imidization rate is not particularly limited, and it is sufficient if it is 100% or less.
• the content of the imide structure in the specific resin is preferably 3 mmol/g or less, more preferably 2.5 mmol/g or less.
• the lower limit of the content is not particularly limited, but can be, for example, 0.5 mmol/g or more.
• the imidization rate is measured, for example, by the following method.
• the infrared absorption spectrum of the resin is measured to determine the peak intensity P1 near 1377 cm ⁇ 1 , which is an absorption peak derived from the imide structure.
• the resin is then heat-treated at 350° C. for 1 hour, and the infrared absorption spectrum is then measured again to determine the peak intensity P2 near 1377 cm ⁇ 1 .
• the specific resin is produced, for example, by the method described in paragraphs 0134 to 0136 of WO 2022/145355. The above description is incorporated herein. In addition, the specific resin may be synthesized with reference to other known methods.
• the content of the specific resin in the photosensitive 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, even more preferably 50% by mass or more, and most preferably 60% by mass or more, based on the total solid content of the photosensitive resin composition.
• the content of the specific resin in the photosensitive 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 photosensitive resin composition.
• the photosensitive resin composition of the present invention may contain another resin (hereinafter, simply referred to as "another resin") different from the specific resin described above.
• the other resin include polyimide precursors, polyimides different from the specific resin, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, polyamideimides, phenolic 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 resins corresponding to polyester resins.
• polyimide precursors include the compounds described in paragraphs 0017 to 0138 of WO 2022/145355. The above descriptions are incorporated herein by reference.
• 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 photosensitive resin composition.
• the content of the other resin in the photosensitive resin composition of the present invention is preferably 80 mass % or less, more preferably 75 mass % or less, even more preferably 70 mass % or less, still more preferably 60 mass % or less, and even more preferably 50 mass % or less, based on the total solid content of the photosensitive 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 photosensitive resin composition.
• the lower limit of the content is not particularly limited, and may be 0% by mass or more.
• the photosensitive 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 photosensitive resin composition of the present invention contains a polymerizable compound A having a nitrogen-containing heterocycle.
• the polymerizable compound A having a nitrogen-containing heterocycle is a compound containing a nitrogen-containing heterocycle structure and a polymerizable group.
• the nitrogen-containing heterocyclic structure in the polymerizable compound A is not particularly limited, and examples thereof include a pyrrolidine ring, a pyrroline ring, a pyrrole ring, a pyrazolidine ring, an imidazolidine ring, an imidazolidinone ring, a pyrazoline ring, an imidazoline ring, a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an oxazole ring, an isoxazole ring, an isothiazole ring, a thiazole ring, an oxadiazole ring, a thiadiazole ring, and a thiazolidinedione ring.
• the polymerizable compound A preferably contains a nitrogen-containing six-membered heterocyclic structure, and more preferably contains an isocyanuric ring or a triazine ring.
• Examples of the polymerizable group in the polymerizable compound A include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, and a benzoxazolyl group. Of these, a group having an ethylenically unsaturated bond or an epoxy group is preferred, and a group having an ethylenically unsaturated bond is more preferred.
• Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloxy group, a maleimide group, and a (meth)acrylamide group.
• the polymerizable compound A preferably contains a (meth)acryloxy group, a vinylphenyl group, a maleimide group or an epoxy group, and more preferably contains a (meth)acryloxy group.
• the polymerizable compound A preferably contains two or more polymerizable groups.
• an embodiment in which the polymerizable compound A contains three or more polymerizable groups is also one of the preferred embodiments of the present invention.
• the number of polymerizable groups is preferably 3 to 6, and more preferably 3.
• the polymerizable groups may be polymerizable groups having the same structure or may be polymerizable groups having different structures.
• the polymerizable compound A may have three acryloxy groups, or may have one vinyl group and two epoxy groups.
• the polymerizable compound A is preferably a trifunctional polymerizable compound containing a (meth)acryloxy group.
• the trifunctional polymerizable compound refers to a compound having three polymerizable groups.
• the trifunctional polymerizable compound containing a (meth)acryloxy group is preferably a trifunctional polymerizable compound having three (meth)acryloxy groups. That is, the trifunctional polymerizable compound containing a (meth)acryloxy group is preferably a polymerizable compound having three (meth)acryloxy groups and not having a group having an ethylenically unsaturated bond other than the (meth)acryloxy group, an epoxy group, an oxetanyl group, or a benzoxazolyl group.
• the polymerizable compound A is preferably a compound represented by the following formula (A-1) or formula (A-2).
• each L 1 independently represents a divalent linking group
• each R 1 independently represents a polymerizable group or a monovalent substituent
• at least two of the R 1 independently represent a polymerizable group.
• each L 2 independently represents a divalent linking group
• each R 2 independently represents a polymerizable group or a monovalent substituent
• at least two of R 2 independently represent a polymerizable group.
• the above-mentioned hydrocarbon group is preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a group represented by a combination thereof, and more preferably a saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms.
• the (poly)oxycarbonylalkylene group is more preferably an oxycarbonylalkylene group or a polyoxycarbonylalkylene group having 2 to 50 repeating units.
• L1 is preferably a group represented by the following formula (L-1), formula (L-2) or formula (L-3).
• n represents an integer of 1 to 10
• * represents a bonding site with the isocyanuric ring in formula (A-1)
• # represents a bonding site with R1 in formula (A-1).
• R 21 each independently represents a substituent
• n represents an integer of 0 to 4
• * represents a bonding site with the isocyanuric ring in formula (A-1)
• # represents a bonding site with R 1 in formula (A-1).
• n represents an integer of 2 to 10
• L21 represents an alkylene group
• m represents an integer of 1 to 50
• * represents a bonding site with the isocyanuric ring in formula (A-1)
• # represents a bonding site with R1 in formula (A-1).
• n is preferably an integer of 1 to 4, more preferably 2 or 3, and even more preferably 2.
• each R 21 is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms.
• n is preferably 1 to 3, and more preferably 3.
• n is preferably an integer of 2 to 4, and more preferably 2.
• L 21 is preferably an alkylene group having 2 to 10 carbon atoms, and more preferably an alkylene group having 4 to 6 carbon atoms.
• m is preferably an integer of 5 to 30, and more preferably an integer of 5 to 20.
• the polymerizable group for R 1 is preferably a (meth)acryloxy group, a vinylphenyl group, a maleimide group or an epoxy group, and more preferably a (meth)acryloxy group.
• R 1 is a monovalent substituent
• examples of the monovalent substituent include a hydroxy group.
• L2 is preferably a group represented by the following formula (L-4).
• L 41 represents an alkylene group
• * represents a bonding site with the triazine ring in formula (A-2)
• # represents a bonding site with R 1 in formula (A-1).
• L 41 is preferably an alkylene group having 2 to 10 carbon atoms, and more preferably an alkylene group having 2 to 6 carbon atoms. L 41 is also preferably a linear alkylene group.
• the polymerizable group for R 2 is preferably a vinyl group, a (meth)acryloxy group, a vinylphenyl group, a maleimide group or an epoxy group, and more preferably a (meth)acryloxy group.
• R2 is a monovalent substituent
• examples of the monovalent substituent include a hydroxy group.
• the molecular weight of the polymerizable compound A is preferably 2,000 or less.
• the molecular weight is preferably 1,500 or less, and more preferably 1,000 or less.
• the molecular weight is preferably 200 or more, more preferably 250 or more, and even more preferably 300 or more.
• the polymerizable group value of the polymerizable compound A is preferably 0.5 to 20 mmol/g, more preferably 1.0 to 15 mmol/g, and even more preferably 2.0 to 10 mmol/g.
• polymerizable compound A examples include, but are not limited to, the compounds described in the examples below.
• the content of the polymerizable compound A is preferably 1 to 30% by mass based on the total solid content of the photosensitive resin composition.
• the lower limit is more preferably 2% by mass or more, and more preferably 5% by mass or more.
• the upper limit is more preferably 25% by mass or less, and even more preferably 20% by mass or less.
• the content of the polymerizable compound A is preferably 1 to 50 parts by mass relative to 100 parts by mass of the specific resin.
• the lower limit is more preferably 2 parts by mass or more, and more preferably 5 parts by mass or more.
• the upper limit is more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.
• the content of the polymerizable compound A is preferably 1 to 50% by mass based on the total mass of the components having a molecular weight of 5,000 or more contained in the composition.
• the lower limit is more preferably 2% by mass or more, and more preferably 5% by mass or more.
• the upper limit is more preferably 40% by mass or less, and even more preferably 30% by mass or less.
• the content of the polymerizable compound A is preferably 1 to 50 parts by mass, based on 100 parts by mass of the total amount of the specific resin and the other resins.
• the lower limit is more preferably 2 parts by mass or more, and more preferably 5 parts by mass or more.
• the upper limit is more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.
• the content of the polymerizable compound A is preferably 1 to 50 parts by mass, based on 100 parts by mass of the total amount of the polyimide and polyimide precursor corresponding to the specific resin and the other resins described above.
• the lower limit is more preferably 2 parts by mass or more, and more preferably 5 parts by mass or more.
• the upper limit is more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.
• the polymerizable 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 thereof is preferably within the above-mentioned respective ranges.
• the photosensitive resin composition of the present invention preferably contains a polymerizable compound B which is a polymerizable compound not corresponding to the polymerizable compound A.
• the polymerizable compound B preferably contains an alkylene group having 8 or more carbon atoms.
• the polymerizable compound B containing an alkylene group having 8 or more carbon atoms will also be referred to as polymerizable compound B1.
• the alkylene group having 8 or more carbon atoms is preferably a linear or cyclic alkylene group, more preferably a linear alkylene group.
• the ring structure in the cyclic alkylene group include a tetrahydrodicyclopentadiene ring structure, an isobornene ring structure, a norbornene ring structure, and an adamantane ring structure.
• the polymerizable compound B1 preferably contains, as a polymerizable group, 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, or a (meth)acryloxy group, and more preferably contains a (meth)acryloxy group.
• the alkylene group preferably has 8 to 20 carbon atoms, and more preferably has 9 to 16 carbon atoms.
• the hydrogen atom in the polymerizable compound B1 may be substituted with a substituent such as a halogen atom, etc.
• the polymerizable compound B1 is preferably a compound having a structure in which a group containing a polymerizable group is bonded to both ends of an alkylene group having 8 or more carbon atoms, and more preferably a compound having a structure in which a polymerizable group is bonded to both ends of an alkylene group having 8 or more carbon atoms.
• the preferred embodiment of the polymerizable group is as described above.
• the number of polymerizable groups in the polymerizable compound B1 is preferably 2 or more, more preferably 2 to 10, and further preferably 2. Preferred specific examples of the polymerizable compound B1 are shown below, but the invention is not limited thereto.
• R represents a hydrogen atom or a methyl group.
• the polymerizable compound B may be a radical crosslinking agent or another crosslinking agent.
• the photosensitive 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 photosensitive 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 polyamine 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 polyamine compounds amides of unsaturated carboxylic acids and polyamine compounds.
• addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sulfanyl groups with mono
• 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.)), and structures in
• 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.)
• esters 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 PME 400 (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 production and developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.
• a difunctional methacrylate or acrylate in the photosensitive resin composition.
• Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, 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-hexyl ...
• EO ethylene oxide
• PO propylene oxide
• PO propylene oxide
• PO propylene oxide
• PEG200 diacrylate refers to polyethylene glycol diacrylate having 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 photosensitive 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 photosensitive resin composition of the present invention preferably contains a crosslinking agent other than 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 a photoacid generator or a 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 content of the polymerizable compound B is preferably more than 0% by mass and not more than 60% by mass based on the total solid content of the photosensitive resin composition.
• the lower limit is more preferably 5% by mass or more.
• the upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
• the polymerizable compound B 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 total mass of the polymerizable compounds contained in the photosensitive resin composition is preferably 1 to 50 parts by mass relative to 100 parts by mass of the specific resin.
• the lower limit is more preferably 2 parts by mass or more, and even more preferably 5 parts by mass or more.
• the upper limit is more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.
• the total mass of the polymerizable compounds contained in the photosensitive resin composition is preferably 1 to 50 parts by mass, where the total amount of the specific resin and the other resins is 100 parts by mass.
• the lower limit is more preferably 2 parts by mass or more, and even more preferably 5 parts by mass or more.
• the upper limit is more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.
• the total mass of the polymerizable compounds contained in the photosensitive resin composition is preferably 1 to 50 parts by mass, assuming that the total amount of the polyimide and polyimide precursor corresponding to the specific resin and the other resins described above is 100 parts by mass.
• the lower limit is more preferably 2 parts by mass or more, and even more preferably 5 parts by mass or more.
• the upper limit is more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less.
• the photosensitive resin composition of the present invention contains a photopolymerization initiator.
• the photopolymerization initiator may be a photoacid generator, but is preferably a photoradical polymerization initiator.
• the photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators.
• a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet to visible regions is preferred.
• the photopolymerization initiator 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:
• photopolymerization initiators that can be used include the compounds described in paragraphs 0113 to 0117 of JP 2023-058585 A. The disclosures are incorporated herein by reference.
• the photosensitive 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 %, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %, based on the total solid content of the photosensitive resin composition.
• the sensitizer may be used alone or in combination of two or more types.
• the photosensitive 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
• the chain transfer agent may also be the compound described in paragraphs 0152-0153 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference.
• the photosensitive resin composition further contains a thermal polymerization initiator.
• 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.
• 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 photosensitive resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. Only one type of thermal polymerization initiator may be included, or two or more types may be included. When two or more types of thermal polymerization initiators are included, it is preferable that the total amount is within the above range.
• the photosensitive resin composition of the present invention preferably contains a titanium compound from the viewpoint of improving the chemical resistance of the cured product, etc.
• the titanium compound refers to a compound containing titanium in the structure, and is preferably an organic titanium complex.
• titanium 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 titanium compound is preferably a metal complex having one or more ⁇ -conjugated sites containing a nitrogen atom (hereinafter also referred to as a "specific metal complex").
• the nitrogen atom is preferably directly bonded to the metal atom in the specific metal complex, and the bond is not particularly limited, but is preferably a coordinate bond.
• the ⁇ -conjugated site may have only one nitrogen atom or may have two or more nitrogen atoms. When the site has two or more nitrogen atoms, it is preferable that one of the nitrogen atoms is directly bonded to the metal atom in the specific metal complex.
• the specific metal complex may have only one or two or more ⁇ -conjugated moieties containing the nitrogen atom, but it is preferable that the specific metal complex has one or two ⁇ -conjugated moieties containing the nitrogen atom.
• the titanium compound preferably contains a structure represented by the following formula (Co-1):
• the structure represented by formula (Co-1) is preferably a ⁇ -conjugated moiety containing a nitrogen atom.
• At least two structures bonded to * may be bonded to form a ring structure.
• the ring structure may be an aliphatic ring structure or an aromatic ring structure, but is preferably an aromatic ring structure.
• formula (T-1) an embodiment in which l1 and l2 are 0 is also one of the preferred embodiments of the present invention.
• m is preferably 2 or 4, and more preferably 2.
• n is preferably 1 or 2, and more preferably 1.
• l1 and l2 are 0, and m is 0, 2 or 4 in formula (T-1).
• R 11 is preferably a substituted or unsubstituted cyclopentadienyl ligand.
• the cyclopentadienyl group, alkoxy group and phenoxy group in R 11 may be substituted, but the unsubstituted embodiment is also one of the preferred embodiments of the present invention.
• R 12 is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms.
• the hydrocarbon group for R 12 may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, with aromatic hydrocarbon groups being preferred.
• the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, with a saturated aliphatic hydrocarbon group being preferred.
• the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group.
• R 12 is preferably a monovalent substituent, such as a halogen atom, etc.
• R 12 is an aromatic hydrocarbon group, it may have an alkyl group as a substituent.
• R 12 is preferably an unsubstituted phenylene group, and the phenylene group in R 12 is preferably a 1,2-phenylene group.
• formula (T-1) when m is 2 or more and two or more R 2s are included, the structures of the two or more R 2s may be the same or different. In formula (T-1), when n is 2 or more and two or more R 3 are included, the structures of the two or more R 3 may be the same or different.
• the content is preferably 0.05 parts by mass to 10 parts by mass, and more preferably 0.1 parts by mass to 5 parts by mass, per 100 parts by mass of the specific resin. If the content is 0.05 parts by mass or more, the heat resistance and chemical resistance are improved, and if it is 10 parts by mass or less, the storage stability is improved.
• the photosensitive resin composition of the present invention preferably contains a solvent.
• 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.
• 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 in consideration of the solubility of components such as a specific resin contained in the photosensitive resin composition, etc.
• 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 photosensitive 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 photosensitive 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, an amino compound, and the like.
• 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- Examples of such compounds include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(amin
• 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 lower limit above, the adhesion between the pattern and the metal layer will be good, and by making the content equal to or less than the upper limit above, 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 photosensitive resin composition of the present invention preferably further contains a migration inhibitor.
• a migration inhibitor for example, when the photosensitive 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.
• Migration inhibitors are not particularly limited, but 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,
• triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, and 2-hydroxy-N-(1H-1,2,4-triazol-5-yl)benzamide
• tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be 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 photosensitive 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 photosensitive 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 photosensitive resin composition of the present invention further contains the above-mentioned azole compound and the above-mentioned silane coupling agent.
• the photosensitive 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.
• 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, and the like.
• the contents of this specification are incorporated herein.
• Other specific examples of the polymerization inhibitor preferably include E-1 to E-9, which are used in the examples described below.
• the content of the polymerization inhibitor is preferably 0.01 to 20 mass % relative to the total solid content of the photosensitive resin composition, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %.
• the photosensitive 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, base generators, aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope of obtaining the effects of the present invention. By appropriately incorporating these components, it is possible to adjust the properties of the film, etc.
• additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, photoacid generators, base generators, aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope of obtaining the effects of the present invention.
• inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
• the average particle size of the inorganic particles is preferably from 0.01 to 2.0 ⁇ m, more preferably from 0.02 to 1.5 ⁇ m, even more preferably from 0.03 to 1.0 ⁇ m, and particularly preferably from 0.04 to 0.5 ⁇ m.
• the above average particle size of the inorganic particles is the primary particle size and also the volume average particle size.
• the volume average particle size can be measured by a dynamic light scattering method using, for example, a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). When the above measurements are difficult, the measurements can also be made by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method.
• Other additives include compounds described in paragraphs 0249 to 0282 and 0316 to 0358 of WO 2022/145355. The above descriptions are incorporated herein by reference.
• the viscosity of the photosensitive resin composition of the present invention can be adjusted by the solid content concentration of the photosensitive 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 photosensitive 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 photosensitive 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 photosensitive 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 photosensitive resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the photosensitive resin composition of the present invention, filtering the raw materials constituting the photosensitive 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.
• 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.
• Examples of 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 storing the photosensitive 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 photosensitive resin composition of the present invention.
• Examples of such containers include the containers described in JP 2015-123351 A.
• a cured product of the photosensitive resin composition By curing the photosensitive resin composition of the present invention, a cured product of the photosensitive resin composition can be obtained.
• the cured product of the present invention is a cured product obtained by curing a photosensitive resin composition.
• the photosensitive 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 photosensitive 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 photosensitive 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 photosensitive 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 breaking elongation of the cured product of the photosensitive 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 photosensitive 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 photosensitive resin composition of the present invention can be prepared by mixing the above-mentioned components.
• the mixing method is not particularly limited, and can be a conventionally known method. Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank.
• the temperature during mixing is preferably from 10 to 30°C, more preferably from 15 to 25°C.
• the filter pore size is, for example, preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, even more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
• the material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. When the material of the filter is polyethylene, it is more preferable that it is HDPE (high density polyethylene).
• the filter may be used after being washed in advance with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel.
• filters with different pore sizes or materials may be used in combination.
• a connection mode an HDPE filter with a pore size of 1 ⁇ m as the first stage and an HDPE filter with a pore size of 0.2 ⁇ m as the second stage may be connected in series.
• various materials may be filtered multiple times. When filtration is performed multiple times, circulation filtration may be performed. Filtration may also be performed under pressure.
• the pressure to be applied is, for example, preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.
• impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined.
• the adsorbent a known adsorbent may be used.
• inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be used.
• the photosensitive resin composition filled in the bottle may be subjected to a degassing step by placing it under reduced pressure.
• the method for producing a cured product of the present invention preferably includes a film formation step of applying the photosensitive 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. Each step will be described in detail below.
• the photosensitive resin composition of the present invention can be used in a film-forming process in which the composition is applied onto a substrate to form a film.
• the method for producing a cured product of the present invention preferably includes a film formation step of applying the photosensitive resin composition onto a substrate to form a film.
• substrate The type of substrate can be appropriately determined according to the application, and is not particularly limited.
• substrates include semiconductor-prepared substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals and substrates in which a metal layer is formed by plating, vapor deposition, etc.), paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, mold substrates, and electrode plates of plasma display panels (PDPs).
• semiconductor-prepared substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals and substrates in which a metal layer is formed by plating,
• the substrate is preferably a semiconductor-prepared substrate, more preferably a silicon substrate, a Cu substrate, or a mold substrate. These substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface.
• HMDS hexamethyldisilazane
• the shape of the substrate is not particularly limited, and may be circular or rectangular.
• the size of the substrate is preferably, for example, a diameter of 100 to 450 mm, more preferably 200 to 450 mm, if it is circular, and preferably, a short side length of 100 to 1000 mm, more preferably 200 to 700 mm, if it is rectangular.
• a plate-shaped substrate preferably a panel-shaped substrate (substrate) is used as the substrate.
• a film is formed by applying a photosensitive resin composition to the surface of a resin layer (e.g., a layer made of a cured material) or to the surface of a metal layer, the resin layer or metal layer serves as the substrate.
• a resin layer e.g., a layer made of a cured material
• the resin layer or metal layer serves as the substrate.
• the photosensitive resin composition is preferably applied to a substrate by coating.
• the means to be applied include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet methods. From the viewpoint of uniformity of the thickness of the film, spin coating, slit coating, spray coating, or inkjet methods are preferred, and from the viewpoint of uniformity of the thickness of the film and productivity, spin coating and slit coating are more preferred.
• a film of a desired thickness can be obtained by adjusting the solid content concentration and coating conditions of the photosensitive resin composition according to the means to be applied.
• the coating method can be appropriately selected depending on the shape of the substrate, and if the substrate is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and if the substrate is a rectangular substrate, slit coating, spray coating, inkjet, etc. are preferred.
• the spin coating method for example, it can be applied for about 10 seconds to 3 minutes at a rotation speed of 500 to 3,500 rpm.
• a coating film formed by applying the coating material to a temporary support in advance using the above-mentioned application method may be transferred onto the substrate.
• the transfer method the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A No.
• 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used.
• a process for removing excess film from the edge of the substrate may be performed, such as edge bead rinsing (EBR) or back rinsing.
• EBR edge bead rinsing
• a pre-wetting step may be employed in which various solvents are applied to the substrate before the photosensitive resin composition is applied to the substrate to improve the wettability of the substrate, and then the photosensitive resin composition is applied.
• the film may be subjected to an exposure step to selectively expose the film to light.
• the method for producing a cured product may include an exposure step of selectively exposing the film formed in the film formation step to light. Selective exposure means that only a portion of the film is exposed, resulting in exposed and unexposed areas of the film.
• the amount of exposure is not particularly limited as long as it can cure the photosensitive resin composition of the present invention, but is preferably 50 to 10,000 mJ/cm 2 , and more preferably 200 to 8,000 mJ/cm 2 , calculated as exposure energy at a wavelength of 365 nm.
• the exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.
• the exposure wavelength may be, in particular, (1) semiconductor laser (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, and i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, (7) second harmonic 532 nm and third harmonic 355 nm of YAG laser, etc.
• semiconductor laser wavelengths 830 nm, 532 nm, 488 nm, 405 n
• the photosensitive resin composition of the present invention exposure by a high-pressure mercury lamp is particularly preferred, and exposure by i-line is more preferred from the viewpoint of exposure sensitivity.
• the exposure method is not particularly limited as long as it is a method in which at least a part of the film made of the photosensitive resin composition of the present invention is exposed, and examples of the exposure method include exposure using a photomask and exposure by a laser direct imaging method.
• the film may be subjected to a step of heating after exposure (post-exposure baking step). That is, the method for producing a cured product of the present invention may include a post-exposure baking step of heating the film exposed in the exposure step.
• the post-exposure baking step can be carried out after the exposure step and before the development step.
• the heating temperature in the post-exposure baking step is preferably from 50°C to 140°C, and more preferably from 60°C to 120°C.
• the heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, and more preferably from 1 minute to 10 minutes.
• the heating rate in the post-exposure heating step is preferably from 1 to 12° C./min, more preferably from 2 to 10° C./min, and even more preferably from 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature.
• the rate of temperature rise may be appropriately changed during heating.
• the heating means in the post-exposure baking step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. can be used. It is also preferable that the heating be performed in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.
• the film may be subjected to a development step in which the film is developed with a developer to form a pattern.
• the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed with a developer to form a pattern. Development removes one of the exposed and unexposed areas of the film to form a pattern.
• development in which the non-exposed portion of the film is removed by the development process is called negative development
• development in which the exposed portion of the film is removed by the development process is called positive development.
• examples of basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
• TMAH tetramethylammonium hydroxide
• potassium hydroxide sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammoni
• the compounds described in paragraph 0387 of WO 2021/112189 can be used as the organic solvent.
• the organic solvent examples include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol
• examples of amides that are suitable include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.
• the organic solvent may be used alone or in combination of two or more.
• a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.
• the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
• the content may be 100% by mass.
• the developer may further comprise other components.
• other components include known surfactants and known defoamers.
• the method of supplying the developer is not particularly limited as long as it can form a desired pattern, and includes a method of immersing a substrate on which a film is formed in the developer, a paddle development method in which a developer is supplied to a film formed on a substrate using a nozzle, and a method of continuously supplying the developer.
• the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
• Methods of supplying the developer in the development step include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept substantially stationary on the substrate, a step in which the developer is vibrated by ultrasonic waves or the like on the substrate, and a combination of these steps.
• the development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes.
• the temperature of the developer during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18°C to 30°C.
• the rinse liquid may be, for example, water.
• the rinse liquid may be, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer).
• the organic solvent may be used alone or in combination of two or more.
• the organic solvent is preferably cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.
• the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the rinse solution. Furthermore, the organic solvent may account for 100% by mass, based on the total mass of the rinse solution.
• the rinse solution may further contain other ingredients.
• other components include known surfactants and known defoamers.
• the method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples of the method include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like.
• the rinse liquid may be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, while from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred.
• the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc.
• the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle.
• the method of supplying the rinsing liquid in the rinsing step may be a step in which the rinsing liquid is continuously supplied to the substrate, a step in which the rinsing liquid is kept substantially stationary on the substrate, a step in which the rinsing liquid is vibrated on the substrate by ultrasonic waves or the like, or a combination of these steps.
• the rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes.
• the temperature of the rinsing liquid during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18°C to 30°C.
• the pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the development step. The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without carrying out a development step, or a film obtained in a film formation step. In the heating step, the resin such as the polyimide precursor is cyclized to become a resin such as a polyimide.
• the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.
• the heating step is preferably performed at a temperature rise rate of 1 to 12° C./min from the starting temperature to the maximum heating temperature.
• the temperature rise rate is more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min.
• the temperature is increased from the starting temperature to the maximum heating temperature at a rate of preferably 1 to 8° C./sec, more preferably 2 to 7° C./sec, and even more preferably 3 to 6° C./sec.
• the temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C.
• the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature begins.
• the photosensitive resin composition of the present invention when applied to a substrate and then dried, it is the temperature of the film (layer) after drying, and it is preferable to raise the temperature from a temperature that is 30 to 200°C lower than the boiling point of the solvent contained in the photosensitive resin composition.
• the heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
• Heating may be performed stepwise. For example, a process may be performed in which the temperature is increased from 25°C to 120°C at 3°C/min, held at 120°C for 60 minutes, increased from 120°C to 180°C at 2°C/min, and held at 180°C for 120 minutes. It is also preferable to treat while irradiating with ultraviolet light as described in U.S. Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film.
• the pretreatment process may be performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
• the pretreatment process may be performed in two or more steps, for example, a first pretreatment process may be performed in the range of 100 to 150°C, and then a second pretreatment process may be performed in the range of 150 to 200°C. Furthermore, after heating, the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C./min.
• the heating step is preferably performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by performing the heating step under reduced pressure, etc.
• the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
• the heating means in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.
• the pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern after the development step is exposed to light instead of or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step.
• the method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
• the method for forming the metal layer is not particularly limited, and existing methods can be applied.
• the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used.
• photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and combinations of these methods are possible.
• examples of the method include a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating.
• a preferred embodiment of plating is electrolytic plating using a copper sulfate or copper cyanide plating solution.
• the thickness of the metal layer at its thickest point is preferably 0.01 to 50 ⁇ m, and more preferably 1 to 10 ⁇ m.
• 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 having 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 photosensitive resin composition of the present invention used to form the layer made of the first cured product and the photosensitive resin composition of the present invention used to form the layer made of the second cured product may be compositions having 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 photosensitive resin composition of the present invention is further formed so as to cover the metal layer.
• a cured product (resin layer) of the photosensitive 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 photosensitive 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.
• the reaction solution was dropped into a mixture of 1.8 L of methanol and 0.6 L of water, and the mixture was stirred for 15 minutes, after which the polyimide resin was filtered.
• the resin was reslurried in 1 L of water, filtered, and then reslurried again in 1 L of methanol, filtered, and dried under reduced pressure at 40° C. for 8 hours.
• the resin dried above was dissolved in 250 g of tetrahydrofuran, 40 g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added, and the mixture was stirred for 4 hours.
• polyimide (AA-1) is a resin having a repeating unit represented by the following formula (AA-1). The subscripts in parentheses of the following repeating units represent the molar ratio of each repeating unit. The structure of the repeating unit was determined from 1 H-NMR spectrum. The weight average molecular weight (Mw), imidization rate (%), and polymerizable group value (ethylenically unsaturated bond value, mmol/g) of the polyimide (AA-1) are shown in the table below.
• reaction solution was dropped into a mixture of 2.0 liters of methanol and 0.5 liters of water, and the mixture was stirred for 15 minutes, after which the polyimide resin was filtered.
• the resin was reslurried in 1 liter of water, filtered, and then reslurried again in 1 liter of methanol, filtered, and dried at 40°C under reduced pressure for 10 hours.
• the structure of the polyimide precursor (AB-1) was a structure represented by the following formula (AB-1):
• Mw weight average molecular weight
• % imidization rate
• mmol/g polymerizable group value
• Polyimide precursors (AB-2) and (AB-3) were synthesized in the same manner as for polyimide precursor (AB-1), except that the raw materials used were appropriately changed.
• Polyimide precursors (AB-2) and (AB-3) are resins having repeating units represented by the following formulas (AB-2) and (AB-3), respectively.
• the structure of each repeating unit was determined from 1H-NMR spectrum. In the structures below, the ratios indicate the molar ratios of each structure.
• the weight average molecular weights (Mw), imidization rates (%), and polymerizable group values (mmol/g) of these resins are shown in the table below.
• Examples and Comparative Examples> the components shown in the following table were mixed to obtain a photosensitive resin composition. Specifically, the content of each component shown in the table is the amount (parts by mass) shown in the "parts by mass” column of each column in the table.
• the photosensitive resin composition and the comparative composition thus obtained were filtered under pressure using a polypropylene filter having a pore width of 0.45 ⁇ m.
• "-" indicates that the composition does not contain the corresponding component.
• BA-1 Compound having the following structure
• BA-2 Compound having the following structure
• BA-3 Compound having the following structure (A-9300S (manufactured by Shin-Nakamura Chemical Co., Ltd.))
• BA-4 A-9300-1CL (manufactured by Shin-Nakamura Chemical Co., Ltd.)
• BA-5 Compound having the following structure
• BA-6 Compound having the following structure
• BA-7 Compound having the following structure
• BA-8 Compound having the following structure
• BA-9 Compound having the following structure
• BA-10 Compound having the following structure BA-11: DD-1 (manufactured by Shikoku Chemical Industry Co., Ltd.)
• BA-12 Compound having the following structure (MA-DGIC)
• BA-13 Compound having the following structure (DA-MGIC)
• BA-14 Compound having the following structure (TG-G)
• BB-1 Compound having the following structure (A-DOD-N (manufactured by Shin-Nakamura Chemical Co., Ltd.))
• ⁇ C-1 Compound with the following structure (TR-PBG-301, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.)
• ⁇ C-2 Compound with the following structure (TR-PBG-304, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.)
• ⁇ C-3 TR-PBG-3057, manufactured by Changzhou Strong Electronics New Materials Co., Ltd.
• C-5 Compounds with the following structure
• [Silane coupling agent] D-1 Compound having the following structure
• D-2 X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.)
• D-3 KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)
• D-4 KBM-573 (manufactured by Shin-Etsu Chemical Co., Ltd.)
• E-1 and E-2 Compounds having the following structure
• E-3 Compound having the following structure (Irganox 1035 (manufactured by BASF))
• E-4 Compound having the following structure (Irganox 1010 (manufactured by BASF))
• E-5 Compound having the following structure (4-benzoyloxy TEMPO (Seiko Chemical Industry Co., Ltd.))
• E-6 Compound having the following structure
• E-7 Compound having the following structure (Adeka STAB CDA-1 (manufactured by ADEKA))
• E-8 Compound having the following structure (Adeka STAB CDA-6S (manufactured by ADEKA))
• E-9 Compound having the following structure (Adeka STAB CDA-10 (manufactured by ADEKA), in the structural formula, tBu represents a tert-butyl group)
• the photosensitive resin composition or the comparative composition was applied to a silicon wafer by the method described in the "Coating Method” column of the table to form a resin composition layer.
• "SP” in the table means spin coating method
• "SL” means slit coating method.
• the silicon wafer to which the obtained resin composition layer was applied was heated on a hot plate at the temperature described in the "Temperature [°C]” column of "SB” in the table for the time described in the "Time [min]” column of "SB” in the table, and a resin composition layer having a uniform thickness of about 15 ⁇ m after film formation on the silicon wafer was obtained.
• the obtained resin composition layer was exposed to the spectral lines described in the "Method” column of the "Exposure” section in the table using a dumbbell-shaped mask with an exposure energy of 600 mJ/ cm2 using an Ushio exposure machine (light source: 500 W/ m2 ultra-high pressure mercury lamp).
• the dumbbell shape was a dumbbell No. 7 shape described in JIS K 6251:2017.
• the resin composition layer (resin layer) after the exposure was developed with cyclopentanone for 15 seconds and rinsed with PGMEA for 30 seconds to remove the unexposed portion.
• the development method was either spray development, paddle development, or development using a straight nozzle according to the description in the "Method” column of "Development” in the table.
• the temperature was raised at a temperature increase rate of 10 ° C./min under a nitrogen atmosphere, and the temperature was heated at the temperature described in the "Temperature [° C.]” column of “Cure” in the table for the time described in the "Time [min]” column of “Cure” in the table.
• the cured resin layer (cured product) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and a dumbbell-shaped cured product (test piece) was peeled off from the silicon wafer (sample width 2 mm, sample length 35 mm).
• the elongation (displacement) of the sample was measured during the temperature increase and decrease processes of (1) to (4) above, and the elongation (displacement) of the sample at 25° C. and 125° C. in process (3) was divided by the temperature to calculate the coefficient of thermal expansion (CTE).
• CTE coefficient of thermal expansion
• the obtained CTE was evaluated according to the following evaluation criteria, and the evaluation results are shown in the "CTE" column of the table.
• C CTE was 65 ppm/° C. or more.
• Tg The Tg of the test piece prepared above was measured using a DMA850 (manufactured by TA Instruments). Specifically, the temperature conditions of the cured product were changed in the following order (1) to (2), and the glass transition temperature was measured. (1) The temperature was increased from 25° C. to 350° C. at a rate of 5° C./min. (2) Cooled from 350°C to 25°C. The obtained Tg was evaluated according to the following evaluation criteria, and the evaluation results are shown in the "Tg" column in the table. -Evaluation criteria- A: Tg was 240° C. or higher. B: Tg was 200°C or higher and lower than 240°C. C: Tg was less than 200°C.
• the entire surface of the silicon wafer was exposed to the resulting resin composition layer using a Ushio exposure machine (light source: 500 W/ m2 ultra-high pressure mercury lamp) with an exposure energy of 600 mJ/ cm2 and the spectral line shown in the "Exposure method” column in the table.
• the resin composition layer after the exposure was heated at a temperature increase rate of 10° C./min under a nitrogen atmosphere, and heated at the temperature shown in the “Temperature [° C.]” column under “Cure” in the table for the time shown in the “Time [min]” column under “Cure” in the table to obtain a cured product.
• the obtained cured product was subjected to a TCT test (ES-57L manufactured by Hitachi Global Life Solutions, Inc., 1000 cycles of -55°C and 150°C).
• the presence or absence of cracks at the interface between the Cu wiring and the cured product was observed with a scanning electron microscope (S-4800) (manufactured by Hitachi High-Technologies Corporation). Evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the "TCT" column in the table.
• (Evaluation Criteria) A: 10 locations were observed and cracks were not found in any locations.
• B Cracks were found in 1 to 3 of 10 observation points.
• C Cracks were observed in all 10 locations.
• the photosensitive resin composition or the comparative composition was applied to a silicon wafer by the method described in the "Coating Method” column of the table to form a resin composition layer.
• the silicon wafer to which the obtained resin composition layer was applied was heated on a hot plate at the temperature described in the "Temperature [°C]” column of "SB” in the table for the time described in the "Time [min]” column of "SB” in the table, to obtain a resin composition layer having a uniform thickness of about 10 ⁇ m after film formation on the silicon wafer.
• the obtained cured film was immersed in a 4.9% by mass aqueous hydrofluoric acid solution and peeled off from the silicon wafer, and the dielectric loss tangent at 28 GHz was determined using a cavity resonator and evaluated according to the following evaluation criteria.
• the evaluation results are shown in the “Dielectric loss tangent” column of the table.
• - Measurement conditions for dielectric tangent - Split Cylinder Resonator (CR-728) Network analyzer: N5230A (manufactured by KEYSIGHT) -Evaluation criteria-
• B The dielectric loss tangent was 0.01 or more and less than 0.02.
• C The dielectric tangent was 0.02 or more.
• the photosensitive resin composition according to the present invention can produce a cured product with a small thermal expansion coefficient.
• the cured products obtained from the compositions according to Comparative Example 1, which does not contain a polyimide having a polymerizable group, and Comparative Example 2, which does not contain a compound corresponding to polymerizable compound A have a large thermal expansion coefficient.
• Example 1001 The photosensitive resin composition used in Example 1 was applied in a layer form by spin coating to the surface of a substrate on which 2 ⁇ m line-and-space copper wiring was formed, and then dried at 110 ° C. for 5 minutes to form a resin composition layer with a film thickness of 5 ⁇ m. The layer was then exposed to light at a wavelength of 365 nm and 300 mJ / cm 2 using an i-line stepper (Canon: FPA-3000i5). The layer was then developed with cyclopentanone for 15 seconds and rinsed with PGMEA for 30 seconds to obtain a pattern. The photosensitive resin composition of Example 1 had excellent resolution in forming an interlayer insulating film for a rewiring layer.
• the temperature was increased at a rate of 10 ° C. / min under a nitrogen atmosphere, and after reaching 230 ° C., the temperature was maintained at 230 ° C. for 3 hours to form an interlayer insulating film for a rewiring layer.
• This interlayer insulating film for a rewiring layer had excellent insulation properties. Furthermore, when semiconductor devices were manufactured using these interlayer insulating films for redistribution layers, it was confirmed that they operated without any problems.
• Polyimides (AD-1) to (AD-3) were synthesized in the same manner as in the synthesis of polyimide (AA-1).
• Polyimides (AD-1) to (AD-3) are resins having repeating units represented by the following formulas (AD-1) to (AD-3), respectively.
• the structure of each repeating unit was determined from 1 H-NMR spectrum. In the following structures, the subscripts in parentheses indicate the molar ratio of each structure.
• the weight average molecular weight (Mw), imidization rate (%), and polymerizable group value (mmol/g) of these resins are also shown in the table below.
• each photosensitive resin composition In each of Examples 133 to 182, the components shown in the table below were mixed to obtain each photosensitive resin composition. Specifically, the content of each component shown in the table is the amount (parts by mass) shown in the "parts by mass” column of each column in the table.
• the photosensitive resin composition and the comparative composition thus obtained were filtered under pressure using a polypropylene filter having a pore width of 0.45 ⁇ m.
• "-" indicates that the composition does not contain the corresponding component.
• BC-1 Light Acrylate 4EG-A (Kyoeisha Chemical Co., Ltd.)
• BC-2 Light Acrylate 3EG-A (Kyoeisha Chemical Co., Ltd.)
• BC-3 Light Acrylate 14EG-A (Kyoeisha Chemical Co., Ltd.)
• BC-1 to BC-3 are compounds corresponding to the polymerizable compound B.
• CA-1 Irgacure OXE02 (manufactured by BASF)
• DA-1 X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.)
• DA-2 KBM-5803 (manufactured by Shin-Etsu Chemical Co., Ltd.)
• DA-3 KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.)
• DA-4 X-12-1050 (manufactured by Shin-Etsu Chemical Co., Ltd.)
• test pieces were prepared in the following manner.
• the photosensitive resin composition or the comparative composition was applied to a silicon wafer by the method described in the "Coating Method” column of the table to form a resin composition layer.
• "SP" in the table means a spin coating method.
• the silicon wafer to which the obtained resin composition layer was applied was heated on a hot plate at the temperature described in the "Temperature [°C]” column of "SB” in the table for the time described in the "Time [min]” column of "SB” in the table, and a resin composition layer having a uniform thickness of about 15 ⁇ m after film formation on the silicon wafer was obtained.
• the obtained resin composition layer was exposed to the spectral lines described in the "Method” column of the "Exposure” section in the table using a dumbbell-shaped mask with an exposure energy of 600 mJ/ cm2 using an Ushio exposure machine (light source: 500 W/ m2 ultra-high pressure mercury lamp).
• the dumbbell shape was a dumbbell No. 7 shape described in JIS K 6251:2017.
• the resin composition layer (resin layer) after the exposure was developed with cyclopentanone until the unexposed portion was removed, and rinsed with PGMEA for 30 seconds.
• the development method was either spray development, paddle development, or development using a straight nozzle, as described in the "Method” column of "Development” in the table.
• the temperature was raised at a temperature increase rate of 10°C/min under a nitrogen atmosphere, and the temperature was heated at the temperature described in the "Temperature [°C]” column of “Cure” in the table for the time described in the "Time [min]” column of “Cure” in the table.
• the cured resin layer (cured product) was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and a dumbbell-shaped cured product (test piece) was peeled off from the silicon wafer (sample width 2 mm, sample length 35 mm).
• Example 133 to 182 The CTE, Tg, dielectric tangent, and TCT of Examples 133 to 182 were tested in the same manner as Examples 1 to 132, except that the test pieces obtained by the above-mentioned method were used. In addition, for Examples 157 to 182, Td1 was evaluated by the following method.
• the Td1 (temperature at which the thermal mass loss becomes 1%) of the test piece prepared above was measured using a TGA550 (manufactured by TA Instruments). Specifically, the temperature conditions of the cured product were changed in the following order of (1) to (5), the sample mass after step (4) was set to 100%, and the temperature at which the thermal mass reduction temperature became 1% in step (5) was calculated. (1) The temperature was increased from 25° C. to 130° C. at a rate of 10° C./min. (2) Hold at 130°C for 20 minutes. (3) The temperature was reduced from 130° C. to 50° C. at a rate of 10° C./min. (4) Hold at 50°C for 10 minutes. (5) The temperature was increased from 50° C.
• Td1 was evaluated according to the following evaluation criteria, and the evaluation results are shown in the "Td1" column in the table.
• Example 1001 a semiconductor device was manufactured in the same manner as in Example 1001, except that the photosensitive resin composition was changed to the photosensitive resin composition of Examples 2 to 182, respectively, and it was confirmed that the device operated without any problems.

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