WO2020255859A1 - Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et polyimide ou précurseur de polyimide - Google Patents

Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et polyimide ou précurseur de polyimide Download PDF

Info

Publication number
WO2020255859A1
WO2020255859A1 PCT/JP2020/023071 JP2020023071W WO2020255859A1 WO 2020255859 A1 WO2020255859 A1 WO 2020255859A1 JP 2020023071 W JP2020023071 W JP 2020023071W WO 2020255859 A1 WO2020255859 A1 WO 2020255859A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
preferable
resin composition
curable resin
Prior art date
Application number
PCT/JP2020/023071
Other languages
English (en)
Japanese (ja)
Inventor
敦靖 野崎
Original Assignee
富士フイルム株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to KR1020217040915A priority Critical patent/KR20220008885A/ko
Priority to JP2021528162A priority patent/JP7289353B2/ja
Priority to CN202080043671.XA priority patent/CN114008527A/zh
Publication of WO2020255859A1 publication Critical patent/WO2020255859A1/fr

Links

Images

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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—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 end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/065—Polyamides; Polyesteramides; Polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • 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
    • C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/32—Compounds containing nitrogen bound to oxygen
    • C08K5/33—Oximes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a curable resin composition, a cured film, a laminate, a method for producing a cured film, a semiconductor device, and a polyimide or a polyimide precursor.
  • Polyimide has excellent heat resistance and insulation properties, so it is applied to various applications.
  • the above application is not particularly limited, and examples of a semiconductor device for mounting include use as a material for an insulating film or a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.
  • the polyimide may be used in the form of a curable resin composition containing polyimide, or may be used in the form of a curable resin composition containing a polyimide precursor.
  • the precursor is cyclized to become polyimide by heating, for example. Since these curable resin compositions can be applied to a base material or the like by a known coating method or the like, for example, there is a degree of freedom in designing the shape, size, application position, etc. of the curable resin composition to be applied. It can be said that it is highly adaptable to manufacturing.
  • a curable resin composition containing at least one resin selected from the group consisting of polyimide and a polyimide precursor is being industrialized.
  • the above application development is expected more and more.
  • Patent Document 1 describes a curable polyimide having a structure having a specific polymerizable group.
  • curable resin composition containing at least one resin selected from the group consisting of polyimide or a polyimide precursor, it is desired to provide a curable resin composition having excellent coatability of the composition.
  • One embodiment of the present invention includes a curable resin composition having excellent coatability, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, a method for producing the cured film, and the above.
  • An object of the present invention is to provide a semiconductor device including a cured film or the above-mentioned laminate.
  • another embodiment of the present invention aims to provide a novel polyimide or a polyimide precursor.
  • ⁇ 1> At least one resin selected from the group consisting of polyimide and polyimide precursors having a polyalkyleneoxy group and a polymerizable group. Polymerization initiator, Polymerizable compounds and A curable resin composition containing a solvent.
  • the curable resin composition according to ⁇ 1> which comprises a structure represented by the following formula (1-1) as a structure having the polyalkyleneoxy group and the polymerizable group.
  • R 1 independently represents a hydrogen atom or an alkyl group
  • Z 1 represents a group containing a polymerizable group
  • n represents an integer of 2 or more
  • m represents an integer of 2 or more.
  • L 1 represents a b + divalent linking group
  • X 2 represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond
  • L 2 represents a single bond or an a + 1 valent linking group.
  • X 1 represents the structure represented by the above equation (1-1)
  • a represents an integer of 1 or more
  • b represents an integer of 1 or more
  • X 2 , L 2 , X 1 or a represents an integer of 1 or more.
  • L 1 represents a b + divalent linking group
  • X 2 represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond
  • L 2 represents a single bond or an a + 1 valent linking group.
  • X 1 represents the structure represented by the above formula (1-1)
  • a represents an integer of 1 or more
  • b represents an integer of 1 or more
  • L 4 represents the following formula (L4-1) or represents a structure represented by the formula (L4-2), if X 2, L 2, X 1 or a presence of a plurality, plural of X 2, L 2, X 1 or a may be the same , May be different.
  • R 115 represents a tetravalent organic group
  • a 1 and A 2 independently represent an oxygen atom or -NH-
  • R 113 and R 114 Independently represent a hydrogen atom or a monovalent organic group.
  • RA11 to RA14 , RA21 to RA24 , RA31 to RA38 , RA41 to RA48 and RA51 to RA58 are independent hydrogen atoms. , Alkyl group, cyclic alkyl group, alkoxy group, hydroxy group, cyano group, alkyl halide group, halogen atom, or bond site with X 2 in the above formula (1-2) or the above formula (1-3).
  • LA31 and LA41 are independently single-bonded, carbonyl group, sulfonyl group, divalent saturated hydrocarbon group, divalent unsaturated hydrocarbon group, heteroatom, heterocyclic group, or alkylene halide.
  • Representing a group, b of R A11 to R A14 , R A21 to R A24 , R A31 to R A38 , R A41 to R A48 and R A51 to R A58 , respectively, are the above formulas (1-2) or the above formulas. It is a binding site with X 2 in (1-3), and * represents a binding site with another structure independently.
  • ⁇ 7> The curable resin composition according to any one of ⁇ 1> to ⁇ 6>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 8> A cured film obtained by curing the curable resin composition according to any one of ⁇ 1> to ⁇ 7>.
  • ⁇ 9> A laminate having two or more cured films according to ⁇ 8> and having a metal layer between the cured films.
  • a method for producing a cured film which comprises a film forming step of applying the curable resin composition according to any one of ⁇ 1> to ⁇ 7> to a substrate to form a film.
  • ⁇ 11> The method for producing a cured film according to ⁇ 10>, which comprises an exposure step of exposing the film and a developing step of developing the film.
  • ⁇ 12> The method for producing a cured film according to ⁇ 10> or ⁇ 11>, which comprises a step of heating the film at 50 to 450 ° C.
  • a semiconductor device comprising the cured film according to ⁇ 8> or the laminate according to ⁇ 9>.
  • R 1 independently represents a hydrogen atom or an alkyl group
  • Z 1 represents a group containing a polymerizable group
  • n represents an integer of 2 or more
  • m represents an integer of 2 or more.
  • And * represents the site of connection with other structures.
  • a curable resin composition having excellent coatability a cured film obtained by curing the curable resin composition, a laminate containing the cured film, a method for producing the cured film, and a method for producing the cured film.
  • the semiconductor device including the cured film or the laminate is provided.
  • a novel polyimide or a polyimide precursor is provided.
  • the present invention is not limited to the specified embodiments.
  • the numerical range represented by using the symbol “ ⁇ ” means a range including the numerical values before and after “ ⁇ ” as the lower limit value and the upper limit value, respectively.
  • the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
  • the notation not describing substitution and non-substituent also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
  • (meth) acrylate means both “acrylate” and “methacrylate”, or either
  • (meth) acrylic means both “acrylic” and “methacrylic", or
  • (meth) acryloyl means both “acryloyl” and “methacrylic", or either.
  • Me in the structural formula represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the total solid content means the total mass of all the components of the composition excluding the solvent.
  • the solid content concentration is the mass percentage of 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 defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
  • GPC measurement gel permeation chromatography
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
  • the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as “upper”.
  • the opposite direction is referred to as "down”.
  • the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component.
  • the content of each component in the composition means the total content of all the compounds corresponding to the component.
  • the temperature is 23 ° C. and the atmospheric pressure is 101,325 Pa (1 atm).
  • the combination of preferred embodiments is a more preferred embodiment.
  • the curable resin composition of the present invention (hereinafter, also simply referred to as “the composition of the present invention”) is at least selected from the group consisting of polyimide and a polyimide precursor having a polyalkyleneoxy group and a polymerizable group. It contains one kind of resin (hereinafter, also referred to as "specific resin"), a polymerization initiator, a polymerizable compound, and a solvent.
  • the curable resin composition of the present invention preferably further contains a thermosetting agent or an onium salt described later.
  • the specific resin is a polyimide precursor, it is preferable that the curable resin composition of the present invention further contains a thermosetting agent or an onium salt described later.
  • the curable resin composition of the present invention is excellent in coatability.
  • excellent coating property of the composition means that the film thickness difference is small in the coating film formed after coating and drying, and there are few defects such as coating unevenness due to air bubbles and unevenness.
  • the specific resin has excellent solubility in a solvent because the specific resin contains a polyalkyleneoxy group and a polymerizable group.
  • the specific resin is unlikely to precipitate even at the stage where the solvent volatilizes during coating and drying of the composition. Therefore, the film thickness of the coating film formed after coating It is considered that the difference is unlikely to occur and the defect is unlikely to occur.
  • the curable resin composition of the present invention is used as a base material having a step, it is considered that a flat film can be easily obtained. Further, since the rigid polyimide structure and the flexible polyalkyleneoxy structure coexist in the cured film obtained after the coating film is cured, it is considered that the strength of the cured film (for example, elongation at break) is likely to be improved.
  • Patent Document 1 does not describe or suggest a resin containing a polyalkyleneoxy group. Further, the curable resin composition in Patent Document 1 has a problem of low coatability.
  • the curable resin composition of the present invention contains a specific resin.
  • the specific resin has a polyalkyleneoxy group and a polymerizable group.
  • the specific resin may have a polyalkyleneoxy group in the main chain, but it is preferably contained in the side chain of the specific resin from the viewpoint of the film strength of the obtained cured film.
  • the "main chain” refers to the relatively longest binding chain among the molecules of the polymer compound constituting the resin
  • the "side chain” refers to other binding chains.
  • the specific resin preferably has a side chain having a polyalkyleneoxy group and a polymerizable group as a side chain.
  • the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
  • the alkylene groups in the plurality of 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 sequence or a sequence having a block. It may be an array having a pattern such as alternating.
  • the carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 50, and 2 to 30. Is more preferable, 2 to 10 is more preferable, 2 to 6 is more preferable, 2 to 4 is particularly preferable, and 2 or 3 is most preferable.
  • the said alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms and the like.
  • the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 100, more preferably 2 to 50, further preferably 2 to 30, and particularly 2 to 10.
  • the polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyloxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups from the viewpoint of achieving both solvent solubility and chemical resistance.
  • a group in which the propyleneoxy group is bonded is preferable, and a polyethyleneoxy group or a polypropyleneoxy group is more preferable.
  • the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.
  • Polymerizable group As the polymerizable group contained in the specific resin, a group containing an ethylenically unsaturated group, a cyclic ether group or a methylol group is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloxy group, etc.
  • a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, or a methylol group is more preferable, and a (meth) acryloxy group, an epoxy group, or a methylol group is more preferable.
  • the polymerizable group contained in the specific resin is directly bonded to one end of the above-mentioned polyalkyleneoxy group. That is, the specific resin preferably has a side chain in which one end of the above-mentioned polyalkyleneoxy group and a polymerizable group are bonded.
  • the specific resin preferably contains a structure represented by the following formula (1-1) as a structure having the polyalkyleneoxy group and the polymerizable group.
  • the specific resin preferably contains a plurality of structures represented by the following formula (1-1).
  • the structures represented by the plurality of formulas (1-1) may be the same or different.
  • R 1 independently represents a hydrogen atom or an alkyl group
  • Z 1 represents a group containing a polymerizable group
  • n represents an integer of 2 or more
  • m represents an integer of 2 or more.
  • And * represents the site of connection with other structures.
  • R 1 is independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom or a methyl group. More preferred.
  • Z 1 represents a group containing a polymerizable group.
  • Z 1 preferably contains at least one group selected from the group consisting of an ethylenically unsaturated group, a cyclic ether group, and a methylol group, and preferably contains a vinyl group and a (meth) allyl group.
  • (Meta) acrylamide group, (meth) acryloxy group, maleimide group, vinylphenyl group, epoxy group, oxetanyl group, or methylol group is more preferable, and (meth) acryloxy group, epoxy group, or methylol group. It is more preferable to include.
  • Z 1 is preferably a group represented by the following formula (Z-1).
  • L represents a single bond or nz + 1 valent linking group
  • nz represents an integer of 1 or more
  • Z 2 represents a polymerizable group
  • * represents oxygen in formula (1-1).
  • the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
  • a hydrocarbon group having 1 to 20 carbon atoms is preferable, and a hydrocarbon group having 1 to 10 carbon atoms is more preferable.
  • nz is preferably an integer of 1 to 10, preferably an integer of 1 to 4, more preferably 1 or 2, and particularly preferably 1.
  • Z 2 has a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, or a methylol group. More preferably, a (meth) acryloxy group, an epoxy group, or a methylol group is more preferable.
  • n is preferably an integer of 2 to 100 independently, more preferably an integer of 2 to 50, and further preferably an integer of 2 to 30. It is particularly preferably an integer of ⁇ 10, and most preferably an integer of 3-10.
  • m is preferably an integer of 2 to 50, more preferably an integer of 2 to 30, and even more preferably an integer of 2 to 10. It is more preferably an integer of ⁇ 6, particularly preferably an integer of 2-4, and most preferably 2 or 3.
  • the specific resin has a structure represented by the following formula (1-1), a structure represented by the following formula (1-1-1), a structure represented by the following formula (1-1-2), and a structure represented by the following formula (1-1-2). It is preferable to include at least one structure selected from the group consisting of the structures represented by 1-1-3).
  • n and Z 1 have the same meaning as n and Z 1 in formula (1-1), respectively, and the preferred embodiments are also the same.
  • * represents a binding site with another structure.
  • the specific resin preferably contains a structure represented by the following formula (1-2) as a structure containing the structure represented by the above formula (1-1).
  • the specific resin preferably contains a structure represented by the formula (1-2) in the main chain. That is, it is preferable that the structure represented by L 1 in the formula (1-2) is included in the main chain of the specific resin.
  • the specific resin preferably contains a plurality of structures represented by the formula (1-2). When the specific resin contains a plurality of structures represented by the formula (1-2), the structures represented by the plurality of formulas (1-2) may be the same or different.
  • L 1 represents a b + divalent linking group
  • X 2 represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond
  • L 2 represents a single bond or an a + 1 valent linking group.
  • X 1 represents the structure represented by the above equation (1-1)
  • a represents an integer of 1 or more
  • b represents an integer of 1 or more
  • X 2 , L 2 , X 1 or a represents an integer of 1 or more.
  • L 1 represents a b + divalent linking group of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or at least one of these groups and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, and -NR N- . It is preferably a group to which at least one is bonded.
  • the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
  • an aliphatic saturated hydrocarbon group having 2 to 30 carbon atoms is preferable, and an aliphatic saturated hydrocarbon group having 2 to 10 carbon atoms is more preferable.
  • a saturated aliphatic hydrocarbon ring group having 6 to 20 ring members is preferable.
  • an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, an aliphatic hydrocarbon group having 6 to 12 carbon atoms is preferable, and an aromatic hydrocarbon group having 6 carbon atoms is more preferable.
  • L 1 is may preferably be a group containing an aliphatic hydrocarbon ring group or an aromatic hydrocarbon ring group, a group containing an aromatic hydrocarbon ring group More preferred. Further, L 1 preferably contains at least one structure selected from the group consisting of structures represented by any of the following formulas (A-1) to (A-5), and the following formula (A-1). It is more preferable that the structure is represented by any of A-1) to the following formula (A-5).
  • RA11 to RA14 , RA21 to RA24 , RA31 to RA38 , RA41 to RA48 and RA51 to RA58 are independent hydrogen atoms.
  • LA31 and LA41 are independently single-bonded, carbonyl group, sulfonyl group, divalent saturated hydrocarbon group, divalent unsaturated hydrocarbon group, heteroatom, heterocyclic group, or alkylene halide.
  • Representing a group, b of R A11 to R A14 , R A21 to R A24 , R A31 to R A38 , R A41 to R A48 and R A51 to R A58 , respectively, are formulas (1-2) or formulas described later. It is a binding site with X 2 in (1-3), and * represents a binding site with another structure independently.
  • L 1 has a structure represented by the formula (A-1), the formula (A-2), the formula (A-3) or the formula (A-4). Is preferable.
  • RA11 to RA14 are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, cyclic alkyl groups having 3 to 12 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and hydroxy. It is preferable to represent a group, a cyano group, an alkyl halide group having 1 to 3 carbon atoms, or a halogen atom, and from the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms.
  • RA11 to RA14 are binding sites with X 2 in the formula (1-2) or the formula (1-3) described later, and whether RA 13 is a binding site with X 2 . or, it is preferable R A12 and R A14 is a bonding site with X 2.
  • halogen atom in the alkyl halide group in RA11 to RA14 or the halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom or a bromine atom is preferable.
  • R A21 ⁇ R A24 are each synonymous with R A11 ⁇ R A14 in formula (A-1), a preferable embodiment thereof is also the same.
  • b of RA21 to RA24 are binding sites with X 2 in the formula (1-2) or the formula (1-3) described later.
  • RA31 to RA38 are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, cyclic alkyl groups having 3 to 12 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and hydroxy. It is preferable to represent a group, a cyano group, an alkyl halide group having 1 to 3 carbon atoms, or a halogen atom, and from the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms.
  • an alkoxy group of 6 or an alkyl halide having 1 to 3 carbon atoms is more preferable, and an alkyl group having a hydrogen atom or 1 to 6 carbon atoms is more preferable.
  • the halogen atom in the alkyl halide group in RA31 to RA38 or the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom or a bromine atom is preferable.
  • b of RA31 to RA38 are binding sites with X 2 in the formula (1-2) or the formula (1-3) described later, and RA 31 and RA 36 are binding sites with X 2. Is preferable.
  • LA31 is a single bond, a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, a divalent unsaturated hydrocarbon group having 5 to 24 carbon atoms, —O—, —S. -, -NR N- , a heterocyclic group, or a halogenated alkylene group having 1 to 6 carbon atoms is preferable, and a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, an -O- or a heterocyclic group. Is preferable, and it is more preferable to represent a single bond or —O—.
  • the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
  • the divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group, but is a divalent aromatic hydrocarbon. It is preferably a group.
  • the heterocyclic group for example, a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocycle is preferable, and a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocycle is preferable.
  • a group obtained by removing two hydrogen atoms from a ring structure such as a tetrahydrofuran ring, a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, a piperidine ring, a tetrahydropyran ring, a pyridine ring, or a morpholin ring.
  • These heterocycles may further have a fused ring with another heterocycle or a hydrocarbon ring.
  • the number of ring members of the heterocycle is preferably 5 to 10, and more preferably 5 or 6.
  • the hetero atom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom.
  • the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom or a bromine atom is preferable.
  • R A41 ⁇ R A48 are each synonymous with R A31 ⁇ R A38 in formula (A-3), preferable embodiments thereof are also the same.
  • b of RA41 to RA48 are binding sites with X 2 in the formula (1-2) or the formula (1-3) described later, and RA 41 and RA 48 are binding sites with X 2.
  • L A41 has the same meaning as L A31 in formula (A-3), preferable embodiments thereof are also the same.
  • R A51 ⁇ R A58 are each synonymous with R A11 ⁇ R A14 in formula (A-1), a preferable embodiment thereof is also the same.
  • * is an independent binding site with the main chain in the resin.
  • X 2 represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, and is preferably an ester bond or an ether bond. Further, X 2 may be determined in consideration of the synthesis method and the like. When X 2 is an ester bond, the carbon atom of the ester bond may be bonded to L 1 or the oxygen atom may be bonded to L 1 . When X 2 is a urethane bond, it is preferable that the oxygen atom of the urethane bond is bonded to L 1 . When X 2 is an amide bond, it is preferable that the carbon atom of the amide bond is bonded to L 1 .
  • L 2 represents a single bond or a + 1 valent linking group, a single bond or an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, ⁇ NR N ⁇ or a group in which two or more of these are bonded is preferable, and a single bond, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group is more preferable.
  • the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
  • a hydrocarbon group having 1 to 20 carbon atoms is preferable, and a hydrocarbon group having 1 to 10 carbon atoms is more preferable.
  • a saturated aliphatic hydrocarbon group is more preferable.
  • the aromatic hydrocarbon group an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, an aromatic hydrocarbon group having 6 to 12 carbon atoms is more preferable, and an aromatic hydrocarbon group having 6 carbon atoms is more preferable. preferable.
  • X 1 represents the structure represented by the above formula (1-1), and the preferred embodiment is as described in the description of the formula (1-1).
  • a represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and 1 It is particularly preferable to have.
  • b represents an integer of 1 or more, preferably an integer of 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and 1 It is particularly preferable to have.
  • the specific resin preferably contains a repeating unit represented by the following formula (1-3) as a repeating unit containing a structure represented by the formula (1-1). Further, the specific resin preferably has a repeating unit represented by the formula (1-3) in the main chain.
  • L 1 represents a b + divalent linking group
  • X 2 represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond
  • L 2 represents a single bond or an a + 1 valent linking group.
  • X 1 represents the structure represented by the above formula (1-1)
  • a represents an integer of 1 or more
  • b represents an integer of 1 or more
  • L 4 represents the following formula (L4-1) or represents a structure represented by the formula (L4-2), if X 2, L 2, X 1 or a presence of a plurality, plural of X 2, L 2, X 1 or a may be the same , May be different.
  • R 115 represents a tetravalent organic group
  • a 1 and A 2 independently represent an oxygen atom or -NH-
  • R 113 and R 114 Independently represent a hydrogen atom or a monovalent organic group.
  • L 1, X 2, L 2, X 1, a and b are, L 1 in each formula (1-2), X 2, L 2, X 1, and a and b It has the same meaning, and the preferred embodiment is the same.
  • R 115 is preferably a tetravalent organic group containing an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).
  • tetravalent organic group represented by R 115 in the formula (L4-1) include tetracarboxylic acid residues remaining after removing the acid dianhydride group from the tetracarboxylic dianhydride. .. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
  • the tetracarboxylic dianhydride is preferably a compound represented by the following formula (7).
  • R 115 represents a tetravalent organic group.
  • R 115 has the same meaning as R 115 in formula (L4-1).
  • tetracarboxylic dianhydride examples include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4 , 4'-diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Dichloride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxy
  • DAA-1 to DAA-5 tetracarboxylic dianhydrides
  • DAA-5 tetracarboxylic dianhydrides
  • a 1 and A 2 independently represent an oxygen atom or -NH-, and are preferably oxygen atoms.
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, and it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and both of them contain a polymerizable group. It is more preferable to contain a polymerizable group. Examples of the polymerizable group in R 113 or R 114 include the same group as the polymerizable group in Z 1 in the above formula (1-1).
  • R 113 or R 114 is a vinyl group, an allyl group, a (meth) acryloyl group, or a group represented by the following formula (III).
  • R200 represents a hydrogen atom or a methyl group, and a methyl group is preferable.
  • R 201 is an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- or a (poly) alkyleneoxy group having 4 to 30 carbon atoms (the alkylene group has 1 carbon atom).
  • ⁇ 12 is preferable, 1 to 6 is more preferable, 1 to 3 is particularly preferable; the number of repetitions is preferably 1 to 12, 1 to 6 is more preferable, and 1 to 3 is particularly preferable).
  • the (poly) alkyleneoxy group means an alkyleneoxy group or a polyalkyleneoxy group.
  • R 201 examples include ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group. , -CH 2 CH (OH) CH 2-, and more preferably an ethylene group, a propylene group, a trimethylene group, and -CH 2 CH (OH) CH 2- .
  • R 200 is a methyl group and R 201 is an ethylene group.
  • * represents a binding site with another structure.
  • the monovalent organic group of R 113 or R 114 in the formula (L4-2) is an aliphatic group, an aromatic group and an aryl having one, two or three, preferably one acid group.
  • Alkyl groups and the like can be mentioned. Specific examples thereof include an aromatic group having an acid group having 6 to 20 carbon atoms and an arylalkyl group having an acid group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acid group and a benzyl group having an acid group can be mentioned.
  • the acid group is preferably a hydroxy group. That is, R 113 or R 114 is preferably a group having a hydroxy group.
  • a substituent that improves the solubility of the developing solution is preferably used.
  • R 113 or R 114 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl from the viewpoint of solubility in an aqueous developer.
  • R 113 or R 114 is preferably a monovalent organic group.
  • a monovalent organic group a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group is preferable, and an alkyl group substituted with an aromatic group is more preferable.
  • the alkyl group preferably has 1 to 30 carbon atoms (3 or more in the case of a cyclic group).
  • the alkyl group may be linear, branched or cyclic. Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group and octadecyl group.
  • the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
  • Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
  • Examples of the polycyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group.
  • an alkyl group substituted with an aromatic group a linear alkyl group substituted with an aromatic group described below is preferable.
  • the cyclic structure constituting the group includes a fluorene ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolin ring, an indol ring, and a benzofuran.
  • Ring benzothiophene ring, isobenzofuran ring, quinolysin ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, aclysin ring, phenanthrene ring, thianthrene ring, chromene ring. , Xanthene ring, phenoxatiin ring, phenothiazine ring or phenazine ring).
  • the polyimide precursor has a fluorine atom in the repeating unit.
  • the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, more preferably 20% by mass or more. There is no particular upper limit, but 50% by mass or less is practical.
  • an aliphatic group having a siloxane structure may be copolymerized with the specific resin.
  • the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (paraaminophenyl) octamethylpentasiloxane.
  • R 115 has the same meaning as R 115 in formula (L4-1), preferable embodiments thereof are also the same.
  • the specific resin when L 4 has a structure represented by a group represented by the formula (L4-1), the specific resin is preferably polyimide. In the formula (1-3), when L 4 has a structure represented by a group represented by the formula (L4-2), the specific resin is preferably a polyimide precursor.
  • the content of the repeating unit represented by the formula (1-3) is 0.1 to 80 mass with respect to the total mass of the specific resin. It is preferably%, more preferably 0.5 to 70% by mass, and even more preferably 1 to 60% by mass.
  • the specific resin may contain only one type of repeating unit represented by the formula (1-3), or may contain two or more types.
  • the specific resin may have a structure represented by the following formula (1-1B) and may have a polymerizable group at another site of the specific resin.
  • the specific resin may have a structure represented by the following formula (1-1B) in the main chain or in the side chain, but from the viewpoint of film strength, it may have in the main chain. preferable. Further, from the viewpoint of coatability, it is preferable to have it in the side chain.
  • R B1 independently represents a hydrogen atom or an alkyl group
  • nB represents an integer of 2 or more
  • mB represents an integer of 2 or more
  • R B1 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, a hydrogen atom or a methyl group More preferred.
  • nB is preferably an integer of 2 to 100, more preferably an integer of 2 to 50, and even more preferably an integer of 2 to 30. It is particularly preferably an integer of ⁇ 10, and most preferably an integer of 3-10.
  • m is preferably an integer of 2 to 50, more preferably an integer of 2 to 30, and even more preferably an integer of 2 to 10. It is more preferably an integer of ⁇ 6, particularly preferably an integer of 2-4, and most preferably 2 or 3.
  • the specific resin preferably contains a structure represented by the following formula (1-2B) or a structure represented by the following formula (1-2C) as a structure containing the formula (1-1B).
  • the specific resin preferably contains a structure represented by the following formula (1-2B) in the main chain.
  • the specific resin preferably contains a structure represented by the following formula (1-2C) at the end of the main chain or the side chain, and the side chain. It is more preferable to include in.
  • the specific resin preferably contains a plurality of structures represented by the formula (1-2B) or a plurality of structures represented by the formula (1-2C).
  • the specific resin contains a structure represented by the formula (1-2B) or a plurality of structures represented by the formula (1-2C)
  • L B1 and L B2 each independently represent a single bond or a divalent linking group
  • L X represents a structure represented by the above formula (1-1B).
  • L B3 represents a single bond or a divalent linking group
  • L X represents a structure represented by the above formula (1-1B)
  • R B2 represents a hydrogen atom, Alternatively, it represents a substituent having no polymerizable group.
  • L B1 and L B2 each independently a single bond or an alkylene group, an arylene group, an ether bond, a carbonyl group, a thioether bond, sulfonyl group, -NR N -, or, these A group having two or more bonds is preferable, a single bond, an alkylene group, or an arylene group is more preferable, and a single bond or an alkylene group is more preferable.
  • the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
  • L X represents a structure represented by the above formula (1-1B), the preferred embodiment is as described in the description in the above formula (1-1B).
  • L B3 has the same meaning as L B1 or L B2 in the above formula (1-2B), preferable embodiments thereof are also the same.
  • L X represents a structure represented by the above formula (1-1B), the preferred embodiment is as described in the description in the above formula (1-1B).
  • R B2 is a hydrogen atom, or an alkyl group, an aryl group, but may be a known substituent such as a halogen atom, a hydrogen atom, an alkyl group or an aryl group preferably a hydrogen atom or Alkyl groups are more preferred, and alkyl groups are even more preferred.
  • an alkyl group having 1 to 20 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is further preferable.
  • an alkyl group having 6 to 20 carbon atoms is preferable, an alkyl group having 6 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is further preferable.
  • the specific resin contains a structure represented by the formula (1-2B)
  • the specific resin preferably contains a repeating unit represented by the following formula (1-3B).
  • L B1 and L B2 each independently represent a single bond or a divalent linking group
  • L X represents a structure represented by the above formula (1-1B)
  • L B4 Represents the structure represented by the formula (L4-1) or the formula (L4-2) in the above formula (1-3).
  • L B1, L B2 and L X are each the same meaning as L B1, L B2 and L X in formula (1-2B), preferable embodiments thereof are also the same.
  • L B4 has the same meaning as L 4 in the above formula (1-3), preferable embodiments thereof are also the same.
  • L B4 is a structure represented by the group represented by the formula (L4-1), is preferably specific resin is polyimide.
  • L B4 is a structure represented by the group represented by the formula (L4-2), is preferably specific resin is a polyimide precursor.
  • the content of the repeating unit represented by the formula (1-3B) is 0.1 to 80 mass with respect to the total mass of the specific resin. %, More preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass.
  • the specific resin may contain only one type of repeating unit represented by the formula (1-3B), or may contain two or more types.
  • the specific resin contains a structure represented by the formula (1-2C)
  • the specific resin has a structure represented by the following formula (1-3C) as a structure including the structure represented by the formula (1-2C). Is preferably included.
  • the specific resin preferably contains a structure represented by the formula (1-3C) in the main chain. That is, the structure represented by L B5 in the formula (l-3C) is preferably contained in the main chain of the specific resin.
  • the specific resin preferably contains a plurality of structures represented by the formula (1-3C). When the specific resin contains a plurality of structures represented by the formula (1-3C), the structures represented by the plurality of formulas (1-3C) may be the same or different.
  • Formula (l-3C) in, L B5 represents NB2 + 2 divalent linking group
  • X B2 is an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond
  • X B1 above formula (l-2C) in represents a structure represented by
  • NB2 represents an integer of 1 or more, if the X B1 or X B2 there are a plurality, plural of X B1 and X B2 may be the same or different.
  • L B5 has the same meaning as L 1 in the above formula (1-2), preferable embodiments thereof are also the same.
  • the formula LB5 includes any one of the structures represented by the formulas (A-1) to (A-5), " RA11 to R” in the description of the formulas (A-1) to (A-5).
  • R A21 to R A24 , R A31 to R A38 , R A41 to R A48, and R A51 to R A58 b of each are X 2 in the formula (1-2) or the formula (1-3) described later.
  • nB2 a binding site for, "is” R A11 ⁇ R A14, R A21 ⁇ R A24, R A31 ⁇ R A38, of R A41 ⁇ R A48 and R A51 ⁇ R A58, the nB2 pieces each formula (2 -1) It is the binding site with X B2 in , and should be read as ".
  • X B2 has the same meaning as X 2 in the above formula (1-2), and the preferred embodiment is also the same.
  • X B1 represents the structure represented by the above formula (1-2C), and the preferred embodiment is as described in the above description of the formula (1-2C).
  • nB2 has the same meaning as b in the above formula (1-2), and the preferred embodiment is also the same.
  • Equation (1-4C) during, L B5 represents NB2 + 2 divalent linking group, X B2 is an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond, X B1 above formula (l-2C) represents structure represented by the, NB2 represents an integer of 1 or more, L B4 represents a structure represented by the formula (L4-1) or formula (L4-2) in the above equation (1-3), If X B1 or X B2 there are a plurality, plural of X B1 and X B2 may be the same or different.
  • L B5, X B2, X B1 and NB2, respectively, L B5 in the above formula (l-3C), have the same meanings as X B2, X B1 and NB2, a preferred embodiment also the same is there.
  • L B4 has the same meaning as L 4 in the above formula (1-3), preferable embodiments thereof are also the same.
  • the content of the repeating unit represented by the formula (1-4C) is 0.1 to 80 mass with respect to the total mass of the specific resin. %, More preferably 10 to 80% by mass, and even more preferably 20 to 75% by mass.
  • the specific resin may contain only one type of repeating unit represented by the formula (1-4C), or may contain two or more types.
  • the specific resin may further contain a repeating unit represented by the following formula (2-1).
  • the specific resin contains a structure represented by the formula (1-2B) or the formula (1-2C)
  • the specific resin has a structure other than the structure represented by the formula (1-2B) or the formula (1-2C).
  • Other structures include polymerizable groups.
  • the specific resin is polyimide
  • the specific resin is a repeating unit represented by the following formula (2-1) as a repeating unit having a polymerizable group
  • L 21 is a repeating unit of the formula (L4-1). It is preferable to include more units.
  • the repeating unit contains a group or is represented by the following formula (2-1) and further contains a repeating unit in which L 21 is the formula (L4-2).
  • L 21 represents a b2 + divalent linking group
  • X 22 represents an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond
  • X 21 represents a group containing a polymerizable group.
  • X 21 and X 22 are groups containing no polyalkyleneoxy group
  • b2 represents an integer of 1 or more
  • L 4 is the formula (L4-1) or the formula (L4-) in the above formula (1-3). It represents a structure represented by 2), if X 22 or X 21 there are a plurality, the plurality of X 22 or X 21 may be the same or different.
  • L 21 , X 22 , b2 and L 4 are synonymous with L 1 , X 2 , b and L 4 in the above formula (1-3), respectively, and the preferred embodiments are also the same. Is.
  • L 21 includes any one of the structures represented by the formulas (A-1) to (A-5), " RA11 to R” in the description of the formulas (A-1) to (A-5).
  • R A21 to R A24 , R A31 to R A38 , R A41 to R A48 and R A51 to R A58 , b are each X 2 in the formula (1-2) or the formula (1-3) described later.
  • the binding site with means that " RA11 to RA14 , RA21 to RA24 , RA31 to RA38 , RA41 to RA48, and RA51 to RA58 , respectively, b2 are formulas ( It is the binding site with X 22 in 2-1). ”
  • X 21 represents a group containing a polymerizable group, and the group represented by the above formula (Z-1) is preferable.
  • the specific resin when L 4 has a structure represented by a group represented by the formula (L4-1), the specific resin is preferably polyimide. In the formula (2-1), when L 4 has a structure represented by a group represented by the formula (L4-2), the specific resin is preferably a polyimide precursor.
  • the specific resin contains a repeating unit represented by the formula (2-1), the content of the repeating unit represented by the formula (1-4C) is 0.1 to 80 mass with respect to the total mass of the specific resin. %, More preferably 10 to 80% by mass, and even more preferably 20 to 75% by mass.
  • the specific resin may contain only one type of repeating unit represented by the formula (2-1), or may contain two or more types.
  • the specific resin may further contain a repeating unit represented by the following formula (4).
  • the specific resin is preferably polyimide.
  • the specific resin preferably contains a repeating unit represented by the following formula (4) in the main chain.
  • R 131 represents a divalent organic group and R 132 represents a tetravalent organic group.
  • the divalent organic group represented by R 131 the same group as R 111 in the formula (1) described later is exemplified, and the preferable range is also the same.
  • the tetravalent organic group represented by R 132 the same group as R 115 in the above formula (L4-1) is exemplified, and the preferable range is also the same.
  • R 1 in the structure represented by the formula (1-1) in the specific resin is a substituent that does not contain a polymerizable group
  • at least one of R 131 and R 132 may contain a polymerizable group, or the polyimide. It may have a structure containing a polymerizable group at the end.
  • the specific resin contains the repeating unit represented by the formula (4) (for example, when the specific resin is polyimide), the specific resin uses the repeating unit represented by the formula (4) as the total mass of the specific resin. On the other hand, it is preferably contained in an amount of 1 to 80% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass. Further, when the specific resin is polyimide, the specific resin may be in a mode in which the repeating unit represented by the formula (4) is substantially not contained. In such a mode, the specific resin is represented by the formula (4).
  • the content of the repeating unit to be formed is preferably 5% by mass or less, and more preferably 1% by mass or less, based on the total mass of the specific resin.
  • Total content of the repeating unit represented by, the repeating unit represented by the formula (2-1), and the repeating unit represented by the formula (4) (among the above repeating units, there is a repeating unit that does not contain. It may be) is preferably 50 to 100% by mass, more preferably 60 to 99% by mass, and further preferably 70 to 95% by mass with respect to the total mass of the specific resin.
  • the specific resin may further contain a repeating unit represented by the following formula (1).
  • the specific resin is preferably a polyimide precursor.
  • the specific resin preferably contains a repeating unit represented by the following formula (1) in the main chain.
  • a 1 and A 2 independently represent an oxygen atom or NH
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 are independent of each other. Represents a hydrogen atom or a monovalent organic group.
  • R 111 represents a divalent organic group.
  • the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a group in which two or more of these are combined, and the number of carbon atoms is exemplified.
  • the group combined as described above is preferable, and an aromatic group having 6 to 20 carbon atoms is more preferable.
  • R 111 in formula (1) is preferably derived from diamine.
  • the diamine used for producing the polyimide precursor include linear or branched-chain aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used.
  • the diamine is a linear aliphatic group having 2 to 20 carbon atoms, a branched or cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or these. It is preferably a diamine containing two or more combined groups, and more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms.
  • aromatic groups include:
  • diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 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 or isophoronediamine; meta or paraphenylenediamine, diaminotoluene, 4,4'-or 3 , 3'-diaminobiphenyl, 4,4'-diaminodiphenyl ether,
  • diamines (DA-1) to (DA-18) shown below are also preferable.
  • a diamine having at least two alkylene glycol units in the main chain is also mentioned as a preferable example.
  • a diamine containing two or more of one or both of an ethylene glycol chain and a propylene glycol chain in one molecule is preferable, and a diamine containing no aromatic ring is preferable.
  • Specific examples include Jeffamine (registered trademark) KH-511, Jeffamine (registered trademark) ED-600, Jeffamine (registered trademark) ED-900, Jeffamine (registered trademark) ED-2003, and Jeffamine (registered trademark).
  • EDR-148 Jeffamine (registered trademark) EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN), 1- (2- (2- (2)) -Aminopropoxy) ethoxy) propoxy) propane-2-amine, 1- (1- (1- (2-aminopropoxy) propoxy-2-yl) oxy) propane-2-amine, etc., but are limited to these. Not done.
  • x, y, and z are arithmetic mean values.
  • R 111 in the formula (1) from the viewpoint of flexibility of the cured film obtained, -Ar 0 -L 0 -Ar 0 - is preferably represented by.
  • Ar 0 is independently an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and a phenylene group is preferable.
  • the preferred range of L 0 is synonymous with A above.
  • R 111 in the formula (1) is preferably a divalent organic group represented by the following formula (51) or the formula (61) from the viewpoint of i-ray transmittance.
  • a divalent organic group represented by the formula (61) is more preferable from the viewpoint of i-ray transmittance and availability.
  • R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, a fluoromethyl group, It is a difluoromethyl group or a trifluoromethyl group, and * independently represents a binding site with another structure.
  • the monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
  • R 58 and R 59 are independently fluorine atoms, fluoromethyl groups, difluoromethyl groups, or trifluoromethyl groups, respectively.
  • Examples of the diamine compound giving the structure of the formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2. Examples thereof include'-bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. One of these may be used, or two or more thereof may be used in combination.
  • the specific resin contains the repeating unit represented by the formula (1) (for example, when the specific resin is a polyimide precursor), the specific resin uses the repeating unit represented by the formula (1) as the whole of the specific resin. It is preferably contained in an amount of 1 to 90% by mass, more preferably 10 to 80% by mass, and even more preferably 20 to 70% by mass with respect to the mass. Further, when the specific resin is a polyimide precursor, the specific resin may be in a mode in which the repeating unit represented by the formula (1) is substantially not contained. In such a mode, the formula (1) is used.
  • the content of the repeating unit represented by is preferably 5% by mass or less, and more preferably 1% by mass or less, based on the total mass of the specific resin.
  • the repeating unit represented by the formula (1-3), the repeating unit represented by the formula (1-3B), and the repeating unit of the formula (1-3B) contained in the specific resin are included.
  • Total content of the repeating unit represented by 4C), the repeating unit represented by the formula (2-1), and the repeating unit represented by the formula (1) (among the above repeating units, the repeating unit not contained) Is preferably 50 to 100% by mass, more preferably 60 to 99% by mass, and further preferably 70 to 95% by mass, based on the total mass of the specific resin. preferable.
  • the content of the specific resin in the curable resin composition of the present invention is 20% by mass or more with respect to the total solid content of the curable resin composition from the viewpoint of improving the breaking elongation of the obtained cured film. It is preferably 30% by mass or more, more preferably 40% by mass or more.
  • the upper limit of the content is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass, from the viewpoint of improving the resolution of the curable resin composition. It is more preferably less than or equal to 97% by mass or less, and even more preferably 95% by mass or less.
  • the weight average molecular weight (Mw) of the specific resin is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000. preferable.
  • the number average molecular weight (Mn) of the specific resin is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
  • the degree of dispersion of the molecular weight of the specific resin is preferably 1.5 to 3.5, more preferably 2 to 3. In the present specification, the degree of molecular weight dispersion means a value obtained by dividing the weight average molecular weight by the number average molecular weight (weight average molecular weight / number average molecular weight).
  • the acid value of the specific resin is preferably 1 mmol / g or less, more preferably 0.5 mmol / g or less, and 0.3 mmol / g or less. Is more preferable.
  • the lower limit of the acid value is not particularly limited, and may be 0 mmol / g or more.
  • the acid value of the specific resin is preferably 1.2 to 7 mmol / g, more preferably 1.5 to 6 mmol / g, 2 It is more preferably ⁇ 5 mmol / g.
  • the acid value means the amount (mmol) of an acid group contained in 1 g of a specific resin.
  • the acid group refers to a group that is neutralized by an alkali having a pH of 12 or higher (for example, sodium hydroxide). Further, the acid group is preferably a group having a pKa of 10 or less.
  • the acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
  • the specific resin is at least one resin selected from the group consisting of polyimide and a polyimide precursor.
  • the repeating unit represented by the equation (1-3) and in which L 4 is the equation (L4-1) is referred to as the repeating unit PI-1.
  • a repeating unit represented by formula (1-3B), L B4 is that units PI-2 repeat repeating units of formula (L4-1).
  • a repeating unit represented by the formula (1-4C), L B4 is that units PI-3 repeating repeating units of formula (L4-1).
  • a repeating unit represented by the formula (2-1) in which L 4 is the repeating unit of the formula (L4-1) is referred to as a repeating unit PI-4.
  • the repeating unit represented by the formula (1-3) and in which L 4 is the formula (L4-2) is called the repeating unit PIP-1.
  • a repeating unit represented by formula (1-3B), L B4 are called Unit PIP-2 repeat repeating units of formula (L4-2).
  • a repeating unit represented by the formula (1-4C), L B4 are called Unit PIP-3 repeating repeating units of formula (L4-2).
  • the repeating unit represented by the formula (2-1), wherein L 4 is the repeating unit of the formula (L4-2), is referred to as a repeating unit PIP-4.
  • the specific resin is polyimide
  • the specific resin is preferably the polyimide described in any of the following PI1 to the following PI3.
  • PI1 Polyimide containing the repetition unit PI-1
  • PI2 Polyimide containing the repetition unit PI-2 and the repetition unit PI-4
  • PI3 Polyimide containing the repetition unit PI-3 and the repetition unit PI-4
  • Polyimide may further contain the repeating unit PIP-1.
  • the polyimide described in PI2 may further contain at least one selected from the group consisting of the repeating unit PIP-2 and the repeating unit PIP-4.
  • the polyimide described in PI3 may further contain at least one selected from the group consisting of the repeating unit PIP-3 and the repeating unit PIP-4.
  • the polyimide described in PI1 may further contain the repetition unit PI-4.
  • the polyimide described in PI1 may further contain the repetition unit PI-4.
  • the polyimides described in PI1 to PI3 may further contain other repeating units such as the repeating unit represented by the formula (4). When the polyimides described in PI1 to PI3 contain the repeating unit represented by the formula (4), the repeating unit represented by the formula (1) may be further contained.
  • the ring closure rate of the specific resin is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
  • the ring closure rate of the specific resin when the specific resin is polyimide is a value represented by the following formula CR (PI).
  • Equation CR (PI): Ring closure rate (%) of the specific resin (molar amount of imide ring in the specific resin) / (molar amount of the imide ring in the specific resin + molar amount of the structure capable of forming the imide ring by closing the ring in the specific resin) ⁇ 100
  • the specific resin is a resin composed of a repeating unit PI-1, a repeating unit PIP-1, a repeating unit represented by the formula (4), and a repeating unit represented by the formula (1)
  • the ring is closed.
  • the rate is a value represented by the following formula CR (PI) 1.
  • the specific resin is a polyimide precursor
  • the specific resin is preferably the polyimide described in any of the following PIP1 to the following PIP5.
  • PIP1 polyimide precursor containing repeating units
  • PIP2 comprise repeating units PIP2
  • L B4 in the formula (1-3B) is formula (L4-2), the formula (L4-2) in the Formula (1), which comprises a polyimide precursor PIP3 in which at least one of R 113 and R 114 contains a polymerizable group: a repeating unit PIP-2 and a polyimide precursor PIP4 containing a repeating unit PIP-4: a repeating unit PIP-3.
  • L B4 in is formula (L4-2), the polyimide precursor PIP5 comprising at least one polymerizable group R 113 and R 114 in formula (L4-2): repeating units PIP-3, And a polyimide precursor containing the repeating unit PIP-4
  • Specific examples of the specific resin include the specific resin used in the examples described later.
  • the specific resin is the polyimide described in PI1
  • the specific resin is synthesized, for example, by sequentially performing the steps described in (1) and (2) below.
  • Diamine having a functional group such as a carboxy group, a hydroxy group or an amino group is reacted with a dicarboxylic acid or a dicarboxylic acid derivative, and after the reaction, thermal imidization or chemical imidization (for example, cyclization by acting a catalyst) Step of forming an imide ring by a method such as (promotion of reaction) to obtain a polyimide
  • a group capable of binding to the functional group for example, a hydroxy group
  • the functional group for example, a hydroxy group
  • a step of reacting a compound having a polyalkyleneoxy group and a polymerizable group for example, polyalkylene glycol-monomethacrylate, etc.
  • a polymerizable group for example, polyalkylene glycol-monomethacrylate, etc.
  • a commercially available product may be used as the compound having a possible group, a polyalkyleneoxy group, and a polymerizable group, and the commercially available products include Blemmer PE-90, PE-200, PE-350, PP-1000, Examples thereof include PP-500, PP-800, AE-90U, AE-200, AE-400, AP-200, AP-400, AP-550, AP-800 (all manufactured by Nichiyu Co., Ltd.).
  • the specific resin is the polyimide described in PI2
  • the specific resin is synthesized, for example, by sequentially performing the steps described in (3) to (4) below.
  • Diamine having a polyalkyleneoxy group for example, bis (2- (3-aminopropoxy) ethyl) ether or the like
  • diamine having a functional group such as a carboxy group, a hydroxy group or an amino group
  • a group capable of binding to the functional group for example, a hydroxy group, a carboxy group which may be halogenated, an isocyanate group, etc.
  • a polymerizable group are added.
  • the specific resin is the polyimide described in PI3
  • the specific resin is synthesized, for example, by sequentially performing the steps described in (5) to (6) below.
  • Diamine having a functional group such as a carboxy group, a hydroxy group or an amino group is reacted with a dicarboxylic acid or a dicarboxylic acid derivative, and after the reaction, thermal imidization or chemical imidization (for example, cyclization by acting a catalyst)
  • a group capable of binding to the functional group for example, a hydroxy group
  • the functional group for example, a hydroxy group
  • a compound having a carboxy group which may be halogenated, an isocyanate group, etc. and a polyalkyleneoxy group for example, polyalkylene glycol monoalkylene ether, etc.
  • a group capable of binding to the functional group for example,.
  • the specific resin is a polyimide precursor
  • a method of reacting a diamine with a dicarboxylic acid derivative in which at least one of a polyalkyleneoxy group and a polymerizable group is introduced into a part of the carboxylic acid is used.
  • the diamine a diamine having a polyalkylene oxy group may be used.
  • the curable resin composition of the present invention may contain another resin (hereinafter, also simply referred to as “other resin”) different from the above-mentioned specific resin.
  • the other resin include a polyimide different from the specific resin, a polyimide precursor, and the like.
  • the specific resin is polyimide
  • the other resin is preferably polyimide.
  • the specific resin is a polyimide precursor
  • the other resin is preferably a polyimide precursor.
  • the polyimide which is another resin, has a repeating unit represented by the above formula (4).
  • the repeating unit represented by the formula (4) may be one kind, or two or more kinds. Further, the polyimide may contain other types of repeating units in addition to the repeating unit of the above formula (4).
  • a polyimide precursor in which 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units is the repeating unit represented by the formula (4) is exemplified. Will be done. As an upper limit, 100 mol% or less is practical.
  • the weight average molecular weight (Mw) of the polyimide is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000.
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
  • the degree of dispersion of the molecular weight of the polyimide is preferably 1.5 to 3.5, more preferably 2 to 3.
  • Polyimide can be obtained, for example, by cyclizing a polyimide precursor, which is another resin described later, by heating or the like.
  • the polyimide precursor (other resin)
  • the polyimide precursor preferably has a repeating unit represented by the above formula (1).
  • the repeating unit represented by the formula (1) may be one kind, but may be two or more kinds. Further, the structural isomer of the repeating unit represented by the formula (1) may be contained. Further, the polyimide precursor may contain other types of repeating units in addition to the repeating units of the above formula (1).
  • the polyimide precursor in the present invention 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units are the repeating units represented by the formula (1). Is exemplified. As an upper limit, 100 mol% or less is practical.
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000.
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
  • the degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
  • the polyimide precursor is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine.
  • the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.
  • the organic solvent may be one kind or two or more kinds.
  • the organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
  • the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
  • the content of the other resin is preferably 0.01% by mass or more with respect to the total solid content of the curable resin composition. It is more preferably 05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and 10% by mass or more. It is even more preferable to have.
  • the content of the other resin in the curable resin composition of the present invention is preferably 80% by mass or less, and preferably 75% by mass or less, based on the total solid content of the curable resin composition. It is more preferably 70% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less.
  • the curable 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 kinds are included, the total amount is preferably in the above range.
  • the curable resin composition of the present invention contains a polymerization initiator.
  • a polymerization initiator a photopolymerization initiator is preferable.
  • the curable resin composition of the present invention preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • the photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators.
  • a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferable.
  • it may be an active agent that produces an active radical by causing some action with the photoexcited sensitizer.
  • the photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol -1 ⁇ cm -1 within the range of about 300 to 800 nm (preferably 330 to 500 nm). Is preferable.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • a known compound can be arbitrarily used.
  • halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like.
  • Oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ethers, aminoacetophenone compounds, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc. Can be mentioned.
  • paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.
  • ketone compound for example, the compound described in paragraph 0087 of JP2015-087611A is exemplified, and the content thereof is incorporated in the present specification.
  • KayaCure DETX manufactured by Nippon Kayaku Co., Ltd.
  • Nippon Kayaku Co., Ltd. is also preferably used.
  • a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.
  • IRGACURE 184 (IRGACURE is a registered trademark)
  • DAROCUR 1173 As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.
  • aminoacetophenone-based initiator commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
  • the compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
  • acylphosphine-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.
  • metallocene compound examples include IRGACURE-784 (manufactured by BASF).
  • An oxime compound is more preferable as the photoradical polymerization initiator.
  • the exposure latitude can be improved more effectively.
  • the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
  • the compound described in JP-A-2001-233842 the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.
  • Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
  • an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator.
  • IRGACURE OXE 01 IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052).
  • the radical polymerization initiator 2) is also preferably used.
  • TR-PBG-304 manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.
  • Adeka Arkuru's NCI-831 and Adeka Arkuru's NCI-930 can also be used.
  • DFI-091 manufactured by Daito Chemix Corp.
  • an oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.
  • Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.
  • the photoradical polymerization initiator is a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triaryl.
  • More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds.
  • At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more preferable.
  • the photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone).
  • 2-benzyl such as benzophenone
  • -2-morpholino-aromatic ketones such as propanol-1, alkylanthraquinone, etc.
  • benzoin ether compounds such as benzoin alkyl ether
  • benzoin compounds such as benzoin and alkyl benzoin
  • benzyl derivatives such as benzyl dimethyl ketal.
  • a compound represented by the following formula (I) can also be used.
  • R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like.
  • R I01 is a group represented by formula (II), the same as R I00
  • the groups are R I02 to R I04, which are independently alkyl having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, or halogen.
  • R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
  • the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/1254669 can also be used.
  • the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total is preferably in the above range.
  • the curable resin composition of the present invention may contain a thermal polymerization initiator as the polymerization initiator, and may particularly contain a thermal radical polymerization initiator.
  • a thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound.
  • thermal radical polymerization initiator examples include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
  • thermosetting initiator When the thermosetting initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. It is more preferably 5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, the total is preferably in the above range.
  • the curable resin composition of the present invention contains a polymerizable compound.
  • a radically polymerizable compound can be used as the polymerizable compound.
  • the radically polymerizable compound is a compound having a radically polymerizable group.
  • examples of the radically polymerizable group include groups having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
  • the radically polymerizable group is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.
  • the number of radically polymerizable groups contained in the radically polymerizable compound may be one or two or more, but the radically polymerizable compound preferably has two or more radically polymerizable groups, and preferably has three or more radically polymerizable groups. More preferred.
  • the upper limit is preferably 15 or less, more preferably 10 or less, and even more preferably 8 or less.
  • the molecular weight of the radically polymerizable compound 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 radically polymerizable compound is preferably 100 or more.
  • the curable resin composition of the present invention preferably contains at least one bifunctional or higher functional radical polymerizable compound containing two or more radical polymerizable groups, and is preferably a trifunctional or higher functional radical polymerizable compound. It is more preferable to contain at least one kind. Further, it may be a mixture of a bifunctional radical polymerizable compound and a trifunctional or higher functional radical polymerizable compound.
  • the number of functional groups of a bifunctional or higher-functional polymerizable monomer means that the number of radically polymerizable groups in one molecule is two or more.
  • the radically polymerizable compound examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, and preferred examples thereof.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group.
  • a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amines or thiols, and a halogeno group.
  • Substitution reactions of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
  • a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
  • examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
  • a compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993.
  • Urethane (meth) acrylates such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.
  • a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
  • radically polymerizable compounds other than the above those described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like have a fluorene ring and have an ethylenically unsaturated bond. It is also possible to use a compound having two or more groups having the above, or a cardo resin.
  • the compound described in Japanese Patent Application Laid-Open No. 10-062986 together with specific examples as formulas (1) and (2) after addition of ethylene oxide or propylene oxide to a polyfunctional alcohol is also (meth) acrylated. It can be used as a radically polymerizable compound.
  • radically polymerizable compound examples include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku).
  • SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
  • SR-209 which is a bifunctional methacrylate having four ethyleneoxy chains.
  • DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd., TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS- 10, UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H ( Nippon Kayaku Co., Ltd., UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.
  • Examples of the radically polymerizable compound include urethane acrylates as described in JP-A-48-041708, JP-A-51-0371993, JP-A-02-032293, and JP-A-02-016765.
  • Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
  • radically polymerizable compound compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. It can also be used.
  • the radically polymerizable compound may be a radically polymerizable compound having an acid group such as a carboxy group or a phosphoric acid group.
  • the radically polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
  • a radically polymerizable compound having a group is more preferable.
  • the aliphatic polyhydroxy compound in a radical polymerizable compound in which an unreacted hydroxy group of an aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to give an acid group, is pentaerythritol or dipenta. It is a compound that is erythritol.
  • examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
  • the preferable acid value of the radically polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
  • the acid value of the radically polymerizable compound is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizable property is good.
  • the acid value is measured according to the description of JIS K 0070: 1992.
  • a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound from the viewpoint of suppressing warpage associated with controlling the elastic modulus of the cured film.
  • the monofunctional radically polymerizable compound include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth).
  • Acrylate derivatives N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used.
  • the monofunctional radical polymerizable compound a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
  • the curable resin composition of the present invention can further contain a polymerizable compound other than the radically polymerizable compound described above.
  • a polymerizable compound other than the above-mentioned radically polymerizable compound include a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group; an epoxy compound; an oxetane compound; and a benzoxazine compound.
  • R 104 represents an organic group having a t-valence of 1 to 200 carbon atoms
  • R 105 is a group represented by -OR 106 or -OCO-R 107.
  • R 106 indicates a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 107 indicates an organic group having 1 to 10 carbon atoms.
  • R 404 represents a divalent organic group having 1 to 200 carbon atoms
  • R 405 represents a group represented by -OR 406 or -OCO-R 407
  • R 406 is a hydrogen atom or carbon.
  • R 407 indicates an organic group having 1 to 10 carbon atoms.
  • U in the formula represents an integer of 3 to 8
  • R 504 represents a u-valent organic group having 1 to 200 carbon atoms
  • R 505 represents a group represented by -OR 506 or -OCO-R 507.
  • R 506 represents a hydrogen atom or an organic group having 1 to 10 carbon atoms
  • R 507 represents an organic group having 1 to 10 carbon atoms.
  • Specific examples of the compound represented by the formula (AM4) include 46DMOC, 46DMOEP (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML.
  • Specific examples of the compound represented by the formula (AM5) include TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, and the like.
  • HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TM-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), NIKALAC MX-280, Examples thereof include NIKALAC MX-270 and NIKALAC MW-100LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.).
  • the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
  • the epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the curable resin composition.
  • the epoxy compound preferably contains a polyethylene oxide group.
  • the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
  • epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether; polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether; polymethyl (glycidi).
  • epoxy groups include, but are not limited to, epoxy group-containing silicones such as loxypropyl) siloxane.
  • an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance.
  • an epoxy resin containing a polyethylene oxide group is preferable because it is excellent in suppressing warpage and heat resistance.
  • Epicron® EXA-4880, Epicron® EXA-4822, and Ricaresin® BEO-60E are preferred because they contain polyethylene oxide groups.
  • oxetane compound compound having an oxetanyl group
  • the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, and the like.
  • examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like.
  • the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone or Two or more kinds may be mixed.
  • benzoxazine compound Preferred examples of the benzoxazine compound are BA type benzoxazine, Bm type benzoxazine (above, trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, phenol novolac type dihydrobenzo.
  • Oxazine compounds can be mentioned. These may be used alone or in combination of two or more.
  • the content of the polymerizable compound is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the curable resin composition of the present invention.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
  • One type of polymerizable compound may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.
  • the curable resin composition of the present invention contains a solvent.
  • a solvent a known solvent can be arbitrarily used.
  • the solvent is preferably an organic solvent.
  • the organic solvent include compounds such as esters, ethers, ketones, aromatic hydrocarbons, sulfoxides, and amides.
  • esters include ethyl acetate, -n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone.
  • alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)
  • 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate
  • Etc. eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate
  • 2-alkyloxy-2-methylpropionate etc.
  • Methyl acid and ethyl 2-alkyloxy-2-methylpropionate eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
  • methyl pyruvate, ethyl pyruvate, pyruvin Propyl acid, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate and the like are preferred.
  • ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol.
  • Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
  • ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like are preferable.
  • aromatic hydrocarbons for example, toluene, xylene, anisole, limonene and the like are preferable.
  • sulfoxides for example, dimethyl sulfoxide is preferable.
  • N-methyl-2-pyrrolidone N-ethyl-2-pyrrolidone
  • N, N-dimethylacetamide N, N-dimethylformamide and the like are preferable.
  • the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
  • the mixed solvent to be mixed is preferable.
  • the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
  • the content of the solvent is preferably such that the total solid content concentration of the curable resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. It is more preferable that the amount is 10 to 70% by mass, and more preferably 40 to 70% by mass.
  • the solvent content may be adjusted according to the desired thickness of the coating film and the coating method.
  • the solvent may contain only one type or two or more types. When two or more kinds of solvents are contained, the total is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a thermosetting agent.
  • the thermoacid generator generates an acid by heating, and is at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound, or a specific resin. It has the effect of promoting the cross-linking reaction of the methylol group contained in.
  • the specific resin preferably contains a methylol group as a polymerizable group.
  • the thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after applying the curable resin composition to the substrate, and final heating (cure: about 100 to 400) after patterning in subsequent exposure and development. It is preferable to select a thermosetting agent that generates an acid at °C) because it can suppress a decrease in sensitivity during development.
  • the thermal decomposition start temperature is obtained as the peak temperature of the exothermic peak, which is the lowest temperature when the thermoacid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule. Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).
  • the acid generated from the thermoacid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane.
  • aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid
  • alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid
  • haloalkyl sulfonic acid such as sulfonic acid is preferable.
  • thermoacid generator include those described in paragraph 0055 of JP2013-072935A.
  • those that generate alkyl sulfonic acid having 1 to 4 carbon atoms or haloalkyl sulfonic acid having 1 to 4 carbon atoms are more preferable from the viewpoint that there is little residue in the cured film and it is difficult to deteriorate the physical properties of the cured film.
  • thermoacid generator the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermoacid generator.
  • the content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin. When it is contained in an amount of 0.01 part by mass or more, the crosslinking reaction is promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved. Further, from the viewpoint of electrical insulation of the cured film, 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is further preferable.
  • the curable resin composition of the present invention preferably contains an onium salt.
  • the specific resin is a polyimide precursor
  • the curable resin composition preferably contains an onium salt.
  • the type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt and phosphonium salt are preferably mentioned.
  • an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability
  • a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.
  • the onium salt is a salt of a cation and an anion having an onium structure, and the cation and the anion may or may not be bonded via a covalent bond. .. That is, the onium salt may be an intermolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are different molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the curable resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
  • an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.
  • the onium salt used in the present invention may be a thermobase generator.
  • the thermal base generator refers to a compound that generates a base by heating, and examples thereof include an acidic compound that generates a base when heated to 40 ° C. or higher.
  • ammonium salt means a salt of an ammonium cation and an anion.
  • ammonium cation As the ammonium cation, a quaternary ammonium cation is preferable.
  • the ammonium cation is preferably a cation represented by the following formula (101).
  • R 1 to R 4 independently represent a hydrogen atom or a hydrocarbon group, and at least two of R 1 to R 4 may be bonded to each other to form a ring.
  • R 1 to R 4 are each independently preferably a hydrocarbon group, more preferably an alkyl group or an aryl group, and an alkyl group having 1 to 10 carbon atoms or 6 to 6 carbon atoms. It is more preferably 12 aryl groups.
  • R 1 to R 4 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group. Examples thereof include a carbonyl group and an acyloxy group.
  • the ring may contain a hetero atom. Examples of the hetero atom include a nitrogen atom.
  • the ammonium cation is preferably represented by any of the following formulas (Y1-1) and (Y1-2).
  • R 101 represents an n-valent organic group
  • R 1 has the same meaning as R 1 in the formula (101)
  • Ar 101 and Ar 102 are each independently , Represents an aryl group
  • n represents an integer of 1 or more.
  • R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms. More preferably, it is a group obtained by removing n hydrogen atoms from the saturated aliphatic hydrocarbon, benzene or naphthalene.
  • n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
  • Ar 101 and Ar 102 are preferably phenyl groups or naphthyl groups, respectively, and more preferably phenyl groups.
  • the anion in the ammonium salt one selected from a carboxylic acid anion, a phenol anion, a phosphoric acid anion and a sulfate anion is preferable, and a carboxylic acid anion is more preferable because both salt stability and thermal decomposability can be achieved.
  • the ammonium salt is more preferably a salt of an ammonium cation and a carboxylic acid anion.
  • the carboxylic acid anion is preferably a divalent or higher carboxylic acid anion having two or more carboxy groups, and more preferably a divalent carboxylic acid anion.
  • the stability, curability and developability of the curable resin composition can be further improved.
  • the stability, curability and developability of the curable resin composition can be further improved.
  • the carboxylic acid anion is preferably represented by the following formula (X1).
  • EWG represents an electron-attracting group.
  • the electron-attracting group means that the substituent constant ⁇ m of Hammett shows a positive value.
  • ⁇ m is a review article by Yusuke Tono, Journal of Synthetic Organic Chemistry, Vol. 23, No. 8 (1965), p. It is described in detail in 631-642.
  • the EWG is preferably a group represented by the following formulas (EWG-1) to (EWG-6).
  • R x1 to R x3 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a hydroxy group or a carboxy group, and Ar is an aromatic group. Represents.
  • the carboxylic acid anion is preferably represented by the following formula (XA).
  • L 10 represents a single bond or an alkylene group, an alkenylene group, an aromatic group, -NR X - represents and divalent connecting group selected from the group consisting a combination thereof, R X is , Hydrogen atom, alkyl group, alkenyl group or aryl group.
  • carboxylic acid anion examples include maleic acid anion, phthalate anion, N-phenyliminodiacetic acid anion and oxalate anion.
  • the onium salt in the present invention contains an ammonium cation as a cation, and the onium salt is an anion from the viewpoint that the cyclization of the specific resin is easily performed at a low temperature and the storage stability of the curable resin composition is easily improved.
  • the lower limit of the pKa is not particularly limited, but it is preferably -3 or more, and preferably -2 or more, from the viewpoint that the generated base is difficult to neutralize and the cyclization efficiency of the specific resin or the like is improved. Is more preferable.
  • the above pKa includes Determination of Organic Strategies by Physical Methods (authors: Brown, HC, McDaniel, D.H., Hafliger, O., Nachod, F. See Nachod, FC; Academic Press, New York, 1955) and Data for Biochemical Research (Author: Dawson, RMC et al; Oxford, Clarendon Press, 19). Can be done. For compounds not described in these documents, the values calculated from the structural formulas using software of ACD / pKa (manufactured by ACD / Labs) shall be used.
  • ammonium salt examples include the following compounds, but the present invention is not limited thereto.
  • the iminium salt means a salt of an iminium cation and an anion.
  • the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
  • a pyridinium cation is preferable.
  • a cation represented by the following formula (102) is also preferable.
  • R 5 and R 6 each independently represent a hydrogen atom or a hydrocarbon group
  • R 7 represents a hydrocarbon group
  • at least two of R 5 to R 7 are bonded to each other to form a ring. It may be formed.
  • R 5 and R 6 are synonymous with R 1 to R 4 in the above formula (101), and the preferred embodiment is also the same.
  • R 7 preferably combines with at least one of R 5 and R 6 to form a ring.
  • the ring may contain a heteroatom. Examples of the hetero atom include a nitrogen atom. Further, as the ring, a pyridine ring is preferable.
  • the iminium cation is preferably represented by any of the following formulas (Y1-3) to (Y1-5).
  • R 101 represents an n-valent organic group
  • R 5 has the same meaning as R 5 in the formula (102)
  • R 7 is R in the formula (102) Synonymous with 7
  • n represents an integer of 1 or more
  • m represents an integer of 0 or more.
  • R 101 is preferably an aliphatic hydrocarbon, an aromatic hydrocarbon, or a group obtained by removing n hydrogen atoms from a structure in which these are bonded, and has 2 to 30 carbon atoms.
  • n is preferably 1 to 4, more preferably 1 or 2, and even more preferably 1.
  • m is preferably 0 to 4, more preferably 1 or 2, and even more preferably 1.
  • iminium salt examples include the following compounds, but the present invention is not limited thereto.
  • the sulfonium salt means a salt of a sulfonium cation and an anion.
  • the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
  • sulfonium cation a tertiary sulfonium cation is preferable, and a triarylsulfonium cation is more preferable. Further, as the sulfonium cation, a cation represented by the following formula (103) is preferable.
  • R 8 to R 10 each independently represent a hydrocarbon group.
  • Each of R 8 to R 10 is preferably an alkyl group or an aryl group independently, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
  • R 8 to R 10 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group.
  • Examples thereof include a carbonyl group and an acyloxy group.
  • an alkyl group or an alkoxy group as the substituent, more preferably to have a branched alkyl group or an alkoxy group, and a branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 1 to 10 carbon atoms. It is more preferable to have 10 alkoxy groups.
  • R 8 to R 10 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
  • the iodonium salt means a salt of an iodonium cation and an anion.
  • the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
  • iodonium cation a diallyl iodonium cation is preferable. Further, as the iodonium cation, a cation represented by the following formula (104) is preferable.
  • R 11 and R 12 each independently represent a hydrocarbon group.
  • R 11 and R 12 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
  • R 11 and R 12 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group.
  • Examples thereof include a carbonyl group and an acyloxy group.
  • R 11 and R 12 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
  • the phosphonium salt means a salt of a phosphonium cation and an anion.
  • the anion the same as the anion in the above-mentioned ammonium salt is exemplified, and the preferred embodiment is also the same.
  • a quaternary phosphonium cation is preferable, and examples thereof include a tetraalkylphosphonium cation and a triarylmonoalkylphosphonium cation. Further, as the phosphonium cation, a cation represented by the following formula (105) is preferable.
  • R 13 to R 16 independently represent a hydrogen atom or a hydrocarbon group.
  • Each of R 13 to R 16 is preferably an alkyl group or an aryl group independently, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, and 6 to 12 carbon atoms. It is more preferably an aryl group, and even more preferably a phenyl group.
  • R 13 to R 16 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group and an aryloxy group.
  • Examples thereof include a carbonyl group and an acyloxy group.
  • R 13 to R 16 may be the same group or different groups, but from the viewpoint of synthetic suitability, they are preferably the same group.
  • the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention.
  • the lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
  • the onium salt one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
  • the curable resin composition of the present invention may contain a thermosetting agent.
  • the curable resin composition preferably contains a thermosetting agent.
  • the thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt. Examples of other thermobase generators include nonionic thermobase generators. Examples of the nonionic thermobase generator include compounds represented by the formula (B1) or the formula (B2).
  • Rb 1 , Rb 2 and Rb 3 are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. Further, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group.
  • the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.
  • Rb 1 , Rb 2 and Rb 3 contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure.
  • the cyclic structure may be either a monocyclic ring or a condensed ring, and a monocyclic ring or a condensed ring in which two monocyclic rings are condensed is preferable.
  • the single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring.
  • a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.
  • Rb 1 and Rb 2 are hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and alkenyl groups (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ⁇ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have substituents as long as the effects of the present invention are exhibited. Rb 1 and Rb 2 may be coupled to each other to form a ring.
  • Rb 1 and Rb 2 are particularly linear, branched or cyclic alkyl groups which may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
  • a cyclohexyl group which may be used is more preferable.
  • an alkyl group preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms
  • an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6.
  • alkoxy group (2 to 24 carbon atoms are preferable, 2 to 12 is more preferable, 2 to 6 is more preferable
  • arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable).
  • an arylalkenyl group (8 to 24 carbon atoms is preferable, 8 to 20 is more preferable, 8 to 16 is more preferable), and an alkoxyl group (1 to 24 carbon atoms is preferable, 2 to 2 to 24).
  • 18 is more preferable, 3 to 12 is more preferable), an aryloxy group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), or an arylalkyloxy group (7 to 12 carbon atoms is more preferable).
  • 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is further preferable).
  • a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable.
  • Rb 3 may further have a substituent as long as the effect of the present invention is exhibited.
  • the compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
  • Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively.
  • Rb 13 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effects of the present invention are exhibited. Of these, Rb 13 is preferably an arylalkyl group.
  • Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms). , 2 to 8 are more preferable, 2 to 3 are more preferable), aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable), arylalkyl groups (7 to 7 carbon atoms are more preferable). 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is further preferable), and a hydrogen atom is preferable.
  • Rb 35 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 12 carbon atoms, 3 to 12 carbon atoms). 8 is more preferable), aryl group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable). , 7-12 is more preferable), and an aryl group is preferable.
  • the compound represented by the formula (B1-1) is also preferable.
  • Rb 11 and Rb 12 have the same meanings as Rb 11 and Rb 12 in the formula (B1-1).
  • Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), aryl group (6 to 22 carbon atoms are preferable, 6 to 18 is more preferable, 6 to 10 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7).
  • Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 12 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
  • the molecular weight of the nonionic thermobase 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.
  • the following compounds can be mentioned as specific examples of the compound which is a thermal base generator or other specific examples of the thermal base generator.
  • the content of the thermosetting agent is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
  • the thermobase generator one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
  • the curable resin composition of the present invention preferably further contains a migration inhibitor.
  • a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the curable resin composition layer.
  • the migration inhibitor is not particularly limited, but heterocycles (pyrazole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
  • triazole-based compounds such as 1,2,4-triazole and benzotriazole and tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.
  • an ion trap agent that traps anions such as halogen ions can also be used.
  • Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656.
  • the compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used.
  • the migration inhibitor include the following compounds.
  • the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the curable resin composition, and is 0. It is more preferably 0.05 to 2.0% by mass, and further preferably 0.1 to 1.0% by mass.
  • the migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a polymerization inhibitor.
  • polymerization inhibitor examples include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, diphenyl-p-benzoquinone, 4,4'.
  • -Thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitroso-N-phenylhydroxyamine aluminum salt, phenothiazine, N-nitrosodiphenylamine , N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1,2-cyclohexanediamine tetraacetic acid, glycol etherdiamine tetraacetic acid, 2,6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1 -Nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N-sulfopropylamino) phenol, N-nitroso-N- (1-naphthyl) hydroxyamine ammonium salt, Bis (4-hydroxy-3,5-ter
  • the content of the polymerization inhibitor shall be 0.01 to 5% by mass with respect to the total solid content of the curable resin composition of the present invention. Is more preferable, 0.02 to 3% by mass is more preferable, and 0.05 to 2.5% by mass is further preferable.
  • the polymerization inhibitor may be only one type or two or more types. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
  • a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
  • the metal adhesiveness improving agent include a silane coupling agent.
  • silane coupling agent examples include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992.
  • Examples include the compounds described in paragraph 0055. 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. Further, it is also preferable to use the following compounds as the silane coupling agent.
  • Et represents an ethyl group.
  • the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used. ..
  • the content of the metal adhesive improving agent is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0. It is in the range of 5 to 5 parts by mass.
  • the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total is preferably in the above range.
  • the curable resin composition of the present invention contains various additives such as a sensitizer such as N-phenyldiethanolamine, a chain transfer agent, a surfactant, a higher fatty acid derivative, inorganic particles, and a curing agent, if necessary.
  • a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an antioxidant and the like can be blended.
  • the total blending amount is preferably 3% by mass or less of the solid content of the curable resin composition.
  • the curable resin composition of the present invention may contain a sensitizer.
  • the sensitizer absorbs specific active radiation and becomes an electron-excited state.
  • the sensitizer in the electron-excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur.
  • the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases.
  • the sensitizer include sensitizers such as N-phenyldiethanolamine.
  • sensitizing dye As a sensitizer, you may use a sensitizing dye as a sensitizer.
  • the description in paragraphs 0161 to 0163 of JP2016-027357A can be referred to, and this content is incorporated in the present specification.
  • the content of the sensitizer may be 0.01 to 20% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass.
  • the sensitizer may be used alone or in combination of two or more.
  • the curable resin composition of the present invention may contain a chain transfer agent.
  • Chain transfer agents are defined, for example, in the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684.
  • As the chain transfer agent for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
  • a thiol compound can be preferably used.
  • the content of the chain transfer agent is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the curable resin composition of the present invention.
  • 1 to 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable.
  • the chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.
  • Each type of surfactant may be added to the curable resin composition of the present invention from the viewpoint of further improving the coatability.
  • the surfactant various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used.
  • the following surfactants are also preferable.
  • the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit
  • the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.
  • the surfactant the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
  • the content of the surfactant is 0.001 to 2.0% by mass based on the total solid content of the curable resin composition of the present invention. It is preferably 0.005 to 1.0% by mass, more preferably 0.005 to 1.0% by mass. Only one type of surfactant may be used, or two or more types may be used. When there are two or more types of surfactant, the total is preferably in the above range.
  • the curable resin composition of the present invention has a curable resin composition in the process of drying after application by adding a higher fatty acid derivative such as behenic acid or behenic acid amide in order to prevent polymerization inhibition due to oxygen. It may be unevenly distributed on the surface of an object.
  • a higher fatty acid derivative such as behenic acid or behenic acid amide
  • the content of the higher fatty acid derivative is 0.1 to 10% by mass with respect to the total solid content of the curable resin composition of the present invention. Is preferable.
  • the higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.
  • the water content of the curable resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties.
  • the metal content of the curable resin composition of the present invention is preferably less than 5 parts by mass (parts per million), more preferably less than 1 parts by mass, and even more preferably less than 0.5 parts by mass, from the viewpoint of insulating properties.
  • the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, it is preferable that the total of these metals is in the above range.
  • a raw material having a low metal content is selected as a raw material constituting the curable resin composition of the present invention.
  • Methods such as filtering the raw materials constituting the curable resin composition of the present invention with a filter, lining the inside of the apparatus with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible can be mentioned. be able to.
  • the curable resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably 200 mass ppm from the viewpoint of wiring corrosiveness. Less than ppm is more preferred. Among them, those existing in the state 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.
  • the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total amount of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
  • a conventionally known storage container can be used as the storage container for the curable resin composition of the present invention.
  • a multi-layer bottle having the inner wall of the container composed of 6 types and 6 layers of resin and 6 types of resin are used. It is also preferable to use a bottle having a layered structure. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
  • the curable resin composition of the present invention can be prepared by mixing each of the above components.
  • the mixing method is not particularly limited, and a conventionally known method can be used.
  • the filter pore diameter is preferably 1 ⁇ m or less, 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.
  • the filter may be one that has been pre-cleaned with an organic solvent.
  • a plurality of types of filters may be connected in series or in parallel. When a plurality of types of filters are used, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times.
  • circulation filtration When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less.
  • impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
  • adsorbent a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
  • the curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer. In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.
  • the cured film of the present invention is obtained by curing the curable resin composition of the present invention.
  • the film thickness of the cured film of the present invention can be, for example, 0.5 ⁇ m or more, and can be 1 ⁇ m or more. Further, the upper limit value can be 100 ⁇ m or less, and can be 30 ⁇ m or less.
  • the cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body.
  • the laminate of the present invention is preferably a laminate having two or more cured films and a metal layer between the cured films. Further, it is preferable that the laminate of the present invention contains two or more cured films and includes a metal layer between any of the cured films.
  • a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferable.
  • the first cured film and the second cured film are both cured films of the present invention. For example, both the first cured film and the second cured film are curable of the present invention.
  • a preferred embodiment is a film obtained by curing the resin composition.
  • the curable resin composition of the present invention used for forming the first cured film and the curable resin composition of the present invention used for forming the second cured film have the same composition.
  • the compositions may be present or have different compositions, but from the viewpoint of production suitability, the compositions having the same composition are preferable.
  • Such a metal layer is preferably used as a metal wiring such as a rewiring layer.
  • Examples of the applicable field of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
  • a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above may be patterned by etching. For these applications, for example, Science & Technology Co., Ltd.
  • the cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially in microelectronics.
  • the method for producing a cured film of the present invention includes a film forming step of applying the curable resin composition of the present invention to a substrate to form a film. Is preferable. Further, the method for producing a cured film of the present invention further includes the film forming step, and further includes an exposure step for exposing the film and a developing step for developing the film (developing the film). Is more preferable. Further, the method for producing a cured film of the present invention may further include the film forming step (and the developing step if necessary) and further include a heating step of heating the film at 50 to 450 ° C. preferable.
  • Exposure step of exposing the film after the film forming step (c) Exposure Development step of developing the developed film
  • the method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention.
  • the steps (a), the steps (a) to (c), or (a) are further performed.
  • )-(D) it is preferable to perform each of the above steps a plurality of times, for example, 2 to 5 times (that is, 3 to 6 times in total) in order.
  • the production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the curable resin composition is applied to a substrate to form a film (layered).
  • the type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film transistor.
  • semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film transistor.
  • magnetic film such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like.
  • a semiconductor-made base material is particularly preferable, and a silicon base material is more preferable.
  • a plate-shaped base material (board) is used as the base material.
  • the resin layer or the metal layer serves as a base material.
  • Coating is preferable as a means for applying the curable resin composition to the base material.
  • the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the curable resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable.
  • a resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the substrate.
  • a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular substrate, a slit coating method or a spray coating method
  • the method, the inkjet method and the like are preferable.
  • the spin coating method for example, it can be applied at a rotation speed of 500 to 2,000 rpm (revolutions per minute) for about 10 seconds to 1 minute. It is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate.
  • the transfer method the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention.
  • the production method of the present invention may include a step of forming the film (curable resin composition layer), followed by a film forming step (layer forming step), and then drying to remove the solvent.
  • the preferred drying temperature is 50 to 150 ° C, more preferably 70 ° C to 130 ° C, still more preferably 90 ° C to 110 ° C.
  • the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
  • the production method of the present invention may include an exposure step of exposing the film (curable resin composition layer).
  • the amount of exposure is not particularly determined as long as the curable resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ /. It is more preferable to irradiate with cm 2 .
  • the exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
  • the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h.
  • the curable resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays. As a result, particularly high exposure sensitivity can be obtained.
  • the production method of the present invention may include a developing step of performing a developing process on the exposed film (curable resin composition layer). By performing the development, the unexposed portion (non-exposed portion) is removed.
  • the developing method is not particularly limited as long as a desired pattern can be formed, and for example, a developing method such as paddle, spray, immersion, or ultrasonic wave can be adopted.
  • the developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
  • alkaline development the case where an alkaline developer is used as the developer
  • solvent development the case where a developer containing 50% by mass or more of an organic solvent is used as the developer.
  • the content of the organic solvent in the developing solution is preferably 10% by mass or less, more preferably 5% by mass or less, and 1% by mass or less with respect to the total mass of the developing solution. Is more preferable, and it is particularly preferable that the organic solvent is not contained.
  • the developing solution in alkaline development is more preferably an aqueous solution having a pH of 9 to 14.
  • Examples of the alkaline compound contained in the developing solution in alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicate. Examples include potassium silicate, ammonia or amine.
  • amines examples include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, and tetramethylammonium hydroxide.
  • TMAH tetraethylammonium hydroxide
  • tetrabutylammonium hydroxide and the like can be mentioned.
  • an alkaline compound containing no metal is preferable, and an ammonium compound is more preferable.
  • the alkaline compound may be only one kind or two or more kinds. When there are two or more alkaline compounds, the total is preferably in the above range.
  • the developer contains 90% or more of an organic solvent.
  • the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3.
  • the ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
  • Organic solvents include, for example, ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone.
  • alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate, etc.)
  • 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • Ke As tons for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and as aromatic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc.
  • Dimethyl sulfoxide is preferably mentioned as the sulfoxides.
  • cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.
  • the developing solution preferably contains 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent. Further, the developing solution may be 100% by mass of an organic solvent.
  • the development time is preferably 10 seconds to 5 minutes.
  • the temperature of the developing solution at the time of development is not particularly specified, but is usually 20 to 40 ° C.
  • rinsing After the treatment with the developing solution, further rinsing may be performed.
  • rinsing is preferably performed using an organic solvent different from the developing solution.
  • rinsing is preferably performed using pure water.
  • the rinsing time is preferably 5 seconds to 1 minute.
  • the production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ° C.
  • the heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step.
  • the curable resin composition of the present invention contains a polymerizable compound other than the specific resin, and this step includes a curing reaction of an unreacted polymerizable compound other than the specific resin, a curing reaction of an unreacted polymerizable group in the specific resin, and the like. Can be advanced with.
  • the heating step for example, a base is generated by decomposition of the thermobase generator, and the polyimide precursor The cyclization reaction proceeds.
  • the heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is particularly preferable, 160 ° C. or higher is more preferable, and 170 ° C. or higher is most preferable.
  • the upper limit is preferably 450 ° C. or lower, more preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and particularly preferably 220 ° C. or lower.
  • the heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
  • a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
  • 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 is started.
  • the temperature of the film (layer) after drying is higher than, for example, the boiling point of the solvent contained in the curable resin composition. It is preferable to gradually raise the temperature from a temperature as low as 30 to 200 ° C.
  • the heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.
  • the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C. from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that at this temperature, the polymerizable groups in the specific resin between the layers proceed with the cross-linking reaction.
  • Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed.
  • the heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547.
  • the pretreatment step is preferably performed in 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.
  • the pretreatment step 1 may be performed in the range of 100 to 150 ° C.
  • the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
  • cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
  • the heating step is performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon in order to prevent decomposition of the specific resin.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
  • the production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the film (curable resin composition layer) after the development treatment.
  • metal layer existing metal types can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, copper and aluminum are more preferable, and copper is preferable. More preferred.
  • the method for forming the metal layer is not particularly limited, and an existing method can be applied.
  • the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used.
  • photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
  • the thickness of the metal layer is preferably 0.1 to 50 ⁇ m, more preferably 1 to 10 ⁇ m in the thickest portion.
  • the production method of the present invention preferably further includes a laminating step.
  • the laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step are performed again on the surface of the cured film (resin layer) or the metal layer. , A series of steps including performing in this order. However, the mode may be such that only the film forming step (a) is repeated. Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated curable resin composition layers all at once.
  • the developing step may be followed by (e) a metal layer forming step, and (d) may be heated each time, or the layers may be laminated a predetermined number of times and then collectively (d). ) May be heated.
  • the laminating step may further include the above-mentioned drying step, heating step, and the like as appropriate.
  • the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step.
  • An example of the surface activation treatment is plasma treatment.
  • the laminating step is preferably performed 2 to 5 times, more preferably 3 to 5 times.
  • the resin layer is 3 or more and 7 or less, such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferable, and 3 or more and 5 or less are more preferable.
  • a cured film (resin layer) of the curable resin composition so as to cover the metal layer after the metal layer is provided.
  • Examples thereof include an embodiment in which the steps, (b) exposure steps, (c) development steps, and (e) metal layer forming steps are repeated in this order, and (d) heating steps are collectively provided at the end or in the middle.
  • the present invention also discloses a semiconductor device containing the cured film or laminate of the present invention.
  • the semiconductor device in which the curable resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer the description in paragraphs 0213 to 0218 and the description in FIG. 1 of JP-A-2016-0273557 are referred to. Yes, these contents are incorporated herein.
  • the polyimide or polyimide precursor of the present invention preferably contains a structure represented by the following formula (1-1).
  • R 1 independently represents a hydrogen atom or an alkyl group
  • Z 1 represents a group containing a polymerizable group
  • n represents an integer of 2 or more
  • m represents an integer of 2 or more.
  • And * represents the site of connection with other structures.
  • the above formula (1-1) has the same meaning as the formula (1-1) in the specific resin, and the preferred embodiment is also the same.
  • the polyimide or polyimide precursor of the present invention has the same meaning as the polyimide or polyimide precursor in the above-mentioned specific resin except that the above formula (1-1) is essential, and the preferred embodiment is also the same.
  • the polyimide or polyimide precursor of the present invention is preferably used as a resin contained in a curable resin composition. Further, in a composition in which a conventional polyimide or a polyimide precursor is used, such as a composition for an interlayer insulating film, the conventional polyimide or a part or all of the polyimide precursor is used in the present invention without particular limitation. It can be used in place of polyimide or a polyimide precursor. Since the polyimide or the composition containing the polyimide precursor of the present invention has excellent coatability, the polyimide or the polyimide precursor of the present invention is coated by coating, for example, a composition for forming an insulating film. It is considered that it is preferably used in a composition used for forming a film.
  • Blemmer PE-200 manufactured by NOF CORPORATION 28.4 g (100 mmol), N, N'-dimethylaminopyridine 0.61 g (5 mmol), p-methoxy 0.06 g of phenol and 130.0 g of N-methylpyrrolidone were added, dissolved, and cooled to 0 ° C. Then, 12.6 g (100 mmol) of diisopropylcarbodiimide was added, and the mixture was stirred at 10 ° C. or lower for 5 hours and heated to room temperature.
  • the polyimide was then precipitated in 2 liters of water and the water-polyimide mixture was stirred at a rate of 2,000 rpm for 30 minutes.
  • the polyimide precursor resin was removed by filtration, stirred again with 1.5 liters of methanol for 30 minutes and filtered again. Then, the obtained polyimide was dried under reduced pressure at 40 ° C. for 1 day to obtain PI-1.
  • the weight average molecular weight (Mw) of PI-1 was 29,500, and the number average molecular weight (Mn) was 13,500.
  • the structure of PI-1 is presumed to be the structure represented by the following formula (PI-1).
  • Blemmer AP-400 manufactured by NOF CORPORATION 33.6 g (80 mmol), N, N'-dimethylaminopyridine 0.61 g (5 mmol), p-methoxy 0.06 g of phenol and 130.0 g of N-methylpyrrolidone were added, dissolved, and cooled to 0 ° C. Then, 12.6 g (90 mmol) of diisopropylcarbodiimide was added, and the mixture was stirred at 10 ° C. or lower for 5 hours and heated to room temperature.
  • the polyimide was then precipitated in 2 liters of water and the water-polyimide mixture was stirred at a rate of 2,000 rpm for 30 minutes.
  • the polyimide precursor resin was removed by filtration, stirred again with 1.5 liters of methanol for 30 minutes and filtered again. Then, the obtained polyimide was dried under reduced pressure at 40 ° C. for 1 day to obtain PI-2.
  • the weight average molecular weight (Mw) of PI-2 was 25,100, and the number average molecular weight (Mn) was 12,100.
  • the structure of PI-2 is presumed to be the structure represented by the following formula (PI-2).
  • C 3 H 6 randomly includes a 1-methylethylene group (below (P1)) and a 2-methylethylene group (below (P2)).
  • P1 1-methylethylene group
  • P2 2-methylethylene group
  • * 1 is bonded to the structure on the carbonyl group side in the formula (PI-2)
  • * 2 is bonded to the structure on the acryloxy group side in the formula (PI-7).
  • Blemmer PE-200 manufactured by NOF CORPORATION 14.2 g (50 mmol), N, N'-dimethylaminopyridine 0.61 g (5 mmol), p-methoxy 0.06 g of phenol and 130.0 g of N-methylpyrrolidone were added, dissolved, and cooled to 0 ° C.
  • PI-3 The weight average molecular weight (Mw) of PI-3 was 31,000, and the number average molecular weight (Mn) was 13,900.
  • the structure of PI-3 is presumed to be the structure represented by the following formula (PI-3).
  • * represents the binding site with the oxygen atom to which R binds.
  • PI-4 The structure of PI-4 is presumed to be the structure represented by the following formula (PI-4).
  • * represents the binding site with the oxygen atom to which R 1 binds.
  • Blemmer AP-400 manufactured by Nichiyu Co., Ltd. 21.3 g (50 mmol), 1-hydroxy-2,3-epoxypropane 2.22 g (30 mmol), N. , N'-Dimethylaminopyridine 0.61 g (5 mmol), p-methoxyphenol 0.06 g, and N-methylpyrrolidone 130.0 g were added, dissolved, and cooled to 0 ° C.
  • the weight average molecular weight (Mw) of PI-5 was 33,300, and the number average molecular weight (Mn) was 15,000.
  • the structure of PI-5 is presumed to be the structure represented by the following formula (PI-5).
  • * represents the binding site with the oxygen atom to which R 1 binds.
  • the description of C 3 H 6 randomly includes a 1-methylethylene group (above (P1)) and a 2-methylethylene group (above (P2)).
  • * 1 is bonded to the structure on the acrylate group side in R 1 in formula (PI-5), and * 2 is the * side in R 1 in formula (PI-5).
  • PI-6 The weight average molecular weight (Mw) of PI-6 was 29,900, and the number average molecular weight (Mn) was 14,300.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • the structure of PI-6 is presumed to be the structure represented by the following formula (PI-6).
  • * represents the binding site with the oxygen atom to which R binds.
  • PI-8 Synthesis of Polyimide (PI-8)> Instead of 2-hydroxyethyl methacrylate and hexaethylene glycol monomethyl ether used in the synthesis of PI-4, glycerin dimethacrylate (manufactured by NOF CORPORATION) 30 (mmol) and Blemmer PE-200 (NOF CORPORATION) PI-8 was synthesized in the same manner as PI-4 except that (70 mmol) was used.
  • the weight average molecular weight (Mw) of PI-8 was 25,900, and the number average molecular weight (Mn) was 12,900.
  • the structure of PI-8 is presumed to be the structure represented by the following formula (PI-8).
  • Blemmer PE-200 manufactured by NOF CORPORATION 14.2 g (50 mmol), N, N'-dimethylaminopyridine 0.61 g (5 mmol), p-methoxy 0.06 g of phenol and 130.0 g of N-methylpyrrolidone were added, dissolved, and cooled to 0 ° C. Then, 6.3 g (50 mmol) of diisopropylcarbodiimide was added, and the mixture was stirred at 10 ° C. or lower for 5 hours and heated to room temperature.
  • PI-9 The weight average molecular weight (Mw) of PI-9 was 31,600, and the number average molecular weight (Mn) was 11,500.
  • the structure of PI-9 is a structure represented by the following formula (PI-9). It is presumed.
  • PI-9 The structure of PI-9 is presumed to be the structure represented by the following formula (PI-9).
  • * represents the binding site with the oxygen atom to which R 1 binds.
  • PA-1 The structure of PA-1 is presumed to be the structure represented by the following formula (PA-1).
  • * represents the binding site with the oxygen atom to which R binds.
  • the description of C 3 H 6 randomly includes a 1-methylethylene group (the above (P1)) and a 2-methylethylene group (the above (P2)).
  • * 1 is bound to the structure on the acryloxy group side in R in formula (PA-1)
  • * 2 is the structure on the * side in R in formula (PA-1).
  • the temperature was raised to 180 ° C. while flowing nitrogen at a flow rate of 200 ml / min, stirred for 6 hours, and cooled to room temperature.
  • 130.0 g of N-methylpyrrolidone was added and diluted, then the polyimide was precipitated in 2 liters of water and the water-polyimide mixture was stirred at a rate of 2000 rpm for 30 minutes.
  • the polyimide precursor resin was removed by filtration, the filter medium was mixed with 1.5 liters of methanol, stirred again for 30 minutes and filtered again. Then, the obtained polyimide was dried under reduced pressure at 40 ° C. for 1 day to obtain A-1.
  • the weight average molecular weight (Mw) of A-1 was 30,100, and the number average molecular weight (Mn) was 14,500.
  • the structure of A-1 is presumed to be the structure represented by the following formula (A-1).
  • the polyimide precursor (A-1) for comparative example does not contain a polyalkyleneoxy group and a polymerizable group, and does not correspond to a specific resin.
  • ⁇ Synthesis Example 12 Synthesis of Polyimide (A-2) for Comparative Example> 155.1 g of 4,4'-oxydiphthalic dianhydride (ODPA) was placed in a separable flask, and 134.0 g of 2-hydroxyethyl methacrylate (HEMA) and 400 ml of ⁇ -butyrolactone were added. A reaction mixture was obtained by adding 79.1 g of pyridine with stirring at room temperature. After the exotherm by the reaction was completed, the mixture was allowed to cool to room temperature and allowed to stand for another 16 hours.
  • ODPA 4,4'-oxydiphthalic dianhydride
  • HEMA 2-hydroxyethyl methacrylate
  • ⁇ -butyrolactone 400 ml of ⁇ -butyrolactone
  • the obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate composed of a crude polymer.
  • the produced crude polymer was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution.
  • the obtained crude polymer solution was added dropwise to 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and then vacuum dried to obtain a powdery polyimide precursor for comparative examples (A-2).
  • Got The weight average molecular weight (Mw) of the polyimide precursor (A-2) for Comparative Example was measured and found to be 20,000.
  • ⁇ Synthesis Example 13 Synthesis of Polyimide Precursor (A-3) for Comparative Example> Synthesis Example 12 except that 147.1 g of 3,3', 4,4'-biphenyltetracarboxylic dianhydride was used in place of 155.1 g of 4,4'-oxydiphthalic acid dianhydride.
  • a polyimide precursor (A-3) for comparative example was obtained.
  • the weight average molecular weight (Mw) of the polyimide precursor (A-3) for Comparative Example was measured and found to be 22,000.
  • Comparative example polyimide precursors (A-2) and (A-3) do not contain polyalkyleneoxy groups and do not correspond to specific resins.
  • DMSO / GBL dimethyl sulfoxide-GBL: ⁇ -butyrolactone-ethyl lactate-NMP: N-methylpyrrolidone
  • GBL 20: 80 (mass ratio). It shows that it was mixed.
  • FIG. 1 is a schematic view of the formed stepped substrate.
  • a total of 10 steps 2 are formed on the surface of the silicon substrate 1 in 5 columns and 2 rows.
  • the step 2 is a step having a depth of 5 ⁇ m with respect to the surface of the portion of the silicon substrate 1 where the step is not formed. Further, within each of the 10 steps, the depth of the steps is almost uniform.
  • A indicates the vertical length of the step 2 and is 100 ⁇ m.
  • B indicates the lateral length of the step 2 and is 20 ⁇ m.
  • the distance between the five steps arranged in the horizontal direction is 1 mm.
  • the distance between the two steps arranged in the vertical direction is 2 mm.
  • Each curable resin composition or comparative composition prepared in each Example and Comparative Example was applied to the stepped substrate shown in FIG. 1 by a spin coating method to form a curable resin composition layer. ..
  • the silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform curable resin composition layer having a thickness of about 15 ⁇ m on the silicon wafer.
  • the surface of the curable resin composition layer after drying was observed with an AFM (atomic force microscope), and the height difference of the film measured by the following formula FL was calculated.
  • the surface of the curable resin composition layer after drying was observed with an optical microscope defect inspection device KLA2360 (manufactured by APPLID MATERIALS) and a review SEM Vision G3 (manufactured by APPLID MATERIALS), and the number of defects per 1 cm 2 was calculated. did.
  • the coatability was evaluated according to the following evaluation criteria. The evaluation results are shown in the "Applicability" column of Table 1. It can be said that the smaller the height difference of the film and the smaller the number of defects, the more excellent the composition is in coatability.
  • -Evaluation criteria- A The height difference of the film was less than 0.3 ⁇ m, and the number of defects was less than 5 pieces / cm 2 .
  • B The height difference of the film was less than 0.3 ⁇ m, and the number of defects was 5 pieces / cm 2 or more and less than 10 pieces / cm 2 .
  • C The height difference of the film was 0.3 ⁇ m or more and less than 0.5 ⁇ m, and the number of defects was less than 10 pieces / cm 2 .
  • D At least one of the conditions of the height difference of the film of 0.5 ⁇ m or more and the number of defects of 10 pieces / cm 2 or more was satisfied.
  • Each curable resin composition or comparative composition prepared in each Example and Comparative Example was applied onto a silicon wafer by a spin coating method to form a curable resin composition layer.
  • the silicon wafer to which the obtained curable resin composition layer was applied was dried on a hot plate at 100 ° C. for 5 minutes to obtain a uniform curable resin composition layer having a thickness of about 15 ⁇ m on the silicon wafer.
  • After the obtained curable resin composition layer (resin layer) is heated at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere and reaches the temperature described in the "curing conditions" column of Table 1. , Heated at this temperature for 3 hours.
  • the cured resin layer (cured film) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the cured film was peeled off from the silicon wafer.
  • the peeled cured film was punched out using a punching machine to prepare a test piece having a width of 3 mm and a sample length of 30 mm.
  • a tensile tester Teencilon
  • the elongation rate (breaking elongation rate) when the film was broken in the longitudinal direction was measured.
  • the evaluation was carried out 5 times in each Example or Comparative Example, and the arithmetic mean value of the measured values of the elongation at break in the 5 measurements was used as an index value.
  • the above index values were evaluated according to the following evaluation criteria, and the evaluation results are shown in Table 1.
  • D The above index value was less than 50%.
  • the curable resin composition containing the specific resin according to the present invention is excellent in coatability.
  • the comparative compositions according to Comparative Examples 1 and 2 do not contain a specific resin. It can be seen that the comparative compositions according to Comparative Examples 1 and 2 are inferior in coatability.
  • Example 101 The curable resin composition according to Example 1 was spun and applied to the surface of the thin copper layer of the resin base material having the thin copper layer formed on the surface so that the film thickness was 20 ⁇ m.
  • the curable resin composition applied to the resin substrate was dried at 100 ° C. for 2 minutes and then exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). The exposure was carried out through a mask of a square pattern (square pattern of 100 ⁇ m each in length and width, number of repetitions of 10) at a wavelength of 365 nm and an exposure amount of 400 mJ / cm 2 to create a remaining square pattern.
  • the interlayer insulating film for the rewiring layer was excellent in insulating property. Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Materials For Photolithography (AREA)
  • Laminated Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

Composition de résine durcissable comprenant au moins une résine choisie dans le groupe constitué par des polyimides et des précurseurs de polyimide contenant un groupe polyalkylèneoxy et un groupe polymérisable, un initiateur de polymérisation, un composé polymérisable et un solvant ; un film durci obtenu par durcissement de la composition de résine durcissable ; un stratifié comprenant le film durci ; un procédé de production du film durci ; un dispositif à semi-conducteur comprenant le film durci ou le stratifié ; et un polyimide ou un précurseur de polyimide.
PCT/JP2020/023071 2019-06-17 2020-06-11 Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et polyimide ou précurseur de polyimide WO2020255859A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020217040915A KR20220008885A (ko) 2019-06-17 2020-06-11 경화성 수지 조성물, 경화막, 적층체, 경화막의 제조 방법, 반도체 디바이스, 및, 폴리이미드, 또는, 폴리이미드 전구체
JP2021528162A JP7289353B2 (ja) 2019-06-17 2020-06-11 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、半導体デバイス、及び、ポリイミド、又は、ポリイミド前駆体
CN202080043671.XA CN114008527A (zh) 2019-06-17 2020-06-11 固化性树脂组合物、固化膜、层叠体、固化膜的制造方法、半导体器件及聚酰亚胺或聚酰亚胺前体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019-111873 2019-06-17
JP2019111873 2019-06-17

Publications (1)

Publication Number Publication Date
WO2020255859A1 true WO2020255859A1 (fr) 2020-12-24

Family

ID=74040036

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/023071 WO2020255859A1 (fr) 2019-06-17 2020-06-11 Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et polyimide ou précurseur de polyimide

Country Status (5)

Country Link
JP (1) JP7289353B2 (fr)
KR (1) KR20220008885A (fr)
CN (1) CN114008527A (fr)
TW (1) TW202110950A (fr)
WO (1) WO2020255859A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112979949A (zh) * 2021-03-03 2021-06-18 广东工业大学 一种透明光敏聚酰亚胺树脂、聚酰亚胺薄膜及其制备方法
WO2022270546A1 (fr) * 2021-06-25 2022-12-29 住友ベークライト株式会社 Polymère photosensible de type négatif, solution de polymère, composition de résine photosensible de type négatif, film durci et dispositif à semi-conducteur
WO2023054221A1 (fr) * 2021-09-30 2023-04-06 富士フイルム株式会社 Polyimide, précurseur de polyimide, composition, et procédé de production de polyimide

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011040399A1 (fr) * 2009-09-30 2011-04-07 日立化成工業株式会社 Composition de résine, préimprégné utilisant celui-ci, feuille métallique avec résine, film adhésif, et laminé de gaine métallique
WO2017002860A1 (fr) * 2015-06-30 2017-01-05 富士フイルム株式会社 Composition de résine photosensible négative, film durci, procédé de production de film durci et dispositif à semi-conducteurs

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20200023403A (ko) 2017-06-24 2020-03-04 디자이너 몰러큘스, 인코퍼레이티드 경화성 폴리이미드

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011040399A1 (fr) * 2009-09-30 2011-04-07 日立化成工業株式会社 Composition de résine, préimprégné utilisant celui-ci, feuille métallique avec résine, film adhésif, et laminé de gaine métallique
WO2017002860A1 (fr) * 2015-06-30 2017-01-05 富士フイルム株式会社 Composition de résine photosensible négative, film durci, procédé de production de film durci et dispositif à semi-conducteurs

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112979949A (zh) * 2021-03-03 2021-06-18 广东工业大学 一种透明光敏聚酰亚胺树脂、聚酰亚胺薄膜及其制备方法
CN112979949B (zh) * 2021-03-03 2023-03-10 广东工业大学 一种透明光敏聚酰亚胺树脂、聚酰亚胺薄膜及其制备方法
WO2022270546A1 (fr) * 2021-06-25 2022-12-29 住友ベークライト株式会社 Polymère photosensible de type négatif, solution de polymère, composition de résine photosensible de type négatif, film durci et dispositif à semi-conducteur
WO2023054221A1 (fr) * 2021-09-30 2023-04-06 富士フイルム株式会社 Polyimide, précurseur de polyimide, composition, et procédé de production de polyimide

Also Published As

Publication number Publication date
CN114008527A (zh) 2022-02-01
TW202110950A (zh) 2021-03-16
KR20220008885A (ko) 2022-01-21
JP7289353B2 (ja) 2023-06-09
JPWO2020255859A1 (fr) 2020-12-24

Similar Documents

Publication Publication Date Title
JP7333383B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
JP7277572B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
WO2020255859A1 (fr) Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et polyimide ou précurseur de polyimide
JP2020154205A (ja) パターン形成方法、硬化性樹脂組成物、膜、硬化膜、積層体、及び、半導体デバイス
TWI802640B (zh) 感光性樹脂組成物、樹脂、硬化膜、積層體、硬化膜之製造方法、半導體元件
JP7477579B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、半導体デバイス、及び、ポリマー前駆体
JP7277573B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
JP7281533B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
JP7023379B2 (ja) 樹脂組成物、硬化膜、積層体、硬化膜の製造方法、および半導体デバイス
JP7086882B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
JP7265627B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、半導体デバイス、及び、ポリイミド、ポリベンゾオキサゾール、ポリイミド前駆体、又は、ポリベンゾオキサゾール前駆体
JP7351896B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、半導体デバイス、及び、熱塩基発生剤
WO2021045126A1 (fr) Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur, résine, et procédé de production de résine
WO2021039782A1 (fr) Composition de résine durcissable, film durci, produit stratifié, procédé de production de film durci, dispositif semi-conducteur et procédé de production de résine
WO2021002383A1 (fr) Composition de résine durcissable, procédé de production de composition de résine durcissable, film durci, corps multicouche, procédé de production de film durci et dispositif à semi-conducteur
JP7334248B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
JP7078744B2 (ja) 樹脂組成物、硬化膜、積層体、硬化膜の製造方法、および半導体デバイス
JP7194278B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、及び、半導体デバイス
JP7426375B2 (ja) 硬化性樹脂組成物、硬化膜、積層体、硬化膜の製造方法、半導体デバイス、及び、熱塩基発生剤

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20827845

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021528162

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 20217040915

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20827845

Country of ref document: EP

Kind code of ref document: A1