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
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • 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
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
  • C08F290/145—Polyamides; Polyesteramides; Polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • 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
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/094—Multilayer resist systems, e.g. planarising layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/16—Coating processes; Apparatus therefor
  • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • 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
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers
• • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
  • Y10S430/1055—Radiation sensitive composition or product or process of making
  • Y10S430/114—Initiator containing

Definitions

• the present invention relates to a photosensitive resin composition, a cured product, a laminate, a method for producing a cured product, and a semiconductor device.
• Cyclized resins such as polyimide are used in a variety of applications due to their excellent heat resistance and insulating properties.
• the use is not particularly limited, but in the case of a semiconductor device for mounting, use as a material for an insulating film or a sealing material, or as a protective film can be mentioned. It is also used as a base film or coverlay for flexible substrates.
• the cyclized resin such as polyimide is used in the form of a resin composition containing at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin.
• a resin composition is applied to a substrate, for example, by coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate.
• a precursor of the cyclized resin such as a polyimide precursor is cyclized, for example, by heating, and becomes a cyclized resin such as polyimide in the cured product.
• the resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the resin composition to be applied. It can be said that it is excellent in sex.
• cyclized resins such as polyimide, from the viewpoint of such excellent manufacturing adaptability, industrial application and development of the above-mentioned resin compositions are increasingly expected.
• Patent Document 1 a polymer precursor selected from a polyimide precursor and a polybenzoxazole precursor, a photoradical polymerization initiator, and a solvent are included, and the pH of the neutralization point contained in the polymer precursor is is in the range of 7.0 to 12.0, the acid value of the acid group is in the range of 2.5 to 34.0 mgKOH / g, and the polymer precursor has a radically polymerizable group, or is other than the polymer precursor
• a photosensitive resin composition is described comprising a radically polymerizable compound of Patent Document 2 discloses a polyimide precursor (c) obtained by reacting an aromatic tetracarboxylic dianhydride or its derivative (a) with an aromatic diamine or its derivative (b) at 30 to 60% by weight,
• a polyimide precursor composition for polyimide extrusion is described comprising 0.1 to 5% by weight of the poor solvent for the polyimide precursor and 35 to 69.9% by weight of the good solvent for the polyimide precursor.
• the resulting cured product have excellent elongation at break.
• the present invention provides a photosensitive resin composition that provides a cured product having excellent elongation at break, a cured product obtained by curing the photosensitive resin composition, a laminate containing the cured product, a method for producing the cured product, and , to provide a semiconductor device comprising the above-mentioned cured product or the above-mentioned laminate.
• cyclized resin or its precursor solvent B having an SP value of 21.0 (J/cm 3 ) 0.5 or more and less than 25.0 (J/cm 3 ) 0.5 ; a solvent C having an SP value of less than 21.0 (J/cm 3 ) 0.5 or 25.0 (J/cm 3 ) 0.5 or more and a boiling point of 60° C. or more; containing a photosensitizer;
• a photosensitive resin composition wherein the content of the solvent C with respect to the total mass of the photosensitive resin composition is 1 ppm or more and 10,000 ppm or less.
• the solvent C is ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, hexane, heptane, benzene, toluene, methanol, ethanol, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol.
• the photosensitive resin composition according to ⁇ 1> which is at least one selected from the group consisting of monomethyl ether acetate, cyclopentanone, and cyclohexanone.
• solvent B having an SP value of 21.0 (J/cm 3 ) 0.5 or more and less than 25.0 (J/cm 3 ) 0.5 ; ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, hexane, heptane, benzene, toluene, methanol, ethanol, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, cyclopentanone, Alternatively, solvent C, which is cyclohexanone, and containing a photosensitizer; A photosensitive resin composition, wherein the content of the solvent C with respect to the total mass of the photosensitive resin composition is 1 ppm or more and 10,000 ppm or less.
• the solvent B contains at least one selected from the group consisting of ⁇ -butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, propylene glycol monomethyl ether, and ethyl lactate, ⁇ 1> to ⁇ 3
• ⁇ 6> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the solvent B contains ⁇ -butyrolactone or N-methyl-2-pyrrolidone.
• the solvent C is toluene, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, or cyclopentanone.
• ⁇ 8> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the solvent C is toluene, tetrahydrofuran, 1,4-dioxane, or diethylene glycol dimethyl ether.
• ⁇ 11> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 10>, further comprising a silane coupling agent.
• ⁇ 12> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 11>, which is used for forming a photosensitive film subjected to negative development.
• ⁇ 13> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 12>, which is used for forming an interlayer insulating film for a rewiring layer.
• ⁇ 14> A cured product obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 13>.
• ⁇ 15> A laminate comprising two or more layers of the cured product according to ⁇ 14> and a metal layer between any of the layers of the cured product.
• ⁇ 16> 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 ⁇ 13> to a substrate to form a film.
• the method for producing a cured product according to ⁇ 16> including an exposure step of exposing the film and a development step of developing the film.
• the method for producing a cured product according to ⁇ 16> or ⁇ 17> comprising a heating step of heating the film at 50 to 450°C.
• a semiconductor device comprising the cured product according to ⁇ 14> or the laminate according to ⁇ 15>.
• a photosensitive resin composition from which a cured product having excellent elongation at break can be obtained, a cured product obtained by curing the photosensitive resin composition, a laminate containing the cured product, and a method for producing the cured product. and a semiconductor device including the cured product or the laminate.
• a numerical range represented by the symbol "to” means a range including the numerical values before and after "to” as lower and upper limits, respectively.
• the term "process” is meant to include not only independent processes, but also processes that are indistinguishable from other processes as long as the desired effects of the process can be achieved.
• a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent.
• alkyl group includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
• exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified.
• Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
• (meth)acrylate means both or either of “acrylate” and “methacrylate”
• (meth)acrylic means both “acrylic” and “methacrylic”
• (meth)acryloyl means either or both of “acryloyl” and “methacryloyl”.
• Me in the structural formulas represents a methyl group
• Et represents an ethyl group
• Bu represents a butyl group
• Ph represents a phenyl group.
• total solid content refers to the total mass of all components of the composition excluding the solvent.
• the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, unless otherwise specified, and are defined as polystyrene conversion values.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, HLC-8220GPC (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel It can be obtained by connecting Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) in series. Unless otherwise stated, their molecular weights were determined using THF (tetrahydrofuran) as an eluent.
• THF tetrahydrofuran
• NMP N-methyl-2-pyrrolidone
• detection in GPC measurement uses a UV ray (ultraviolet) wavelength detector of 254 nm.
• UV ray ultraviolet
• a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other.
• the direction in which the layers are stacked with respect to the base material is referred to as "upper", or when there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as “upper”. and the opposite direction is called “down”.
• the composition may contain two or more compounds corresponding to each component contained in the composition.
• the content of each component in the composition means the total content of all compounds corresponding to that component.
• the temperature is 23° C.
• the pressure is 101,325 Pa (1 atm)
• the relative humidity is 50% RH, unless otherwise stated. Combinations of preferred aspects are more preferred aspects herein.
• the photosensitive resin composition of the first aspect of the present invention comprises a cyclized resin or a precursor thereof, and an SP value of 21.0 (J/cm 3 ) 0.5 or more and 25.0 (J/cm 3 ) 0 Solvent B is less than 0.5, SP value is less than 21.0 (J/cm 3 ) 0.5 or 25.0 (J/cm 3 ) 0.5 or more, and boiling point is 60° C. or more
• the solvent C and the photosensitive agent are included, and the content of the solvent C is 1 ppm or more and 10,000 ppm or less with respect to the total mass of the photosensitive resin composition.
• the photosensitive resin composition of the second aspect of the present invention comprises a cyclized resin or a precursor thereof, and an SP value of 21.0 (J/cm 3 ) 0.5 or more and 25.0 (J/cm 3 ) 0 less than .5 solvent B, ethyl acetate, isopropyl acetate, n-propyl acetate, butyl acetate, hexane, heptane, benzene, toluene, methanol, ethanol, tetrahydrofuran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol It contains a solvent C that is monomethyl ether acetate, cyclopentanone, or cyclohexanone, and a photosensitive agent, and the content of the solvent C relative to the total weight of the photosensitive resin composition is 1 ppm or more and 10,000 ppm or less.
• photosensitive resin composition or "resin composition”
• photosensitive resin composition refers to both the photosensitive resin composition of the first aspect and the photosensitive resin composition of the second aspect.
• the above-mentioned cyclized resin or its precursor is also called “specific resin.”
• ppm is a mass standard
• the content of the solvent C with respect to the total mass of the photosensitive resin composition is a value represented by the following formula.
• the content (ppm) of the solvent C with respect to the total mass of the photosensitive resin composition the content mass of the solvent C / the total mass of the photosensitive resin composition ⁇ 1,000,000
• the SP value is the Hansen solubility parameter
• the HSP value obtained from the following formula using ⁇ D, ⁇ P, and ⁇ H calculated by Hansen Solubility Parameter in Practice (HSPiP) Ver.5.1.02 Say.
• HSP value ( ⁇ D 2 + ⁇ P 2 + ⁇ H 2 ) 0.5
• the resin composition of the present invention is preferably used for forming a photosensitive film subjected to exposure and development, and is preferably used for forming a film subjected to exposure and development using a developer containing an organic solvent. More preferred.
• INDUSTRIAL APPLICABILITY The resin composition of the present invention can be used, for example, to form an insulating film for semiconductor devices, an interlayer insulating film for rewiring layers, a stress buffer film, and the like, and can be used to form an interlayer insulating film for rewiring layers. preferable. Further, the resin composition of the present invention may be used for forming a photosensitive film for positive development, or may be used for forming a photosensitive film for negative development.
• negative development refers to development in which non-exposed areas are removed by development in exposure and development
• positive development refers to development in which exposed areas are removed by development.
• the exposure method, the developer, and the development method include, for example, the exposure method described in the exposure step, the developer and the development method described in the development step in the description of the method for producing a cured product described later. is used.
• a cured product having excellent elongation at break can be obtained.
• photosensitive resin compositions containing cyclized resins or their precursors, solvents, and photosensitive agents have been used in various fields.
• the photosensitive resin composition of the first aspect or the photosensitive resin composition of the second aspect the cured product obtained from the photosensitive resin composition breaks. It was found that elongation is improved. This is because the photosensitive resin composition has an SP value of less than 21.0 (J/cm 3 ) 0.5 or 25.0 (J/cm 3 ) 0.5 or more and a boiling point of 60° C. or more.
• the presence of a certain solvent C causes the solvent C to remain in the film before curing, and promotes aggregation of the cyclized resin or its precursor, which has a low solubility in this solvent C, during curing. be. Moreover, if the content of the solvent C is within the above range, the elongation at break can be improved while maintaining the applicability of the photosensitive resin composition. That is, it is presumed that the photosensitive resin composition of the present invention is also excellent in film thickness uniformity when applied to a substrate or the like.
• the photosensitive agent is uniformly dispersed in the film, and the cross-linking reaction proceeds efficiently in the exposed area, so the film thickness change rate of the exposed area before and after development is small. It is assumed that
• Patent Documents 1 and 2 do not describe the inclusion of a specific amount of solvent C.
• the resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of cyclized resins and precursors thereof.
• the cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in its main chain structure.
• the main chain represents the relatively longest connecting chain in the resin molecule.
• cyclized resins include polyimide, polybenzoxazole, and polyamideimide.
• the precursor of the cyclized resin refers to a resin that undergoes a change in chemical structure by an external stimulus to become a cyclized resin, preferably a resin that undergoes a change in chemical structure by heat to become a cyclized resin.
• a resin that becomes a cyclized resin by forming a ring structure is more preferable.
• Precursors of the cyclized resin include polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, and the like. That is, the resin composition of the present invention contains, as a specific resin, at least one selected from the group consisting of polyimides, polyimide precursors, polybenzoxazoles, polybenzoxazole precursors, polyamideimides, and polyamideimide precursors. It preferably contains a resin (specific resin).
• the resin composition of the present invention preferably contains polyimide or a polyimide precursor as the specific resin.
• the specific resin preferably contains a precursor of a cyclized resin, and more preferably contains a polyimide precursor. Moreover, the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
• the resin composition of the present invention preferably contains a radical polymerization initiator described later, and contains a radical polymerization initiator described later and a radical cross-linking agent described later. is more preferred. Further, if necessary, a sensitizer described later can be included. For example, a negative photosensitive film is formed from the resin composition of the present invention.
• the specific resin may have a polarity conversion group such as an acid-decomposable group.
• the resin composition of the present invention preferably contains a photoacid generator, which will be described later. From such a resin composition of the present invention, for example, a chemically amplified positive photosensitive film or negative photosensitive film is formed.
• polyimide precursor Although the type of the polyimide precursor used in the present invention is not particularly limited, it preferably contains a repeating unit represented by the following formula (2).
• a 1 and A 2 each independently represent an oxygen atom or -NH-
• R 111 represents a divalent organic group
• R 115 represents a tetravalent organic group
• R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group.
• a 1 and A 2 in formula (2) each independently represent an oxygen atom or —NH—, preferably an oxygen atom.
• R 111 in formula (2) represents a divalent organic group.
• divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
• the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the cyclic aliphatic group and the aromatic group, the ring member hydrocarbon group is a hetero atom.
• may be substituted with a group containing Groups represented by -Ar- and -Ar-L-Ar- are exemplified as preferred embodiments of the present invention, and groups represented by -Ar-L-Ar- are particularly preferred.
• Ar is each independently an aromatic group
• L is a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO -, -S-, -SO 2 - or -NHCO-, or a group consisting of a combination of two or more of the above. Preferred ranges for these are as described above.
• R 111 is preferably derived from a diamine.
• Diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferably a diamine containing, more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. In the straight-chain or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom. may be substituted with a group containing Examples of groups containing aromatic groups include:
• * represents a binding site with other structures.
• diamines include compounds described in paragraphs 0078 to 0088 of International Publication No. 2021/045126.
• R 111 is preferably represented by -Ar-L-Ar- from the viewpoint of the flexibility of the resulting organic film.
• Ar is each independently an aromatic group
• L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- , —SO 2 — or —NHCO—, or a group consisting of a combination of two or more of the above.
• Ar is preferably a phenylene group
• L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms optionally substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 - .
• the aliphatic hydrocarbon group here is preferably an alkylene group.
• R 111 is preferably a divalent organic group represented by the following formula (51) or (61).
• a divalent organic group represented by Formula (61) is more preferable.
• Equation (51) In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoro It is a methyl group, and each * independently represents a binding site to the nitrogen atom in formula (2).
• the monovalent organic groups represented by R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.
• R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is each independently a bonding site to the nitrogen atom in formula (2) show.
• Diamines that give the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′-bis (Fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. These may be used alone or in combination of two or more.
• R 115 in formula (2) represents a tetravalent organic group.
• a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or (6) is more preferable.
• each * independently represents a binding site to another structure.
• R 112 is a single bond or a divalent linking group, a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally substituted with a fluorine atom, —O—, -CO-, -S-, -SO 2 -, and -NHCO-, and preferably a group selected from a combination thereof, having 1 to 1 carbon atoms optionally substituted by a single bond or a fluorine atom 3 alkylene group, -O-, -CO-, -S- and -SO 2 -, and -CH 2 -, -C(CF 3 ) 2 -, -C( It is more preferably a divalent group selected from the group consisting of CH 3 ) 2 -, -O-, -CO-, -S- and -SO 2 -.
• R 115 includes a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride.
• the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue as a structure corresponding to R115 , or may contain two or more types thereof.
• the tetracarboxylic dianhydride is preferably represented by the following formula (O).
• R 115 represents a tetravalent organic group.
• the preferred range of R 115 is synonymous with R 115 in formula (2), and the preferred range is also the same.
• tetracarboxylic dianhydrides include compounds described in paragraphs 0029 to 0031 of International Publication No. 2021/045126.
• R 111 and R 115 has an OH group. More specifically, R 111 includes residues of bisaminophenol derivatives.
• R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
• the monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
• At least one of R 113 and R 114 preferably contains a polymerizable group, more preferably both contain a polymerizable group. It is also preferred that at least one of R 113 and R 114 contains two or more polymerizable groups.
• the polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, or the like, and is preferably a radically polymerizable group.
• the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. be done.
• a group having an ethylenically unsaturated bond is preferred.
• Groups having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), and a (meth)acrylamide group.
• a (meth)acryloyloxy group a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
• R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
• * represents a binding site with another structure.
• R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
• a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
• the alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
• the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or a block arrangement. Alternatively, it may be arranged in a pattern such as an alternating pattern.
• the number of carbon atoms in the alkylene group is preferably 2 or more, more preferably 2 to 10, and 2 to 6. is more preferred, 2 to 5 is more preferred, 2 to 4 is even more preferred, 2 or 3 is particularly preferred, and 2 is most preferred.
• the said alkylene group may have a substituent.
• Preferred substituents include alkyl groups, aryl groups, and halogen atoms.
• the number of alkyleneoxy groups contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
• a group to which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable.
• the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in a pattern such as alternately. Preferred embodiments of the number of repetitions of ethyleneoxy groups and the like in these groups are as described above.
• the polyimide precursor when R 113 is a hydrogen atom, or when R 114 is a hydrogen atom, the polyimide precursor may form a tertiary amine compound having an ethylenically unsaturated bond and a counter salt. good.
• tertiary amine compounds having ethylenically unsaturated bonds include N,N-dimethylaminopropyl methacrylate.
• R 113 and R 114 may be a polarity conversion group such as an acid-decomposable group.
• the acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxyl group. , a tertiary alkyl ester group and the like are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.
• the polyimide precursor preferably has a fluorine atom in its structure.
• the content of fluorine atoms in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
• the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
• an aliphatic group having a siloxane structure there is an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.
• the repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one polyimide precursor used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
• a 1 and A 2 represent an oxygen atom
• R 111 and R 112 each independently represent a divalent organic group
• R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group
• at least one of R 113 and R 114 is a group containing a polymerizable group, and both are preferably groups containing a polymerizable group.
• a 1 , A 2 , R 111 , R 113 and R 114 are each independently synonymous with A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and preferred ranges are also the same.
• R 112 has the same definition as R 112 in formula (5), and the preferred range is also the same.
• the polyimide precursor may contain one type of repeating unit represented by formula (2), but may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may also contain other types of repeating units in addition to the repeating units of formula (2) above.
• the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units.
• the total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %.
• the upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor excluding terminals may be repeating units represented by formula (2).
• the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. Also, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
• the polyimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyimide precursor's molecular weight dispersity is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
• the molecular weight dispersity is a value calculated by weight average molecular weight/number average molecular weight.
• the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polyimide precursors as one resin are within the ranges described above.
• the polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide soluble in a developer containing an organic solvent as a main component.
• the alkali-soluble polyimide refers to a polyimide that dissolves in 100 g of a 2.38% by mass tetramethylammonium aqueous solution at 23° C. by 0.1 g or more, and from the viewpoint of pattern formation, 0.5 g or more. It is preferably a polyimide that dissolves, and more preferably a polyimide that dissolves 1.0 g or more. Although the upper limit of the dissolved amount is not particularly limited, it is preferably 100 g or less.
• the polyimide is preferably a polyimide having a plurality of imide structures in its main chain from the viewpoint of the film strength and insulating properties of the resulting organic film.
• the term "main chain” refers to the relatively longest linking chain in the molecule of the polymer compound that constitutes the resin, and the term “side chain” refers to the other linking chain.
• the polyimide preferably has a fluorine atom.
• a fluorine atom is preferably included in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later, and the formula ( It is more preferably contained as a fluorinated alkyl group in R 132 in the repeating unit represented by 4) or R 131 in the repeating unit represented by formula (4) described later.
• the amount of fluorine atoms relative to the total mass of polyimide is preferably 5% by mass or more and preferably 20% by mass or less.
• the polyimide preferably has a silicon atom.
• a silicon atom for example, is preferably contained in R 131 in a repeating unit represented by formula (4) described later, and R 131 in a repeating unit represented by formula (4) described later is an organically modified (poly ) is more preferably contained as a siloxane structure.
• the silicon atom or the organically modified (poly)siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
• the amount of silicon atoms relative to the total mass of polyimide is preferably 1% by mass or more, and more preferably 20% by mass or less.
• the polyimide preferably has an ethylenically unsaturated bond.
• the polyimide may have an ethylenically unsaturated bond at the end of its main chain or in a side chain, preferably in a side chain.
• the ethylenically unsaturated bond preferably has radical polymerizability.
• the ethylenically unsaturated bond is preferably contained in R 132 in a repeating unit represented by the formula (4) described later, or R 131 in a repeating unit represented by the formula (4) described later.
• the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by formula (4) described later, and ethylene is contained in R 131 in the repeating unit represented by formula (4) described later It is more preferably included as a group having a polyunsaturated bond.
• the group having an ethylenically unsaturated bond includes a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acrylamide group, a (meth) Examples include an acryloyloxy group and a group represented by the following formula (IV).
• R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
• R 21 is an alkylene group having 2 to 12 carbon atoms, —O—CH 2 CH(OH)CH 2 —, —C( ⁇ O)O—, —O(C ⁇ O)NH— , a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12, 1 to 6 are more preferred, and 1 to 3 are particularly preferred), or a group in which two or more of these are combined.
• the alkylene group having 2 to 12 carbon atoms may be a linear, branched, cyclic, or a combination of these alkylene groups.
• an alkylene group having 2 to 8 carbon atoms is preferable, and an alkylene group having 2 to 4 carbon atoms is more preferable.
• R 21 is preferably a group represented by any one of the following formulas (R1) to (R3), more preferably a group represented by formula (R1).
• L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are combined
• X represents an oxygen atom or a sulfur atom
• * represents a bonding site with another structure
• ⁇ represents a bonding site with the oxygen atom to which R 21 in formula (IV) bonds.
• a preferred embodiment of an alkylene group having 2 to 12 carbon atoms or a (poly)alkyleneoxy group having 2 to 30 carbon atoms in L is the above-mentioned R 21 having 2 to 12 carbon atoms. It is the same as the preferred embodiment of the 12 alkylene group or the (poly)alkyleneoxy group having 2 to 30 carbon atoms.
• X is preferably an oxygen atom.
• * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
• the structure represented by formula (R1) is, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group, and a compound having an isocyanato group and an ethylenically unsaturated bond (e.g., 2-isocyanatoethyl methacrylate, etc.). Obtained by reaction.
• the structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (eg, 2-hydroxyethyl methacrylate, etc.).
• the structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (e.g., glycidyl methacrylate, etc.) can get.
• a polyimide having a hydroxy group such as a phenolic hydroxy group
• a compound having a glycidyl group and an ethylenically unsaturated bond e.g., glycidyl methacrylate, etc.
• * represents a binding site with another structure, preferably a binding site with the main chain of polyimide.
• the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001-0.1 mol/g, more preferably 0.0005-0.05 mol/g.
• Polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
• Polymerizable groups other than groups having an ethylenically unsaturated bond include cyclic ether groups such as an epoxy group and an oxetanyl group, alkoxymethyl groups such as a methoxymethyl group, and methylol groups.
• a polymerizable group other than a group having an ethylenically unsaturated bond is preferably included, for example, in R 131 in a repeating unit represented by formula (4) described below.
• the amount of the polymerizable group other than the group having an ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. more preferred.
• the polyimide may have a polar conversion group such as an acid-decomposable group.
• the acid-decomposable group in the polyimide is the same as the acid-decomposable group described for R 113 and R 114 in formula (2) above, and preferred embodiments are also the same.
• Polar conversion groups are included, for example, at R 131 and R 132 in the repeating unit represented by formula (4) described later, the terminal of polyimide, and the like.
• the acid value of polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more, from the viewpoint of improving developability. is more preferable. Moreover, the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less. Further, when the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, "solvent development” described later), the acid value of the polyimide is preferably 1 to 35 mgKOH/g, and 2 to 30 mgKOH.
• the acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.
• an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable, from the viewpoint of both storage stability and developability.
• the pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is represented by its negative common logarithm pKa.
• pKa is a value calculated by ACD/ChemSketch (registered trademark).
• the values listed in the Chemical Society of Japan, Revised 5th Edition, Basics of Chemistry may be referred to.
• the acid group is a polyvalent acid such as phosphoric acid
• the pKa is the first dissociation constant.
• the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, more preferably a phenolic hydroxy group.
• the polyimide preferably has a phenolic hydroxy group from the viewpoint of making the development speed with an alkaline developer appropriate.
• Polyimide may have a phenolic hydroxy group at the end of the main chain or in the side chain.
• a phenolic hydroxy group is preferably contained in, for example, R 132 in a repeating unit represented by formula (4) described later or R 131 in a repeating unit represented by formula (4) described later.
• the amount of phenolic hydroxy groups relative to the total weight of the polyimide is preferably 0.1-30 mol/g, more preferably 1-20 mol/g.
• the polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide structure, but it preferably contains a repeating unit represented by the following formula (4).
• R 131 represents a divalent organic group and R 132 represents a tetravalent organic group.
• the polymerizable group may be located on at least one of R 131 and R 132 , and the terminal of the polyimide as shown in the following formula (4-1) or (4-2) may be located in Formula (4-1)
• R 133 is a polymerizable group, and other groups are the same as in formula (4).
• Formula (4-2) At least one of R 134 and R 135 is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups are as defined in formula (4).
• R 131 represents a divalent organic group.
• the divalent organic group are the same as those for R 111 in formula (2), and the preferred range is also the same.
• R 131 also includes a diamine residue remaining after removal of the amino group of the diamine. Diamines include aliphatic, cycloaliphatic or aromatic diamines. A specific example is the example of R 111 in formula (2) of the polyimide precursor.
• R 131 is preferably a diamine residue having at least two alkylene glycol units in its main chain from the viewpoint of more effectively suppressing warping during baking. More preferably, it is a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and more preferably the above diamine, which does not contain an aromatic ring. is.
• Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy) propoxy)propan-2-amine, 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine, and the like.
• R 132 represents a tetravalent organic group.
• examples of the tetravalent organic group are the same as those for R 115 in formula (2), and the preferred range is also the same.
• four bonds of a tetravalent organic group exemplified as R 115 combine with four —C( ⁇ O)— moieties in the above formula (4) to form a condensed ring.
• R 132 includes a tetracarboxylic acid residue remaining after removal of the anhydride group from the tetracarboxylic dianhydride.
• a specific example is the example of R 115 in formula (2) of the polyimide precursor. From the viewpoint of strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
• R 131 and R 132 has an OH group. More specifically, R 131 is 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2- Bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18) are preferred examples. and more preferred examples of R 132 are the above (DAA-1) to (DAA-5).
• the polyimide preferably has a fluorine atom in its structure.
• the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.
• the polyimide may be copolymerized with an aliphatic group having a siloxane structure.
• the diamine component include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.
• the main chain end of the polyimide is blocked with a terminal blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound.
• a terminal blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound.
• terminal blocking agents include terminal blocking agents described in paragraph 0090 of International Publication No. 2021/045126.
• the imidization rate (also referred to as "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of the film strength, insulation properties, etc. of the resulting organic film. More preferably, it is 90% or more.
• the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
• the imidization rate is measured, for example, by the method described below. The infrared absorption spectrum of the polyimide is measured, and the peak intensity P1 near 1377 cm ⁇ 1 , which is the absorption peak derived from the imide structure, is obtained. Next, after heat-treating the polyimide at 350° C.
• the polyimide may contain repeating units represented by the above formula (4) that all contain one type of R 131 or R 132 , and the above formula ( 4) may contain a repeating unit. Moreover, the polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Other types of repeating units include, for example, repeating units represented by formula (2) above.
• polyimide for example, a method of reacting a tetracarboxylic dianhydride and a diamine (partially replaced with a monoamine terminal blocker) at a low temperature, a method of reacting a tetracarboxylic dianhydride (partially with an acid anhydride) at a low temperature a monoacid chloride compound or a monoactive ester compound) and a diamine, a diester is obtained by a tetracarboxylic dianhydride and an alcohol, and then a diamine (a part of which is a monoamine A method of reacting in the presence of a condensing agent) with a condensing agent, a diester is obtained by tetracarboxylic acid dianhydride and alcohol, then the remaining dicarboxylic acid is acid chloride, diamine (part of which is a monoamine Using a method such as a method of reacting with a terminal blocking agent) to obtain a polyimide precursor
• the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. By setting the weight average molecular weight to 5,000 or more, the folding resistance of the cured film can be improved. A weight-average molecular weight of 15,000 or more is particularly preferable in order to obtain an organic film having excellent mechanical properties (e.g., elongation at break). Also, the number average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000. The polyimide has a molecular weight distribution of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
• the upper limit of the polyimide molecular weight dispersion is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
• the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated using the above plural types of polyimides as one resin are within the above ranges.
• polybenzoxazole precursor Although the structure of the polybenzoxazole precursor used in the present invention is not particularly defined, it preferably contains a repeating unit represented by the following formula (3).
• R 121 represents a divalent organic group
• R 122 represents a tetravalent organic group
• R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group. show.
• R 123 and R 124 each have the same meaning as R 113 in formula (2), and the preferred ranges are also the same. That is, at least one is preferably a polymerizable group.
• R 121 represents a divalent organic group.
• the divalent organic group a group containing at least one of an aliphatic group and an aromatic group is preferred.
• the aliphatic group a linear aliphatic group is preferred.
• R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
• the polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2).
• R 117 represents a trivalent organic group
• R 111 represents a divalent organic group
• a 2 represents an oxygen atom or —NH—
• R 113 represents a hydrogen atom or a monovalent represents an organic group.
• Polyimide precursors and the like for example, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature to obtain a polyamic acid, a condensing agent or an alkylating agent A method of esterification using a tetracarboxylic dianhydride and an alcohol to obtain a diester, followed by a reaction with a diamine in the presence of a condensing agent, a method of reacting a tetracarboxylic dianhydride and an alcohol to obtain a diester, After that, the remaining dicarboxylic acid can be acid-halogenated using a halogenating agent and reacted with a diamine.
• the method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenating the remaining dicarboxylic acid with a halogenating agent, and reacting it with a diamine is more preferable.
• the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, trifluoroacetic anhydride and the like can be mentioned.
• alkylating agent examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate and triethyl orthoformate.
• halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.
• organic solvent In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. One type of organic solvent may be used, or two or more types may be used.
• the organic solvent can be appropriately determined depending on the raw material, but pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, ⁇ -butyrolactone, and the like. are exemplified.
• a basic compound In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction.
• One type of basic compound may be used, or two or more types may be used.
• the basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-amino Pyridine and the like are exemplified.
• terminal blocking agents include monoalcohols, phenols, thiols, thiophenols, monoamines, and the like. It is more preferable to use monoalcohols, phenols and monoamines from the viewpoint of their properties.
• Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol and 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantane alcohol.
• Preferable phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.
• Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6- aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-amin
• Preferred capping agents for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromide, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides, etc., more preferably carboxylic acid anhydrides and carboxylic acid chlorides. preferable.
• Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like. are mentioned.
• Preferred carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantanecarbonyl chloride. , heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.
• a step of depositing a solid may be included in the production of the polyimide precursor or the like. Specifically, after filtering off the water absorption by-products of the dehydration condensation agent coexisting in the reaction solution as necessary, water, aliphatic lower alcohol, or a poor solvent such as a mixture thereof, the obtained A polyimide precursor or the like can be obtained by adding a polymer component and depositing the polymer component, depositing it as a solid, and drying it. In order to improve the degree of purification, operations such as re-dissolving, re-precipitation, drying, etc. of the polyimide precursor may be repeated. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.
• the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more with respect to the total solid content of the resin composition. is more preferable, and 50% by mass or more is even more preferable. Further, the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, more preferably 98% by mass, based on the total solid content of the resin composition. % or less, more preferably 97 mass % or less, and even more preferably 95 mass % or less.
• the resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
• the resin composition of the present invention preferably contains at least two resins.
• the resin composition of the present invention may contain a total of two or more of the specific resin and other resins described later, or may contain two or more of the specific resins. It is preferable to include two or more kinds.
• the resin composition of the present invention contains two or more specific resins, for example, two or more polyimides that are polyimide precursors and have different dianhydride-derived structures (R 115 in the above formula (2)) It preferably contains a precursor.
• the resin composition of the present invention may contain the specific resin described above and other resins different from the specific resin (hereinafter also simply referred to as "other resins").
• Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. etc.
• a resin composition having excellent applicability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
• a high polymerizable group value having a weight average molecular weight of 20,000 or less for example, the molar amount of the polymerizable group in 1 g of the resin is 1 ⁇ 10 ⁇ 3 mol/g or more
• the coating properties of the resin composition and the solvent resistance of the pattern (cured product) can be improved. can.
• the content of the other resins is preferably 0.01% by mass or more, and 0.05% by mass or more, relative to the total solid content of the resin composition. More preferably, it is more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and further preferably 10% by mass or more. More preferred.
• the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, based on the total solid content of the resin composition. It is more preferably 60% by mass or less, even more preferably 50% by mass or less.
• the content of other resins may be low.
• the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less relative to the total solid content of the resin composition. is more preferable, 5% by mass or less is even more preferable, and 1% by mass or less is even more preferable.
• the lower limit of the content is not particularly limited as long as it is 0% by mass or more.
• the resin composition of the present invention may contain only one kind of other resin, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.
• the resin composition of the present invention contains a solvent B having an SP value of 21.0 (J/cm 3 ) 0.5 or more and less than 25.0 (J/cm 3 ) 0.5 .
• Solvent B is preferably an organic solvent.
• the SP value of Solvent B is preferably 21.5 (J/cm 3 ) 0.5 or more, more preferably 22.0 (J/cm 3 ) 0.5 or more.
• it is preferably 24.0 (J/cm 3 ) 0.5 or less, more preferably 23.0 (J/cm 3 ) 0.5 or less.
• the solubility of the specific resin in solvent B is preferably 5 g/100 g or more, more preferably 10 g/100 g or more, and even more preferably 20 g/100 g or more with respect to 100 g of solvent B at 25°C. .
• the solubility in each combination of at least one specific resin and at least one solvent B is within the above range. inside.
• Solvent B is ⁇ -butyrolactone (GBL), dimethylsulfoxide (DMSO), N-methyl-2-pyrrolidone (NMP), 3-methoxy-N,N-dimethylpropanamide, 1,3-dimethyl-2-imidazolidine It preferably contains at least one selected from the group consisting of non (DMI), tetramethylurea (TMU), propylene glycol monomethyl ether (PGME), and ethyl lactate. Moreover, from the viewpoint of the elongation at break of the cured product to be obtained and the film thickness uniformity of the resin composition when applied to the substrate, the solvent B may be a mixture of two or more solvents.
• the solvent B preferably contains GBL, 3-methoxy-N,N-dimethylpropanamide, DMI or NMP, and may be one of the combinations shown in (B1) to (B10) below. more preferred.
• the solvent B preferably contains GBL, 3-methoxy-N,N-dimethylpropanamide, DMI or NMP, and may be one of the combinations shown in (B1) to (B10) below. more preferred.
• B1 containing NMP and ethyl lactate (B2) containing NMP and PGME (B3) containing GBL and DMSO (B4) containing GBL and NMP (B5) containing GBL and 3-methoxy-N,N-dimethylpropanamide (B6) including GBL and DMI (B7) including 3-methoxy-N,N-dimethylpropanamide and ethyl lactate (B8) including 3-methoxy-N,N-dimethylpropanamide and PGME (B9) DMI and ethyl lactate (B10) containing DMI and PGME.
• the content of the solvent used is 5% by mass or less (preferably 1% by mass or less, more preferably 0.1% by mass or less) is also one of the preferred embodiments of the present invention.
• the content of ethyl lactate is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass when the content of NMP is 100 parts by mass.
• the content of PGME is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass when the content of NMP is 100 parts by mass.
• the content of DMSO is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass when the content of GBL is 100 parts by mass.
• the content of NMP is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass.
• the content of 3-methoxy-N,N-dimethylpropanamide when the content of GBL is 100 parts by mass is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass. is more preferable.
• the content of DMI is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass when the content of GBL is 100 parts by mass.
• the content of ethyl lactate when the content of 3-methoxy-N,N-dimethylpropanamide is 100 parts by mass, the content of ethyl lactate is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass. Part is more preferred.
• the content of PGME when the content of 3-methoxy-N,N-dimethylpropanamide is 100 parts by mass is preferably 5 to 50 parts by mass, and 10 to 40 parts by mass. is more preferable.
• the content of DMI when the content of DMI is 100 parts by mass
• the content of ethyl lactate when the content of ethyl lactate is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass.
• the content of PGME is preferably 5 to 50 parts by mass, more preferably 10 to 40 parts by mass when the content of DMI is 100 parts by mass.
• the content of the solvent B with respect to the total mass of the photosensitive resin composition is preferably 40% by mass or more and less than 90% by mass, more preferably 50 to 80% by mass, and 55 to 75% by mass. is more preferable.
• the photosensitive resin composition of the present invention contains solvent C.
• the solvent C has an SP value of less than 21.0 (J/cm 3 ) 0.5 or 25.0 (J/cm 3 ) 0.5 or more. and a solvent having a boiling point of 60° C. or higher. The above boiling points are values at 1 atmosphere (101,325 Pa).
• the solvent C is ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, hexane, heptane, benzene, toluene, methanol, ethanol, tetrahydrofuran, 1,4-dioxane.
• the solvent C is ethyl acetate, isopropyl acetate, normal propyl acetate, butyl acetate, hexane, heptane, benzene, toluene, methanol, ethanol, tetrahydrofuran, 1,4-dioxane.
• the solvent C in the photosensitive resin composition of the second aspect of the present invention has an SP value of less than 21.0 (J/cm 3 ) 0.5 or 25.0 (J/cm 3 ) 0.5 . 5 or higher and a boiling point of 60° C. or higher.
• the solvent C contained in the photosensitive resin composition of the present invention is toluene, tetrahydrofuran, 1 ,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, or cyclopentanone, and more preferably toluene, tetrahydrofuran, 1,4-dioxane, or diethylene glycol dimethyl ether.
• the content of the solvent C with respect to the total mass of the photosensitive resin composition is 1 ppm or more and 10,000 ppm or less. From the viewpoint of the elongation at break of the resulting cured product, the content is preferably 5 ppm or more, more preferably 10 ppm or more, and even more preferably 20 ppm or more. From the viewpoint of film thickness uniformity of the resin composition when applied to a substrate, the content is preferably 5,000 ppm or less, more preferably 2,000 ppm or less, and 500 ppm or less. is more preferred.
• the content of the solvent C with respect to 100 parts by mass of the specific resin is preferably 0.0003 to 3.5, more preferably 0.002 to 2, and 0.003 to 3.5. 005 to 0.3 is more preferable.
• the content of the solvent C with respect to 100 parts by mass of the polymerizable compound is preferably 0.001 to 50, more preferably 0.004 to 5, and 0.01 ⁇ 3 is more preferred.
• the content of the solvent C with respect to 100 parts by mass of the polymerization inhibitor is preferably 0.5 to 10000, more preferably 1 to 5000, and 10 to 500. is more preferred.
• the content of the solvent C with respect to 100 parts by mass of the metal adhesion improver is preferably 0.01 to 300, more preferably 0.02 to 200, and 0 0.2 to 100 is more preferred.
• the content of the solvent C with respect to 100 parts by mass of the migration inhibitor is preferably 1 to 20,000, more preferably 2 to 15,000, and more preferably 10 to 10,000. More preferred.
• the content of solvent C with respect to 100 parts by mass of antioxidant is preferably 0.02 to 300, more preferably 0.03 to 200, and 0.1 ⁇ 100 is more preferred.
• the SP value of the solvent C contained in the photosensitive resin composition of the present invention is less than 21.0 (J/cm 3 ) 0.5 or 25.0 (J/cm 3 ) 0.5 or more, 17.0 (J/cm 3 ) 0.5 or more and 21.0 (J/cm 3 ) less than 0.5 , or 25.0 (J/cm 3 ) 0.5 or more and 27.0 (J/cm 3 ) ) is preferably less than 0.5 , more preferably 18.0 (J/cm 3 ) 0.5 or more and 21.0 (J/cm 3 ) less than 0.5 .
• the boiling point of the solvent C contained in the photosensitive resin composition of the present invention is 60° C. or higher, preferably 65° C. or higher, more preferably 70° C. or higher.
• the upper limit of the boiling point is preferably 250°C or less. If the boiling point is equal to or higher than the above lower limit, volatilization of the solvent C is suppressed during heating, for example, and it is considered that the effect of improving the elongation at break of the cured product is more likely to be obtained.
• the solubility of the specific resin in solvent C is preferably less than 20 g/100 g, more preferably less than 10 g/100 g, and even more preferably less than 5 g/100 g with respect to 100 g of solvent C at 25°C. .
• the lower limit of the solubility is not particularly limited, it is preferably 0.1 g/100 g or more, for example.
• the solubility in the combination of at least one specific resin and at least one solvent C is within the above range. I wish I had.
• the photosensitive resin composition of the present invention contains a photosensitizer.
• the photosensitive agent includes a photopolymerization initiator, a photoacid generator, and the like, preferably containing a photopolymerization initiator, and more preferably containing a radical photopolymerization initiator.
• the photopolymerization initiator is preferably a photoradical polymerization initiator.
• the radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators.
• a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. It may also be an activator that produces an active radical by producing some action with a photoexcited sensitizer.
• the radical photopolymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 within the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). is preferred.
• the molar extinction coefficient of a compound can be measured using known methods. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
• any known compound can be used as the photoradical polymerization initiator.
• halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
• acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc.
• ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the content of which is incorporated herein.
• Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd. is also suitably used.
• a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used as the radical photopolymerization initiator. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used. incorporated.
• ⁇ -hydroxyketone initiators include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE -2959 and IRGACURE 127 (trade names: both manufactured by BASF) can be used.
• ⁇ -aminoketone initiators examples include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all BASF company) can be used.
• the compound described in JP-A-2009-191179 whose maximum absorption wavelength is matched to a wavelength light source such as 365 nm or 405 nm can also be used, the content of which is incorporated herein.
• Acylphosphine oxide initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
• Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF) can also be used.
• metallocene compounds examples include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF) and Keycure VIS 813 (manufactured by King Brother Chem).
• the photoradical polymerization initiator is more preferably an oxime compound.
• an oxime compound By using an oxime compound, the exposure latitude can be improved more effectively.
• Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.
• oxime compound examples include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-019766, compounds described in Patent No.
• Preferred oxime compounds include, for example, compounds having the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy( iminobutan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1- phenylpropan-1-one, 3-((4-toluenesulfonyloxy)(imino))butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one, etc.
• an oxime compound an oxime-based radical photopolymerization initiator
• DFI-091 manufactured by Daito Chemix Co., Ltd.
• SpeedCure PDO manufactured by SARTOMER ARKEMA
• an oxime compound having the following structure can be used.
• An oxime compound having a fluorene ring can also be used as the photoradical polymerization initiator.
• Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466 and compounds described in Japanese Patent No. 06636081, the contents of which are incorporated herein.
• an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
• Specific examples of such oxime compounds include compounds described in WO2013/083505, the contents of which are incorporated herein.
• oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. and compound (C-3) described in paragraph 0101 of JP-A-164471, the contents of which are incorporated herein.
• An oxime compound having a nitro group can be used as the photopolymerization initiator.
• the oxime compound having a nitro group is also preferably a dimer.
• Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Included are compounds described in paragraphs 0007-0025 of Japanese Patent No. 4223071, the contents of which are incorporated herein.
• the oxime compound having a nitro group also includes ADEKA Arkles NCI-831 (manufactured by ADEKA Co., Ltd.).
• An oxime compound having a benzofuran skeleton can also be used as the photoradical polymerization initiator.
• Specific examples include OE-01 to OE-75 described in WO 2015/036910.
• an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
• photoinitiators include compounds such as those described in WO2019/088055, the contents of which are incorporated herein.
• an oxime compound having an aromatic ring group Ar 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used.
• the electron-withdrawing group of the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group.
• An acyl group and a nitro group are preferred, an acyl group is more preferred, and a benzoyl group is even more preferred because a film having excellent light resistance can be easily formed.
• the oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.
• R X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group
• R X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group,
• R X12 is an electron-withdrawing group
• R X10 , R X11 , R X13 and R X14 are preferably hydrogen atoms.
• oxime compound OX examples include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.
• oxime compounds having specific substituents shown in JP-A-2007-269779 and oxime compounds having a thioaryl group shown in JP-A-2009-191061. incorporated herein.
• photoradical polymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds; are preferred.
• More preferred radical photopolymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, and acetophenone compounds.
• At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferred, and metallocene compounds or oxime compounds are even more preferred. .
• the photoradical polymerization initiator includes benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthraquinones, etc.
• benzophenone N,N'-tetraalkyl-4,4'-diaminobenzophenone
• 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthr
• benzoin ether compounds such as benzoin alkyl ether
• benzoin compounds such as benzoin and alkylbenzoin
• benzyl derivatives such as benzyl dimethyl ketal
• a compound represented by the following formula (I) can also be used.
• R 100 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, Alternatively, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, a carbon number interrupted by one or more oxygen atoms a phenyl group or a biphenyl group substituted with at least one of an alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms, and R I01 is a group represented by formula (II); It is the same group as R 100 , and each of R 102 to R 104 is independently an alkyl group having 1 to 12 carbon atoms
• R 105 to R 107 are the same as R 102 to R 104 in formula (I) above.
• radical photopolymerization initiator a difunctional or trifunctional or higher radical photopolymerization initiator may be used.
• a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained.
• the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation becomes difficult over time, and the stability over time of the resin composition can be improved.
• Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
• a photopolymerization initiator When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , more preferably 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further advanced by heating with an oven, a hot plate, or the like.
• the resin composition may contain a sensitizer.
• a sensitizer absorbs specific actinic radiation and enters an electronically excited state.
• the sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes electron transfer, energy transfer, heat generation, or the like.
• the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids or bases.
• Sensitizers that can be used include compounds described in paragraph 0269 of WO2021/045126.
• the content of the sensitizer is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. more preferably 0.5 to 10% by mass.
• the sensitizers may be used singly or in combination of two or more.
• the resin composition of the present invention may contain a chain transfer agent.
• the chain transfer agent is defined, for example, in Kobunshi Jiten, 3rd edition (edited by Kobunshi Gakkai, 2005), pp. 683-684.
• Chain transfer agents include, for example, a group of compounds having —S—S—, —SO 2 —S—, —NO—, SH, PH, SiH, and GeH in the molecule, RAFT (Reversible Addition Fragmentation Chain Transfer )
• Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used for polymerization are used. They can either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
• thiol compounds can be preferably used.
• chain transfer agent can also use the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, the contents of which are incorporated herein.
• the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. 1 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is even more preferable.
• One type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total is preferably within the above range.
• Photoacid generator A quinonediazide compound is preferable as the photoacid generator.
• photoacid generators known in the field of photosensitive resin compositions may also be used.
• Examples of the quinonediazide compound include polyhydroxy compounds in which quinonediazide sulfonic acid is ester-bonded, polyamino compounds in which quinonediazide sulfonic acid is bonded via sulfonamide, and polyhydroxypolyamino compounds in which quinonediazide sulfonic acid is ester-bonded and/or sulfone-bonded. Examples include those bound by amide. Although not all the functional groups of these polyhydroxy compounds, polyamino compounds, and polyhydroxypolyamino compounds may be substituted with quinonediazide, it is preferred that 40 mol % or more of all functional groups on average be substituted with quinonediazide. .
• a positive photosensitive resin composition sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) can be obtained.
• the content of the quinonediazide compound contained in the photosensitive resin composition of the present invention is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and 50 parts by mass with respect to 100 parts by mass of the total resin in the photosensitive resin composition. Parts or less is preferable, and 40 parts by mass or less is more preferable.
• the resin composition of the present invention preferably contains a polymerizable compound.
• Polymerizable compounds include radically polymerizable compounds (radical cross-linking agents) or other cross-linking agents.
• the resin composition of the present invention preferably further contains a radical polymerizable compound (radical cross-linking agent).
• the resin composition of the present invention preferably contains a radical cross-linking agent.
• a radical cross-linking agent is a compound having a radically polymerizable group.
• the radically polymerizable group a group containing an ethylenically unsaturated bond is preferred.
• Examples of the group containing an ethylenically unsaturated bond include groups containing an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
• the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and more preferably a (meth)acryloyl group from the viewpoint of reactivity.
• the radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more.
• the radical cross-linking agent may have 3 or more ethylenically unsaturated bonds.
• the compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and 2 to 6.
• the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferred to include
• the molecular weight of the radical cross-linking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
• the lower limit of the molecular weight of the radical cross-linking agent is preferably 100 or more.
• Specific examples of the radical cross-linking agent include compounds described in paragraphs 0143 to 0154 of WO2021/045126.
• the resin composition preferably uses a bifunctional methacrylate or acrylate.
• Specific compounds include compounds described in paragraph 0155 of International Publication No. 2021/045126.
• a radical cross-linking agent When a radical cross-linking agent is contained, its content is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention. More preferably, the lower limit is 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
• a single radical cross-linking agent may be used alone, or two or more may be used in combination. When two or more are used in combination, the total amount is preferably within the above range.
• the resin composition of the present invention also preferably contains other cross-linking agents different from the radical cross-linking agents described above.
• the resin composition of the present invention may contain a base generator.
• the base generator is a compound capable of generating a base by physical or chemical action.
• Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
• the resin composition when the resin composition contains a cyclized resin precursor, the resin composition preferably contains a base generator.
• the base generator may be an ionic base generator or a non-ionic base generator.
• bases generated from base generators include secondary amines and tertiary amines. There are no particular restrictions on the base generator used in the present invention, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amine imides.
• the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention.
• the lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
• the upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
• One or two or more base generators can be used. When two or more are used, the total amount is preferably within the above range.
• the resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, and the like.
• metal adhesion improvers include alkoxysilyl group-containing silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, and ⁇ -ketoesters. compounds, amino compounds, and the like.
• the resin composition of the present invention preferably further contains a silane coupling agent.
• silane coupling agent examples include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and paragraphs of WO 2011/080992.
• Compounds described in 0063-0071, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594 Compounds described in paragraph 0055, compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein.
• Aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.
• the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the specific resin. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the pattern and the metal layer is improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the pattern are improved.
• One type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.
• the resin composition of the present invention preferably further contains a migration inhibitor.
• a migration inhibitor By containing the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.
• Migration inhibitors are not particularly limited, but heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenolic compounds , salicylic acid derivative-based compounds, and hydrazide derivative-based compounds.
• heterocyclic rings pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring,
• triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
• an ion trapping agent that traps anions such as halogen ions can be used.
• the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the resin composition of the present invention. , more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.
• migration inhibitor Only one type of migration inhibitor may be used, or two or more types may be used. When two or more migration inhibitors are used, the total is preferably within the above range.
• the resin composition of the present invention preferably contains a polymerization inhibitor.
• Polymerization inhibitors include phenol compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, metal compounds and the like.
• the content of the polymerization inhibitor is preferably 0.01 to 20% by mass with respect to the total solid content of the resin composition of the present invention. It is more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass.
• polymerization inhibitor Only one type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
• the resin composition of the present invention preferably contains an acid scavenger in order to reduce performance changes over time from exposure to heating.
• the acid scavenger refers to a compound that can scavenge the generated acid when present in the system, and is preferably a compound with low acidity and high pKa.
• the acid scavenger is preferably a compound having an amino group, preferably a primary amine, secondary amine, tertiary amine, ammonium salt, tertiary amide, etc. Primary amine, secondary amine, tertiary amine, ammonium salt are preferred, and secondary amines, tertiary amines and ammonium salts are more preferred.
• acid scavengers include compounds having an imidazole structure, diazabicyclo structure, onium structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives having hydroxyl groups and/or ether bonds, and anilines having hydroxyl groups and/or ether bonds. Derivatives and the like can be mentioned preferably.
• the acid scavenger is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid less acidic than the acid generated by the acid generator. is preferred.
• compositions according to the present invention may or may not contain an acid scavenger, but when it does, the content of the acid scavenger is usually from 0.001 to 0.001 based on the total solid content of the composition. 10% by mass, preferably 0.01 to 5% by mass.
• the acid generator/acid scavenger (molar ratio) is more preferably 5.0-200, still more preferably 7.0-150.
• the resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, as long as the effects of the present invention can be obtained.
• additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, as long as the effects of the present invention can be obtained.
• Organic titanium compounds, antioxidants, anti-agglomerating agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (eg, antifoaming agents, flame retardants, etc.), etc. can be blended. Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No.
• the total blending amount is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
• surfactant various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used.
• the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
• the liquid properties (especially fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving are further improved. can do. That is, when a film is formed using a coating liquid to which a composition containing a surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved. , the coatability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with little unevenness in thickness.
• the surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
• a higher fatty acid derivative such as behenic acid or behenic acid amide is added in order to prevent polymerization inhibition caused by oxygen. may be unevenly distributed on the surface of the resin composition of the present invention
• the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types thereof may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
• the resin composition of the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator.
• a thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be advanced, so that the solvent resistance can be further improved.
• the photopolymerization initiator described above may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
• thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.
• thermal polymerization initiator When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , more preferably 0.5 to 15% by mass.
• One type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.
• the resin composition of the present invention may contain inorganic fine particles.
• inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
• the average particle diameter of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, still more preferably 0.03 to 1.0 ⁇ m, and 0.04 to 0.5 ⁇ m. Especially preferred.
• the average particle size of the fine particles is the primary particle size and the volume average particle size.
• the volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, the centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method can be used.
• the composition of the present invention may contain an ultraviolet absorber.
• an ultraviolet absorber As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
• the above various ultraviolet absorbers may be used singly or in combination of two or more.
• the composition of the present invention may or may not contain an ultraviolet absorber, but when it does, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid mass of the composition of the present invention. It is preferably at least 1% by mass, more preferably at least 0.01% by mass and not more than 0.1% by mass.
• the resin composition of this embodiment may contain an organic titanium compound.
• an organic titanium compound By containing the organic titanium compound in the resin composition, it is possible to form a resin layer having excellent chemical resistance even when cured at a low temperature.
• Organotitanium compounds that can be used include those in which organic groups are attached to titanium atoms through covalent or ionic bonds. Specific examples of organotitanium compounds are shown below in I) to VII): I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the resin composition is good and a good curing pattern can be obtained.
• the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin.
• the amount is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance more effectively. Excellent.
• compositions of the present invention may contain antioxidants.
• antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like.
• the amount of antioxidant to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin.
• the addition amount 0.1 parts by mass or more By making the addition amount 0.1 parts by mass or more, the effect of improving elongation characteristics and adhesion to metal materials can be easily obtained even in a high-temperature and high-humidity environment.
• the interaction with the agent improves the sensitivity of the resin composition.
• Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
• the resin composition of the present embodiment may contain an anti-aggregation agent as necessary.
• Anti-aggregating agents include sodium polyacrylate and the like.
• the aggregation inhibitor may be used alone or in combination of two or more.
• the composition of the present invention may or may not contain an anti-aggregating agent, but when it is included, the content of the anti-aggregating agent is 0.01% by mass relative to the total solid mass of the composition of the present invention. It is preferably at least 10% by mass, more preferably at least 0.02% by mass and not more than 5% by mass.
• the resin composition of the present embodiment may contain a phenolic compound as necessary.
• phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F (these are trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) and the like.
• one type of phenolic compound may be used alone, or two or more types may be used in combination.
• the composition of the present invention may or may not contain a phenolic compound, but if it does, the content of the phenolic compound is 0.01% by mass relative to the total solid mass of the composition of the present invention. It is preferably at least 30% by mass, more preferably at least 0.02% by mass and not more than 20% by mass.
• Other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolac resins, resole resins, polyhydroxystyrene resins, and copolymers thereof.
• Other polymer compounds may be modified products into which cross-linking groups such as methylol groups, alkoxymethyl groups and epoxy groups have been introduced.
• composition of the present invention may or may not contain other polymer compounds, but when it does, the content of the other polymer compound is 0 relative to the total solid mass of the composition of the present invention. It is preferably 0.01% by mass or more and 30% by mass or less, and more preferably 0.02% by mass or more and 20% by mass or less.
• the viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and 2,500 mm 2 /s to 8,000 mm. 2 /s is more preferred. If it is the said range, it will become easy to obtain a coating film with high uniformity. If it is 1,000 mm 2 /s or more , it is easy to apply the film with a film thickness required, for example, as an insulating film for rewiring. A coating is obtained.
• the water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.
• the metal content of the resin composition of the present invention is preferably less than 5 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
• metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are included, the total of these metals is preferably within the above range.
• a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention.
• the raw material constituting the product is filtered through a filter, or the inside of the apparatus is lined with polytetrafluoroethylene or the like to perform distillation under conditions in which contamination is suppressed as much as possible.
• the resin composition of the present invention preferably has a halogen atom content of less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass from the viewpoint of wiring corrosion. is more preferred.
• those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
• Halogen atoms include chlorine and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges.
• ion exchange treatment and the like are preferably mentioned.
• a conventionally known container can be used as the container for the resin composition of the present invention.
• the inner wall of the container is a multi-layer bottle composed of 6 types and 6 layers of resin, and 6 types of resin are used. It is also preferred to use bottles with a seven-layer structure. Examples of such a container include the container described in JP-A-2015-123351.
• a cured product of this resin composition By curing the resin composition of the present invention, a cured product of this resin composition can be obtained.
• the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention. Curing of the resin composition is preferably by heating, and the heating temperature is more preferably in the range of 120 ° C. to 400 ° C., further preferably in the range of 140 ° C. to 380 ° C., and 160 ° C. It is particularly preferred to be in the range of ⁇ 350°C.
• the form of the cured product of the resin composition is not particularly limited, and can be selected from film-like, rod-like, spherical, pellet-like, etc. according to the application.
• this cured product is preferably in the form of a film.
• pattern processing of the resin composition can be used to form protective films on walls, form via holes for conduction, adjust impedance, capacitance or internal stress, and impart heat dissipation functions. You can also choose the shape.
• the film thickness of the cured product (film made of the cured product) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
• the shrinkage ratio when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
• the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or higher, more preferably 80% or higher, and even more preferably 90% or higher. If it is 70% or more, a cured product having excellent mechanical properties may be obtained.
• the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
• the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.
• the resin composition of the present invention can be prepared by mixing the components described above.
• the mixing method is not particularly limited, and conventionally known methods can be used. Mixing can be performed by mixing with a stirring blade, mixing with a ball mill, mixing by rotating the tank itself, or the like.
• the temperature during mixing is preferably 10-30°C, more preferably 15-25°C.
• the filter pore size is, for example, 5 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
• the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. HDPE (high density polyethylene) is more preferable when the material of the filter is polyethylene.
• a filter that has been pre-washed with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel for use.
• filters with different pore sizes or materials may be used in combination.
• a connection mode for example, a mode in which an HDPE filter with a pore size of 1 ⁇ m is connected in series as a first stage and an HDPE filter with a pore size of 0.2 ⁇ m as a second stage are connected in series.
• various materials may be filtered multiple times.
• circulation filtration may be used.
• you may filter by pressurizing.
• the pressure to be applied is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less.
• impurities may be removed using an adsorbent.
• You may combine filter filtration and the impurity removal process using an adsorbent.
• a known adsorbent can be used as the adsorbent. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
• the resin composition filled in the bottle may be subjected to a degassing step under reduced pressure.
• the method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition onto a substrate to form a film. Further, the method for producing a cured product of the present invention includes the film forming step, an exposure step of selectively exposing the film formed in the film forming step, and developing the film exposed in the exposure step using a developer. It is more preferable to include a developing step of forming a pattern by The method for producing a cured product of the present invention includes the film forming step, the exposure step, the developing step, and a heating step of heating the pattern obtained by the developing step, and after the development of exposing the pattern obtained by the developing step. It is particularly preferred to include at least one of the exposure steps. Moreover, the manufacturing method of the present invention preferably includes the film forming step and the step of heating the film. Details of each step will be described below.
• the resin composition of the present invention can be used in a film-forming step in which a film is formed by applying it onto a substrate.
• the method for producing a cured product of the present invention preferably includes a film forming step of applying the resin composition onto a substrate to form a film.
• the type of base material can be appropriately determined according to the application, and includes semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals, and substrates having metal layers formed by plating, vapor deposition, etc.) ), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, plasma display panel (PDP) electrode plates, etc., and are not particularly limited.
• semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals, and substrates having metal layers formed by plating, vapor deposition, etc.
• a semiconductor fabrication substrate is particularly preferable, and a silicon substrate, a Cu substrate and a mold substrate are more preferable.
• these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
• HMDS hexamethyldisilazane
• the shape of the substrate is not particularly limited, and may be circular or rectangular.
• the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm.
• the short side length is, for example, 100 to 1000 mm, preferably 200 to 700 mm.
• the base material for example, a plate-like base material (substrate), preferably a panel-like base material (substrate) is used.
• the resin layer or metal layer serves as the base material.
• Specific means to be applied include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, An inkjet method and the like are exemplified. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet method is more preferable, and spin coating from the viewpoint of uniformity of film thickness and productivity. and slit coating methods are preferred.
• a film having a desired thickness can be obtained by adjusting the solid content concentration and application conditions of the resin composition according to the method.
• the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, ink jet method, etc.
• slit coating and spray coating are preferable for rectangular substrates.
• method, inkjet method, and the like are preferred.
• spin coating for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
• a method of transferring a coating film, which is formed on a temporary support in advance by the above application method, onto a base material can also be applied.
• the transfer method the manufacturing methods described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can also be suitably used in the present invention.
• a step of removing excess film at the edge of the substrate may be performed.
• processes include edge bead rinsing (EBR), back rinsing, and the like.
• EBR edge bead rinsing
• a pre-wetting process may also be employed in which the substrate is coated with various solvents before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.
• the film may be subjected to a step of drying the formed film (layer) to remove the solvent (drying step) after the film forming step (layer forming step). That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step. Moreover, the drying step is preferably performed after the film formation step and before the exposure step.
• the drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. Moreover, you may dry by pressure reduction.
• the drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 2 minutes to 7 minutes.
• the film may be subjected to an exposure step that selectively exposes the film. That is, the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed in the film forming step. Selectively exposing means exposing a portion of the film. Also, by selectively exposing, the film is formed with exposed regions (exposed portions) and non-exposed regions (non-exposed portions). The amount of exposure is not particularly defined as long as the resin composition of the present invention can be cured . is more preferred.
• the exposure wavelength can be appropriately determined in the range of 190-1,000 nm, preferably 240-550 nm.
• the exposure wavelength is as follows: (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc.
• the resin composition of the present invention exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, particularly high exposure sensitivity can be obtained.
• the method of exposure is not particularly limited as long as at least a part of the film made of the resin composition of the present invention is exposed. mentioned.
• the film may be subjected to a step of heating after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the exposed film in the exposure step.
• the post-exposure heating step can be performed after the exposure step and before the development step.
• the heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.
• the heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
• the heating rate in the post-exposure heating step is preferably 1 to 12° C./min, more preferably 2 to 10° C./min, still more preferably 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature. Also, the rate of temperature increase may be appropriately changed during heating.
• the heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters and the like can be used. Moreover, it is also preferable to carry out the heating in an atmosphere of low oxygen concentration by, for example, flowing an inert gas such as nitrogen, helium or argon.
• the film after exposure may be subjected to a development step in which the film is developed using a developer to form a pattern.
• the method for producing a cured product of the present invention may include a development step of developing a film exposed in the exposure step with a developer to form a pattern. By performing development, one of the exposed and non-exposed portions of the film is removed to form a pattern.
• development in which the unexposed portion of the film is removed by the development process is called negative development
• development in which the exposed portion of the film is removed by the development process is called positive development.
• Examples of the developer used in the development process include an aqueous alkaline solution and a developer containing an organic solvent.
• basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. .
• the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, based on the total mass of the developer. is more preferred.
• the organic solvent may be an ester such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, Methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
• 3-alkyloxypropionate alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3-methoxy methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.
• 2-alkyloxypropionate alkyl esters e.g.
• methyl 2-alkyloxypropionate, 2- ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid ethyl
• methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate e.g.
• ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene Glycol monoethyl ether acetate
• the organic solvent can be used singly or in combination of two or more.
• a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, and cyclopentanone and ⁇ -butyrolactone. and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.
• the content of the organic solvent relative to the total weight of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more. is more preferable, and 90% by mass or more is particularly preferable. Moreover, the content may be 100% by mass.
• the developer may further contain other components.
• Other components include, for example, known surfactants and known antifoaming agents.
• the method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and a method of immersing the substrate on which the film is formed in the developer, and supplying the developer to the film formed on the substrate using a nozzle. There is a method of puddle development or a method of continuously supplying the developer.
• the type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned.
• the development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
• the temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.
• Rinse liquid When the developer is an alkaline aqueous solution, water, for example, can be used as the rinse.
• the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) is used as the rinse liquid. be able to.
• the rinse time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
• the temperature of the rinsing liquid during rinsing is not particularly specified, but is preferably 10 to 45°C, more preferably 18 to 30°C.
• the pattern obtained by the development step may be subjected to a heating step of heating the pattern obtained by the development. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained by the developing step. Moreover, the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing the developing step or a film obtained by the film forming step. In the heating step, a resin such as a polyimide precursor is cyclized into a resin such as polyimide.
• the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, still more preferably 150 to 250°C, even more preferably 160 to 250°C, particularly 160 to 230°C. preferable.
• the heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor in the pattern by the action of the base generated from the base generator by heating.
• the pattern obtained by the development step (the pattern after rinsing when the rinsing step is performed) is subjected to a post-development exposure step of exposing the pattern after the development step instead of or in addition to the heating step.
• a post-development exposure step of exposing the pattern after the development step instead of or in addition to the heating step.
• the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step.
• the pattern obtained by the development step may be subjected to a metal layer forming step of forming a metal layer on the pattern. That is, the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on the pattern obtained by the developing step (preferably subjected to at least one of the heating step and the post-development exposure step). is preferred.
• Fields to which the cured product of the present invention can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, and stress buffer films.
• pattern formation by etching of a sealing film, a substrate material (a base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting as described above may be used.
• the method for producing the cured product of the present invention or the cured product of the present invention can also be used for the production of plates such as offset plates or screen plates, for etching molded parts, for protective lacquers and dielectrics in electronics, especially microelectronics. It can also be used for the production of layers and the like.
• the laminate of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
• the laminate of the present invention is a laminate containing two or more layers made of a cured product, and may be a laminate in which three or more layers are laminated. Of the two or more layers of the cured product contained in the laminate, at least one is a layer made of the cured product of the present invention, and the shrinkage of the cured product, or the deformation of the cured product due to the shrinkage, etc. From the viewpoint of suppression, it is also preferable that all the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.
• the method for producing the laminate of the present invention preferably includes the method for producing the cured product of the present invention, and more preferably includes repeating the method for producing the cured product of the present invention multiple times.
• the laminate of the present invention includes two or more layers made of the cured material and a metal layer between any of the layers made of the cured material.
• the metal layer is preferably formed by the metal layer forming step. That is, it is preferable that the method for producing the laminate of the present invention further includes a metal layer forming step of forming a metal layer on the layer made of the cured product between the production methods for the cured product that are performed multiple times. Preferred aspects of the metal layer forming step are as described above.
• the laminate for example, a laminate containing at least a layer structure in which three layers of a layer made of the first cured product, a metal layer, and a layer made of the second cured product are laminated in this order is preferable. be done.
• both the layer comprising the first cured product and the layer comprising the second cured product are layers comprising the cured product of the present invention.
• the resin composition of the present invention used for forming the layer comprising the first cured product and the resin composition of the present invention used for forming the layer comprising the second cured product have the same composition. It may be a product or a composition having a different composition.
• the metal layer in the laminate of the present invention is preferably used as a metal wiring such as a rewiring layer.
• the method for manufacturing the laminate of the present invention includes a lamination step.
• the lamination step means that the surface of the pattern (resin layer) or metal layer is again subjected to (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step and development It is a series of steps including performing at least one of the post-exposure steps in this order. However, at least one of (a) the film forming step and (d) the heating step and the post-development exposure step may be repeated. Moreover, after at least one of the (d) heating step and the post-development exposure step, (e) a metal layer forming step may be included. Needless to say, the lamination step may further include the drying step and the like as appropriate.
• a surface activation treatment process may be further performed.
• a plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.
• the method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least part of the metal layer and the resin composition layer to surface activation treatment.
• the surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer is subjected to surface activation treatment. After performing the steps, the metal layer forming step may be performed.
• the present invention also discloses a semiconductor device comprising the cured product of the present invention or the laminate of the present invention.
• the present invention also discloses a method for producing a semiconductor device including the method for producing the cured product of the present invention or the method for producing the laminate of the present invention.
• Specific examples of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer can refer to the description of paragraphs 0213 to 0218 of JP-A-2016-027357 and the description of FIG. The contents of which are incorporated herein.
• a white precipitate of pyridinium hydrochloride was obtained.
• the mixture was then warmed to room temperature and stirred for 2 hours before adding 9.7 g (0.123 mol) of pyridine and 25 ml of N-methylpyrrolidone (NMP) to give a clear solution.
• NMP N-methylpyrrolidone
• a solution of 11.8 g (0.0587 mol) of 4,4'-diaminodiphenyl ether in 100 ml of NMP was then added dropwise to the clear solution over a period of 1 hour. The viscosity increased during the addition of the 4,4'-diaminodiphenyl ether. After adding 10.0 g of ethanol to the mixture, the mixture was stirred for 2 hours.
• the polyimide precursor resin was then precipitated in 4 liters of water and the water-polyimide precursor resin mixture was stirred at a speed of 5000 rpm for 15 minutes.
• the polyimide precursor resin was filtered off, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was vacuum-dried to obtain powdery polyimide precursor resin A-1-1.
• the resulting reaction solution was put into 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer.
• the resulting crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution.
• the resulting crude polymer solution was dropped into 28 liters of water to precipitate the polyimide precursor resin, and the resulting precipitate was collected by filtration and vacuum dried to give powdery polyimide precursor resin A-1-2. got
• the resulting reaction solution was put into 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer.
• the resulting crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution.
• the resulting crude polymer solution was dropped into 28 liters of water to precipitate the polyimide precursor resin, and the resulting precipitate was collected by filtration and vacuum dried to obtain powdery polyimide precursor resin A-2. rice field.
• the resulting reaction solution was put into 3 liters of ethyl alcohol to produce a precipitate consisting of a crude polymer.
• the resulting crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution.
• the resulting crude polymer solution was dropped into 28 liters of water to precipitate the polyimide precursor resin, and the resulting precipitate was collected by filtration and vacuum dried to obtain powdery polyimide precursor resin A-3. rice field.
• Examples and Comparative Examples> the components shown in the table below were mixed to obtain each photosensitive resin composition.
• the components shown in the table below were mixed to obtain each comparative composition.
• the content (compounding amount) of each component described in the table was set to the amount (parts by mass) described in the "addition amount” column of each column of the table.
• the content of the solvent C was adjusted so that the content mass part of the solvent C with respect to the total mass of the composition was the value (ppm) described in the column "Content [ppm] in the entire composition".
• the resulting photosensitive resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter with a pore width of 0.8 ⁇ m.
• NMP/ethyl lactate and "160/40" in the table indicate that 160 parts by mass of NMP and 40 parts by mass of ethyl lactate were used.
• the description of "-" indicates that the composition does not contain the corresponding component.
• Resins A-1-1 to A-1-2, A-2 to A-8 Resins A-1-1 to A-1-2, A-2 to A-8 obtained by the above synthesis examples
• ⁇ Antioxidant ⁇ ⁇ J-1 a compound having the following structure
• each photosensitive resin composition or comparative composition immediately after preparation was applied (applied) as a layer onto a circular silicon wafer having a diameter of 8 inches by spin coating.
• the coated silicon wafer was dried on a hot plate at 100° C. for 4 minutes to form a resin film having a thickness of 19 ⁇ m on the silicon wafer.
• the film thickness was the arithmetic mean value of the film thicknesses at 10 points in the plane.
• the film thickness of the resin film is measured at a total of ten equally spaced points including both ends of the resin film, and the difference between the maximum value and the minimum value of the measured values at the ten points is calculated.
• the in-plane maximum film thickness difference ( ⁇ m) was used.
• the film thickness uniformity of the film formed from the composition immediately after preparation was evaluated according to the following evaluation criteria. The evaluation results are shown in the column of "Thickness uniformity after drying" in the table. It can be said that the smaller the in-plane maximum film thickness difference ( ⁇ m), the better the coatability.
• -Evaluation criteria- A The in-plane maximum film thickness difference ( ⁇ m) was 0.5 ⁇ m or less.
• B The in-plane maximum film thickness difference ( ⁇ m) exceeded 0.5 ⁇ m and was 0.8 ⁇ m or less.
• C The in-plane maximum film thickness difference ( ⁇ m) exceeded 0.8 ⁇ m and was 1.0 ⁇ m or less.
• D The in-plane maximum film thickness difference ( ⁇ m) exceeded 1.0 ⁇ m.
• each photosensitive resin composition or comparative composition immediately after preparation was applied in a layer by spin coating onto a circular silicon wafer having a diameter of 8 inches.
• the coated silicon wafer was dried on a hot plate at 100° C. for 4 minutes to form a resin film having a thickness of 19 ⁇ m on the silicon wafer.
• the arithmetic average value of the film thickness at 10 points in the plane of the resin film was taken as the film thickness before development.
• the entire surface of the resin film on the silicon wafer was exposed using a stepper (Nikon NSR 2005 i9C).
• the i-line was used for the exposure, and the exposure was performed at a wavelength of 365 nm and 200 mJ/cm 2 .
• the exposed resin film was developed with cyclopentanone for 60 seconds, it was rinsed with PGMEA for 60 seconds.
• the film thickness after development was defined as the arithmetic average value of the film thicknesses at 10 locations in the surface of the resin film after development, and the film thickness change rate (%) of the exposed portion before and after development was determined by the following formula.
• the evaluation was carried out according to the following evaluation criteria, and the evaluation results are shown in the column of "Thickness change rate of exposed area before and after development" in the table. In addition, the actual evaluation was not performed for the examples in which "-" was written in the evaluation result column.
• Film thickness change rate (%) of exposed area before and after development (1 - film thickness after development / film thickness before development) x 100 -Evaluation criteria-
• D The film thickness change rate (%) before and after development of the exposed area was 10% or more.
• each photosensitive resin composition or comparative composition shown in the table was applied onto a silicon wafer by spin coating to form a resin composition layer.
• the silicon wafer to which the resulting resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to obtain a uniform resin composition layer having a thickness of about 15 ⁇ m on the silicon wafer.
• the obtained resin composition layer (resin layer) was heated in a nitrogen atmosphere at a heating rate of 10° C./min, and after reaching 230° C., heated for 3 hours.
• the cured resin layer (cured film) was immersed in a 4.9% hydrofluoric acid solution, and the cured film was peeled off from the silicon wafer.
• test piece having a width of 3 mm and a sample length of 30 mm was prepared from the peeled cured film using a punching machine.
• a tensile tester Tetrachloride
• the obtained test piece was subjected to JIS-K6251 under an environment of 25 ° C. and 65% RH (relative humidity) in the longitudinal direction at a crosshead speed of 300 mm / min. Measured according to Each evaluation was performed 5 times, and the average value was used for the elongation rate (elongation at break) when the test piece broke.
• the evaluation was carried out according to the following criteria, and the evaluation results are shown in the "elongation at break" column in the table.
• the comparative composition in Comparative Example 1 does not contain Solvent C.
• the comparative compositions according to Comparative Examples 2 and 3 do not have a solvent C content within the range of 1 ppm or more and 10,000 ppm or less.
• the boiling point of the solvent is not 60°C or higher. It can be seen that in the embodiments according to these comparative examples, the resulting cured product is inferior in elongation at break (film strength).
• Example 101 The resin composition used in Example 1 was applied in a layer by spin coating to the surface of the thin copper layer of the resin substrate having the thin copper layer formed on the surface, and dried at 100° C. for 5 minutes to obtain a film thickness. After forming a photosensitive film of 20 ⁇ m, it was exposed using a stepper (NSR1505 i6 manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 ⁇ m). After the above exposure, the film was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
• NSR1505 i6 manufactured by Nikon Corporation
• the temperature was raised at a rate of 10° C./min, reaching 230° C., and then maintained at 230° C. for 180 minutes to form an interlayer insulating film for rewiring layers.
• This interlayer insulating film for rewiring layer was excellent in insulating properties.
• a semiconductor device was manufactured using these interlayer insulating films for rewiring layers, it was confirmed that the device operated without any problem.

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