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
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • 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
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/105—Esters; Ether-esters of monocarboxylic acids with phenols
  • C08K5/107—Esters; Ether-esters of monocarboxylic acids with phenols with polyphenols
• • 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
• • 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 invention relates to a resin composition, an insulating film, and a method for producing an interlayer insulating film for a redistribution layer.
• Patent Document 1 describes a method for producing a semiconductor device using a resin composition containing a polyimide precursor having a specific structure, a crosslinking agent (specifically, tetraethylene glycol dimethacrylate), and a solvent.
• Patent Document 2 describes a retardation plate having an alignment film formed by stretching a film containing a polymer having a specific structure, and an optically anisotropic layer containing a liquid crystal compound whose alignment is controlled by the alignment film.
• the fifth generation mobile communication system uses the millimeter wave (10 GHz to 80 GHz) frequency band, which enables high speed and large capacity, low signal latency, and simultaneous connection of multiple terminals that were not possible with conventional communications.
• the millimeter wave band the effect of transmission loss in the signal wiring of the printed wiring board is large, and there are concerns about heat generation and transmission delays.
• Polyimide compositions are widely used as packaging materials due to their excellent film properties.
• polyimides have polar imide groups
• photosensitive polyimide precursor compositions contain many polar compounds such as photopolymerization initiators and crosslinking agents, resulting in high dielectric constants and dielectric loss tangents, and there is a demand for reduced dielectric properties.
• an object of the present invention is to provide a resin composition that can give a film with a low dielectric tangent.
• Another object of the present invention is to provide an insulating film having a low dielectric tangent, and a method for producing an interlayer insulating film for a redistribution layer using the above resin composition.
• a resin composition comprising at least one polymer selected from the group consisting of polyimides and polyimide precursors, a liquid crystal compound, and a solvent.
• the solvent comprises at least one selected from the group consisting of N-methyl-2-pyrrolidone, ⁇ -butyrolactone, and dimethylsulfoxide.
• R 1 to R 6 each independently represent an organic group having 3 or more carbon atoms.
• the resin composition according to any one of [1] to [11] wherein the content of the colorant in the total solid content is 1 mass% or less.
• the present invention it is possible to provide a resin composition which can give a film having a low dielectric tangent. Furthermore, according to the present invention, it is possible to provide an insulating film having a low dielectric tangent, and a method for producing an interlayer insulating film for a redistribution layer using the above resin composition.
• a numerical range expressed using the symbol "to” means a range that includes the numerical values before and after "to” as the lower limit and upper limit, respectively.
• the term “step” includes not only an independent step, but also a step that cannot be clearly distinguished from another step, so long as the intended effect of the step can be achieved.
• groups (atomic groups) when there is no indication of whether they are substituted or unsubstituted, the term encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups).
• an "alkyl group” encompasses not only alkyl groups without a substituent (unsubstituted alkyl groups) but also alkyl groups with a substituent (substituted alkyl groups).
• exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and actinic rays or radiation such as electron beams.
• (meth)acrylate means both or either of “acrylate” and “methacrylate”
• (meth)acrylic means both or either of “acrylic” and “methacrylic”
• (meth)acryloyl means both or either of “acryloyl” and “methacryloyl”.
• Me represents a methyl group
• Et represents an ethyl group
• Bu represents a butyl group
• Ph represents a phenyl group.
• the total solid content refers to the total mass of all components of the composition excluding the solvent
• the solid content concentration refers to the mass percentage of the other components excluding the solvent with respect to the total mass of the composition.
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) unless otherwise specified, and are defined as polystyrene equivalent values.
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series as columns.
• these molecular weights are measured using THF (tetrahydrofuran) as the eluent.
• THF tetrahydrofuran
• NMP N-methyl-2-pyrrolidone
• detection in GPC measurement is performed using a UV (ultraviolet) ray (wavelength 254 nm detector).
• a third layer or element may be interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer.
• the direction in which the layers are stacked on the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as “upper”, and the opposite direction is referred to as "lower”. Note that such a vertical direction is set for the convenience of this specification, and in an actual embodiment, the "upper” direction in this specification may be different from the vertical upward direction.
• the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component.
• the content of each component in the composition means the total content of all compounds corresponding to that component.
• the temperature is 23° C.
• the pressure is 101,325 Pa (1 atm)
• the relative humidity is 50% RH.
• combinations of preferred aspects are more preferred aspects.
• the resin composition of the present invention contains at least one polymer selected from the group consisting of polyimides and polyimide precursors, a liquid crystal compound, and a solvent.
• the resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and is preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent.
• the resin composition of the present invention can be used, for example, to form an insulating film for a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer.
• the resin composition of the present invention may also be used to form a photosensitive film to be subjected to negative development.
• negative development refers to a development in which the non-exposed areas are removed by development during exposure and development
• positive development refers to a development in which the exposed areas are removed by development.
• the exposure method, the developer, and the development method for example, the exposure method described in the exposure step and the developer and development method described in the development step in the description of the production method of the cured product described later can be used.
• a film having a low dielectric tangent can be obtained.
• the mechanism by which the above effect is obtained is unclear, but is presumed to be as follows. It is believed that in a film formed using a resin composition containing at least one polymer selected from the group consisting of polyimides and polyimide precursors, a liquid crystal compound, and a solvent, the liquid crystal compound is oriented and polymer stacking is promoted, resulting in suppression of polymer movement and a decrease in the dielectric tangent.
• the film obtained from the resin composition of the present invention is a film with excellent elongation. It is believed that the film obtained from the resin composition of the present invention has improved elongation due to the formation of a three-dimensional network structure caused by the polymer stacking via the liquid crystal compound described above.
• the resin composition of the present invention contains at least one kind of polymer (also referred to as a specific resin) selected from the group consisting of polyimides and polyimide precursors.
• the specific resin is preferably a resin containing an imide ring structure in the main chain structure.
• the term "main chain” refers to the relatively longest bonding chain in a resin molecule, and the term “side chain” refers to any other bonding chain.
• the polyimide precursor refers to a resin that changes its chemical structure in response to an external stimulus to become a polyimide.
• a resin that changes its chemical structure in response to heat to become a polyimide is preferred, and a resin that changes its chemical structure in response to heat to become a polyimide by forming a ring structure is more preferred.
• the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
• the resin composition of the present invention preferably contains a radical polymerization initiator, more preferably contains a radical polymerization initiator and a radical crosslinking agent. If necessary, it can further contain a sensitizer.
• a negative photosensitive film is formed from such a resin composition.
• the specific resin may also have a polarity conversion group such as an acid-decomposable group.
• the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive-type photosensitive film or negative-type photosensitive film is formed.
• polyimide precursor used in the present invention is not particularly limited in type, but preferably contains a repeating unit represented by the following formula (2).
• A1 and A2 each independently represent an oxygen atom or -NRz-
• R111 represents a divalent organic group
• R115 represents a tetravalent organic group
• R113 and R114 each independently represent a hydrogen atom or a monovalent organic group
• Rz represents a hydrogen atom or a monovalent organic group.
• a 1 and A 2 each independently represent an oxygen atom or —NR z —, and preferably an oxygen atom.
• Rz represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.
• R 111 in formula (2) represents a divalent organic group. Examples of the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, and a group containing an aromatic group.
• a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferred, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferred.
• the linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a heteroatom, and the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a heteroatom.
• R 111 in formula (2) examples include groups represented by -Ar- and -Ar-L-Ar-, and a group represented by -Ar-L-Ar- is preferred.
• each Ar is independently an aromatic group
• L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 - or -NHCO-, or a group consisting of a combination of two or more of the above.
• the preferred ranges of these are as described above.
• R 111 is preferably derived from a diamine.
• the diamine used in the production of the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used.
• R 111 is preferably a diamine containing a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms.
• the linear or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom
• the cyclic aliphatic group and aromatic group may have a hydrocarbon group in the ring substituted with a group containing a hetero atom.
• groups containing an aromatic group include the following.
• * represents a bonding site with other structures.
• diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3-, or 1,4-diaminocyclohexane, 1,2-, 1,3-, or 1,4-bis(aminomethyl)cyclohexane, bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane, and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diamino
• diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of WO 2017/038598.
• diamines having two or more alkylene glycol units in the main chain are also preferably used.
• diamines having two or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of WO 2017/038598.
• R 111 is preferably represented by -Ar-L-Ar-.
• each Ar is independently an aromatic group
• L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 - or -NHCO-, or a group consisting of a combination of two or more of the above.
• Ar is preferably a phenylene group
• L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 -.
• the aliphatic hydrocarbon group here is preferably an alkylene group.
• R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61).
• R 111 is more preferably a divalent organic group represented by formula (61).
• R 50 to R 57 each independently represent a hydrogen atom, a fluorine atom, or a monovalent organic group, at least one of R 50 to R 57 represents a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2).
• the monovalent organic group for R 50 to R 57 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms).
• R 58 and R 59 each independently represent a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site to the nitrogen atom in formula (2).
• diamines that give the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'-bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, etc. These may be used alone or in combination of two or more.
• R 115 represents a tetravalent organic group.
• a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
• * each independently represents a bonding site with another structure.
• R 112 is a single bond or a divalent linking group and is preferably a single bond, or a group selected from an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 -, -NHCO-, and a combination thereof, more preferably a single bond, or an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, and -SO 2 -, and still more preferably a divalent group selected from the group consisting of -CH 2 -, -C(CF 3 ) 2 -, -C(CH 3 ) 2 -, -O-, -CO-, -S-, and -SO 2 -.
• R 115 include tetracarboxylic acid residues remaining after removal of anhydride groups from tetracarboxylic dianhydride.
• the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue or two or more types of tetracarboxylic dianhydride residues as the structure corresponding to R 115 .
• the tetracarboxylic dianhydride is preferably represented by the following formula (O).
• R 115 represents a tetravalent organic group.
• the preferred range of R 115 is the same as that of R 115 in formula (2), and the preferred range is also the same.
• tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfide tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl methane tetracarboxylic dianhydride, 2 ,2',3,3'-diphenylmethane tetracarboxylic dianhydride, 2,3,3',4'-biphenyl tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 4,4'-oxy
• tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.
• R 111 and R 115 may have an OH group. More specifically, R 111 may be a residue of a bisaminophenol derivative.
• R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
• the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
• the polymerizable group is a group capable of crosslinking by the action of heat, radicals, etc., and is preferably a radical polymerizable group.
• the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group.
• a group having an ethylenically unsaturated bond is preferable.
• Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.
• R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
• * represents a bonding site with another structure.
• R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
• R 201 examples include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-butanediyl group, -CH 2 CH(OH)CH 2 -, and polyalkyleneoxy groups, of which alkylene groups such as ethylene group and propylene group, -CH 2 CH(OH)CH 2 -, cyclohexyl group, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene group and propylene group, or polyalkyleneoxy groups are even more preferred.
• alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-but
• the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
• the alkylene groups in the multiple alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
• the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement, an arrangement having blocks, or an arrangement having a pattern such as alternating.
• the number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent, when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2.
• the alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom.
• the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.
• polyethyleneoxy group from the viewpoint of solvent solubility and solvent resistance, polyethyleneoxy group, polypropyleneoxy group, polytrimethyleneoxy group, polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded is preferred, polyethyleneoxy group or polypropyleneoxy group is more preferred, and polyethyleneoxy group is even more preferred.
• the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating. The preferred embodiment of the number of repetitions of the ethyleneoxy group etc. in these groups is as described above.
• the polyimide precursor when R 113 is a hydrogen atom or when R 114 is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond.
• a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.
• R 113 and R 114 may be a polarity conversion group such as an acid-decomposable group.
• the acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred.
• the acid-decomposable group examples include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
• the polyimide precursor has fluorine atoms in its structure.
• the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and 20% by mass or less.
• the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
• Specific examples include those using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. as the diamine.
• the repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one of the polyimide precursors used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
• a 1 and A 2 represent an oxygen atom
• R 111 and R 112 each independently represent a divalent organic group
• R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group
• at least one of R 113 and R 114 is a group containing a polymerizable group, and it is preferable that both are groups containing a polymerizable group.
• a 1 , A 2 , R 111 , R 113 and R 114 each independently have the same meaning as A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and the preferred range is also the same.
• R 112 has the same meaning as R 112 in formula (5), and the preferred range is also the same.
• the polyimide precursor may contain one type of repeating unit represented by formula (2), or may contain two or more types. It may also contain a structural isomer of the repeating unit represented by formula (2).
• the polyimide precursor may contain other types of repeating units in addition to the repeating unit of formula (2).
• One embodiment of the polyimide precursor of the present invention is one in which the content of the repeating unit represented by formula (2) is 50 mol% or more of all repeating units.
• the total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%.
• all repeating units in the polyimide precursor except for the terminals may be repeating units represented by formula (2).
• the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000.
• the number average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000.
• the polyimide precursor has a molecular weight dispersity of preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
• the upper limit of the molecular weight dispersity of the polyimide precursor is not particularly specified, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
• the dispersity of molecular weight is a value calculated by weight average molecular weight/number average molecular weight.
• the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide precursor are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as one resin are each within the above ranges.
• the polyimide used in the present invention may be an alkali-soluble polyimide, or may be a polyimide that is soluble in a developer containing an organic solvent as a main component.
• the alkali-soluble polyimide refers to a polyimide that dissolves at 0.1 g or more in 100 g of a 2.38 mass % aqueous tetramethylammonium solution at 23° C., and from the viewpoint of pattern formability, a polyimide that dissolves at 0.5 g or more is preferable, and a polyimide that dissolves at 1.0 g or more is more preferable.
• the upper limit of the dissolution amount is not particularly limited, but it is preferably 100 g or less.
• the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.
• the polyimide contains fluorine atoms.
• the fluorine atom is preferably contained, for example, in R 132 in the repeating unit represented by formula (4) described later or in R 131 in the repeating unit represented by formula (4) described later, and more preferably contained as a fluorinated alkyl group in R 132 in the repeating unit represented by formula (4) described later or in R 131 in the repeating unit represented by formula (4) described later.
• the amount of fluorine atoms relative to the total mass of the polyimide is preferably 5% by mass or more and 20% by mass or less.
• the polyimide contains a silicon atom.
• the silicon atom is preferably contained in R 131 in the repeating unit represented by formula (4) described later, and more preferably contained in R 131 in the repeating unit represented by formula (4) described later as an organically modified (poly)siloxane structure described later.
• the silicon atom or the organic modified (poly)siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
• the amount of silicon atoms relative to the total mass of the polyimide is preferably 1 mass % or more, and more preferably 20 mass % or less.
• the polyimide preferably has an ethylenically unsaturated bond.
• the polyimide may have an ethylenically unsaturated bond at the end of the main chain or in a side chain, but preferably in the side chain.
• the ethylenically unsaturated bond is preferably radically polymerizable.
• the ethylenically unsaturated bond is preferably contained in R 132 or R 131 in the repeating unit represented by formula (4) described below, and more preferably contained in R 132 or R 131 as a group having an ethylenically unsaturated bond.
• the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by formula (4) described below, and more preferably contained in R 131 as a group having an ethylenically unsaturated bond.
• the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, a group having an optionally substituted vinyl group directly bonded to an aromatic ring such as a vinylphenyl group, a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (IV).
• R 20 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
• R 21 represents an alkylene group having 2 to 12 carbon atoms, -O-CH 2 CH(OH)CH 2 -, -C( ⁇ O)O-, -O(C ⁇ O)NH-, a (poly)alkyleneoxy group having 2 to 30 carbon atoms (the number of carbon atoms in the alkylene group is preferably 2 to 12, more preferably 2 to 6, and particularly preferably 2 or 3; the number of repetitions in the alkyleneoxy group is preferably 1 to 12, more preferably 1 to 6, and particularly preferably 1 to 3), or a group consisting of a combination of two or more of these.
• the alkylene group having 2 to 12 carbon atoms may be any of linear, branched, and cyclic alkylene groups, and alkylene groups represented by a combination thereof.
• the alkylene group having 2 to 12 carbon atoms is preferably an alkylene group having 2 to 8 carbon atoms, and more preferably an alkylene group having 2 to 4 carbon atoms.
• R 21 is preferably a group represented by any one of the following formulae (R1) to (R3), and more preferably a group represented by formula (R1).
• L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly)alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded together;
• X represents an oxygen atom or a sulfur atom; * represents a bonding site with another structure; and
• ⁇ represents a bonding site with the oxygen atom to which R21 in formula (IV) is bonded.
• formulas (R1) to (R3) preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as L are the same as the preferred embodiments of the alkylene group having 2 to 12 carbon atoms or the (poly)alkyleneoxy group having 2 to 30 carbon atoms as R 21 in formula (IV).
• X is preferably an oxygen atom.
• * has the same meaning as * in formula (IV), and preferred embodiments are also the same.
• the structure represented by formula (R1) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate).
• the structure represented by formula (R2) can be obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate, etc.).
• the structure represented by formula (R3) can be obtained, for example, by reacting a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate, etc.).
• * represents a bonding site with another structure, and is preferably a bonding site with the main chain of the polyimide.
• the amount of ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.0005 to 0.05 mol/g.
• the polyimide may have a polymerizable group other than the group having an ethylenically unsaturated bond.
• the polymerizable group other than the group having an ethylenically unsaturated bond include an epoxy group, a cyclic ether group such as an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
• the polymerizable group other than the group having an ethylenically unsaturated bond is preferably included in, for example, R 131 in the repeating unit represented by formula (4) described below.
• the amount of polymerizable groups other than groups having ethylenically unsaturated bonds relative to the total mass of the polyimide is preferably 0.0001 to 0.1 mol/g, and more preferably 0.001 to 0.05 mol/g.
• the polyimide may have a polarity conversion group such as an acid-decomposable group.
• the acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R 113 and R 114 in the above formula (2), and preferred embodiments are also the same.
• the polarity conversion group is contained, for example, in R 131 and R 132 in the repeating unit represented by formula (4) described later, or at the terminal of the polyimide.
• the acid value of the polyimide is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, and even more preferably 70 mgKOH/g or more.
• the acid value is preferably 500 mgKOH/g or less, more preferably 400 mgKOH/g or less, and even more preferably 200 mgKOH/g or less.
• the acid value of the polyimide is preferably from 1 to 35 mgKOH/g, more preferably from 2 to 30 mgKOH/g, and even more preferably from 5 to 20 mgKOH/g.
• the acid value is measured by a known method, for example, the method described in JIS K 0070:1992.
• the acid group contained in the polyimide is preferably an acid group having a pKa of 0 to 10, more preferably 3 to 8, from the viewpoint of achieving both storage stability and developability.
• pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm pKa.
• pKa is a value calculated using ACD/ChemSketch (registered trademark) unless otherwise specified.
• ACD/ChemSketch registered trademark
• pKa the value listed in "Revised 5th Edition Chemistry Handbook: Basics” edited by the Chemical Society of Japan may be referred to.
• the acid group is a polyacid, such as phosphoric acid
• the pKa is the first dissociation constant.
• the polyimide preferably contains at least one type selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.
• the polyimide preferably has a phenolic hydroxy group.
• the polyimide may have a phenolic hydroxy group at the end of the main chain or on a side chain.
• the phenolic hydroxy group is preferably contained in, for example, R 132 or R 131 in the repeating unit represented by formula (4) described below.
• the amount of the phenolic hydroxy group relative to the total mass of the polyimide is preferably 0.1 to 30 mol/g, and more preferably 1 to 20 mol/g.
• the polyimide used in the present invention is not particularly limited as long as it is a polymeric compound having an imide structure, but it is preferable that it contains a repeating unit represented by the following formula (4).
• R 131 represents a divalent organic group
• R 132 represents a tetravalent organic group.
• the polymerizable group may be located at least one of R 131 and R 132 , or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2).
• R 133 is a polymerizable group, and the other groups are the same as those in formula (4).
• At least one of R 134 and R 135 is a polymerizable group, and when it is not a polymerizable group, it is an organic group, and the other groups have the same meanings as in formula (4).
• R 131 represents a divalent organic group.
• the divalent organic group include the same as those of R 111 in formula (2), and the preferred range is also the same.
• R 131 may be a diamine residue remaining after removal of the amino group of the diamine.
• the diamine may be an aliphatic, cycloaliphatic or aromatic diamine. Specific examples include the example of R 111 in the formula (2) of the polyimide precursor.
• R 131 is preferably a diamine residue having at least two alkylene glycol units in the main chain in order to more effectively suppress the occurrence of warping during firing, more preferably a diamine residue containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule, and even more preferably a diamine residue of the above diamine that does not contain an aromatic ring.
• Diamines containing two or more ethylene glycol chains, propylene glycol chains, or both in one molecule include, but are not limited to, Jeffamine (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (all trade names, manufactured by HUNTSMAN Co., Ltd.), 1-(2-(2-(2-aminopropoxy)ethoxy)propoxy)propan-2-amine, and 1-(1-(1-(2-aminopropoxy)propan-2-yl)oxy)propan-2-amine.
• R 132 represents a tetravalent organic group.
• examples of the tetravalent organic group include the same as those of R 115 in formula (2), and the preferred range is also the same.
• the four bonds of the tetravalent organic group exemplified as R 115 bond to the four —C( ⁇ O)— portions in formula (4) to form a condensed ring.
• R 132 may be a tetracarboxylic acid residue remaining after removal of the anhydride group from a tetracarboxylic dianhydride.
• a specific example is R 115 in the formula (2) of the polyimide precursor. From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
• R 131 and R 132 has an OH group. More specifically, preferred examples of R 131 include 2,2-bis(3-hydroxy-4-aminophenyl)propane, 2,2-bis(3-hydroxy-4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and the above (DA-1) to (DA-18), and more preferred examples of R 132 include the above (DAA-1) to (DAA-5).
• the polyimide has fluorine atoms in its structure.
• the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and more preferably 20% by mass or less.
• the polyimide may be copolymerized with an aliphatic group having a siloxane structure.
• diamine components include bis(3-aminopropyl)tetramethyldisiloxane and bis(p-aminophenyl)octamethylpentasiloxane.
• the main chain ends of the polyimide are blocked with a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
• a terminal blocking agent such as a monoamine, an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound.
• monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-amino
• the imidization rate of the polyimide (also referred to as the "ring closure rate") is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. There is no particular upper limit to the imidization rate, and it is sufficient if it is 100% or less.
• the imidization rate is measured, for example, by the following method. The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near 1377 cm ⁇ 1 , which is an absorption peak derived from the imide structure. Next, the polyimide is heat-treated at 350° C.
• the polyimide may contain repeating units represented by the above formula (4) in which all of the repeating units have the same combination of R 131 and R 132 , or may contain repeating units represented by the above formula (4) containing two or more different combinations of R 131 and R 132.
• the polyimide may contain other types of repeating units in addition to the repeating units represented by the above formula (4). Examples of other types of repeating units include the repeating units represented by the above formula (2).
• Polyimides can be synthesized, for example, by reacting tetracarboxylic dianhydride with diamine (partially substituted with a terminal blocking agent that is a monoamine) at low temperature, by reacting tetracarboxylic dianhydride (partially substituted with a terminal blocking agent that is an acid anhydride, monoacid chloride compound, or monoactive ester compound) with diamine at low temperature, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine) in the presence of a condensing agent, by obtaining a diester from tetracarboxylic dianhydride with alcohol and then converting the remaining dicarboxylic acid into an acid chloride and reacting it with diamine (partially substituted with a terminal blocking agent that is a monoamine), or by using a method in which a polyimide precursor is obtained and then completely
• the weight average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By making the weight average molecular weight 5,000 or more, the folding resistance of the film after curing can be improved. In order to obtain an organic film having excellent mechanical properties (e.g., breaking elongation), the weight average molecular weight is particularly preferably 15,000 or more.
• the number average molecular weight (Mn) of the polyimide is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and even more preferably from 4,000 to 20,000.
• the polyimide preferably has a molecular weight dispersity of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
• the upper limit of the polyimide molecular weight dispersity is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
• the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimides as one resin are each within the above ranges.
• the polyimide precursor or the like can be obtained by, for example, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid, and then esterifying the polyamic acid using a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then reacting the diamine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the diamine, etc.
• the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, and then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and then reacting the diamine is more preferable.
• the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.
• alkylating agent examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.
• halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride, and the like.
• the organic solvent may be one type or two or more types.
• the organic solvent can be appropriately selected depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and ⁇ -butyrolactone.
• a basic compound may be one type or two or more types.
• the basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.
• -End-capping agent- In the method for producing a polyimide precursor or the like, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the polyimide precursor or the like in order to further improve storage stability.
• examples of the terminal capping agent include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and it is more preferable to use monoalcohols, phenols, or monoamines in terms of reactivity and film stability.
• Preferred examples of monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol.
• primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol
• secondary alcohols such as isopropanol, 2-butanol, cycl
• Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.
• Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples of such an acid include 2-carboxy-7-aminonaphthalene, 2-car
• blocking agents for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, and the like, and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides.
• Preferred compounds of carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, and the like.
• carboxylic acid chloride examples include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.
• the method for producing a polyimide precursor or the like may include a step of precipitating a solid. Specifically, after filtering off the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction solution as necessary, the obtained polymer component is poured into a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid, and then dried to obtain a polyimide precursor or the like. In order to improve the degree of purification, the polyimide precursor or the like may be repeatedly subjected to operations such as redissolving, reprecipitation, and drying. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.
• the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition.
• the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition.
• the resin composition of the present invention may contain only one specific resin, or may contain two or more specific resins. When two or more specific resins are contained, the total amount is preferably within the above range.
• the resin composition of the present invention contains at least two types of resins.
• the resin composition of the present invention may contain a total of two or more types of the specific resin and the other resins described below, or may contain two or more types of specific resins, but it is preferable that the resin composition contains two or more types of specific resins.
• the resin composition of the present invention contains two or more specific resins, it preferably contains, for example, two or more polyimide precursors having different dianhydride-derived structures (R 115 in the above formula (2)).
• the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, simply referred to as "another resin").
• the other resins include polybenzoxazole, polybenzoxazole precursor, polyamideimide, polyamideimide precursor, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane resin, butyral resin, styryl resin, polyether resin, and polyester resin.
• the polybenzoxazole precursor includes the compounds described in paragraphs 0073 to 0095 of WO 2022/145355.
• Examples of polybenzoxazoles include compounds described in paragraphs 0096 to 0103 of WO 2022/145355.
• the above descriptions are incorporated herein by reference.
• Examples of polyamideimide precursors include compounds described in paragraphs 0104 to 0119 of WO 2022/145355.
• Examples of polyamideimides include the compounds described in paragraphs 0120 to 0133 of WO 2022/145355. The above descriptions are incorporated herein by reference.
• a resin composition having excellent coatability can be obtained, and a pattern (cured product) having excellent solvent resistance can be obtained.
• a (meth)acrylic resin having a weight average molecular weight of 20,000 or less and a high polymerizable group value for example, the molar content of polymerizable groups per 1 g of resin is 1 ⁇ 10 ⁇ 3 mol/g or more
• the coatability of the resin composition and the solvent resistance of the pattern (cured product) can be improved.
• the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the resin composition.
• the content of other resins in the resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, still more preferably 60 mass% or less, and even more preferably 50 mass% or less, based on the total solid content of the resin composition.
• the content of the other resin may be low.
• the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition.
• the lower limit of the content is not particularly limited, and may be 0% by mass or more.
• the resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.
• the resin composition of the present invention contains a liquid crystal compound.
• a liquid crystal compound is a compound having molecular orientation.
• the liquid crystal compound is preferably a rod-like liquid crystal compound or a discotic liquid crystal compound, and more preferably a discotic liquid crystal compound.
• the liquid crystal compound is preferably a compound represented by the following formula (1).
• R 1 to R 6 each independently represent an organic group having 3 or more carbon atoms.
• the organic group represented by R 1 to R 6 preferably has 3 or more and 30 or less carbon atoms, and more preferably has 5 or more and 20 or less carbon atoms.
• R 1 to R 6 are an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an acyl group, an acyloxy group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an arylcarbonyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an alkylamino group, a cycloalkylamino group, an arylamino group, or a group formed by combining two or more of these.
• the liquid crystal compound may or may not be a polymerizable compound, but is preferably a polymerizable compound.
• the liquid crystal compound preferably has a radically polymerizable unsaturated bond, and more preferably has an ethylenically unsaturated bond.
• a liquid crystal compound having a radically polymerizable unsaturated bond can function as a radical crosslinking agent.
• the liquid crystal compound is a compound represented by the above formula (1), and it is preferable that at least one of R 1 to R 6 has an ethylenically unsaturated bond, and it is more preferable that at least two of R 1 to R 6 have an ethylenically unsaturated bond.
• the liquid crystal compound may have an ethylenically unsaturated bond in the form of a group having an ethylenically unsaturated bond.
• the group having an ethylenically unsaturated bond include the group represented by the above formula (III), and specifically include a vinyl group, an allyl group, a (meth)acrylamide group, and a (meth)acryloyloxy group, and the (meth)acryloyloxy group is particularly preferred.
• the molecular weight of the liquid crystal compound is preferably 600 to 2500, more preferably 1000 to 2300, and even more preferably 1500 to 1900.
• the content of the liquid crystal compound is preferably more than 1% by mass and not more than 60% by mass based on the total solid content of the resin composition.
• the lower limit of the content of the liquid crystal compound is more preferably 5% by mass or more.
• the upper limit of the content of the liquid crystal compound is more preferably 50% by mass or less, and even more preferably 40% by mass or less.
• the liquid crystal compound may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably within the above range.
• the liquid crystal compound can be synthesized by a known method.
• M B /M A which is the ratio of the mass of the liquid crystal compound (total mass of the liquid crystal compound) M B to the mass of at least one polymer selected from the group consisting of polyimide and polyimide precursor (total mass of polyimide and polyimide precursor), M A , is preferably 0.01 to 0.60, more preferably 0.05 to 0.30, and further preferably 0.10 to 0.20.
• the resin composition of the present invention preferably contains a polymerizable compound.
• the polymerizable compound may include a radical crosslinking agent or other crosslinking agents.
• the polymerizable compound may be the above liquid crystal compound or a compound other than the above liquid crystal compound.
• the resin composition of the present invention preferably contains a radical crosslinking agent.
• the radical crosslinking agent is a compound having a radical polymerizable group.
• the radical polymerizable group is preferably a group containing an ethylenically unsaturated bond.
• Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
• a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.
• the radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds.
• the radical crosslinking agent may have three or more ethylenically unsaturated bonds.
• a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 ethylenically unsaturated bonds is even more preferable.
• the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the above-mentioned compound having three or more ethylenically unsaturated bonds.
• the molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
• the lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
• radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds.
• unsaturated carboxylic acids e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
• esters and amides preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds
• amides of unsaturated carboxylic acids and polyvalent amine compounds amides of unsaturated carboxylic acids and polyvalent amine compounds.
• addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sul
• addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable.
• the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure.
• Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021/112189, the contents of which are incorporated herein by reference.
• radical crosslinking agents other than those mentioned above include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021/112189, the contents of which are incorporated herein by reference.
• Preferred radical crosslinking agents are dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in which
• radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates with four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, TPA-330, a trifunctional acrylate with three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers.
• SR-494 a tetrafunctional acrylate with four ethyleneoxy chains
• SR-209, 231, and 239 which are difunctional methacrylates with four ethyleneoxy chains (all manufactured by Sartomer Corporation)
• DPCA-60 a hexafunctional acrylate with six pentyleneoxy chains
• TPA-330 a trifunctional acrylate with three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.)
• Examples include UAS-10 and UAB-140 (all manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (all manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corp.).
• radical crosslinking agents urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417, and JP-B-62-039418 are also suitable.
• radical crosslinking agents compounds having an amino structure or sulfide structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, can also be used.
• the radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group.
• the radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride.
• a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol.
• examples of commercially available products include polybasic acid modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.
• the acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, more preferably 1 to 100 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, the agent has excellent handling properties during manufacturing and developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.
• the radical crosslinking agent a radical crosslinking agent having at least one bond selected from the group consisting of a urea bond and a urethane bond (hereinafter, also referred to as "crosslinking agent U") is also preferred.
• a urethane bond is a bond represented by *--O--C(.dbd.O)-- NR.sub.N --*, where R.sub.N represents a hydrogen atom or a monovalent organic group, and * represents a bonding site with a carbon atom.
• R.sub.N represents a hydrogen atom or a monovalent organic group
• * represents a bonding site with a carbon atom.
• the crosslinking agent U may have only one urea bond or one urethane bond, may have one or more urea bonds and one or more urethane bonds, may have no urethane bonds but two or more urea bonds, or may have no urea bonds but two or more urethane bonds.
• the total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
• crosslinking agent U When crosslinking agent U has no urethane bond, the number of urea bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. When the crosslinking agent U has no urea bond, the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
• the radical polymerizable group in the crosslinking agent U is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. Of these, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred.
• the crosslinking agent U has two or more radically polymerizable groups, the structures of the respective radically polymerizable groups may be the same or different.
• the number of radical polymerizable groups in the crosslinking agent U may be only one or may be two or more, and is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.
• the radically polymerizable group value (mass of compound per mole of radically polymerizable group) in the crosslinking agent U is preferably 150 to 400 g/mol.
• the lower limit of the radically polymerizable group value is more preferably 200 g/mol or more, even more preferably 210 g/mol or more, still more preferably 220 g/mol or more, even more preferably 230 g/mol or more, still more preferably 240 g/mol or more, and particularly preferably 250 g/mol or more.
• the upper limit of the radically polymerizable group value is more preferably 350 g/mol or less, further preferably 330 g/mol or less, and particularly preferably 300 g/mol or less.
• the polymerizable group value of the crosslinking agent U is preferably from 210 to 400 g/mol, and more preferably from 220 to 400 g/mol.
• the crosslinking agent U preferably has a structure represented by the following formula (U-1):
• R U1 is a hydrogen atom or a monovalent organic group
• A is -O- or -NR N -
• R N is a hydrogen atom or a monovalent organic group
• Z U1 is an m-valent organic group
• Z U2 is an (n+1)-valent organic group
• X is a radical polymerizable group
• n is an integer of 1 or more
• m is an integer of 1 or more.
• R U1 is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
• R 3 N is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
• the above-mentioned hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms.
• the above-mentioned hydrocarbon group includes a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a combination thereof.
• R N represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.
• the hydrocarbon group includes the same as those exemplified for ZU1 , and preferred embodiments are also the same.
• X is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group.
• a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferable, and a (meth)acryloxy group is more preferable.
• n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably 1 or 2, and particularly preferably 1.
• m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.
• the cross-linking agent U has at least one of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group.
• the hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group, but is preferably an alcoholic hydroxy group.
• the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, even more preferably an alkyleneoxy group having 2 to 4 carbon atoms, still more preferably an ethylene group or propylene group, and particularly preferably an ethylene group.
• the alkyleneoxy group may be contained as a polyalkyleneoxy group in the crosslinking agent U.
• the number of repetitions of the alkyleneoxy group is preferably 2 to 10, and more preferably 2 to 6.
• crosslinking agent U has an amide group
• R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group.
• the crosslinking agent U may have, in the molecule, two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (when a polyalkyleneoxy group is formed, the group is a polyalkyleneoxy group), an amide group, and a cyano group. An embodiment having only one such structure in the molecule is also preferred.
• the hydroxy group, alkyleneoxy group, amide group and cyano group may be present at any position of the crosslinking agent U.
• the crosslinking agent U is such that at least one selected from the group consisting of the hydroxy group, alkyleneoxy group, amide group and cyano group and at least one radical polymerizable group contained in the crosslinking agent U are linked via a linking group containing a urea bond or a urethane bond (hereinafter, also referred to as "linking group L2-1").
• the crosslinking agent U contains only one radically polymerizable group
• the radically polymerizable group contained in the crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group are linked via a linking group containing a urea bond or a urethane bond (hereinafter also referred to as "linking group L2-2").
• the crosslinking agent U contains an alkyleneoxy group (however, when a polyalkyleneoxy group is constituted, a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2
• the structure bonded to the side of the alkyleneoxy group (however, when a polyalkyleneoxy group is constituted, a polyalkyleneoxy group) opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof.
• hydrocarbon group a hydrocarbon group having 20 or less carbon atoms is preferable, a hydrocarbon group having 18 or less carbon atoms is more preferable, and a hydrocarbon group having 16 or less carbon atoms is even more preferable.
• hydrocarbon group a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group represented by a bond thereof can be mentioned.
• a preferred embodiment of the radically polymerizable group is the same as the preferred embodiment of the radically polymerizable group in the crosslinking agent U described above.
• the structure bonded to the side of the amide group opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof.
• the hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms.
• examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a bond between these groups.
• a preferred embodiment of the radically polymerizable group is the same as the preferred embodiment of the radically polymerizable group in the crosslinking agent U described above.
• the carbon atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2, or the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or the linking group L2-2.
• the crosslinking agent U has a hydroxy group.
• the crosslinking agent U preferably contains an aromatic group.
• the aromatic group is preferably directly bonded to a urea bond or a urethane bond contained in the crosslinking agent U.
• the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group.
• the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably an aromatic hydrocarbon group.
• the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and even more preferably a group in which two or more hydrogen atoms have been removed from a benzene ring structure.
• the aromatic heterocyclic group is preferably a 5-membered or 6-membered aromatic heterocyclic group.
• aromatic heterocyclic ring in such an aromatic heterocyclic group examples include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. These rings may be further condensed with other rings, such as indole and benzimidazole.
• the heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
• the aromatic group is preferably contained in a linking group that links two or more radically polymerizable groups and contains a urea bond or a urethane bond, or a linking group that links at least one selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, amide group, and cyano group to at least one radically polymerizable group contained in the crosslinking agent U.
• the number of atoms (linking chain length) between the urea bond or urethane bond and the radical polymerizable group in the crosslinking agent U is not particularly limited, but is preferably 30 or less, more preferably 2 to 20, and even more preferably 2 to 10.
• the crosslinking agent U contains two or more urea bonds or urethane bonds in total, when it contains two or more radically polymerizable groups, or when it contains two or more urea bonds or urethane bonds and two or more radically polymerizable groups, the minimum number of atoms (linking chain length) between the urea bond or urethane bond and the radically polymerizable group may be within the above range.
• the "number of atoms (linking chain length) between a urea bond or a urethane bond and a polymerizable group” refers to the chain of atoms on the path connecting two atoms or groups of atoms to be linked that links these objects with the shortest length (minimum number of atoms).
• the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.
• the crosslinking agent U is a compound having a structure that does not have an axis of symmetry.
• the fact that the crosslinking agent U does not have an axis of symmetry means that the compound is a bilaterally asymmetric compound that does not have an axis that would produce an identical molecule to the original molecule by rotating the entire compound.
• the structural formula of the crosslinking agent U is written on paper, the fact that the crosslinking agent U does not have an axis of symmetry means that the structural formula of the crosslinking agent U cannot be written in a form that has an axis of symmetry. It is believed that since the crosslinking agent U does not have an axis of symmetry, aggregation of the crosslinking agents U within the composition film is suppressed.
• the molecular weight of the crosslinking agent U is preferably 100-2,000, more preferably 150-1500, and even more preferably 200-900.
• the method for producing the crosslinking agent U is not particularly limited, but it can be obtained, for example, by reacting a compound having a radical polymerizable compound and an isocyanate group with a compound having at least one of a hydroxy group or an amino group.
• cross-linking agent U Specific examples of cross-linking agent U are shown below, but cross-linking agent U is not limited to these.
• a difunctional methacrylate or acrylate for the resin composition.
• Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 Hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO (ethylene glycol diacrylate, triethylene glycol dimethacryl
• PEG200 diacrylate refers to polyethylene glycol diacrylate having a formula weight of about 200 for the polyethylene glycol chain.
• a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent.
• the monofunctional radical crosslinking agent a compound having a boiling point of 100° C. or more under normal pressure is also preferred in order to suppress volatilization before exposure.
• the difunctional or higher radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.
• the content of the radical crosslinking agent is preferably more than 0 mass% and not more than 60 mass% based on the total solid content of the resin composition.
• the lower limit is more preferably 5 mass% or more.
• the upper limit is more preferably 50 mass% or less, and even more preferably 30 mass% or less.
• the radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total amount is within the above range.
• cross-linking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022/145355, the disclosures of which are incorporated herein by reference.
• the resin composition of the present invention contains a solvent.
• the solvent may be any known solvent.
• the solvent is preferably an organic solvent.
• Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
• Esters for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -valerolactone, alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (for example,
• alkyloxypropionic acid alkyl esters include alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc.
• Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, di
• ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.
• cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.
• dimethyl sulfoxide is preferred.
• amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.
• ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.
• Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.
• toluene is further added to these combined solvents in an amount of about 1 to 10% by mass based on the total mass of the solvent is one of the preferred embodiments of the present invention.
• an embodiment containing ⁇ -valerolactone as a solvent is one of the preferred embodiments of the present invention.
• the content of ⁇ -valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more.
• the upper limit of the content is not particularly limited and may be 100% by mass.
• the content may be determined taking into consideration the solubility of components such as a specific resin contained in the resin composition, and the like.
• the solvent preferably contains 60 to 90 mass% of ⁇ -valerolactone and 10 to 40 mass% of dimethyl sulfoxide, more preferably 70 to 90 mass% of ⁇ -valerolactone and 10 to 30 mass% of dimethyl sulfoxide, and even more preferably 75 to 85 mass% of ⁇ -valerolactone and 15 to 25 mass% of dimethyl sulfoxide, relative to the total mass of the solvent.
• the resin composition of the present invention preferably contains a solvent in which at least one polymer selected from the group consisting of polyimides and polyimide precursors has a solubility of 1 mass % or more at 23° C., more preferably contains a solvent in which the solubility is 5 mass % or more and 60 mass % or less, and even more preferably contains a solvent in which the solubility is 10 mass % or more and 50 mass % or less.
• the solvent preferably contains at least one selected from the group consisting of N-methyl-2-pyrrolidone (NMP), ⁇ -butyrolactone, and dimethylsulfoxide (DMSO).
• the content of the solvent is preferably an amount that results in a total solids concentration of the resin composition of the present invention of 5 to 80 mass%, more preferably an amount that results in a total solids concentration of 5 to 75 mass%, even more preferably an amount that results in a total solids concentration of 10 to 70 mass%, and even more preferably an amount that results in a total solids concentration of 20 to 70 mass%.
• the content of the solvent may be adjusted according to the desired thickness of the coating film and the coating method. When two or more types of solvents are contained, the total amount is preferably within the above range.
• the resin composition of the present invention preferably contains a polymerization initiator.
• the polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable that the resin composition contains a photopolymerization initiator.
• the photopolymerization initiator is preferably a photoradical polymerization initiator.
• the photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet to visible regions is preferable. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.
• the photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 in a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm).
• the molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.
• halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
• acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles
• oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, ⁇ -aminoketone compounds such as aminoacetophenones, ⁇ -hydroxyketone compounds such as hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc.
• ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference.
• Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd.
• Nippon Kayaku Co., Ltd. is also preferably used.
• hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used, the contents of which are incorporated herein by reference.
• ⁇ -Hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).
• Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.
• aminoacetophenone initiator acylphosphine oxide initiator, and metallocene compound
• aminoacetophenone initiator acylphosphine oxide initiator, and metallocene compound
• the compounds described in paragraphs 0161 to 0163 of WO 2021/112189 can also be suitably used.
• the contents of this specification are incorporated herein.
• an oxime compound is more preferably used as a photoradical polymerization initiator.
• an oxime compound By using an oxime compound, it becomes possible to more effectively improve the exposure latitude.
• Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.
• oxime compounds include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, the compounds described in JP-A-2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.
• Preferred oxime compounds include, for example, compounds having the following structure, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one.
• an oxime compound as a photoradical polymerization initiator.
• oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (all manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA CORPORATION, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA CORPORATION), DFI-091 (manufactured by Daito Chemistry Co., Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Additionally, oxime compounds with the following structure can also be used.
• an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of WO 2021/112189 an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, or an oxime compound having a fluorine atom can be used.
• oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl group-containing substituent bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of WO 2021/020359 can also be used. The contents of these compounds are incorporated herein by reference.
• an oxime compound having an aromatic ring group Ar OX1 in which an electron-withdrawing group is introduced into an aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used.
• the electron-withdrawing group of the aromatic ring group Ar OX1 includes an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group.
• the benzoyl group may have a substituent.
• the substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group, or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group, and further preferably an alkoxy group, an alkyl
• the oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and is more preferably the compound represented by formula (OX2).
• R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group, or a sulfamoyl group; R X2 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsul
• R X12 is an electron-withdrawing group
• R X10 , R X11 , R X13 and R X14 are each a hydrogen atom.
• oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.
• oxime compounds include oxime compounds having specific substituents as disclosed in JP 2007-269779 A and oxime compounds having thioaryl groups as disclosed in JP 2009-191061 A, the contents of which are incorporated herein by reference.
• the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.
• the photoradical polymerization initiator is a trihalomethyltriazine compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound.
• At least one compound selected from the group consisting of a trihalomethyltriazine compound, an ⁇ -aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, or a benzophenone compound is more preferred, and a metallocene compound or an oxime compound is even more preferred.
• a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photoradical polymerization initiator.
• two or more radicals are generated from one molecule of the photoradical polymerization initiator, resulting in good sensitivity.
• crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time, and improving the stability of the resin composition over time.
• bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-2015/004565, WO-2016-532675, paragraphs 0407 to 0412, and WO-2017/033680, paragraphs 0039 to 0055; compound (E) and compound (G) described in WO-T-2013-522445; Examples of such initiators include Cmpd1 to 7 described in Japanese Patent Publication No.
• the content is preferably 0.1 to 30 mass% based on the total solid content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking caused by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.
• the resin composition may contain a sensitizer.
• the sensitizer absorbs specific active radiation and becomes electronically excited.
• the sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur.
• the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and are decomposed to generate a radical, an acid, or a base.
• Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based compounds, and the like.
• sensitizer examples include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, and p-dimethylaminobenzylidene indanone.
• the content of the sensitizer is preferably 0.01 to 20 mass % relative to the total solid content of the resin composition, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %.
• the sensitizer may be used alone or in combination of two or more types.
• the resin composition of the present invention may contain a chain transfer agent.
• the chain transfer agent is defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684.
• Examples of the chain transfer agent include compounds having -S-S-, -SO 2 -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation chain Transfer) polymerization.
• RAFT Reversible Addition Fragmentation chain Transfer
• chain transfer agent may be the compound described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference.
• the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total solid content of the resin composition.
• the chain transfer agent may be one type or two or more types. When there are two or more types of chain transfer agents, the total is preferably within the above range.
• the resin composition of the present invention may contain a base generator.
• the base generator is a compound that can generate a base by physical or chemical action.
• Preferred base generators include a thermal base generator and a photobase generator.
• the resin composition contains a precursor of a cyclized resin such as a polyimide precursor
• the resin composition preferably contains a base generator.
• the thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product become good, and the performance as an interlayer insulating film for a rewiring layer contained in a semiconductor package becomes good.
• the base generator may be an ionic base generator or a nonionic base generator.
• Examples of the base generated from the base generator include secondary amines and tertiary amines.
• the base generator is not particularly limited, and a known base generator can be used.
• Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, ⁇ -lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds.
• Specific examples of the non-ionic base generator include the compounds described in paragraphs 0249 to 0277 of WO 2022/145355. The above descriptions are incorporated herein.
• the molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
• the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
• Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018/038002.
• ammonium salts include, but are not limited to, the following compounds:
• iminium salts include, but are not limited to, the following compounds:
• the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition.
• the lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
• the upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.
• the base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.
• the resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc.
• the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a ⁇ -ketoester compound, and an amino compound.
• silane coupling agents include compounds described in paragraph 0316 of International Publication No. 2021/112189 and compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. It is also preferable to use the following compound as the silane coupling agent. In the following formula, Me represents a methyl group and Et represents an ethyl group.
• silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2 -(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethy
• Aluminum-based adhesion promoter examples include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.
• metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A, the contents of which are incorporated herein by reference.
• the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By making the content equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer will be good, and by making the content equal to or less than the above upper limit, the heat resistance and mechanical properties of the pattern will be good. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total is within the above range.
• the resin composition of the present invention preferably further contains a migration inhibitor.
• a migration inhibitor for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively suppressed.
• the migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (e.g., pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring, etc.), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds.
• a heterocycle e.g., pyrrole ring, furan ring, thiophene ring, imidazole ring
• triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole
• tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.
• an ion trapping agent that captures anions such as halogen ions can also be used.
• Other migration inhibitors that can be used include, for example, the rust inhibitors described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, the compounds described in paragraph 0052 of JP 2011-059656 A, the compounds described in paragraphs 0114, 0116, and 0118 of JP 2012-194520 A, and the compounds described in paragraph 0166 of WO 2015/199219 A, the contents of which are incorporated herein by reference.
• migration inhibitors include the following compounds:
• the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass %, based on the total solid content of the resin composition.
• the migration inhibitor may be one type or two or more types. When two or more types of migration inhibitors are used, it is preferable that the total is within the above range.
• the resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.
• a polymerization inhibitor such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.
• polymerization inhibitor examples include the compounds described in paragraph 0310 of WO 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, and phenoxazine. The contents of this specification are incorporated herein by reference.
• the content of the polymerization inhibitor is preferably 0.01 to 20 mass % relative to the total solid content of the resin composition, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %.
• the polymerization inhibitor may be one type or two or more types. When two or more types of polymerization inhibitors are used, it is preferable that the total is within the above range.
• the resin composition of the present invention may contain an organometallic complex.
• the organometallic complex is not particularly limited as long as it is an organic complex compound containing a metal atom. However, it is preferably a complex compound containing a metal atom and an organic group, more preferably a compound in which an organic group is coordinated to a metal atom, and further preferably a metallocene compound.
• the metallocene compound refers to an organometallic complex having two cyclopentadienyl anion derivatives, which may have a substituent, as ⁇ 5-ligands.
• the organic group is not particularly limited, but is preferably a hydrocarbon group or a group consisting of a combination of a hydrocarbon group and a heteroatom, preferably an oxygen atom, a sulfur atom, or a nitrogen atom. At least one of the organic groups is preferably a cyclic group, and more preferably at least two of the organic groups are cyclic groups.
• the cyclic group is preferably selected from a 5-membered cyclic group and a 6-membered cyclic group, and more preferably a 5-membered cyclic group.
• the cyclic group may be a hydrocarbon ring or a heterocyclic ring, with a hydrocarbon ring being preferred.
• the five-membered cyclic group is preferably a cyclopentadienyl group.
• the organometallic complex preferably contains 2 to 4 cyclic groups in one molecule.
• the metal contained in the organometallic complex is not particularly limited, but is preferably a metal belonging to Group 4 elements, more preferably at least one metal selected from the group consisting of titanium, zirconium, and hafnium, even more preferably at least one metal selected from the group consisting of titanium and zirconium, and particularly preferably titanium.
• the resin composition of the present invention preferably contains a compound containing titanium (Ti).
• the organometallic complex may contain two or more metal atoms or only one metal atom, but preferably contains only one metal atom. When the organometallic complex contains two or more metal atoms, it may contain only one type of metal atom, or it may contain two or more types of metal atoms.
• the organometallic complex is preferably a ferrocene compound, a titanocene compound, a zirconocene compound, or a hafnocene compound, more preferably a titanocene compound, a zirconocene compound, or a hafnocene compound, even more preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.
• an embodiment in which the organometallic complex has a photoradical polymerization initiation ability is also preferred.
• having photoradical polymerization initiation ability means that it is possible to generate free radicals that can initiate radical polymerization by irradiation with light.
• a composition containing a radical crosslinking agent and an organometallic complex is irradiated with light in a wavelength range in which the organometallic complex absorbs light and the radical crosslinking agent does not absorb light
• the presence or absence of photoradical polymerization initiation ability can be confirmed by confirming whether or not the radical crosslinking agent disappears.
• the organometallic complex is preferably a metallocene compound, more preferably a titanocene compound, a zirconocene compound or a hafnocene compound, further preferably a titanocene compound or a zirconocene compound, and particularly preferably a titanocene compound.
• the organometallic complex is preferably at least one compound selected from the group consisting of titanocene compounds, tetraalkoxytitanium compounds, titanium acylate compounds, titanium chelate compounds, zirconocene compounds, and hafnocene compounds, more preferably at least one compound selected from the group consisting of titanocene compounds, zirconocene compounds, and hafnocene compounds, even more preferably at least one compound selected from the group consisting of titanocene compounds and zirconocene compounds, and particularly preferably a titanocene compound.
• the molecular weight of the organometallic complex is preferably 50 to 2,000, and more preferably 100 to 1,000.
• organometallic complexes include compounds represented by the following formula (P):
• M is a metal atom, and each R is independently a substituent. It is preferred that each R is independently selected from an aromatic group, an alkyl group, a halogen atom, and an alkylsulfonyloxy group.
• the metal atom represented by M in formula (P) is preferably an iron atom, a titanium atom, a zirconium atom or a hafnium atom, more preferably a titanium atom, a zirconium atom or a hafnium atom, still more preferably a titanium atom or a zirconium atom, and particularly preferably a titanium atom.
• the aromatic group for R in formula (P) includes aromatic groups having 6 to 20 carbon atoms, and is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, such as a phenyl group, a 1-naphthyl group, or a 2-naphthyl group.
• the alkyl group for R in formula (P) is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group.
• the halogen atom in R includes F, Cl, Br and I.
• the alkyl group constituting the alkylsulfonyloxy group in R is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an octyl group, an isopropyl group, a t-butyl group, an isopentyl group, a 2-ethylhexyl group, a 2-methylhexyl group, and a cyclopentyl group.
• the R may further have a substituent.
• substituents examples include a halogen atom (F, Cl, Br, I), a hydroxy group, a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, and a diarylamino group.
• halogen atom F, Cl, Br, I
• a hydroxy group a carboxy group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, and a diaryla
• organometallic complexes include, but are not limited to, tetraisopropoxytitanium, tetrakis(2-ethylhexyloxy)titanium, diisopropoxybis(ethylacetoacetate)titanium, diisopropoxybis(acetylacetonato)titanium, bis( ⁇ 5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, pentamethylcyclopentadienyltitanium trimethoxide, bis( ⁇ 5-2,4-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, and the following compounds.
• the content of the organometallic complex is preferably 0.1 to 30% by mass based on the total solid content of the resin composition.
• the lower limit is more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, and particularly preferably 3.0% by mass or more.
• the upper limit is more preferably 25% by mass or less.
• the organometallic complexes may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.
• the content of the colorant in the total solid content is preferably 1 mass % or less.
• the colorant refers to colored organic pigments and organic dyes, for example, colorants used for color filters.
• the resin composition of the present invention preferably does not contain a colorant (that is, the content of the colorant in the total solid content is 0 mass %).
• the resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope in which the effects of the present invention can be obtained.
• additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope in which the effects of the present invention can be obtained.
• auxiliaries e.g., defoamers, flame retardants, etc.
• the resin composition of the present invention is preferably used for organic solvent development (i.e., for organic solvent development).
• Organic solvent development is development using an organic solvent as a developer, and will be described in detail below.
• the viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the coating film thickness, 1,000 mm 2 /s to 12,000 mm 2 /s is preferable, 2,000 mm 2 /s to 10,000 mm 2 /s is more preferable, and 2,500 mm 2 /s to 8,000 mm 2 /s is even more preferable. If it is within the above range, it is easy to obtain a coating film with high uniformity.
• the water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If the water content is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.
• the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
• metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, it is preferable that the total of these metals is within the above range.
• methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention, lining the inside of the apparatus with polytetrafluoroethylene or the like and performing distillation under conditions that suppress contamination as much as possible, etc.
• the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosion.
• those present in the form of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
• Halogen atoms include chlorine atoms and bromine atoms.It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range.
• a preferred method for adjusting the content of halogen atoms is ion exchange treatment.
• a conventionally known container can be used as the container for the resin composition of the present invention.
• the container it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six layers of resin, or a bottle with a seven-layer structure of six types of resin, in order to prevent impurities from being mixed into the raw materials or the resin composition of the present invention.
• An example of such a container is the container described in JP 2015-123351 A.
• a cured product of the resin composition By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.
• the cured product of the present invention is a cured product obtained by curing a resin composition.
• the resin composition is preferably cured by heating, and the heating temperature is more preferably 120°C to 400°C, further preferably 140°C to 380°C, and particularly preferably 170°C to 350°C.
• the form of the cured product of the resin composition is not particularly limited, and can be selected according to the application, such as film-like, rod-like, spherical, pellet-like, etc.
• the cured product is preferably in the form of a film.
• the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming a via hole for conduction, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function.
• the film thickness of the cured product (film made of the cured product) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
• the shrinkage percentage of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
• the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.
• the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
• the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.
• the insulating film of the present invention contains at least one kind of polymer selected from the group consisting of polyimides and polyimide precursors, and a liquid crystal compound.
• the insulating film of the present invention can be formed by curing the above-mentioned resin composition of the present invention. That is, the insulating film of the present invention is a preferred embodiment of a cured product of the above-mentioned resin composition.
• the at least one polymer selected from the group consisting of polyimides and polyimide precursors, and the liquid crystal compound are as described above.
• the insulating film of the present invention may contain at least one polymer selected from the group consisting of polyimides and polyimide precursors, and a liquid crystal compound, as well as other components, such as the components that can be contained in the resin composition of the present invention described above.
• the liquid crystal compound contained in the insulating film of the present invention is preferably a discotic liquid crystal compound.
• the insulating film of the present invention is preferably an interlayer insulating film for a redistribution layer.
• the resin composition of the present invention can be prepared by mixing the above-mentioned components.
• the mixing method is not particularly limited, and can be a conventionally known method. Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank.
• the temperature during mixing is preferably from 10 to 30°C, more preferably from 15 to 25°C.
• the filter pore size is, for example, preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, even more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
• the material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. When the material of the filter is polyethylene, it is more preferable that it is HDPE (high density polyethylene).
• the filter may be used after being washed in advance with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel.
• filters with different pore sizes or materials may be used in combination.
• a connection mode an HDPE filter with a pore size of 1 ⁇ m as the first stage and an HDPE filter with a pore size of 0.2 ⁇ m as the second stage may be connected in series.
• various materials may be filtered multiple times. When filtration is performed multiple times, circulation filtration may be performed. Filtration may also be performed under pressure.
• the pressure to be applied is, for example, preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.
• impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined.
• the adsorbent a known adsorbent may be used.
• inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be used.
• the resin composition filled in the bottle may be subjected to a degassing step by placing it under reduced pressure.
• the method for producing the cured product of the present invention preferably includes a film-forming step of applying the resin composition onto a substrate to form a film.
• the method for producing the insulating film of the present invention is also the same as the method for producing the cured product. It is more preferable that the method for producing a cured product includes the above-mentioned film formation step, an exposure step of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern.
• the method for producing a cured product includes the above-mentioned film-forming step, the above-mentioned exposure step, the above-mentioned development step, and at least one of a heating step of heating the pattern obtained by the development step and a post-development exposure step of exposing the pattern obtained by the development step.
• the method for producing a cured product preferably includes the film-forming step and a step of heating the film. Each step will be described in detail below.
• the resin composition of the present invention can be used in a film-forming process in which the resin composition is applied onto a substrate to form a film.
• the method for producing a cured product of the present invention preferably includes a film formation step of applying the resin composition onto a substrate to form a film.
• the type of substrate can be appropriately determined according to the application, and is not particularly limited.
• substrates include semiconductor-prepared substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals and substrates in which a metal layer is formed by plating, vapor deposition, etc.), paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, mold substrates, and electrode plates of plasma display panels (PDPs).
• semiconductor-prepared substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals and substrates in which a metal layer is formed by plating, vapor
• the substrate is preferably a semiconductor-prepared substrate, more preferably a silicon substrate, a Cu substrate, or a mold substrate. These substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface.
• HMDS hexamethyldisilazane
• the shape of the substrate is not particularly limited, and may be circular or rectangular.
• the size of the substrate is preferably, for example, a diameter of 100 to 450 mm, more preferably 200 to 450 mm, if it is circular, and is preferably, for example, a short side length of 100 to 1000 mm, more preferably 200 to 700 mm, if it is rectangular.
• a plate-shaped substrate preferably a panel-shaped substrate (substrate) is used as the substrate.
• a resin composition When a film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer made of a cured material) or to the surface of a metal layer, the resin layer or metal layer serves as the substrate.
• a resin layer e.g., a layer made of a cured material
• the resin layer or metal layer serves as the substrate.
• the resin composition is preferably applied to a substrate by coating.
• the means to be applied include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet methods. From the viewpoint of uniformity of the thickness of the film, spin coating, slit coating, spray coating, or inkjet methods are preferred, and from the viewpoint of uniformity of the thickness of the film and productivity, spin coating and slit coating are more preferred.
• a film of a desired thickness can be obtained by adjusting the solid content concentration and coating conditions of the resin composition according to the means to be applied.
• the coating method can be appropriately selected depending on the shape of the substrate, and if the substrate is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and if the substrate is a rectangular substrate, slit coating, spray coating, inkjet, etc. are preferred.
• the spin coating method for example, it can be applied for about 10 seconds to 3 minutes at a rotation speed of 500 to 3,500 rpm.
• a coating film formed by applying the coating material to a temporary support in advance using the above-mentioned application method may be transferred onto the substrate.
• the transfer method the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A No.
• 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used.
• a process for removing excess film from the edge of the substrate may be performed, such as edge bead rinse (EBR) and back rinse.
• EBR edge bead rinse
• a pre-wetting step may be employed in which, before applying the resin composition to the substrate, the substrate is coated with various solvents to improve the wettability of the substrate, and then the resin composition is applied.
• the above-mentioned film may be subjected to a step of drying the formed film (layer) (drying step) in order to remove the solvent.
• the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.
• the drying step is preferably carried out after the film-forming step and before the exposure step.
• the drying temperature of the film in the drying step is preferably 50 to 150° C., more preferably 70 to 130° C., and even more preferably 90 to 110° C. Drying may be performed under reduced pressure.
• the drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.
• the film may be subjected to an exposure step to selectively expose the film to light.
• the method for producing a cured product may include an exposure step of selectively exposing the film formed in the film formation step to light. Selective exposure means that only a portion of the film is exposed, and selective exposure results in exposed and unexposed areas of the film.
• the amount of exposure light is not particularly limited as long as it can cure the resin composition of the present invention, but is preferably 50 to 10,000 mJ/cm 2 , and more preferably 200 to 8,000 mJ/cm 2 , calculated as exposure energy at a wavelength of 365 nm.
• the exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.
• the exposure wavelength may be, in particular, (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, (7) second harmonic 532 nm, third harmonic 355 nm, etc.
• semiconductor laser wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 3
• the exposure method is not particularly limited as long as it is a method that exposes at least a part of the film made of the resin composition of the present invention, and examples of the exposure method include exposure using a photomask and exposure by a laser direct imaging method.
• the film may be subjected to a step of heating after exposure (post-exposure baking step). That is, the method for producing a cured product of the present invention may include a post-exposure baking step of heating the film exposed in the exposure step.
• the post-exposure baking step can be carried out after the exposure step and before the development step.
• the heating temperature in the post-exposure baking step is preferably from 50°C to 140°C, and more preferably from 60°C to 120°C.
• the heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, and more preferably from 1 minute to 10 minutes.
• the heating rate in the post-exposure heating step is preferably from 1 to 12° C./min, more preferably from 2 to 10° C./min, and even more preferably from 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature.
• the rate of temperature rise may be appropriately changed during heating.
• the heating means in the post-exposure baking step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. can be used. It is also preferable that the heating be performed in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.
• the film after exposure may be subjected to a development step in which the film is developed with a developer to form a pattern.
• the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed with a developer to form a pattern. Development removes one of the exposed and unexposed areas of the film to form a pattern.
• development in which the non-exposed portion of the film is removed by the development process is called negative development
• development in which the exposed portion of the film is removed by the development process is called positive development.
• the developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.
• examples of basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
• TMAH tetramethylammonium hydroxide
• potassium hydroxide sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammoni
• the compounds described in paragraph 0387 of WO 2021/112189 can be used as the organic solvent.
• the organic solvent examples include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol
• examples of amides that are suitable include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.
• the organic solvent may be used alone or in combination of two or more.
• a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.
• the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
• the content may be 100% by mass.
• the developer may further contain at least one of a basic compound and a base generator.
• the performance of the pattern such as the breaking elongation, may be improved.
• an organic base is preferred.
• a basic compound having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, or the like is preferable.
• a primary amine, a secondary amine, a tertiary amine, or an ammonium salt is preferable, a secondary amine, a tertiary amine, or an ammonium salt is more preferable, a secondary amine or a tertiary amine is further more preferable, and a tertiary amine is particularly preferable.
• the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and even more preferably 100°C to 230°C at normal pressure (101,325 Pa).
• the boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C.
• the basic compound used preferably has a boiling point of 80° C. or higher, and more preferably has a boiling point of 100° C. or higher.
• the developer may contain only one kind of basic compound, or may contain two or more kinds of basic compounds.
• basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diamino Examples include pentane, N-methylhexy
• the preferred embodiment of the base generator is the same as the preferred embodiment of the base generator contained in the composition described above.
• the base generator is a thermal base generator.
• the content of the basic compound or the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the developer.
• the lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
• the content of the basic compound or base generator is preferably 70 to 100% by mass based on the total solid content of the developer.
• the developer may contain at least one of a basic compound and a base generator, or may contain two or more of them. When at least one of a basic compound and a base generator is two or more, the total amount of them is preferably within the above range.
• the developer may further comprise other components.
• other components include known surfactants and known defoamers.
• the method of supplying the developer is not particularly limited as long as it can form a desired pattern, and includes a method of immersing a substrate on which a film is formed in the developer, a paddle development method in which a developer is supplied to a film formed on a substrate using a nozzle, and a method of continuously supplying the developer.
• the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
• a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, a method of supplying the developer through a spray nozzle is more preferred.
• a process may be adopted in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate. This process may be repeated multiple times.
• Methods of supplying the developer in the development step include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept substantially stationary on the substrate, a step in which the developer is vibrated by ultrasonic waves or the like on the substrate, and a combination of these steps.
• the development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes.
• the temperature of the developer during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18°C to 30°C.
• the pattern may be washed (rinsed) with a rinse solution. Also, a method may be adopted in which a rinse solution is supplied before the developer in contact with the pattern has completely dried.
• the rinse liquid may be, for example, water.
• the rinse liquid may be, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer).
• the organic solvent include the same organic solvents as those exemplified when the developer contains an organic solvent.
• the organic solvent contained in the rinse liquid is preferably different from the organic solvent contained in the developer, and more preferably has a lower solubility for the pattern than the organic solvent contained in the developer.
• the organic solvent may be used alone or in a mixture of two or more.
• the organic solvent is preferably cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA), or propylene glycol monomethyl ether (PGME), more preferably cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.
• the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the rinse solution. Furthermore, the organic solvent may account for 100% by mass, based on the total mass of the rinse solution.
• the rinse liquid may contain at least one of a basic compound and a base generator.
• a basic compound and a base generator when the developer contains an organic solvent, an embodiment in which the rinsing liquid contains an organic solvent and at least one of a basic compound and a base generator is also one of the preferred embodiments of the present invention.
• the basic compound and base generator contained in the rinse solution include the compounds exemplified as the basic compound and base generator that may be contained in the above-mentioned developer containing an organic solvent, and preferred embodiments thereof are also the same.
• the basic compound and base generator contained in the rinse solution may be selected in consideration of the solubility in the solvent in the rinse solution.
• the content of the basic compound or the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the rinse solution.
• the lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
• the content of the basic compound or base generator is also preferably 70 to 100 mass % based on the total solid content of the rinse liquid.
• the rinse solution may contain only one kind of at least one of the basic compound and the base generator, or may contain two or more kinds.
• the total amount thereof is preferably within the above range.
• the rinse solution may further contain other ingredients.
• other components include known surfactants and known defoamers.
• the method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples of the method include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like.
• the rinse liquid may be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, while from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred.
• the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc.
• the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle.
• the method of supplying the rinsing liquid in the rinsing step may be a step in which the rinsing liquid is continuously supplied to the substrate, a step in which the rinsing liquid is kept substantially stationary on the substrate, a step in which the rinsing liquid is vibrated on the substrate by ultrasonic waves or the like, or a combination of these steps.
• the rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes.
• the temperature of the rinsing liquid during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18°C to 30°C.
• the development step may include a step of contacting the pattern with a processing liquid after treatment with a developer or after washing the pattern with a rinse liquid. Also, a method may be employed in which the processing liquid is supplied before the developer or rinse liquid in contact with the pattern is completely dried.
• the treatment liquid includes a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator.
• Preferred aspects of the organic solvent, and at least one of the basic compound and the base generator are the same as the preferred aspects of the organic solvent, and at least one of the basic compound and the base generator used in the above-mentioned rinse solution.
• the method of supplying the processing liquid to the pattern can be the same as the above-mentioned method of supplying the rinsing liquid, and the preferred embodiments are also the same.
• the content of the basic compound or base generator in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the treatment liquid.
• the lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
• the content of the basic compound or base generator is preferably 70 to 100 mass % based on the total solid content of the treatment liquid.
• the treatment liquid may contain only one kind of at least one of the basic compound and the base generator, or may contain two or more kinds.
• the total amount thereof is preferably within the above range.
• the pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the developing step. The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without carrying out a development step, or a film obtained in a film formation step. In the heating step, the resin such as the polyimide precursor is cyclized to become a resin such as a polyimide.
• the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.
• the heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of the base generated from the base generator through heating.
• the heating step is preferably performed at a temperature rise rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature.
• the temperature rise rate is more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min.
• the temperature is increased from the starting temperature to the maximum heating temperature at a rate of preferably 1 to 8° C./sec, more preferably 2 to 7° C./sec, and even more preferably 3 to 6° C./sec.
• the temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C.
• the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature begins.
• the resin composition of the present invention when applied to a substrate and then dried, it is the temperature of the film (layer) after drying, and it is preferable to raise the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.
• the heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
• the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, even more preferably 100° C. or higher, and particularly preferably 120° C. or higher.
• the upper limit of the heating temperature is preferably 350° C. or less, more preferably 250° C. or less, and even more preferably 240° C. or less.
• Heating may be performed stepwise. For example, a process may be performed in which the temperature is increased from 25°C to 120°C at 3°C/min, held at 120°C for 60 minutes, increased from 120°C to 180°C at 2°C/min, and held at 180°C for 120 minutes. It is also preferable to treat while irradiating with ultraviolet light as described in U.S. Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film.
• the pretreatment process is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
• the pretreatment may be performed in two or more steps, for example, a first pretreatment process may be performed in the range of 100 to 150°C, and then a second pretreatment process may be performed in the range of 150 to 200°C. Furthermore, after heating, the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C./min.
• the heating step is preferably performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by performing the heating step under reduced pressure, etc.
• the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
• the heating means in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.
• the pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern after the development step is exposed to light instead of or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step.
• the method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
• the post-development exposure step for example, a reaction in which cyclization of a polyimide precursor or the like proceeds due to exposure of a photobase generator to light, or a reaction in which elimination of an acid-decomposable group proceeds due to exposure of a photoacid generator to light, can be promoted.
• the post-development exposure step it is sufficient that at least a part of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed.
• the exposure dose in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , and more preferably 100 to 15,000 mJ/cm 2 , calculated as exposure energy at a wavelength to which the photosensitive compound has sensitivity.
• the post-development exposure step can be carried out, for example, using the light source in the exposure step described above, and it is preferable to use broadband light.
• the pattern obtained by the development step may be subjected to a metal layer forming step in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the development step (preferably subjected to at least one of a heating step and a post-development exposure step).
• the metal layer can be made of any existing metal type without any particular limitations, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.
• the method for forming the metal layer is not particularly limited, and existing methods can be applied.
• the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used.
• photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and combinations of these methods are possible.
• examples of the method include a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating.
• a preferred embodiment of plating is electrolytic plating using a copper sulfate or copper cyanide plating solution.
• the thickness of the metal layer at its thickest point is preferably 0.01 to 50 ⁇ m, and more preferably 1 to 10 ⁇ m.
• the method for producing an interlayer insulating film for a redistribution layer of the present invention includes a photosensitive film forming step of applying the above-mentioned resin composition of the present invention onto a substrate to form a photosensitive film; an exposure step of exposing the photosensitive film to light to form an exposed film; The exposed film is developed with a developer to form an insulating pattern.
• the developer is preferably an organic solvent.
• Examples of the method for producing the cured product of the present invention or the fields in which the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc.
• Other examples include etching patterns of sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or insulating films for mounting applications such as those described above.
• the method for producing the cured product of the present invention or the cured product of the present invention can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, and for producing protective lacquers and dielectric layers in electronics, especially microelectronics.
• the laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention.
• the laminate is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers.
• at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.
• the method for producing the laminate of the present invention preferably includes the method for producing the cured product of the present invention, and more preferably includes repeating the method for producing the cured product of the present invention multiple times.
• the laminate of the present invention preferably includes two or more layers made of a cured product, and includes a metal layer between any two of the layers made of the cured product.
• the metal layer is preferably formed by the metal layer forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer made of a cured product between the steps for producing a cured product which are performed multiple times.
• a preferred embodiment of the metal layer forming step is as described above.
• a laminate including at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order can be mentioned as a preferred example.
• the layer made of the first cured product and the layer made of the second cured product are preferably layers made of the cured product of the present invention.
• the resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions.
• the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
• the method for producing the laminate of the present invention preferably includes a lamination step.
• the lamination process is a series of processes including performing at least one of (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) a heating process and a post-development exposure process again on the surface of the pattern (resin layer) or metal layer in this order.
• at least one of (a) the film formation process and (d) the heating process and the post-development exposure process may be repeated.
• a metal layer formation process may be included. It goes without saying that the lamination process may further include the above-mentioned drying process and the like as appropriate.
• a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step.
• An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.
• the lamination step is preferably carried out 2 to 20 times, and more preferably 2 to 9 times.
• a structure of 2 to 20 resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a structure of 2 to 9 resin layers is more preferred.
• the layers may be the same or different in composition, shape, film thickness, etc.
• a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.
• a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.
• the following may be repeated in this order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step; or (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step.
• the method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment.
• the surface activation treatment step is usually carried out after the metal layer formation step, but after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be subjected to a surface activation treatment step before the metal layer formation step is carried out.
• the surface activation treatment may be performed on at least a part of the metal layer, or on at least a part of the resin composition layer after exposure, or on at least a part of both the metal layer and the resin composition layer after exposure.
• the surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the area of the metal layer on which the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) provided on the surface can be improved. It is preferable to perform the surface activation treatment on a part or the whole of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion with the metal layer or the resin layer provided on the surface that has been surface-activated.
• the resin composition layer when performing negative development, etc., when the resin composition layer is cured, it is less likely to be damaged by the surface treatment, and the adhesion is likely to be improved.
• the surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of WO 2021/112189, the contents of which are incorporated herein by reference.
• the present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention.
• the present invention also discloses a method for producing a semiconductor device, which includes the method for producing the cured product or the method for producing the laminate of the present invention.
• semiconductor devices using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer the descriptions in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-027357 can be referred to, and the contents of these are incorporated herein by reference.
• Examples and Comparative Examples> the components shown in Table 1 below were mixed to obtain each resin composition. Specifically, the content of each component shown in Table 1 was the amount (parts by mass) shown in the "Amount" column of each column in the table. The obtained resin composition was pressure filtered using a polytetrafluoroethylene filter having a pore width of 0.5 ⁇ m. In the table, the notation "-" indicates that the resin composition does not contain the corresponding component. In addition, for all of the resin compositions in the Examples and Comparative Examples, the content of colorant in the total solid content was 0 mass % (i.e., all of the resin compositions in the Examples and Comparative Examples did not contain a colorant).
• Polyimide precursors PIP-1 to PIP-3 and polyimides PI-1 to PI-3 were used. Their structural formulas are shown below. The weight average molecular weight (Mw) and polydispersity (PD) of each of PIP-1 to PIP-3 are also shown below.
• DLC-1 to DLC-4 which are discotic liquid crystal compounds having radically polymerizable unsaturated bonds
• SLC-1 to SLC-3 which are rod-shaped liquid crystal compounds having radically polymerizable unsaturated bonds
• DLN-1 which is a discotic liquid crystal compound having no radically polymerizable unsaturated bonds
• SLN-1 which is a rod-shaped liquid crystal compound having no radically polymerizable unsaturated bonds
• L-1 and L-2 represented by the following structural formulas were used.
• A-4 and A-5 represented by the following structural formulas were used.
• the resin composition was applied onto a silicon wafer by spin coating to form a coating film.
• the silicon wafer having the coating film was dried on a hot plate at 100° C. for 5 minutes to obtain a uniform film having a thickness of 15 ⁇ m on the silicon wafer.
• the entire surface of the resulting film was exposed to i-line light at an exposure energy of 500 mJ/cm 2 using a stepper (Nikon NSR 2005 i9C).
• the exposed film was heated in a nitrogen atmosphere at a heating rate of 10° C./min. until it reached 230° C., and then heated at 230° C. for 3 hours. In this manner, the cured films of the respective Examples and Comparative Examples were prepared.
• the following table shows the evaluations of dielectric tangent and elongation for each of the examples and comparative examples.
• the following table also shows the ratio M B /M A of the mass of the liquid crystal compound M B to the mass M A of the resin, and the solubility of the resin in the solvent at 23°C.
• Example 101 The resin composition used in Example 1 was applied by spin coating to the surface of the copper thin layer of the resin substrate on which the copper thin layer was formed, and dried at 100°C for 4 minutes to form a film with a thickness of 20 ⁇ m, and then exposed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line and space pattern and a line width of 10 ⁇ m). After exposure, the film was heated at 100°C for 4 minutes. After the heating, the film was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
• a stepper Nakon Corporation, NSR1505 i6
• Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line and space pattern and a line width of 10 ⁇ m). After exposure, the film was heated at 100°C for 4 minutes. After the heating, the
• the temperature was increased at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 3 hours to form an interlayer insulating film for a rewiring layer.
• This interlayer insulating film for a rewiring layer had excellent insulating properties. Furthermore, when semiconductor devices were manufactured using these interlayer insulating films for redistribution layers, it was confirmed that they operated without any problems.
• the present invention it is possible to provide a resin composition which can give a film having a low dielectric tangent. Furthermore, according to the present invention, it is possible to provide an insulating film having a low dielectric tangent, and a method for producing an interlayer insulating film for a redistribution layer using the above resin composition.

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• 2023
  • 2023-09-13 JP JP2024550064A patent/JPWO2024070713A1/ja active Pending
  • 2023-09-13 WO PCT/JP2023/033446 patent/WO2024070713A1/ja not_active Ceased
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