Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • 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
  • G03F7/032—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

Definitions

• the present disclosure relates to a method for producing a polyimide precursor, a polyimide precursor, a photosensitive resin composition, a cured product, a method for producing a patterned cured product, and an electronic component.
• Organic materials having high heat resistance such as polyimide resins, are widely used as protective film materials for semiconductor integrated circuits (LSIs) (see, for example, Japanese Patent Application Laid-Open No. 2003-233634).
• 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.
• NMP N-methyl-2-pyrrolidone
• the present disclosure has been made in consideration of the above-mentioned conventional circumstances, and aims to provide a method for producing a polyimide precursor having a low fluorine content, a method for producing a polyimide precursor, a photosensitive resin composition, a cured product, a patterned cured product, and an electronic component.
• a method for producing a polyimide precursor comprising esterifying an isoimide polymer with an alcohol having an unsaturated double bond using a fluorine-free acid or base as a catalyst.
• the condensing agent contains a carbodiimide compound.
• ⁇ 4> The method for producing a polyimide precursor according to any one of ⁇ 1> to ⁇ 3>, wherein the fluorine-free acid has a pKa of 1 or less in water at 25° C.
• ⁇ 5> The method for producing a polyimide precursor according to any one of ⁇ 1> to ⁇ 3>, wherein the fluorine-free base has a pKa of 7 or more in water at 25° C.
• ⁇ 6> The method for producing a polyimide precursor according to any one of ⁇ 1> to ⁇ 5>, wherein the alcohol having an unsaturated double bond includes an alcohol represented by the following general formula (2): [In formula (2), 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.]
• 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.
• ⁇ 7> The method for producing a polyimide precursor according to any one of ⁇ 1> to ⁇ 6>, wherein the polyimide precursor contains a compound represented by the following formula (6): (In general formula (6), X represents a tetravalent organic group, and Y represents a divalent organic group.
• R 6 and R 7 each independently represent a hydrogen atom, a group represented by the following general formula (7), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and at least one of R 6 and R 7 represents a group represented by the following general formula (7).
• R 8 to R 10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and q represents an integer of 1 to 10.
• ⁇ 8> The method for producing a polyimide precursor according to any one of ⁇ 1> to ⁇ 7>, wherein an esterification rate in the esterification is 74% or more.
• a polyimide precursor comprising an ester of an isoimide polymer and an alcohol having an unsaturated double bond, the polyimide precursor having a fluorine content of 13 ppm by mass or less.
• R 6 and R 7 each independently represent a hydrogen atom, a group represented by the following general formula (7), or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and at least one of R 6 and R 7 represents a group represented by the following general formula (7).
• R 8 to R 10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and q represents an integer of 1 to 10.
• a photosensitive resin composition comprising a polyimide precursor having an unsaturated double bond, a polymerizable monomer, and a solvent, and having a fluorine content of 10 ppm by mass or less.
• ⁇ 17> The cured product according to ⁇ 16>, which is a patterned cured product.
• ⁇ 18> The cured product according to ⁇ 16> or ⁇ 17>, which is used as an interlayer insulating film, a cover coat layer, or a surface protective film.
• ⁇ 19> An electronic part comprising the cured product according to any one of ⁇ 16> to ⁇ 18>.
• the present disclosure provides a method for producing a polyimide precursor having a low fluorine content, a method for producing a polyimide precursor, a photosensitive resin composition, a cured product, a 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.
• 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 range indicated using “to” includes 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.
• 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 or the like. In the present disclosure, when the thickness of the layer or film can be measured directly, it is measured using a micrometer. On the other hand, when the thickness of one layer or the total thickness of multiple layers is measured, it may be measured by observing the cross section of the measurement target using an electron microscope.
• the method for producing a polyimide precursor according to the present disclosure is a method for esterifying an isoimide polymer with an alcohol having an unsaturated double bond using a fluorine-free acid or base as a catalyst, which makes it possible to obtain a polyimide precursor having a low fluorine content.
• One method for synthesizing a polyimide precursor having an unsaturated double bond is to react a tetracarboxylic dianhydride with an alcohol having an unsaturated double bond in an organic solvent to produce a diester derivative, and then to react the diester derivative with a diamine compound.
• NMP is generally used as the organic solvent.
• An alternative synthesis method includes an isoimide method in which a tetracarboxylic dianhydride is reacted with a diamine compound to form a polyamic acid polymer, which is then isoimidized in the presence of a condensing agent, and an alcohol having an unsaturated double bond is further added to the isoimidized polymer to effect esterification.
• a condensing agent e.g., it was found that the polyimide precursor obtained by this method has a high fluorine content, and it was found that the cause is due to the acid compound used as a condensing agent.
• the acid compound as a condensing agent not only functions as a condensing agent in the isoimidization step, but also functions as a catalyst in the esterification reaction step. Therefore, it was found that the acid compound remains in the finally obtained polyimide precursor, and as a result, the fluorine content is increased.
• a fluorine-free acid or base is used as a catalyst in the esterification reaction between an isoimide polymer and an alcohol having an unsaturated double bond.
• a fluorine-free acid or base as a catalyst for the esterification reaction, it is possible to obtain a polyimide precursor with a low fluorine content.
• some of the fluorine-free acids or bases can improve the esterification rate compared to conventional catalysts.
• the isoimide polymer is not particularly limited, and examples thereof include compounds having a structural unit represented by the following formula (6-1).
• X represents a tetravalent organic group
• Y represents a divalent organic group.
• the isoimide polymer may have a plurality of structural units represented by the general formula (6-1), and X and Y in the plurality of structural units 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 or an alicyclic 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 alicyclic ring include a cycloalkane structure having 3 to 8 carbon atoms and a spiro ring structure having 5 to 25 carbon atoms.
• the tetravalent organic group represented by X is preferably an aromatic hydrocarbon group.
• 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.
• the 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 one to four benzene rings, more preferably contains one to three benzene rings, and even more preferably contains one or two benzene rings.
• the respective 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 A 's independently represents a hydrogen atom, an alkyl group, or a
• 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, both A and B cannot 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 be a structure represented by the following formula (
• 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 the above 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 tetravalent organic group represented by X may contain an alicyclic ring from the viewpoint of adjusting the thermal expansion coefficient when the cured product is formed.
• examples of the alicyclic ring include a ring structure that does not contain an unsaturated bond such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a decahydronaphthalene ring, a norbornane ring, an adamantane ring, a bicyclo[2.2.2]octane ring, and a ring structure that contains an unsaturated bond such as a cyclohexene ring.
• Examples of the alicyclic ring include a spiro ring structure that contains these ring structures.
• a specific example of the tetravalent organic group represented by X having a spiro ring structure is represented by the following formula (P).
• 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) to (H).
• the group represented by the following formula (H) is preferred, and in the following formula (H), D is more preferably a group containing a single bond or an ether bond, and even more preferably a single bond or an ether bond.
• R each independently represents an alkyl group, an alkoxy group, a hydroxyl 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.
• 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 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.
• 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''').
• 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 method for producing the isoimide polymer is not particularly limited, but a polyamic acid polymer may be isoimidized in the presence of a condensing agent.
• the polyamic acid polymer may be obtained by reacting a tetracarboxylic dianhydride with a diamine compound.
• the tetracarboxylic dianhydride used as the raw material for isoimide polymers is represented by the following general formula (8):
• X is the same as X in the general formula (6-1), and specific examples and preferred examples are also the same.
• Specific examples of tetracarboxylic dianhydrides include pyromellitic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride (ODPA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 1,4,5,8-naphthalene Tetracarboxylic acid dianhydride, 3,4,9,10-perylenetetracarboxylic acid dianhydride, m-
• the diamine compound used as the raw material of the isoimide polymer may be a diamine compound represented by H 2 N-Y-NH 2 , where Y is the same as Y in general formula (6-1), and specific examples and preferred examples are also the same.
• Specific examples of the diamine compound include 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP), 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'
• diamine compound 2,2'-dimethylbiphenyl-4,4'-diamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, and 1,3-bis(3-aminophenoxy)benzene are preferred.
• the diamine compounds may be used alone or in combination of two or more kinds.
• the condensing agent preferably contains a carbodiimide compound from the viewpoint of not increasing the fluorine content in the polyimide precursor and efficiently producing an isoimide.
• the carbodiimide compound as the condensing agent include 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC), N,N'-dicyclohexylcarbodiimide (DCC), N,N'-diisopropylcarbodiimide (DIC), and the like. It is preferable to contain at least one selected from the group consisting of EDC, DCC, and DIC, and it is more preferable to contain EDC.
• the carbodiimide compounds may be used alone or in combination of two or more kinds.
• the condensing agent may contain other condensing agents other than the carbodiimide compound.
• the other condensing agents include imidazole compounds, triazine compounds, uronium compounds, and haluronium compounds.
• the other condensing agents may be used alone or in combination of two or more.
• the condensing agent preferably does not contain a fluorine atom.
• the content of the carbodiimide compound in the total condensing agent is preferably 30% by mass or more, more preferably 50% by mass or more, and may be 100% by mass.
• a reaction scheme for obtaining an isoimide polymer is shown below when a tetracarboxylic dianhydride represented by general formula (8) is used as the tetracarboxylic dianhydride and a diamine compound represented by H 2 N-Y-NH 2 is used as the diamine compound.
• D represents a condensing agent.
• the synthesis of the isoimide polymer is preferably carried out in a solvent.
• the solvent is preferably one that can dissolve the condensing agent, but may be one that does not dissolve the condensing agent.
• Examples of the solvent include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, dimethoxyimidazolidinone, 3-methoxy-N,N-dimethylpropionamide, N,N-dimethylpropionamide, and N,N-dimethylacetoacetamide, and among these, 3-methoxy-N,N-dimethylpropionamide is preferred.
• the amount of the solvent used is not particularly limited, and is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, and more preferably 300 parts by mass or more, per 100 parts by mass of the total amount of the tetracarboxylic dianhydride and the diamine compound.
• the amount of diamine compound added per mole of tetracarboxylic dianhydride is preferably 0.1 mole to 1.5 moles, more preferably 0.35 mole to 1.25 moles, and even more preferably 0.5 mole to 1.0 mole.
• the amount of the condensing agent used is preferably 0.5 to 3.5 moles, more preferably 1.0 to 3.0 moles, and even more preferably 1.5 to 2.5 moles, per mole of tetracarboxylic dianhydride.
• the reaction temperature in the isoimidization may be from 0°C to 60°C, although it varies depending on the types of tetracarboxylic dianhydride and diamine compound used as raw materials, and the type of condensing agent.
• the reaction time for isoimidization varies depending on the types of tetracarboxylic dianhydride and diamine compound as raw materials, the type of condensing agent, the reaction temperature, etc., but may be 0.5 to 24 hours.
• the alcohol includes an alcohol having an unsaturated double bond.
• the alcohol having an unsaturated double bond is not particularly limited as long as it is a compound represented by R-OH (R is a group having an unsaturated double bond), and it is more preferable to include an alcohol represented by the following general formula (2).
• R-OH R is a group having an unsaturated double bond
• 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.
• the alcohol represented by general formula (2) is preferably an alcohol represented by the following general formula (2'):
• R 8 to R 10 in formula (2′) each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms and have the same meaning as R 8 to R 10 in formula (2).
• 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 alcohol may be used in combination with other alcohols other than those having an unsaturated double bond.
• the other alcohols include alcohols having an aliphatic hydrocarbon group with 1 to 4 carbon atoms, and are preferably methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, or t-butanol, and more preferably methanol or ethanol.
• the other alcohols may be used alone or in combination with two or more types.
• fluorine-free acids and bases A fluorine-free acid or base is used as a catalyst for the esterification reaction between the isoimide polymer and the alcohol having an unsaturated double bond. From the viewpoint of suppressing the conversion reaction to imide and increasing the esterification rate, it is preferable to use an acid that does not contain a fluorine element.
• the fluorine-free acid preferably has a pKa of less than 5, more preferably 1 or less, further preferably 0 or less, and particularly preferably ⁇ 1 or less.
• the pKa here is a value in water at 25° C. The pKa is measured by neutralization titration.
• fluorine-free acids include methanesulfonic acid, formic acid, acetic acid, p-toluenesulfonic acid, benzoic acid, and citric acid, with methanesulfonic acid being preferred.
• the fluorine-free acids may be used alone or in combination of two or more kinds.
• the fluorine-free base preferably has a pKa of 5 or more, more preferably 7 or more, even more preferably 8 or more, and particularly preferably 10 or more.
• the pKa is the value in water at 25°C.
• fluorine-free base examples include pyridine, 1,4-diazabicyclo[2.2.2]octane, and 1,8-diazabicycloundecene, with 1,8-diazabicycloundecene being preferred.
• the fluorine-free base may be used alone or in combination of two or more kinds.
• the isoimide polymer is esterified with an alcohol having an unsaturated double bond.
• an alcohol having an unsaturated double bond For example, the reaction scheme when a compound having a structural unit represented by formula (6-1) is used as the isoimide polymer and a compound represented by R-OH (R is a group having an unsaturated double bond) is used as the alcohol having an unsaturated double bond is shown below.
• the alcohol used in the esterification of the isoimide polymer includes an alcohol having an unsaturated double bond, and other alcohols may be used in combination.
• the content of the alcohol having an unsaturated double bond in the total alcohol is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 100% by mass.
• the total amount of alcohol is preferably 1.5 moles or more, more preferably 1.8 moles or more, and even more preferably 2 moles or more, per mole of isoimide polymer.
• the amount of fluorine-free acid or base used as a catalyst is preferably 0.01 moles or more, more preferably 0.1 moles or more, and more preferably 1 mole or more per mole of isoimide polymer.
• Esterification may be carried out in a solvent.
• the solvent include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, dimethoxyimidazolidinone, and 3-methoxy-N,N-dimethylpropionamide, and among these, 3-methoxy-N,N-dimethylpropionamide is preferred. There is no particular restriction on the amount of the solvent used.
• the reaction temperature in the esterification may be from 0°C to 50°C, although it varies depending on the type of alcohol, the type of catalyst, etc.
• the reaction time for isoimidization varies depending on the type of alcohol, the type of catalyst, the reaction temperature, etc., but may be 0.5 to 12 hours.
• washing liquids include purified water and organic solvents
• organic solvents include alcohols such as methanol and ethanol, and acetone. These may be used alone or in combination of two or more.
• An example of a combination of two or more types is a mixture of purified water, acetone, methanol, and ethanol.
• the synthesis solution obtained by the above reaction is mixed with 2 to 10 times the amount of washing solution, and the synthesis solution and washing solution are stirred and suction filtered.
• the obtained wet cake is added to 2 to 10 times the amount of washing solution, stirred for 5 to 30 minutes at 50 to 500 rpm, and suction filtered. This operation may be repeated 1 to 5 times. After that, it is dried under reduced pressure at 20°C to 50°C for 1 to 72 hours to obtain a washed polyimide precursor.
• the polyimide precursor of the present disclosure contains an ester of an isoimide polymer and an alcohol having an unsaturated double bond, and preferably has a fluorine content of 50 ppm by mass or less.
• the polyimide precursor of the present disclosure is a polyimide precursor having an unsaturated double bond, and the fluorine content is preferably 100 ppm by mass or less, more preferably 50 ppm by mass or less, even more preferably 20 ppm by mass or less, and particularly preferably 13 ppm by mass or less.
• the polyimide precursor of the present disclosure may have a fluorine content of 5 ppm by mass or more, 8 ppm by mass or more, or 10 ppm by mass or more.
• the fluorine content in the polyimide precursor can be measured by combustion ion chromatography as described in the examples.
• the esterification rate of the polyimide precursor is preferably 74% or more, more preferably 78% or more, and even more preferably 80% or more.
• the esterification rate is the ratio (%) of the ester groups formed in the isoimide polymer by reaction with the alcohol to the total of the ester groups formed in the isoimide polymer by reaction with the alcohol and the carboxy groups not reacted with the alcohol.
• the esterification rate of the polyimide precursor can be measured by nuclear magnetic resonance (NMR) analysis.
• the polyimide precursor includes a polyimide precursor having an unsaturated double bond (hereinafter, may be referred to as an unsaturated polyimide precursor).
• the unsaturated double bond may be a carbon-carbon double bond.
• the unsaturated polyimide precursor may be, for example, a polyimide precursor having a structural unit represented by the following general formula (6): When the unsaturated polyimide precursor has a structural unit represented by the general formula (6), it tends to have high i-line transmittance and to form a good cured product even when cured at a low temperature of 300° C. or less.
• X represents a tetravalent organic group
• Y represents a divalent organic group
• R6 and R7 each independently represent a hydrogen atom, a group represented by formula (7) below, or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and at least one of R6 and R7 represents a group represented by formula (7) below.
• 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.
• X and Y in the general formula (6) have the same meanings as X and Y in the above general formula (6-1), respectively.
• the --COOR 6 group and the --CONH-- group are in the ortho position relative to each other
• the --COOR 7 group and the --CO-- group are in the ortho position relative to each other.
• the number of carbon atoms in the aliphatic hydrocarbon group represented by R6 and R7 in general formula (6) is 1 to 4, and preferably 1 or 2.
• Specific examples of the aliphatic hydrocarbon group represented by R6 and R7 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and the like.
• R 8 to R 10 in formula (7) have the same definitions as R 8 to R 10 in formula (2) above.
• R 6 and R 7 is a group represented by the general formula (7), and it is more preferable that both of R 6 and R 7 are a group represented by the general formula (7).
• the weight average molecular weight of the unsaturated polyimide precursor is preferably 10,000 to 200,000.
• 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 contains a polyimide precursor having an unsaturated double bond, a polymerizable monomer, and a solvent.
• the polyimide precursor having an unsaturated double bond may be a polyimide precursor having an unsaturated double bond obtained by the production method of the present disclosure.
• the photosensitive resin composition of the present disclosure preferably has a fluorine content of 30 ppm by mass or less, more preferably 20 ppm by mass or less, and even more preferably 10 ppm by mass or less.
• the fluorine content in the photosensitive resin composition can be measured by combustion ion chromatography, as described in the Examples.
• the photosensitive resin composition of the present disclosure is preferably a negative type photosensitive resin composition.
• the polyimide precursor having an unsaturated double bond may be a polyimide precursor having an unsaturated double bond obtained by the manufacturing method of the present disclosure.
• the unsaturated polyimide precursor may be a polyimide precursor having a structural unit represented by the above general formula (6).
• the content of the structural unit represented by the following general formula (6) in the unsaturated polyimide precursor is preferably 50 mol% or more, more preferably 80 mol% or more, and even more preferably 90 mol% or more, based on the total structural units contained in the unsaturated polyimide precursor.
• the upper limit is not particularly limited, and may be 100 mol%.
• the unsaturated polyimide precursor may have a structural unit other than the structural unit represented by general formula (6).
• the structural unit other than the structural unit represented by general formula (6) include a structural unit in which R 6 and R 7 in general formula (6) are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, that is, a structural unit in which neither R 6 nor R 7 in general formula (6) is a group represented by general formula (7).
• the photosensitive resin composition of the present disclosure contains a polymerizable monomer.
• the polymerizable monomer may be used alone or in combination of two or more.
• the polymerizable monomer may be a compound having at least one polymerizable unsaturated bond in the molecule, and is preferably a compound having two or more polymerizable unsaturated bonds in the molecule.
• Examples of the group containing a polymerizable unsaturated bond include an allyl group, an acryloyloxy group, a methacryloyloxy group, etc. Among these, an acryloyloxy group or a methacryloyloxy group is preferred.
• the molecular weight of the polymerizable monomer is preferably 50 to 1000, more preferably 75 to 800, and even more preferably 100 to 500.
• the polymerizable monomer is preferably a compound having two acryloyloxy groups or methacryloyloxy groups, and more preferably a compound in which two acryloyloxy groups or methacryloyloxy groups are linked by an aliphatic cyclic skeleton (hereinafter also referred to as an alicyclic monomer), or a compound in which two acryloyloxy groups or methacryloyloxy groups are linked by a linear divalent organic group (hereinafter also referred to as a linear monomer).
• Examples of the alicyclic skeleton in the alicyclic monomer 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, an isobornyl skeleton, etc.
• a tricyclodecane skeleton is preferable.
• the alicyclic monomer is preferably a compound represented by formula (1).
• 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 (2): n1 represents 0 or 1, n2 represents an integer of 0 to 2, and n1+n2 is 2 or 3. At least two of the n1 R1s and n2 R2s are groups represented by the following general formula (2).
• n is an integer from 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 (1) may be a compound represented by the following formula (3):
• the compound represented by formula (3) is available, for example, as DCP (tricyclodecane dimethanol dimethacrylate) from Shin-Nakamura Chemical Co., Ltd.
• the linear 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 an alkylene group having 1 to 8 carbon atoms
• R5 's represent an 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 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 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 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.
• polymerizable monomers besides alicyclic monomers and linear monomers include compounds represented by the following general formulas (13) to (16), styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N,N-dimethylacrylamide, and N-methylolacrylamide.
• R 111 and R 113 to R 115 are each independently a hydrogen atom, an acryloyl group, or a methacryloyl group
• L 1 is each independently a single bond, an alkylene group having 1 to 10 carbon atoms (preferably, a methylene group or an ethylene group), or a -R 116 -(OR 117 ) n1 - group
• R 112 is an alkyl group having 1 to 10 carbon atoms (preferably, a methyl group or an ethyl group).
• A is a substituted or unsubstituted heterocycle having 3 to 20 ring atoms.
• m is an integer of 2 to 6 (preferably, 3 or 4).
• R 116 is a single bond or an alkylene group having 1 to 10 carbon atoms (preferably, a methylene group or an ethylene group), and R 117 is an alkylene group having 1 to 10 carbon atoms (preferably, a methylene group or an ethylene group).
• n1 is an integer of 1 to 15.
• R 111 are acryloyl groups or methacryloyl groups
• R 113 are acryloyl groups or methacryloyl groups
• R 114 are acryloyl groups or methacryloyl groups
• R 115 are acryloyl groups or methacryloyl groups.
• a plurality of R 111 , R 113 to R 115 and L 1 may be the same or different.
• the plurality of R 116 and R 117 may be the same or different.
• R 111 is preferably an acryloyl group.
• R 113 is preferably an acryloyl group.
• R 114 is preferably an acryloyl group.
• R 115 is preferably a hydrogen atom or an acryloyl group.
• heterocyclic ring having 3 to 20 ring atoms for A examples include an isocyanuric acid ring and a triazine ring.
• substituent of the heterocyclic ring having 3 to 20 ring atoms include an alkyl group, a halogenated alkyl group, and a hydroxyl group.
• the sum of the multiple n1s is preferably 25 to 40, and more preferably 30 to 40.
• Specific examples of the compounds represented by general formulas (13) to (16) include trimethylolpropane diacrylate, trimethylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanuric acid triacrylate, ethoxylated isocyanuric acid trimethacrylate, acryl
• the content of the polymerizable monomer is not particularly limited, and is preferably 1 part by mass to 50 parts by mass, for example, relative to 100 parts by mass of the unsaturated polyimide precursor. From the viewpoint of improving the hydrophobicity of the cured product, it is more preferably 3 parts by mass to 50 parts by mass, and further preferably 5 parts by mass to 35 parts by mass.
• the content of the polymerizable monomer is within the above range, a practical relief pattern is easily obtained and post-development residues in unexposed areas are easily suppressed.
• the photosensitive resin composition of the present disclosure contains a solvent.
• the solvent include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, methyl 3-methoxypropionate, N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, methyl amyl ketone, and N-dimethylmorpholine, and are not particularly limited as long as they can sufficiently dissolve each component contained in the photosensitive resin composition. From the viewpoint of international regulations, it is preferable to limit the use of N-methyl-2-pyrrolidone. As
• 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-dimethylpropionamide (for example, trade name "KJCMPA-100" (manufactured by KJ Chemicals Co., Ltd.)).
• the solvent may be used alone or in combination of two or more kinds.
• the content of the solvent is not particularly limited, but is generally 50 parts by mass to 1,000 parts by mass per 100 parts by mass of the total amount of the polyamic acid ester polymer and the polymerizable monomer.
• the photosensitive resin composition of the present disclosure may contain a photopolymerization initiator.
• the photopolymerization initiator is not particularly limited as long as it is a compound capable of generating radicals when irradiated with actinic rays, such as ultraviolet rays such as i-rays, visible light, and radiation.
• Photopolymerization initiators include oxime compounds, acylphosphine oxide compounds, acyldialkoxymethane compounds, etc.
• the photopolymerization initiator preferably contains at least one compound selected from the group consisting of compounds represented by the following general formula (9) and compounds represented by the following general formula (10).
• 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 (10) include the compound represented by the following formula (10-1), available as "IRGACURE OXE 01" manufactured by BASF Japan Ltd. Also included is the compound represented by the following formula (10-2), available as "NCI-930" manufactured by ADEKA Corporation.
• the photopolymerization initiator may be used alone or in combination of two or more types.
• the content of the photopolymerization initiator 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 total amount of the polyamic acid ester polymer and the polymerizable monomer.
• content of the photopolymerization initiator is within the above range, photocrosslinking tends to be uniform in the film thickness direction, making it easier to obtain a practical relief pattern.
• 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 a polyamic acid ester polymer 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 polyamic acid ester polymer, 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 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, benzil dimethyl ketal, benzil diethyl ketal, diphenyl disulfide
• Sensitizers may be used alone or in combination of two or more.
• the amount of the sensitizer 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 polyamic acid ester polymer.
• 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, and the compound represented by the following formula F1.
• Stabilizers may be used alone or in combination of two or more types.
• 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 total amount of the polyamic acid ester polymer and the polymerizable monomer.
• the photosensitive resin composition of the present disclosure may contain a coupling agent.
• the functional group portion of the coupling agent reacts with the polyamic acid ester polymer and the siloxane portion reacts with the substrate, thereby further improving the adhesion between the obtained cured product and the substrate.
• a preferred coupling agent is a silane coupling agent having a urea bond (-NH-CO-NH-), which can further increase the adhesion to the substrate even when curing is performed at a low temperature of 200° C. or less.
• the compound represented by the following general formula (12-1) is more preferred in that it exhibits excellent adhesiveness when cured at low temperatures.
• R 31 and R 32 each independently represent an alkyl group having 1 to 5 carbon atoms, a represents an integer of 1 to 10, and b represents an integer of 1 to 3.
• compounds represented by general formula (12-1) include ureidomethyltrimethoxysilane, ureidomethyltriethoxysilane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, and the like, with 3-ureidopropyltriethoxysilane being preferred.
• a silane coupling agent having a hydroxyl group or a glycidyl group may be used as the coupling agent.
• a silane coupling agent having a hydroxyl group or a glycidyl group and a silane coupling agent having a urea bond in the molecule are used in combination, the adhesion of the cured product to the substrate during low-temperature curing can be further improved.
• silane coupling agent having a hydroxy group or a glycidyl group examples include methylphenylsilanediol, ethylphenylsilanediol, n-propylphenylsilanediol, isopropylphenylsilanediol, n-butylphenylsilanediol, isobutylphenylsilanediol, t-butylphenylsilanediol, diphenylsilanediol, ethylmethylphenylsilanol, n-propylmethylphenylsilanol, isopropylmethylphenylsilanol, n-butylmethylphenylsilanol, isobutylmethylphenylsilanol, t-butylmethylphenylsilanol, ethyl n-propylphenyl
• R 33 is a monovalent organic group having a hydroxy group or a glycidyl group
• R 34 and R 35 each independently are an alkyl group having 1 to 5 carbon atoms
• c is an integer of 1 to 10
• d is an integer of 1 to 3.
• Examples of the compound represented by the general formula (12-2) include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 4-hydroxybutyltrimethoxysilane, 4-hydroxybutyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, 2-glycidoxyethyltrimethoxysilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 4-glycidoxybutyltrimethoxysilane, 4-glycidoxybutyltriethoxysilane, etc.
• silane coupling agent having a hydroxy group or a glycidyl group preferably further contains a nitrogen atom, and a silane coupling agent having an amino group or an amide bond is preferred.
• silane coupling agents having a hydroxy group or a glycidyl group and also having an amino group include bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, bis(2-hydroxyethyl)-3-aminopropyltrimethoxysilane, bis(2-glycidoxyethyl)-3-aminopropyltriethoxysilane, and bis(2-glycidoxyethyl)-3-aminopropyltrimethoxysilane.
• Examples of silane coupling agents having a hydroxy group or a glycidyl group and an amide bond include compounds represented by R 36 -(CH 2 ) e -CO-NH-(CH 2 ) f -Si(OR 37 ) 3 (R 36 is a hydroxy group or a glycidyl group, e and f each independently are an integer of 1 to 3, and R 37 is a methyl group, an ethyl group, or a propyl group).
• R 38 is an alkyl group, g is an integer of 1 to 3, and R 39 is a methyl group, an ethyl group, or a propyl group).
• the coupling agent may be used alone or in combination of two or more types.
• 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 3 parts by mass to 10 parts by mass, relative to 100 parts by mass of the polyamic acid ester polymer.
• the photosensitive resin composition of the present disclosure may contain at least one of a surfactant and a leveling agent.
• a surfactant and a leveling agent When the photosensitive resin composition contains at least one of a surfactant and a leveling agent, the coating property (e.g., suppression of striation (unevenness in film thickness)) and the developability can be improved.
• Surfactants or leveling agents include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, etc.
• Commercially available products include products under the trade names "Megafac (registered trademark) F171", “F173", and “R-08” (all manufactured by DIC Corporation), “Fluorad FC430” and “FC431” (all manufactured by Sumitomo 3M Limited), and “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 polyamic acid ester polymer.
• the photosensitive resin composition of the present disclosure may contain a rust inhibitor.
• a rust inhibitor When the photosensitive resin composition contains a rust inhibitor, corrosion of copper and copper alloys can be suppressed and discoloration can be prevented.
• the rust inhibitor include triazole derivatives and tetrazole derivatives.
• the rust inhibitors may be used alone or in combination of two or more.
• 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 total amount of the polyamic acid ester polymer and the polymerizable monomer.
• the cured product of the present disclosure can be obtained by curing the photosensitive resin composition of the present disclosure.
• the cured product of the present disclosure may be used as a patterned cured product or as a non-patterned cured product.
• the average thickness of the cured product of the present disclosure is preferably 5 ⁇ m to 20 ⁇ m.
• the method for producing a patterned cured product of the present disclosure includes the steps of applying the photosensitive resin composition of the present disclosure 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 using a developer to obtain a patterned resin film, and heat-treating the patterned resin film. This allows a patterned cured product to be obtained.
• a method for producing a patternless cured product includes, for example, a step of forming a photosensitive resin film of the present disclosure and a step of heat treatment. It may further include a step of exposure 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 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 polyamic acid ester polymer 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 polyamic acid ester polymer 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 protection film. Furthermore, the cured product of the present disclosure can be used as a passivation film, a buffer coat film, etc.
• the electronic components of the present disclosure include the cured product of the present disclosure.
• 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 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.
• a 30 ml sample tube was filled with an NMP solution containing 5% by mass of N-butylamine, and approximately 0.5 ml of the reaction solution obtained above was added to it and shaken for about 10 seconds. Five drops of this solution were added to 3 ml of acetonitrile, and the components were analyzed using a high performance liquid chromatograph (HPLC).
• HPLC high performance liquid chromatograph
• Catalyst A Trifluoroacetic anhydride (TFA) (pKa: -0.3)
• Catalyst B methanesulfonic acid (MSA) (pKa: -2.6)
• Catalyst C acetic acid (AA) (pKa: 4.76)
• Catalyst D pyridine (pKa: 5.2)
• Catalyst E 1,4-diazabicyclo[2.2.2]octane (DABCO) (pKa: 8.8)
• Catalyst F 1,8-diazabicycloundecene (DBU) (pKa: 12)
• Esterification products were produced when any of catalysts A to F was used.
• catalysts with lower pKa values promoted esterification and suppressed imidization. Therefore, it was found that, from the viewpoint of esterification rate, MSA was preferable among the catalysts tested. Furthermore, when catalyst A was used, the fluorine content in the esterified product was high.
• the esterification rate hardly changed even when the reaction time was changed from 1 to 20 minutes.
• the esterification rate increased with increasing reaction time, and remained high for 10 minutes or more.
• the esterification rate remained at the same high level as when the catalyst was 0.1 mol eq, even with a reaction time of 1 minute.
• Example 1 3,3',4,4'-biphenylethertetracarboxylic dianhydride (ODPA) was dried in a dryer at 160° C. In addition, 2,2'-dimethylbiphenyl-4,4'-diamine (DMAP) was dried under reduced pressure at 40° C.
• ODPA 3,3',4,4'-biphenylethertetracarboxylic dianhydride
• DMAP 2,2'-dimethylbiphenyl-4,4'-diamine
• KJCMPA-100 3-methoxy-N,N-dimethylpropionamide
• DABCO 1,4-diazabicyclo[2.2.2]octane
• HEMA 2-hydroxyethyl methacrylate
• the weight average molecular weight Mw was 22,200 and the dispersity (Mw/Mn) was 1.5.
• the obtained polyamic acid ester polymer was subjected to NMR measurement under the following conditions to calculate the esterification rate (the ratio of ester groups reacted with HEMA to the total of ester groups reacted with HEMA and carboxy groups unreacted with HEMA) which was 83.2 mol%.
• the fluorine content of the obtained polyamic acid ester polymer was measured by the following method.
• the fluorine content was 12.0 mg/kg (ppm by mass).
• the detection limit of the fluorine content in the following measurement method is 10.0 mg/kg.
• the measurement sample was heated and burned using the combustion tube decomposition-ion chromatography method, the generated gas was absorbed in an absorption liquid, and the amount of ions in the absorption liquid was quantified using ion chromatography.
• the analysis conditions were as follows:
• Example 2 A polyamic acid ester polymer was synthesized in the same manner as in Example, except that the amount of methanesulfonic acid (MSA) was changed to 7.6 g (1 mol eq).
• the weight average molecular weight Mw of the obtained polyamic acid ester polymer was 23,900, the polydispersity (Mw/Mn) was 1.5, the esterification rate was 75.8 mol%, and the fluorine content was 12.4 mg/kg (ppm by mass).
• a polyimide precursor having a low fluorine content can be obtained according to the method for producing a polyimide precursor of the present disclosure.
• acetic acid, pyridine, 1,4-diazabicyclo[2.2.2]octane, and 1,8-diazabicycloundecene can also be used as a catalyst other than methanesulfonic acid (MSA).
• MSA methanesulfonic acid
• a catalyst with a low pKa is preferable, and methanesulfonic acid (pKa: -2.6) showed a higher esterification rate than trifluoroacetic anhydride (pKa: -0.3).

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• 2022
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