Classifications

• • 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
• • 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
  • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

• This disclosure relates to a photosensitive resin composition, a patterned cured product, a method for producing the patterned cured product, and an electronic component.
• an object of one embodiment of the present disclosure is to provide a photosensitive resin composition capable of achieving high resolution, a patterned cured product using the photosensitive resin composition, a method for producing the patterned cured product, and an electronic component.
• a photosensitive resin composition comprising a polyimide precursor having a polymerizable unsaturated bond, a tri- or higher functional polymerizable monomer, and a photopolymerization initiator, the photosensitive resin composition being heated at 100° C. for 120 seconds and then at 110° C. for 120 seconds to form a 7 ⁇ m-thick photosensitive resin film having an i-line transmittance of 30% or less.
• the photosensitive resin composition according to ⁇ 1> wherein the polyimide precursor having a polymerizable unsaturated bond has a structural unit represented by the following general formula (1): (In general formula (1), X represents a tetravalent organic group, and Y represents a divalent organic group. R6 and R7 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R6 and R7 has a polymerizable unsaturated bond.) ⁇ 3> The photosensitive resin composition according to ⁇ 1> or ⁇ 2>, further comprising at least one selected from the group consisting of a sensitizer and an ultraviolet absorber.
• ⁇ 4> The photosensitive resin composition according to ⁇ 1> or ⁇ 2>, wherein the photopolymerization initiator contains an oxime compound.
• ⁇ 5> A step of applying the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 4> onto a substrate and drying the composition to form a photosensitive resin film; a step of exposing the photosensitive resin film to a pattern to obtain a resin film; developing the resin film after the patterned exposure with a developer to obtain a patterned resin film; and heat-treating the patterned resin film.
• ⁇ 6> A patterned cured product obtained by curing the photosensitive resin composition according to any one of ⁇ 1> to ⁇ 4>.
• ⁇ 7> The patterned cured product according to ⁇ 6>, which is used as an interlayer insulating film, a cover coat layer, or a surface protective film.
• ⁇ 8> An electronic part comprising the patterned cured product according to ⁇ 6> or ⁇ 7>.
• a photosensitive resin composition capable of achieving high resolution, as well as a patterned cured product using this photosensitive resin composition, a method for producing the patterned cured product, and an electronic component.
• FIGS. 1A to 1C are diagrams illustrating a manufacturing process for an electronic component according to an embodiment of the present disclosure.
• 1A is a cross-sectional FIB-SEM photograph of a via pattern formed using the photosensitive resin composition of Example 1
• FIG. 1B is a cross-sectional SEM photograph of a via pattern formed using the photosensitive resin composition of Comparative Example 1.
• the term "step” includes not only a step that is independent of other steps, but also a step that cannot be clearly distinguished from other steps as long as the purpose of the step is achieved.
• the numerical ranges indicated using “to” include the numerical values before and after "to” as the minimum and maximum values, respectively.
• the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages.
• the upper or lower limit value of the numerical range may be replaced with a value shown in the examples.
• each component may contain multiple types of corresponding substances.
• the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified.
• the terms “layer” and “film” include cases where the layer or film is formed over the entire area when the area in which the layer or film is present is observed, as well as cases where the layer or film is formed over only a portion of the area.
• a "(meth)acryloyl group” means at least one of an acryloyl group and a methacryloyl group
• a “(meth)acryloyloxy group” means at least one of an acryloyloxy group and a methacryloyloxy group.
• the average thickness of a layer or film is defined as the arithmetic mean value of thicknesses measured at five points on the layer or film of interest.
• the thickness of the layer or film can be measured using a micrometer, a scanning stylus meter, an optical interference film thickness measuring device, etc.
• the thickness of the layer or film can be measured directly, it is measured using an optical interference film thickness measuring device.
• the thickness of one layer or the total thickness of multiple layers it may be measured by observing the cross section of the measurement target using an electron microscope.
• the photosensitive resin composition of the present disclosure is a photosensitive resin composition containing a polyimide precursor having a polymerizable unsaturated bond and a tri- or higher functional polymerizable monomer, and the i-line transmittance of a 7 ⁇ m-thick photosensitive resin film obtained by heating the photosensitive resin composition at 100° C. for 120 seconds and then at 110° C. for 120 seconds is 30% or less.
• the "polyimide precursor having a polymerizable unsaturated bond” is also referred to as the "unsaturated polyimide precursor”
• the "tri- or higher functional polymerizable monomer” is also referred to as the "specific polymerizable monomer”.
• the photosensitive resin composition having the above-mentioned constitution, it is possible to achieve high resolution.
• bifunctional monomers are used as polymerizable monomers.
• they become linear polymers, and the crosslink density of the cured film is low. Therefore, the pattern obtained by developing the cured film swells in the developer, making it difficult to obtain a high-resolution pattern.
• trifunctional or higher polymerizable monomers are highly reactive, and react with a small amount of radicals generated from a photopolymerization initiator by light reflected from the substrate to the unexposed area, resulting in a pattern shape different from that expected.
• a cured product is formed at the bottom of the pattern, or a bridge-like cured product (so-called microbridge) is formed above the bottom in the thickness direction, which tends to cause noticeable defects in the pattern shape.
• the use of tri- or higher functional monomers increases the crosslink density, suppressing swelling in the developer, while reducing the amount of i-rays that reach the substrate, suppressing light reflected from the substrate to the unexposed areas and suppressing polymerization reactions in the unexposed areas, presumably resulting in high resolution.
• the photosensitive resin composition of the present disclosure is heated at 100° C. for 120 seconds and then at 110° C. for 120 seconds to obtain a 7 ⁇ m-thick photosensitive resin film (hereinafter referred to as the "photosensitive resin film"), which has an i-line transmittance of 30% or less, preferably 25% or less, more preferably 20% or less, and even more preferably 18% or less.
• the i-line transmittance of the photosensitive resin film is preferably 5% or more, and more preferably 10% or more.
• the i-line transmittance is measured in accordance with the method described in the Examples.
• the i-line transmittance of a photosensitive resin film can be adjusted by adding ultraviolet absorbers, sensitizers, and compounds with i-line absorption ability and adjusting the amount added, selecting the type of photopolymerization initiator, unsaturated polyimide precursor, etc., and adjusting the amount added. For example, if a rust inhibitor has i-line absorption ability, the rust inhibitor corresponds to a compound with i-line absorption ability.
• the photosensitive resin composition of the present disclosure is preferably a negative type photosensitive resin composition.
• 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").
• the polymerizable unsaturated bond may be a carbon-carbon double bond.
• the unsaturated polyimide precursor may be synthesized using a tetracarboxylic dianhydride and a diamine compound.
• the unsaturated polyimide precursor may be synthesized using a tetracarboxylic acid instead of a tetracarboxylic dianhydride.
• the unsaturated polyimide precursor preferably has a structural unit represented by the following general formula (1):
• X represents a tetravalent organic group
• Y represents a divalent organic group
• R6 and R7 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R6 and R7 has a polymerizable unsaturated bond.
• the unsaturated polyimide precursor may have a plurality of structural units represented by the above general formula (1), and X, Y, R6 and R7 in the plurality of structural units may be the same or different.
• R 6 and R 7 are each independently a hydrogen atom or a monovalent organic group, the combination is not particularly limited.
• at least one of R 6 and R 7 may be a hydrogen atom, and the remaining may be a monovalent organic group described below, or they may be the same or different monovalent organic groups.
• the combination of R 6 and R 7 of each structural unit may be the same or different.
• the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 5 to 13 carbon atoms, and even more preferably 6 to 12 carbon atoms.
• the tetravalent organic group represented by X may contain an aromatic ring.
• the aromatic ring include aromatic hydrocarbon groups (e.g., aromatic rings having 6 to 20 carbon atoms) and aromatic heterocyclic groups (e.g., heterocyclic rings having 5 to 20 atoms).
• the tetravalent organic group represented by X is preferably an aromatic hydrocarbon group. Examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, and a phenanthrene ring.
• each aromatic ring may have a substituent or may be unsubstituted.
• substituent of the aromatic ring include an alkyl group, a fluorine atom, a halogenated alkyl group, a hydroxyl group, and an amino group.
• the tetravalent organic group represented by X when 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, more preferably contains 1 to 3 benzene rings, and even more preferably contains 1 or 2 benzene rings.
• the benzene rings may be linked by a single bond, or may be linked by a linking group such as an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a silylene bond (-Si(R A ) 2 -; each of the two R A 's independently represents a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O-(Si(R B ) 2 -O-) n ; each of the two R B 's 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 composite linking group formed by combining at least two of these linking groups.
• the two R B 's independently represents a hydrogen atom, an alkyl group, or a phen
• the --COOR 6 group and the --CONH-- group are preferably located at the ortho position relative to each other, and the --COOR 7 group and the --CO-- group are preferably located at the ortho position relative to each other.
• tetravalent organic group represented by X include groups represented by the following formulae (A) to (F).
• a group represented by the following formula (E) is preferred, and in the following formula (E), C is more preferably a group containing an ether bond, and even more preferably an ether bond.
• the following formula (F) is a structure in which C in the following formula (E) is a single bond. It should be noted that the present disclosure is not limited to the following specific examples.
• a and B are each independently a single bond or a divalent group not conjugated with a benzene ring. However, A and B cannot both be single bonds.
• the divalent group not conjugated with a benzene ring include a methylene group, a halogenated methylene group, a halogenated methylmethylene group, a carbonyl group, a sulfonyl group, an ether bond (-O-), a sulfide bond (-S-), a silylene bond (-Si(R A ) 2 -; each of the two R A 's independently represents a hydrogen atom, an alkyl group, or a phenyl group).
• a and B are each independently preferably a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a sulfide bond, or the like, and more preferably an ether bond.
• C preferably contains an ether bond, and is preferably an ether bond.
• the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 12 to 18 carbon atoms.
• the skeleton of the divalent organic group represented by Y may be the same as the skeleton of the tetravalent organic group represented by X, and a preferred skeleton of the divalent organic group represented by Y may be the same as the preferred skeleton of the tetravalent organic group represented by X.
• the skeleton of the divalent organic group represented by Y may be a structure in which two bonding positions of the tetravalent organic group represented by X are substituted with atoms (e.g., hydrogen atoms) or functional groups (e.g., alkyl groups).
• 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 examples include a divalent aromatic hydrocarbon group (e.g., an aromatic ring having 6 to 20 carbon atoms) and a divalent aromatic heterocyclic group (e.g., a heterocyclic ring having 5 to 20 atoms), and the like, with a divalent aromatic hydrocarbon group being preferred.
• a divalent aromatic hydrocarbon group e.g., an aromatic ring having 6 to 20 carbon atoms
• a divalent aromatic heterocyclic group e.g., a heterocyclic ring having 5 to 20 atoms
• divalent aromatic group represented by Y include groups represented by the following formulae (G) and (H).
• the group represented by the following formula (H) is preferred, and among these, in the following formula (H), D is more preferably a group containing a single bond or an ether bond, even more preferably a group containing a single bond or an ether bond, particularly preferably a group containing an ether bond, and extremely preferably an ether bond.
• R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom
• n each independently represents an integer of 0 to 4.
• D may also be a structure represented by formula (C1) above.
• Specific examples of D in formula (H) are the same as the specific examples of C in formula (E). It is preferable that each D in formula (H) independently represents a single bond, an ether bond, a group containing an ether bond and a phenylene group, a group containing an ether bond, a phenylene group and an alkylene group, or the like.
• the alkyl group represented by R in formulas (G) to (H) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms.
• Specific examples of the alkyl group represented by R in formulae (G) to (H) 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, and a t-butyl group.
• the alkoxy group represented by R in formulas (G) to (H) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and even more preferably an alkoxy group having 1 or 2 carbon atoms.
• Specific examples of the alkoxy group represented by R in formulae (G) to (H) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, an s-butoxy group, and a t-butoxy group.
• the halogenated alkyl group represented by R in Formulae (G) to (H) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, more preferably a halogenated alkyl group having 1 to 3 carbon atoms, and even more preferably a halogenated alkyl group having 1 or 2 carbon atoms.
• Specific examples of the halogenated alkyl group represented by R in formulas (G) to (H) include alkyl groups in which at least one hydrogen atom contained in the alkyl group represented by R in formulas (G) to (H) is substituted with a halogen atom such as a fluorine atom or a chlorine atom.
• a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, etc. are preferred.
• n is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.
• divalent aliphatic group represented by Y include linear or branched alkylene groups, cycloalkylene groups, and divalent groups having a polyalkylene oxide structure.
• the linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and even more preferably an alkylene group having 1 to 10 carbon atoms.
• alkylene group represented by Y examples 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, a 2-methylpentamethylene group, a 2-methylhexamethylene group, a 2-methylheptamethylene group, a 2-methyloctamethylene group, a 2-methylnonamethylene group, and a 2-methyldecamethylene group.
• the cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, and more preferably a cycloalkylene group having 3 to 6 carbon atoms.
• Specific examples of the cycloalkylene group represented by Y include a cyclopropylene group, a cyclohexylene group, and the like.
• the unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and even more preferably an alkylene oxide structure having 1 to 4 carbon atoms.
• the polyalkylene oxide structure is preferably a polyethylene oxide structure or a polypropylene 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 type or two or more types.
• the divalent organic group represented by Y may be a divalent group having a polysiloxane structure.
• Examples of the divalent group having a polysiloxane structure represented by Y include divalent groups having a polysiloxane structure in which 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.
• alkyl group having 1 to 20 carbon atoms bonded to a 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, an n-octyl group, a 2-ethylhexyl group, an n-dodecyl group, etc.
• 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.
• substituent when the aryl group has a substituent include a halogen atom, an alkoxy group, and a hydroxy group.
• aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, and a benzyl group. Of these, a phenyl group is preferred.
• 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 type or of two or more types.
• the silicon atom constituting the divalent group having a polysiloxane structure represented by Y may be bonded to the NH group in general formula (1) via an alkylene group such as a methylene group or an ethylene group, or an arylene group such as a phenylene group.
• the group represented by formula (G) is preferably a group represented by the following formula (G'), and the group represented by formula (H) is preferably a group represented by the following formula (H'), formula (H") or formula (H'"), and from the viewpoint of having a flexible skeleton and excellent bonding properties, a group represented by the following formula (H') or formula (H") is more preferable.
• each R independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, or a halogen atom.
• R is preferably an alkyl group, and more preferably a methyl group.
• the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y is not particularly limited.
• Examples of the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y include the following.
• a combination in which X is a group represented by formula (E) and Y is a group represented by formulas (G) and (H).
• the combination in which X is a group represented by formula (E) and Y is a group represented by formula (H) is preferred.
• R 6 and R 7 each independently represent a hydrogen atom or a monovalent organic group, with the proviso that at least one of them has a polymerizable unsaturated bond.
• the monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, more preferably any one of a group represented by the following general formula (2), an ethyl group, an isobutyl group, or a t-butyl group, and further preferably contains an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2).
• at least one of R 6 and R 7 is a group represented by general formula (2).
• the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), at least a part of the unsaturated double bond moiety is eliminated by the compound (C).
• aliphatic hydrocarbon groups having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, and t-butyl groups, with ethyl, isobutyl, and t-butyl groups being preferred.
• R 8 to R 10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R x represents a divalent linking group.
• the carbon number of the aliphatic hydrocarbon group represented by R 8 to R 10 in general formula (2) is 1 to 3, and preferably 1 or 2.
• 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, etc., and a methyl group is preferred.
• R 8 to R 10 in the general formula (2) a combination in which R 8 and R 9 are hydrogen atoms and R 10 is a hydrogen atom or a methyl group is preferred.
• R x is a divalent linking group, and is preferably a hydrocarbon group having 1 to 10 carbon atoms.
• the hydrocarbon group having 1 to 10 carbon atoms include linear or branched alkylene groups.
• the number of carbon atoms in R x is preferably 1 to 10, more preferably 2 to 5, and further preferably 2 or 3.
• R6 and R7 are a group represented by general formula (2), and it is more preferable that both of R6 and R7 are groups represented by general formula (2).
• the ratio of R6 and R7 which are groups represented by general formula (2), to the sum of R6 and R7 of all structural units contained in the compound is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more.
• the upper limit is not particularly limited, and may be 100 mol%.
• the above ratio may be 0 mol % or more and less than 60 mol %.
• the group represented by general formula (2) is preferably a group represented by the following general formula (2'):
• R 8 to R 10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms; q represents an integer of 1 to 10.
• q is an integer from 1 to 10, preferably an integer from 2 to 5, and more preferably 2 or 3.
• the content of the structural unit represented by general formula (1) contained in the compound having the structural unit represented by general formula (1) is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more, based on the total structural units.
• the upper limit of the aforementioned content is not particularly limited, and may be 100 mol%.
• the unsaturated polyimide precursor may be synthesized using a tetracarboxylic dianhydride and a diamine compound.
• X corresponds to a residue derived from the tetracarboxylic dianhydride
• Y corresponds to a residue derived from the diamine compound.
• the unsaturated polyimide precursor may be synthesized using a tetracarboxylic acid instead of the tetracarboxylic dianhydride.
• tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, and 1,4,5,8-naphthalenetetracarboxylic dianhydride.
• dianhydride 3,4,9,10-perylenetetracarboxylic dianhydride, m-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3',4,4'-tetracarboxylic dianhydride, 1,1,4,4'-(4,4'-isopropylidenediphenoxy)diphthalic anhydride, 4,4'-oxydiphthalic anhydride, 1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hexafluoro-2,2- Bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxy
• At least one selected from the group consisting of 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, pyromellitic dianhydride, 4,4'-oxydiphthalic anhydride, and 3,3',4,4'-biphenyl tetracarboxylic dianhydride is preferable, at least one selected from the group consisting of pyromellitic dianhydride and 4,4'-oxydiphthalic anhydride is more preferable, and from the viewpoint of bonding at lower temperatures, it is even more preferable to include 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride.
• the tetracarboxylic dianhydrides may be used alone or in combination of two or more kinds.
• diamine compound examples include 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 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'-diaminodiphenyl sulfone, 3,4'
• diamine compound 2,2'-dimethylbiphenyl-4,4'-diamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 1,3-bis(3-aminophenoxy)benzene are preferred.
• At least one selected from the group consisting of 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenyl ether, m-phenylenediamine, and 1,3-bis(3-aminophenoxy)benzene is more preferable, and from the viewpoint of having a flexible skeleton and excellent adhesiveness, at least one selected from the group consisting of 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, and 2,2-bis ⁇ 4-(4'-aminophenoxy)phenyl ⁇ propane is even more preferable.
• the diamine compounds may be used alone or in combination of two or more kinds.
• a compound having a structural unit represented by general formula (1) in which at least one of R6 and R7 in general formula (1) is a monovalent organic group can be obtained, for example, by the following method (a) or (b).
• a tetracarboxylic dianhydride preferably a tetracarboxylic dianhydride represented by the following general formula (8)
• R-OH a compound represented by R-OH
• diester derivative is subjected to a condensation reaction with a diamine compound represented by H 2 N-Y-NH 2 .
• a tetracarboxylic dianhydride is reacted with a diamine compound represented by H 2 N-Y-NH 2 in an organic solvent to obtain a polyamic acid solution, and a compound represented by R-OH is added to the polyamic acid solution and reacted in the organic solvent to introduce an ester group.
• At least one of R 6 and R 7 in the general formula (1) has a polymerizable unsaturated bond
• at least one of R—OH in which R has a polymerizable unsaturated bond is used.
• Y in the diamine compound represented by H 2 N-Y-NH 2 is the same as Y in general formula (1), and specific examples and preferred examples are also the same.
• R in the compound represented by R-OH represents a monovalent organic group, and specific examples and preferred examples are the same as R 6 and R 7 in general formula (1).
• the tetracarboxylic dianhydride represented by the general formula (8), the diamine compound represented by H 2 N-Y-NH 2 , and the compound represented by R-OH may each be used alone or in combination of two or more.
• An unsaturated polyimide precursor may be synthesized by reacting a polyamic acid solution with a dehydration condensation agent together with the compound represented by R-OH.
• the dehydration condensation agent preferably contains at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC) and 1,3-diisopropylcarbodiimide (DIC).
• the above-mentioned compound contained in the unsaturated polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, then reacting it with a chlorinating agent such as thionyl chloride to convert it into an acid chloride, and then reacting a diamine compound represented by H 2 N-Y-NH 2 with the acid chloride.
• the above-mentioned compound contained in the unsaturated polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, and then reacting the diamine compound represented by H 2 N-Y-NH 2 with the diester derivative in the presence of a carbodiimide compound.
• the above-mentioned compound contained in the unsaturated polyimide precursor can be obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a diamine compound represented by H 2 N-Y-NH 2 to form a polyamic acid, then isoimidizing the polyamic acid in the presence of a dehydrating condensing agent such as trifluoroacetic anhydride, and then reacting the compound represented by R-OH.
• a compound represented by R-OH may be reacted in advance with a part of the tetracarboxylic dianhydride to react the partially esterified tetracarboxylic dianhydride with the diamine compound represented by H 2 N-Y-NH 2 .
• X is the same as X in general formula (1), and specific examples and preferred examples are also the same.
• the compound represented by R-OH used in the synthesis of the above-mentioned compound contained in the unsaturated polyimide precursor may be a compound in which a hydroxy group is bonded to R x of the group represented by general formula (2), a compound in which a hydroxy group is bonded to the terminal methylene group of the group represented by general formula (2'), etc.
• Specific examples of the compound represented by R-OH include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, etc., among which 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate are preferred.
• the weight average molecular weight of the unsaturated polyimide precursor is preferably 10,000 to 200,000, and more preferably 10,000 to 100,000.
• the weight average molecular weight can be measured, for example, by gel permeation chromatography, and can be calculated using a standard polystyrene calibration curve.
• the photosensitive resin composition of the present disclosure may further contain a dicarboxylic acid, and the unsaturated polyimide precursor contained in the photosensitive resin composition may have a structure in which a part of the amino group in the unsaturated polyimide precursor reacts with a carboxy group in the dicarboxylic acid.
• a part of the amino group of a diamine compound may react with a carboxy group of the dicarboxylic acid.
• the dicarboxylic acid may be a dicarboxylic acid having a (meth)acrylic group, for example, a dicarboxylic acid represented by the following formula:
• a dicarboxylic acid represented by the following formula: when synthesizing the unsaturated polyimide precursor, a part of the amino group of the diamine compound is reacted with a carboxy group of the dicarboxylic acid, whereby a methacryl group derived from the dicarboxylic acid can be introduced into the unsaturated polyimide precursor.
• the photosensitive resin composition of the present disclosure may contain a polyimide resin in addition to the unsaturated polyimide precursor.
• a polyimide resin By combining the unsaturated polyimide precursor and the polyimide resin, it is possible to suppress the generation of volatile substances due to dehydration cyclization during imide ring formation, and therefore tends to suppress the generation of voids.
• the polyimide resin referred to here refers to a resin having an imide skeleton in all or part of the resin skeleton. It is preferable that the polyimide resin is soluble in a solvent in the photosensitive resin composition using the unsaturated polyimide precursor.
• the polyimide resin is not particularly limited as long as it is a polymeric compound having a plurality of structural units including imide bonds, and it is preferable that the polyimide resin contains, for example, a compound having a structural unit represented by the following general formula (X). This tends to result in a semiconductor device having an insulating film that exhibits high reliability.
• X represents a tetravalent organic group
• Y represents a divalent organic group.
• Preferred examples of the substituents X and Y in general formula (X) are the same as the preferred examples of the substituents X and Y in general formula (1) described above.
• the ratio of the polyimide resin to the total of the unsaturated polyimide precursor and the polyimide resin may be 15% by mass to 50% by mass, or 10% by mass to 20% by mass.
• the photosensitive resin composition of the present disclosure may contain other resins in addition to the unsaturated polyimide precursor and polyimide resin.
• the other resins include novolac resins, acrylic resins, polyether nitrile resins, polyether sulfone resins, epoxy resins, polyethylene terephthalate resins, polyethylene naphthalate resins, polyvinyl chloride resins, etc., from the viewpoint of heat resistance.
• the other resins may be used alone or in combination of two or more.
• the content of the unsaturated polyimide precursor relative to the total amount of solids is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and even more preferably 90% by mass to 100% by mass.
• the solid content refers to the residue when the photosensitive resin composition is applied to a substrate, heated at 100° C. for 120 seconds, and then heated at 110° C. for 120 seconds to remove the solvent and the like.
• the photosensitive composition of the present disclosure contains a trifunctional or higher polymerizable monomer (specific polymerizable monomer).
• the functional group in the polymerizable monomer refers to a group that can react with the polymerizable unsaturated bond of the unsaturated polyimide precursor.
• the specific polymerizable monomer has three or more such functional groups, and may have four or more.
• the number of functional groups of the specific polymerizable monomer is preferably 8 or less, more preferably 6 or less, and even more preferably 5 or less.
• the number of functional groups of the specific polymerizable monomer is preferably 3 or 4.
• the specific polymerizable monomer may be used alone or in combination of two or more kinds.
• Functional groups include vinyl groups, allyl groups, propargyl groups, butenyl groups, ethynyl groups, phenylethynyl groups, maleimide groups, nadimide groups, (meth)acryloyl groups, etc., and from the viewpoint of polymerization reactivity, (meth)acryloyl groups and vinyl groups are preferred, and (meth)acryloyl groups are more preferred.
• the specific polymerizable monomer is preferably a compound represented by the following general formula (6).
• R x and R 8 to R 10 in formula (6) have the same definitions as R x and R 8 to R 10 in formula (2), respectively.
• Each R x is preferably —(CH 2 ) q —, and q has the same definition as q in general formula (2′).
• n represents an integer of 3 to 6, preferably 3 to 5, and more preferably 3 or 4.
• each p is independently 0 or an integer of 1 or more, and is preferably 0 to 30, more preferably 0 to 20, and even more preferably 0 to 5.
• A is an n-valent organic group, which may be linear, cyclic, or branched.
• the n-valent organic group include an n-valent hydrocarbon group which may contain an oxygen atom, an n-valent group derived from bisphenol, an n-valent group derived from fluorene, an n-valent group derived from tricyclodecane, and an n-valent group derived from an isocyanuric group.
• n-valent hydrocarbon groups which may contain an oxygen atom examples include n-valent aliphatic hydrocarbon groups which may contain an oxygen atom, and n-valent aromatic hydrocarbon groups which may contain an oxygen atom, with n-valent aliphatic hydrocarbon groups which may contain an oxygen atom being preferred.
• n-valent aliphatic hydrocarbon groups that may contain oxygen atoms include the following:
• n independently represents an integer of 0 or 1 or more, and is preferably 0 or 1.
• Each n independently represents an integer of 0 or 1 or more, and is preferably 0 or 1.
• m represents an integer of 2 or more. * indicates the position at which the structure enclosed in brackets in formula (6) is linked, or a hydroxyl group.
• a in formula (6) is preferably an n-valent aliphatic hydrocarbon group which may contain an oxygen atom, or an n-valent group derived from an isocyanuric group, and more preferably an n-valent aliphatic hydrocarbon group which may contain an oxygen atom, or an n-valent group derived from an isocyanuric group.
• specific examples of specific polymerizable monomers include tris-(2-acryloxyethyl)isocyanurate and ethoxylated pentaerythritol tetraacrylate.
• the specific polymerizable monomer may be obtained by synthesis, or a commercially available product may be used.
• commercially available products include NK Ester A-9300 (trifunctional) and ATM-4E (tetrafunctional) manufactured by Shin-Nakamura Chemical Co., Ltd.
• a bifunctional polymerizable monomer may be used in combination.
• the functional group in the bifunctional polymerizable monomer the functional groups described in the specific polymerizable monomer can be mentioned, and a (meth)acryloyl group and a phenylethynyl group are preferable, and a (meth)acryloyl group is more preferable.
• the difunctional polymerizable monomer includes an alicyclic polymerizable monomer and a linear polymerizable monomer.
• the aliphatic cyclic skeleton contained in the alicyclic polymerizable monomer is not particularly limited, and examples thereof include a tricyclodecane skeleton, a cyclohexane skeleton, a cyclopentane skeleton, a 1,3-adamantane skeleton, a hydrogenated bisphenol A skeleton, a hydrogenated bisphenol F skeleton, a hydrogenated bisphenol S skeleton, and an isobornyl skeleton.
• a tricyclodecane skeleton is preferred.
• alicyclic polymerizable monomer a compound represented by the following general formula (3) is preferred.
• R1 and R2 are each independently an aliphatic hydrocarbon group having 1 to 4 carbon atoms or a group represented by the following general formula (3-1): n1 represents 0 or 1, n2 represents an integer of 0 to 2, and n1+n2 is 1 or 2. At least two of the n1 R1s and n2 R2s are groups represented by the following general formula (3-1).
• R 1A represents a hydrogen atom or a methyl group
• m represents an integer of 1 to 10.
• Specific examples of the aliphatic hydrocarbon group having 1 to 4 carbon atoms represented by R 1 and R 2 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group.
• the compound represented by general formula (3) may be a compound represented by the following formula (3A) or (3B):
• the compound represented by formula (3A) is available, for example, as A-DCP (tricyclodecane dimethanol diacrylate) from Shin-Nakamura Chemical Co., Ltd.
• the compound represented by formula (3B) is available, for example, as DCP (tricyclodecane dimethanol dimethacrylate) from Shin-Nakamura Chemical Co., Ltd.
• the linear polymerizable monomer is preferably a compound represented by the following general formula (4) or the following general formula (5).
• R3 's each independently represent a hydrogen atom or a methyl group
• R4 's represent a linear alkylene group having 1 to 8 carbon atoms
• R5 's represent a linear alkylene group having 1 to 8 carbon atoms
• p's represent an integer of 2 to 5.
• Multiple R3 's and R5 's may be the same or different.
• R3 in formula (4) or (5) is preferably a methyl group.
• Specific examples of the linear alkylene group having 1 to 8 carbon atoms represented by R 4 in the general formula (4) include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, and an octamethylene group.
• Specific examples of the linear alkylene group having 1 to 8 carbon atoms represented by R5 in general formula (5) include a methylene group, an ethylene group, a trimethylene group, a methylethylene group, a dimethylmethylene group, a tetramethylene group, a hexamethylene group, and an octamethylene group. Of these, a methylethylene group and an ethylene group are preferred, and an ethylene group is more preferred.
• p is preferably an integer of 3 or 4.
• linear polymerizable monomers include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, and 1,6-hexanediol dimethacrylate. Of these, tetraethylene glycol dimethacrylate is preferred.
• the ratio of the specific polymerizable monomer to the total content of polymerizable monomers is not particularly limited, and can be adjusted appropriately in consideration of the i-line transmittance of the photosensitive resin film, the film characteristics, etc.
• the ratio of the specific polymerizable monomer to the total content of polymerizable monomers may be 5 mass% or more, 15 mass% or more, or 50 mass% or more.
• the ratio of the specific polymerizable monomer to the total content of polymerizable monomers may be 100 mass% or less, 80 mass% or less, or 70 mass% or less.
• the total content of the polymerizable monomers is preferably 1 to 50 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.
• the photosensitive composition of the present disclosure contains a photopolymerization initiator.
• the photopolymerization initiator is not particularly limited as long as it is a compound capable of generating radicals by irradiation with actinic rays. Examples of actinic rays include ultraviolet rays such as i-rays, visible light, and radiation.
• the photopolymerization initiator may be used alone or in combination of two or more kinds.
• Photopolymerization initiators include oxime compounds, acylphosphine oxide compounds, acyldialkoxymethane compounds, etc.
• the photopolymerization initiator may be a compound represented by the following general formula (9A), a compound represented by the following general formula (9B), a compound represented by the following general formula (10A), or a compound represented by the following general formula (10B).
• R 11 is an alkyl group having 1 to 12 carbon atoms, and a1 is an integer of 0 to 5.
• R 12 is a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.
• R 13 and R 14 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, or a tolyl group.
• R 11 may be the same or different.
• R 11 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.
• a1 is preferably 1.
• R 12 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an ethyl group.
• R 13 and R 14 are preferably each independently an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.
• R 15 is -OH, -COOH, -OCH 2 OH, -O(CH 2 ) 2 OH, -COOCH 2 OH or -COO(CH 2 ) 2 OH
• R 16 and R 17 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group or a tolyl group.
• b1 is an integer of 0 to 5. When b1 is an integer of 2 or more, R 15 may be the same or different.
• R 15 is preferably —O(CH 2 ) 2 OH.
• b1 is preferably 0 or 1.
• R 16 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a methyl group or a hexyl group.
• R 17 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably a methyl group or a phenyl group.
• Examples of the compound represented by general formula (9B) include the compound represented by the following formula (9B-1), available as "IRGACURE OXE 01" manufactured by BASF Japan Ltd. Also included is the compound represented by the following formula (9B-2), available as "NCI-930" manufactured by ADEKA Corporation.
• R 21 is an alkyl group having 1 to 12 carbon atoms
• R 22 and R 23 are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms (preferably having 1 to 4 carbon atoms), an alkoxy group having 1 to 12 carbon atoms (preferably having 1 to 4 carbon atoms), a cycloalkyl group having 4 to 10 carbon atoms, a phenyl group, or a tolyl group
• c1 is an integer of 0 to 5.
• R 21 may be the same or different.
• c1 is preferably 0.
• R 22 is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group.
• R 24 and R 25 are each independently an alkyl group having 1 to 12 carbon atoms (preferably 1 to 4 carbon atoms), d and e are each independently an integer of 0 to 5, s and t are each independently an integer of 0 to 3, and the sum of s and t is 3.
• d is an integer of 2 or more
• R 24 may be the same or different.
• e is an integer of 2 or more
• R 25 may be the same or different.
• s is an integer of 2 or more
• the groups in the parentheses may be the same or different.
• t is an integer of 2 or more
• the groups in the parentheses may be the same or different.
• d is preferably 0.
• R 25 is preferably each independently an alkyl group having 1 to 4 carbon atoms, and is preferably a methyl group.
• e is preferably an integer of 2 to 4, and more preferably 3.
• the combination of s and t (s, t) is preferably (1, 2) or (2, 1).
• Examples of the compound represented by general formula (10B) include a compound represented by the following formula (10B-1), which is available as "IRGACURE TPO" manufactured by BASF Japan Ltd. Also included are compounds represented by the following formula (10B-2), which is available as "IRGACURE 819" manufactured by BASF Japan Ltd.
• At least one type of photopolymerization initiator selected from the group consisting of compounds represented by general formula (9A), compounds represented by general formula (9B), and compounds represented by general formula (10A) it is more preferable to use at least one type of compound selected from the group consisting of compounds represented by general formula (9A) and compounds represented by general formula (9B), it is even more preferable to use a compound represented by general formula (9B), and it is particularly preferable to use a compound represented by formula (9B-1).
• the compound represented by formula (9B-1) decomposes when exposed to i-rays, and the decomposition product has a higher i-ray transmittance than the compound represented by formula (9B-1) before decomposition. Therefore, when a coating film of a photosensitive resin composition is exposed to i-rays, the i-ray transmittance is low at the beginning of the exposure, suppressing light reflection on the substrate. Then, as the exposure irradiation progresses, the i-ray transmittance increases, and the i-rays reach the bottom of the coating film close to the substrate. As a result, the rectangularity of the cross-sectional pattern shape is high, resulting in an excellent pattern shape.
• the content of the photopolymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 6 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.
• the photosensitive resin composition may further contain at least one selected from the group consisting of a sensitizer and an ultraviolet absorber. By further containing at least one selected from the group consisting of a sensitizer and an ultraviolet absorber, the i-line transmittance of the photosensitive resin film may be adjusted.
• the ultraviolet absorber preferably has an absorbance at 365 nm of 0.05 or more, and more preferably 0.1 or more, at a concentration of 10 mg/L.
• the ultraviolet absorbent include benzotriazole-based compounds, salicylic acid ester-based compounds, benzophenone-based compounds, diphenylacrylate-based compounds, cyanoacrylate-based compounds, diphenylcyanoacrylate-based compounds, benzothiazole-based compounds, azobenzene-based compounds, polyphenol-based compounds, nickel complex salt-based compounds, etc.
• the ultraviolet absorbent may be used alone or in combination of two or more kinds.
• Benzotriazole compounds include 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chloro-2H-benzotriazole, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl)phenol, 2- (2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole, 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-
• salicylic acid ester compounds examples include phenyl salicylate and 4-tert-butylphenyl salicylate.
• benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 4-n-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2,2',4,4'-tetrahydroxybenzophenone, and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone.
• Diphenylacrylate compounds include ethyl 2-cyano-3,3-diphenylacrylate.
• diphenyl cyanoacrylate compounds examples include 2-cyano-3,3-diphenylacrylic acid (2'-ethylhexyl).
• azobenzene compounds include 4-[ethyl(2-hydroxyethyl)amino]-4'-nitroazobenzene.
• Polyphenol compounds include pyrogallol, phloroglycine, catechin, epicatechin, gallocatechin, catechin gallate, gallocatechin gallate, epicatechin gallate, epigallocatechin gallate, epigallocatechin, rutin, quercetin, quercetagin, quercetagetin, gossypetin, pelargonidin, cyanidin, aurantidin, luteolinidin, peonidin, rosinidin, (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione (curcumin), 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione, etc.
• polyphenol compounds examples include [2,2'-thiobis(4-tert-octylphenolate)]-2-ethylhexylamine nickel(II).
• At least one ultraviolet absorbent selected from the group consisting of benzotriazole-based compounds, benzophenone-based compounds, azobenzene-based compounds, and polyphenol-based compounds.
• At least one ultraviolet absorber selected from the group consisting of 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-p-cresol), 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-[ethyl(2-hydroxyethyl)amino]-4'-nitroazobenzene, (1E,6E)-1,7-bis(4-hydroxy-3-methoxyphenyl)-1,6-heptadiene-3,5-dione, and 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-3,5-dione.
• the content of the ultraviolet absorber is, from the viewpoint of resolution, preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and even more preferably 0.2 parts by mass or more, relative to 100 parts by mass of the unsaturated polyimide precursor. Furthermore, from the viewpoint of preventing insufficient photocuring inside the coating film, the amount is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 2 parts by mass or less.
• the photosensitive resin composition of the present disclosure may contain a sensitizer.
• a sensitizer it is possible to maintain both the remaining film rate and good resolution over a wide range of exposure doses.
• Sensitizers include Michler's ketone, benzoin, 2-methylbenzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, anthraquinone, methylanthraquinone, 4,4'-bis(diethylamino)benzophenone, acetophenone, benzophenone, thioxanthone, 1,5-acenaphthene, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, diacetyl benzyl, and benzyl dimethyl ketone.
• the sensitizers may be used alone or in combination of two or more.
• the amount of the sensitizer is not particularly limited, but is preferably 0.1 parts by mass to 1.0 parts by mass, and more preferably 0.2 parts by mass to 0.8 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.
• the photosensitive resin composition preferably further contains at least one selected from the group consisting of a stabilizer and a solvent.
• the photosensitive resin composition may also contain a rust inhibitor, an antioxidant, an imidization accelerator, a coupling agent, a thermal polymerization initiator, a surfactant, a leveling agent, an unavoidable component, and the like.
• solvent examples include ester solvents, ether solvents, ketone solvents, hydrocarbon solvents, aromatic hydrocarbon solvents, sulfoxide solvents, etc.
• the solvents may be used alone or in combination of two or more.
• Ester solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkoxy acetates such as methyl alkoxy acetate, ethyl alkoxy acetate, and butyl alkoxy acetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate), alkyl 3-alkoxypropionates such as methyl 3-alkoxypropionate and ethy
• 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate and ethyl 2-ethoxypropionate, methyl 2-alkoxy-2-methylpropionate such as methyl 2-methoxy-2-methylpropionate, ethyl 2-alkoxy-2-methylpropionate such as ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.
• ether solvents include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
• Examples of the ketone solvent include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone (NMP).
• Examples of the hydrocarbon solvent include limonene.
• Examples of aromatic hydrocarbon solvents include toluene, xylene, and anisole.
• An example of a solvent for sulfoxides is dimethyl sulfoxide.
• N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N,N-dimethylformamide and N,N-dimethylacetamide, dimethylsulfoxide, etc. are preferred from the viewpoint of excellent solubility of each component and coatability when forming a photosensitive resin film.
• a compound represented by the following general formula (11) may be used as the solvent.
• R 41 to R 43 each independently represent an alkyl group having 1 to 10 carbon atoms.
• the alkyl groups represented by R 41 to R 43 in formula (11) preferably have 1 to 3 carbon atoms, and more preferably 1 or 3 carbon atoms.
• Specific examples of the alkyl group having 1 to 10 carbon atoms represented by R 41 to R 43 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group.
• the compound represented by the general formula (11) is preferably 3-methoxy-N,N-dimethylpropanamide (for example, trade name "KJCMPA-100" (manufactured by KJ Chemicals Co., Ltd.)).
• the content of the solvent can be adjusted appropriately depending on the viscosity of the photosensitive resin composition, and may be, for example, 100 parts by mass or more, 200 parts by mass or more, or 400 parts by mass or more relative to 100 parts by mass of the unsaturated polyimide precursor. From the viewpoint of reducing the drying energy required when forming a coating film, it is not necessary to contain more solvent than necessary, and for example, the content of the solvent relative to 100 parts by mass of the unsaturated polyimide precursor may be less than 100 parts by mass, 75 parts by mass or less, or 50 parts by mass or less.
• the proportion of N-methyl-2-pyrrolidone in the total amount of solvent is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and it is particularly preferable that no N-methyl-2-pyrrolidone is contained (0% by mass).
• the photosensitive resin composition of the present disclosure may contain a stabilizer.
• the storage stability can be improved.
• Stabilizers include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, ortho-dinitrobenzene, para-dinitrobenzene, meta-dinitrobenzene, phenanthraquinone, N-phenyl-2-naphthylamine, cupferron, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosamines, azo compounds, hindered amine compounds, hindered phenol compounds, etc.
• the stabilizer may be used alone or in combination of two or more types. By combining two or more stabilizers, the photosensitive characteristics tend to be easier to adjust due to differences in reactivity.
• the hindered phenol compound may have both the function of a stabilizer and the function of an antioxidant described below, or it may have only one function.
• Stabilizers include, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-methylenebis(2,6-di-t-butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butyl Phenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thio-d
• the content of the stabilizer is preferably 0.05 parts by mass to 1.0 parts by mass, and more preferably 0.1 parts by mass to 0.8 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.
• the photosensitive resin composition of the present disclosure may contain an antioxidant from the viewpoint of suppressing a decrease in adhesiveness by capturing oxygen radicals and peroxide radicals generated during high-temperature storage, reflow treatment, etc.
• an antioxidant When the photosensitive resin composition of the present disclosure contains an antioxidant, oxidation of the electrode during an insulation reliability test can be suppressed.
• antioxidants include the compounds exemplified above as the hindered phenol compounds, 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, and 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid.
• the antioxidants may be used alone or in combination of two or more.
• the content of the antioxidant is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.1 parts by mass to 10 parts by mass, and even more preferably 0.1 parts by mass to 5 parts by mass, relative to 100 parts by mass of the unsaturated polyimide precursor.
• Hindered phenol compounds as antioxidants include 1,3,5-tris(3-hydroxy-2,6-dimethyl-4-isopropylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris(4-s-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-(1-ethylpropyl)- 3-hydroxy-2,6-dimethylbenzyl]-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, 1,3,5-tris[4-triethyl
• the resin composition of the present disclosure may contain an imidization accelerator from the viewpoint of promoting the imidization reaction.
• the imidization accelerator include N-phenyldiethanolamine, 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, 4-aminobenzamide, 2-aminobenzamide, nicotinamide, 4-amino-N-methylbenzamide, 4-aminoacetanilide, 4-aminoacetophenone, etc., and among these, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, etc. are preferred.
• the nitrogen-containing compounds may be used alone or in combination of two or more.
• the content of the imidization accelerator is preferably 0.1 parts by mass to 20 parts by mass relative to 100 parts by mass of the unsaturated polyimide precursor, and from the viewpoint of storage stability, it is more preferably 0.3 parts by mass to 15 parts by mass, and even more preferably 0.5 parts by mass to 10 parts by mass.
• the coupling agent is not particularly limited, and examples thereof include 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]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethylphenyl ...
• silane coupling agents such as benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-4,4'-dicarboxylic acid, benzene-1,4-bis(N-[3-triethoxysilyl]propylamido)-2,5-dicarboxylic acid, 3-(triethoxysilyl)propyl succinic anhydride, N-phenylaminopropyltrimethoxysilane, N,N'-bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane; aluminum-based adhesion aids such as aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.
• the coupling agents may be used alone or in combination of two or more.
• the content of the coupling agent is preferably 0.1 parts by mass to 20 parts by mass, more preferably 1 part by mass to 10 parts by mass, and even more preferably 2 parts by mass to 10 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.
• the resin composition of the present disclosure may contain a rust inhibitor from the viewpoint of inhibiting corrosion and preventing discoloration of copper and copper alloys.
• the rust inhibitor is not particularly limited, and examples thereof include azole compounds and purine derivatives.
• the rust inhibitors may be used alone or in combination of two or more.
• azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H-triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis( ⁇ , ⁇ -dimethylbenzyl)phenyl]-benzotriazole, benzotriazole, 2-(3,5-di-t-butyl
• purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-amino Examples include noadenine, 6-amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl)guanine, N-(3-ethylphenyl)guanine, 2-azaa
• the content of the rust inhibitor is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass, and even more preferably 0.5 parts by mass to 3 parts by mass, per 100 parts by mass of the unsaturated polyimide precursor.
• surfactant or leveling agents examples include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like.
• Commercially available products include products under the trade names "Megafac (registered trademark) F171", “F173", and “R-08” (all manufactured by DIC Corporation), product names “Fluorad FC430" and “FC431” (all manufactured by Sumitomo 3M Limited), and product names "Organosiloxane Polymer KP341", “KBM303", and “KBM803” (all manufactured by Shin-Etsu Chemical Co., Ltd.).
• the surfactants and leveling agents may be used alone or in combination of two or more.
• the total content of the surfactant and leveling agent is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.05 parts by mass to 5 parts by mass, and even more preferably 0.05 parts by mass to 3 parts by mass, per 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 promoting the polymerization reaction.
• a thermal polymerization initiator a compound that does not decompose when heated (dried) to remove a solvent during film formation but decomposes when heated during curing to generate radicals and promotes a polymerization reaction between polymerizable monomers or between an unsaturated polyimide precursor and a polymerizable monomer is preferred.
• the thermal polymerization initiator is preferably a compound having a decomposition point of 110° C. to 200° C., and from the viewpoint of promoting the polymerization reaction at a lower temperature, a compound having a decomposition point of 110° C. to 175° C. is more preferable.
• thermal polymerization initiator examples include ketone peroxides such as methyl ethyl ketone peroxide, peroxyketals such as 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy)cyclohexane, and 1,1-di(t-butylperoxy)cyclohexane, hydroperoxides such as 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, dialkyl peroxides such as dicyclohexane, dicyclohexane, and dicyclohexane.
• ketone peroxides such as methyl ethyl ketone peroxide
• peroxyketals such as 1,1-di(
• peroxyester examples include diacyl peroxides such as diuroyl peroxide and dibenzoyl peroxide; peroxydicarbonates such as di(4-t-butylcyclohexyl)peroxydicarbonate and di(2-ethylhexyl)peroxydicarbonate; peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxybenzoate and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate; and bis(1-phenyl-1-methylethyl)peroxide.
• Commercially available products include those under the trade names "Percumyl D", “Percumyl P", and "Percumyl H” (all manufactured by NOF Corporation).
• the content of the thermal polymerization initiator is preferably 0.1 parts by mass to 20 parts by mass relative to 100 parts by mass of the unsaturated polyimide precursor, more preferably 0.2 parts by mass to 20 parts by mass to ensure good flux resistance, and even more preferably 0.3 parts by mass to 10 parts by mass from the viewpoint of suppressing a decrease in solubility due to decomposition during drying.
• the total amount of the unsaturated polyimide precursor, the crosslinking agent, the photopolymerization initiator, the sensitizer, the UV absorber, and the solvent may be 80% by mass or more, 90% by mass or more, or 95% by mass or more.
• the total amount of the unsaturated polyimide precursor, the crosslinking agent, the photopolymerization initiator, the sensitizer, the UV absorber, the solvent, the stabilizer, the imidization accelerator, the rust inhibitor, the antioxidant, and the coupling agent may be 80% by mass or more, 90% by mass or more, 95% by mass or more, 97% by mass or more, 98% by mass or more, or 99% by mass or more.
• 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 can be suitably used as a patterned cured product.
• the average thickness of the cured product is preferably 5 ⁇ m to 20 ⁇ m.
• the method for producing a patterned cured product of the present disclosure includes a step of applying the photosensitive resin composition of the present disclosure onto a substrate and drying to form a photosensitive resin film, a step of exposing the photosensitive resin film to a pattern to obtain a resin film, a step of developing the resin film after the patterned exposure using a developer to obtain a patterned resin film, and a step of heat-treating the patterned resin film. In this way, a patterned cured product can be obtained.
• the substrate examples include semiconductor substrates such as glass substrates and Si substrates (silicon wafers), metal oxide insulator substrates such as TiO2 substrates and SiO2 substrates, silicon nitride substrates, copper substrates, and copper alloy substrates.
• the drying can be carried out using a hot plate, an oven, or the like.
• the drying temperature is preferably from 90° C. to 150° C., and from the viewpoint of ensuring the dissolution contrast, it is more preferably from 90° C. to 120° C.
• the drying time is preferably from 30 seconds to 5 minutes. The drying may be carried out two or more times. This makes it possible to obtain a photosensitive resin film in which the photosensitive resin composition of the present disclosure is formed into a film shape.
• the average thickness of the photosensitive resin film is preferably 5 ⁇ m to 100 ⁇ m, more preferably 6 ⁇ m to 50 ⁇ m, and even more preferably 7 ⁇ m to 30 ⁇ m.
• the pattern exposure is performed by exposing a predetermined pattern through a photomask, for example.
• the actinic rays to be irradiated include ultraviolet rays such as i-rays, visible light, and radiation, and are preferably i-rays.
• a parallel exposure device, an aligner, a projection exposure device, a stepper, a scanner exposure device, or the like can be used as the exposure device.
• a resin film having a pattern formed thereon By developing, a resin film having a pattern formed thereon (patterned resin film) can be obtained.
• a developer As the developer, a good solvent for the photosensitive resin film can be used alone, or a suitable mixture of a good solvent and a poor solvent can be used.
• the good solvent include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, cyclopentanone, and cyclohexanone.
• 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 amount added is preferably 0.01 parts by weight to 10 parts by weight, and more preferably 0.1 parts by weight to 5 parts by weight, per 100 parts by weight of the developer.
• the development time can be set to, for example, twice the time required for the photosensitive resin film to be immersed and completely dissolved.
• the developing time varies depending on the unsaturated polyimide precursor used, but is preferably from 10 seconds to 15 minutes, more preferably from 10 seconds to 5 minutes, and from the viewpoint of productivity, further preferably from 20 seconds to 5 minutes.
• washing may be carried out with a rinsing liquid.
• a rinsing liquid distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used alone or in appropriate mixture, or in stepwise combination.
• a patterned cured product By subjecting the patterned resin film to a heat treatment, a patterned cured product can be obtained.
• the unsaturated polyimide precursor undergoes a dehydration ring-closing reaction during the heat treatment step to become the corresponding polyimide resin.
• the temperature of the heat treatment is preferably 250°C or lower, more preferably 120°C to 250°C, and even more preferably 160°C to 200°C.
• the heat treatment time is preferably 5 hours or less, and more preferably 30 minutes to 3 hours. When the heat treatment time is within the above range, the crosslinking reaction or the dehydration ring-closing reaction can proceed sufficiently.
• the heat treatment may be performed in air or in an inert atmosphere such as nitrogen, but is preferably performed in a nitrogen atmosphere from the viewpoint of preventing oxidation of the patterned resin film.
• Equipment used for heat treatment includes quartz tube furnaces, hot plates, rapid thermal annealing, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, microwave curing furnaces, etc.
• 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, etc. Using one or more selected from the group consisting of the above passivation films, buffer coat films, interlayer insulating films, cover coat layers, and surface protection films, etc., highly reliable electronic components such as semiconductor devices, multilayer wiring boards, various electronic devices, and stacked devices (multi-die fan-out wafer level packages, etc.) can be manufactured.
• 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 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.
• a first conductor layer 3 is formed on the exposed circuit elements.
• an interlayer insulating film 4 is formed on the semiconductor substrate 1.
• the interlayer insulating film 4 from which the window 6A is exposed is selectively etched to provide a window 6B.
• the photosensitive resin layer 5 is removed using an etching solution that will corrode the photosensitive resin layer 5 without corroding the first conductor layer 3 exposed through the windows 6B.
• a second conductor layer 7 is formed by using a known photolithography technique, and is electrically connected to the first conductor layer 3 .
• the above-mentioned steps can be repeated to form each layer.
• the photosensitive resin composition of the present disclosure is used to open windows 6C by pattern exposure to form a surface protective film 8.
• the surface protective film 8 protects the second conductor layer 7 from external stress, ⁇ -rays, and the like, and the resulting semiconductor device has excellent reliability.
• the interlayer insulating film 4 can also be formed using the photosensitive resin composition of the present disclosure.
• Examples 1 to 9 and Comparative Examples 1 to 7 Each component shown in Table 1 or Table 2 was mixed in the amount shown in Table 1 or Table 2 to prepare a homogeneous solution. The resulting solution was filtered through a polytetrafluoroethylene (PTFE) membrane filter having a pore size of 1 ⁇ m to obtain the photosensitive resin compositions of Examples 1 to 9 and Comparative Examples 1 to 7. The amount of each component in Tables 1 and 2 is based on parts by mass. In Tables 1 and 2, "-" means that the corresponding component is not contained. Details of each component described in Tables 1 and 2 are as follows.
• polyimide precursor polymer I 380 g of N-methyl-2-pyrrolidone (NMP, Mitsubishi Chemical Corporation) was placed in a 2 L separable flask, and 47.08 g (152 mmol) of 4,4'-oxydiphthalic anhydride (ODPA, Manac Corporation) was added and dissolved while stirring.
• NMP N-methyl-2-pyrrolidone
• ODPA 4,4'-oxydiphthalic anhydride
• the reaction solution was poured into purified water, and the precipitate was collected, washed with purified water, and then dried under reduced pressure to obtain polymer I as an unsaturated polyimide precursor.
• the weight average molecular weight (Mw) of Polymer I was 22,100.
• the weight average molecular weight of the polymer was calculated from a calibration curve of TSKgel standard polystyrene (Tosoh Corporation) by gel permeation chromatography (GPC). The equipment and conditions are shown below.
• Polymerizable monomer I Triethylene glycol dimethacrylate (bifunctional) II: Tricyclodecane dimethanol diacrylate (bifunctional) III: Polyethoxylated pentaerythritol tetraacrylate (4 functional) IV: Tris-(2-acryloxyethyl)isocyanurate (trifunctional)
• Photopolymerization initiator I ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(o-acetyloxime)
• II 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone
• III 1-phenyl-1,2-propanedione-2-[o-(ethoxycarbonyl)oxime]
• Sensitizer 4,4'-bis(diethylamino)benzophenone (EMK, Merck)
• UV absorber curcumin
• the obtained photosensitive resin composition was spin-coated onto quartz glass using a coating device Spin Coater MS-B150 (manufactured by Mikasa Co., Ltd.), and pre-baked by heating at 100°C for 120 seconds and then at 110°C for 120 seconds to prepare a photosensitive resin film with a thickness of 7 ⁇ m.
• the transmittance of the obtained photosensitive resin film with respect to i-line was measured using a U-3900H spectrophotometer (manufactured by Hitachi High-Tech Science Corporation).
• a photosensitive resin film having a thickness of 7 ⁇ m was obtained in the same manner as in the measurement of the i-line transmittance described above.
• the developing time was set to 1.2 times the time required for the photosensitive resin film to be immersed in cyclopentanone and completely dissolved.
• a photosensitive resin film was prepared in the same manner as above, and the obtained photosensitive resin film was exposed to light using an i-line stepper FPA-3000iW (manufactured by Canon Inc.) at an exposure dose of 900 mJ cm2 by irradiating the via formation photomask.
• the exposed resin film was paddle-developed with cyclopentanone for the above-mentioned developing time, and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.
• PMEA propylene glycol monomethyl ether acetate
• the resulting patterned resin film was heated in a vertical diffusion furnace ⁇ -TF (manufactured by Koyo Thermo Systems Co., Ltd.) at 170°C for 3 hours in a nitrogen atmosphere to obtain a patterned cured product (film thickness after curing: 5 ⁇ m).
• ⁇ -TF manufactured by Koyo Thermo Systems Co., Ltd.
• the resulting patterned cured product was observed using an optical microscope, and the resolution was determined as the smallest diameter at which an opening was formed that exposed 55% or more of the substrate surface relative to the area of the via mask dimensions. The results are shown in Table 2.
• FIG. 2(A) shows a cross-sectional SEM photograph of a via pattern formed using the photosensitive resin composition of Example 1
• FIG. 2(B) shows a cross-sectional SEM photograph of a via pattern formed using the photosensitive resin composition of Comparative Example 1. Note that this cross-sectional SEM photograph was taken after drilling with an ion beam (FIB) so that the cross section of the via pattern could be observed.
• FIB ion beam
• Comparative Example 1 contains a polymerizable monomer with three or more functionalities, and the i-line transmittance when cured exceeds 30%, so it is believed that the i-line reflected by the substrate caused the polymerization reaction to proceed excessively.

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