WO2022137294A1 - 感光性樹脂組成物、硬化物及び電子部品 - Google Patents

感光性樹脂組成物、硬化物及び電子部品 Download PDF

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Publication number
WO2022137294A1
WO2022137294A1 PCT/JP2020/047736 JP2020047736W WO2022137294A1 WO 2022137294 A1 WO2022137294 A1 WO 2022137294A1 JP 2020047736 W JP2020047736 W JP 2020047736W WO 2022137294 A1 WO2022137294 A1 WO 2022137294A1
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group
photosensitive resin
general formula
resin composition
mass
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English (en)
French (fr)
Japanese (ja)
Inventor
篤太郎 吉澤
伸行 斉藤
康平 水野
大作 松川
俊明 板橋
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HD MicroSystems Ltd
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HD MicroSystems Ltd
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Priority to PCT/JP2020/047736 priority Critical patent/WO2022137294A1/ja
Priority to PCT/JP2021/047425 priority patent/WO2022138674A1/ja
Priority to TW110147963A priority patent/TW202234157A/zh
Priority to JP2022571523A priority patent/JPWO2022138674A1/ja
Publication of WO2022137294A1 publication Critical patent/WO2022137294A1/ja
Anticipated expiration legal-status Critical
Priority to JP2025085803A priority patent/JP2025109967A/ja
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    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029

Definitions

  • the present disclosure relates to photosensitive resin compositions, cured products and electronic components.
  • a protective film using such a cured film of polyimide resin is obtained by heating and curing a resin film formed by applying a polyimide precursor or a resin composition containing a polyimide precursor on a substrate and drying it. can get.
  • NMP N-methyl-2-pyrrolidone
  • the present disclosure has been made in view of the above-mentioned conventional circumstances, and one embodiment of the present disclosure includes a photosensitive resin composition containing an organic solvent other than NMP and having excellent photosensitive characteristics, and this photosensitive resin composition. It is an object of the present invention to provide a cured product and an electronic component using the above.
  • a polyimide precursor having a polymerizable unsaturated bond, a photopolymerization initiator, and a solvent are contained.
  • ⁇ 3> The photosensitive resin composition according to ⁇ 1>, wherein the proportion of N-ethyl-2-pyrrolidone in the solvent is 50% by mass or more.
  • ⁇ 4> The photosensitive resin composition according to ⁇ 1>, wherein the ratio of 1,3-dimethyl-2-imidazolidinone to the solvent is 50% by mass or more.
  • ⁇ 5> The photosensitive resin composition according to ⁇ 1>, wherein the proportion of tetramethylurea in the solvent is 50% by mass or more.
  • ⁇ 6> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the polyimide precursor has a structural unit represented by the following general formula (6).
  • R 6 and R 7 are independently represented by hydrogen atoms and the following general formula (7). Is a group or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and at least one of R 6 and R 7 is a group represented by the following general formula (7).
  • R 8 to R 10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and q represents an integer of 1 to 10.
  • ⁇ 7> The photosensitive resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the photopolymerization initiator contains an oxime derivative.
  • ⁇ 8> A cured product obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 7>.
  • ⁇ 9> The cured product according to ⁇ 8>, which is a pattern cured product.
  • ⁇ 11> An electronic component containing the cured product according to any one of ⁇ 8> to ⁇ 10>.
  • a photosensitive resin composition containing an organic solvent other than NMP and having excellent photosensitive characteristics it is possible to provide a photosensitive resin composition containing an organic solvent other than NMP and having excellent photosensitive characteristics, and a cured product and electronic components using this photosensitive resin composition. ..
  • the term "process” includes, in addition to a process independent of other processes, the process as long as the purpose of the process is achieved even if it cannot be clearly distinguished from the other process. ..
  • the numerical range indicated by using "-" includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description. ..
  • the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
  • each component may contain a plurality of applicable substances.
  • the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
  • the term "layer” or “membrane” is used only in a part of the region, in addition to the case where the layer or the membrane is formed in the entire region when the region is observed. The case where it is formed is also included.
  • the photosensitive resin composition of the present disclosure contains a polyimide precursor having a polymerizable unsaturated bond (hereinafter, may be referred to as an unsaturated polyimide precursor), a photopolymerization initiator, and a solvent.
  • the solvent is N-ethyl-2-pyrrolidone (hereinafter, may be referred to as NEP), 1,3-dimethyl-2-imidazolidinone (hereinafter, may be referred to as DMI) and tetramethylurea. It contains at least one selected from the group consisting of (hereinafter, may be referred to as TMU) (hereinafter, these solvents may be referred to as "specific solvent").
  • the present inventors have found that a photosensitive resin composition having excellent photosensitive characteristics can be obtained by using a specific solvent, and have completed the present invention. Further, since the unsaturated polyimide precursor exhibits the same solubility as NMP in a specific solvent, even if a specific solvent is used, the unsaturated polyimide precursor is not saturated in the photosensitive resin composition to the same extent as when NMP is used. It is possible to secure the polyimide precursor concentration.
  • the photosensitive resin composition of the present disclosure is preferably a negative type photosensitive resin composition.
  • each component contained in the photosensitive resin composition of the present disclosure will be described.
  • the photosensitive resin composition of the present disclosure contains an unsaturated polyimide precursor.
  • the polymerizable unsaturated bond include a carbon-carbon double bond.
  • the unsaturated polyimide precursor may be, for example, a polyimide precursor having a structural unit represented by the following general formula (6). Since the unsaturated polyimide precursor has a structural unit represented by the general formula (6), the i-ray transmittance is high and there is a tendency that a good cured product can be formed even when cured at 380 ° C. or lower.
  • the content of the structural units represented by the following general formula (6) in the unsaturated polyimide precursor is preferably 50 mol% or more with respect to all the structural units contained in the unsaturated polyimide precursor. 80 mol% or more is more preferable, and 90 mol% or more is further preferable.
  • the upper limit is not particularly limited and may be 100 mol%.
  • the unsaturated polyimide precursor may be synthesized by using a tetracarboxylic acid dianhydride and a diamine compound.
  • X corresponds to a residue derived from tetracarboxylic acid dianhydride
  • Y corresponds to a residue derived from a diamine compound.
  • the unsaturated polyimide precursor may be synthesized by using tetracarboxylic acid instead of tetracarboxylic acid dianhydride.
  • X represents a tetravalent organic group and Y represents a divalent organic group.
  • R 6 and R 7 are each independently a hydrogen atom, a group represented by the following general formula (7), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and at least one of R 6 and R 7 is a hydrogen atom.
  • R 8 to R 10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and q represents an integer of 1 to 10.
  • the tetravalent organic group represented by X preferably has 3 to 20 carbon atoms, more preferably 5 to 15 carbon atoms, and further preferably 7 to 13 carbon atoms. ..
  • the tetravalent organic group represented by X may contain an aromatic ring.
  • examples of the aromatic ring include a benzene ring, a naphthalene ring, and a phenanthrene ring.
  • a benzene ring is preferable from the viewpoint of improving the light transmission in the ultraviolet region of the unsaturated polyimide precursor.
  • each aromatic ring may have a substituent or may be unsubstituted.
  • substituent of the aromatic ring include an alkyl group, a fluorine atom, an alkyl halide group, a hydroxyl group, an amino group and the like.
  • the tetravalent organic group represented by X contains a benzene ring
  • the tetravalent organic group represented by X preferably contains 1 to 4 benzene rings, and 1 to 3 benzene rings. It is more preferable to contain one or two benzene rings.
  • each benzene ring may be linked by a single bond, or may be an alkylene group, a halogenated alkylene group, a carbonyl group, or a sulfonyl group.
  • RA independently represents a hydrogen atom, an alkyl group or a phenyl group), Siloxane bond (-O- (Si (RB) 2 - O-) n ;
  • RB independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more).
  • Etc., or a composite linking group in which at least two of these linking groups are combined may be bonded.
  • the two benzene rings may be bonded at two points by at least one of a single bond and a linking group to form a 5-membered ring or a 6-membered ring containing a linking group between the two benzene rings.
  • the -COOR 6 group and the -CONH- group are in the ortho position with each other, and the -COOR 7 group and the -CO- group are in the ortho position. It is preferable that they are in the ortho position with each other.
  • tetravalent organic group represented by X include groups represented by the following general formulas (A) to (E), but the present disclosure is limited to the following specific examples. It's not something.
  • a and B are independently single bond, methylene group, methylene halide group, carbonyl group, sulfonyl group, ether bond (—O—), sulfide bond (—S—) or silylene.
  • C is a single bond, or an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), or a silylene bond (—Si).
  • RA independently represents a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (-O- (Si (RB) 2 - O-) n ;
  • RB is , Each independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more) or a divalent group in which at least two of these are combined.
  • C may have a structure represented by the following formula (C1).
  • the alkylene group represented by C in the general formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and has a carbon number of 1 to 5. It is more preferably 1 or 2 alkylene groups.
  • Specific examples of the alkylene group represented by C in the general formula (E) include a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; a methylmethylene group.
  • Examples thereof include a branched chain alkylene group such as a group, a 2,2-dimethyltetramethylene group, a 1,3-dimethyl
  • the halogenated alkylene group represented by C in the general formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, and preferably a halogenated alkylene group having 1 to 5 carbon atoms. More preferably, it is a halogenated alkylene group having 1 to 3 carbon atoms.
  • at least one hydrogen atom contained in the alkylene group represented by C in the above general formula (E) is a fluorine atom or a chlorine atom. Examples thereof include an alkylene group substituted with a halogen atom such as. Among these, a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group and the like are preferable.
  • the alkyl group represented by RA or RB contained in the silylene bond or the siloxane bond is preferably an alkyl group having 1 to 10 carbon atoms and preferably an alkyl group having 1 to 5 carbon atoms. Is more preferable, and an alkyl group having 1 or 2 carbon atoms is further preferable.
  • Specific examples of the alkyl group represented by RA or RB include a methyl group, an ethyl group, an n - propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group and the like. Can be mentioned.
  • the combination of A and B in the general formula (D) is not particularly limited, and a combination of a methylene group and an ether bond, a combination of a methylene group and a sulfide bond, a combination of a carbonyl group and an ether bond, and the like are preferable.
  • C in the general formula (E) a single bond, an ether bond, a carbonyl group and the like are preferable.
  • the aliphatic hydrocarbon group represented by R 6 and R 7 in the general formula (6) has 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms.
  • Specific examples of the aliphatic hydrocarbon group represented by R 6 and R 7 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and the like.
  • the aliphatic hydrocarbon group represented by R 8 to R 10 in the general formula (7) has 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms.
  • Specific examples of the aliphatic hydrocarbon group represented by R 8 to R 10 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group and the like, and a methyl group is preferable.
  • R 8 to R 10 in the general formula (7) a combination of R 8 and R 9 is a hydrogen atom, and R 10 is a hydrogen atom or a methyl group is preferable.
  • Q in the general formula (7) is preferably an integer of 1 to 10, more preferably an integer of 2 to 5, and even more preferably 2 or 3.
  • R 6 and R 7 are a group represented by the general formula (7), and both R 6 and R 7 are in the general formula (7). It is more preferable that it is a group represented.
  • X corresponds to a residue derived from tetracarboxylic acid dianhydride
  • specific examples of the tetracarboxylic acid dianhydride that is the source of the residue include pyromellitic acid dianhydride, 2, 3, 6, 7.
  • the divalent organic group represented by Y preferably has 1 to 30 carbon atoms, more preferably 5 to 25 carbon atoms, and further preferably 10 to 20 carbon atoms. ..
  • the divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group.
  • divalent aromatic group represented by Y include the groups represented by the following general formula (F) and the following general formula (G).
  • R independently represents an alkyl group, an alkoxy group, an alkyl halide group, a carboxy group or a phenyl group, and n independently represents 0 to 4, respectively. Represents an integer.
  • D is a single bond, or an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), or a silylene bond (—Si).
  • RA independently represents a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (-O- (Si (RB) 2 - O-) n ;
  • RB is , Each independently represents a hydrogen atom, an alkyl group or a phenyl group, and n represents an integer of 1 or 2 or more) or a divalent group in which at least two of these are combined.
  • D may have a structure represented by the above formula (C1).
  • the alkyl group represented by R in the general formula (F) or the general formula (G) is preferably an alkyl group having 1 to 10 carbon atoms, and preferably an alkyl group having 1 to 5 carbon atoms. More preferably, it is an alkyl group having 1 or 4 carbon atoms.
  • Specific examples of the alkyl group represented by R in the general formula (F) or the general formula (G) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and an s-butyl. Groups, t-butyl groups and the like can be mentioned.
  • the alkoxy group represented by R in the general formula (F) or the general formula (G) is preferably an alkoxy group having 1 to 10 carbon atoms, and preferably an alkoxy group having 1 to 5 carbon atoms. More preferably, it is an alkoxy group having 1 or 4 carbon atoms.
  • Specific examples of the alkoxy group represented by R in the general formula (F) or the general formula (G) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, and s-. Examples thereof include a butoxy group and a t-butoxy group.
  • the alkyl halide group represented by R in the general formula (F) or the general formula (G) is preferably an alkyl halide group having 1 to 10 carbon atoms, and a halogenated group having 1 to 5 carbon atoms. It is more preferably an alkyl group, and even more preferably a halogenated alkyl group having 1 or 2 carbon atoms.
  • Specific examples of the alkyl halide group represented by R in the general formula (F) or the general formula (G) include at least the alkyl group represented by R in the general formula (F) or the general formula (G). Examples thereof include an alkyl group in which one hydrogen atom is substituted with a halogen atom such as a fluorine atom and a chlorine atom. Among these, a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group and the like are preferable.
  • n in the general formula (F) or the general formula (G) is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.
  • D may be a divalent group represented by the following formula (D1) or (D2).
  • Ar represents a phenylene group or a naphthylene group which may have a substituent.
  • Q is a single bond or an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), and a silylene bond (-Si ( RA )", respectively.
  • RA independently represents a hydrogen atom, an alkyl group or a phenyl group), and a siloxane bond (-O- (Si (RB) 2 - O-) n ; RB are independent, respectively.
  • the positional relationship between the two Qs bound to each Ar may be the ortho position, the meta position, or the para position.
  • substituents that the phenylene group or naphthylene group represented by Ar may have are the same as the group represented by R in the general formula (F) or the general formula (G).
  • the number of substituents that the phenylene group or naphthylene group represented by Ar may have is not particularly limited.
  • D excluding the formulas (D1) and (D2) in the general formula (G) and the specific examples of Q in the formulas (D1) and (D2) are the same as the specific examples of C in the general formula (E). Is.
  • D in the general formula (G) a single bond or an ether bond is preferable.
  • divalent aliphatic group represented by Y examples include a linear or branched alkylene group, a cycloalkylene group, a divalent group having a polyalkylene oxide structure, and a divalent group having a polysiloxane structure. The basics of.
  • the linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and carbon. More preferably, it is an alkylene group having a number of 1 to 3.
  • Specific examples of the alkylene group represented by Y include a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, and a 2-methylpentamethylene group. , 2-Methylhexamethylene group, 2-methylheptamethylene group, 2-methyloctamethylene group, 2-methylnonamethylene group, 2-methyldecamethylene group and the like.
  • the cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 20 carbon atoms, more preferably a cycloalkylene group having 3 to 10 carbon atoms, and 3 to 6 carbon atoms. It is more preferably the cycloalkylene group of.
  • Specific examples of the cycloalkylene group represented by Y include a cyclopropylene group and a cyclohexylene group.
  • the alkylene oxide structure having 1 to 10 carbon atoms is preferable, the alkylene oxide structure having 1 to 8 carbon atoms is more preferable, and the alkylene oxide structure having 1 to 8 carbon atoms is more preferable.
  • the alkylene oxide structure of 1 to 4 is more preferable.
  • the polyethylene oxide structure or the polypropylene oxide structure is preferable as the polyalkylene oxide structure.
  • the alkylene group in the alkylene oxide structure may be linear or branched.
  • the unit structure in the polyalkylene oxide structure may be one kind or two or more kinds.
  • a silicon atom in the polysiloxane structure is bonded to a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms.
  • Examples thereof include a divalent group having a polysiloxane structure.
  • Specific examples of the alkyl group having 1 to 20 carbon atoms bonded to the silicon atom in the polysiloxane structure include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group and an n-.
  • Examples thereof include an octyl group, a 2-ethylhexyl group and an n-dodecyl group. Among these, a methyl group is preferable.
  • the aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent. Specific examples of the substituent when the aryl group has a substituent include a halogen atom, an alkoxy group, a hydroxy group and the like. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, a benzyl group and the like.
  • the alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be of one kind or two or more kinds.
  • the silicon atom constituting the divalent group having a polysiloxane structure represented by Y is an NH group in the general formula (6) via an alkylene group such as a methylene group and an ethylene group and an arylene group such as a phenylene group. May be combined with.
  • Y corresponds to a residue derived from a diamine compound
  • specific examples of the diamine compound that is the source of the residue include 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2, 2'-Difluoro-4,4'-diaminobiphenyl, 3,5-diaminobenzoic acid, p-phenylenediamine, m-phenylenediamine, p-xylylene diamine, m-xylylene diamine, 1,5-diaminonaphthalene, Benzidine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone , 3,4'
  • the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in the general formula (6) is not particularly limited. In one embodiment, since the cyclization reaction of the polyimide proceeds at a low temperature, a tetravalent organic group represented by X and a divalent organic group represented by Y in the general formula (6) are exhibited from the viewpoint of low temperature curability.
  • X is a group represented by the general formula (E)
  • C in the general formula (E) is represented by a single bond or an ether bond
  • Y is represented by the general formula (G).
  • a combination of groups in which D in G) is represented by a single bond or an ether bond is preferable.
  • the tetravalent organic group represented by X in the general formula (6) and the divalent represented by Y are represented from the viewpoint of transparency.
  • X is a group represented by the general formula (E)
  • C in the general formula (E) is represented by an ether bond
  • Y is represented by the general formula (G).
  • a combination of groups in which D in G) is represented by an ether bond is preferable.
  • Y may include a group represented by the general formula (F).
  • the general formula (F) occupying Y is used.
  • the proportion of the represented groups is preferably 5 mol% to 30 mol%, more preferably 6 mol% to 15 mol%.
  • the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in the general formula (6) is of X. At least a part thereof is a group represented by the general formula (A), and examples thereof include a combination of any divalent organic group in which Y is arbitrary.
  • X may be a combination of a group represented by the general formula (A) and a group represented by the general formula (E).
  • the ratio of the general formula (A) to X is 10 mol% to 80 mol%. It is preferably 30 mol% to 70 mol%, and more preferably 30 mol% to 70 mol%.
  • the unsaturated polyimide precursor may have a structural unit other than the structural unit represented by the general formula (6).
  • R 6 and R 7 in the general formula (6) are independently hydrogen atoms or aliphatic hydrocarbons having 1 to 4 carbon atoms. Examples thereof include structural units that are groups, that is, structural units in which neither R 6 nor R 7 in the general formula (6) is represented by the general formula (7).
  • the unsaturated polyimide precursor is obtained by reacting a tetracarboxylic acid dianhydride represented by the following general formula (8) with a compound represented by R-OH in an organic solvent such as N-methyl-2-pyrrolidone. It can be obtained by subjecting the diester derivative to a diester derivative and then subjecting the diester derivative to a condensation reaction with a diamine compound represented by H2NY—NH 2 . Further, the unsaturated polyimide precursor is a polyamic by reacting a tetracarboxylic acid dianhydride represented by the following general formula (8) with a diamine compound represented by H2NY—NH 2 in an organic solvent.
  • R in the diamine compound represented by H 2 N Y—NH 2 is the same as Y in the general formula (6), and specific examples and preferred examples are also the same.
  • R in the compound represented by R—OH represents a group represented by the general formula (7) or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and specific examples and preferable examples are the general formula ( This is the same as the case of R 6 and R 7 in 6).
  • the tetracarboxylic acid dianhydride represented by the formula (8), the diamine compound represented by H2NY — NH2 , and the compound represented by R—OH may be used alone. Two or more kinds may be combined. Further, the unsaturated polyimide precursor is obtained by reacting a tetracarboxylic acid dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, and then chlorinating thionyl chloride or the like. It can be obtained by reacting an agent to convert it into an acid chloride, and then reacting the diamine compound represented by H2NY-NH 2 with the acid chloride.
  • the unsaturated polyimide precursor is obtained by reacting a tetracarboxylic acid dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, and then in the presence of a carbodiimide compound. It can be obtained by reacting a diamine compound represented by H2NY — NH2 with a diester derivative. Further, the unsaturated polyimide precursor is obtained by reacting a tetracarboxylic acid dianhydride represented by the following general formula (8) with a diamine compound represented by H2NY—NH 2 to obtain a polyamic acid.
  • X is the same as the X in the general formula (6), and the specific example and the preferable example are also the same.
  • Examples of the compound represented by R-OH used for synthesizing the unsaturated polyimide precursor include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate and the like. Can be mentioned.
  • the molecular weight of the unsaturated polyimide precursor is not particularly limited, but the weight average molecular weight is preferably 10,000 to 200,000.
  • the weight 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 photosensitive resin composition of the present disclosure may contain a polymerizable monomer.
  • the polymerizable monomer may be a compound containing at least one polymerizable unsaturated bond in the molecule, and is preferably a compound containing two or more polymerizable unsaturated bonds in the molecule.
  • Examples of the group containing a polymerizable unsaturated bond include an allyl group, an acryloyloxy group, and a methacryloyloxy group. Among these, acryloyloxy group or methacryloyloxy group is preferable.
  • the molecular weight of the polymerizable monomer is preferably 50 to 1000, more preferably 75 to 800, and even more preferably 100 to 500.
  • a compound containing at least two of an acryloyloxy group and a methacryloyloxy group in the molecule is preferable, and the two acryloyloxy groups or methacryloyloxy groups contained in the molecule are linear 2 It is more preferably a compound linked with a valent organic group, and is a compound represented by the following general formula (4) or the following general formula (5) (hereinafter, may be referred to as a specific polymerizable monomer). Is even more preferable.
  • R 3 independently represents a hydrogen atom or a methyl group
  • R 4 represents an alkylene group having 1 to 8 carbon atoms
  • R 5 represents 1 to 8 carbon atoms. It represents an alkylene group of 8 and p represents an integer of 2-5.
  • the plurality of R3s may be the same or different.
  • the plurality of R5s may be the same or different.
  • a methyl group is preferable.
  • the alkylene group having 1 to 8 carbon atoms represented by R4 in the general formula (4) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, an octamethylene group and the like. ..
  • Specific examples of the alkylene group having 1 to 8 carbon atoms represented by R5 in the general formula ( 5 ) include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a dimethylmethylene group, a tetramethylene group and a hexamethylene group. , Octamethylene group and the like.
  • the p in the general formula (5) is preferably an integer of 3 to 4.
  • Specific examples of the specific polymerizable monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and 1,4-butanediol.
  • Examples thereof include diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, and 1,6-hexanediol dimethacrylate.
  • tetraethylene glycol dimethacrylate is preferable.
  • polymerizable monomer other polymerizable monomers other than the specific polymerizable monomer may be used.
  • specific examples of other polymerizable monomers include trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and pentaerythritol triacrylate.
  • the polymerizable monomer one type may be used alone or two or more types may be used in combination.
  • the content of the polymerizable monomer is not particularly limited, and for example, 1 part by mass to 50 parts by mass is preferable with respect to 100 parts by mass of the unsaturated polyimide precursor. From the viewpoint of improving the hydrophobicity of the cured product, it is more preferably 3 parts by mass to 50 parts by mass, and further preferably 5 parts by mass to 35 parts by mass.
  • the content of the polymerizable monomer is within the above range, a practical relief pattern can be easily obtained, and post-development residue in the unexposed portion can be easily suppressed.
  • the content of the other polymerizable monomer is not particularly limited, and for example, 1 part by mass with respect to 100 parts by mass of the specific polymerizable monomer. It is preferably about 300 parts by mass, more preferably 10 parts by mass to 200 parts by mass, and further preferably 20 parts by mass to 150 parts by mass.
  • the photosensitive resin composition of the present disclosure contains a photopolymerization initiator.
  • a photopolymerization initiator By containing the photopolymerization initiator in the photosensitive resin composition, it is possible to impart photosensitivity to the resin composition containing the unsaturated polyimide precursor and the polymerizable monomer.
  • the photopolymerization initiator is not particularly limited as long as it is a compound capable of generating radicals by irradiation with active light. Examples of the active ray include ultraviolet rays such as i-rays, visible rays, and radiation.
  • photopolymerization initiator examples include benzophenone; N, N'-tetramethyl-4,4'-diaminobenzophenone (Mihiler ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-.
  • the content of the photopolymerization initiator is preferably 0.1 part by mass to 20 parts by mass, more preferably 1 part by mass to 15 parts by mass, and further preferably 5 with respect to 100 parts by mass of the unsaturated polyimide precursor. It is a mass part to 12 parts by mass.
  • the content of the photopolymerization initiator is within the above range, the photocrosslinking tends to be uniform in the film thickness direction, and a practical relief pattern can be easily obtained.
  • the photosensitive resin composition of the present disclosure may contain a coupling agent.
  • the coupling agent preferably contains an unsaturated polyimide precursor, a polyimide resin or a functional group capable of interacting with the substrate.
  • the functional group that the coupling agent may contain include a hydroxy group, a glycidyl group, a phenyl group, a (meth) acrylic group, a carboxy group, and a group having a urea bond.
  • the phenyl group may be substituted with a polar group such as a hydroxy group, a carboxy group or an amine group.
  • the coupling agent is a silane coupling agent
  • the coupling agent contains the above-mentioned functional groups, so that the functional group portion reacts with the unsaturated polyimide precursor and the siloxane portion is with the substrate in the heat treatment after development. react. Thereby, the adhesiveness between the obtained cured product and the substrate can be further improved.
  • the coupling agent are not particularly limited.
  • the coupling agent 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3 -Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) Succinimide, N- [3- (triethoxysilyl) propyl] phthalamide acid, benzophenone-3,3'-bis (N- [3-triethoxysilyl] propylamide) -4,4'-dicarboxylic acid, benzen
  • the coupling agent may be used alone or in combination of two or more.
  • the content of the coupling agent is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the unsaturated polyimide precursor. By mass to 10 parts by mass is more preferable, and 3 parts by mass to 10 parts by mass is even more preferable.
  • the photosensitive resin composition of the present disclosure contains a specific solvent.
  • the total proportion of N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and tetramethylurea in the solvent is preferably 50% by mass or more, preferably 70% by mass. The above is more preferable, and 90% by mass or more is further preferable.
  • the upper limit is not particularly limited and may be 100% by mass.
  • the proportion of N-ethyl-2-pyrrolidone in the solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and more preferably 90% by mass or more. More preferred.
  • the upper limit is not particularly limited and may be 100% by mass.
  • the proportion of 1,3-dimethyl-2-imidazolidinone in the solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more. Is more preferable.
  • the upper limit is not particularly limited and may be 100% by mass.
  • the proportion of tetramethylurea in the solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.
  • the upper limit is not particularly limited and may be 100% by mass.
  • the photosensitive resin composition of the present disclosure may contain other solvents other than N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and tetramethylurea.
  • Other solvents include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, methyl 3-methoxypropionate, N.
  • the solvent preferably contains at least one of NEP and TMU from the viewpoint of improving the viscosity of the photosensitive resin composition and improving the thick film forming property when the content of the unsaturated polyimide precursor is constant. ..
  • the solvent may be used alone or in combination of two or more.
  • the content of the solvent is not particularly limited, but is generally 50 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the unsaturated polyimide precursor.
  • the photosensitive resin composition of the present disclosure may further contain a thermal polymerization initiator from the viewpoint of accelerating the polymerization reaction.
  • a thermal polymerization initiator it does not decompose under the condition of heating and drying to remove the solvent during film formation, but decomposes by heating during curing to generate radicals, and polymerizable monomers or unsaturated polyimides are used. Compounds that promote the polymerization reaction of the precursor and the polymerizable monomer are preferable.
  • the thermal polymerization initiator 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.
  • thermal polymerization initiator examples include ketone peroxides such as methyl ethyl ketone peroxide, 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, and 1,1-di (t-hexylperoxy).
  • Cyclohexane, peroxyketal such as 1,1-di (t-butylperoxy) cyclohexane, 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, p-menthanehydroperoxide, Hydroperoxides such as diisopropylbenzene hydroperoxides, dicumyl peroxides, dialkyl peroxides such as di-t-butyl peroxides, diacyl peroxides such as dilauroyl peroxides and dibenzoyl peroxides, di (4-t-butylcyclohexyl) peroxydicarbonates, Peroxydicarbonates such as di (2-ethylhexyl) peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzo
  • the content of the thermal polymerization initiator is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the unsaturated polyimide precursor.
  • 0.2 parts by mass to 20 parts by mass is more preferable, and from the viewpoint of suppressing deterioration of solubility due to decomposition during drying, 0.3 parts by mass to 10 parts by mass is further preferable.
  • the photosensitive resin composition of the present disclosure may contain a sensitizer. Since the photosensitive resin composition contains a sensitizer, it is possible to achieve both maintenance of the residual film ratio and good resolution in a wide range of exposure amounts.
  • sensitizer examples include Michler's ketone, benzoin, 2-methylbenzoin, benzoinmethyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butyl anthraquinone, 1,2-benzo-9,10-anthraquinone and anthraquinone.
  • Methylanthraquinone 4,4'-bis- (diethylamino) benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaften, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl- [4- (Methylthio) phenyl] -2-morpholino-1-propanone, diacetylbenzyl, benzyldimethylketal, benzyldiethylketal, diphenyldisulfide, anthracene, phenanthrenequinone, riboflavintetrabutyrate, acridin orange, erythrosin, phenance Renquinone, 2-isopropylthioxanthone, 2,6-bis (p-diethylaminobenziliden) -4-methyl-4-azacyclohexanone, 6-bis (p-(p
  • the sensitizer may be used alone or in combination of two or more.
  • the blending amount of the sensitizer is preferably 0.1 part by mass to 1.0 part by mass with respect to 100 parts by mass of the unsaturated polyimide precursor. , 0.2 part by mass to 0.8 part by mass is more preferable.
  • the photosensitive resin composition of the present disclosure may contain a stabilizer.
  • the stabilizer include a radical scavenger and the like.
  • the stability after standing can be improved.
  • Stabilizers include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cuperone. , 2,5-Tulquinone, tannic acid, parabenzylaminophenol, nitrosoamines and the like.
  • the stabilizer may be used alone or in combination of two or more.
  • the content of the stabilizer is preferably 0.05 part by mass to 1.0 part by mass with respect to 100 parts by mass of the unsaturated polyimide precursor, and is 0. .1 part by mass to 0.8 part by mass is more preferable.
  • the photosensitive resin composition of the present disclosure may contain at least one of a surfactant and a leveling agent.
  • a surfactant and a leveling agent By containing at least one of the surfactant and the leveling agent in the photosensitive resin composition, the developability can be improved, and further, the unevenness of the film thickness such as striation can be suppressed to improve the coatability. Can be done.
  • surfactant or leveling agent examples include polyoxyethylene uralyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether and the like.
  • the surfactant and the leveling agent may be used alone or in combination of two or more.
  • the total content of the surfactant and the leveling agent is 0.01 with respect to 100 parts by mass of the unsaturated polyimide precursor. It is preferably from 10 parts by mass to 10 parts by mass, more preferably 0.05 part by mass to 5 parts by mass, and even more preferably 0.05 part by mass to 3 parts by mass.
  • the photosensitive resin composition of the present disclosure may contain a rust preventive. Since the photosensitive resin composition contains a rust preventive, it is possible to suppress corrosion and prevent discoloration of copper and copper alloys.
  • the rust preventive include a triazole derivative such as benzotriazole and a tetrazole derivative.
  • the rust inhibitor may be used alone or in combination of two or more.
  • the content of the rust preventive agent is preferably 0.01 part by mass to 10 parts by mass with respect to 100 parts by mass of the unsaturated polyimide precursor. 1 part by mass to 5 parts by mass is more preferable, and 0.5 part by mass to 3 parts by mass is further preferable.
  • the photosensitive resin composition of the present disclosure includes an unsaturated polyimide precursor, a photopolymerization initiator and a solvent, and optional components such as a polymerizable monomer, a coupling agent, a thermal polymerization initiator, a sensitizer, a stabilizer, and a surfactant. It may contain an activator, a leveling agent, and a rust preventive, and may contain other components and unavoidable impurities as long as the effects of the present disclosure 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 disclosure.
  • the cured product of the present disclosure can be obtained by curing the photosensitive resin composition of the present disclosure.
  • the cured product of the present disclosure may be a patterned cured product having a predetermined pattern, or may be a cured product having no pattern.
  • the average thickness of the cured product of the present disclosure is preferably 5 ⁇ m to 20 ⁇ m.
  • the method for producing a cured pattern of the present disclosure includes a step of applying the photosensitive resin composition of the present disclosure on a substrate and drying it to form a photosensitive resin film, and a pattern exposure of the photosensitive resin film to make a resin.
  • the process includes a step of obtaining a film, a step of developing the resin film after pattern exposure with a developer to obtain a pattern resin film, and a step of heat-treating the pattern resin film. Thereby, a pattern cured product can be obtained.
  • the method for producing a cured product without a pattern includes, for example, a step of forming the photosensitive resin film of the present disclosure and a step of heat treatment. Further, a step of exposing may be provided.
  • the substrate examples include a glass substrate, a semiconductor substrate such as 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.
  • a semiconductor substrate such as a Si substrate (silicon wafer)
  • a metal oxide insulator substrate such as a TiO 2 substrate and a SiO 2 substrate
  • silicon nitride substrate silicon nitride substrate
  • copper substrate examples include a copper alloy substrate.
  • the method for applying the photosensitive resin composition of the present disclosure is not particularly limited, and can be applied using a spinner or the like.
  • Drying can be performed using a hot plate, an oven, or the like.
  • the drying temperature is preferably 80 ° C. to 150 ° C., and more preferably 90 ° C. to 135 ° C. from the viewpoint of ensuring the dissolution contrast.
  • the drying time is preferably 30 seconds to 5 minutes. Drying may be performed twice or more. When drying twice or more, it is preferable that the drying time per time is within the above range. When drying twice or more, the drying times may be the same or different. Further, the drying temperature may be the same or different. Thereby, a photosensitive resin film obtained by forming the photosensitive resin composition of the present disclosure in the form of a film can be obtained.
  • the average thickness of the photosensitive resin film is preferably 3 ⁇ m to 30 ⁇ m, more preferably 5 ⁇ m to 20 ⁇ m, and even more preferably 5 ⁇ m to 15 ⁇ m.
  • the pattern exposure exposes a predetermined pattern through, for example, a photomask.
  • the activated light beam to be irradiated include ultraviolet rays such as i-rays, visible rays, and radiation, but i-rays are preferable.
  • a parallel exposure machine, an aligner, a projection exposure machine, a stepper, a scanner exposure machine and the like can be used.
  • a patterned resin film (patterned resin film) can be obtained.
  • a good solvent of the photosensitive resin film can be used alone, or a good solvent and a poor solvent can be appropriately mixed and used.
  • Good solvents 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, water and the like.
  • a surfactant may be added to the developer.
  • the amount to be added is preferably 0.01 part by mass to 10 parts by mass, more preferably 0.1 part by mass to 5 parts by mass with respect to 100 parts by mass of the developer.
  • the development time can be, for example, twice the time required for the photosensitive resin film to be immersed and completely dissolved.
  • the development time varies depending on the unsaturated polyimide precursor used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and even more preferably 20 seconds to 5 minutes from the viewpoint of productivity.
  • a rinsing solution distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and the like may be used alone or in an appropriate mixture, or may be used in a stepwise combination. good.
  • a cured pattern can be obtained by heat-treating the pattern resin film.
  • the unsaturated polyimide precursor undergoes a dehydration ring closure reaction in the heat treatment step to become the corresponding polyimide resin.
  • the temperature of the heat treatment is preferably 380 ° C. or lower, more preferably 250 ° C. to 350 ° C., and even more preferably 270 ° C. to 320 ° C.
  • the temperature of the heat treatment is within the above range, damage to the substrate or the device can be suppressed to a small extent, the device can be produced at a high yield, and energy saving of the process can be realized.
  • the heat treatment time is preferably 5 hours or less, more preferably 30 minutes to 3 hours. When the heat treatment time is within the above range, the crosslinking reaction or the dehydration ring closure reaction can be sufficiently proceeded.
  • the atmosphere of the heat treatment may be in the atmosphere or in an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferable from the viewpoint of preventing oxidation of the pattern resin film.
  • Examples of the device used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace, and the like.
  • the cured product of the present disclosure can be used as an interlayer insulating film, a cover coat layer or a surface protective film. Furthermore, the cured product of the present disclosure can be used as a passivation film, a buffer coat film, or the like. Highly reliable semiconductor devices, multilayer wiring boards, various electronic devices, and multis using one or more selected from the group consisting of the passivation film, buffer coat film, interlayer insulating film, cover coat layer, surface protective film, and the like. It is possible to manufacture electronic components such as laminated devices such as die fan out wafer level packages.
  • FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure, which is an electronic component according to an embodiment of the present disclosure.
  • a semiconductor substrate 1 such as a Si substrate having a circuit element is covered with a protective film 2 such as a silicon oxide film except for a predetermined portion of the circuit element, and a first conductor layer 3 is formed on the exposed circuit element. It is formed. After that, the interlayer insulating film 4 is formed on the semiconductor substrate 1.
  • a photosensitive resin layer 5 such as a rubber chloride type or a phenol novolac type is formed on the interlayer insulating film 4, and the window 6A is provided so that the interlayer insulating film 4 in a predetermined portion is exposed by a known photographic etching technique. It will be provided.
  • the interlayer insulating film 4 in which the window 6A is exposed is selectively etched to provide the window 6B.
  • the photosensitive resin layer 5 is removed by using an etching solution that corrodes the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed from the window 6B.
  • the second conductor layer 7 is formed and electrically connected to the first conductor layer 3.
  • the above steps can be repeated to form each layer.
  • the window 6C is opened by pattern exposure to form the surface protective film 8.
  • the surface protective film 8 protects the second conductor layer 7 from external stress, ⁇ rays, and the like, and the obtained semiconductor device is excellent in reliability.
  • the interlayer insulating film 4 can also be formed by using the photosensitive resin composition of the present disclosure.
  • -Solvent 1 NMP -Solvent 2: NEP -Solvent 3: DMI -Solvent 4: TMU -Polymerizable monomer: Tetraethylene glycol dimethacrylate-Photopolymerization initiator: 1-Phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime (PDO, Rambson) ⁇ Rust inhibitor: Benzotriazole (BTA) -Unsaturated polyimide precursor A1 synthesized by the following method
  • Measuring device Detector L4000UV manufactured by Hitachi, Ltd. Pump: L6000 manufactured by Hitachi, Ltd.
  • solubility The solubility of the unsaturated polyimide precursor A1 in a specific solvent was evaluated by the following method. NMP was also evaluated for comparison with a specific solvent. 10 g of unsaturated polyimide precursor A1 was put into a predetermined amount of solvent and stirred at 23 ° C. After 30 minutes from the start of stirring, it was visually confirmed whether or not the unsaturated polyimide precursor A1 was dissolved. The above operation was repeated while increasing the amount of solvent by 0.5 g to determine the minimum amount of solvent required to dissolve the unsaturated polyimide precursor A1. The results obtained are shown in Table 1. At the same time, the viscosity of the solution at 25 ° C.
  • Film thickness uniformity [%] (maximum film thickness at 41 points after coating-minimum film thickness at 41 points after coating) / average film thickness at 41 points x 100 Criteria for selecting measurement points: 41 points set concentrically from the entire remaining area except for the area 10 mm from the outer peripheral edge of the wafer were set as measurement points. The average film thickness was the average value of each film thickness measured at 41 measurement points.
  • the unsaturated polyimide precursor A1 exhibits the same solubility as NMP in a specific solvent. Further, when a specific solvent was used instead of NMP, the film thickness uniformity was improved.
  • the high-viscosity coating liquid is excellent in thick film forming property.
  • the high viscosity of the coating liquid adjusted with the minimum required amount of solvent indicates that a thicker film can be formed during film formation. Thin film formation can be achieved by adding a solvent to reduce the viscosity of the coating liquid. It can be said that the high viscosity of the coating liquid is excellent as a "material having a wide film thickness film forming margin".
  • this method of increasing the viscosity by a special combination of the solvent and the unsaturated polyimide precursor is applied using an additive such as a thickener.
  • additives are less likely to remain in the polyimide film, and there is an advantage that the characteristics of the polyimide film are not impaired. If the spin coating for film formation can be performed at high rotation speed, it is possible to improve the film thickness uniformity, but if the viscosity of the coating liquid is low, it is at least necessary when the spin coating is performed at high rotation speed. It may be difficult to secure the film thickness of the coating film.
  • the viscosity of the coating liquid is improved, so that the film thickness is less likely to be thinned even when the spin coating is performed at high rotation speed. Therefore, it is possible to perform spin coating at high rotation speed when forming a film, and it is presumed that the film thickness uniformity is improved.
  • composition characteristics The characteristics of the photosensitive resin composition were evaluated as follows.
  • the photosensitive resin composition was obtained by blending each component shown in Table 2 in the blending amount shown in Table 2.
  • the blending amount of each component in Table 2 is based on parts by mass.
  • the obtained photosensitive resin composition was spin-coated on a 6-inch silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Co., Ltd.), dried at 90 ° C. for 200 seconds, and then dried at 100 ° C. for 200 seconds (pre-baking). ) To form a photosensitive resin film having a dry film thickness of 15 ⁇ m.
  • the rotation time was fixed at 30 seconds, and the rotation speed was adjusted so that the dry film thickness was 15 ⁇ m. In this evaluation, the range was 2000 rpm to 2500 rpm.
  • a photosensitive resin film was prepared in the same manner as above, and the i-line stepper FPA-3000iW (manufactured by Canon Inc.) was applied to the entire surface of the obtained photosensitive resin film. It was exposed by irradiating with i-line of 700 mJ / cm 2 .
  • the photosensitive resin film after exposure was paddle-developed with cyclopentanone using Act8 for the above-mentioned development time, and then rinse-washed with propylene glycol monomethyl ether acetate (PGMEA).
  • the dissolution rate (DR2) of the exposed portion was calculated using the following formula.
  • DR2 (Thickness after prebaking-Thickness after development) / Development time
  • Dissolution rate of the unexposed part of the photosensitive resin film obtained as described above The dissolution rate of DR1 and the exposed part of the photosensitive resin film
  • the dissolution contrast (DR1 / DR2) was calculated based on DR2. The results obtained are shown in Table 2.
  • the obtained photosensitive resin composition was spin-coated on a 6-inch silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Co., Ltd.), dried at 90 ° C. for 200 seconds, and then dried at 100 ° C. for 200 seconds (pre-baking). ) To form a photosensitive resin film having a dry film thickness of 15 ⁇ m.
  • the rotation time was fixed at 30 seconds, and the rotation speed was adjusted so that the dry film thickness was 15 ⁇ m. In this evaluation, the range was 2000 rpm to 2500 rpm.
  • the obtained photosensitive resin film was immersed in cyclopentanone, and twice the time until the photosensitive resin film was completely dissolved was set as the development time. Further, a photosensitive resin film was prepared in the same manner as described above, and an i-line stepper FPA-3000iW (manufactured by Canon Inc.) was used on the obtained photosensitive resin film to obtain i of 100 mJ / cm 2 to 1100 mJ / cm 2 . The line was irradiated to a predetermined pattern with an exposure amount of 100 mJ / cm in 2 increments to perform exposure.
  • FPA-3000iW manufactured by Canon Inc.
  • the photosensitive resin film after exposure was paddle-developed with cyclopentanone using Act8 for the above-mentioned development time, and then rinse-washed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a predetermined pattern resin film. ..
  • the obtained photosensitive resin composition was spin-coated on a 6-inch silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Co., Ltd.), dried at 90 ° C. for 200 seconds, and then dried at 100 ° C. for 200 seconds (pre-baking). ) To form a photosensitive resin film having a dry film thickness of 15 ⁇ m.
  • the rotation time was fixed at 30 seconds, and the rotation speed was adjusted so that the dry film thickness was 15 ⁇ m. In this evaluation, the range was 2000 rpm to 2500 rpm.
  • the obtained photosensitive resin film was immersed in cyclopentanone, and twice the time until the photosensitive resin film was completely dissolved was set as the development time.
  • a photosensitive resin film was prepared in the same manner as described above, and an i-line stepper FPA-3000iW (manufactured by Canon Inc.) was used on the obtained photosensitive resin film to generate an i-line of 700 mJ / cm 2 (Example 3). Then, 800 mJ / cm 2 ) was applied to the photosensitive resin film via a photomask.
  • the photosensitive resin film after exposure was paddle-developed with cyclopentanone using Act8 for the above-mentioned development time, and then rinse-washed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a predetermined pattern resin film. ..
  • the predetermined pattern was a hole pattern and a line-and-space pattern having a line width ratio of 1: 1.
  • the diameter of the smallest hole that could be patterned without peeling and residue and the line width of the line were taken as the resolution and evaluated according to the following criteria.
  • “resolution (L / S)” indicates the resolution of the line-and-space pattern
  • “resolution (hole)” indicates the resolution of the hole pattern.
  • B The diameter of the smallest hole and the line width of the line were both in the range of more than 20 ⁇ m and 50 ⁇ m or less.
  • C The diameter of the smallest hole and the line width of the line were both in the range exceeding 50 ⁇ m.
  • the photosensitive resin composition containing the specific solvent exhibits the same or better photosensitive characteristics as the photosensitive resin composition containing NMP.

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