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WO2025135175A1 - Composition de résine photosensible, procédé de production de motif, produit durci, composant électronique et dispositif d'affichage - Google Patents

Composition de résine photosensible, procédé de production de motif, produit durci, composant électronique et dispositif d'affichage Download PDF

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Publication number
WO2025135175A1
WO2025135175A1 PCT/JP2024/045275 JP2024045275W WO2025135175A1 WO 2025135175 A1 WO2025135175 A1 WO 2025135175A1 JP 2024045275 W JP2024045275 W JP 2024045275W WO 2025135175 A1 WO2025135175 A1 WO 2025135175A1
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Prior art keywords
group
resin
electron
resin composition
photosensitive resin
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English (en)
Japanese (ja)
Inventor
昇 小清水
優 荘司
勇剛 谷垣
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Toray Industries Inc
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Toray Industries Inc
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    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to a photosensitive resin composition, a method for producing a pattern, a cured product, an electronic component, and a display device.
  • Polyimides and polybenzoxazoles which have excellent heat resistance, electrical insulation, and mechanical properties, are widely used for surface protection films and interlayer insulating films used in electronic components, insulating layers in organic electroluminescent devices, and planarizing films for TFT (thin film transistor) substrates.
  • photosensitive resin compositions in which these resins themselves or their precursors have been given photosensitivity have come into use. The use of photosensitive resin compositions can simplify the pattern processing process and shorten the complicated manufacturing process.
  • Photosensitive resin compositions include positive-type materials in which the exposed areas are easily soluble in developer and can be patterned, and negative-type materials in which the composition itself is easily soluble and the exposed areas are insoluble in developer.
  • Known positive-type photosensitive resin compositions include, for example, polyimide, polyamideimide, polybenzoxazole, and precursors thereof to which a quinone diazide compound has been added (see, for example, Patent Document 1).
  • Known negative-type photosensitive resin compositions include, for example, polyimide, polyamideimide, polybenzoxazole, and precursors thereof to which a photopolymerizable compound and a photopolymerization initiator have been added (see, for example, Patent Document 2).
  • Patent Document 1 has problems in that the difference in dissolution contrast between the unexposed and exposed areas is small, limiting the amount of film thickness reduction that can be achieved during development, and there is also a problem that the quinone diazide compound remaining in the film after development reduces heat resistance.
  • Patent Document 2 has the problem of reduced heat resistance because (meth)acrylate is used as a photopolymerization initiator.
  • the object of the present invention is to provide a photosensitive resin composition that has excellent heat resistance, reduces film loss during development, and is highly sensitive.
  • the photosensitive resin composition of the present invention has the following configurations [1] to [18].
  • [1] (a) one or more resins selected from the group consisting of polyimide, polyamideimide, polybenzoxazole, and precursors thereof (hereinafter referred to as “resin (a)”); (b) an amine compound; and (c) a photoacid generator, the (b) amine compound is a primary amine or a secondary amine,
  • a photosensitive resin composition comprising the (b) amine compound in an amount of 35 parts by mass or more per 100 parts by mass of the (a) resin.
  • the resin (a) has an electron-withdrawing group, and the resin (a) is (a1) a polyimide or polyamideimide containing a structural unit represented by formula (1) (hereinafter referred to as “(a1) resin”), (a2) a polyimide precursor or a polyamideimide precursor containing a structural unit represented by formula (2) (hereinafter referred to as “(a2) resin”), (a3) a polyamideimide containing a structural unit represented by formula (3) (hereinafter referred to as “(a3) resin”), (a4) a polybenzoxazole containing a structural unit represented by formula (4) (hereinafter referred to as "(a4) resin”), and (a5) a polybenzoxazole precursor containing a structural unit represented by formula (5) (hereinafter referred to as "(a5) resin”);
  • the photosensitive resin composition according to any one of the above [1] to [9], comprising one or more resins selected from the group consisting of:
  • L 1 is
  • L 1 is linked to any one of X 1 to X 4 and any one of X 5 to X 8.
  • L 1 is neither a sulfonyl group nor >C(CF 3 ) 2
  • L 2 is a single bond, a sulfonyl group, >C(CF 3 ) 2 , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms.
  • L 2 is linked to any one of X 11 to X 14 and any one of X 15 to X 18.
  • L 2 is neither a sulfonyl group nor >C(CF 3 ) 2
  • R n has an electron-withdrawing group. * indicates a bonding site.
  • L 3 is an amide bond.
  • L 3 is linked to any one of the positions of X 19 to X 22.
  • * indicates a bonding site.
  • L 4 is a single bond, a sulfonyl group, >C(CF 3 ) 2 , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms.
  • L 4 is linked to any one of X 31 to X 35 and any one of X 36 to X 40.
  • the photosensitive resin composition according to the embodiment of the present invention contains one or more resins selected from the group consisting of (a) polyimide, polyamideimide, polybenzoxazole, and precursors thereof (hereinafter referred to as "(a) resin").
  • the (a) resin is preferably one or more selected from the group consisting of polyimide, polyamideimide, and polyamide, since it has high reactivity with the (b) amine compound.
  • the (a) resin is preferably polyamide from the viewpoint of improving sensitivity.
  • the (a) resin is more preferably a polyimide precursor, a polyamideimide precursor, or a polybenzoxazole precursor from the viewpoint of improving reactivity with the (b) amine compound and improving sensitivity.
  • Polyimide is a polymer containing imide bonds in the repeating unit.
  • Polyimide can be synthesized by known methods. For example, there is a resin obtained by dehydrating and ring-closing a reactant obtained by reacting a tetracarboxylic acid, a corresponding tetracarboxylic dianhydride, or a tetracarboxylic diester dichloride with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine, by heating or a reaction using a catalyst such as an acid or a base.
  • a catalyst such as an acid or a base.
  • Polybenzoxazole is a polymer containing a benzoxazole structure in the repeating unit.
  • Polybenzoxazole can be synthesized by known methods. For example, there is a resin obtained by dehydrating and ring-closing the reaction product obtained by reacting a bisamino-phenol compound with a dicarboxylic acid or the corresponding dicarboxylic acid chloride or dicarboxylic acid active ester, or the like, through heating or a reaction using a catalyst such as an acid, a base, acetic anhydride, or a carbodiimide compound.
  • a catalyst such as an acid, a base, acetic anhydride, or a carbodiimide compound.
  • Polyamide is a polymer containing an amide bond in the repeating unit.
  • Polyamide can be synthesized by a known method.
  • the polyamide is preferably a polyimide precursor, a polyamideimide precursor, or a polybenzoxazole precursor.
  • the (a) resin contains an amide bond in the repeating unit, and is more preferably a polyimide precursor, a polyamideimide precursor, or a polybenzoxazole precursor.
  • Polyimide precursors are polyamides that can be converted to polyimides by heating. By incorporating a polyimide precursor, a resin film with high heat resistance can be obtained. Polyimide precursors can be synthesized by known methods. For example, there are resins obtained by reacting tetracarboxylic acids, the corresponding tetracarboxylic dianhydrides or tetracarboxylic diester dichlorides, etc. with diamines, the corresponding diisocyanate compounds, trimethylsilylated diamines, etc.
  • the polyamide-imide precursor is a polyamide that can be converted to polyamide-imide by heating.
  • a resin film with high heat resistance can be obtained.
  • the polyamide-imide precursor can be synthesized by a known method. For example, there can be mentioned a resin obtained by reacting trimellitic acid chloride, the corresponding trimellitic anhydride chloride, or a compound in which some of the hydrogen atoms on the benzene ring of these are substituted with a nitro group, an amino group, a sulfo group, or the like, with a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine, or the like.
  • Polybenzoxazole precursors are polyamides that can be converted to polybenzoxazole by heating. By incorporating polybenzoxazole precursors, it is possible to obtain resin films with high heat resistance. Polybenzoxazole precursors can be synthesized by known methods. For example, there are resins obtained by reacting bisamino-phenol compounds with dicarboxylic acids, the corresponding dicarboxylic acid chlorides, or dicarboxylic acid activated esters.
  • the polyamide may be a resin that does not fall under the category of polyimide precursor, polyamideimide precursor, or polybenzoxazole precursor.
  • a resin obtained by reacting a diamine, a corresponding diisocyanate compound, or a trimethylsilylated diamine with a dicarboxylic acid, a corresponding dicarboxylic acid chloride, or a dicarboxylic acid active ester.
  • Tetracarboxylic acids used in the synthesis of polyimides and polyimide precursors include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic acid, pyromellitic acid, 4,4'-biphenyltetracarboxylic acid, 4,4'-carbonyldiphthalic acid, 3,3',4,4'-biphenylethertetracarboxylic acid, 3,3',4,4'-biphenylsulfonetetracarboxylic acid, 4,4'-(hexafluoroisopropylidene)diphthalic acid, 2,2'-bis(3,4-dicarboxyphenyl)propanoic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 4,4'-(9H-fluorene-9,9-diyl)diphthalic acid, and compounds in which some of the hydrogen atoms on the benzene rings of these are replaced with nitro groups
  • Tetracarboxylic dianhydrides used in the synthesis of polyimides and polyimide precursors include, but are not limited to, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-biphenyltetracarboxylic dianhydride, 4,4'-carbonyldiphthalic anhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 2,2'-bis(3,4-dicarboxyphenyl)propanoic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 5,5'-(9H-fluorene-9,9-diyl)bis(2-benz
  • tetracarboxylic acid diester dichlorides used in the synthesis of polyimides and polyimide precursors include, but are not limited to, compounds in which the carboxylic acid in the compounds described above as examples of tetracarboxylic acids has been changed to an ester chloride.
  • Diamines used in the synthesis of polyimides, polyamideimides, polyimide precursors and polyamideimide precursors include, for example, p-phenylenediamine, m-phenylenediamine, 4,4-diamino-diphenyl ether, 3,4'-diamino-diphenyl ether, 3,3'-diamino-diphenyl ether, 4,4'-diamino-diphenyl sulfide, 3,4'-diamino-diphenyl sulfide, 3,3'-diamino-diphenyl sulfide, 4,4'-diamino-diphenyl sulfone, 3,4'-diamino-diphenyl sulfone, 3,3'-diamino- Diphenyl sulfone, 4,4'-diamino-biphenyl, 3,4'-diamino-biphen
  • Diisocyanate compounds used in the synthesis of polyimides, polyamideimides, polyimide precursors, and polyamideimide precursors include, but are not limited to, compounds in which the amino groups of the compounds described above as examples of diamines have been changed to isocyanate groups.
  • Trimethylsilylated diamines used in the synthesis of polyimides, polyamideimides, polyimide precursors, and polyamideimide precursors include, but are not limited to, compounds in which some of the hydrogen atoms on the benzene ring of the compounds described above as examples of diamines have been substituted with trimethylsilyl groups.
  • Bisamino-phenol compounds used in the synthesis of polybenzoxazole and polybenzoxazole precursors include, for example, bis(3-amino-4-hydroxyphenyl)ether, bis(3-amino-4-hydroxyphenyl)methylene, bis[N-(3-amino-benzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis[N-(4-amino-benzoyl)-3-amino-4-hydroxyphenyl]sulfone, bis(3-amino-4-hydroxyphenyl)sulfone, bis(3- 2,2'-bis[N-(3-amino-benzoyl)-3-amino-4-hydroxyphenyl]propane, 2,2'-bis[N-(4-amino-benzoyl)-3-amino-4-hydroxyphenyl]propane, 9,9-bis[N-(3-amino-benzoyl)-3-amino-4-hydroxy
  • Dicarboxylic acids used in the synthesis of polybenzoxazole and polybenzoxazole precursors include, but are not limited to, terephthalic acid, isophthalic acid, dimer acid, diphenyl ether dicarboxylic acid, bis(carboxyphenyl)hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, triphenyl dicarboxylic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.
  • Dicarboxylic acid chlorides used in the synthesis of polybenzoxazole and polybenzoxazole precursors include, but are not limited to, compounds in which the carboxylic acid in the compounds described above as examples of dicarboxylic acids is changed to a carboxylic acid chloride.
  • Dicarboxylic acid active esters used in the synthesis of polybenzoxazole and polybenzoxazole precursors include, but are not limited to, compounds in which the carboxylic acid of the compounds described above as examples of dicarboxylic acids is changed to a carboxylic acid active ester such as a thioester or a phenyl ester.
  • the diamine, diisocyanate compound, trimethylsilylated diamine, dicarboxylic acid, dicarboxylic acid chloride and dicarboxylic acid active ester used in the synthesis of such polyamide include, but are not limited to, the compounds described above.
  • the (a) resin is preferably capped at the main chain end with a terminal blocking agent such as a known monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound.
  • a terminal blocking agent such as a known monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound.
  • the ratio of monoamine used as a terminal blocking agent to the total amine components constituting the (a) resin is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, and preferably 60 mol% or less, and particularly preferably 50 mol% or less.
  • the ratio of acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound used as a terminal blocking agent to the diamine components constituting the (a) resin is preferably 0.1 mol% or more, particularly preferably 5 mol% or more, and preferably 100 mol% or less, and particularly preferably 90 mol% or less.
  • a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.
  • the weight average molecular weight of the resin is preferably 3,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more, in order to suppress the dissolution of the unexposed parts in the developer and to improve the mechanical properties and heat resistance.
  • the weight average molecular weight is preferably 100,000 or less, more preferably 60,000 or less, and even more preferably 30,000 or less.
  • the weight average molecular weight is determined by the method described below in terms of polystyrene using gel permeation chromatography.
  • the resin (a) preferably has an electron-withdrawing group.
  • the resin (a) more preferably has two or more electron-withdrawing groups. It is even more preferable that the resin (a) has an electron-withdrawing group in a repeating unit.
  • an electron-withdrawing group is a group whose substituent constant ⁇ p0 value is positive as defined in the Basic Chemistry Handbook, 5th Revised Edition, II-379 to II-380 (edited by the Chemical Society of Japan, published by Maruzen Co., Ltd.).
  • Specific examples include halogen atoms, cyano groups, oxy groups, carbonyl groups, carbonyloxy groups, oxycarbonyl groups, nitrile groups, nitro groups, sulfonyl groups, sulfinyl groups, sulfo groups, halo(cyclo)alkyl groups or haloaryl groups, and combinations of these.
  • halo(cyclo)alkyl groups refer to alkyl and cycloalkyl groups that are at least partially halogenated
  • haloaryl groups refer to aryl groups that are at least partially halogenated.
  • the electron-withdrawing group is preferably one or more groups selected from the group consisting of a nitro group, a cyano group, a sulfo group, and a sulfonyl group, and more preferably one or more groups selected from the group consisting of a nitro group, a cyano group, and a sulfo group.
  • the (a) resin has an electron-withdrawing group in the repeating unit.
  • the (a) resin when the (a) resin contains an amide bond in the repeating unit and is a polyimide precursor, a polyamideimide precursor, or a polybenzoxazole precursor, the (a) resin preferably has an electron-withdrawing group, and more preferably the electron-withdrawing group is one or more groups selected from the group consisting of a nitro group, a cyano group, a sulfo group, and a sulfonyl group.
  • the (a) resin has an acidic group in at least one of the main chain, side chain, and end of the resin.
  • the acidic group is preferably a phenolic hydroxyl group, a hydroxyimide group, a hydroxyamide group, a silanol group, a mercapto group, a carboxy group, a carboxylic anhydride group, or a sulfonic acid group.
  • the (a) resin does not have a carboxy group, a carboxylic anhydride group, or a sulfonic acid group.
  • the acid equivalent of the (a) resin is preferably 200 g/mol or more, and more preferably 400 g/mol or more.
  • the acid equivalent of the (a) resin is preferably 500 g/mol or more, more preferably 700 g/mol or more, even more preferably 1,000 g/mol or more, even more preferably 1,500 g/mol or more, and particularly preferably 2,000 g/mol or more.
  • the acid equivalent of the (a) resin is preferably 4,000 g/mol or less, more preferably 3,000 g/mol or less, and even more preferably 2,500 g/mol or less.
  • the carboxylic acid equivalent of the (a) resin is preferably 200 g/mol or more, more preferably 400 g/mol or more.
  • the carboxylic acid equivalent of the (a) resin is preferably 500 g/mol or more, more preferably 700 g/mol or more, even more preferably 1,000 g/mol or more, even more preferably 1,500 g/mol or more, and particularly preferably 2,000 g/mol or more.
  • the carboxylic acid equivalent of the (a) resin is preferably 4,000 g/mol or less, more preferably 3,000 g/mol or less, and even more preferably 2,500 g/mol or less.
  • the (a) resin does not have a carboxy group.
  • the acid equivalent of the (a) resin is 500 g/mol or more and the carboxylic acid equivalent of the (a) resin is 500 g/mol or more, or that the (a) resin does not have a carboxy group.
  • the (a) resin contains an amide bond in the repeating unit and is a polyimide precursor, a polyamideimide precursor, or a polybenzoxazole precursor.
  • the polyimide precursor has two amide acid structures, two amide acid ester structures, two amide acid amide structures, an amide acid structure and an amide acid ester structure, an amide acid structure and an amide acid amide structure, or an amide acid ester structure and an amide acid amide structure in a repeating unit containing an amine residue and a carboxylic acid residue.
  • the amide acid structure refers to a structure having one carboxylic acid amide bond and one carboxy group.
  • the amide acid ester structure refers to a structure having one carboxylic acid amide bond and one carboxylic acid ester bond.
  • the amide acid amide structure refers to a structure having one carboxylic acid amide bond and another carboxylic acid amide bond.
  • the polybenzoxazole precursor has two hydroxyamide structures in a repeating unit containing an amine residue and a carboxylic acid residue.
  • the polyamideimide precursor has an amide structure and an amide acid structure, an amide structure and an amide acid ester structure, or an amide structure and an amide acid amide structure in a repeating unit containing an amine residue and a carboxylic acid residue.
  • the polyimide precursor preferably has a total content ratio of amic acid ester structures (hereinafter “esterification rate”) and amic acid amide structures (hereinafter “amidation rate”) in the total of amic acid structures, amic acid ester structures, amic acid amide structures, and imide closed ring structures of 40 mol% or more, more preferably 50 mol% or more, even more preferably 60 mol% or more, even more preferably 70 mol% or more, and particularly preferably 80 mol% or more.
  • esterification rate amic acid ester structures
  • amic acid amide structures hereinafter “amidation rate”
  • the total content ratio of amic acid ester structures and amic acid amide structures is preferably 100 mol% or less, more preferably 99 mol% or less, even more preferably 95 mol% or less, and even more preferably 90 mol% or less.
  • the amic acid ester structure of the polyimide precursor is preferably an ester structure of a monovalent organic group having 1 to 20 carbon atoms.
  • the monovalent organic group is not particularly limited, but examples include aliphatic hydrocarbon groups (alkyl groups, alkenyl groups, alkynyl groups, etc.), alicyclic hydrocarbon groups (cycloalkyl groups, cycloalkylalkyl groups, alkylcycloalkyl groups, etc.), aromatic hydrocarbon groups (aryl groups, arylalkyl groups, alkylaryl groups, etc.), hydroxyalkyl groups, alkoxy groups, alkenyloxy groups, alkoxyalkyl groups, acyl groups, and acylalkyl groups.
  • the resin (a) has an electron-withdrawing group from the viewpoint of improving reactivity with the amine compound (b), and the resin (a) is (a1) a polyimide or polyamideimide containing a structural unit represented by formula (1) (hereinafter referred to as “(a1) resin”), (a2) a polyimide precursor or a polyamideimide precursor containing a structural unit represented by formula (2) (hereinafter referred to as “(a2) resin”), (a3) a polyamideimide containing a structural unit represented by formula (3) (hereinafter referred to as “(a3) resin”), (a4) a polybenzoxazole containing a structural unit represented by formula (4) (hereinafter referred to as “(a4) resin”), and (a5) a polybenzoxazole precursor containing a structural unit represented by formula (5) (hereinafter referred to as “(a5) resin”), It is preferable that the resin composition contains one or more resins selected from the group consisting of:
  • the (a) resin is the (a2) resin or the (a5) resin.
  • L 1 is a single bond, a sulfonyl group, >C(CF 3 ) 2 , an oxygen atom or a divalent organic group having 1 to 20 carbon atoms.
  • Cycloalkylene groups are not particularly limited, but examples include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, cyclodecylene, cyclododecylene, cyclohexadecylene, and cyclooctadecylene groups.
  • the arylene group is not particularly limited, but examples include a phenylene group, a naphthylene group, a methylphenylene group, an ethylphenylene group, a methylnaphthylene group, and a dimethylnaphthylene group.
  • L 1 is linked to any one of the positions of X 1 to X 4 and any one of the positions of X 5 to X 8. * indicates a bonding site.
  • the monovalent organic group is not particularly limited, but examples include aliphatic hydrocarbon groups (alkyl groups, alkenyl groups, alkynyl groups, etc.), alicyclic hydrocarbon groups (cycloalkyl groups, cycloalkylalkyl groups, alkylcycloalkyl groups, etc.), aromatic hydrocarbon groups (aryl groups, arylalkyl groups, alkylaryl groups, etc.), hydroxyalkyl groups, alkoxy groups, alkenyloxy groups, alkoxyalkyl groups, acyl groups, acylalkyl groups, etc.
  • cycloalkyl groups, alkylcycloalkyl groups, aryl groups, and alkylaryl groups are more preferred due to their excellent heat resistance, and cycloalkyl groups and aryl groups are particularly preferred.
  • the alkyl group is not particularly limited, but examples include methyl, ethyl, propyl, isopropyl, butyl, 1,2-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, heptyl, octyl, nonyl, and decyl groups.
  • Cycloalkyl groups are not particularly limited, but examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclodecyl, cyclododecyl, cyclohexadecyl, and cyclooctadecyl groups.
  • Alkylcycloalkyl groups include groups that combine the above alkyl groups with cycloalkyl groups.
  • the aryl group is not particularly limited, but examples include a phenyl group, a naphthyl group, a methylphenyl group, an ethylphenyl group, a methylnaphthyl group, and a dimethylnaphthyl group.
  • the alkylaryl group is not particularly limited, but examples include groups that combine the above alkyl groups with aryl groups.
  • L 2 is a single bond, a sulfonyl group, >C(CF 3 ) 2 , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms.
  • the divalent organic group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include the organic groups exemplified as the divalent organic group having 1 to 20 carbon atoms for L 1 in formula (1).
  • L 2 is linked at any one position of X 11 to X 14 and any one position of X 15 to X 18. * indicates a bonding site.
  • L 3 is an amide bond. L 3 is linked to any one of the positions of X 19 to X 22.
  • L 4 is a single bond, a sulfonyl group, >C(CF 3 ) 2 , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms.
  • the divalent organic group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include the organic groups exemplified as the divalent organic group having 1 to 20 carbon atoms for L 1 in formula (1).
  • L 4 is linked to any one of positions X 31 to X 35 and any one of positions X 36 to X 40.
  • * 1 is linked to any one of positions X 23 to X 26.
  • * 2 is linked to any one of positions X 27 to X 30.
  • * 1 and * 2 indicate binding sites.
  • L 4 is a sulfonyl group or >C(CF 3 ) 2
  • L 5 is a single bond, a sulfonyl group, >C(CF 3 ) 2 , an oxygen atom, or a divalent organic group having 1 to 20 carbon atoms.
  • the divalent organic group having 1 to 20 carbon atoms is not particularly limited, and examples thereof include the organic groups exemplified as the divalent organic group having 1 to 20 carbon atoms for L 1 in formula (1).
  • L 5 is linked to any one of X 49 to X 53 and any one of X 54 to X 58.
  • * 3 is linked to any one of X 41 to X 44.
  • * 4 is linked to any one of X 45 to X 48.
  • * 3 and * 4 indicate binding sites.
  • the (a) resin satisfies the following condition (P1 ⁇ ). It is more preferable that the (a) resin further satisfies the following condition (P2 ⁇ ).
  • P1 ⁇ (a) The content of fluorine element in the resin structure is 10,000 ppm by mass or less.
  • P2 ⁇ (a) The content of fluoride ions in the resin structure is 10,000 ppm by mass or less.
  • the content of fluorine element in the resin structure is preferably 0 ppm by mass or more, more preferably 0.010 ppm by mass or more, even more preferably 0.030 ppm by mass or more, even more preferably 0.050 ppm by mass or more, particularly preferably 0.070 ppm by mass or more, and most preferably 0.10 ppm by mass or more.
  • the content of fluorine element is preferably 10,000 ppm by mass or less, more preferably 5,000 ppm by mass or less, even more preferably 1,000 ppm by mass or less, even more preferably 500 ppm by mass or less, particularly preferably 300 ppm by mass or less, and most preferably 100 ppm by mass or less. Furthermore, the content of fluorine element is preferably 50 ppm by mass or less, more preferably 30 ppm by mass or less, even more preferably 10 ppm by mass or less, even more preferably 5 ppm by mass or less, particularly preferably 3 ppm by mass or less, and most preferably 1 ppm by mass or less.
  • the preferred range of the content of fluoride ions in the structure of the (a) resin is the same as the preferred range of the content of elemental fluorine in the structure of the (a) resin described above.
  • the amount of fluorine element in the resin structure may be 0 ppm by mass.
  • the amount of fluoride ion in the resin structure may also be 0 ppm by mass.
  • the effect of improving sensitivity is remarkable because the steric hindrance derived from fluorine elements and fluoride ions is suppressed, and the reaction between resin (a) and amine compound (b) is promoted, resulting in a remarkable effect of improving sensitivity.
  • the photosensitive resin composition of the present invention preferably satisfies at least one of the above condition (P1 ⁇ ) and the following condition (1 ⁇ ). It is more preferable that the photosensitive resin composition of the present invention further satisfies at least one of the above condition (P2 ⁇ ) and the following condition (2 ⁇ ).
  • the content of fluorine element in the total solid content of the photosensitive resin composition is 1,000 mass ppm or less.
  • the content of fluoride ions in the total solid content of the photosensitive resin composition is 1,000 mass ppm or less.
  • the content of fluorine element in the total solid content of the photosensitive resin composition is preferably 0 ppm by mass or more, more preferably 0.010 ppm by mass or more, even more preferably 0.030 ppm by mass or more, even more preferably 0.050 ppm by mass or more, particularly preferably 0.070 ppm by mass or more, and most preferably 0.10 ppm by mass or more.
  • the content of fluorine element is preferably 1,000 ppm by mass or less, more preferably 500 ppm by mass or less, even more preferably 300 ppm by mass or less, and particularly preferably 100 ppm by mass or less.
  • the content of fluorine element is preferably 50 ppm by mass or less, more preferably 30 ppm by mass or less, even more preferably 10 ppm by mass or less, even more preferably 5 ppm by mass or less, particularly preferably 3 ppm by mass or less, and most preferably 1 ppm by mass or less.
  • the content of compounds containing fluorine atoms in their structures and components containing fluorine elements in the photosensitive resin composition By setting the content of compounds containing fluorine atoms in their structures and components containing fluorine elements in the photosensitive resin composition to a specific value or less, the content of fluorine elements, fluoride ions, or anions containing fluorine elements derived from these components will be set to a specific value or less.
  • protons in the photosensitive resin composition are locally activated due to interactions such as hydrogen bonds between the components in the photosensitive resin composition. Therefore, it is considered that the effect of improving sensitivity is remarkable while suppressing the amount of film thickness reduction during development due to the local dissolution promotion action in the developer.
  • the content of the (a) resin is preferably 3% by mass or more relative to 100% by mass of the photosensitive resin composition.
  • the content of the (a) resin is preferably 30% by mass or less relative to 100% by mass of the photosensitive resin composition.
  • the photosensitive resin composition of the present invention preferably contains a monoamine compound which is a primary amine or a secondary amine.
  • the monoamine compound include a compound represented by R 59 NH 2 , a compound represented by R 60 2 NH, a cyclic compound such as pyrrolidine, piperidine, indole, or pyrrole, or a heteroaromatic compound.
  • the monovalent organic group is preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group or alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, a cycloalkylalkyl group or alkylcycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or alkylaryl group having 7 to 20 carbon atoms, a hydroxyalkyl group or alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group or alkoxyalkyl group having 2 to 20 carbon atoms, or an acyl group or acylalkyl group having 1 to 20 carbon atoms.
  • Hydroxyalkyl groups are not particularly limited, but examples include groups in which some of the hydrogen atoms in the above-mentioned alkyl groups having 1 to 20 carbon atoms are replaced with hydroxy groups.
  • Alkoxy groups or alkenyloxy groups are not particularly limited, but examples include groups in which an oxygen atom is bonded to the above-mentioned alkyl groups having 1 to 20 carbon atoms or alkenyl groups having 2 to 20 carbon atoms.
  • Alkoxyalkyl groups are not particularly limited, but examples include groups in which some of the single bonds in the above-mentioned alkyl groups having 1 to 20 carbon atoms are replaced with ether bonds.
  • the alicyclic amine refers to a compound in which the above-mentioned alicyclic hydrocarbon group is bonded to the nitrogen atom of the amino group.
  • the cyclic amine refers to a compound in which the nitrogen atom of the amino group is a ring member atom of a ring structure that is not heteroaromatic.
  • the (b) amine compound is also preferably an aromatic amine or a heteroaromatic amine from the viewpoint of controlling the reactivity with the (a) resin and improving the storage stability of the photosensitive resin composition.
  • the aromatic amine refers to a compound in which the above-mentioned aromatic hydrocarbon group is bonded to the nitrogen atom of the amino group.
  • the heteroaromatic amine refers to a compound in which the nitrogen atom of the amino group is a ring member atom of a heteroaromatic ring.
  • amine compounds include, but are not limited to, primary amines such as methylamine, ethylamine, propylamine, isopropylamine, butylamine, 1,2-dimethylethylamine, pentylamine, 1-methylbutylamine, 2-methylbutylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, amino-methanol, amino-ethanol, 3-amino-1 -propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8
  • Monoamine compounds having a pKb of 6 or less include, but are not limited to, methylamine, ethylamine, propylamine, isopropylamine, butylamine, 1,2-dimethylethylamine, pentylamine, 1-methylbutylamine, 2-methylbutylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, amino-methanol, amino-ethanol, 3-amino -1-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 8-
  • the (b) amine compound can be removed by heating during or after the reaction with the (a) resin in order to reduce the amount of the (b) amine compound remaining in the unexposed areas and reduce the amount of development film loss. Also, in order to prevent deterioration of the cured product due to heating at high temperatures, it is preferable that the (b) amine compound can be removed at a moderate temperature. From these viewpoints, the boiling point of the (b) amine compound at 1 atmosphere is preferably 300°C or less, more preferably 250°C or less, and even more preferably 200°C or less.
  • the boiling point of the (b) amine compound at 1 atmosphere is preferably 100°C or more, more preferably 130°C or more.
  • the (b) amine compound is preferably an amine salt from the viewpoints of controlling the reactivity with the (a) resin and improving the storage stability of the photosensitive resin composition.
  • the amine salt is preferably a compound containing a cationic species having a primary amine structure or a secondary amine structure and an anionic species from the viewpoints of improving the reactivity with the (a) resin and the (b) amine compound and improving the sensitivity.
  • the cationic species in the amine salt preferably contains a structure derived from one or more selected from the group consisting of the monoamine compounds, diamine compounds, triamine compounds, and tetramine compounds.
  • the cationic species in the amine salt also preferably contains a structure derived from the polyamine compounds having five or more amino groups in the molecule.
  • the cationic species in the amine salt is preferably composed of each of the amine compounds described above. Examples and preferred descriptions of each of the amine compounds are the same as those described above.
  • the sulfonate ion preferably has a monovalent organic group having 1 to 20 carbon atoms.
  • the monovalent organic group is not particularly limited, but examples include aliphatic hydrocarbon groups (alkyl groups, alkenyl groups, alkynyl groups, etc.), alicyclic hydrocarbon groups (cycloalkyl groups, cycloalkylalkyl groups, alkylcycloalkyl groups, etc.), aromatic hydrocarbon groups (aryl groups, arylalkyl groups, alkylaryl groups, etc.), hydroxyalkyl groups, alkoxy groups, alkenyloxy groups, alkoxyalkyl groups, acyl groups, and acylalkyl groups.
  • the monovalent organic group is preferably an alkyl group having 1 to 20 carbon atoms, an alkenyl group or alkynyl group having 2 to 20 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, a cycloalkylalkyl group or alkylcycloalkyl group having 5 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an arylalkyl group or alkylaryl group having 7 to 20 carbon atoms, a hydroxyalkyl group or alkoxy group having 1 to 20 carbon atoms, an alkenyloxy group or alkoxyalkyl group having 2 to 20 carbon atoms, or an acyl group or acylalkyl group having 1 to 20 carbon atoms.
  • the content of the (b) amine compound is 35 parts by mass or more per 100 parts by mass of the (a) resin in the photosensitive resin composition.
  • the content of the monoamine compound is preferably 35 parts by mass or more per 100 parts by mass of the (a) resin in the photosensitive resin composition.
  • the content of the (b) amine compound is preferably 50 parts by mass or more per 100 parts by mass of the (a) resin, and more preferably 80 parts by mass or more.
  • the content of the (b) amine compound is preferably 1000 parts by mass or less per 100 parts by mass of the (a) resin in the photosensitive resin composition, more preferably 500 parts by mass or less, and even more preferably 300 parts by mass or less.
  • the photosensitive resin composition according to the embodiment of the present invention contains (c) a photoacid generator.
  • the photoacid generator is a compound that has a function of generating an acid upon exposure to light. Any known photoacid generator (c) can be used as long as it does not impair the effects of the present invention.
  • Photoacid generators include onium salt-type ionic photoacid generators and nonionic photoacid generators.
  • An onium salt is a compound that is generated when a compound that has an electron pair that is not involved in a chemical bond forms a coordinate bond with another cationic compound through that electron pair.
  • the cationic part of the onium salt determines the photochemical properties (molar absorption coefficient, absorption wavelength, quantum yield), while the anionic part determines the strength of the acid generated.
  • nonionic photoacid generators are photoacid generators in which the part that absorbs light and the acid are connected via an ester bond.
  • triorganosulfonium salt compounds include, for example, methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, 4-toluenesulfonate, and perfluoro-1-butanesulfonate of triphenylsulfonium ("SP-056", product name, manufactured by ADEKA Corporation); the above sulfonates of dimethyl-1-naphthylsulfonium; the above sulfonates of dimethyl(4-hydroxy-1-naphthyl)sulfonium; the above sulfonates of dimethyl(4,7-dihydroxy-1-naphthyl)sulfonium; and the above sulfonates of diphenyliodonium.
  • SP-056 triphenylsulfonium
  • diazomethane compounds diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylate compounds, sulfonimide compounds, phosphate compounds, sulfonebenzotriazole compounds, etc. can be used.
  • diazomethane compounds include bis(4-methylphenylsulfonyl)diazomethane (product name "WPAG-199", manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
  • sulfone compounds include ⁇ -ketosulfone compounds and ⁇ -sulfonylsulfone compounds.
  • Preferred sulfone compounds include 2-(p-toluenesulfonyl)acetophenone and bis(phenylsulfonyl)methane.
  • sulfonate ester compounds include alkylsulfonate esters, haloalkylsulfonate esters, arylsulfonate esters, and iminosulfonate ester compounds.
  • Preferred examples include benzoin-4-tolylsulfonate, pyrogallol tris(methylsulfonate), nitrobenzyl-9,10-diethoxyanthryl-2-sulfonate, and 2,6-(dinitrobenzyl)phenylsulfonate.
  • carboxylate ester compounds include 2-nitrobenzyl carboxylate.
  • the photoacid generator contains a nonionic photoacid generator.
  • a photosensitive resin composition with higher sensitivity can be obtained.
  • the (c) photoacid generator contains a photoacid generator in which the acid dissociation constant (pKa) of the acid group generated by light is in the range of -14 to 2. This allows the acid group generated by light to efficiently act as an acid in the reaction between the (a) resin and the (b) amine compound.
  • pKa acid dissociation constant
  • the photoacid generator contains an oxime sulfonate compound and/or an imide sulfonate compound.
  • Oxime sulfonate compounds and imide sulfonate compounds are nonionic photoacid generators, and the acidic group generated by light is a sulfo group, so that the pKa is high and a more sensitive photosensitive resin composition can be obtained.
  • Oxime sulfonate compounds can be represented by the following structure:
  • R 61 is a monovalent organic group having 1 to 12 carbon atoms.
  • the monovalent organic group having 1 to 12 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a trifluoromethanesulfonic acid group, a nonafluorobutyl group, a perfluorooctyl group, a (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl)methyl group, a benzyl group, a phenyl group, a tosyl group, and a naphthyl group.
  • R 62 and R 63 are monovalent organic groups having 1 to 30 carbon atoms.
  • R 63 and R 64 may be the same or different.
  • Specific examples of the monovalent organic groups having 1 to 30 carbon atoms include a cyano group, a trifluoromethyl group, a hexafluoropropyl group, a pentafluorobutyl group, a dodecafluorohexyl group, a phenyl group, a 4-methoxyphenyl group, a 2-fluorenyl group, and a 4-(3-(4-(2,2,2-trifluoro-1-(((propylsulfonyl)oxy)imino)ethyl)phenoxy)propoxy)phenyl group.
  • R 64 is a monovalent organic group having 3 to 30 carbon atoms. Specific examples of the monovalent organic group having 3 to 30 carbon atoms include the following structures.
  • oxime sulfonates include "Irgacure” (registered trademark), PAG-103 (benzeneacetonitrile, 2-methyl- ⁇ -[[(propylsulfonyl)oxy]imino]-3(2H)-thienylidene), PAG-121 (benzeneacetonitrile, 2-methyl- ⁇ -[[(4-methylphenyl)oxy]imino]-3(2H)-thienylidene), PAG-108 (benzeneacetonitrile, 2-methyl- ⁇ -[[(n-octyl)oxy]imino]-3(2H)-thienylidene), PAG-203 (all manufactured by BASF Japan), and PAI-101 ((Z)-4-methoxy-N-(tosyloxy)benzimidoyl cyanide, manufactured by Midori Chemical Co., Ltd.).
  • Irgacure registered trademark
  • PAG-103 benzeneacetonitrile,
  • Imidosulfonate compounds can be represented by the following structure:
  • the photosensitive resin composition according to the embodiment of the present invention preferably further contains a solvent.
  • a solvent By including a solvent, a film of the composition can be formed on a substrate with a desired thickness, and the effect of improving the thickness uniformity of the coating film becomes significant.
  • the solvent preferably contains a solvent having a carbonyl group, a solvent having an ester bond, a solvent having at least three ether bonds, or a solvent having an alcoholic hydroxyl group.
  • the solvent is preferably a compound having a boiling point of 110°C or more under atmospheric pressure.
  • the carbonyl group is preferably an alkylcarbonyl group, a dialkylcarbonyl group, or a formyl group.
  • the ester bond is preferably a carboxylate bond, a carbonate bond, or a formate bond. Among the carboxylate bonds, an acetate bond, a propionate bond, or a butyrate bond is more preferable.
  • the carbonyl group is more preferably a cyclic carbonyl group.
  • the carboxylate bond is more preferably a cyclic carboxylate bond.
  • the carbonate bond is more preferably a cyclic carbonate bond.
  • solvents having an ester bond examples include 3-methoxy-n-butyl acetate, 3-methyl-3-methoxy-n-butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate, diethylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, cyclohexanol acetate, propylene glycol diacetate, 1,4-butanediol diacetate, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, and ⁇ -butyrolactone.
  • the total content of the solvent having a carbonyl group, the solvent having an ester bond, the solvent having at least three ether bonds, and the solvent having an alcoholic hydroxyl group in the solvent is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, even more preferably 70 to 100% by mass, and particularly preferably 90 to 100% by mass.
  • the total content ratio of the solvent having a carbonyl group and the solvent having an ester bond in the solvent is preferably 30 to 100 mass%, more preferably 50 to 100 mass%, even more preferably 70 to 100 mass%, and particularly preferably 90 to 100 mass%.
  • the photosensitive resin composition according to the embodiment of the present invention may contain other additives in addition to those mentioned above.
  • additives include a dissolution promoter, a sensitizer, a silane coupling agent, a surfactant, etc.
  • a method for producing a pattern using a photosensitive resin composition according to an embodiment of the present invention includes the steps of: A step of applying the photosensitive resin composition of the present invention to a substrate (hereinafter referred to as "step (a-1)”); A step of exposing the coated product through a photomask (hereinafter, referred to as “step (b-1)”); A step of heating the coating simultaneously with or after exposure through the photomask (hereinafter, referred to as “step (b-2)”); The method includes a step of developing the coated product after heating (hereinafter, “step (c-1)"), and a step of heating the coated product after development (hereinafter, "step (d-1)”).
  • the above-mentioned step (a-1) is a step of applying the photosensitive resin composition to a substrate.
  • the substrate is not particularly limited, but is preferably selected from the group consisting of glass, silicon wafers, ceramic deposition substrates, metal-plated substrates, sapphire, and gallium arsenide.
  • Light sources used in exposure include, for example, various lasers, light-emitting diodes (LEDs), ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, and metal halide lamps. If necessary, the wavelength of the irradiated light may be adjusted through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a bandpass filter.
  • a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a bandpass filter.
  • the heating time is preferably 10 seconds to 1 hour, and even more preferably 30 seconds to 30 minutes.
  • the cured product obtained by the pattern manufacturing method according to the embodiment of the present invention is a cured product mainly composed of polyimide, polyamideimide, or polybenzoxazole, and therefore has excellent heat resistance.
  • the cured product obtained by curing the photosensitive resin composition according to the embodiment of the present invention can be used as an insulating film or a protective film constituting an electronic component.
  • the electronic component include active components having a semiconductor, such as transistors, diodes, integrated circuits (ICs), and memories, and passive components, such as resistors, capacitors, and inductors.
  • active components having a semiconductor such as transistors, diodes, integrated circuits (ICs), and memories
  • passive components such as resistors, capacitors, and inductors.
  • Electronic components using semiconductors are also called semiconductor devices or semiconductor packages.
  • the cured product obtained by curing the photosensitive resin composition according to the embodiment of the present invention can be used as an insulating film or a protective film constituting a display device.
  • the cured product of the photosensitive resin composition of the present invention can be suitably used as a planarizing layer or an insulating layer constituting an organic EL display device.
  • the organic EL display device has a driving circuit, a planarizing layer, a first electrode, an insulating layer, a light-emitting layer, and a second electrode on a substrate, and the planarizing layer and/or the insulating layer includes the cured film.
  • a substrate such as glass or a resin film has a TFT and wiring located on the side of the TFT and connected to the TFT, a planarizing layer is provided thereon so as to cover the unevenness, and a display element is further provided on the planarizing layer.
  • the display element and the wiring are connected through a contact hole formed in the planarizing layer.
  • the cured product obtained by curing the photosensitive resin composition according to the embodiment of the present invention has excellent planarization properties and pattern dimensional stability, so it is preferable to provide it as a planarization layer in an organic EL display device.
  • flexible organic EL display devices have become mainstream in recent years, and the organic EL display device may have a substrate having the aforementioned driving circuitry made of a resin film.
  • BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • NBPDA 6-nitro-3,3',4,4'-biphenyltetracarboxylic dianhydride
  • DSDA 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride
  • BP-HBT A mixture of dicarboxylic acid derivatives obtained by reacting 4,4'-biphenyldicarboxylic acid with 1-hydroxy-1,2,3-benzotriazole
  • BPDCC 4,4'-biphenyldicarboxylic acid dichloride
  • TMAC Trimellitic anhydride chloride ⁇ amine derivative>
  • DABP 4,4'-diamino-biphenyl DADHBP: 3,3'-diamino-4,4'-dihydroxybiphenyl
  • DFA N,N-dimethylformamide dimethyl acetal ((b) amine compound)
  • HA Hexylamine (primary aliphatic amine, boiling point 133°C, pKb 3.4)
  • DBA Dibutylamine (secondary aliphatic amine, boiling point 159°C, pKb 2.7)
  • TBA Tributylamine (tertiary aliphatic amine, boiling point 216°C, pKb 4.0)
  • BEA Benzylamine (primary aromatic amine, boiling point 185° C., pKb 4.7)
  • AN Aniline (primary aromatic amine, boiling point 184°C, pKb 9.4)
  • BA Butylamine (primary aliphatic amine, boiling point 78°C, pKb 3.2)
  • PA Pentylamine (primary aliphatic amine, boiling point 104°C, pKb 3.8)
  • OA Octylamine
  • Fc-1 2,2-bis(4-hydroxyphenyl)hexafluoropropane
  • FI-1 (decyltriethyl)ammonium fluoride.
  • Weight Average Molecular Weight The weight average molecular weight (Mw) in terms of polystyrene was measured using a GPC analyzer under the following conditions. Measuring device: Waters 2695 (manufactured by Waters Corporation) Column temperature: 50°C Flow rate: 0.4mL/min Detector: 2489 UV/Vis Detector (measurement wavelength 260 nm) Developing solvent: NMP (containing 0.21% by weight of lithium chloride and 0.48% by weight of phosphoric acid) Guard column: TOSOH TSK guard column (manufactured by Tosoh Corporation) Column: TOSOH TSK-GEL a-2500, TOSOH TSK-GEL a-4000 in series (both manufactured by Tosoh Corporation).
  • composition contains multiple resins having phenolic hydroxyl groups or carboxyl groups
  • separable components in the composition are removed by methods such as centrifugation, liquid-liquid separation extraction, and column chromatography, and then each resin is separated by GPC fractionation.
  • the carboxylic acid equivalent (unit: g/mol) is then calculated based on the method for measuring the phenol equivalent or carboxylic acid equivalent described above.
  • each of the above resins was dissolved in GBL to a concentration of 35 mass% to prepare a resin solution.
  • Each of the obtained resin solutions was applied to a silicon wafer using a spin coater (1H-DX; manufactured by Mikasa Co., Ltd.), and then baked at 120 ° C. for 180 seconds to prepare a resin film with a film thickness of 4 to 5 ⁇ m.
  • the prepared silicon wafer with the resin film was divided into two, and one of them was heated at 140 ° C.
  • a resin film with a thickness of 4 to 5 ⁇ m was prepared in the same manner as above.
  • the prepared silicon wafer with the resin film was divided into two, and one was heated at 320° C. for 30 minutes using a buzzer hot plate (HPD-3000BZN; manufactured by AS ONE Corporation) to completely close the benzoxazole ring (resin film after heating).
  • the other was used as is without heat treatment (resin film before heating).
  • FT-720 infrared spectrophotometer
  • each unit of polyimide unit (imide structure), polyimide precursor unit (amic acid structure and amic acid ester structure), polybenzoxazole unit (benzoxazole structure), polybenzoxazole precursor unit (hydroxyamide structure), and polyamideimide unit (imide structure and amide structure) and the structure of the copolymerization monomers constituting them were obtained.
  • each copolymerization monomer was prepared as a standard sample, and the peaks specific to each copolymerization monomer were confirmed by proton nuclear magnetic resonance spectroscopy.
  • the molar ratio of each unit in the resin and the copolymerization monomers constituting them was calculated from the area ratio of the peaks in the proton nuclear magnetic resonance spectroscopy spectrum of each resin.
  • 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.
  • the film was exposed through a mask having a pattern of 10 ⁇ m contact holes at an exposure dose in the range of 5 to 300 mJ/ cm2 at intervals of 5 mJ/ cm2 .
  • the resist was heated at 170° C. for 30 minutes, and developed for 80 seconds using the ACT-8 developing device with 2.38% by mass TMAH (manufactured by Tama Chemicals Co., Ltd.) as a developer.
  • the resist was then rinsed with distilled water, shaken off, and heated at 310° C. for 10 minutes to obtain a relief pattern.
  • the amount of film loss after development was calculated by subtracting the film thickness after development from the film thickness before development in the unexposed area. The results were evaluated as follows, and A+ to B, which indicates that the amount of film loss is less than 0.4 ⁇ m, was deemed to be acceptable.
  • A+ The amount of reduction in the developed film is less than 0.15 ⁇ m.
  • B+ The amount of reduction in the developed film is 0.2 ⁇ m or more and less than 0.3 ⁇ m.
  • B The amount of reduction in the developed film is 0.3 ⁇ m or more and less than 0.4 ⁇ m.
  • C The amount of reduction in the developed film is 0.4 ⁇ m or more.
  • Synthesis Example 1 Synthesis of polyimide precursor (PA-1) which is a polyamide Under a dry nitrogen stream, 18.42 g (100 mmol) of DABP as a diamine and 180 g of NMP were weighed and dissolved in a four-neck flask. 26.48 g (90 mmol) of BPDA as an acid dianhydride was added thereto together with 40 g of NMP, and the mixture was stirred at 40 ° C. for 1 hour. Next, 2.96 g (20 mmol) of phthalic anhydride was added together with 40 g of NMP, and the mixture was reacted at 40 ° C. for 1 hour, and then stirred at 200 ° C. for 4 hours.
  • Synthesis Examples 2 to 3 Synthesis of polyimide precursors (PA-2 to 3) which are polyamides
  • the polyimide precursors were synthesized in the same manner as in Synthesis Example 1, except that the amine derivative, carboxylic acid derivative, and end-capping agent were changed to the types and amounts shown in Table 1.
  • the Mw and acid equivalent of the obtained resins are shown in Table 1.
  • Synthesis Example 4 Synthesis of polyimide precursor (PA-4) which is a polyamide Under a dry nitrogen gas flow, 26.48 g (90 mmol) of BPDA as an acid dianhydride and 500 g of NMP were weighed and dissolved in a four-neck flask. 18.42 g (100 mmol) of DABP as a diamine was added together with 50 g of NMP, and the mixture was stirred at 40 ° C. for 2 hours. Next, 2.96 g (20 mmol) of phthalic anhydride was added together with 50 g of NMP, and the mixture was reacted at 50 ° C. for 2 hours.
  • PA-4 polyimide precursor
  • Synthesis Example 7 Synthesis of polyimide (PI-1) Under a dry nitrogen stream, 18.42 g (100 mmol) of DABP as a diamine and 180 g of NMP were weighed and dissolved in a four-neck flask. 26.48 g (90 mmol) of BPDA as an acid dianhydride was added thereto together with 40 g of NMP, and the mixture was stirred at 40 ° C. for 1 hour. Next, 2.96 g (20 mmol) of phthalic anhydride was added together with 40 g of NMP, and the mixture was reacted at 40 ° C. for 1 hour, and then stirred at 200 ° C. for 4 hours.
  • PI-1 polyimide
  • Synthesis Example 8 Synthesis of polyimide (PI-2) A polyimide was synthesized in the same manner as in Synthesis Example 7, except that the amine derivative, carboxylic acid derivative, and end-capping agent were changed to the types and amounts shown in Table 1. The Mw and acid equivalent of the obtained resin are shown in Table 1.
  • Synthesis Example 9 Synthesis of polybenzoxazole precursor (PA-7) which is a polyamide Under a dry nitrogen stream, 180 mmol of a mixture of dicarboxylic acid derivatives obtained by reacting 4,4'-biphenyldicarboxylic acid (180 mmol) with a mixture of dicarboxylic acid derivatives (360 mmol) obtained by reacting 1-hydroxy-1,2,3-benzotriazole, DABP (130 mmol), and DADHBP (70 mmol) were dissolved in 570 g of NMP, and then reacted at 75 ° C. for 12 hours.
  • PA-7 polybenzoxazole precursor
  • Synthesis Example 10 Synthesis of polybenzoxazole precursor (PA-8), which is a polyamide
  • PA-8 polybenzoxazole precursor
  • a polybenzoxazole precursor was synthesized in the same manner as in Synthesis Example 9, except that the amine derivative, carboxylic acid derivative, and end-capping agent were changed to the types and amounts shown in Table 1.
  • the Mw and acid equivalent of the obtained resin are shown in Table 1.
  • Synthesis Example 11 Synthesis of polybenzoxazole (PBO-1) Under a dry nitrogen stream, 21.62 g (100 mmol) of DADHBP was dissolved in 75 g of NMP, and then the temperature of the solution was cooled to -15°C. A solution of 34.89 g (125 mmol) of BPDCC dissolved in 30 g of NMP was added dropwise so that the temperature in the reaction system did not exceed 0°C. After the dropwise addition was completed, stirring was continued at 20°C for 6 hours. After the reaction was completed, the above solution was poured into 3 L of pure water containing 10 wt% methanol to precipitate a white precipitate.
  • Synthesis Example 12 Synthesis of polybenzoxazole (PBO-2) Synthesis was performed in the same manner as in Synthesis Example 11, except that the types and amounts of the amine derivative, carboxylic acid derivative, and end-capping agent in Synthesis Example 11 were changed to those shown in Table 1. The Mw and acid equivalent of the obtained resin are shown in Table 1.
  • Synthesis Example 13 Synthesis of polyamideimide (PAI-1) Synthesis Example 13 was synthesized by a known method based on the method described in Synthesis Example 9 in paragraph [0160] of WO 2018/159384, by appropriately changing the monomer compound to be the monomer and the copolymerization ratio.
  • the amine derivative, carboxylic acid derivative, and end-capping agent were as shown in Table 1, and the Mw and acid equivalent of the obtained resin were also shown in Table 1.
  • Example 1 Under yellow light, (a) 2.50 g of PA-1 as a resin, (b) 2.50 g of HA as an amine compound, (c) 0.20 g of PAG-103 as a photoacid generator, and 30 g of CP as a solvent were added and stirred to obtain a photosensitive resin composition.
  • Comparative Example 1 the content of the (b) amine compound does not satisfy the invention specific items of the present invention.
  • the (b) amine compound does not contain a primary amine or a secondary amine. Therefore, it is understood that Comparative Examples 1 and 2 are inferior in various properties.
  • the photosensitive resin composition does not contain the (b) amine compound or the (c) photoacid generator. Therefore, it is understood that Comparative Examples 3 and 4 cannot form a pattern and do not achieve the effect of the present invention.
  • the present invention is suitable for use with highly sensitive photosensitive resin compositions that have excellent heat resistance, little film loss during development, and are highly sensitive.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Materials For Photolithography (AREA)

Abstract

Le but de la présente invention est de fournir une composition de résine photosensible qui présente une excellente résistance à la chaleur, peu de réduction de film pendant le développement et une sensibilité élevée. La présente invention concerne une composition de résine photosensible qui contient (a) au moins une résine (ci-après « résine (a) ») choisie parmi les polyimides, les polyamide-imides, les polybenzoxazoles et les précurseurs de ceux-ci, (b) un composé amine, et (c) un générateur de photoacide, le composé amine (b) étant une amine primaire ou une amine secondaire, et le composé amine (b) étant contenu selon une quantité supérieure ou égale à 35 parties en masse par rapport à 100 parties en masse de la résine (a).
PCT/JP2024/045275 2023-12-22 2024-12-20 Composition de résine photosensible, procédé de production de motif, produit durci, composant électronique et dispositif d'affichage Pending WO2025135175A1 (fr)

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PCT/JP2024/045275 Pending WO2025135175A1 (fr) 2023-12-22 2024-12-20 Composition de résine photosensible, procédé de production de motif, produit durci, composant électronique et dispositif d'affichage

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009157326A (ja) * 2007-12-28 2009-07-16 Ist Corp 感光性ポリイミド前駆体組成物及びこれを用いた電子部品
WO2017126409A1 (fr) * 2016-01-20 2017-07-27 Ｊｘエネルギー株式会社 Procédé de production de film polyimide, film polyimide, solution d'acide polyamide, et composition photosensible
JP2018136462A (ja) * 2017-02-22 2018-08-30 住友ベークライト株式会社 感光性樹脂組成物、樹脂膜及び樹脂膜を備える電子装置
WO2019146436A1 (fr) * 2018-01-26 2019-08-01 日本ゼオン株式会社 Composition de résine photosensible et lentille

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI763883B (zh) * 2017-07-14 2022-05-11 日商富士軟片股份有限公司 熱硬化性樹脂組成物及其硬化膜、積層體、半導體裝置、以及該等的製造方法
TWI851752B (zh) * 2019-07-01 2024-08-11 日商富士軟片股份有限公司 硬化性樹脂組成物、硬化性樹脂組成物的製造方法、硬化膜、積層體、硬化膜的製造方法及半導體器件
TWI859361B (zh) * 2019-11-21 2024-10-21 日商富士軟片股份有限公司 圖案形成方法、光硬化性樹脂組成物、積層體的製造方法及電子元件的製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009157326A (ja) * 2007-12-28 2009-07-16 Ist Corp 感光性ポリイミド前駆体組成物及びこれを用いた電子部品
WO2017126409A1 (fr) * 2016-01-20 2017-07-27 Ｊｘエネルギー株式会社 Procédé de production de film polyimide, film polyimide, solution d'acide polyamide, et composition photosensible
JP2018136462A (ja) * 2017-02-22 2018-08-30 住友ベークライト株式会社 感光性樹脂組成物、樹脂膜及び樹脂膜を備える電子装置
WO2019146436A1 (fr) * 2018-01-26 2019-08-01 日本ゼオン株式会社 Composition de résine photosensible et lentille

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