Classifications

• • 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
  • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
  • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
  • C08G73/1014—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)anhydrid
• • 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
  • C08G73/1003—Preparatory processes
  • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
  • C08G73/101—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents
  • C08G73/1017—Preparatory processes from tetracarboxylic acids or derivatives and diamines containing chain terminating or branching agents in the form of (mono)amine
• • 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
  • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
  • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
• • 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
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
  • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
• • 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
  • C08G73/12—Unsaturated polyimide precursors
• • 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
  • C08G73/22—Polybenzoxazoles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • 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
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • 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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0387—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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
• • 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
• • 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
  • C08G73/14—Polyamide-imides

Definitions

• the present invention relates to a negative-type photosensitive resin composition, a method for producing a relief pattern using the same, a cured product, and an electronic component.
• Polyimides and polybenzoxazoles have excellent electrical and mechanical properties, and are highly heat resistant to temperatures of 300°C or higher, making them useful as surface protective films for semiconductor elements, interlayer insulating films, and wiring protective insulating films for circuit boards.
• resist materials are used to form circuits in semiconductor integrated circuits and multilayer printed wiring boards, and the process is complicated and diverse, including film formation on the substrate, exposure to light at specified locations, removal of unnecessary areas by etching, and cleaning of the substrate surface.
• photosensitive resin compositions have increasingly been used as permanent resists, which are left as insulating materials even after pattern formation.
• polyimide-containing photosensitive resin compositions Many examples have been reported to date. Among them, a polyimide-containing photosensitive resin composition has been proposed that contains a ring-closed polyimide that does not undergo curing shrinkage of the film associated with the ring-closing reaction from a polyimide precursor to polyimide, and that is capable of forming a film with high-resolution patterns and excellent heat resistance (see, for example, Patent Documents 1 and 2).
• the pattern formed in the photosensitive resin composition may suffer from a phenomenon called undercut, in which a notch is formed at the bottom end of the pattern.
• undercut occurs, the conductive pattern such as wiring is not sufficiently embedded, causing voids, which cause peeling or cracking of the pattern, and cause poor conductivity.
• the present invention aims to provide a photosensitive resin composition that can form rectangular patterns without undercutting during pattern processing, even in thick films, and can form films with excellent heat resistance.
• the present invention has the following configuration.
• a negative-type photosensitive resin composition comprising (A) an alkali-soluble resin, (B) a photopolymerization initiator having photobleachability, (C) a polymerizable compound, and (D) a sensitizer,
• the negative type photosensitive resin composition wherein the alkali-soluble resin (A) contains one or more resins selected from the group consisting of (A-1) a polyimide precursor, (A-2) a polybenzoxazole precursor, and (A-3) a copolymer thereof.
• R 1 and R 2 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group.
• R 3 represents an alkyl group having 0 to 5 carbon atoms, -OH, -COOH, -O(CH 2 )OH, -O(CH 2 ) 2 OH, -COO(CH 2 ) OH, or -COO(CH 2 ) 2 OH.
• the polymerizable compound (C) contains (C-1) a polyethylene glycol dimethacrylate represented by formula (2) and (C-2) a polyethylene glycol dimethacrylate represented by formula (3),
• the negative type photosensitive resin composition according to any one of [1] to [3], comprising 4 to 20 parts by mass of the component (C-2) per 100 parts by mass of the component (C-1).
• the (C) polymerizable compound contains (C-3) a polymerizable compound having a blocked isocyanate structure,
• the (D) sensitizer contains (D-1) a thioxanthone-based sensitizer,
• the negative type photosensitive resin composition according to any one of [1] to [7], comprising 5 to 30 parts by mass of the thioxanthone sensitizer (D-1) relative to 100 parts by mass of the photopolymerization initiator having photobleachability (B).
• X1 represents a tetravalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms.
• Y1 represents a divalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms, which has a fluorine atom.
• a plurality of R4s and R5s may be the same or different.
• Each of R4s and R5s independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having an ethylenically unsaturated double bond.
• the alkali-soluble resin (A) contains a repeating structural unit of a polyimide precursor (A-1),
• a negative-type photosensitive resin composition according to any one of [1] to [8], in which the alkali-soluble resin (A) contains a repeating structural unit of a polybenzoxazole precursor (A-2) represented by formula (5).
• X2 represents a divalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms.
• Y2 represents a tetravalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms. At least one of X2 and Y2 has a fluorine atom.
• R6 and R7 each independently represent a hydrogen atom, a monovalent alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having an ethylenically unsaturated double bond.
• Y 1 contains a structure represented by formula (7) or a structure represented by formula (8)
• the negative type photosensitive resin composition according to [9] wherein the total content [mol %] of the structure represented by formula (7) and the structure represented by formula (8) is in the range of 70 mol % to 100 mol % inclusive, based on 100 mol % of all diamine residues in the polyimide precursor (A-1) having a repeating structural unit represented by formula (4).
• Y2 contains a structure represented by formula (21) or a structure represented by formula (22),
• a method for producing a relief pattern comprising the steps of applying the negative photosensitive resin composition according to any one of [1] to [16] onto a substrate and drying the composition, exposing the composition to light, developing the composition with an alkaline developer, and heat treating the composition.
• the present invention makes it possible to obtain a photosensitive resin composition that can form rectangular patterns without undercutting during pattern processing, even in thick films, and can form films with excellent heat resistance.
• the negative type photosensitive resin composition of the present invention is a negative type photosensitive resin composition containing (A) an alkali-soluble resin (hereinafter, may be referred to as component (A)), (B) a photopolymerization initiator having photobleachability (hereinafter, may be referred to as component (B)), (C) a polymerizable compound (hereinafter, may be referred to as component (C)), and (D) a sensitizer (hereinafter, may be referred to as component (D)),
• the (A) alkali-soluble resin contains one or more resins selected from the group consisting of (A-1) a polyimide precursor (hereinafter, may be referred to as component (A-1)), (A-2) a polybenzoxazole precursor (hereinafter, may be referred to as component (A-2)), and (A-3) a copolymer thereof (hereinafter, may be referred to as component (A-3)).
• the negative photosensitive resin composition of the present invention can form rectangular patterns without undercutting during pattern processing even in thick films.
• the above-mentioned thick film refers to a cured film obtained from the negative photosensitive resin composition according to the present invention having a thickness of 15 ⁇ m or more.
• the thickness of the coating film needs to be about 30 ⁇ m or more after the process of applying the above-mentioned negative photosensitive resin composition onto a substrate and drying it to form a coating film.
• the i-line transmittance of the coating film which is formed by applying a negative photosensitive resin composition and drying it at 100°C for 5 minutes and has a film thickness of 5 ⁇ m, is preferably 20% or more, more preferably 30% or more, and even more preferably 50% to 80%. If it is less than 20%, the i-line will not reach deep inside, and sufficient radicals will not be generated from the component (B) described below, which may result in undercutting during development and other deterioration of the photosensitive properties.
• the i-line transmittance is high even after exposure.
• the i-line transmittance of the coating film after coating and drying the negative photosensitive resin composition and exposing it to an i-line equivalent illuminance of 1,000 mJ/ cm2 is preferably 15% or more, more preferably 25% or more, and even more preferably 40% to 80%. If it is less than 15%, the i-line does not reach deep inside, and radicals are not sufficiently generated from the component (B) described later, so that there is a risk of undercutting during development and other deterioration in photosensitive properties.
• the i-line transmittance is measured from the transmitted UV spectrum using a spectrophotometer U-2910 (manufactured by Hitachi High-Tech Science Corporation).
• alkali solubility refers to a dissolution rate of 50 nm/min or more, determined from a decrease in film thickness, when a solution of a resin dissolved in ⁇ -butyrolactone (hereinafter sometimes abbreviated as GBL) is applied onto a silicon wafer and prebaked at 120° C.
• GBL ⁇ -butyrolactone
• the prebaked film is immersed in an alkaline aqueous solution selected from a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, a 1% by mass aqueous solution of potassium hydroxide, or a 1% by mass aqueous solution of sodium hydroxide at 23 ⁇ 1° C. for 1 minute, and then rinsed with pure water.
• an alkaline aqueous solution selected from a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, a 1% by mass aqueous solution of potassium hydroxide, or a 1% by mass aqueous solution of sodium hydroxide at 23 ⁇ 1° C. for 1 minute, and then rinsed with pure water.
• the (A) component preferably has an acidic group in the repeating structural unit of the resin and/or at the end of its main chain in order to impart alkali solubility.
• acidic groups include carboxy groups, phenolic hydroxyl groups, and sulfonic acid groups.
• the (A) component preferably contains 2 parts by mass or more and 50 parts by mass or less of fluorine atoms per 100 parts by mass of the (A) component in order to impart water repellency.
• the (A) component contains one or more resins selected from the group consisting of the (A-1) component, the (A-2) component, and the (A-3) component.
• the (A) component preferably contains the (A-1), (A-2) and/or (A-3) components from the viewpoints of improving the i-line transmittance during thick film processing, the mechanical properties of the cured film, and the heat resistance of the cured film.
• Examples of the component (A-1) include those obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, or a tetracarboxylic diester dichloride, etc., with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine, etc., and have a tetracarboxylic acid residue and/or a derivative residue thereof, and a diamine residue and/or a derivative residue thereof.
• Examples of the component (A-1) include polyamic acid, polyamic acid ester, polyamic acid amide, and polyisoimide.
• component (A-1) contains a polyamic acid ester.
• Component (A-1) is a thermosetting resin that is thermally cured at high temperatures and dehydrated and cyclized to form highly heat-resistant imide bonds, resulting in a polyimide.
• Component (A-1) is a resin whose heat resistance improves after dehydration and cyclization, making it ideal for applications that require both the properties of the precursor structure before dehydration and cyclization and the heat resistance of the cured film.
• component (A) contains a resin containing the repeating structural unit of component (A-1) represented by formula (4).
• X 1 represents a tetravalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms.
• Y 1 represents a divalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms, which has a fluorine atom.
• a plurality of R 4s and R 5s may be the same or different.
• R 4s and R 5s each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having an ethylenically unsaturated double bond.
• the ratio of all polyamic acid ester repeating structural units in the component (A-1) is the esterification rate of the component (A-1).
• the esterification rate in the present invention is derived from NMR measurements. Specifically, the esterification rate is calculated by a method in which the peak intensity derived from all aromatic ring hydrogens in the polyimide precursor is compared with the peak intensity derived from the hydrogens of the hydrocarbons directly bonded to the ester groups of all polyamic acid esters in all tetracarboxylic acid and derivative residues thereof, and all dicarboxylic acid and derivative residues thereof.
• the component (A) contains the repeating structural unit of the component (A-1), and the esterification rate of the component (A-1) is preferably 40 mol% or more and 80 mol% or less, and more preferably 65 mol% or more and 80 mol% or less.
• X1 represents a tetracarboxylic acid residue and/or a residue of a derivative thereof
• Y1 represents a diamine residue and/or a residue of a derivative thereof.
• residues of tetracarboxylic acids or their derivatives include pyromellitic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 2,2',3,3'-biphenyltetracarboxylic acid, 3,3',4,4'-diphenylethertetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 2,2',3,3'-benzophenonetetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 1,1-bis(3,4-dicarboxyphenyl)ethane, 1,1-bis(2,3-dicarboxyphenyl)ethane, bis(3,4-dicarboxyphenyl)methane, bis
• R 11 represents an oxygen atom, C(CF 3 ) 2 , or C(CH 3 ) 2 .
• R 12 to R 15 represent a hydrogen atom or a hydroxyl group. * represents a bond that bonds to an amide structure.
• X 1 in the formula (4) contains a structure represented by formula (9) or formula (10).
• * represents a bond that bonds to an amide structure, a carboxylic acid structure, or a carboxylic acid ester structure.
• examples of the residue of a diamine or a derivative thereof having a fluorine atom include residues of 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, or compounds in which the amine moiety of these has been isocyanated or trimethylsilylated.
• residues may be contained alone or in combination of two or more kinds in component (A-1).
• R 16 to R 23 each represent a hydrogen atom or a hydroxyl group.
• Y1 contains a structure represented by formula (7) or a structure represented by formula (8), and the total content [mol %] of the structure represented by formula (7) and the structure represented by formula (8) is in the range of 70 mol % to 100 mol % inclusive, based on 100 mol % of all diamine residues in the polyimide precursor (A-1) having a repeating structural unit represented by formula (4).
• * represents a bond that bonds to the amide structure.
• the (A-1) component may have a residue of a known diamine that does not have a fluorine atom and/or a derivative thereof.
• the residue of a diamine that does not have a fluorine atom or a derivative thereof include bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)methylene, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxy)biphenyl, bis(3-amino-4-hydroxyphenyl)fluorene, 3-sulfonic acid-4,4'-diaminodiphenyl ether, dimercaptophenylenediamine, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether ...
• R4 and R5 preferably contain a monovalent organic group having an ethylenically unsaturated double bond represented by the following formula (18) or (19):
• R 24 represents a hydrogen atom or a methyl group.
• R 25 and R 26 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms. * represents a bond.
• R 27 and R 32 represent a hydrogen atom or a methyl group.
• R 28 to R 31 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms. * represents a bond.
• the content ratio of the repeating structural unit represented by formula (4) in 100 mol% of all repeating structural units in component (A-1) is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and even more preferably 70 to 100 mol%.
• a content ratio of 50 to 100 mol% can improve heat resistance.
• Examples of the component (A-2) include those obtained by reacting a dicarboxylic acid, a corresponding dicarboxylic acid dichloride, or a dicarboxylic acid active diester with a diamine such as a bisaminophenol compound, and have a dicarboxylic acid residue and/or a derivative residue thereof, and a bisaminophenol compound residue and/or a derivative residue thereof.
• Examples of the component (A-2) include polyhydroxyamide.
• Component (A-2) is a thermosetting resin that is thermally cured at high temperatures and dehydrated and cyclically closed to form highly heat-resistant and rigid benzoxazole rings, resulting in polybenzoxazole. Therefore, by incorporating component (A-2) into a negative photosensitive resin composition, the heat resistance of the resulting cured film can be significantly improved. This makes it suitable for use in applications where high heat resistance is required.
• component (A-2) is a resin whose heat resistance improves after dehydration and cyclic closure, making it suitable for use in applications where it is desired to achieve both the properties of the precursor structure before dehydration and cyclic closure and the heat resistance of the cured film.
• component (A) contains a repeating structural unit of component (A-2) represented by formula (5).
• X2 represents a divalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms.
• Y2 represents a tetravalent organic group having an aliphatic structure having 2 to 20 carbon atoms, an alicyclic structure having 4 to 20 carbon atoms, or an aromatic structure having 4 to 40 carbon atoms. At least one of X2 and Y2 has a fluorine atom.
• R6 and R7 each independently represent a hydrogen atom, a monovalent alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having an ethylenically unsaturated double bond.
• X2 represents a dicarboxylic acid residue and/or a derivative residue thereof
• Y2 represents a bisaminophenol compound residue and/or a derivative residue thereof.
• the dicarboxylic acid derivative include dicarboxylic acid anhydrides, dicarboxylic acid chlorides, dicarboxylic acid active esters, tricarboxylic acid anhydrides, tricarboxylic acid chlorides, tricarboxylic acid active esters, and diformyl compounds.
• residues of dicarboxylic acids or derivatives thereof include, but are not limited to, residues of terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, e
• X2 in the formula (5) contains a structure represented by the formula (11).
• residues of bisaminophenol compounds or derivatives thereof include 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis[3-(3-aminobenzamido)-4-hydroxyphenyl]hexafluoropropane, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)methylene, bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-amino benzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3-amino-4-hydroxyphenyl)propane, 2,2'-bis[N-(3-aminobenzoyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(3-
• Y2 contains a structure represented by formula (21) or a structure represented by formula (22), and the total content [mol %] of the structure represented by formula (21) and the structure represented by formula (22) is in the range of 70 mol % or more and 100 mol % or less, based on 100 mol % of all diamine residues of the polybenzoxazole precursor (A-2) having a repeating structural unit represented by formula (5).
• R 6 and R 7 preferably have an ethylenically unsaturated double bond represented by the formula (20).
• R 33 represents a hydrogen atom or a methyl group.
• R 34 and R 35 each independently represent a hydrogen atom or an organic group having 1 to 3 carbon atoms. * represents a bond.
• the (A-2) component preferably contains a repeating structural unit represented by formula (5) as the main component, and the content ratio of the repeating structural unit represented by formula (5) in all repeating structural units in the (A-2) component is preferably 50 to 100 mol%, more preferably 60 to 100 mol%, and even more preferably 70 to 100 mol%. A content ratio of 50 to 100 mol% can improve the resolution.
• the component (A-3) can be obtained, for example, by reacting the raw material for the polyimide precursor (A-1) and the raw material for the polybenzoxazole precursor (A-2) at once to obtain a random copolymer containing a polyimide repeating structural unit and a polybenzoxazole repeating structural unit, or by separately synthesizing the repeating structural unit of the polyimide precursor and the repeating structural unit of the polybenzoxazole precursor and then reacting the respective structural units to obtain a block copolymer having the repeating structural unit of the polyimide precursor and the repeating structural unit of the polybenzoxazole precursor.
• the (A-3) component preferably has, for example, both a repeating structural unit of a polyimide precursor, represented by formula (4), and a repeating structural unit of a polybenzoxazole precursor, represented by formula (5).
• the (A-3) component has a repeating structural unit represented by formula (4).
• the (A) component contains the (A-3) component, and the (A-3) has a repeating structural unit represented by formula (4), which is preferable because it improves the heat resistance of the cured product of the (A-3) component.
• the component (A-3) contains a repeating structural unit represented by formula (4), in which Y 1 contains a structure represented by formula (7) or a structure represented by formula (8), and the total content [mol %] of the structure represented by formula (7) and the structure represented by formula (8) is in the range of 70 mol % or more and 100 mol % or less, based on 100 mol % of all diamine residues in the polyimide precursor (A-1) having the repeating structural unit represented by formula (4).
• At least one selected from the group consisting of the (A-1), (A-2) and (A-3) components preferably contains a structural unit derived from a diamine having a silyl group or a siloxane bond, and/or a structural unit derived from a derivative thereof.
• At least one selected from the group consisting of the (A-1), (A-2) and (A-3) components contains a structural unit derived from a diamine having a silyl group or a siloxane bond, and/or a structural unit derived from a derivative thereof, the interaction at the interface between the cured film of the negative photosensitive resin composition and the underlying substrate is increased, and the adhesion to the underlying substrate and the chemical resistance of the cured film can be improved.
• At least one of the resins selected from the group consisting of the component (A-1), the component (A-2) and the component (A-3) may be end-capped with an end-capping agent such as a monoamine, a dicarboxylic acid anhydride, a monocarboxylic acid, a monocarboxylic acid chloride or a monocarboxylic acid active ester.
• an end-capping agent such as a monoamine, a dicarboxylic acid anhydride, a monocarboxylic acid, a monocarboxylic acid chloride or a monocarboxylic acid active ester.
• the storage stability of the coating liquid of the resin composition containing one or more components selected from (A-1) and (A-2) can be improved.
• the ends of the resin are capped with a terminal capping agent having a heat-reactive group.
• terminal capping agents having a heat-reactive group include, but are not limited to, 4-ethynylaniline, 4-aminostyrene, 5-norbornene-2,3-dicarboxylic acid, maleic anhydride, and 4-phenylethynylphthalic anhydride. Caping the ends of the resin with a terminal capping agent having a heat-reactive group can improve the chemical resistance and elongation of the cured film after heat treatment.
• the component (A) in the present invention is synthesized by a known method.
• One example of a method for producing polyamic acid, which is an example of the component (A-1), is to react a tetracarboxylic dianhydride with a diamine compound in a solvent at low temperature.
• a method for producing a polyamic acid ester which is another example of component (A-1)
• a method for obtaining a diester from a tetracarboxylic dianhydride and an alcohol which is then reacted with an amine in a solvent in the presence of a condensing agent
• a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol which is then converted into an acid chloride of the remaining dicarboxylic acid, which is then reacted with an amine in a solvent, and the like.
• esterifying agent there are no particular limitations on the esterifying agent, and known methods can be applied, but N,N-dimethylformamide dialkyl acetal is preferred because the resulting resin can be easily purified.
• Examples of methods for producing polyhydroxyamide include a method in which a bisaminophenol compound and a dicarboxylic acid are subjected to a condensation reaction in a solvent.
• a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid and then a bisaminophenol compound is added to the reaction
• a solution of a dicarboxylic acid dichloride is added dropwise to a solution of a bisaminophenol compound to which a tertiary amine such as pyridine has been added.
• the method for producing component (A-3) can be, for example, a combination of the method for producing the polyimide precursor (A-1) and the method for producing the polybenzoxazole precursor (A-2).
• the weight average molecular weight (hereinafter, Mw) of one or more selected from the (A-1), (A-2) and (A-3) components is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more, in terms of polystyrene measured by gel permeation chromatography (hereinafter, GPC).
• Mw is 1,000 or more, the resolution after development can be improved.
• Mw is preferably 500,000 or less, more preferably 300,000 or less, and even more preferably 100,000 or less. When Mw is 500,000 or less, the leveling property during coating and the pattern processability in an alkaline developer can be improved.
• Mn The number average molecular weight (hereinafter, Mn), calculated as polystyrene equivalent as measured by GPC, is preferably 1,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more. If Mn is 1,000 or more, the resolution after development can be improved. On the other hand, Mn is preferably 500,000 or less, more preferably 300,000 or less, and even more preferably 100,000 or less. If Mn is 500,000 or less, the leveling property during application and the pattern processability in an alkaline developer can be improved.
• the Mw and Mn of components (A-1), (A-2), and (A-3) are measured by GPC as polystyrene equivalent values.
• the content ratio of structural units derived from various carboxylic acid residues, diamine residues, monoamine residues, and derivatives thereof in component (A-1), component (A-2), and/or component (A-3) is determined by the following method.
• the negative photosensitive resin composition or the component (A-1), the component (A-2), and/or the component (A-3) is directly analyzed by 1H -NMR.
• the (A-1), (A-2) and/or (A-3) components are hydrolyzed with an alkali, and each monomer component after decomposition is separated by HPLC. Substituent information of each obtained fragment is analyzed by FT-IR, and structural information is identified by 1 H-NMR and 13 C-NMR. If identification is difficult, GC/MS analysis is further performed, and the copolymerization components are identified by combining the mass information.
• the negative photosensitive resin composition of the present invention further contains a component (B).
• a photopolymerization initiator is a compound that generates radicals through bond cleavage and/or reaction upon exposure to light.
• a compound having a structural unit that generates radicals through bond cleavage and/or reaction upon exposure to light is defined as a photopolymerization initiator.
• Photobleachable refers to a decrease in absorbance in the ultraviolet wavelength range (less than 380 nm) and/or in part or all of the visible light wavelength range (380 nm or more and 780 nm or less) due to bond dissociation and/or reaction caused by UV light during exposure. Photobleachable properties improve transparency upon exposure to light, allowing light to penetrate to the inside, and rectangular patterns can be formed without undercuts during pattern processing, even in thick films.
• photopolymerization initiators with photobleaching properties include acylphosphine oxide photopolymerization initiators, fluorene-type oxime initiators, diphenyl sulfide-type oxime initiators, and oxime initiators in which an oxime ester group is bonded to carbazole or the like via a carbonyl group.
• Photobleachability is examined by the following method.
• the photopolymerization initiator is dissolved in a soluble solvent, and the absorbance is measured using a spectrophotometer. The concentration of the solution is adjusted so that it falls within the measurement range of the spectrophotometer.
• a solvent that does not interfere with the measurement of the absorbance of the photopolymerization initiator such as methanol, ethanol, chloroform, acetonitrile, propylene glycol monomethyl ether acetate, or ethyl lactate, is used.
• the photopolymerization initiator solution is sufficiently exposed to light of a wavelength at which the photopolymerization initiator absorbs and reacts, and the absorbance is measured again.
• the absorbance before exposure Abs (before exposure) is calculated, at which the absorbance in the longer wavelength region than the maximum absorption wavelength is 20%. If there are two or more maximum absorption wavelengths, the maximum absorption wavelength in the longer wavelength region is used. Next, the absorbance Abs (after exposure) after exposure at the same wavelength as Abs (before exposure) is determined, and Abs (before exposure) is compared with Abs (after exposure). If Abs (before exposure) > Abs (after exposure), this indicates that the photopolymerization initiator has photobleaching properties.
• component (B) examples include IRGACURE 819 (manufactured by BASF), NCI-930 (trade name, manufactured by ADEKA Corporation), NCI-730 (trade name, manufactured by ADEKA Corporation), OXE-01 (trade name, manufactured by BASF Corporation), OXE-04 (trade name, manufactured by BASF Corporation), PBG-305 (trade name, manufactured by TRONLY Corporation), PBG-3057 (trade name, manufactured by TRONLY Corporation), PBG-345 (trade name, manufactured by TRONLY Corporation), and PBG-358 (trade name, manufactured by TRONLY Corporation).
• component (B) has a structure represented by the following formula (1).
• the transmittance of i-line does not decrease during photopolymerization, and the occurrence of undercuts can be suppressed even in thick film processing.
• R 1 and R 2 each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group.
• R3 represents an alkyl group having 0 to 5 carbon atoms, -OH, -COOH, -O( CH2 )OH, -O( CH2 ) 2OH , -COO( CH2 )OH or -COO( CH2 ) 2OH .
• component (B) having the structure represented by formula (1) examples include NCI-930 (trade name, manufactured by ADEKA CORPORATION) and some of the compounds described in WO 2015/036910.
• the content of the (B) component in the negative photosensitive resin composition of the present invention is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 0.7 parts by mass or more, and particularly preferably 1 part by mass or more, when the total of the (A) component and the (C) component is 100 parts by mass. If the content is 0.1 parts by mass or more, the sensitivity during exposure can be improved.
• the content of the (B) component is preferably 10 parts by mass or more, more preferably 12 parts by mass or more, even more preferably 14 parts by mass or more, and particularly preferably 15 parts by mass or more.
• the content of the (B) component is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, even more preferably 22 parts by mass or less, and particularly preferably 20 parts by mass or less.
• the transmittance of i-line (wavelength 365 nm) during photopolymerization is not reduced, and undercutting can be suppressed even in thick film processing.
• the negative photosensitive resin composition of the present invention further contains a component (C).
• the component (C) is a compound having a plurality of ethylenically unsaturated double bond groups in the molecule.
• radical polymerization of the component (C) proceeds due to radicals generated from the component (B), and the exposed area of the resin composition film becomes insoluble in an alkaline developer, forming a negative pattern. It can be formed.
• component (C) By including component (C), UV curing during exposure is accelerated, improving sensitivity during exposure. In addition, the crosslink density after thermal curing is improved, improving the hardness of the cured film.
• the component (C) a compound having a (meth)acrylic group, which easily undergoes radical polymerization, is preferred. From the viewpoint of improving the sensitivity during exposure and the hardness of the cured film, a compound having two or more (meth)acrylic groups in the molecule is more preferred. From the viewpoint of improving the sensitivity during exposure, the double bond equivalent of the component (C) is preferably 80 to 800 g/mol.
• component (C) examples include (C-1) polyethylene glycol dimethacrylate represented by formula (2), (C-2) polyethylene glycol dimethacrylate represented by formula (3), and (C-3) a polymerizable compound having a blocked isocyanate structure, which will be described later, as well as other compounds other than those mentioned above, such as trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)
• acrylic acid ester examples include bisphenol A di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, pentapentaerythritol undeca(meth)acrylate, pentapentaerythritol dodeca(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 2,2-bis[4-(3-(meth)acryloxy-2-hydroxypropoxy)
• n is an integer from 1 to 12.
• Me represents a methyl group and Et represents an ethyl group.
• the content of component (C) in the negative photosensitive resin composition of the present invention is preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, and particularly preferably 30% by mass or more, when the total of components (A) and (C) is 100% by mass. If the content is 15% by mass or more, the sensitivity during exposure can be improved and a cured film with a low taper pattern shape can be obtained. On the other hand, the content of component (C) is preferably 65% by mass or less, more preferably 60% by mass or less, even more preferably 55% by mass or less, and particularly preferably 50% by mass or less. If the content is 65% by mass or less, the pattern opening dimensional width can be controlled and the heat resistance of the cured film can be improved.
• the residual rate of the polymer of component (C) is 10 mass % or less when the polymer of component (C) is heated in a nitrogen atmosphere from room temperature to 380°C at a heating rate of 10°C/min in a thermogravimetric analyzer and heat-treated at 380°C for 1 hour.
• Preferred (C) components which have a low residual rate after heat treatment of the polymer, include polyethylene glycol (meth)acrylate, alkoxy polyethylene glycol (meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, alkyl (meth)acrylate, and alkyl di(meth)acrylate.
• the negative type photosensitive resin composition of the present invention further contains polyethylene glycol dimethacrylate represented by formula (2) (C-1) (hereinafter, sometimes referred to as component (C-1)) and polyethylene glycol dimethacrylate represented by formula (3) (C-2) (hereinafter, sometimes referred to as component (C-2)), and it is preferable that the component (C) contains 4 to 20 parts by mass of component (C-2) per 100 parts by mass of component (C-1). Without decreasing the compatibility with component (A), the pattern shape can be processed into a rectangle with a low exposure dose even in thick film processing.
• a represents an integer from 4 to 9.
• b represents an integer from 1 to 3.
• examples of compounds in which a is an integer from 4 to 9 include polyethylene glycol #200 dimethacrylate and polyethylene glycol #400 dimethacrylate.
• polyethylene glycol #200 dimethacrylate is preferred.
• examples of compounds in which b is an integer from 1 to 3 include monoethylene glycol dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate.
• monoethylene glycol dimethacrylate is preferred.
• the negative photosensitive resin composition of the present invention further contains (C-4) polyethylene glycol dimethacrylate represented by formula (23) and component (C-2), and preferably contains 15 to 50 parts by mass of component (C-2) per 100 parts by mass of component (C-4). In this preferred range, a rectangular pattern shape can be obtained with a low exposure dose in thick film processing, and the polymer of component (C-4) decomposes and volatilizes during heat treatment, improving the heat resistance of the cured film.
• c represents an integer of 9 to 14.
• examples of the compound where c is an integer of 9 to 14 include polyethylene glycol #400 dimethacrylate and polyethylene glycol #600 dimethacrylate.
• polyethylene glycol #400 dimethacrylate and polyethylene glycol #600 dimethacrylate are preferred.
• the component (C) contains (C-3) a polymerizable compound having a blocked isocyanate structure (hereinafter, may be referred to as component (C-3)), and preferably contains 0.5 to 15 parts by mass of component (C-3) per 100 parts by mass of component (A).
• the component (C-3) can be obtained by reacting a compound having an isocyanate group and an unsaturated bond in the molecule with a compound containing an active hydrogen group (blocking agent).
• the unsaturated bond refers to a group capable of undergoing chain polymerization in the presence of an active species such as a radical or a cation.
• Examples of the unsaturated bond include unsaturated double bonds such as a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group, and unsaturated triple bonds such as a propargyl group. Of these, conjugated vinyl groups, acryloyl groups, and methacryloyl groups are preferred in terms of polymerizability.
• the compound having an isocyanate group and an unsaturated bond in the molecule is not particularly limited, but is preferably a structure represented by formula (12) or formula (13), for example.
• a polymerizable compound having a blocked isocyanate structure and an unsaturated bond with an active hydrogen group-containing compound (blocking agent), a compound represented by formula (12) or formula (13) can be obtained.
• R 36 and R 38 each independently represent a hydrogen atom or a methyl group.
• R 37 represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms of the hydrocarbon group may be substituted with a group having one or more atoms selected from the group consisting of N, O, F, S, and P.
• R 37 is preferably a methylene group, an ethylene group, a propylene group, a phenylene group, or a group in which a portion of the hydrogen atoms of these groups have been substituted with a methyl group or an ethyl group.
• k represents an integer of 1 to 3, and in terms of reactivity with an active hydrogen group-containing compound (blocking agent), k is particularly preferably 1.
• Specific examples of the compound represented by formula (12) include 2-isocyanatoethyl acrylate, 2-isocyanatoethyl methacrylate, 3-isocyanatopropyl acrylate, 3-isocyanatopropyl methacrylate, 2-isocyanato-1-methylethyl acrylate, 2-isocyanato-1-methylethyl methacrylate, 3-acryloyloxyphenyl isocyanate, 3-methacryloyloxyphenyl isocyanate, 3-isocyanato-2-methylbutyl acrylate, 3-isocyanato-2-methylbutyl methacrylate, 4-acryloyloxyphenyl
• Examples of the compound represented by formula (13) include acryloyl isocyanate, 4-methacryloyloxyphenyl isocyanate, 3-acryloyloxyphenyl isocyanate, 3-methacryloyloxyphenyl isocyanate, 2-acryloyloxyphenyl isocyan
• the blocking agent is not particularly limited as long as it is a compound having active hydrogen, but examples include thiols, phenols, oximes, amines, imines, carbazoles, amides, imides, ureas, alkyl acetoacetates, alkyl malonates, pyrazoles, imidazoles, and triazoles.
• These blocking agents have a low dissociation temperature of generally 200°C or less, so dissociation proceeds more effectively by low-temperature heat treatment (cure), further improving chemical resistance, making them preferable.
• blocking agents include thiols such as methanethiol, ethanethiol, and benzenethiol; phenols such as phenol, o-nitrophenol, m-nitrophenol, p-nitrophenol, cresol, 1-naphthol, and 2-naphthol; oximes such as acetone oxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime; amines such as dibutylamine, diphenylamine, and aniline; imines such as ethyleneimine and propyleneimine; carbazoles such as unsubstituted carbazole, 1,3,6,8-tetranitrocarbazole, and 3,6-dibromocarbazole; and amides such as acetanilide, acetic acid amide, and ⁇ -caprolactam.
• thiols such as methanethiol, ethane
• imides such as succinimide, N-hydroxysuccinimide,
• R 39 and R 42 each independently represent a hydrogen atom or a methyl group.
• R 40 represents a hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atoms of the hydrocarbon group may be substituted with a group having one or more atoms selected from the group consisting of N, O, F, S, and P.
• R 41 and R 43 represent an active hydrogen compound residue excluding alcohols.
• m represents an integer of 1 to 3. m is preferably 1 in terms of small steric hindrance and higher reactivity of the isocyanate group during heat treatment (curing).
• the (C-3) component may be used alone or in combination of two or more. It is preferable that the component contains a compound represented by formula (14) and/or a compound represented by formula (15).
• the content of component (C-3) is preferably 0.5 parts by mass or more and 15 parts by mass or less, based on 100 parts by mass of the total amount of component (A).
• the content of component (C-3) 0.5 parts by mass or more, it is possible to prevent elution of exposed areas during development, to obtain a resin composition with less film thickness reduction after development and excellent chemical resistance after curing, and by making the content 15 parts by mass or less, it is possible to suppress whitening of the film during film formation.
• the negative photosensitive resin composition of the present invention further contains a sensitizer, which is a compound capable of absorbing energy due to exposure, generating excited triplet electrons through internal conversion and intersystem crossing, and mediating energy transfer to the above-mentioned component (B) or the like.
• a sensitizer which is a compound capable of absorbing energy due to exposure, generating excited triplet electrons through internal conversion and intersystem crossing, and mediating energy transfer to the above-mentioned component (B) or the like.
• component (D) By including component (D), it is possible to improve sensitivity during exposure, suppress undercutting, and obtain a rectangular pattern. This is presumably because the sensitizer absorbs long-wavelength light that is not absorbed by components such as (B), and this energy is transferred from the sensitizer to components such as (B), improving the photoreaction efficiency.
• the component (D) contains a thioxanthone sensitizer (D-1) (hereinafter, sometimes referred to as component (D-1)), and preferably contains 5 to 30 parts by mass of the component (D-1) per 100 parts by mass of the component (B). Within this preferred range, sensitivity during exposure is improved, undercut is suppressed, and a rectangular pattern can be obtained.
• D-1 thioxanthone sensitizer
• Examples of the component (D-1) include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-propylthioxanthone, 4-methylthioxanthone, 4-ethylthioxanthone, 4-propylthioxanthone, 2-methyl-4-ethylthioxanthone, 2-ethyl-4-propylthioxanthone, 2-ethyl-4-methylthioxanthone, 2-ethyl-4-propylthioxanthone, 2-propyl-4-methylthioxanthone, 2-propyl-4-ethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dipropylthioxanthone, and 2,4-dichlorothioxanthone.
• the content of component (D) in the negative photosensitive resin composition of the present invention is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, and particularly preferably 1 part by mass or more, when the total of components (A) and (C) is 100 parts by mass.
• a content of 0.01 parts by mass or more can improve the sensitivity during exposure.
• the content of the sensitizer is preferably 15 parts by mass or less, more preferably 13 parts by mass or less, even more preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less.
• a content of 15 parts by mass or less can suppress undercutting and process the pattern shape into a rectangle.
• the content of the (D-1) component in the negative photosensitive resin composition of the present invention is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, and particularly preferably 1 part by mass or more, when the total of the (A) component and the (C) component is 100 parts by mass.
• the content of the sensitizer is preferably 15 parts by mass or less, more preferably 13 parts by mass or less, even more preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less.
• the negative type photosensitive resin composition of the present invention preferably contains a compound represented by formula (6) from the viewpoint of further enhancing the effect of improving development adhesion.
• R 8 , R 9 and R 10 each independently represent an alkyl group having 1 to 6 carbon atoms.
• the ⁇ -alkoxypropionamide compound represented by formula (6) is preferably 3-methoxy-N,N-dimethylpropionamide or 3-butoxy-N,N-dimethylpropionamide from the viewpoint of compatibility with component (A).
• the content of ⁇ -alkoxypropionamide is preferably 0.1 parts by mass or more, and more preferably 1 part by mass or more, per 100 parts by mass of component (A) from the viewpoint of improving development adhesion.
• the content is preferably 15 parts by mass or less, and more preferably 7 parts by mass or less.
• the negative photosensitive resin composition of the present invention may further contain additives such as a polymerization inhibitor, a crosslinking agent, a silane coupling agent, a surfactant, etc., if necessary.
• the polymerization inhibitor is preferably a phenol-based polymerization inhibitor.
• the phenol-based polymerization inhibitor include "IRGANOX” (registered trademark) 245, 259, 565, 1010, 1035, 1076, 1098, 1135, 1330, 1425, 1520, 1726, and 3114 (all manufactured by BASF).
• the crosslinking agent is preferably a compound having two or more thermally crosslinkable groups in the molecule, such as an alkoxymethyl group, a methylol group, an epoxy group, or an oxetanyl group.
• the compound having two or more alkoxymethyl groups or methylol groups in the molecule include DML-PC, DML-OC, DML-PTBP, DML-PCHP, DML-MBPC, DML-MTrisPC, DMOM-PC, DMOM-PTBP, TriML-P, TriML-35XL, TML-HQ, TML-BPA, TML-BPAF, TMLBPAP, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPHAP, and HMOM-TPHAP (all manufactured by Honshu Chemical Industry Co., Ltd.), or "NIKALAC" (registered trademark) MX-290, MX-280, MX-270, MX-279, MW-100LM,
• the silane coupling agent is preferably a trifunctional organosilane, a tetrafunctional organosilane, or a silicate compound.
• trifunctional organosilanes include vinyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 4-styryltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride, 3-aminopropyltrimethoxysilane, 3-(4-aminophenyl)propyltrimethoxysilane, 1-(3-trimethoxysilylpropyl)urea, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 1,3,5-tris(3-trimethoxysilylpropy
• a silane coupling agent increases the interaction at the interface between the cured film of the resin composition and the underlying substrate, improving adhesion to the underlying substrate and the chemical resistance of the cured film.
• the surfactant is preferably a fluororesin-based surfactant, a silicone-based surfactant, a polyoxyalkylene ether-based surfactant, or an acrylic resin-based surfactant.
• the surface tension of the resin composition can be adjusted as desired, improving the leveling properties during application and improving the uniformity of the coating thickness.
• the photosensitive resin composition of the present invention may contain a solvent.
• the solvent include polar aprotic solvents such as N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, N,N'-dimethylpropyleneurea, N,N-dimethylisobutyric acid amide, and methoxy-N,N-dimethylpropionamide; ethers such as tetrahydrofuran, dioxane, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; ketones such as acetone, methyl ethyl ketone, and diisobutyl ketone; esters such as ethyl acetate, butyl a
• the content ratio of the solvent in the negative-type photosensitive resin composition of the present invention can be adjusted as appropriate depending on the application method, etc. For example, when forming a coating film by spin coating, the content is generally 50 to 95 mass % of the entire negative-type photosensitive resin composition.
• the negative photosensitive resin composition of the present invention is not limited in shape as long as it contains the above-mentioned components (A), (B), (C), and (D), and may be, for example, in the form of a paste or a sheet.
• the photosensitive sheet of the present invention refers to a sheet-like product obtained by applying the photosensitive resin composition of the present invention onto a support, drying the composition at a temperature and for a time within a range that allows the solvent to volatilize, and not curing completely, and which is soluble in an organic solvent or an alkaline aqueous solution.
• the support is not particularly limited, but various commercially available films such as polyethylene terephthalate (PET) film, polyphenylene sulfide film, and polyimide film can be used.
• PET polyethylene terephthalate
• the joint surface between the support and the photosensitive resin composition may be surface-treated with silicone, a silane coupling agent, an aluminum chelating agent, polyurea, or the like to improve adhesion and peelability.
• the thickness of the support is not particularly limited, but from the viewpoint of workability, it is preferably in the range of 10 to 100 ⁇ m.
• a protective film may be provided on the film surface. This makes it possible to protect the surface of the photosensitive resin composition from contaminants such as dust and dirt in the air.
• Methods for applying the photosensitive resin composition to a support include rotary application using a spinner, spray application, roll coating, screen printing, blade coater, die coater, calendar coater, meniscus coater, bar coater, roll coater, comma roll coater, gravure coater, screen coater, and slit die coater.
• the thickness of the applied film varies depending on the application method, the solids concentration of the composition, the viscosity, etc., but it is usually preferable that the film thickness after drying is 0.5 ⁇ m or more and 100 ⁇ m or less from the viewpoint of the uniformity of the coating film.
• drying an oven, a hot plate, infrared rays, etc. can be used.
• the drying temperature and drying time may be within a range that allows the solvent to volatilize, and it is preferable to set the drying temperature and time appropriately within a range that allows the photosensitive resin composition to be in an uncured or semi-cured state.
• drying is preferably performed in the range of 40°C to 150°C for one minute to several tens of minutes.
• the temperature may be increased stepwise by combining these temperatures, for example, heat treatment may be performed at 80°C and 90°C for two minutes each.
• the photosensitive resin composition of the present invention is applied to a substrate, or the photosensitive sheet is laminated to a substrate.
• the substrate may be, but is not limited to, a copper-plated metal substrate, a silicon wafer, a silicon carbide substrate, or a gallium nitride substrate, and the material may be, but is not limited to, ceramics, gallium arsenide, or the like.
• Coating methods include rotary coating using a spinner, spray coating, and roll coating. The coating thickness varies depending on the coating method, the solids concentration of the composition, the viscosity, and other factors, but is usually applied so that the film thickness after drying is 0.1 to 150 ⁇ m.
• the substrate can be pretreated with the aforementioned silane coupling agent.
• the substrate can be surface-treated by spin coating, immersion, spray coating, steam treatment, or the like with a solution prepared by dissolving 0.5 to 20% by mass of the silane coupling agent in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate.
• a heat treatment up to 50°C to 300°C is then performed to promote the reaction between the substrate and the silane coupling agent.
• a photosensitive resin composition is applied, or the substrate laminated with the photosensitive sheet of the present invention is dried to obtain a photosensitive resin composition coating. Drying is preferably carried out using an oven, a hot plate, infrared rays, or the like, at a temperature in the range of 50°C to 150°C for 1 minute to several hours. Note that in the case of a photosensitive sheet, it is not necessarily necessary to go through a drying process.
• this photosensitive resin composition film is exposed to actinic radiation through a mask having a desired pattern.
• Actinic radiation used for exposure includes ultraviolet light, visible light, electron beams, and X-rays, but in the present invention, it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) from a mercury lamp.
• the temperature is preferably in the range of 50 to 180°C, and more preferably in the range of 60 to 150°C. There is no particular limit to the time, but from the viewpoint of subsequent developability, a bake time of 10 seconds to several hours is preferable.
• the developer used for development is preferably a good solvent for the negative photosensitive resin composition, or a combination of the good solvent and a poor solvent.
• the developer used for development dissolves and removes the alkaline aqueous solution-soluble polymer, and is typically an alkaline aqueous solution in which an alkaline compound is dissolved.
• alkaline compounds include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine, and hexamethylenediamine.
• polar solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone, and dimethylacrylamide
• alcohols such as methanol, ethanol, and isopropanol
• esters such as ethyl lactate and propylene glycol monomethyl ether acetate
• ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added to these aqueous alkaline solutions, either alone or in combination.
• water After development, it is preferable to perform a rinsing process with water. If water is used, alcohols such as ethanol or isopropyl alcohol, or esters such as ethyl lactate or propylene glycol monomethyl ether acetate may also be added to the water for rinsing.
• alcohols such as ethanol or isopropyl alcohol
• esters such as ethyl lactate or propylene glycol monomethyl ether acetate may also be added to the water for rinsing.
• a temperature of 150°C to 400°C is applied to promote a thermal crosslinking reaction, improving heat resistance and chemical resistance.
• This heat treatment is carried out by selecting a temperature and gradually increasing the temperature, or by selecting a certain temperature range and continuously increasing the temperature for 5 minutes to 5 hours. As an example, heat treatment is carried out at 130°C and 200°C for 30 minutes each.
• the lower limit of the curing conditions in this invention is preferably 170°C or higher, but 180°C or higher is more preferable in order to promote sufficient curing.
• the upper limit of the curing conditions is preferably 450°C or lower.
• the cured product of the present invention is a product obtained by curing the photosensitive resin composition of the present invention.
• the cured product can be obtained by applying the photosensitive resin composition to a substrate and drying it to evaporate the solvent. After that, exposure and post-exposure baking steps are performed as necessary, followed by curing at a temperature of 150°C to 400°C. This heat treatment is performed for 5 minutes to 5 hours by selecting a temperature and gradually increasing the temperature, or by selecting a certain temperature range and continuously increasing the temperature. As an example, heat treatment is performed at 130°C and 200°C for 30 minutes each.
• the lower limit of the curing conditions in this invention is preferably 170°C or higher, but more preferably 180°C or higher to allow sufficient curing to proceed.
• the upper limit of the curing conditions is preferably 450°C or lower.
• the electronic component of the present invention comprises the cured product of the present invention.
• the cured product formed from the photosensitive resin composition of the present invention can be used as an insulating film or protective film that constitutes electronic components.
• examples of electronic components include active components that have semiconductors, such as transistors, diodes, integrated circuits (ICs), and memories, as well as passive components, such as resistors, capacitors, and inductors.
• active components such as transistors, diodes, integrated circuits (ICs), and memories
• passive components such as resistors, capacitors, and inductors.
• Electronic components that use semiconductors are also called semiconductor devices or semiconductor packages.
• hardened materials used in electronic components include passivation films for semiconductors, surface protective films for semiconductor elements and TFTs (Thin Film Transistors), interlayer insulating films such as interlayer insulating films between rewirings in multilayer wiring for high-density mounting of 2 to 10 layers, insulating films and protective films for touch panel displays, and insulating layers for organic electroluminescent elements, but are not limited to these and can take on a variety of structures.
• the electronic component of the present invention preferably comprises a substrate having the cured product of the present invention on the surface thereof.
• the substrate surface on which the cured product is formed can be appropriately selected depending on the application and process.
• the substrate include silicon substrates, silicon carbide substrates, gallium nitride substrates, ceramics, gallium arsenide, metals, and epoxy resins.
• a silicon substrate, silicon carbide substrate, or gallium nitride substrate is preferable.
• (A) Weight Average Molecular Weight of Alkali-Soluble Resin The weight average molecular weight (Mw) of the alkali-soluble resin or alkali-soluble resin solution obtained in each Example and Comparative Example was measured using a GPC (gel permeation chromatography) apparatus Waters 2690-996 (manufactured by Nippon Waters K.K.) and N-methyl-2-pyrrolidone (hereinafter, NMP) as a developing solvent in terms of polystyrene.
• GPC gel permeation chromatography
• ⁇ Combustion and absorption conditions System: AQF-2100H, GA-210 (manufactured by Mitsubishi Chemical Corporation) Electric furnace temperature: Inlet 900°C, Outlet 1000°C Gas: Ar/ O2 200mL/min, O2 400mL/min Absorbing solution: H2O2 0.1 % Amount of absorbed liquid: 5 mL ⁇ Ion chromatography/anion analysis conditions> System: ICS1600 (manufactured by DIONEX) Mobile phase: 2.7 mmol/L Na 2 CO 3 , 0.3 mmol/L NaHCO 3 Flow rate: 1.50mL/min Detector: electrical conductivity detector Injection volume: 100 ⁇ L.
• i-line transmittance of negative photosensitive resin composition The varnish was spin-coated on a glass substrate using a spin coater 1H-360S (manufactured by Mikasa Co., Ltd.), and then pre-baked at 100° C. for 5 minutes using a hot plate (SCW-636 manufactured by Dai-Nippon Screen Mfg. Co., Ltd.) to produce a pre-baked film having a thickness of 5 ⁇ m.
• the i-line transmittance of the obtained pre-baked film was measured from the transmitted UV spectrum using a spectrophotometer U-2910 (manufactured by Hitachi High-Tech Science Co., Ltd.).
• the film was exposed to light at an exposure dose range of 100 to 2000 mJ/ cm2 at intervals of 50 mJ/ cm2 through a mask having a 1:1 line and space pattern of 30 ⁇ m and 100 ⁇ m.
• the resist was post-exposure baked at 120° C. for 1 minute, and then paddle developed for 120 seconds using the ACT-8 developing device with a 2.38% by mass aqueous solution of tetramethylammonium (manufactured by Tama Chemicals Co., Ltd.; hereinafter, TMAH) as a developer.
• TMAH tetramethylammonium
• the film thickness was measured, and the minimum exposure amount at which the remaining film rate in the light area exceeded 90% was defined as the sensitivity.
• Pattern Shape The line and space pattern obtained by the same method as in (6) above was heated from 50°C to 380°C in 100 minutes under a nitrogen stream (oxygen concentration 20 ppm or less) using an inert oven (manufactured by Koyo Thermo Systems Co., Ltd.), and the negative photosensitive resin composition layer was cured at 380°C for 1 hour.
• the silicon wafer was cut perpendicular to the line pattern to expose the cross section of the pattern.
• the taper angle between the surface of the silicon wafer (substrate surface) and the side surface of the pattern was measured, and a taper angle of 85° or more and less than 90° was evaluated as A, a taper angle of 80° or more and less than 85° was evaluated as B, a taper angle of 75° or more and less than 80° was evaluated as C, a taper angle of 70° or more and less than 75° was evaluated as D, and a taper angle of less than 70° was evaluated as "E”.
• a reverse taper shape with a taper angle of 90° or more in the cross section of the pattern was evaluated as defective "F".
• the obtained pattern was observed at 20x magnification using an FDP microscope MX61 (Olympus Corporation) to determine the minimum size of the convex pattern that remained in close contact with the substrate without peeling.
• Viscosity change rate
• Viscosity change rate is 20% or more. (10) Heat resistance (measured at 5% thermal weight loss temperature) The photosensitive resin composition was exposed to light without using a photomask, and the remaining processing was carried out in the same manner as in (7) above, thereby producing a cured film of the photosensitive resin composition. The obtained cured film was peeled off from the silicon wafer to produce a single film. The 5% thermal weight loss temperature of the produced cured film was measured using a differential thermal and thermogravimetric simultaneous measurement device DTG-60A (manufactured by Shimadzu Corporation). This measurement was carried out under the following conditions: test temperature: room temperature (25°C) to 550°C, heating rate: 10°C/min, measurement atmosphere: nitrogen, sample weight: 15 mg.
• the heat resistance in the examples and comparative examples was evaluated based on the 5% thermal weight loss temperature of the single film (cured film) measured in this manner, and the obtained 5% thermal weight loss temperature [°C] was used as the evaluation result.
• (11) Method for preparing a polymer of component (C) and method for measuring the residue after heating the polymer at 380° C. for 1 hour at a heating rate of 10° C./min in a nitrogen atmosphere using a thermogravimetric analyzer: 2 g of component (C) was placed in an aluminum cup, and 3 g of a 0.4 mass % solution of azobisisobutyronitrile in propylene glycol monomethyl ether acetate was added thereto. The mixture was heated on a hot plate at 130° C. for 10 minutes, then heated to 200° C. and continued to be heated for 30 minutes after reaching 200° C., to obtain a polymer of component (C).
• the residual rate of the polymer of component (C) after heat treatment at 380°C for 1 hour was measured using a differential thermal and thermogravimetric simultaneous analyzer DTG-60A (manufactured by Shimadzu Corporation). The measurements were performed under the following conditions: test temperature: room temperature (25°C) to 380°C, held at 380°C for 1 hour, heating rate: 10°C/min, measurement atmosphere: nitrogen, sample weight: 15 mg.
• Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound (HA) 18.3 g (0.05 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (manufactured by Central Glass Co., Ltd., hereinafter referred to as BAHF) was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide (manufactured by Tokyo Chemical Industry Co., Ltd.), and cooled to -15°C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of the dropwise addition, the mixture was stirred at -15°C for 4 hours, and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50°C.
• BAHF 2,2-bis(3-amino-4-hydroxyphenyl
• HA hydroxyl group-containing diamine compound
• the reaction solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed twice with water, and once with isopropanol, and then dried in a vacuum dryer at 50°C for 72 hours to obtain a polyimide precursor (PAA-4).
• Synthesis Example 9 Synthesis of polyimide (PI-1) Under a dry nitrogen stream, 29.3 g (0.08 mol) of BAHF, 1.2 g (0.005 mol) of SiDA, and 3.3 g (0.03 mol) of MAP as a terminal blocking agent were dissolved in 80 g of NMP. 31.2 g (0.1 mol) of ODPA was added thereto together with 20 g of NMP, and the mixture was reacted at 60° C. for 1 hour, and then stirred at 180° C. for 4 hours. After stirring, the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed three times with water, and then dried in a vacuum dryer at 80° C.
• ⁇ Synthesis Example 14 Synthesis of polyimide precursor (PAA-10)> A polyimide precursor (PAA-10) was obtained in the same manner as in Synthesis Example 11, except that the amount of DFA was changed from 17.9 g (0.15 mol) to 25.0 g (0.21 mol).
• ⁇ Synthesis Example 15 Synthesis of polyimide precursor (PAA-11)> A polyimide precursor (PAA-11) was obtained in the same manner as in Synthesis Example 11, except that the amount of DFA was changed from 17.9 g (0.15 mol) to 26.2 g (0.22 mol).
• ⁇ Synthesis Example 17 Synthesis of polyimide precursor (PAA-12)> A polyimide precursor (PAA-12) was obtained in the same manner as in Synthesis Example 14, except that NMP was changed to MPA.
• ⁇ Synthesis Example 18 Synthesis of polybenzoxazole precursor (PHA-4)> A polybenzoxazole precursor (PHA-4) was obtained in the same manner as in Synthesis Example 16, except that NMP was changed to MPA.
• Table 1 shows the measurement results of the components (molar ratio), molecular weight (Mw), fluorine concentration, esterification rate, and ⁇ -alkoxypropionamide content (contained as an impurity in the obtained powder) for Synthesis Examples 2 to 18.
• HA Hydroxyl group-containing diamine compound
• ODPA 4,4'-oxydiphthalic anhydride
• ODPA-HEMA Reaction mixture of 4,4'-oxydiphthalic anhydride and 2-hydroxyethyl methacrylate
• SiDA 1,3-bis(3-aminopropyl)tetramethyldisiloxane
• BAHF 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane
• MAP 3-aminophenol
• DAE 4,4'-diaminodiphenyl ether
• MPA 3-methoxy-N,N-dimethylpropanamide
• OBBOC 4,4'-oxybenzoyl chloride
• BAP 2,2-bis(3-amino-4-hydroxyphenyl)propane NA: 5-norbornene-2,3-dicarboxylic anhydride ⁇ Examples and Comparative Examples> The components shown in the table below were mixed to obtain each
• Tables 2-1 to 2-3 the numbers in parentheses indicate the mass parts of the solid content of each component.
• the ⁇ -alkoxypropionamide in Examples 11, 13, 14, 55, and 56 is an impurity contained in the component (A) used.
• the ⁇ -alkoxypropionamide in Examples 57 to 59 was 3-methoxy-N,N-dimethylpropanamide (KJ Chemicals Co., Ltd.) added.
• GBL was used as a solvent to prepare the composition so that the solid content concentration was 50 mass%.
• Photopolymerization initiator other than component (B) "IRGACURE” (registered trademark) OXE 02 (manufactured by BASF) (not having photobleaching properties). In Table 2-3, this is abbreviated as “OXE 02”.
• the polymer (c-1) was heated in a thermogravimetric analyzer in a nitrogen atmosphere from room temperature to 380° C. at a heating rate of 10° C./min., and the residual ratio after heat treatment at 380° C. for 1 hour was 3 mass %.
• (c-1) corresponds to the component (C-1) represented by formula (2).
• (c-2) corresponds to the component (C-2) represented by formula (3).
• the polymer (c-3) was heated in a thermogravimetric analyzer in a nitrogen atmosphere from room temperature to 380° C. at a heating rate of 10° C./min., and the residual ratio after heat treatment at 380° C. for 1 hour was 17% by mass.
• (c-3) corresponds to the component (C-3) having a blocked isocyanate structure.
• the polymer (c-4) was heated in a thermogravimetric analyzer in a nitrogen atmosphere from room temperature to 380° C. at a heating rate of 10° C./min., and the residual ratio after heat treatment at 380° C. for 1 hour was 26 mass %.
• (c-4) does not fall under any of the components (C-1) to (C-4).
• the polymer (c-5) was heated in a thermogravimetric analyzer in a nitrogen atmosphere from room temperature to 380° C. at a heating rate of 10° C./min., and the residual ratio after heat treatment at 380° C. for 1 hour was 0.9 mass %.
• (c-5) corresponds to the component (C-4) represented by formula (23).
• the cured product of the negative photosensitive resin composition of the present invention can be used favorably for applications such as surface protection films for semiconductor elements, interlayer insulating films, wiring protection insulating films for circuit boards, and permanent resists.

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