Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/12—Unsaturated polyimide precursors

Definitions

• the present disclosure relates to a method for producing a polyimide precursor, a method for producing a photosensitive resin composition, a method for producing a cured product, a polyimide precursor, a polyimide precursor composition, a photosensitive resin composition, and a semiconductor device.
• Such a protective film (cured film) using a polyimide resin can be obtained by applying a polyimide precursor or a resin composition containing a polyimide precursor onto a substrate, drying the applied resin film, and then heating the resulting film to cure it.
• the present disclosure has been made in view of the above, and has an object to provide a method for producing a polyimide precursor that can produce a photosensitive resin composition having excellent photosensitivity characteristics and can produce a polyimide precursor in a simple manner, as well as a method for producing a photosensitive resin composition and a method for producing a cured product using the production method. Furthermore, the present disclosure has an object to provide a polyimide precursor capable of producing a photosensitive resin composition having excellent photosensitivity properties, and a polyimide precursor composition, a photosensitive resin composition, and a semiconductor device using the polyimide precursor.
• a method for producing a polyimide precursor comprising a step of reacting a polyamic acid with a vinyl ether compound having a (meth)acryloyl group in the presence of a polymerization inhibitor.
• the method for producing a polyimide precursor according to ⁇ 1> further comprising a step of reacting a tetracarboxylic dianhydride or a tetracarboxylic acid with a diamine compound to obtain the polyamic acid.
• ⁇ 3> The method for producing a polyimide precursor according to ⁇ 1> or ⁇ 2>, wherein the polymerization inhibitor includes 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide.
• ⁇ 4> The method for producing a polyimide precursor according to any one of ⁇ 1> to ⁇ 3>, wherein a molar ratio of the vinyl ether compound to a total of the tetracarboxylic dianhydride and the tetracarboxylic acid is 2 to 5.
• ⁇ 5> The method for producing a polyimide precursor according to any one of ⁇ 1> to ⁇ 4>, wherein the vinyl ether compound includes 2-(2-vinyloxyethoxy)ethyl (meth)acrylate.
• ⁇ 6> The method for producing a polyimide precursor according to any one of ⁇ 1> to ⁇ 5>, wherein in the step of obtaining the polyamic acid, the tetracarboxylic dianhydride and the diamine compound are reacted in a solvent, and the solvent contains a compound not containing a nitrogen atom and a sulfur atom in the molecule.
• ⁇ 7> The method for producing a polyimide precursor according to ⁇ 6>, wherein the solvent includes at least one selected from the group consisting of ⁇ -butyrolactone, cyclopentanone, a mixed solvent of 3-methoxy-3-methyl-1-butanol and propylene carbonate, and a mixed solvent of ⁇ -butyrolactone and 3-methoxy-N,N-dimethylpropanamide.
• the solvent includes at least one selected from the group consisting of ⁇ -butyrolactone, cyclopentanone, a mixed solvent of 3-methoxy-3-methyl-1-butanol and propylene carbonate, and a mixed solvent of ⁇ -butyrolactone and 3-methoxy-N,N-dimethylpropanamide.
• a method for producing a photosensitive resin composition comprising the steps of: ⁇ 9>
• a method for producing a cured product comprising the steps of producing a photosensitive resin composition by using the method for producing a photosensitive resin composition according to ⁇ 8>, and curing the produced photosensitive resin composition to produce a cured product.
• X represents a tetravalent organic group
• R6 and R7 each independently represent a hydrogen atom or a monovalent organic group
• at least one of R6 and R7 contained in the polyimide precursor is a monovalent organic group containing a (meth)acryloyl group
• * represents a bonding site
• Y represents a divalent organic group
• * represents a bonding site
• R 1 , R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group
• R 8 represents a monovalent organic group containing a (meth)acryloyl group
• * represents a bonding position
• a polyimide precursor composition comprising:
• X represents a tetravalent organic group
• R6 and R7 each independently represent a hydrogen atom or a monovalent organic group
• at least one of R6 and R7 contained in the polyimide precursor has a structure formed by a reaction between a vinyl group and a carboxy group in a vinyl ether compound having a (meth)acryloyl group and is a monovalent organic group containing a (meth)acryloyl group
• * represents a bonding site
• Y represents a divalent organic group, and * represents a bonding site.
• R 1 , R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group
• R 8 represents a monovalent organic group containing a (meth)acryloyl group
• * represents a bonding position
• ⁇ 14> The polyimide precursor composition according to ⁇ 12> or ⁇ 13>, wherein the polymerization inhibitor includes 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide.
• a photosensitive resin composition comprising the polyimide precursor according to ⁇ 10> or ⁇ 11> or the polyimide precursor composition according to any one of ⁇ 12> to ⁇ 14>.
• a semiconductor device comprising a cured product obtained by curing the photosensitive resin composition according to ⁇ 15>.
• a method for producing a polyimide precursor that can produce a photosensitive resin composition having excellent photosensitivity properties and can produce a polyimide precursor in a simple manner, as well as a method for producing a photosensitive resin composition and a method for producing a cured product using the production method.
• a polyimide precursor capable of producing a photosensitive resin composition having excellent photosensitivity properties as well as a polyimide precursor composition, a photosensitive resin composition, and a semiconductor device using the polyimide precursor.
• 1A to 1C are diagrams illustrating a manufacturing process for an electronic component according to an embodiment of the present disclosure.
• 1 is a graph showing the relationship between the exposure dose and the film remaining rate in each of the examples and comparative 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.
• the thickness of a layer or film refers to the maximum thickness of the layer or film in question.
• the thickness of the layer or film can be measured using an optical interference film thickness measuring device, a micrometer, etc.
• the thickness of the layer or film can be measured directly, it is measured using an optical interference film thickness measuring device or a micrometer.
• 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.
• (meth)acrylic means “acrylic” and “methacrylic”
• (meth)acrylate means “acrylate” and “methacrylate”
• (meth)acryloyl group means “acryloyl group” and “methacryloyl group”.
• the term "insulating film” is a concept that also encompasses an insulating layer.
• the number of carbon atoms in the functional group means the total number of carbon atoms including the number of carbon atoms in the substituent.
• the method for producing a polyimide precursor according to the present disclosure includes a step of reacting a polyamic acid with a vinyl ether compound having a (meth)acryloyl group in the presence of a polymerization inhibitor.
• a polyamic acid is reacted with a vinyl ether compound having a (meth)acryloyl group (hereinafter also referred to as a "specific vinyl ether compound”) in the presence of a polymerization inhibitor.
• a polymerization inhibitor e.g., a polymerization inhibitor for a reaction between a carboxy group contained in the polyamic acid and a vinyl group contained in the specific vinyl ether compound, resulting in a polyimide precursor having a (meth)acryloyl group.
• a polyimide precursor can be suitably used for preparing a photosensitive resin composition.
• a photosensitive resin composition containing a polyimide precursor produced by the production method disclosed herein has excellent photosensitive properties, such as being capable of producing a cured product with a high residual film rate and having a high dissolution rate in a solvent during development.
• the polyamic acid to be reacted with the specific vinyl ether compound is preferably a compound obtained by reacting a tetracarboxylic dianhydride or a tetracarboxylic acid with a diamine compound.
• the method for producing a polyimide precursor of the present disclosure may further include a step of reacting a tetracarboxylic dianhydride or a tetracarboxylic acid with a diamine compound to obtain the polyamic acid.
• 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, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, m-terpheny 1,3,3,3-hexafluoro-2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1,1,3,3,3-hex,2-
• 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, or 4,4'-oxydiphthalic dianhydride is preferable, and from the viewpoint of bonding at lower temperatures, it is 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.
• tetracarboxylic acids include the various compounds listed above for the specific examples of tetracarboxylic dianhydrides, excluding the term "dianhydride.”
• dianhydride 3,3',4,4'-biphenyl ether tetracarboxylic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, or 4,4'-oxydiphthalic acid are preferred, and from the standpoint of bonding at lower temperatures, it is more preferred to include 3,3',4,4'-biphenyl ether tetracarboxylic acid.
• 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.
• 4,4'-diaminodiphenyl ether, 1,3-bis(3-aminophenoxy)benzene, and 2,2-bis ⁇ 4-(4'-aminophenoxy)phenyl ⁇ propane are more preferred from the viewpoint of having a flexible skeleton and excellent adhesiveness.
• the diamine compounds may be used alone or in combination of two or more kinds.
• the polyamic acid may have a non-volatile crosslinking group at the end of the main chain.
• the non-volatile crosslinking group is a functional group capable of crosslinking that is located at the end of the main chain of the polyamic acid and does not volatilize due to heating, drying, etc.
• the non-volatile crosslinking group may be a functional group that contains an unsaturated double bond.
• a polyamic acid is obtained by reacting a tetracarboxylic dianhydride or a tetracarboxylic acid with a diamine compound, a compound that forms a nonvolatile crosslinking group at the main chain end of the polyamic acid (hereinafter, also referred to as a nonvolatile crosslinking group forming compound) may be further reacted.
• a nonvolatile crosslinking group forming compound a compound that forms a nonvolatile crosslinking group at the main chain end of the polyamic acid
• nonvolatile crosslinking group forming compound examples include maleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, methacrylic anhydride, 2-isocyanatoethyl methacrylate, 2-isocyanatoethyl acrylate, 4-ethynylphthalic anhydride, 4-vinylphthalic anhydride, and di-t-butyl dicarbonate. These compounds react with amino groups derived from the diamine compound to obtain a compound having a nonvolatile crosslinking group at the main chain end.
• the non-volatile crosslinking group-forming compounds may be used alone or in combination of two or more.
• the molar ratio of the total of the tetracarboxylic dianhydride and tetracarboxylic acid (which may be read as "the total of the tetracarboxylic dianhydride, tetracarboxylic acid, and non-volatile cross-linking group-forming compound") to the diamine compound (total of the tetracarboxylic dianhydride and tetracarboxylic acid:diamine compound) may be 5:10 to 15:10, 7:10 to 10:10, or 8:10 to 9.5:10.
• an organic solvent may be used.
• the organic solvent may be used alone or in combination of two or more kinds.
• the organic solvent preferably contains a compound that does not contain a nitrogen atom or a sulfur atom in the molecule, which tends to facilitate the reaction between the tetracarboxylic dianhydride or tetracarboxylic acid and the diamine compound.
• the organic solvent may be composed of a compound that does not contain a nitrogen atom or a sulfur atom in the molecule, or may be a mixed solvent of a compound that does not contain a nitrogen atom or a sulfur atom in the molecule and a compound that contains at least one of a nitrogen atom and a sulfur atom in the molecule.
• the aforementioned organic solvents include ⁇ -butyrolactone, cyclopentanone, a mixed solvent of 3-methoxy-3-methyl-1-butanol and propylene carbonate, and a mixed solvent of ⁇ -butyrolactone and 3-methoxy-N,N-dimethylpropanamide.
• the amount of organic solvent used may be 1 to 10 times, or 2 to 5 times, the total mass of the raw materials used in the production of polyamic acid.
• a polyimide precursor is produced by reacting a polyamic acid with a vinyl ether compound (a specific vinyl ether compound) having a (meth)acryloyl group in the presence of a polymerization inhibitor.
• the polyamic acid may be a liquid containing polyamic acid, or may be, for example, a liquid containing polyamic acid and an organic solvent.
• polymerization inhibitor examples include 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide, 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, etc.
• 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide is preferred.
• the polymerization inhibitor may be used alone or in combination of two or more kinds.
• the specific vinyl ether compound includes 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, of which 2-(2-vinyloxyethoxy)ethyl acrylate is preferred.
• the specific vinyl ether compounds may be used alone or in combination of two or more.
• vinyl ether compounds other than the specific vinyl ether compounds may be used.
• examples of other vinyl ether compounds include vinyl ether compounds that do not have a (meth)acryloyl group.
• vinyl ether compounds having a linear or branched saturated or unsaturated hydrocarbon skeleton such as isopropyl vinyl ether, sec-butyl vinyl ether, and sec-pentyl vinyl ether
• vinyl ether compounds containing an alicyclic saturated hydrocarbon skeleton such as cyclohexyl vinyl ether, tricyclodecanyl vinyl ether, and pentacyclopentadecanyl vinyl ether
• vinyl ethers containing an ether bond in a linear or branched saturated or unsaturated hydrocarbon skeleton such as 1-methoxyethyl vinyl ether, 1-ethoxyethyl vinyl ether, 1-methyl-2-methoxyethyl vinyl ether, and 1-methyl-2-ethoxyethyl vinyl ether.
• the amount of the specific vinyl ether compound used may be 50% by mass to 100% by mass, 70% by mass to 90% by mass, or 90% by mass to 100% by mass, based on the total mass of the specific vinyl ether compound and the other vinyl ether compounds.
• the molar ratio of the vinyl ether compound (vinyl ether/tetracarboxylic acid + tetracarboxylic acid dianhydride) to the total of the tetracarboxylic acid and tetracarboxylic acid (which may be read as "the total of the tetracarboxylic acid dianhydride, the tetracarboxylic acid, and the non-volatile cross-linking group-forming compound”) may be 2 to 5, 2.5 to 4.5, or 3 to 4.
• the polyimide precursor of the present disclosure includes a structural unit represented by general formula (1) and a structural unit represented by general formula (2), and the ratio of the structure formed by the reaction of a vinyl group and a carboxy group in a vinyl ether compound having a (meth)acryloyl group to the structure formed by the reaction of a vinyl group and a carboxy group in a vinyl ether compound in the total of R 6 and R 7 of the structural unit represented by general formula (1) (hereinafter also referred to as a specific ratio) is 40 mol% or more.
• the polyimide precursor of the present disclosure can produce a photosensitive resin composition having excellent photosensitive properties.
• the specific ratio may be 50 mol% to 100 mol%, or may be 70 mol% to 100 mol%.
• X represents a tetravalent organic group
• R6 and R7 each independently represent a hydrogen atom or a monovalent organic group
• at least one of R6 and R7 contained in the polyimide precursor is a monovalent organic group containing a (meth)acryloyl group
• * represents a bonding site
• Y represents a divalent organic group
• * represents a bonding site
• reaction formula between a vinyl ether compound (compound (b) shown below) and a compound having a carboxy group (compound (a) shown below) is as follows. This produces compound (c) having a structure formed by the reaction between the vinyl group and the carboxy group in the vinyl ether compound. Note that the following reaction is an example, and the present disclosure is not limited thereto.
• the polyimide precursor may have a plurality of structural units represented by the above general formula (1) or a plurality of structural units represented by the above general formula (2), 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 combinations 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 contains a benzene ring
• the tetravalent organic group represented by X preferably contains one to four benzene rings, more preferably contains one to three benzene rings, and even more preferably contains one or two 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 --CO-- 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 further 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.
• C may include a structure represented
• the alkylene group represented by C in 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 even more preferably an alkylene group having 1 or 2 carbon atoms.
• alkylene group represented by C in formula (E) examples include linear alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; a methylmethylene group, a methylethylene group, an ethylmethylene group, a dimethylmethylene group, a 1,1-dimethylethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, an ethylethylene group, a 1-methyltetramethylene group, a 2-methyltetramethylene group, a 1-ethyltrimethylene group, a 2-ethyltrimethylene group, a 1,1-dimethyl branched alkylene groups such as ethyltrimethylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group
• the halogenated alkylene group represented by C in formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, more preferably a halogenated alkylene group having 1 to 5 carbon atoms, and even more preferably a halogenated alkylene group having 1 to 3 carbon atoms.
• Specific examples of the halogenated alkylene group represented by C in formula (E) include alkylene groups in which at least one hydrogen atom contained in the alkylene group represented by C in formula (E) is substituted with a halogen atom such as a fluorine atom or a chlorine atom.
• a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group, etc. are preferred.
• the alkyl group represented by R A or R B contained in the silylene bond or siloxane bond is preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an alkyl group having 1 or 2 carbon atoms.
• Specific examples of the alkyl group represented by R A or R B 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.
• tetravalent organic group represented by X may be groups represented by the following formulae (J) to (O).
• 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).
• 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 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 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''').
• 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.
• R6 and R7 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R6 and R7 contained in the polyimide precursor is a monovalent organic group containing a (meth)acryloyl group.
• At least one of R 6 and R 7 contained in the polyimide precursor is preferably a structural unit represented by the following general formula (3).
• R 1 , R 2 and R 3 each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group
• R 8 represents a monovalent organic group containing a (meth)acryloyl group
• * represents a bonding position.
• R 1 , R 2 and R 3 are preferably hydrogen atoms.
• the monovalent organic group containing a (meth)acryloyl group for R 8 may have 1 to 10 carbon atoms, or 2 to 5 carbon atoms, excluding the (meth)acryloyl group.
• the monovalent organic group containing a (meth)acryloyl group for R 8 may be a group represented by the following general formula (4).
• R 9 to R 11 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms
• R x represents a divalent linking group
• * represents a bonding position
• the carbon number of the aliphatic hydrocarbon group represented by R 9 to R 11 in general formula (4) is 1 to 3, and preferably 1 or 2.
• Specific examples of the aliphatic hydrocarbon group represented by R 9 to R 11 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc., and a methyl group is preferred.
• R 9 to R 11 in the general formula (4) a combination in which R 9 and R 10 are hydrogen atoms and R 11 is a hydrogen atom or a methyl group is preferable.
• R x is a divalent linking group and may have 1 to 10 carbon atoms, or may have 2 to 5 carbon atoms.
• R x preferably contains an ether bond.
• R6 and R7 are a group represented by general formula (4), and it is more preferable that both of R6 and R7 are groups represented by general formula (4).
• the ratio of R6 and R7 which are groups represented by general formula (4), 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. There is no particular upper limit. It may be 100 mol %. The above ratio may be 0 mol % or more and less than 60 mol %.
• the polyimide precursor composition of the present disclosure includes a polyimide precursor including a structural unit represented by the above-mentioned general formula (1) and a structural unit represented by the above-mentioned general formula (2), and a polymerization inhibitor.
• the polyimide precursor composition of the present disclosure can produce a photosensitive resin composition having excellent photosensitivity properties.
• the polyimide precursor contained in the polyimide precursor composition of the present disclosure differs from the polyimide precursor of the present disclosure described above in that the ratio of the structure formed by a reaction between a vinyl group and a carboxy group in a vinyl ether compound having a (meth)acryloyl group to the structure formed by a reaction between a vinyl group and a carboxy group in a vinyl ether compound is not particularly limited.
• a preferred embodiment of the polyimide precursor contained in the polyimide precursor composition of the present disclosure is the same as the preferred embodiment of the polyimide precursor of the present disclosure described above.
• polymerization inhibitor contained in the polyimide precursor composition of the present disclosure examples include 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide, 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, etc.
• 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide is preferred.
• the polymerization inhibitor may be used alone or in combination of two or
• the content of the polymerization inhibitor may be 0.1% by mass to 1.0% by mass, 0.2% by mass to 0.8% by mass, or 0.2% by mass to 0.5% by mass relative to the total amount of the polyimide precursor composition.
• the method for producing a photosensitive resin composition of the present disclosure includes a step of producing a polyimide precursor by the method for producing a polyimide precursor of the present disclosure, and a step of producing a photosensitive resin composition using the polyimide precursor.
• a photosensitive resin composition can be produced by mixing the polyimide precursor produced by the method for producing a polyimide precursor of the present disclosure with other components.
• the other components are not particularly limited and include solvents, polymerizable monomers, photopolymerization initiators, sensitizers, coupling agents, thermal polymerization initiators, polymerization inhibitors, antioxidants, surfactants, leveling agents, rust inhibitors, nitrogen-containing compounds, dicarboxylic acids, fillers, etc., and the composition may contain at least one component selected from these.
• the polyimide precursor produced by the method for producing a polyimide precursor according to the present disclosure may be, for example, a polyimide precursor solution in which a polyimide precursor is dissolved in an organic solvent, or the polyimide precursor solution may be mixed with the other components described above.
• the photosensitive resin composition of the present disclosure includes the polyimide precursor of the present disclosure or the polyimide precursor composition of the present disclosure.
• the photosensitive resin composition may include other components exemplified in the method for producing a polyimide precursor of the present disclosure.
• the method for producing a cured product of the present disclosure includes a step of producing a photosensitive resin composition using the method for producing a photosensitive resin composition of the present disclosure, and curing the produced photosensitive resin composition to produce a cured product.
• the photosensitive resin composition used for producing the cured product may be either negative or positive.
• the cured product may be a patterned cured product or a non-patterned cured product.
• the average thickness of the cured product is preferably 5 ⁇ m to 20 ⁇ m.
• the method for producing the patterned cured product preferably includes the steps of applying a photosensitive resin composition onto a substrate and drying to form a photosensitive resin film, exposing the photosensitive resin film to a pattern to obtain a resin film, developing the resin film after the pattern exposure with a developer to obtain a patterned resin film, and heat-treating the patterned resin film.
• the method for producing the patternless cured product includes a step of forming a photosensitive resin film and a step of performing a heat treatment. It may further include a step of exposing to light.
• 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 80° C. to 150° C., and from the viewpoint of ensuring the dissolution contrast, it is more preferably 80° 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. In this way, a photosensitive resin film can be obtained in which the photosensitive resin composition 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 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 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 can be used as an interlayer insulating film, a cover coat layer, or a surface protective film, and further, the cured product can be used as a passivation film, a buffer coat film, etc.
• a passivation film a buffer coat film, 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.
• the semiconductor device of the present disclosure includes a cured product obtained by curing the above-described photosensitive resin composition of the present disclosure.
• FIG. 1 is a manufacturing process diagram of a semiconductor device having a multilayer wiring structure 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.
• Example 1 (Synthesis Example 1 (Synthesis of A1)) 48.38 parts by mass of ⁇ -butyrolactone as a solvent was added to a 100 mL separable flask, followed by the addition of 1.75 parts by mass (0.0162 mol) of paraphenylenediamine (PPD) as a diamine compound and 3.44 parts by mass (0.0162 mol) of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) as a diamine compound, and the diamine compound was dissolved in the solvent by stirring.
• PPD paraphenylenediamine
• DMAP 2,2'-dimethylbiphenyl-4,4'-diamine
• reaction liquid containing the polyamic acid 0.129 parts by mass of 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide as a polymerization inhibitor was added, and 26.81 parts by mass (0.1440 mol) of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark) as a vinyl ether compound was further added, and the mixture was stirred at 60° C. for 6 hours to obtain a reaction liquid containing a polyimide precursor (A1).
• VEEA 2-(2-vinyloxyethoxy)ethyl acrylate
• Example 2 A reaction liquid containing a polyimide precursor (A2) was obtained in the same manner as in Example 1, except that the amount of the polymerization inhibitor was changed to 0.119 parts by mass, and the amount of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark) was changed to 23.46 parts by mass (0.1260 mol).
• VEEA 2-(2-vinyloxyethoxy)ethyl acrylate
• Example 3 A reaction liquid containing a polyimide precursor (A3) was obtained in the same manner as in Example 1, except that the amount of the polymerization inhibitor was changed to 0.109 parts by mass and the amount of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark) was changed to 20.11 parts by mass (0.1080 mol).
• VEEA 2-(2-vinyloxyethoxy)ethyl acrylate
• Example 4 (Synthesis of A4) 45.4 parts by mass of ⁇ -butyrolactone as a solvent was added to a 100 mL separable flask, followed by the addition of 1.75 parts by mass (0.0162 mol) of paraphenylenediamine (PPD) as a diamine compound and 3.44 parts by mass (0.0162 mol) of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) as a diamine compound, and the diamine compound was dissolved in the solvent by stirring.
• PPD paraphenylenediamine
• DMAP 2,2'-dimethylbiphenyl-4,4'-diamine
• reaction liquid containing polyamic acid 0.126 parts by mass of 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide as a polymerization inhibitor was added, and 26.81 parts by mass (0.1440 mol) of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark) as a vinyl ether compound was further added, and the mixture was stirred at 60° C. for 6 hours to obtain a reaction liquid containing a polyimide precursor (A4).
• VEEA 2-(2-vinyloxyethoxy)ethyl acrylate
• Example 5 (Synthesis Example 5 (Synthesis of A5)) 44.54 parts by mass of ⁇ -butyrolactone as a solvent was added to a 100 mL separable flask, followed by the addition of 1.75 parts by mass (0.0162 mol) of paraphenylenediamine (PPD) as a diamine compound and 3.44 parts by mass (0.0162 mol) of 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) as a diamine compound, and the diamine compound was dissolved in the solvent by stirring.
• PPD paraphenylenediamine
• DMAP 2,2'-dimethylbiphenyl-4,4'-diamine
• reaction liquid containing the polyamic acid 0.125 parts by mass of 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide as a polymerization inhibitor was added, and 26.81 parts by mass (0.1440 mol) of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark) as a vinyl ether compound was further added, and the mixture was stirred at 60° C. for 6 hours to obtain a reaction liquid containing a polyimide precursor (A5).
• VEEA 2-(2-vinyloxyethoxy)ethyl acrylate
• reaction liquid containing the polyamic acid 0.135 parts by mass of 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-2,3-dioxide as a polymerization inhibitor was added, and 26.81 parts by mass (0.1440 mol) of 2-(2-vinyloxyethoxy)ethyl acrylate (VEEA: registered trademark) as a vinyl ether compound was further added, followed by stirring at 60° C. for 6 hours to obtain a reaction liquid containing a polyimide precursor (A6).
• VEEA 2-(2-vinyloxyethoxy)ethyl acrylate
• the obtained photosensitive resin composition was spin-coated on a silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Limited) and dried at 100° C. for 200 seconds to form a photosensitive resin film having a dry film thickness as shown in Table 1.
• the photosensitive resin film thus obtained was immersed in cyclopentanone for 7 seconds, and the dissolved film thickness was measured.Furthermore, the dissolution rate ( ⁇ m/s) was measured from the remaining film thickness. The results are shown in Table 1.
• the obtained photosensitive resin composition was spin-coated on a silicon wafer using a coating device Act8 (manufactured by Tokyo Electron Limited) and dried at 100° C. for 200 seconds to form a photosensitive resin film.
• the dry film thickness of the obtained photosensitive resin film was measured.
• the rotation speed during spin coating was 1000 rpm (revolutions/min) in each example and 2700 rpm in Comparative Example 1.
• a photosensitive resin film was formed in the same manner as above, and the obtained photosensitive resin film was exposed to light using an i-line stepper NES2WA06 (manufactured by Nikon Corporation) at an exposure dose of 100 mJ/cm 2 to 1100 mJ/cm 2 .
• the resin film after exposure and heating was paddle-developed in cyclopentanone using Act8 for a development time of 20 seconds (each Example) or 66 seconds (Comparative Example 1), and then rinsed with propylene glycol monomethyl ether acetate (PGMEA) to obtain a patterned resin film.

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• 2023
  • 2023-09-25 WO PCT/JP2023/034787 patent/WO2025069157A1/ja active Pending
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