WO2020255825A1 - Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et polyimide, polybenzoxazole, précurseur de polyimide ou précurseur de polybenzoxazole - Google Patents

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

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Publication number
WO2020255825A1
WO2020255825A1 PCT/JP2020/022855 JP2020022855W WO2020255825A1 WO 2020255825 A1 WO2020255825 A1 WO 2020255825A1 JP 2020022855 W JP2020022855 W JP 2020022855W WO 2020255825 A1 WO2020255825 A1 WO 2020255825A1
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group
formula
preferable
resin composition
curable resin
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PCT/JP2020/022855
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English (en)
Japanese (ja)
Inventor
敦靖 野崎
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富士フイルム株式会社
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Priority to JP2021528140A priority Critical patent/JP7265627B2/ja
Publication of WO2020255825A1 publication Critical patent/WO2020255825A1/fr

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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
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • 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
    • C08G73/22—Polybenzoxazoles
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—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, a polybenzoxazole, a polyimide precursor, or a polybenzoxazole precursor.
  • Resins such as polyimide and polybenzoxazole have excellent heat resistance and insulating properties, and are therefore 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.
  • resins such as polyimide and polybenzoxazole may be used in the form of a curable resin composition containing these resins, or precursors of these resins (polyimide precursor, polybenzoxazole). It may also be used in the form of a curable resin composition containing (precursor, etc.). The precursor is cyclized into a resin such as polyimide or polybenzoxazole 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.
  • At least one resin selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor and polybenzoxazole precursor from the viewpoint of excellent manufacturing adaptability in addition to the high performance of polyimide resin and the like.
  • Patent Document 1 describes a curable polyimide having a structure having a specific polymerizable group.
  • One embodiment of the present invention is a curable resin composition excellent in breaking elongation of the obtained cured film, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and production of the cured film.
  • An object of the present invention is to provide a method and a semiconductor device including the cured film or the laminate.
  • Another embodiment of the present invention is an object of providing a novel polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor.
  • Polymerization initiator and Contains polymerizable compounds The resin contains a structure represented by the following formula (1-1). Curable resin composition. Equation (1-1), R 1 represents a hydrogen atom or a substituent, when R 1 is a substituent group containing no is or polymerizable group a hydrogen atom, the resin has the formula (1-1) As a structure other than the structure represented by, a structure having a polymerizable group is included.
  • the curable resin composition according to ⁇ 1> wherein the structure represented by the above formula (1-1) is a structure represented by the following formula (1-2).
  • X 1 represents a single bond or an n + 1 valent linking group
  • Z 1 represents a group having a polymerizable group
  • n represents an integer of 1 or more.
  • the curable resin composition according to ⁇ 1> or ⁇ 2> which comprises a structure represented by the following formula (1-3) as a structure containing the structure represented by the above formula (1-1). ..
  • X 31 independently represents a single bond or an n31 + 1 valent linking group
  • Z 31 independently represents a hydrogen atom or a group having a polymerizable group.
  • n31 represents an integer of 1 or more
  • X 32 independently represents a single bond or an n32 + 1 valent linking group
  • Z 32 independently represents a hydrogen atom or a group having a polymerizable group.
  • N 32 represents an integer of 1 or more
  • L 1 represents a divalent linking group
  • at least one of Z 31 and Z 32 is a group having a polymerizable group.
  • L 1 , L 2 and L 3 each independently represent a divalent linking group
  • X 41 represents a single bond or n41 + 1 valent linking group
  • X 42 represents a single bond or n42 + 1
  • Z 41 and Z 42 independently represent a hydrogen atom or a group having a polymerizable group
  • at least one of Z 41 and Z 42 is a group having a polymerizable group.
  • n41 and n42 independently represent an integer of 1 or more
  • L 4 represents a structure represented by any one of the following formulas (L4-1) ⁇ formula (L4-4).
  • R 115 represents a tetravalent organic group
  • R 122 represents a tetravalent organic group
  • a 1 and A 2 are independently oxygen atoms or or.
  • -NH-, R 113 and R 114 independently represent a hydrogen atom or a monovalent organic group
  • R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group, respectively.
  • the above-mentioned L 1 , the above L 2 and the above L 3 each independently contain at least one ring structure selected from the group consisting of an aliphatic ring structure and an aromatic ring structure, according to ⁇ 4>. Curable resin composition.
  • At least L 1 , the above L 2 and the above L 3 are independently selected from the group consisting of the structures represented by any of the following formulas (A-1) to (A-5).
  • RA11 to RA14 , RA21 to RA24 , RA31 to RA38 , RA41 to RA48 and RA51 to RA58 are independently hydrogen atoms.
  • Alkyl group, cyclic alkyl group, alkoxy group, hydroxy group, cyano group, alkyl halide group, or halogen atom, and LA31 and LA41 are independently single bond, carbonyl group, sulfonyl group and divalent, respectively.
  • ⁇ 7> The above-mentioned one of ⁇ 4> to ⁇ 6>, wherein at least one of Z 41 and Z 42 contains an ethylenically unsaturated group, a cyclic ether group or a methylol group as the polymerizable group.
  • the curable resin composition according to. ⁇ 9> The curable resin composition according to any one of ⁇ 1> to ⁇ 8>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 10> A cured film obtained by curing the curable resin composition according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 11> A laminate having two or more cured films according to ⁇ 10> and having a metal layer between the cured films.
  • ⁇ 12> 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 ⁇ 9> to a substrate to form a film.
  • the method for producing a cured film according to ⁇ 12> which comprises an exposure step of exposing the film and a developing step of developing the film.
  • ⁇ 14> The method for producing a cured film according to ⁇ 12> or ⁇ 13>, which comprises a step of heating the film at 50 to 450 ° C.
  • a semiconductor device comprising the cured film according to ⁇ 10> or the laminate according to ⁇ 11>.
  • X 1 represents a single bond or an n + 1 valent linking group
  • Z 1 represents a group having a polymerizable group
  • n represents an integer of 1 or more.
  • a curable resin composition having excellent breaking elongation of the obtained cured film, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and the cured film. And the semiconductor device including the cured film or the laminate.
  • a novel polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole 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”) was selected from the group consisting of polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor. It contains at least one kind of resin (hereinafter, also referred to as "specific resin"), a polymerization initiator, and a polymerizable compound, and the resin contains a structure represented by the following formula (1-1).
  • R 1 represents a hydrogen atom or a substituent, when R 1 is a substituent group containing no is or polymerizable group a hydrogen atom, the resin has the formula (1-1) As a structure other than the structure represented by, a structure having a polymerizable group is included.
  • the curable resin composition of the present invention is excellent in breaking elongation of the obtained cured film.
  • the mechanism by which the above effect is obtained is not clear, but it is presumed that when the specific resin contains the structure represented by the formula (1-1), the resin interacts with each other and the elongation at break is improved. Further, it is considered that strain is generated in the structure of the specific resin because the specific resin contains the structure represented by the formula (1-1). Due to the above strain, the curable resin composition of the present invention, or the composition film formed by applying the curable resin composition of the present invention to a substrate, for example, transmits ultraviolet light having a wavelength of around 400 nm. It is thought that it is easy to have excellent sex.
  • the transparency of ultraviolet light is excellent and the curing is easy to proceed, so that the resulting cured film is more easily stretched at break.
  • the curable resin composition of the present invention can easily obtain a cured film having excellent chemical resistance due to the above-mentioned interaction between the resins. Further, it is considered that these resins are likely to have improved solubility in a solvent due to the occurrence of the above strain and the like.
  • Patent Document 1 does not describe or suggest a resin containing a structure represented by the formula (1-1). Further, the cured film obtained by curing the curable resin composition in Patent Document 1 has a problem that the elongation at break is low.
  • the curable resin composition of the present invention contains a specific resin.
  • the specific resin is a polyimide, a polybenzoxazole, a polyimide precursor or a polybenzoxazole precursor, and is a resin containing a structure represented by the formula (1-1).
  • the specific resin may have a structure represented by the formula (1-1) in the main chain of the resin or in the side chain.
  • the structure represented by the formula (1-1) is provided in the side chain of the resin, one of the two binding sites in the structure represented by the formula (1-1) constitutes the main chain of the resin. It may be directly bonded to the atom.
  • the "main chain” refers to the relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the "side chain” refers to other binding chains.
  • the specific resin preferably contains a plurality of structures represented by the formula (1-1).
  • the structures represented by the plurality of formulas (1-1) may be the same or different.
  • R 1 represents a hydrogen atom or a substituent, and is preferably a substituent containing a polymerizable group.
  • 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.
  • R 1 is a substituent containing a polymerizable group, it is preferable that R 1 is a group represented by the following formula (R1-1).
  • X 1 , Z 1 and n are synonymous with X 1 , Z 1 and n in the formula (1-2) described later, respectively, and the preferred embodiments are also the same, and * is the formula (*). It represents the binding site with the nitrogen atom in 1-1).
  • R 1 when R 1 does not contain a polymerizable group, R 1 is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.
  • R 1 when R 1 is a hydrogen atom or a substituent not containing a polymerizable group, the specific resin has a structure containing a polymerizable group as a structure other than the structure represented by the formula (1-1). Have.
  • 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, a maleimide group and vinyl are preferable.
  • a phenyl 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 specific resin may contain a structure represented by the formula (1-1) as a divalent group in the molecular chain, or may be contained as a monovalent group represented by the following formula (1-1B). Good.
  • the monovalent group represented by the formula (1-1B) is contained in the specific resin as, for example, the end of the side chain.
  • R 1 has the same meaning as R 1 in the formula (1-1), preferable embodiments thereof are also the same.
  • R 2 is a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, a hydrocarbon group or a heterocyclic group, and a hydrogen atom, an aromatic hydrocarbon group or an aromatic heterocyclic group. More preferably, a hydrogen atom, a phenyl group, or a nitrogen-containing aromatic heterocyclic group is further preferable, a hydrogen atom, a phenyl group, or a pyridyl group is further preferable, and a hydrogen atom is particularly preferable.
  • X 1 represents a single bond or an n + 1 valent linking group
  • Z 1 represents a group having a polymerizable group
  • n represents an integer of 1 or more.
  • 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.
  • X 1 is preferably a single bond or a group having a total number of atoms of 2 to 40, more preferably a single bond or a group having a total number of atoms of 2 to 30, and a single bond.
  • the group has a total number of atoms of 2 to 20.
  • Z 1 is preferably a group containing an ethylenically unsaturated group, a cyclic ether group or a methylol group as a polymerizable group, and is preferably a vinyl group, a (meth) allyl group, or (meth) acrylamide.
  • the polymerizable group in Z 1 is a group that polymerizes with the polymerizable group in the polymerizable compound described later is also preferably mentioned.
  • n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1. ..
  • the specific resin preferably contains a structure represented by the following formula (1-3) as a structure containing the structure represented by the above formula (1-1). Further, from the viewpoint of solvent solubility, the specific resin preferably has a structure represented by the formula (1-3) in the main chain.
  • the specific resin preferably contains a plurality of structures represented by the formula (1-3). When the specific resin contains a plurality of structures represented by the formula (1-3), the structures represented by the plurality of formulas (1-3) may be the same or different.
  • X 31 independently represents a single bond or an n31 + 1 valent linking group
  • Z 31 independently represents a hydrogen atom or a group having a polymerizable group
  • n31 represents an integer greater than or equal to 1
  • X 32 independently represents a single bond or an n32 + 1 valent linking group
  • Z 32 independently represents a hydrogen atom or a group having a polymerizable group.
  • n32 represents an integer of 1 or more
  • L 1 represents a divalent linking group
  • at least one of Z 31 and Z 32 is a group having a polymerizable group.
  • X 31 and X 32 are independently synonymous with X 1 in formula (1-2), and the preferred embodiment is also the same.
  • Z 31 and Z 32- It is preferable that at least one of Z 31 and Z 32 is a group having a polymerizable group, and both are groups having a polymerizable group.
  • Z 31 or Z 32 is a group having a polymerizable group
  • Z 31 or Z 32 is synonymous with Z 1 in the formula (1-2), and the preferred embodiment is also the same.
  • n31 and n32 are independently synonymous with n in formula (1-2), and the preferred embodiment is also the same.
  • L 1 is preferably a group containing at least one selected from the group consisting of an aliphatic ring structure and an aromatic ring structure, and is an aliphatic hydrocarbon.
  • a group containing a ring structure or an aromatic hydrocarbon ring structure is more preferable, and a group containing an aromatic hydrocarbon ring structure is further preferable.
  • 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 independently hydrogen atoms.
  • LA31 and LA41 are independently single bond, carbonyl group, sulfonyl group and divalent, respectively.
  • the structure represented by the formula (A-1) or the formula (A-3) is preferable.
  • RA11 to RA14 are independently hydrogen atoms, carbonyl groups, sulfonyl groups, alkyl groups having 1 to 6 carbon atoms, cyclic alkyl groups having 3 to 12 carbon atoms, and 1 to 1 carbon atoms. It is preferable to represent an alkoxy group of 6 or a hydroxy group, a cyano group, an alkyl halide group having 1 to 3 carbon atoms, or a halogen atom.
  • a hydrogen atom or an alkyl having 1 to 6 carbon atoms A group, an alkoxy group having 1 to 6 carbon atoms, or an alkyl halide group having 1 to 3 carbon atoms is more preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferable.
  • the halogen atom in the alkyl halide group in RA11 to RA14 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.
  • at least two of RA11 to RA14 are preferably hydrogen atoms, and at least three are more preferably hydrogen atoms. ..
  • R A21 ⁇ R A24 are each synonymous with R A11 ⁇ R A14 in formula (A-1), a preferable embodiment thereof is also the same.
  • 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.
  • at least two of RA31 to RA34 are preferably hydrogen atoms, and at least three are more preferably hydrogen atoms.
  • LA31 is a single bond, a divalent saturated hydrocarbon group having 1 to 4 carbon atoms, a divalent unsaturated hydrocarbon group having 5 to 24 carbon atoms, —O—, —S.
  • a heterocyclic group, or a halogenated alkylene group having 1 to 6 carbon atoms is preferable, and a single bond, a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, -O- or It preferably represents a heterocyclic group, more preferably 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.
  • 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.
  • the specific resin preferably contains a repeating unit represented by the following formula (1-4) as a repeating unit containing the structure represented by the above formula (1-1). Further, the specific resin preferably has a repeating unit represented by the formula (1-4) in the main chain.
  • L 1 , L 2 and L 3 each independently represent a divalent linking group
  • X 41 represents a single bond or n41 + 1 valent linking group
  • X 42 represents a single bond or n42 + 1
  • Z 41 and Z 42 independently represent a hydrogen atom or a group having a polymerizable group
  • at least one of Z 41 and Z 42 is a group having a polymerizable group.
  • L 4 represents a structure represented by any one of the following formulas (L4-1) ⁇ formula (L4-4).
  • R 115 represents a tetravalent organic group
  • R 122 represents a tetravalent organic group
  • a 1 and A 2 are independently oxygen atoms or or.
  • -NH-, R 113 and R 114 independently represent a hydrogen atom or a monovalent organic group
  • R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group, respectively.
  • X 41 , X 42 , Z 41 , Z 42 , n 41 and n 42 are the same as X 31 , X 32 , Z 31 , Z 32 , n 31 and n 32 in formula (1-3), respectively. It has the same meaning, and the preferred embodiment is also the same.
  • at least one of Z 41 and Z 42 preferably contains an ethylenically unsaturated group, a cyclic ether group or a methylol group as the polymerizable group, and is preferably a vinyl group, a (meth) allyl group, or a (meth) acrylamide group.
  • (Meta) acryloxy group, vinylphenyl group, epoxy group, oxetanyl group, or methylol group is preferably contained, and more preferably contains (meth) acrylamide group, (meth) acryloxy group, glycidyl group, or methylol group. preferable.
  • L 1 has the same meaning as L 1 in formula (1-3), preferable embodiments thereof are also the same.
  • L 2 and L 3 are independently groups containing at least one selected from the group consisting of an aliphatic ring structure and an aromatic ring structure. Is more preferable, and a group containing an aliphatic hydrocarbon ring structure or an aromatic hydrocarbon ring structure is more preferable, and a group containing an aromatic hydrocarbon ring structure is further preferable. Further, in the formula (1-4), L 2 and L 3 were independently selected from the group consisting of the structures represented by any of the above formulas (A-1) to (A-5).
  • L 1 , L 2 and L 3 each independently contain at least one ring structure selected from the group consisting of an aliphatic ring structure and an aromatic ring structure.
  • L 1 , L 2 and L 3 independently, at least one structure selected from the group consisting of the structures represented by any of the above formulas (A-1) to (A-5). It is more preferable to include it.
  • At least two of RA11 to RA14 in the formula (A-1) are alkyl groups, and at least two of them are alkyl groups. More preferably, three are alkyl groups.
  • at least two of RA21 to RA24 in the formula (A-2) are preferably alkyl groups, and at least two are alkyl groups. More preferably, three are alkyl groups.
  • At least two of RA31 to RA34 in the formula (A-3) are preferably alkyl groups, and at least two are alkyl groups. More preferably, three are alkyl groups.
  • at least two of RA35 to RA38 in the formula (A-3) are preferably alkyl groups, and at least two are alkyl groups. More preferably, three are alkyl groups.
  • L 2 and L 3 in formula (1-4) from the viewpoint of solvent solubility, among the R A41 ⁇ R A44 in formula (A-4), preferably at least two of an alkyl group, at least More preferably, three are alkyl groups.
  • L 2 and L 3 in formula (1-4) from the viewpoint of solvent solubility, among the R A45 ⁇ R A48 in formula (A-4), preferably at least two of an alkyl group, at least More preferably, three are alkyl groups.
  • at least two of RA51 to RA54 in the formula (A-5) are preferably alkyl groups, and at least two are alkyl groups. More preferably, three are alkyl groups.
  • At least two of RA55 to RA58 in the formula (A-5) are preferably alkyl groups, and at least two are alkyl groups. More preferably, three are alkyl groups.
  • 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 Dihydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxy
  • DAA-1 to DAA-5 tetracarboxylic dianhydrides
  • DAA-5 tetracarboxylic dianhydrides
  • Equation (L4-2) R 122 has the same meaning as R 115 in the formula (L4-1), and the preferred embodiment is also the same.
  • R 122 is derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane or 4,4'-diamino-3,3'-dihydroxybiphenyl. Is preferable.
  • 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 R 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 (L4-3) has 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.
  • aromatic group examples include a substituted or unsubstituted aromatic hydrocarbon group (the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an inden ring, and an azulene ring.
  • the cyclic structure constituting the group includes a benzene ring, a naphthalene ring, a biphenyl ring, a fluorene ring, a pentalene ring, an inden ring, and an azulene ring.
  • 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 for the purpose of improving the adhesion to the base material.
  • 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.
  • Equation (L4-4) R 122 has the same meaning as R 122 in the above formula (L4-2), preferable embodiments thereof are also the same.
  • R 123 and R 124 are synonymous with R 113 and R 114 in the above formula (L4-3), respectively, and the preferred embodiments are also the same.
  • -Diamine compound having a sulfonamide group- In the formula (1-4), excluding the structure is L 4, is preferably a structure derived from a diamine compound having a sulfonamide group, in the structure obtained by removing two amino groups from a diamine compound having a sulfonamide group It is more preferable to have.
  • the diamine compound having a sulfonamide group a compound represented by the following formula (1-4-N) is preferable.
  • L 1 , L 2 , L 3 , X 41 , X 42 , Z 41 , Z 42 , n 41 and n 42 are L 1 , L 2 in formula (1-4), respectively.
  • X 41 , X 42 , Z 41 , Z 42 , n 41 and n 42 are also the same.
  • an embodiment in which X 41 and X 42 are single bonds and Z 41 and Z 42 are hydrogen atoms is also a preferable embodiment.
  • Z 41 or Z 42 in the above formula (1-4-N) can be reacted. It is possible to introduce a polymerizable group at the position of.
  • a specific resin can be obtained by introducing a polymerizable group by the above method after the reaction of the above-mentioned tetracarboxylic dianhydride with a compound having the following structure.
  • a preferable embodiment of the diamine compound having a sulfonamide group includes a compound having the following structure.
  • diamine compounds having a sulfonamide group can be obtained, for example, by the method described in Examples described later or the method described in International Publication No. 2018/003405.
  • 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 (1-4), when L 4 has a structure represented by a group represented by the formula (L4-2), the specific resin is preferably polybenzoxazole. In the formula (1-4), when L 4 has a structure represented by a group represented by the formula (L4-3), the specific resin is preferably a polyimide precursor. In the formula (1-4), when L 4 has a structure represented by a group represented by the formula (L4-4), the specific resin is preferably a polybenzoxazole precursor.
  • the content of the repeating unit represented by the formula (1-4) is 0.1 to 80 mass with respect to the total mass of the specific resin. It is preferably%, more preferably 1 to 70% by mass, and even more preferably 20 to 70% by mass.
  • the specific resin may contain only one type of repeating unit represented by the formula (1-4), or may contain two or more types.
  • the specific resin contains a structure represented by the formula (1-1B)
  • the specific resin is represented by the formula (1-2B) as a structure including the structure represented by the formula (1-1B). It preferably contains a structure.
  • L B1 represents a trivalent linking group
  • R 1 represents a hydrogen atom or a substituent
  • R 2 represents a hydrogen atom or a monovalent organic group
  • * is independently Represents a binding site with other structures.
  • L B1 it is trivalent linking group containing preferably a trivalent linking group containing an aromatic hydrocarbon ring or an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring Is more preferable, and a group obtained by removing three hydrogen atoms from the aromatic hydrocarbon ring is more preferable, and a group obtained by removing three hydrogen atoms from the benzene ring is particularly preferable.
  • Aromatic hydrocarbon ring or an aliphatic hydrocarbon ring in the L B1 may have a substituent, and examples of the substituent include an alkyl group, an aryl group, or, preferably a halogen atom, having 1 to 4 carbon atoms An alkyl group, an aryl group having 6 to 12 carbon atoms, or a halogen atom is more preferable, and an alkyl group having 1 to 4 carbon atoms is further preferable.
  • R 1 and R 2 have the same meanings as R 1 and R 2 in the above formula (1-1B), preferable embodiments thereof are also the same. In the formula (1-2B), it is preferable that all * are bonded to the main chain of the specific resin.
  • L B1, R 1 and R 2 each have the same meaning as L B1, R 1 and R 2 in the formula (1-2B), preferable embodiments thereof are also the same.
  • L 4 has the same meaning as L 4 in the above formula (1-4), preferable embodiments thereof are also the same.
  • -Diamine compound having a sulfonamide group- Wherein (1-3B), excluding the structure L 4, is preferably a structure derived from a diamine compound having a sulfonamide group, in the structure obtained by removing two amino groups from a diamine compound having a sulfonamide group It is more preferable to have.
  • the diamine compound having a sulfonamide group a compound represented by the following formula (1-3BN) is preferable.
  • L B1 , R 1 and R 2 each have the same meaning as L B1, R 1 and R 2 in the formula (1-3B), preferable embodiments thereof are also the same.
  • R 1 is a hydrogen atom
  • the position of R 1 in the above formula (1-3BN) can be obtained. It is possible to introduce a polymerizable group.
  • a specific resin can be obtained by introducing a polymerizable group by the above method after the reaction of the above-mentioned tetracarboxylic dianhydride with a compound having the following structure.
  • a preferable embodiment of the diamine compound having a sulfonamide group includes a compound having the following structure.
  • diamine compounds having a sulfonamide group can be obtained, for example, by the method described in International Publication No. 2017/002407.
  • 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 (1-3B), when L 4 has a structure represented by a group represented by the formula (L4-2), the specific resin is preferably polybenzoxazole. Wherein (1-3B), when L 4 is a structure represented by the group represented by the formula (L4-3), is preferably specific resin is a polyimide precursor. In the formula (1-3B), when L 4 has a structure represented by a group represented by the formula (L4-4), the specific resin is preferably a polybenzoxazole 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 1 to 70% by mass, and even more preferably 5 to 50% 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 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.
  • the specific resin contains a repeating unit represented by the following formula (4), it is a repeating unit represented by the formula (1-4), and L 4 in the formula (1-4) is the formula (L4-1).
  • repetition unit PI-1 (Hereinafter, also referred to as “repetition unit PI-1”) and the repetition unit represented by the equation (1-3B), where L 4 in the equation (1-3B) is the equation (1-3B).
  • 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 10 to 70% by mass, more preferably 1 to 80% 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.
  • the repeating unit represented by the formula (1-4), the repeating unit represented by the formula (1-3B), and the repeating unit represented by the formula (4) contained in the specific resin are represented by the formula (4).
  • the total content with the repeating unit to be formed is preferably 50 to 100% by mass, more preferably 60 to 99% by mass, and 70 to 95% by mass with respect to the total mass of the specific resin. Is more preferable.
  • the specific resin preferably contains a repeating unit represented by the formula (X).
  • the specific resin is preferably polybenzoxazole.
  • the specific resin preferably contains a repeating unit represented by the following formula (X) in the main chain.
  • the specific resin contains a repeating unit represented by the formula (X)
  • the specific resin is a repeating unit represented by the formula (1-4)
  • L 4 in the formula (1-4) is the formula ( L4-2) is a repeating unit (hereinafter, also referred to as “repeating unit PB-1”) and a repeating unit represented by the formula (1-3B), and L in the formula (1-3B).
  • It is represented by the following formula (X) and at least one type of repeating unit selected from the group consisting of the repeating unit (hereinafter, also referred to as “repetition unit PB-2”) in which 4 is the formula (L4-2).
  • R 133 represents a divalent organic group
  • R 134 represents a tetravalent organic group.
  • Examples of the divalent organic group represented by R 133 include an aliphatic or aromatic group.
  • the group described by R 121 of the formula (2) described later can be mentioned, and the preferable range is also the same.
  • As the tetravalent organic group represented by R 134 the same group as R 122 in the above formula (L4-2) is exemplified, and the preferable range is also the same.
  • the specific resin contains a repeating unit represented by the formula (X) (for example, when the specific resin is polybenzoxazole), the specific resin uses the repeating unit represented by the formula (X) as the whole of the specific resin. 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 with respect to the mass. Further, when the specific resin is polybenzoxazole, the specific resin may be in a mode that does not substantially contain the repeating unit represented by the formula (X). In such a mode, the formula (X) 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 (1-4), the repeating unit represented by the formula (1-3B), and the repeating unit of the formula (4) contained in the specific resin are included.
  • the total content with the repeating unit represented by is preferably 50 to 100% by mass, more preferably 60 to 99% by mass, and 70 to 95% by mass with respect to the total mass of the specific resin. It is more preferable to have.
  • the specific resin may further contain a repeating unit represented by the formula (SL) described later.
  • 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.
  • the specific resin contains a repeating unit represented by the following formula (1), it is a repeating unit represented by the formula (1-4), and L 4 in the formula (1-4) is the formula (L4-3).
  • repetition unit PIP-1 (Hereinafter, also referred to as “repetition unit PIP-1”) and the repetition unit represented by the formula (1-3B), where L 4 in the formula (1-3B) is the formula.
  • 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.
  • 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 0.1 to 80% by mass, more preferably 1 to 70% by mass, and further preferably 10 to 60% 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 (1-4), the repeating unit represented by the formula (1-3B), and the formula (1) contained in the specific resin are included.
  • the total content with the repeating unit represented by is preferably 50 to 100% by mass, more preferably 60 to 99% by mass, and 70 to 95% by mass with respect to the total mass of the specific resin. It is more preferable to have.
  • the specific resin may further contain a repeating unit represented by the following formula (2).
  • the specific resin is preferably a polybenzoxazole precursor.
  • the specific resin preferably contains a repeating unit represented by the following formula (2) in the main chain.
  • the specific resin contains a repeating unit represented by the following formula (2), it is a repeating unit represented by the formula (1-4), and L 4 in the formula (1-4) is the formula (L4-4).
  • repetition unit PBP-1 (Hereinafter, also referred to as “repetition unit PBP-1”) and the repetition unit represented by the equation (1-3B), where L 4 in the equation (1-3B) is the equation.
  • At least one type of repeating unit selected from the group consisting of the repeating unit (L4-4) (hereinafter, also referred to as “repeating unit PBP-2”), and the repeating unit represented by the following formula (2). Is preferably included.
  • R 121 represents a divalent organic group
  • R 122 represents a tetravalent organic group
  • R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group. Represent.
  • R 121 represents a divalent organic group.
  • the divalent organic group includes an aliphatic group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 6 carbon atoms) and an aromatic group (preferably 6 to 22 carbon atoms, 6 to 14 carbon atoms). Is more preferable, and a group containing at least one of 6 to 12 is particularly preferable).
  • the aromatic group constituting R 121 include R 111 of the above formula (1).
  • the aliphatic group a linear aliphatic group is preferable.
  • R 121 is preferably derived from 4,4'-oxydibenzoyl chloride.
  • R 122 represents a tetravalent organic group.
  • the tetravalent organic group has the same meaning as R 115 in the above formula (1), and the preferable range is also the same.
  • R 122 is preferably derived from 2,2'-bis (3-amino-4-hydroxyphenyl) hexafluoropropane.
  • R -R 123 and R 124- R 123 and R 124 independently represent a hydrogen atom or a monovalent organic group, and have the same meaning as R 113 and R 114 in the above formula (1), and the preferable range is also the same.
  • the specific resin may contain other types of repeating units in addition to the repeating units of the above formula (2).
  • the diamine residue represented by the following formula (SL) is a repeating unit of another type in that the occurrence of warpage of the cured film due to ring closure can be suppressed. It is preferable to further include as.
  • R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and R 2s.
  • Is a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms), and at least one of R 3s , R 4s , R 5s , and R 6s is aromatic. It is a group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, particularly preferably 6 to 10 carbon atoms), and the rest is a hydrogen atom or 1 to 30 carbon atoms (preferably 1 to 18 carbon atoms).
  • the a structure and the b structure may be block polymerization or random polymerization.
  • the a structure is 5 to 95 mol%
  • the b structure is 95 to 5 mol%
  • a + b is 100 mol%.
  • preferred Z includes those in which R 5s and R 6s in the b structure are phenyl groups.
  • the molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000.
  • the molecular weight can be determined by commonly used gel permeation chromatography. By setting the molecular weight in the above range, the elastic modulus of the polybenzoxazole precursor after dehydration ring closure can be lowered, and the effect of suppressing warpage and the effect of improving solubility can be achieved at the same time.
  • the specific resin contains a diamine residue represented by the formula (SL) as another type of repeating unit, it further improves the alkali solubility of the curable resin composition, and further, the tetracarboxylic dianhydride to the acid. It is preferable to include the tetracarboxylic acid residue remaining after the removal of the dianhydride group as a repeating unit. Examples of such a tetracarboxylic acid residue include the example of R 115 in the formula (1).
  • the specific resin may further contain a repeating unit represented by the formula (P-1).
  • R 1 in the formula (1-1) is a hydrogen atom or a substituent not containing a polymerizable group
  • the specific resin is represented by the formula (1) as a repeating unit having a polymerizable group. It is preferable to include the repeating unit represented by P-1).
  • the specific resin preferably has a repeating unit represented by the formula (P-1) in the main chain.
  • L P1 represents a + 2-valent connecting group
  • X P2 is an ester bond, a urethane bond, a urea bond, an amide bond or an ether bond
  • X P1 represents a group containing a polymerizable group
  • A represent an integer of 1 or more
  • L P4 represents any of the structures represented by the formulas (L4-1) to (L4-4) in the above formula (1-4), and a is 1 or more. It represents an integer, if X P2 or X P1 there are a plurality, plural of X P2 or X P1 may be the same or different.
  • LP1 represents an a + divalent linking group, which is 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, or a sulfonyl. It is preferable that the group is a group to which at least one of -NR N- 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, LP1 preferably contains a structure represented by any of the above formulas (A-1) to (A-5), and any of the above formulas (A-1) to (A-5). It is more preferable that the structure is represented by.
  • the formula L 21 includes any one of the structures represented by the formulas (A-1) to (A-5), in the description of the formulas (A-1) to (A-5), RA11 to R A14, R A21 ⁇ R A24, R A31 ⁇ R A38, of R A41 ⁇ R A48 and R A51 ⁇ R A58, a number respectively the bonding site with X P2 in the formula (P-1).
  • -X P2 - XP2 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.
  • X 2 may be determined in consideration of the synthesis method and the like. If X P2 is an ester bond, to a carbon atom of the ester bond may be attached with L 1, the oxygen atom may be bonded to L 1. If X P2 is a urethane bond, it is preferable that the oxygen atom of the urethane bond is bound to L 1. If X P2 is an amide bond, it is preferred that the carbon atom of the amide bond is bonded to L 1.
  • -X P1 - XP1 represents a group containing a polymerizable group.
  • XP1 preferably contains, as the polymerizable group, 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.
  • the X P1 is preferably a group represented by the following formula (X-1).
  • (X-1) L represents a single bond or nx + 1 valent connecting group, nx represents an integer of 1 or more, Z 2 represents a polymerizable group, and * X P2 of formula P-1) in Represents the binding site with.
  • 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.
  • aliphatic hydrocarbon group a saturated aliphatic hydrocarbon group is more preferable.
  • 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.
  • the embodiment in which L contains a (poly) alkyleneoxy group is also one of the preferred embodiments.
  • the (poly) alkyleneoxy group means an alkyleneoxy group or a polyalkyleneoxy group.
  • 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 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 in the (poly) alkyleneoxy group is preferably 2 or more, and more preferably 2 to 50.
  • 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 is preferably 2 to 100, more preferably 2 to 50, further preferably 2 to 30, and particularly 2 to 10. Preferably, 3 to 10 are most preferable.
  • 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.
  • nx 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.
  • -A- a represents an integer of 1 or more, and is preferably an integer of 1 to 10, more preferably 1 to 4, further preferably 1 or 2, and particularly preferably 1.
  • the content of the repeating unit represented by the formula (P-1) is 0.1 to 80 mass with respect to the total mass of the specific resin. %, More preferably 1 to 70% by mass, and even more preferably 1 to 50% by mass.
  • the specific resin may contain only one type of repeating unit represented by the formula (P-4), or may contain two or more types.
  • 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. It is more preferably 10,000 to 50,000.
  • the number average molecular weight (Mn) of the specific resin is preferably 800 to 250,000, more preferably 2,000 to 50,000, and 4, It is more preferably 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 weight average molecular weight (Mw) of the specific resin is preferably 2,000 to 500,000, preferably 5,000 to 100,000. Is more preferable, and 10,000 to 50,000 is even more preferable.
  • the number average molecular weight (Mn) of the specific resin is preferably 800 to 250,000, more preferably 2,000 to 50,000. It is preferably 4,000 to 25,000, and more preferably 4,000 to 25,000.
  • the dispersity of the molecular weight of the specific resin is preferably 1.5 to 3.5, more preferably 2 to 3.
  • 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, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor.
  • the specific resin preferably contains at least one repeating unit selected from the group consisting of the repeating unit PI-1 and the repeating unit PI-2, and the repeating unit PI-1 and the repeating unit It is more preferable to include at least one repeating unit selected from the group consisting of PI-2 and a repeating unit represented by the formula (4). Further, the specific resin may further contain other repeating units. Further, the specific resin may further contain at least one repeating unit selected from the group consisting of the repeating unit PIP-1 and the repeating unit PIP-2 described above and the repeating unit represented by the formula (1).
  • 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 when the specific resin is a polyimide precursor, the specific resin preferably contains at least one repeating unit selected from the group consisting of the repeating unit PIP-1 and the repeating unit PIP-2, and the repeating unit PIP-1 and It is more preferable to include at least one repeating unit selected from the group consisting of the repeating unit PIP-2 and the repeating unit represented by the formula (1). Further, the specific resin may further contain other repeating units.
  • the specific resin when the specific resin is polybenzoxazole, the specific resin preferably contains at least one repeating unit selected from the group consisting of the repeating unit PB-1 and the repeating unit PB-2, and the repeating unit PB-1 and It is more preferable to include at least one repeating unit selected from the group consisting of the repeating unit PB-2 and the repeating unit represented by the formula (X). Further, the specific resin may further contain other repeating units. Further, the specific resin may further contain at least one repeating unit selected from the group consisting of the repeating unit PBP-1 and the repeating unit PBP-2 described above and the repeating unit represented by the formula (2).
  • 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 polybenzoxazole is a value represented by the following formula CR (PB).
  • Equation CR (PB): Ring closure rate (%) of the specific resin (molar amount of benzoxazole ring in the specific resin) / (molar amount of benzoxazole ring in the specific resin + molar amount of structure capable of forming a benzoxazole ring by closing the ring in the specific resin) ⁇ 100
  • the specific resin is a resin composed of a repeating unit PB-1, a repeating unit PBP-1, a repeating unit represented by the formula (X), and a repeating unit represented by the formula (2)
  • the rate is a value represented by the following formula CR (PB) 1.
  • the specific resin when the specific resin is a polybenzoxazole precursor, the specific resin preferably contains at least one repeating unit selected from the group consisting of the repeating unit PBP-1 and the repeating unit PBP-2, preferably the repeating unit PBP-. It is more preferable to include at least one repeating unit selected from the group consisting of 1 and the repeating unit PBP-2, and the repeating unit represented by the formula (2). Further, the specific resin may further contain other repeating units.
  • Specific examples of the specific resin include the specific resin used in the examples described later.
  • the specific resin is synthesized, for example, by the synthesis method shown in the synthesis example in the examples described later.
  • the specific resin is polyimide
  • a sulfonamide group-containing diamine is reacted with a dicarboxylic acid or a dicarboxylic acid derivative, and after the reaction, thermal imidization or chemical imidization (for example, a catalyst is allowed to act).
  • thermal imidization or chemical imidization for example, a catalyst is allowed to act.
  • a method of forming an imide ring by a method such as (promotion of cyclization reaction) to obtain a polyimide can be mentioned.
  • the specific resin is polyimide
  • the polyimide may be synthesized by cyclizing a polyimide precursor which is a specific resin by heating or the like.
  • Examples of the synthesis method when the specific resin is a polyimide precursor include a method of reacting a sulfonamide group-containing diamine with a dicarboxylic acid or a dicarboxylic acid derivative.
  • Examples of the synthesis method when the specific resin is polybenzoxazole include a method of reacting a diamine compound having a sulfonamide group with a dicarboxylic acid halide compound having a benzoxazole structure.
  • the specific resin is a polybenzoxazole precursor, as a synthetic method, a compound having a benzene ring having two or more hydroxy groups and having an amino group adjacent to the hydroxy group, and a sulfonamide-containing diamine are used.
  • a method of reacting with a dicarboxylic acid halide compound can be mentioned. Further, the polyimide, polyimide precursor, polybenzoxazole or polybenzoxazole precursor obtained by the above method is reacted with a carboxylic acid halide compound having a polymerizable group such as methacrylic acid halide and contained in the sulfonamide group. A polymerizable group may be added to the hydrogen atom.
  • 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.
  • other resins include polyimide, polyimide precursor, polybenzoxazole, polybenzoxazole 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 specific resin is polybenzoxazole
  • the other resin is preferably polybenzoxazole.
  • the specific resin is a polybenzoxazole precursor
  • the other resin is preferably a polybenzoxazole 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 polybenzoxazole preferably contains a repeating unit represented by the above formula (X).
  • polybenzoxazole may also contain other types of repeating units.
  • Polybenzoxazole preferably further contains a diamine residue represented by the above formula (SL) as another type of repeating unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.
  • SL diamine residue represented by the above formula (SL) as another type of repeating unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.
  • polybenzoxazole contains a diamine residue represented by the formula (SL) as another kind of repeating unit, it is further derived from tetracarboxylic dianhydride in that it improves the alkali solubility of the curable resin composition. It is preferable to include the tetracarboxylic acid residue remaining after the removal of the acid dianhydride group as a repeating unit. Examples of such a tetracarboxylic acid residue include the example of R 115 in the formula (1).
  • the weight average molecular weight (Mw) of polybenzoxazole is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and even more 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 polybenzoxazole is preferably 1.5 to 3.5, more preferably 2 to 3.
  • the polybenzoxazole precursor preferably contains a repeating unit represented by the above formula (2).
  • polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units of the above formula (2).
  • the polybenzoxazole precursor preferably further contains a diamine residue represented by the above formula (SL) as another type of repeating unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.
  • SL diamine residue represented by the above formula (SL) as another type of repeating unit in that the occurrence of warpage of the cured film due to ring closure can be suppressed.
  • the tetracarboxylic dianhydride is further provided in that it improves the alkali solubility of the curable resin composition. It is preferable that the tetracarboxylic acid residue remaining after the removal of the acid dianhydride group from the product is contained as a repeating unit. Examples of such a tetracarboxylic acid residue include the example of R 115 in the formula (1).
  • the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. is there.
  • 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 polybenzoxazole precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
  • 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 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 polybenzoxazole 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 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 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 50% by mass or less, more preferably 40% by mass or less, and 30% 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 10 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) or tetraethylammonium hydroxide and the like.
  • TMAH tetraethylammonium hydroxide
  • metal-free alkaline compounds are preferable, and amines are 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 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.
  • solvent development it is preferable to rinse with 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, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor of the present invention preferably contains a structure represented by the following formula (1-2).
  • X 1 represents a single bond or an n + 1 valent linking group
  • Z 1 represents a group having a polymerizable group
  • n represents an integer of 1 or more.
  • the above formula (1-2) is synonymous with the formula (1-2) in the specific resin, and the preferred embodiment is also the same.
  • the polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor of the present invention requires the structure represented by the above formula (1-2), but the polyimide, polybenzo in the above-mentioned specific resin is essential. It is synonymous with oxazole, polyimide precursor, or polybenzoxazole precursor, and the preferred embodiment is also the same.
  • the polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor of the present invention is preferably used as the resin contained in the curable resin composition.
  • the composition in which the conventional polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor is used such as a composition for an interlayer insulating film, is not particularly limited, and the conventional polyimide, polybenzoxazole, etc.
  • a part or all of the polyimide precursor or the polybenzoxazole precursor can be used in place of the polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor of the present invention.
  • the polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor of the present invention has excellent breaking elongation of the obtained cured film
  • the polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole of the present invention It is considered that the precursor is preferably used as a material for a member such as an insulating film, which requires the strength of a cured film.
  • the reaction mixture was cooled to room temperature with stirring, added dropwise to 1 L of ice water and 1 L of a chloroform mixture, stirred for 30 minutes, transferred to a separating funnel, and the organic layer (chloroform layer) was taken out.
  • the chloroform solution was transferred to a separatory funnel again, washed with saturated multilayer water, washed twice with pure water, and then washed with saturated brine.
  • the organic layer (chloroform layer) was transferred to an Erlenmeyer flask, 30 g of magnesium sulfate was added, the mixture was stirred, and the solid matter was removed by filtration. Chloroform was distilled off using an evaporator, and the mixture was vacuum-dried at room temperature for 24 hours.
  • reaction mixture was returned to room temperature, stirred for 2 hours, and then 615 g of a 1 mol / L sodium hydroxide aqueous solution and 500 g of pure water were added and dissolved.
  • the reaction solution was transferred to a separating funnel, washed three times with 500 mL of ethyl acetate, and the aqueous layer was recovered. 33.7 g of ammonium chloride (manufactured by Kanto Chemical Co., Inc.) was weighed in a beaker, dissolved in 2 L of pure water, and stirred at room temperature.
  • the aqueous layer was dropped into a beaker, the precipitated crystals were collected by filtration, the crystals were washed with 1 L of pure water and then the crystals were collected by filtration, and then the crystals were washed with 500 mL of chloroform and then the crystals were collected by filtration.
  • the mixture was vacuum dried at ° C. for 24 hours to obtain 56.5 g of the target product (SA-1). It was confirmed from the NMR spectrum that it was the target product.
  • the target product (SA-1) was analyzed by 1 1 H-NMR. The results are shown below.
  • PI-1 The weight average molecular weight (Mw) of PI-1 was 28,900, and the number average molecular weight (Mn) was 12,300.
  • the structure of PI-1 is a structure represented by the following formula (PI-1). It is presumed.
  • the precipitated polyimide resin was removed by filtration, washed with 1.5 liters of water, mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again.
  • 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 30,900, and the number average molecular weight (Mn) was 13,800.
  • the structure of PI-2 is presumed to be the structure represented by the following formula (PI-2).
  • the precipitated polyimide resin was removed by filtration, washed with 1.5 liters of water, mixed with 2 liters of methanol, stirred again for 30 minutes, and filtered again.
  • the obtained polyimide was dried under reduced pressure at 40 ° C. for 1 day to obtain PI-3.
  • the weight average molecular weight (Mw) of PI-3 was 29,500, and the number average molecular weight (Mn) was 12,900.
  • the structure of PI-3 is presumed to be the structure represented by the following formula (PI-3).
  • PI-4 The weight average molecular weight (Mw) of PI-4 was 32,400, and the number average molecular weight (Mn) was 13,500.
  • the structure of PI-4 is presumed to be the structure represented by the following formula (PI-4).
  • PI-5 Synthesis of Polyimide (PI-5)>
  • PI-5 was synthesized by the same method as the synthesis of PI-4 except that the compound represented by the following formula (Cl—A) was used instead of the methacrylic acid chloride. ..
  • the weight average molecular weight (Mw) of PI-5 was 33,500, and the number average molecular weight (Mn) was 14,800.
  • the structure of PI-5 is presumed to be the structure represented by the following formula (PI-5).
  • PI-6 The weight average molecular weight (Mw) of PI-6 was 33,500, and the number average molecular weight (Mn) was 14,800.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • the weight average molecular weight (Mw) of PI-7 was 24,300, and the number average molecular weight (Mn) was 10,800.
  • the structure of PI-7 is presumed to be the structure represented by the following formula (PI-7).
  • * 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 (below (P1)) and a 2-methylethylene group (below (P2)).
  • * 1 is bonded to the structure on the acrylate group side in R 1 in the formula (PI-7), and * 2 is * in R 1 in the formula (PI-7).
  • the weight average molecular weight (Mw) of PI-8 was 32,300, and the number average molecular weight (Mn) was 12,800.
  • the structure of PI-8 is presumed to be the structure represented by the following formula (PI-8).
  • * represents the binding site with the oxygen atom to which R binds.
  • PI-9 The weight average molecular weight (Mw) of PI-9 was 27,600, and the number average molecular weight (Mn) was 10,300.
  • the structure of PI-9 is a structure represented by the following formula (PI-9). It is presumed. The structure of PI-9 is presumed to be the structure represented by the following formula (PI-9). In formula (PI-9), * represents the binding site with the oxygen atom to which R 1 binds.
  • PB-1 The weight average molecular weight (Mw) of PB-1 was 23,500, and the number average molecular weight (Mn) was 10,900.
  • Mw weight average molecular weight
  • Mn number average molecular weight
  • the structure of PB-1 is a structure represented by the following formula (PB-1). It is presumed. In formula (PB-1), * represents the binding site with the nitrogen atom to which R 1 binds.
  • the weight average molecular weight (Mw) of PBA-1 was 24,600, and the number average molecular weight (Mn) was 11,000.
  • the structure of PBA-1 is presumed to be the structure represented by the following formula (PBA-1).
  • * represents a binding site with an oxygen atom or a nitrogen atom to which R 1 is bonded.
  • PBA-1 The structure of PBA-1 is presumed to be the structure represented by the following formula (PBA-2).
  • * represents the binding site of R 1 with an oxygen atom or a nitrogen atom.
  • the subscripts in square brackets represent the content ratio (molar ratio) of each repeating unit.
  • ⁇ Synthesis Example 17 Synthesis of Polyimide (A-1) for Comparative Example> 20.0 g (100 mmol) of 1,3-phenylenediamine N-methylpyrrolidone (NMP) 200. While removing water in a drying reactor equipped with a flat bottom joint equipped with a stirrer, condenser and internal thermometer. It was dissolved in 0 g. Subsequently, 44.4 g (100 mmol) of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride was added, and the mixture was stirred at a temperature of 40 ° C. for 2 hours. Then, after adding 50 mL of toluene, the temperature was raised to 180 ° C.
  • NMP 1,3-phenylenediamine N-methylpyrrolidone
  • the polyimide (A-1) for comparative example does not include the structure represented by the formula (1-1) and does not correspond to the specific resin.
  • 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 polymer A-2.
  • the weight average molecular weight (Mw) of this polymer A-2 was measured and found to be 20,000.
  • -PI-1 to PI-7 PI-1 to PI-7 synthesized above -PA-1 to PA-2: PA-1 to PA-2 synthesized above -PB-1: PB-1 synthesized above -PBA-1 to PBA-2: PBA-1 to PBA-2 synthesized above -A-1 to A-2: A-1 to A-2 synthesized above
  • DMSO / GBL dimethyl sulfoxide-GBL: ⁇ -butyrolactone-ethyl lactate-NMP: N-methylpyrrolidone
  • GBL 20: 80 (mass ratio). It shows that it was mixed.
  • 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.
  • the entire surface of the curable resin composition layer on the silicon wafer was exposed to an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C).
  • the obtained curable resin composition layer (resin layer) was heated at a temperature rising rate of 10 ° C./min under a nitrogen atmosphere to the temperature described in the "curing conditions" column of Table 1. After reaching this temperature, it was 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 (Tencilon) was used to fabricate the film in accordance with JIS-K6251 in an environment with a crosshead speed of 300 mm / min, 25 ° C., and 65% RH (relative humidity).
  • 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.
  • B The index value was 55% or more and less than 60%.
  • C The above index value was 50% or more and less than 55%.
  • D The above index value was less than 50%.
  • Each curable resin composition or comparative composition prepared in each Example and Comparative Example was applied on 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 form a curable resin composition layer having a uniform thickness of 15 ⁇ m on the silicon wafer.
  • the curable resin composition layer on the silicon wafer was exposed to an exposure energy of 500 mJ / cm 2 using a stepper (Nikon NSR 2005 i9C), and the exposed curable resin composition layer (resin layer) was subjected to a nitrogen atmosphere.
  • the temperature is raised at a heating rate of 10 ° C./min, and the cured layer (resin layer) of the curable resin composition layer is heated at the temperature shown in the “Curing conditions” column of Table 1 for 180 minutes. Obtained.
  • the obtained resin layer was immersed in the following chemical solution under the following conditions, and the dissolution rate was calculated.
  • Chemical solution Mixture of dimethyl sulfoxide (DMSO) and 25 mass% tetramethylammonium hydroxide (TMAH) aqueous solution at 90:10 (mass ratio)
  • Evaluation conditions Immerse the resin layer in the chemical solution at 75 ° C. for 15 minutes before and after. The film thicknesses were compared and the dissolution rate (nm / min) was calculated. The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in Table 1.
  • the dissolution rate was less than 200 nm / min.
  • B The dissolution rate was 200 nm / min or more and less than 300 nm / min.
  • C The dissolution rate was 300 nm / min or more and less than 400 nm / min.
  • D The dissolution rate was 400 nm / min or more.
  • the curable resin composition containing the specific resin according to the present invention is excellent in the film strength (break elongation) of the obtained cured film.
  • 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 film strength (break elongation).
  • Examples 101 to 121> The curable resin composition according to any one of Examples 1 to 21 has a film thickness of 20 ⁇ m on the surface of the resin base material on which the copper thin layer is formed on the copper thin layer side. Spinned and applied. The curable resin composition applied to the resin substrate was dried at 100 ° C.
  • 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.
  • After exposure for examples described as "solvent” in the "Development method” column of Table 1, develop with cyclopentanone for 30 seconds, rinse with propylene glycol monomethyl ether acetate (PGMEA) for 20 seconds, and pattern.
  • PMEA propylene glycol monomethyl ether acetate

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Abstract

L'invention concerne une composition de résine durcissable comprenant une résine spécifiée, un initiateur de polymérisation et un composé polymérisable, ladite résine comprenant une structure représentée par la formule (1–1) ; un film durci formé 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 de nouveaux polyimide, polybenzoxazole, précurseur de polyimide ou précurseur de polybenzoxazole.
PCT/JP2020/022855 2019-06-17 2020-06-10 Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur et polyimide, polybenzoxazole, précurseur de polyimide ou précurseur de polybenzoxazole WO2020255825A1 (fr)

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WO2023032475A1 (fr) * 2021-08-31 2023-03-09 富士フイルム株式会社 Procédé de production de produit durci, procédé de production de corps multicouche, procédé de production de dispositif à semi-conducteur, et solution de traitement et composition de résine
JP7405309B2 (ja) 2021-06-25 2023-12-26 住友ベークライト株式会社 ネガ型感光性ポリマー、ポリマー溶液、ネガ型感光性樹脂組成物、硬化膜および半導体装置

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JPH05119323A (ja) * 1991-10-25 1993-05-18 Fuji Photo Film Co Ltd 配向膜
WO2017056595A1 (fr) * 2015-09-28 2017-04-06 富士フイルム株式会社 Composition de résine photosensible de type négatif, plaque originale d'impression lithographique de type négatif, et procédé de production de plaque d'impression lithographique
WO2017175598A1 (fr) * 2016-04-05 2017-10-12 富士フイルム株式会社 Membrane de séparation de gaz, module de séparation de gaz, dispositif de séparation de gaz, et procédé de séparation de gaz

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JPH05119323A (ja) * 1991-10-25 1993-05-18 Fuji Photo Film Co Ltd 配向膜
WO2017056595A1 (fr) * 2015-09-28 2017-04-06 富士フイルム株式会社 Composition de résine photosensible de type négatif, plaque originale d'impression lithographique de type négatif, et procédé de production de plaque d'impression lithographique
WO2017175598A1 (fr) * 2016-04-05 2017-10-12 富士フイルム株式会社 Membrane de séparation de gaz, module de séparation de gaz, dispositif de séparation de gaz, et procédé de séparation de gaz

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Publication number Priority date Publication date Assignee Title
JP7405309B2 (ja) 2021-06-25 2023-12-26 住友ベークライト株式会社 ネガ型感光性ポリマー、ポリマー溶液、ネガ型感光性樹脂組成物、硬化膜および半導体装置
WO2023032475A1 (fr) * 2021-08-31 2023-03-09 富士フイルム株式会社 Procédé de production de produit durci, procédé de production de corps multicouche, procédé de production de dispositif à semi-conducteur, et solution de traitement et composition de résine

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