WO2020071201A1 - 感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品 - Google Patents

感光性樹脂組成物、パターン硬化物の製造方法、硬化物、層間絶縁膜、カバーコート層、表面保護膜及び電子部品

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Publication number
WO2020071201A1
WO2020071201A1 PCT/JP2019/037558 JP2019037558W WO2020071201A1 WO 2020071201 A1 WO2020071201 A1 WO 2020071201A1 JP 2019037558 W JP2019037558 W JP 2019037558W WO 2020071201 A1 WO2020071201 A1 WO 2020071201A1
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WIPO (PCT)
Prior art keywords
group
photosensitive resin
component
resin composition
formula
Prior art date
Application number
PCT/JP2019/037558
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English (en)
French (fr)
Japanese (ja)
Inventor
則孝 松家
米田　聡
榎本　哲也
Original Assignee
日立化成デュポンマイクロシステムズ株式会社
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Application filed by 日立化成デュポンマイクロシステムズ株式会社 filed Critical 日立化成デュポンマイクロシステムズ株式会社
Priority to CN201980065315.5A priority Critical patent/CN113196169A/zh
Priority to JP2020550330A priority patent/JPWO2020071201A1/ja
Priority to KR1020217008589A priority patent/KR20210068419A/ko
Publication of WO2020071201A1 publication Critical patent/WO2020071201A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C08F290/145—Polyamides; Polyesteramides; Polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a photosensitive resin composition, a method for producing a cured pattern, a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component.
  • a multi-die fan-out wafer-level package (Multi-die Fanout Wafer Level Packaging) is a package that collectively seals a plurality of dies in one package, and has been conventionally proposed. It has attracted a great deal of attention because it can be expected to have lower cost and higher performance than conventional fan-out wafer level packages (where one die is encapsulated in one package).
  • composition containing a polyimide precursor is disclosed as a resin composition or a photosensitive composition (for example, see Patent Documents 3 and 4).
  • An object of the present invention is to produce a cured product excellent in insulation reliability, adhesion and migration even at a low temperature curing of 230 ° C. or lower, a photosensitive resin composition excellent in sensitivity, a method for producing a cured pattern product, An object of the present invention is to provide a cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component.
  • the following photosensitive resin composition and the like are provided.
  • A a polyimide precursor
  • B a polymerizable monomer
  • C a photopolymerization initiator
  • D a rust inhibitor
  • E an antioxidant
  • 2. The photosensitive resin composition according to 1, wherein the component (A) has a polymerizable unsaturated bond.
  • 3. The photosensitive resin composition according to 1 or 2, wherein the component (A) is a polyimide precursor having a structural unit represented by the following formula (1).
  • X 1 is a tetravalent group having one or more aromatic groups, and the —COOR 1 group and the —CONH— group are located at ortho positions to each other, and the —COOR 2 group and the —CO And the groups are at ortho positions to each other, Y 1 is a divalent aromatic group, R 1 and R 2 are each independently a hydrogen atom, a group represented by the following formula (2), or a carbon number (1-4) wherein at least one of R 1 and R 2 is a group represented by the formula (2).) (In the formula (2), R 3 to R 5 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m is an integer of 1 to 10.) 4. 4.
  • R 6 and R 7 are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4).
  • N1 is 0 or 1
  • N2 is an integer of 0 to 2
  • n1 + n2 is 1 or more.
  • At least one of n1 R 6 and n2 R 7 is a group represented by the following formula (4).
  • R 9 to R 11 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and 1 is an integer of 0 to 10.
  • the component (F) comprises N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N, N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine and 2,2 '-(4- 10.
  • 11. 10 The photosensitive resin composition according to any one of 1 to 9, wherein the component (F) contains a compound represented by the following formula (17).
  • R 31A to R 33A each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group. And at least one of R 31A to R 33A is a monovalent aromatic group. R 31A to R 33A may form a ring with adjacent groups. 12. 12. The photosensitive resin composition according to any one of 1 to 11, further comprising (H) a thermal polymerization initiator. 13.
  • a cured product excellent in insulation reliability, adhesion and migration can be formed, a photosensitive resin composition excellent in sensitivity, a method for producing a pattern cured product, A cured product, an interlayer insulating film, a cover coat layer, a surface protective film, and an electronic component can be provided.
  • a or B may include either one of A and B, and may include both.
  • the term “step” is used not only for an independent step but also for the case where the intended action of the step is achieved even if it cannot be clearly distinguished from other steps. included.
  • the numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the content of each component in the composition if there are a plurality of substances corresponding to each component in the composition, unless otherwise specified, the total of the plurality of substances present in the composition Means quantity.
  • the exemplified materials may be used alone or in combination of two or more unless otherwise specified.
  • the “(meth) acryl group” in the present specification means “acryl group” and “methacryl group”.
  • the photosensitive resin composition of the present invention comprises (A) a polyimide precursor (hereinafter, also referred to as “component (A)”), (B) a polymerizable monomer (hereinafter, also referred to as “component (B)”), (C) a photopolymerization initiator (hereinafter also referred to as “component (C)”), (D) a rust inhibitor (hereinafter also referred to as “component (D)”), and (E) an antioxidant (hereinafter referred to as “component (D)”).
  • a photosensitive resin composition hereinafter, also referred to as “component (A)”
  • component (B) a polymerizable monomer
  • component (C) a photopolymerization initiator
  • component (D) a
  • a cured product having excellent insulation reliability, adhesiveness, and migration can be formed, and the sensitivity is excellent.
  • the wiring width is as thin as 2 ⁇ m or less, it is possible to form a cured product which can maintain excellent insulation properties and can suppress peeling from the electrode and Cu migration.
  • the photosensitive resin composition of the present invention is preferably a negative photosensitive resin composition.
  • the photosensitive resin composition of the present invention is preferably a material for electronic components.
  • the photosensitive resin composition of the present invention is preferably used for a fine Cu wiring pattern having a width of 2 ⁇ m and an interval of 2 ⁇ m. Further, the photosensitive resin composition of the present invention is preferably used for a WLP (wafer level package) having thousands of input / output pins (currently, the number of input / output pins is several hundred). In addition, the photosensitive resin composition of the present invention is preferably used for a device in which a device divided into two or more chips is integrated into one chip. This makes it possible to provide an extremely space-saving, lightweight and highly functional package. Further, the photosensitive resin composition of the present invention is preferably used for devices such as smart watches, smart glasses, smart contact lenses, and nano drones.
  • the component (A) is not particularly limited, but is preferably a polyimide precursor which has a high transmittance when i-line is used as a light source at the time of patterning and shows high cured product properties even at a low temperature of 230 ° C or lower.
  • the component (A) preferably has a polymerizable unsaturated bond from the viewpoint of improving photosensitivity.
  • the polymerizable unsaturated bond include a carbon-carbon double bond.
  • the component (A) is preferably a polyimide precursor having a structural unit represented by the following formula (1).
  • the content of the structural unit represented by the formula (1) is preferably at least 50 mol%, more preferably at least 80 mol%, and preferably at least 90 mol%, based on all the constituent units of the component (A). More preferred.
  • the upper limit is not particularly limited, and may be 100 mol%.
  • X 1 is a tetravalent group having one or more aromatic groups, and the —COOR 1 group and the —CONH— group are located at ortho positions to each other, and the —COOR 2 group and the —CO And the groups are at ortho positions to each other, Y 1 is a divalent aromatic group, R 1 and R 2 are each independently a hydrogen atom, a group represented by the following formula (2), or a carbon number (1-4) wherein at least one of R 1 and R 2 is a group represented by the formula (2).
  • R 3 to R 5 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and m is an integer of 1 to 10 (preferably an integer of 2 to 5) , More preferably 2 or 3).
  • the aromatic group may be an aromatic hydrocarbon group, It may be a group heterocyclic group. Aromatic hydrocarbon groups are preferred.
  • Examples of the aromatic hydrocarbon group represented by X 1 in the formula (1) include a divalent to tetravalent (divalent, trivalent, or tetravalent) group formed from a benzene ring, and a divalent to tetravalent group formed from naphthalene. And divalent to tetravalent groups formed from perylene.
  • Examples of the tetravalent group having one or more aromatic groups represented by X 1 in the formula (1) include, but are not limited to, a tetravalent group represented by the following formula (6).
  • X and Y each independently represent a divalent group or a single bond that is not conjugated to a benzene ring to which they are bonded.
  • Z is an ether group (—O—) or a sulfide group (—S -) (Preferably -O-).
  • the divalent group that is not conjugated to the benzene ring to which each of X and Y is bonded is —O—, —S—, a methylene group, a bis (trifluoromethyl) methylene group, or a difluoromethylene group. And more preferably -O-.
  • the divalent aromatic group of Y 1 in the formula (1) may be a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group. Divalent aromatic hydrocarbon groups are preferred.
  • Examples of the divalent aromatic hydrocarbon group represented by Y 1 in the formula (1) include, but are not limited to, a group represented by the following formula (7).
  • R 12 to R 19 are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group or a monovalent organic group having a halogen atom.
  • Examples of the monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms) represented by R 12 to R 19 in the formula (7) include a methyl group.
  • R 12 and R 15 to R 19 may be a hydrogen atom
  • R 13 and R 14 may be a monovalent aliphatic hydrocarbon group.
  • the monovalent organic group having a halogen atom (preferably a fluorine atom) represented by R 12 to R 19 in the formula (7) is a monovalent aliphatic hydrocarbon group having a halogen atom (preferably having 1 to 10 carbon atoms, It preferably has 1 to 6 carbon atoms, and examples thereof include a trifluoromethyl group.
  • Examples of the aliphatic hydrocarbon group having 1 to 4 (preferably 1 or 2) carbon atoms for R 1 and R 2 in the formula (1) include a methyl group, an ethyl group, an n-propyl group, a 2-propyl group, and an n- Butyl group and the like.
  • At least one of R 1 and R 2 in the formula (1) is a group represented by the formula (2), and both are preferably groups represented by the formula (2).
  • Examples of the aliphatic hydrocarbon group having 1 to 3 (preferably 1 or 2) carbon atoms represented by R 3 to R 5 in the formula (2) include a methyl group, an ethyl group, an n-propyl group, and a 2-propyl group. Can be A methyl group is preferred.
  • the polyimide precursor having the structural unit represented by the formula (1) is, for example, a tetracarboxylic dianhydride represented by the following formula (8) and a diamino compound represented by the following formula (9):
  • a tetracarboxylic dianhydride represented by the following formula (8) and a diamino compound represented by the following formula (9) By reacting in an organic solvent such as -methyl-2-pyrrolidone to obtain a polyamic acid, adding a compound represented by the following formula (10), and reacting in an organic solvent to partially introduce an ester group.
  • the tetracarboxylic dianhydride represented by the formula (8) and the diamino compound represented by the formula (9) may be used alone or in a combination of two or more.
  • X 1 is a group corresponding to X 1 of the formula (1).
  • R is a group represented by the above formula (2).
  • the component (A) may have a structural unit other than the structural unit represented by the formula (1).
  • Examples of the structural unit other than the structural unit represented by Formula (1) include a structural unit represented by Formula (11).
  • X 2 is a tetravalent group having one or more aromatic groups
  • -COOR 51 group and -CONH- group are at ortho positions to each other
  • -COOR 52 group and -COOR Y 2 is a divalent aromatic group
  • R 51 and R 52 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.
  • Examples of the tetravalent group having one or more aromatic groups of X 2 in the formula (11) include the same as the tetravalent group having one or more aromatic groups of X 1 in the formula (1).
  • Examples of the divalent aromatic group of Y 2 in the formula (11) include the same as the divalent aromatic group of Y 1 in the formula (1).
  • Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms represented by R 51 and R 52 in the formula (11) include the same as the aliphatic hydrocarbon groups having 1 to 4 carbon atoms represented by R 1 and R 2 .
  • the structural unit other than the structural unit represented by the formula (1) may be used alone or in combination of two or more.
  • the content of the structural unit other than the structural unit represented by the formula (1) is preferably less than 50 mol% with respect to all the constituent units of the component (A).
  • the ratio of the carboxy group esterified with the group represented by the formula (2) to all carboxy groups and all carboxy esters is preferably 50 mol% or more, and 60 to 100 mol%. Mol% is more preferable, and 70 to 90 mol% is still more preferable.
  • the molecular weight of the component (A) is not particularly limited, but is preferably 10,000 to 200,000 in number average molecular weight.
  • the number average molecular weight can be measured, for example, by a gel permeation chromatography method, and can be determined by conversion using a standard polystyrene calibration curve.
  • the component (B) is preferably a group containing (preferably two or more) polymerizable unsaturated double bonds from the viewpoint of improving the hydrophobicity of the cured product (preferably, it can be polymerized by a photopolymerization initiator. (Meth) acrylic group). In order to improve the crosslink density and photosensitivity and to suppress the swelling of the pattern after development, it is preferable to have a few groups containing a polymerizable unsaturated double bond.
  • the component (B) preferably contains a polymerizable monomer having an aliphatic cyclic skeleton (preferably having 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms).
  • a polymerizable monomer having an aliphatic cyclic skeleton preferably having 4 to 15 carbon atoms, more preferably 5 to 12 carbon atoms.
  • the component (B) preferably contains a polymerizable monomer represented by the following formula (3).
  • R 6 and R 7 are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following formula (4).
  • N1 is 0 or 1
  • N2 is an integer of 0 to 2
  • n1 + n2 is 1 or more (preferably 2 or 3.)
  • At least one (preferably 2 or 3) of n1 R 6 and n2 R 7 is It is a group represented by the formula (4).
  • the two R 7 may be the same or different.
  • R 9 to R 11 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and 1 is an integer of 0 to 10 (preferably 0, 1 or 2 ).)
  • the component (B) contains a polymerizable monomer represented by the following formula (5).
  • component (B) for example, the following polymerizable monomers may be used.
  • R 21 to R 24 are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the above formula (4).
  • n3 is an integer of 1 to 3 (preferably 2 or 3).
  • n4 is an integer of 1 to 3 (preferably 2 or 3).
  • n5 is 0 or 1
  • n6 is 0 or 1.
  • n5 + n6 is 1 or more (preferably 2).
  • two or more R 21 When two or more R 21 are present, two or more R 21 may be the same or different. When two or more R 22 are present, two or more R 22 may be the same or different.
  • At least one (preferably 2 or 3) of the n3 R 21 is a group represented by the above formula (4).
  • At least one (preferably 2 or 3) of the n4 R 22 is a group represented by the above formula (4).
  • n5 or at least one of R 23 and n6 amino R 24 (preferably 2) is a group represented by the above formula (4).
  • Examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms represented by R 6 and R 7 in the formula (3) and R 21 to R 24 in the formula (12) include a carbon atom having 1 carbon atom represented by R 1 and R 2 in the formula (1). And the same as the aliphatic hydrocarbon groups (1) to (4).
  • the aliphatic hydrocarbon group having 1 to 3 carbon atoms represented by R 9 to R 11 in the formula (4) is the same as the aliphatic hydrocarbon group having 1 to 3 carbon atoms represented by R 3 to R 5 in the formula (2). Things.
  • (B) component may contain a polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton.
  • Examples of the polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton include, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol dimethacrylate.
  • the component (B) may be used alone or in combination of two or more.
  • the component (B) may contain a polymerizable monomer having an aliphatic cyclic skeleton and a polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton from the viewpoint of achieving both the mechanical strength of the cured product and the improvement in hydrophobicity. preferable.
  • a polymerizable monomer having an aliphatic cyclic skeleton and a polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton are contained, the content of the polymerizable monomer having an aliphatic cyclic skeleton is set to 100 parts by mass of the component (A). On the other hand, 1 to 40 parts by mass is preferable.
  • the amount is more preferably 5 to 35 parts by mass.
  • the content of the polymerizable monomer other than the polymerizable monomer having an aliphatic cyclic skeleton is preferably from 1 to 20 parts by mass based on 100 parts by mass of the component (A). From the viewpoint of improving the hydrophobicity of the cured product, the amount is more preferably 5 to 15 parts by mass.
  • the content of the component (B) is preferably 1 to 50 parts by mass based on 100 parts by mass of the component (A). From the viewpoint of improving the hydrophobicity of the cured product, the amount is more preferably 3 to 50 parts by mass, and still more preferably 5 to 40 parts by mass. When the content is within the above range, a practical relief pattern is easily obtained, and residues after development of the unexposed portions are easily suppressed.
  • component (C) examples include benzophenone derivatives such as benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenylketone, dibenzylketone, and fluorenone; Acetophenone derivatives such as 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone and 1-hydroxycyclohexylphenyl ketone; Thioxanthone derivatives such as thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone; Benzyl derivatives such as benzyl, benzyldimethyl ketal, benzyl- ⁇ -methoxyethyl acetal, Benzoin derivatives such as benzoin and benzoin methyl ether, and 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl
  • oxime esters are preferred in terms of photosensitivity.
  • the component (C) preferably contains (C1) a compound represented by the following formula (15) (hereinafter, also referred to as “(C1) component”).
  • the component (C1) preferably has a higher sensitivity to actinic rays than the component (C2) described below, and is preferably a highly sensitive photosensitizer.
  • R 11A is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5.
  • R 12A is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
  • R 13A and R 14A each independently represent a hydrogen atom, an alkyl group having 1 to 12 (preferably 1 to 4) carbon atoms, a phenyl group or a tolyl group.
  • R 11A may be the same or different.
  • R 11A is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group. a1 is preferably 1.
  • R 12A is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an ethyl group.
  • R 13A and R 14A are preferably each independently an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
  • the compound represented by the formula (15) includes, for example, a compound represented by the following formula (15A), and is available as “IRGACURE OXE 02” manufactured by BASF Japan Ltd.
  • the component (C) preferably contains (C2) a compound represented by the following formula (16) (hereinafter, also referred to as “(C2) component”).
  • the component (C2) preferably has lower sensitivity to actinic rays than the component (C1), and is preferably a photosensitive agent having a standard sensitivity.
  • R 21A is an alkyl group having 1 to 12 carbon atoms
  • R 22A and R 23A are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (preferably having 1 to 4 carbon atoms).
  • c1 is an integer of 2 or more, R 21A may be the same or different.
  • R 22A is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
  • R 23A is preferably an alkoxy group having 1 to 12 carbon atoms, more preferably an alkoxy group having 1 to 4 carbon atoms, even more preferably a methoxy group or an ethoxy group.
  • Examples of the compound represented by the formula (16) include a compound represented by the following formula (16A), which is available as “G-1820 (PDO)” manufactured by Lambson.
  • the component (C) may be used alone or in combination of two or more.
  • the component (C) preferably contains at least one selected from the group consisting of the component (C1) and the component (C2). Further, the component (C) preferably contains the component (C1) and the component (C2).
  • the content of the component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and further preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the component (A). 5 parts by mass. When it is in the above range, photocrosslinking tends to be uniform in the film thickness direction, and a practical relief pattern is easily obtained.
  • the content of the component (C1) is usually 0.05 to 5.0 parts by mass, preferably 0.07 to 2.0 parts by mass, per 100 parts by mass of the component (A).
  • the amount is 5 parts by mass, more preferably 0.09 to 1.0 part by mass.
  • the content of the component (C2) is usually from 0.5 to 15.0 parts by mass, preferably from 1.0 to 15.0 parts by mass, per 100 parts by mass of the component (A). 0 parts by mass.
  • the content of the component (C1) is 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the component (A), and the component (C2) Is preferably 0.5 to 15.0 parts by mass with respect to 100 parts by mass of the component (A).
  • the mass ratio of the content of the component (C1) to the content of the component (C2) is preferably from 1: 2 to 1:15, more preferably from 1: 3 to 1:15. 1:10.
  • component (D) By containing the component (D), it is possible to suppress the corrosion of copper and copper alloy and prevent discoloration.
  • the component (D) include a triazole derivative and a tetrazole derivative.
  • Component (D) includes 5-aminotetrazole (eg, 5-amino-1H-tetrazole), benzotriazole, 1-hydroxybenzotriazole, 1H-benzotriazole-1-acetonitrile, benzotriazole-5-carboxylic acid, and 1H- Benzotriazole-1-methanol, carboxybenzotriazole, mercaptobenzoxazole and the like can be mentioned. Among these, 5-aminotetrazole, benzotriazole or 1-hydroxybenzotriazole is preferred.
  • the component (D) one type may be used alone, or two or more types may be used in combination.
  • the content of the component (D) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.5 to 3 parts by mass based on 100 parts by mass of the component (A). .
  • oxygen radicals and peroxide radicals generated during high-temperature storage or insulation reliability test can be supplemented, and a decrease in adhesion (adhesion) can be further suppressed.
  • the component (E) includes N, N′-bis [2- [2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethylcarbonyloxy] ethyl] oxamide, N, N′-bis- 3- (3,5-di-tert-butyl-4'-hydroxyphenyl) propionylhexamethylenediamine, 1,3,5-tris (3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-thio-bis (3-methyl-6-
  • the component (E) may be used alone or in combination of two or more.
  • the content of the component (E) is preferably from 0.1 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass, and still more preferably from 0.1 to 10 parts by mass, per 100 parts by mass of the component (A). 5 parts by mass.
  • the photosensitive resin composition of the present invention contains (F) a cyclization catalyst.
  • the component (F) includes 2- (methylphenylamino) ethanol, 2- (ethylanilino) ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N, N It is preferably at least one selected from the group consisting of '-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine and 2,2'-(4-methylphenylimino) diethanol, and N-phenyldiethanolamine; Selected from the group consisting of N-methylaniline, N-ethylaniline, N, N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine and 2,2 '-(4-methylphenylimino) diethanol More preferably, it is 1 or more.
  • the component (F) preferably contains a compound represented by the following formula (17).
  • R 31A to R 33A each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group.
  • the at least one R 31A ⁇ R 33A (preferably 1 or 2) is a monovalent aromatic group .
  • R 31A ⁇ R 33A ring adjacent groups e.g., substituents (e.g., methyl A 5- or 6-membered ring which may have a phenyl group).
  • At least one of R 31A to R 33A is a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aromatic group.
  • Examples of the monovalent aliphatic hydrocarbon group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms) represented by R 31A to R 33A in the formula (17) include a methyl group and an ethyl group.
  • the monovalent aliphatic hydrocarbon group having a hydroxy group represented by R 31A to R 33A in the formula (17) one or more (preferably 1 to 3) is added to the monovalent aliphatic hydrocarbon group represented by R 31A to R 33A.
  • Specific examples include a methylol group and a hydroxyethyl group. Hydroxyethyl groups are preferred.
  • the monovalent aromatic group represented by R 31A to R 33A in the formula (17) may be a monovalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms). It may be a valent aromatic heterocyclic group. Monovalent aromatic hydrocarbon groups are preferred. Examples of the monovalent aromatic hydrocarbon group include a phenyl group and a naphthyl group.
  • the component (F) one type may be used alone, or two or more types may be used in combination.
  • the content of the component (F) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A) from the viewpoint of sufficiently trapping oxygen radicals. From the viewpoint of suppressing a decrease in the glass transition temperature (Tg), the amount is more preferably 0.3 to 15 parts by mass, and still more preferably 0.5 to 10 parts by mass.
  • the photosensitive resin composition of the present invention contains (G) a solvent.
  • G) Components include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, N-dimethyl morpholine and the like.
  • N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N, N-dimethylformamide are preferred from the viewpoint of excellent solubility of each component and coatability in forming a photosensitive resin film.
  • N, N-Dimethylacetamide is preferably used.
  • component (G) a compound represented by the following formula (21) may be used.
  • R 41 to R 43 are each independently an alkyl group having 1 to 10 carbon atoms.
  • examples of the alkyl group having 1 to 10 (preferably 1 to 3, more preferably 1 or 3) carbon atoms of R 41 to R 43 include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. , N-butyl, t-butyl, pentyl, hexyl, heptyl, octyl and the like.
  • the compound represented by the formula (21) is preferably 3-methoxy-N, N-dimethylpropanamide (for example, trade name “KJCMPA-100” (manufactured by KJ Chemicals Corporation)).
  • the component (G) one type may be used alone, or two or more types may be used in combination.
  • the content of the component (G) is not particularly limited, but is generally 50 to 1000 parts by mass with respect to 100 parts by mass of the component (A).
  • the photosensitive resin composition of the present invention may further contain (H) a thermal polymerization initiator (hereinafter, also referred to as “(H) component”) from the viewpoint of accelerating the polymerization reaction.
  • the component (H) is not decomposed by heating (drying) for removing a solvent during film formation, but is decomposed by heating during curing to generate radicals.
  • Compounds that promote the polymerization reaction of component (B) are preferred.
  • the component (H) is preferably a compound having a decomposition point of 110 ° C to 200 ° C, and more preferably a compound having a decomposition point of 110 ° C to 175 ° C from the viewpoint of accelerating the polymerization reaction at a lower temperature.
  • ketone peroxides such as methyl ethyl ketone peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, Peroxy ketals such as 1-di (t-butylperoxy) cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, dicumyl peroxide, dicumyl peroxide Dialkyl peroxides such as -t-butyl peroxide and the like, diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide, di (4-t-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbon
  • the content of the component (H) is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the component (A), and is 0 to ensure good flux resistance.
  • the content is more preferably from 2 to 20 parts by mass, and even more preferably from 0.3 to 10 parts by mass from the viewpoint of suppressing the decrease in solubility due to decomposition during drying.
  • the photosensitive resin composition of the present invention may further contain a coupling agent (adhesion aid), a surfactant or a leveling agent, a polymerization inhibitor, and the like.
  • the coupling agent reacts with the component (A) in the heat treatment after development to crosslink, or the coupling agent itself is polymerized in the heat treatment step. Thereby, the adhesiveness between the obtained cured product and the substrate can be further improved.
  • Preferred silane coupling agents include compounds having a urea bond (—NH—CO—NH—). Thereby, even when curing is performed at a low temperature of 230 ° C. or lower, the adhesiveness to the substrate can be further improved.
  • the compound represented by the following formula (13) is more preferable because it exhibits excellent adhesion when cured at a low temperature.
  • R 31 and R 32 are each independently an alkyl group having 1 to 5 carbon atoms. A is an integer of 1 to 10, and b is an integer of 1 to 3.
  • Specific examples of the compound represented by the formula (13) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, and 3-ureidopropyltrimethoxysilane. And 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, and the like, with 3-ureidopropyltriethoxysilane being preferred.
  • silane coupling agent a silane coupling agent having a hydroxy group or a glycidyl group may be used.
  • silane coupling agent having a hydroxy group or a glycidyl group and a silane coupling agent having a urea bond in a molecule are used in combination, it is possible to further improve the adhesion of a cured product to a substrate during low-temperature curing.
  • silane coupling agent having a hydroxy group or a glycidyl group examples include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, and tert-silane.
  • R 33 is a monovalent organic group having a hydroxy group or a glycidyl group
  • R 34 and R 35 are each independently an alkyl group having 1 to 5 carbon atoms.
  • An integer of 10 and d is an integer of 1 to 3.
  • Examples of the compound represented by the formula (14) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, Hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2- Glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyl Triethoxysilane, and the like.
  • the silane coupling agent having a hydroxy group or a glycidyl group preferably further contains a group having a nitrogen atom, and more preferably a silane coupling agent having an amino group or an amide bond.
  • the silane coupling agent having an amino group include bis (2-hydroxymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane, bis (2-glycidyl) (Xymethyl) -3-aminopropyltriethoxysilane, bis (2-hydroxymethyl) -3-aminopropyltrimethoxysilane and the like.
  • R 36 (CH 2 ) e —CO—NH— (CH 2 ) f —Si (OR 37 ) 3
  • R 36 is a hydroxy group or a glycidyl group
  • f are each independently an integer of 1 to 3
  • R 37 is a methyl group, an ethyl group or a propyl group).
  • the silane coupling agent may be used alone or in combination of two or more.
  • the content of the silane coupling agent is preferably 0.1 to 20 parts by mass, more preferably 1 to 10 parts by mass, and more preferably 0.3 to 10 parts by mass, per 100 parts by mass of the component (A). -10 parts by mass is more preferred.
  • surfactant or the leveling agent examples include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, and the like.
  • the surfactant and the leveling agent may be used alone or in a combination of two or more.
  • the content of the surfactant or the leveling agent is preferably from 0.01 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass, per 100 parts by mass of the component (A).
  • the amount is 0.05 to 3 parts by mass.
  • the polymerization inhibitor By including a polymerization inhibitor, good storage stability can be ensured.
  • the polymerization inhibitor include a radical polymerization inhibitor and a radical polymerization inhibitor.
  • polymerization inhibitor examples include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, and N-phenyl-2-ene.
  • examples include naphthylamine, cuperon, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines and the like.
  • the polymerization inhibitor may be used alone or in combination of two or more.
  • the content of the polymerization inhibitor is preferably 0 to 100 parts by mass of the component (A) from the viewpoint of storage stability of the photosensitive resin composition and heat resistance of the obtained cured product. 0.01 to 30 parts by mass, more preferably 0.01 to 10 parts by mass, even more preferably 0.05 to 5 parts by mass.
  • the photosensitive resin composition of the present invention essentially comprises the components (A) to (G), and optionally the component (H), a coupling agent, a surfactant, a leveling agent, and a polymerization inhibitor.
  • unavoidable impurities may be contained as long as the effects of the present invention are not impaired. For example, 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the photosensitive resin composition of the present invention, (A) to (G) components, It may be composed of components (A) to (H) or components (A) to (G), and optionally component (H), a coupling agent, a surfactant, a leveling agent, and a polymerization inhibitor.
  • the cured product of the present invention can be obtained by curing the above-described photosensitive resin composition.
  • the cured product of the present invention may be used as a pattern cured product or a cured product without a pattern.
  • the thickness of the cured product of the present invention is preferably 5 to 20 ⁇ m.
  • a step of applying the above-described photosensitive resin composition on a substrate and drying to form a photosensitive resin film, and pattern-exposing the photosensitive resin film to form a resin film includes a step of obtaining, a step of developing the resin film after pattern exposure using an organic solvent to obtain a pattern resin film, and a step of heat-treating the pattern resin film. Thereby, a cured pattern can be obtained.
  • a method for producing a cured product having no pattern includes, for example, a step of forming the above-described photosensitive resin film and a step of performing heat treatment. Further, a step of exposing may be provided.
  • the substrate examples include a semiconductor substrate such as a glass substrate and a Si substrate (silicon wafer), a metal oxide insulator substrate such as a TiO 2 substrate and a SiO 2 substrate, a silicon nitride substrate, a copper substrate, and a copper alloy substrate.
  • the coating method is not particularly limited, but can be performed using a spinner or the like.
  • Drying can be performed using a hot plate, an oven, or the like.
  • the drying temperature is preferably from 90 to 150 ° C., and more preferably from 90 to 120 ° C. from the viewpoint of ensuring the dissolution contrast.
  • the drying time is preferably 30 seconds to 5 minutes. Drying may be performed two or more times. Thereby, a photosensitive resin film in which the above-described photosensitive resin composition is formed in a film shape can be obtained.
  • the thickness of the photosensitive resin film is preferably 5 to 100 ⁇ m, more preferably 6 to 50 ⁇ m, and still more preferably 7 to 30 ⁇ m.
  • a predetermined pattern is exposed through a photomask.
  • the actinic rays to be radiated include ultraviolet rays such as i-rays, visible rays, and radiation, and are preferably i-rays.
  • a parallel exposure device, a projection exposure device, a stepper, a scanner exposure device, or the like can be used as the exposure device.
  • a patterned resin film (patterned resin film) can be obtained.
  • a negative photosensitive resin composition when used, unexposed portions are removed with a developer.
  • the organic solvent used as the developer a good solvent for the photosensitive resin film can be used alone, or a good solvent and a poor solvent can be appropriately mixed.
  • the good solvent include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, Cyclopentanone, cyclohexanone and the like can be mentioned.
  • the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and water.
  • a surfactant may be added to the developer.
  • the addition amount is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the developer.
  • the development time can be, for example, twice as long as the time until the photosensitive resin film is immersed and completely dissolved.
  • the development time varies depending on the component (A) used, but is preferably from 10 seconds to 15 minutes, more preferably from 10 seconds to 5 minutes, and further preferably from 20 seconds to 5 minutes from the viewpoint of productivity.
  • washing may be performed with a rinsing solution.
  • a rinsing solution distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or the like may be used alone or in a suitable mixture, or may be used in a stepwise combination. Good.
  • the polyimide precursor of the component (A) undergoes a dehydration and ring closure reaction by the heat treatment step, and usually becomes a corresponding polyimide.
  • the temperature of the heat treatment is preferably 250 ° C. or lower, more preferably 120 to 250 ° C., and further preferably 230 ° C. or lower or 160 to 230 ° C. By being within the above range, damage to the substrate and the device can be suppressed small, the device can be produced with high yield, and energy saving in the process can be realized.
  • the time of the heat treatment is preferably 5 hours or less, more preferably 30 minutes to 3 hours. When the content is within the above range, the crosslinking reaction or the dehydration ring-closing reaction can sufficiently proceed.
  • the atmosphere for the heat treatment may be the air or an inert atmosphere such as nitrogen, but is preferably under a nitrogen atmosphere from the viewpoint of preventing oxidation of the pattern resin film.
  • Examples of the apparatus used for the heat treatment include a quartz tube furnace, a hot plate, rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.
  • the cured product of the present invention can be used as a passivation film, a buffer coat film, an interlayer insulating film, a cover coat layer, a surface protective film, or the like.
  • a highly reliable semiconductor device, multilayer wiring board, various electronic devices, laminated Electronic components such as devices (such as a multi-die fan-out wafer level package) can be manufactured.
  • FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure as an electronic component according to an embodiment of the present invention.
  • a semiconductor substrate 1 such as a Si substrate having circuit elements is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit elements, and a first conductor layer 3 is formed on the exposed circuit elements. It is formed. After that, an interlayer insulating film 4 is formed on the semiconductor substrate 1.
  • a photosensitive resin layer 5 of a chlorinated rubber type, a phenol novolak type or the like is formed on the interlayer insulating film 4, and a window 6A is formed by a known photolithography technique so that a predetermined portion of the interlayer insulating film 4 is exposed.
  • the interlayer insulating film 4 with the window 6A exposed is selectively etched to provide a window 6B.
  • the photosensitive resin layer 5 is completely removed by using an etching solution that corrodes only the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B.
  • the second conductor layer 7 is formed by using a known photolithography technique, and is electrically connected to the first conductor layer 3.
  • each layer can be formed by repeating the above steps.
  • a window 6C is opened by pattern exposure using the above-mentioned photosensitive resin composition, and a surface protective film 8 is formed.
  • the surface protection film 8 protects the second conductor layer 7 from external stress, ⁇ -rays and the like, and the obtained semiconductor device has excellent reliability.
  • the interlayer insulating film can be formed using the photosensitive resin composition of the present invention.
  • Synthesis Example 1 (Synthesis of A1) 7.07 g of 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride (ODPA) and 4.12 g of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) were converted to N-methyl- It was dissolved in 30 g of 2-pyrrolidone (NMP) and stirred at 30 ° C. for 4 hours and then at room temperature overnight to obtain a polyamic acid. Under water cooling, 9.45 g of trifluoroacetic anhydride was added thereto, and the mixture was stirred at 45 ° C. for 3 hours, and 7.08 g of 2-hydroxyethyl methacrylate (HEMA) was added.
  • ODPA 3,3 ', 4,4'-diphenylethertetracarboxylic dianhydride
  • DMAP 2,2'-dimethylbiphenyl-4,4'-diamine
  • the reaction solution was dropped into distilled water, the precipitate was collected by filtration, and dried under reduced pressure to obtain a polyimide precursor A1.
  • the number average molecular weight was determined by gel permeation chromatography (GPC) under the following conditions in terms of standard polystyrene.
  • the number average molecular weight of A1 was 40,000.
  • THF tetrahydrofuran
  • DMF dimethylformamide
  • esterification rate of A1 (reaction rate of the carboxy group of ODPA with HEMA) was calculated by performing NMR measurement under the following conditions.
  • the esterification rate was 80 mol% based on the total carboxy groups of the polyamic acid (the remaining 20 mol% was carboxy groups).
  • Examples 1 to 3 and Comparative Examples 1 to 3 (Preparation of photosensitive resin composition)
  • the photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were prepared using the components and amounts shown in Table 1.
  • the compounding amounts in Table 1 are parts by mass of each component with respect to 100 parts by mass of A1.
  • E Component: Antioxidant E1: ANTAGE HP200 (N, N'-bis [2- [2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethylcarbonyl] manufactured by Kawaguchi Chemical Industry Co., Ltd.) [Oxy] ethyl] oxamide, a compound represented by the following formula E1)
  • Thermal polymerization initiator H1 Park Mill D (manufactured by NOF CORPORATION, bis (1-phenyl-1-methylethyl) peroxide, a compound represented by the following formula)
  • the obtained photosensitive resin composition is spin-coated on a silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Limited), dried at 100 ° C. for 2 minutes, and then dried at 110 ° C. for 2 minutes to form a dried film.
  • a photosensitive resin film having a thickness of 11 to 14 ⁇ m was formed.
  • the development time was set to twice the time required for the obtained photosensitive resin film to be completely dissolved by immersion in cyclopentanone.
  • a photosensitive resin film was prepared in the same manner as described above, and an i-line of 50 to 550 mJ / cm 2 was applied to the obtained photosensitive resin film using an i-line stepper FPA-3000iW (manufactured by Canon Inc.). Exposure was performed by irradiating a predetermined pattern at an irradiation amount of 50 mJ / cm 2 . The exposed resin film was paddle-developed to cyclopentanone using Act8 for the above-described development time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.
  • PMEA propylene glycol monomethyl ether acetate
  • the sensitivity was defined as the lower limit of the exposure amount at which the thickness of the obtained pattern resin film exceeded 75% of the thickness of the photosensitive resin film before exposure.
  • the film thickness was measured by exposing the silicon wafer by scribing a part of the film and measuring the height from the exposed silicon wafer surface to the film surface using a needle-type profiler Dektak 150 (manufactured by Bruker). The measurement of the thickness is the same hereinafter).
  • the case where the sensitivity was less than 300 mJ / cm 2 was designated as A.
  • B was 300 to 400 mJ / cm 2 .
  • C was over 300 mJ / cm 2 . Table 1 shows the results.
  • a test substrate for a biasHAST (high-speed accelerated life test) (a wafer having a layer structure of silicon wafer / SiO 2 layer (1 ⁇ m) / TiCu seed layer (100 nm) / Cu layer (3.5 ⁇ m), silicon wafer / SiO 2 layer / TiCu seed)
  • the wafer having a layer configuration of layers is manufactured by Advanced Material Technology Co., Ltd.
  • the TiCu seed layer and Cu layer have a comb pattern (line width of comb teeth: 2 ⁇ m, number of teeth: 9 anodes, 9 cathodes, interval: 2 ⁇ m).
  • the obtained photosensitive resin composition was spin-coated on a test substrate for biasHAST, and dried at 120 ° C.
  • a pad portion was provided on the surface of the biasHAST test substrate, and application was performed so that the photosensitive resin composition was not applied to the pad portion.
  • the obtained photosensitive resin film was heated at 200 ° C. for 1 hour in a nitrogen atmosphere using ⁇ -TF to obtain a test substrate with a cured product (after-cured film thickness 8 ⁇ m). Thereafter, the pad portion of the test substrate with the cured product is soldered, connected to a migration tester MIG-8600B (manufactured by IMV Co., Ltd.), and placed in a thermostat HASTEST PC-R8D (manufactured by Hirayama Seisakusho) at 130 ° C.
  • test substrate with the cured product after the above-mentioned insulation reliability evaluation was Pt sputtered and arranged on JSM-7800F-prime.
  • the current value was measured at an acceleration voltage of 2 kV under a condition of a beam 16 (2.7 nA) over 1 hour.
  • the photosensitive resin composition of the present invention can be used for an interlayer insulating film, a cover coat layer, a surface protective film, and the like, and the interlayer insulating film, the cover coat layer, or the surface protective film of the present invention can be used for electronic components and the like. Can be.

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