WO2021045126A1 - Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur, résine, et procédé de production de résine - Google Patents

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

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Publication number
WO2021045126A1
WO2021045126A1 PCT/JP2020/033326 JP2020033326W WO2021045126A1 WO 2021045126 A1 WO2021045126 A1 WO 2021045126A1 JP 2020033326 W JP2020033326 W JP 2020033326W WO 2021045126 A1 WO2021045126 A1 WO 2021045126A1
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group
preferable
formula
compound
resin composition
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PCT/JP2020/033326
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English (en)
Japanese (ja)
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敦靖 野崎
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富士フイルム株式会社
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Priority to JP2021544011A priority Critical patent/JP7254194B2/ja
Publication of WO2021045126A1 publication Critical patent/WO2021045126A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G59/22—Di-epoxy compounds
    • C08G59/28—Di-epoxy compounds containing acyclic nitrogen atoms
    • 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
    • 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

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, a resin, and a method for producing a resin.
  • Resins such as polyimide are applied to various applications because they have excellent heat resistance and insulating properties.
  • the above application is not particularly limited, and examples of a semiconductor device for mounting include use as a material for an insulating film and a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.
  • a resin such as polyimide may be used in the form of a curable resin composition containing a polyimide precursor or the like.
  • the precursor is cyclized to become a resin such as polyimide by heating, for example.
  • these curable resin compositions can be applied to a base material or the like by a known coating method or the like, for example, there is a degree of freedom in designing the shape, size, application position, etc. of the curable resin composition to be applied. It can be said that it is highly adaptable to manufacturing.
  • curable resin compositions containing resins such as polyimide precursors are expected to be increasingly applied in industry. There is.
  • Patent Document 1 describes a reactive transparent polyimide precursor having a specific structure.
  • Patent Document 2 describes a photosensitive resin composition containing (A) a polyamic acid having a specific structural unit, (B) a photopolymerizable compound, and (C) a photopolymerization initiator. There is.
  • curable resin composition containing polyimide it is desired to provide a curable resin composition having excellent chemical resistance of the obtained cured film.
  • One embodiment of the present invention comprises a curable resin composition having excellent chemical resistance 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. It is an object of the present invention to provide a manufacturing method and a semiconductor device including the cured film or the laminate. Another embodiment of the present invention aims to provide a novel resin and a method for producing the above resin.
  • ⁇ 1> Contains a resin containing a repeating unit represented by the formula (1-1) and a photosensitizer.
  • the resin contains 50 mol% or more of the repeating units represented by the following formula (1-1) with respect to all the repeating units of the resin.
  • X 1 represents a tetravalent group containing an aromatic hydrocarbon group, and all of the bonding sites with the four carbonyl groups in formula (1-1) in X 1 are aromatic hydrocarbons.
  • Y 1 represents an n + divalent group containing an aromatic hydrocarbon group
  • a 1 represents a group containing a polymerizable group
  • G 1 and G 2 are independent hydrogen atoms or substituents, respectively.
  • n represents an integer of 1 or more.
  • the curable resin composition according to ⁇ 1> wherein the ratio of the molar amount of G 1 or the above G 2 is 0 to 30%.
  • ⁇ 3> With respect to the total molar amount of G 1 and G 2 in all the repeating units represented by the above formula (1-1) contained in the resin, the number of carbon atoms which may contain a hetero atom is 1 to 30.
  • the G which is an organic group having a polyalkyleneoxy group, with respect to the total molar amount of G 1 and G 2 in all the repeating units represented by the above formula (1-1) contained in the resin.
  • the above X 1 includes at least one structure selected from the group consisting of the structures represented by the following formulas (A-1) to (A-5), and the above Y 1 is the following formula.
  • 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 are independently single-bonded, carbonyl group, sulfonyl group, and divalent, respectively.
  • R A2-1 ⁇ (A2-5), R A211 ⁇ R A214, R A221 ⁇ R A224, R A231 ⁇ R A238, R A241 ⁇ R A248 and R A251 ⁇ R A258 are each independently a hydrogen atom , Alkyl group, cyclic alkyl group, alkoxy group, hydroxy group, cyano group, alkyl halide group, or halogen atom, and LA231 and LA241 are independently single-bonded, carbonyl group, sulfonyl group and divalent, respectively.
  • R A211 ⁇ R A214 at least one of R a 221 ⁇ R A224 one, at least one of R A231 ⁇ R A238, at least one of R a 241 ⁇ R A248, and, at least one of R A251 ⁇ R A258 is between a 1 in the formula (1-1) It may be a binding site, and each independently represents a binding site with another structure.
  • ⁇ 6> The curing according to any one of ⁇ 1> to ⁇ 5>, wherein A 1 contains a group containing an ethylenically unsaturated bond, a cyclic ether group, a methylol group or an alkoxymethyl group as the polymerizable group.
  • ⁇ 7> The curable resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the photosensitizer is a photopolymerization initiator.
  • ⁇ 8> The curable resin composition according to any one of ⁇ 1> to ⁇ 7>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 9> A cured film obtained by curing the curable resin composition according to any one of ⁇ 1> to ⁇ 8>.
  • ⁇ 10> A laminate having two or more cured films according to ⁇ 9> and having a metal layer between any of the cured films.
  • a method for producing a cured film which comprises a film forming step of applying the curable resin composition according to any one of ⁇ 1> to ⁇ 8> to a substrate to form a film.
  • the method for producing a cured film according to ⁇ 11> which comprises a step of heating the film at 50 to 450 ° C.
  • ⁇ 13> A semiconductor device having the cured film according to ⁇ 9> or the laminate according to ⁇ 10>.
  • X 1 represents a tetravalent group containing an aromatic hydrocarbon group
  • the bonding sites with the four carbonyl groups in the formula (1-1) in X 1 are all aromatic.
  • Group hydrocarbon groups Y 1 represents an n + divalent group containing an aromatic hydrocarbon group
  • a 1 represents a group containing a polymerizable group
  • G 1 and G 2 are independent hydrogen atoms or groups. It represents a substituent and n represents an integer of 1 or more.
  • the resin according to ⁇ 14> which has an acid value of 0 to 2.0 mmol / g. ⁇ 16>
  • the method for producing a resin according to ⁇ 14> or ⁇ 15> A compound A having two nitro groups, at least one reactive group and an aromatic hydrocarbon group is reacted with a group capable of forming a bond with the reactive group and a compound B having a polymerizable group.
  • a curable resin composition having excellent chemical resistance of the obtained cured film, a cured film obtained by curing the curable resin composition, a laminate containing the cured film, and the curing A method for producing a film and a semiconductor device including the cured film or the laminate are provided. Further, according to another embodiment of the present invention, a novel resin and a method for producing the above resin are provided.
  • the present invention is not limited to the specified embodiments.
  • the numerical range represented by 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-substitution 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 an electron beam and an ion beam. 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 “methacryl”, or
  • Either, and "(meth) acryloyl” means both “acryloyl” and “methacryloyl”, 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 curable resin composition layer, the direction from the base material to the curable resin composition layer. Is called “upper”, and the opposite direction is called “lower”. It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "upward" direction in the present specification may be different from the vertical upward direction.
  • the composition may contain, as each component contained in the composition, two or more kinds of compounds corresponding to the component. Unless otherwise specified, 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). In the present specification, 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”) contains a resin containing a repeating unit represented by the following formula (1-1) and a photosensitizer.
  • the resin contains 50 mol% or more of the repeating units represented by the following formula (1-1) with respect to all the repeating units of the resin.
  • a resin containing 50 mol% or more of the repeating unit represented by the formula (1-1) with respect to all the repeating units of the resin is also referred to as a “specific resin”.
  • X 1 represents a tetravalent group containing an aromatic hydrocarbon group, and all of the bonding sites with the four carbonyl groups in formula (1-1) in X 1 are aromatic hydrocarbons. It is a hydrogen group, Y 1 represents an n + divalent group containing an aromatic hydrocarbon group, A 1 represents a group containing a polymerizable group, and G 1 and G 2 are independent hydrogen atoms or substituents, respectively. Represents, and n represents an integer of 1 or more.
  • the curable resin composition of the present invention may be a negative type curable resin composition or a positive type curable resin composition, but is preferably a negative type curable resin composition. ..
  • the negative type curable resin composition refers to a composition in which an unexposed portion (non-exposed portion) is removed by a developing solution when a layer formed from the curable resin composition is exposed.
  • the positive type curable resin composition refers to a composition in which an exposed portion (exposed portion) is removed by a developing solution when a layer formed from the curable resin composition is exposed.
  • the curable resin composition of the present invention is excellent in chemical resistance of the obtained cured film.
  • the mechanism by which the above effect is obtained is not clear, but it is presumed as follows.
  • the curable resin composition of the present invention contains a resin having a repeating unit represented by the above formula (1-1) (hereinafter, also referred to as “specific resin”).
  • specific resin a resin having a repeating unit represented by the above formula (1-1)
  • the bonding sites with the four carbonyl groups in X 1 are all aromatic hydrocarbon groups
  • Y 1 contains a polymerizable group.
  • the obtained cured film has a polymerizable group.
  • the density of the crosslinked structure formed by the crosslinking increases. It is presumed that due to the increase in the crosslink density, a cured film having excellent chemical resistance can be obtained according to the curable resin composition of the present invention.
  • the cured film has excellent chemical resistance, for example, another curable resin composition containing a solvent is further applied and cured on the cured film obtained by curing the curable resin composition of the present invention, and the laminated body is cured. It is considered that the dissolution of the cured film is suppressed even if the cured film comes into contact with the developing solution or other curable resin composition in the case of producing.
  • a polar solvent such as dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP)
  • an alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution
  • TMAH tetramethylammonium hydroxide
  • the polyimide precursor is cyclized (imidized) by heating or the like and used as a resin such as polyimide.
  • the amount of the polymerizable group introduced at the position corresponding to G 1 or G 2 in the formula (1-1) is reduced, or the position corresponding to G 1 or G 2 is reduced. It is also possible to adopt a mode in which a polymerizable group is not introduced into the product. Therefore, it is presumed that the specific resin is easier to cyclize than the conventionally used polyimide resin, and the ring closure rate is improved. In addition, it is presumed that cyclization is likely to occur even when heated at a low temperature. Further, for example, it is possible to design to introduce a group other than the polymerizable group (for example, a polyalkyleneoxy group) at the position corresponding to the above G 1 or G 2.
  • a group other than the polymerizable group for example, a polyalkyleneoxy group
  • Patent Documents 1 and 2 do not describe or suggest a resin containing 50 mol% or more of the repeating unit represented by the formula (1-1) with respect to all the repeating units of the resin. Further, the curable resin composition in Patent Document 1 or 2 has a problem that the chemical resistance of the obtained cured film is low.
  • the curable resin composition of the present invention contains a specific resin.
  • the specific resin contains 50 mol% or more of the repeating units represented by the formula (1-1) with respect to all the repeating units of the specific resin.
  • the specific resin may have a repeating unit represented by the formula (1-1) in the side chain, but preferably has a repeating unit represented by the formula (1-1) in the main chain.
  • the "main chain” refers to the relatively longest binding chain among the molecules of the polymer compound constituting the resin
  • the "side chain” refers to other binding chains.
  • X 1 represents a tetravalent group containing an aromatic hydrocarbon group, and all of the bonding sites with the four carbonyl groups in formula (1-1) in X 1 are aromatic hydrocarbons. It is a hydrogen group.
  • an aromatic hydrocarbon group for X 1 is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms More preferably, it is a group obtained by removing four hydrogen atoms from the benzene ring or the naphthalene ring, and particularly preferably, it is a group obtained by removing four hydrogen atoms from the benzene ring.
  • the aromatic hydrocarbon group may have a substituent as long as the effect of the present invention can be obtained.
  • substituents include an alkyl group, a cyclic alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkyl halide group, a hydroxy group, a carboxy group, a sulfo group, a halogen atom and the like.
  • these groups when simply describing "aliphatic hydrocarbon group”, “saturated aliphatic hydrocarbon group”, “alkyl group”, “alkylene group”, etc., these groups have a branched structure and a cyclic structure unless otherwise specified. It may have at least one of the structures.
  • alkyl group includes a linear alkyl group, a branched alkyl group, a cyclic alkyl group, and an alkyl group represented by a combination thereof, unless otherwise specified.
  • Bonds 1a to 4a may each be bonded to the same aromatic hydrocarbon group among the aromatic hydrocarbon groups contained in X 1, or may be bonded to different aromatic hydrocarbon groups.
  • the existence of two binding sites at adjacent positions in a ring structure means that a ring member in the ring structure in which a certain binding site is present and a ring member in the ring structure in which another binding site is present are defined. It means that it is an adjacent ring member in the ring structure.
  • the adjacent position is the ortho position.
  • X 1 preferably contains at least one structure selected from the group consisting of the structures represented by the following formulas (A-1) to (A-5), and the following formula is preferable. It is more preferable that the structure is 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 independent hydrogen atoms.
  • LA31 and LA41 are independently single-bonded, carbonyl group, sulfonyl group, and divalent, respectively.
  • saturated hydrocarbon group, a divalent unsaturated hydrocarbon group, a hetero atom, a heterocyclic group, or, a halogenated alkylene group, two of R A11 ⁇ R A14, two of R A21 ⁇ R A24 , 2 of RA31 to RA38 , 2 of RA41 to RA48 , and 2 of RA51 to RA58 are binding sites with the carbonyl group in the above formula (1-1).
  • * represents the site of connection with other structures independently.
  • RA11 to RA14 are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, cyclic alkyl groups having 3 to 12 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, and hydroxy. It is preferable to represent a group, a cyano group, an alkyl halide group having 1 to 3 carbon atoms, or a halogen atom, and from the viewpoint of solvent solubility, a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or 1 to 6 carbon atoms.
  • an alkoxy group of 6 and an alkyl group having 1 to 3 carbon atoms are 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 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.
  • two * in the formula (A-1) and two of RA11 to RA14 are binding sites with the carbonyl group in the above formula (1-1), and two.
  • *, RA12 and RA14 are binding sites with the carbonyl group in the above formula (1-1). Further, in the formula (A-1), it is preferable that the binding site between the binding 1a and the binding 2a and the binding site between the binding 3a and the binding 4a are all located in the ortho position.
  • R A21 ⁇ R A24 are each synonymous with R A11 ⁇ R A14 in formula (A-1), a preferable embodiment thereof is also the same. Further, it is preferable that two * in the formula (A-2) and two of RA21 to RA24 , a total of four, are binding sites with the carbonyl group in the above formula (1-1), and two. It is more preferable that *, RA22 and RA24 are binding sites with the carbonyl group in the above formula (1-1). Further, in the formula (A-2), it is preferable that the binding site between the binding 1a and the binding 2a and the binding site between the binding 3a and the binding 4a are all located in the ortho position.
  • 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.
  • two * in the formula (A-3) and two of RA31 to RA38 , a total of four, are binding sites with the carbonyl group in the above formula (1-1), and two.
  • R A31 ⁇ R A34, and, more preferably one of R A35 ⁇ R A38 is a bonding site with the carbonyl group in the formula (1-1), two *, R It is more preferable that A31 and RA38 are binding sites for the carbonyl group in the above formula (1-1). Further, in the formula (A-3), it is preferable that the binding site between the binding 1a and the binding 2a and the binding site between the binding 3a and the binding 4a are all located in the ortho position.
  • LA31 is a single bond, a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, a divalent unsaturated hydrocarbon group having 5 to 24 carbon atoms, —O—, —S.
  • a halogenated alkylene group having 1 to 6 carbon atoms is preferable, and a single bond, a saturated hydrocarbon group having 1 to 6 carbon atoms, an -O- or a heterocyclic group. Is preferable, and it is more preferable to represent a single bond or —O—.
  • the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
  • the divalent unsaturated hydrocarbon group may be a divalent aliphatic unsaturated hydrocarbon group or a divalent aromatic hydrocarbon group, but is a divalent aromatic hydrocarbon. It is preferably a group.
  • the heterocyclic group for example, a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocycle is preferable, and a group obtained by removing two hydrogen atoms from an aliphatic or aromatic heterocycle is preferable.
  • a group obtained by removing two hydrogen atoms from a ring structure such as a tetrahydrofuran ring, a tetrahydrothiophene ring, a pyrrole ring, a furan ring, a thiophene ring, a piperidine ring, a tetrahydropyran ring, a pyridine ring, or a morpholin ring.
  • These heterocycles may further form a fused ring with another heterocycle or 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, L A41 have the same meanings as R A31 ⁇ R A38, L A31 in formula (A-3), preferable embodiments thereof are also the same. Further, it is preferable that two * in the formula (A-4) and two of RA41 to RA48 , a total of four, are binding sites with the carbonyl group in the above formula (1-1), and two. It is more preferable that one of R A41 to R A44 and one of R A45 to R A48 are the binding sites with the carbonyl group in the above formula (1-1), and two * and R It is more preferable that A41 and RA48 are binding sites with the carbonyl group in the above formula (1-1). Further, in the formula (A-4), it is preferable that the binding site between the binding 1a and the binding 2a and the binding site between the binding 3a and the binding 4a are all located in the ortho position.
  • R A51 ⁇ R A58 are each synonymous with R A11 ⁇ R A14 in formula (A-1), a preferable embodiment thereof is also the same. Further, it is preferable that a total of four of the two * in the formula (A-5) and two of RA51 to RA58 are binding sites with the carbonyl group in the above formula (1-1), and two *, one of R A51 ⁇ R A54, and, more preferably one of R A55 ⁇ R A58 is a bonding site with the carbonyl group in the formula (1-1), two *, R A52 and It is more preferable that RA56 is a binding site with a carbonyl group in the above formula (1-1). Further, in the formula (A-5), it is preferable that the binding site between the binding 1a and the binding 2a and the binding site between the binding 3a and the binding 4a are all located in the ortho position.
  • X 1 is preferably a group represented by the following formula (X-1) or the following formula (X-2).
  • RX11 and RX12 are synonymous with RA11 and RA13 in formula (A-1), respectively, and preferred embodiments are also the same.
  • formula (X-1) or formula (X-2) of the two * one is the binding site with the above-mentioned bond 1a and the other is the binding site with the above-mentioned bond 2a.
  • tetravalent group represented by X 1 in the formula (1-1) include a tetracarboxylic acid residue 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 is synonymous with X 1 in equation (1-1).
  • tetracarboxylic dianhydride examples include pyromellitic acid, pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4 , 4'-diphenylsulfide tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylmethanetetracarboxylic dianhydride, 2,2', 3,3'-diphenylmethanetetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid Dichloride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxy
  • DAA-1 to DAA-5 tetracarboxylic dianhydrides
  • DAA-5 tetracarboxylic dianhydrides
  • G 1 and G 2 are independent substituents.
  • the substituent in G 1 and G 2 include a group containing a polymerizable group or an organic group which may contain a hetero atom, and is poly from the viewpoint of chemical resistance, developability and solvent solubility of a specific resin.
  • a group containing an alkyleneoxy group is preferable.
  • Groups containing polymerizable groups As the polymerizable group contained in the group containing a polymerizable group in G 1 or G 2 , a group containing an ethylenically unsaturated group, a cyclic ether group, a methylol group or an alkoxymethyl group is preferable, and a vinyl group and a (meth) allyl group are preferable. Groups, (meth) acrylamide groups, (meth) acryloxy groups, maleimide groups, vinylphenyl groups, epoxy groups, oxetanyl groups, methylol groups or alkoxymethyl groups are more preferred, and (meth) acryloxy groups, (meth) acrylamide groups, epoxys.
  • Groups, methylol groups or alkoxymethyl groups are more preferred.
  • the number of polymerizable groups contained in the group containing the polymerizable group is 1 or more, preferably 1 to 15, more preferably 1 to 10, and 1 to 5. More preferably, 1 or 2 is particularly preferable, and 1 is most preferable.
  • the group containing the above-mentioned polymerizable group is preferably a vinyl group, an allyl group, a (meth) acryloyl group, or a group represented by the following formula (III).
  • R200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and a hydrogen atom or 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.
  • alkylene group —CH 2 CH (OH) CH 2 ⁇
  • ethylene group, propylene group, trimethylene group, ⁇ CH 2 CH (OH) CH 2 ⁇ are more preferable.
  • R 200 is a methyl group and R 201 is an ethylene group.
  • * represents a binding site with another structure.
  • Organic groups that may contain heteroatoms are preferably an organic group that does not have a polymerizable group.
  • the hetero atom in the organic group which may contain the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom and the like, and an oxygen atom is preferable.
  • the hetero atom is preferably contained as an ether bond (—O—).
  • the organic group which may contain a heteroatom is preferably an organic group having 1 to 30 carbon atoms which may contain a heteroatom, and preferably an organic group having 2 to 20 carbon atoms which may contain a heteroatom. More preferred.
  • the organic group that may contain the heteroatom is preferably an organic group having a polyalkyleneoxy group.
  • the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
  • the alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
  • the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
  • the carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6.
  • 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 20, more preferably 2 to 10, further preferably 2 to 5, and particularly preferably 2 to 4.
  • 2 is most preferred.
  • 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 bonded to the propyleneoxy group of the above is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further 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.
  • the organic group having a polyalkyleneoxy group is preferably a group represented by the following formula (PO-1).
  • R P1 each independently represent an alkylene group
  • R P2 represents a monovalent organic group
  • n represents an integer of 2 or more
  • L P1 is connected a single bond or a divalent
  • * represents a binding site with an oxygen atom to which G 1 or G 2 in the formula (1-1) is bonded.
  • R P1 each independently is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, an ethylene group (-CH 2 -CH 2- ) or propylene group (-CH 2- CH (CH 3 )-or-CH (CH 3 ) -CH 2- ) is more preferable, and an ethylene group is further preferable.
  • RP2 represents a monovalent organic group, preferably an alkyl group, an aromatic hydrocarbon group, an aralkyl group, or a group containing a polymerizable group, and is preferably an alkyl group. Is more preferable.
  • alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 2 to 4 carbon atoms is more preferable, and an ethyl group is further preferable.
  • aromatic hydrocarbon group an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is further preferable.
  • an aralkyl group having 7 to 30 carbon atoms is preferable, an aralkyl group having 7 to 20 carbon atoms is more preferable, and a benzyl group is more preferable.
  • the polymerizable group contained in the above-mentioned group containing a polymerizable group an ethylenically unsaturated group, a cyclic ether group, a methylol group or a group containing an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group and a (meth) acrylamide group are preferable.
  • n is preferably an integer of 2 to 20, more preferably an integer of 2 to 10, further preferably an integer of 2 to 5, particularly preferably an integer of 2 to 4, and most preferably 2.
  • LP1 represents a single bond or a divalent linking group, and a single bond is preferable.
  • divalent linking group a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N- , or a group in which two or more of these are bonded is preferable, and a hydrocarbon group, an ether bond, or a carbonyl group is preferable.
  • a group, -NR N- , or a group in which two or more of these are bonded is more preferable, and a hydrocarbon group, an ester bond, an amide bond, a urethane bond, a urea bond, or a group in which two or more of these are combined is further preferable.
  • the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
  • the hydrocarbon group represented by L P1 saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or, a group represented by a combination thereof
  • the number of carbon atoms More preferably, it is a saturated aliphatic hydrocarbon group of 1 to 10, a group obtained by removing two or more hydrogen atoms from the benzene ring, or a group represented by a bond thereof.
  • the organic group which may contain a hetero atom may be a hydrocarbon group substituted with a halogen atom.
  • the halogen atom in the hydrocarbon group substituted with the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • the hydrocarbon group an alkyl group or an aromatic hydrocarbon group is preferable, and an alkyl group is more preferable.
  • an alkyl group having 1 to 30 carbon atoms is preferable, an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 2 to 4 carbon atoms is further preferable.
  • an aromatic hydrocarbon group an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, and a phenyl group is further preferable. That is, the hydrocarbon group substituted with a halogen atom is preferably an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. By including the hydrocarbon group substituted with a halogen atom as the G 1 or the G 2 , the film strength of the obtained cured film is improved.
  • the G 1 or G 2 may be another substituent.
  • substituents include hydrocarbon groups having an acid group and the like.
  • hydrocarbon group having an acid group include an alkyl group having an acid group, an aromatic hydrocarbon group having an acid group, and an aralkyl group having an acid group.
  • alkyl group in the alkyl group having an acid group an alkyl group having 1 to 30 carbon atoms is preferable, an alkyl group having 1 to 20 carbon atoms is more preferable, and an alkyl group having 1 to 10 carbon atoms is further preferable.
  • Examples of the acid group in the alkyl group having an acid group include a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group and the like, and a carboxy group is preferable.
  • a carboxy group an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is further preferable.
  • As the aralkyl group having an acid group an aralkyl group having 7 to 30 carbon atoms is preferable, an aralkyl group having 7 to 20 carbon atoms is more preferable, and a benzyl group is more preferable.
  • Examples of the acid group in the aromatic hydrocarbon group having the acid group or the aralkyl group having the acid group include a phenolic hydroxy group, a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group and the like, and phenol.
  • a sex hydroxy group or a carboxy group is preferable, and a phenolic hydroxy group is more preferable.
  • an aromatic hydrocarbon group having an acid group or an aralkyl group having an acid group is preferable, and an aromatic having a phenolic hydroxy group is preferable.
  • a group hydrocarbon group or an aralkyl group having a phenolic hydroxy group is more preferable, and a phenyl group having a phenolic hydroxy group or a benzyl group having a phenolic hydroxy group is further preferable.
  • an ethylenically unsaturated group with respect to the total molar amount of G 1 and G 2 in the repeating unit represented by the formula (1-1) contained in the specific resin is preferably 0 to 30%.
  • the above ratio is preferably 0 to 10%, more preferably 0 to 5%, and even more preferably 0 to 3%.
  • the above ratio is preferably 10 to 30%, more preferably 15 to 30%.
  • the ratio of the molar amount of the G 1 or the G 2 which is an organic group having 1 to 30 carbon atoms which may contain a hetero atom to the amount is preferably 20 to 100%.
  • the lower limit of the above ratio is preferably 30% or more, more preferably 40% or more, further preferably 50% or more, and particularly preferably 60% or more. It is preferably 70% or more, and most preferably 70% or more.
  • the upper limit of the above ratio is preferably 95% or less, more preferably 90% or less, further preferably 85% or less, and more preferably 80% or less. It is particularly preferable, and most preferably 70% or less.
  • the ratio of the molar amount of the G 1 or the G 2 which is an organic group having a polyalkylene oxy group to the amount is preferably 20 to 100%.
  • the organic group having a polyalkyleneoxy group in the above ratio description may be an organic group further containing a polymerizable group as long as it is an organic group containing a polyalkyleneoxy group, but contains a polyalkyleneoxy group. Moreover, it is preferably an organic group having no polymerizable group.
  • the lower limit of the above ratio is preferably 30% or more, more preferably 40% or more, further preferably 50% or more, and particularly preferably 60% or more. It is preferably 70% or more, and most preferably 70% or more. From the viewpoint of chemical resistance, the upper limit of the above ratio is preferably 95% or less, more preferably 90% or less, further preferably 85% or less, and more preferably 80% or less. It is particularly preferable, and most preferably 70% or less.
  • Y 1 represents an n + divalent group containing an aromatic hydrocarbon group.
  • Aromatic hydrocarbon group for Y 1 is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, 2 or more benzene rings It is more preferable that the group has the hydrogen atom removed from the group, and it is particularly preferable that the group has 3 or more hydrogen atoms removed from the benzene ring.
  • binding site of the two nitrogen atoms according to formula (1-1) is preferably either an aromatic hydrocarbon group.
  • binding site of the A 1 is preferably either an aromatic hydrocarbon group. That is, it is preferable that A 1 is directly bonded to the aromatic hydrocarbon ring structure contained in Y 1.
  • Y 1 preferably contains at least one structure selected from the group consisting of the structures represented by the following formulas (A2-1) to (A2-5), and the above formulas (A2-1) to Y1. It is more preferable that the structure is at least one selected from the group consisting of the structures represented by the formula (A2-5).
  • R A211 ⁇ R A214, R A221 ⁇ R A224, R A231 ⁇ R A238, R A241 ⁇ R A248 and R A251 ⁇ R A258 are each independently a hydrogen atom , Alkyl group, cyclic alkyl group, alkoxy group, hydroxy group, cyano group, alkyl halide group, or halogen atom, and LA231 and LA241 are independently single-bonded, carbonyl group, sulfonyl group and divalent, respectively.
  • R A211 ⁇ R A214 at least one of R a 221 ⁇ R A224 one, at least one of R A231 ⁇ R A238, at least one of R a 241 ⁇ R A248, and, at least one of R A251 ⁇ R A258 is between a 1 in the formula (1-1) It may be a binding site, and each independently represents a binding site with another structure.
  • Y 1 preferably contains a structure represented by any of the formulas (A2-1) to (A2-4), and is preferably the formula (A2-2) or the formula (A2-2). It is more preferable to include the structure represented by any one of A2-4).
  • R A211 to R A214 , R A221 to R A224 , R A231 to R A238 , R A241 to R A248 and R A251 to R A258 are the above formulas (1-).
  • At least one of R A211 ⁇ R A214 is preferably a binding site to the A 1 in the formula (1-1), one of the A of R A211 ⁇ R A214 more preferably a binding site with 1, it is preferred that R A213 is a bond site of the a 1.
  • at least one of R A 221 ⁇ R A224 is preferably a binding site to the A 1 in the formula (1-1), one of the A of R A221 ⁇ R A224 more preferably a binding site with 1, it is preferred that R a 223 is a binding site for the a 1.
  • At least one of R A231 ⁇ R A238, is preferably a binding site to the A 1 in the formula (1-1), two of R A231 ⁇ R A238, the more preferably a binding site to the a 1, bract one of R A231 ⁇ R A234, more preferably two one meter of the R A235 ⁇ R A238 is a binding site to the a 1, R A231 and two of R A238, it is particularly preferably a binding site between the a 1.
  • At least one of R A 241 ⁇ R A248, is preferably a binding site to the A 1 in the formula (1-1), two of R A241 ⁇ R A248, the more preferably a binding site to the a 1, bract one of R A241 ⁇ R A244, more preferably two one meter of the R A245 ⁇ R A248 is a binding site to the a 1, R A241 and two of R A248, it is particularly preferably a binding site between the a 1.
  • At least one of R A251 ⁇ R A258, is preferably a binding site to the A 1 in the formula (1-1), two of R A251 ⁇ R A258, the more preferably a binding site to the a 1, bract one of R A251 ⁇ R A254, more preferably two one meter of the R A255 ⁇ R A258 is a binding site to the a 1, R A253 and two of R A257, it is particularly preferably a binding site between the a 1.
  • each of the two *'s is a binding site with a nitrogen atom to which Y 1 in formula (1-1) binds. That is, the two nitrogen atoms to which Y 1 in the formula (1-1) is bonded can be directly bonded to the positions represented by two * in the formulas (A2-1) to (A2-5). preferable.
  • Y 1 is preferably a group represented by the following formula (Y-1) or (Y-2).
  • R Y11 , R Y12, R Y13 each has the same meaning as R A211, R A212 and R A214 in formula (A2-1), preferable embodiments thereof are also the same.
  • R Y21 ⁇ R Y26 each of R Y21 ⁇ R Y26, have the same meanings as R A242 ⁇ R A247 in formula (A2-4), preferable embodiments thereof are also the same.
  • the specific resin contains at least one structure selected from the group in which the above-mentioned X 1 in the formula (1-1) consists of the structures represented by the formulas (A-1) to (A-5). Moreover, it is preferable that Y 1 contains at least one structure selected from the group consisting of the structures represented by the formulas (A2-1) to (A2-5). Further, the specific resin has at least one structure selected from the group in which the above-mentioned X 1 in the formula (1-1) consists of the structures represented by the formulas (A-1) to (A-5). It is more preferable that Y 1 is at least one structure selected from the group consisting of the structures represented by the formulas (A2-1) to (A2-5). The preferred embodiment of the structure represented by each of these equations is as described above.
  • a 1 represents a group containing a polymerizable group.
  • a group containing an ethylenically unsaturated group, a cyclic ether group, a methylol group or an alkoxymethyl group is preferable, and a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloxy group and a maleimide group are preferable.
  • a group, a vinylphenyl group, an epoxy group, an oxetanyl group, a methylol group or an alkoxymethyl group is more preferable, and a (meth) acryloxy group, a (meth) acrylamide group, an epoxy group, a methylol group or an alkoxymethyl group is further preferable.
  • the number of polymerizable groups contained in A 1 is 1 or more, preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5. It is particularly preferable to have one or two, and most preferably one.
  • a 1 is preferably a group represented by the following formula (P-1).
  • L 1 represents a single bond or m + 1 valent linking group
  • a 2 represents a polymerizable group
  • m represents an integer of 1 or more
  • * represents a binding site with Y 1. ..
  • L 1 is preferably a single bond, or a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N- , or a group in which two or more of these are bonded, preferably a single bond.
  • a bond, or a hydrocarbon group, an ether bond, a carbonyl group, -NR N- , or a group in which two or more of these are bonded is more preferable.
  • the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
  • the hydrocarbon group represented by L 1, saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or, a group represented by a combination thereof
  • the number of carbon atoms More preferably, it is a saturated aliphatic hydrocarbon group of 1 to 10, a group obtained by removing two or more hydrogen atoms from the benzene ring, or a group represented by a bond thereof.
  • a 2 is 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, a methylol group or an alkoxymethyl group.
  • Groups are preferred, with (meth) acryloxy groups, (meth) acrylamide groups, epoxy groups, methylol groups or alkoxymethyl groups being more preferred.
  • m is preferably an integer of 1 to 15, more preferably an integer of 1 to 10, further preferably an integer of 1 to 5, and 1 or 2. Is particularly preferable, and 1 is most preferable.
  • a 1 is preferably a group represented by the following formula (P-2) or formula (P-3).
  • a 2 represents a polymerizable group, and * represents a binding site with Y 1.
  • a 2 has the same meaning as A 2 in Formula (P-1), a preferable embodiment thereof is also the same.
  • a 2 represents a polymerizable group, and L 2 is a hydrocarbon group or a hydrocarbon group and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N- , or.
  • a 2 has the same meaning as A 2 in Formula (P-1), a preferable embodiment thereof is also the same.
  • L 2 is preferably a hydrocarbon group, a (poly) alkyleneoxy group, or a group represented by a combination thereof.
  • the hydrocarbon group is preferably an alkylene group, a divalent aromatic hydrocarbon group, or a group represented by a combination thereof, and more preferably an alkylene group.
  • the (poly) alkyleneoxy group means an alkyleneoxy group or a polyalkyleneoxy group.
  • the polyalkyleneoxy group means a group in which two or more alkyleneoxy groups are directly bonded.
  • the alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
  • the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
  • an alkylene group having 1 to 30 carbon atoms is preferable, an alkylene group having 1 to 20 carbon atoms is more preferable, and an alkylene group having 1 to 10 carbon atoms is further preferable.
  • an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, an aromatic hydrocarbon group having 6 to 20 carbon atoms is more preferable, a phenylene group or a naphthylene group is more preferable, and a phenylene group is preferable. Especially preferable.
  • alkylene group in the (poly) alkyleneoxy group an alkylene group having 2 to 10 carbon atoms is preferable, an alkylene group having 2 to 4 carbon atoms is more preferable, an ethylene group or a propylene group is more preferable, and an ethylene group is further preferable. ..
  • the number of alkyleneoxy groups contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, further preferably 2 to 5, and particularly preferably 2 to 4. preferable.
  • Z 1 represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond, or a carbonate bond, and an ester bond, a urethane bond, a urea bond, or an amide bond is more preferable.
  • the direction of these bonds is not limited.
  • the binding site with L 2 in Z 1 may be a carbon atom in the ester bond or an oxygen atom.
  • n represents an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and further preferably an integer of 1 to 4. It is preferably 1 or 2, and most preferably 1. Further, when n is an integer of 2 or more, n pieces of A 1 may each be the same or may be different.
  • the structure represented by Y 1 , A 1 and n in the formula (1-1) is preferably a structure derived from a diamine.
  • a diamine represented by the following formula (DA-1) is preferable, and specifically, diamines (AA-1) to diamines (AA-8) synthesized in Examples described later are preferable.
  • DA-1 diamines (AA-1) to diamines (AA-8) synthesized in Examples described later are preferable.
  • Y 1 , A 1 , and n are synonymous with Y 1 , A 1 , and n in formula (1-1), respectively, and the preferred embodiments are also the same.
  • the content of the repeating unit represented by the formula (1-1) in the specific resin is 50 mol% or more, more preferably 60 mol% or more, and 70 mol% or more, based on all the repeating units of the specific resin.
  • the above is more preferable, and 80 mol% or more is particularly preferable.
  • the upper limit of the content is not particularly limited, and may be 100 mol% or less.
  • the content of the repeating unit represented by the formula (1-1) in the specific resin is preferably 50% by mass or more, more preferably 60% by mass or more, based on the mass of the specific resin. It is more preferably 70% by mass or more, and particularly preferably 80% by mass or more.
  • the upper limit of the content is not particularly limited, and may be 100% by mass or less.
  • the specific resin may contain one type of repeating unit represented by the formula (1-1) alone, or may contain two or more types of repeating units represented by the formula (1-1) having different structures.
  • the total content of the repeating units represented by the formula (1-1) contained in the specific resin is , It is preferable that the content is within the above range.
  • the specific resin may further contain other repeating units.
  • the other repeating unit include a repeating unit represented by the following formula (1).
  • the repeating unit corresponding to the repeating unit represented by the above formula (1-1) shall not correspond to the repeating unit represented by the following formula (1).
  • the specific resin preferably contains a repeating unit represented by the following formula (1) in the main chain.
  • a A1 and A A2 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 independently represents a hydrogen atom or a monovalent organic group.
  • a A1 and A A2 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 are polymerizable. More preferably, it contains a group.
  • the polymerizable group in R 113 or R 114 include the same groups as the polymerizable group in A 1 in the above formula (1-1).
  • the structure of R 115 is preferably the same as that of X 1 in the formula (1-1).
  • the preferred embodiment of R 115 is the same as the preferred embodiment of X 1 described above.
  • the binding site with the four carbonyl groups in the formula (1-1) may have an aliphatic hydrocarbon ring structure.
  • examples of R 115 include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride.
  • Anhydrous, bicyclooctene-2,3,5,6-tetracarboxylic dianhydride, 5- (2,5-dioxohydrocarbon-3yl) -3-methylcyclohexene-1,2-dicarboxylic acid anhydride ( DOCDA), 4- (2,5-dioxohydrocarbon-3-yl) -tetraline-1,2-dicarboxylic acid anhydride and the like can be mentioned.
  • R 111 preferably has a structure containing no polymerizable group.
  • R 111 has an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or at least one of these groups bonded to at least one of an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, and -NR N- . It is preferably a group.
  • RN is as described above.
  • As the aliphatic hydrocarbon group 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.
  • R 111 is preferably a group containing an aliphatic hydrocarbon ring group or an aromatic hydrocarbon ring group, and is preferably a group containing an aromatic hydrocarbon ring group. More preferred.
  • R 111 in the formula (1) is preferably represented by ⁇ Ar 0 ⁇ L 0 ⁇ Ar 0 ⁇ from the viewpoint of the flexibility of the obtained cured film.
  • 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.
  • L 0 has the same meaning as LA 31 in the above formula (A-3), and the preferred embodiment is also the same.
  • 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 or 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. * Each independently represents a binding site with another structure.
  • R 111 in the formula (1) preferably has a structure derived from a diamine.
  • the diamine include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane; 1,2- or 1,3-diamino.
  • 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 the diamine is more preferably the diamine and does not contain an aromatic ring.
  • 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 EDR-148, Jeffamine® 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.
  • Examples of the diamine giving the structure of the above formula (51) or (61) include dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, and the like. Examples thereof include 2,2'-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.
  • diamines can also be preferably used.
  • a diamine having a siloxane structure such as bis (3-aminopropyl) tetramethyldisiloxane or bis (paraaminophenyl) octamethylpentasiloxane may be used as the diamine component. Good.
  • the total content of the repeating units represented by the formula (1) in the specific resin is not particularly limited, but is preferably 30% by mass or less, and preferably 20% by mass or less, based on the total mass of the specific resin. More preferably, it is 10% by mass or less.
  • the lower limit of the total content is not particularly limited, and may be 0% by mass or more.
  • one aspect of the specific resin is a mode that does not substantially contain the repeating unit represented by the formula (1).
  • the total content of the repeating units represented by the formula (1) is preferably 5% by mass or less, more preferably 3% by mass or less, based on the total mass of the specific resin.
  • the specific resin may contain one type of repeating unit represented by the formula (1) alone, or may contain two or more types of repeating units represented by the formula (1) having different structures. When the specific resin contains two or more repeating units represented by the formula (1) having different structures, the total content of the repeating units represented by the formula (1) contained in the specific resin is the above-mentioned content. It is preferable that it is included in the range of.
  • the terminal of the specific resin is not particularly limited, but in order to improve the storage stability of the composition, the terminal is an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactive ester compound. It may be sealed with. Of these end-capping agents, it is preferable to use monoalcohol, phenol, thiol, thiophenol, and monoamine.
  • Preferred compounds of monoalcohols include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, flufuryl alcohol, and isopropanol.
  • Preferred compounds of phenols include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol and the like.
  • Examples of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-.
  • sealing agents for amino groups include carboxylic acid anhydride, carboxylic acid chloride, carboxylic acid bromide, sulfonic acid chloride, sulfonic acid anhydride, sulfonic acid carboxylic acid anhydride and the like, and carboxylic acid anhydride and carboxylic acid chloride are more preferable. preferable.
  • Preferred compounds of the carboxylic acid anhydride include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride and the like.
  • Preferred compounds of carboxylic acid chloride include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantancarbonyl chloride. , Heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.
  • 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 200,000, and further preferably 10,000 to 100,000. preferable.
  • the number average molecular weight (Mn) of the specific resin is preferably 800 to 250,000, more preferably 2,000 to 100,000, and even more preferably 4,000 to 50,000.
  • 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 degree of dispersion of the molecular weight of the specific resin is preferably 1.8 or more, more preferably 2.0 or more, and further preferably 2.2 or more.
  • the upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly determined, but for example, 7.0 or less is preferable, 6.5 or less is more preferable, and 6.0 or less is further preferable.
  • the acid value of the specific resin is preferably 0 to 2.0 mmol / g, more preferably 0 to 1.5 mmol / g, and even more preferably 0 to 1.0 mmol / g.
  • 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 refers to the amount (mmol) of acid groups contained in 1 g of the specific resin.
  • the acid group refers to a group 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. Examples of the acid group include a phenolic hydroxy group, a carboxy group, a sulfo group and the like, and a carboxy group is preferable.
  • the molar amount of the polymerizable group (polymerizable base value, unit is mmol / g) contained in 1 g of the specific resin is preferably 0.05 to 10 mmol / g, and is 0.1 to 5 mmol / g. Is more preferable.
  • the polymerizable group is contained in, for example, A 1 , G 1 , G 2 and the like in the repeating unit represented by the formula (1-1).
  • the molar amount of the ethylenically unsaturated bond contained in 1 g of the specific resin is preferably 0.05 to 10 mmol / g, and 0.1 to 0.1 to g. More preferably, it is 5 mmol / g.
  • the specific resin contains a polymerizable group such as a cyclic ether group, a methylol group, or an alkoxymethyl group as a polymerizable group
  • the molar amount of the polymerizable group contained in 1 g of the specific resin is 0.05 to 10 mmol / g. It is preferably 0.1 to 5 mmol / g, and more preferably 0.1 to 5 mmol / g.
  • 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. Further, in the method for producing the specific resin, a diamine is reacted with a tetravalent carboxylic acid compound having a structure in which all four carboxy groups are bonded to an aromatic hydrocarbon group, or a derivative of the above-mentioned tetravalent carboxylic acid compound. It is preferable to include a step of causing the compound (precursor production step).
  • the diamine used in the precursor production step examples include the diamine represented by the above formula (DA-1). Further, by further using the diamine described in the description of the formula (1), the repeating unit represented by the formula (1) can be introduced into the specific resin.
  • the tetravalent carboxylic acid compound used in the precursor production step may be a carboxylic acid dianhydride, or two of the four carboxy groups are modified by esterification, halogenation or the like. It may be a compound having a different structure. Preferably, a compound in which two of the four carboxy groups are esterified can be mentioned. It is preferable that G 1 and G 2 in the above formula (1-1) are introduced by the above esterification.
  • the compound in which two of the above four carboxy groups are esterified is halogenated with a halogenating agent and then reacted with a diamine.
  • the reaction conditions in the precursor production step can be appropriately determined with reference to known esterification conditions.
  • 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-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone.
  • the precursor manufacturing step preferably includes a step of precipitating a solid.
  • the specific resin in the reaction solution can be precipitated in water, and a polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
  • the method for producing the specific resin is a compound A having two nitro groups, at least one reactive group, and an aromatic hydrocarbon group, a group capable of forming a bond with the reactive group, and a polymerizable group.
  • a step of reducing the nitro group in compound C to obtain a diamine having an aromatic hydrocarbon group (diamine production step). ) May be included.
  • the diamine obtained in the diamine production process is used as the diamine in the precursor production process.
  • the reactive group in compound A is not particularly limited, and examples thereof include an amino group, a hydroxy group, and a carboxy group.
  • Compound A preferably has a structure in which two nitro groups and at least one reactive group are directly bonded to the aromatic hydrocarbon group.
  • the group capable of forming a bond with the reactive group in the compound B is not particularly limited, and examples thereof include a hydroxy group, a carboxy group, a carboxylic acid halide group, an epoxy group, and an isocyanate group.
  • the polymerizable group in the compound B include exemplified groups as the group included in A 1 in the above equation (1-1).
  • Compound C is a group obtained by reacting compound A with compound B, and is a compound having two nitro groups and a group containing at least one polymerizable group.
  • a diamine compound is obtained by reducing the nitro group in compound C.
  • known methods such as Beshan reduction, hydrogenation reaction using a metal catalyst such as palladium, platinum and nickel and a hydrogen source such as hydrogen gas and ammonium formate, and a reduction method using metal hydride as a reducing agent are used. be able to.
  • the synthesis of the dinitro compound (A-1) in the examples described later is compound C by reacting compound A 3,5-dinitrobenzoyl chloride with compound B 2-hydroxyethyl methacrylate. This is a reaction for obtaining a dinitro compound (A-1).
  • the synthesis of diamine (AA-1) in the examples described later is a reaction of reducing two nitro groups in the dinitro compound (A-1) which is compound C to obtain diamine (AA-1).
  • the curable resin composition of the present invention contains a photosensitizer.
  • a photosensitizer a photopolymerization initiator is preferable.
  • the curable resin composition of the present invention preferably contains a photopolymerization initiator as the photosensitizer.
  • 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 rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator 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 as the photoradical polymerization initiator.
  • 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.
  • 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.
  • Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are 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).
  • the photoradical polymerization initiator is more preferably an oxime compound.
  • 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-acetoxyiminovtan-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).
  • a 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 Co., Ltd.
  • Daito Chemix Co., Ltd. can be used.
  • 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 benzyldimethylketal 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
  • 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.
  • RI00 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 the formula (II)
  • R I00 R I02 to R I04 are independently alkyl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, or halogen atoms.
  • 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 amount is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a photoacid generator as a photosensitizer.
  • a photoacid generator for example, acid is generated in the exposed part of the curable resin composition layer, the solubility of the exposed part in the developing solution (for example, an alkaline aqueous solution) is increased, and the exposed part becomes A positive relief pattern that is removed by the developer can be obtained.
  • the curable resin composition contains a photoacid generator and a polymerizable compound other than the radically polymerizable compound described later, for example, the cross-linking reaction of the polymerizable compound is caused by the acid generated in the exposed portion. It is also possible to make the exposed portion more difficult to be removed by the developing solution than the non-exposed portion. According to such an aspect, a negative type relief pattern can be obtained.
  • the photoacid generator is not particularly limited as long as it generates an acid by exposure, but is an onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime.
  • onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime.
  • examples thereof include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl sulfonate.
  • the quinonediazide compound includes a polyhydroxy compound in which quinonediazide sulfonic acid is ester-bonded, a polyamino compound in which quinonediazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinonediazide sulfonic acid is ester-bonded and a sulfonamide bond.
  • Examples thereof include those bonded by at least one of the above. In the present invention, for example, it is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.
  • the quinone diazide either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used.
  • the 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
  • the 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
  • a 4-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed.
  • a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group may be contained in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound may be contained. It may be contained.
  • the naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinone diazido sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.
  • Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds of these compounds. Be done.
  • Examples of the onium salt compound or the sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.
  • a commercially available product may be used as the photoacid generator.
  • Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-376, WPAG-370, WPAG-469, WPAG-638, and WPAG-699. (Manufactured by Kojunyaku Co., Ltd.) and the like.
  • the content thereof is preferably 0.1 to 30% by mass, preferably 0.1 to 20% by mass, based on the total solid content of the curable resin composition of the present invention. Is more preferable, and 2 to 15% by mass is further preferable. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more photoacid generators are contained, the total is preferably in the above range.
  • the curable resin composition of the present invention preferably 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 curable resin composition is particularly preferably a compound having two radically polymerizable groups.
  • 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, an amine or a thiol, 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 compounds 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 (commercially available).
  • 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 Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 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 acid value of the radically polymerizable compound having an acid group is preferably 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.
  • the acid value of the radical cross-linking agent having an acid group is preferably 0.1 to 300 mgKOH / g, and particularly preferably 1 to 100 mgKOH / g.
  • the polymerizability is good.
  • the acid value is measured according to the description of JIS K 0070: 1992.
  • the curable resin composition of the present invention it is preferable to use bifunctional metaacrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
  • the compound include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, and PEG200 diacrylate (polyethylene glycol diacrylate having a formula of polyethylene glycol chain).
  • a monofunctional radically polymerizable compound can be preferably used as the radically polymerizable compound.
  • the monofunctional radical polymerizable compound include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth).
  • N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allylglycidyl ether and the like 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 bifunctional or higher-functional polymerizable compound allyl compounds such as diallyl phthalate and triallyl trimellitate may be used.
  • 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 (methylol 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 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).
  • alkylene glycol type epoxy resin such as propylene glycol diglycidyl ether
  • polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether
  • polymethyl (glycidi) examples 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.
  • 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 are BA type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, FA type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), poly.
  • examples thereof include a benzoxazine adduct of a hydroxystyrene resin and a phenol novolac type dihydrobenzoxazine compound. 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 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, cyclic hydrocarbons, sulfoxides, amides, and alcohols.
  • esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -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.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)
  • 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, ethyl 2-alkyl
  • 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, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.
  • ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like are preferable.
  • cyclic hydrocarbons for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.
  • sulfoxides for example, dimethyl sulfoxide is preferable.
  • N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylisobutyramide, 3-methoxy-N, N- Dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide and the like are preferable.
  • Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
  • 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 solvent content 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 preferably 10 to 70% by mass, further preferably 20 to 70% by mass, and even 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 may contain two or more types. When two or more kinds of solvents are contained, the total amount is preferably in the above range.
  • the curable resin composition of the present invention may contain a thermal polymerization initiator, and in particular, a thermal radical polymerization initiator may be contained.
  • 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. By adding the thermal radical polymerization initiator, the polymerization reaction of the specific resin and the polymerizable compound can be allowed to proceed in the heating step described later, so that the chemical resistance can be further improved.
  • thermal radical polymerization initiator examples include the 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 kinds of thermal polymerization initiators are contained, the total amount is preferably in the above range.
  • the curable resin composition of the present invention may contain 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 methylol groups and the like contained in.
  • the specific resin preferably contains a methylol group or an alkoxymethyl 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 when the curable resin composition is applied to the substrate and then dried (prebak: about 70 to 140 ° C.), 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.
  • 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.
  • 0.01 part by mass or more the cross-linking reaction is promoted, so that the mechanical properties and chemical resistance of the cured film can be further improved.
  • 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 may contain another resin (hereinafter, also simply referred to as “other resin”) different from the above-mentioned specific resin.
  • other resins include polyimide precursors of a type different from the specific resin.
  • the polyimide precursor (other resin)
  • the polyimide precursor preferably has a repeating unit represented by the above formula (1).
  • the repeating unit represented by the formula (1) may be one kind, but may be two or more kinds. Further, the structural isomer of the repeating unit represented by the formula (1) may be contained. Further, the polyimide precursor may contain other types of repeating units in addition to the repeating units of the above formula (1).
  • the polyimide precursor in the present invention 50 mol% or more, more 70 mol% or more, particularly 90 mol% or more of all the repeating units are the repeating units represented by the formula (1). Is exemplified. As an upper limit, 100 mol% or less is practical.
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, and further preferably 10,000 to 50,000.
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, and even more preferably 4,000 to 25,000.
  • the degree of dispersion of the molecular weight of the polyimide precursor is preferably 1.5 to 3.5, more preferably 2 to 3.
  • the polyimide precursor is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine.
  • the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent and then reacting it with a diamine.
  • the organic solvent may be one kind or two or more kinds.
  • the organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
  • the polyimide precursor in the reaction solution can be precipitated in water, and the polyimide precursor such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
  • the content of the other resin is preferably 0.01% by mass or more with respect to the total solid content of the curable resin composition. It is more preferably 05% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, and 10% by mass or more. It is even more preferable to have.
  • the content of the other resin in the curable resin composition of the present invention is preferably 80% by mass or less, and preferably 75% by mass or less, based on the total solid content of the curable resin composition. It is more preferably 70% by mass or less, further preferably 60% by mass or less, and even more preferably 50% by mass or less.
  • the content of the other resin may be low.
  • the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less, based on the total solid content of the curable resin composition. It is more preferably 5% by mass or less, and even more preferably 1% by mass or less.
  • the lower limit of the content is not particularly limited, and may be 0% by mass or more.
  • 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 preferably contains an onium salt.
  • 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, and 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 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.
  • R 1 to R 4 each 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 Hammett's substituent constant ⁇ m shows a positive value.
  • ⁇ m is a review 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.
  • the onium salt is an anion.
  • the lower limit of 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 the structure to 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.
  • R 8 to R 10 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 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 each 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 when the curable resin composition contains a polyimide precursor as another resin, 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 carbon atoms). 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) and an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6).
  • ⁇ 10 is more preferable
  • alkoxy group (2 to 24 carbon atoms is 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 preferred, 3 to 12 is more preferred), aryloxy groups (6 to 22 carbons are preferred, 6 to 18 are more preferred, 6 to 12 are even more preferred), or arylalkyloxy groups (7 to 12 carbons).
  • 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more 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), 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, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
  • 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, still more preferably 1 to 3 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
  • 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is even more preferable), and a hydrogen atom is preferable.
  • Rb 35 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferable), aryl group (6 to 22 carbon atoms are 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 a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably 7 to 23 carbon atoms, 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 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
  • the molecular weight of the nonionic thermobase generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
  • the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
  • the following compounds can be mentioned as specific examples of the compound which is a thermal base generator or other specific examples of the thermal base generator.
  • the content of the thermosetting agent is preferably 0.1 to 50% by mass with respect to the total solid content of the curable resin composition of the present invention.
  • the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
  • the thermobase generator one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
  • the curable resin composition of the present invention preferably further contains a migration inhibitor.
  • a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the curable resin composition layer.
  • the migration inhibitor is not particularly limited, but heterocycles (pyrazole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, etc.
  • triazole-based compounds such as 1,2,4-triazole and benzotriazole
  • 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 amount is preferably in the above range.
  • the curable resin composition of the present invention preferably contains a polymerization inhibitor.
  • polymerization inhibitor examples include hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, and diphenyl-p-benzoquinone.
  • the content of the polymerization inhibitor is, for example, 0.01 to 20.0% by mass with respect to the total solid content of the curable resin composition of the present invention. It is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and further preferably 0.05 to 2.5% by mass. Further, when the storage stability of the photosensitive resin composition solution is required, an embodiment of 0.02 to 15.0% by mass is also preferable, and in that case, 0.05 to 10.0% by mass is more preferable. Is.
  • 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 amount 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 adhesion improver include a silane coupling agent, an aluminum-based adhesive aid, a titanium-based adhesive aid, a compound having a sulfonamide structure and a compound having a thiourea structure, a phosphoric acid derivative compound, a ⁇ -ketoester compound, and an amino compound. And so on.
  • 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 JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent.
  • Et represents an ethyl group.
  • silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glyceride.
  • 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. ..
  • Aluminum-based adhesive aid examples include aluminum tris (ethylacetacetate), aluminumtris (acetylacetoneate), ethylacetacetate aluminum diisopropirate, and the like.
  • 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 amount 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 electronically 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 can be mentioned. Moreover, you may use a sensitizing dye as a sensitizer.
  • sensitizing dye the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 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.
  • Examples of the chain transfer agent include RAFT (Reversible Addition Fragmentation chain Transfer), a group of compounds having -S-S-, -SO 2-S-, -NO-, SH, PH, SiH, and GeH in the molecule.
  • Dithiobenzoate, trithiocarbonate, dithiocarbamate, xantate compound and the like having a thiocarbonylthio group used for polymerization are 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 amount 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 with respect to 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.
  • the surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total amount 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 amount 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 mass ppm (parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm, 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, the total of these metals is preferably 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 layered bottle. 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 may be, for example, 5 ⁇ m or less, preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, still more preferably 0.1 ⁇ m or less.
  • the filter material 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 using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times.
  • circulation filtration may be used.
  • the pressure to be pressurized is, for example, 0.01 MPa or more and 1.0 MPa or less, preferably 0.03 MPa or more and 0.9 MPa or less, and more preferably 0.05 MPa or more and 0.7 MPa or less. , 0.05 MPa or more and 0.3 MPa or less is more preferable.
  • impurities may be removed using an adsorbent. Filter filtration and impurity removal treatment using an adsorbent may be combined.
  • the 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, or 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 applicable fields 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.
  • Other examples include forming a pattern by etching on 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.
  • 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 includes the film forming step (and the developing step if necessary), and further includes 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 method for producing the laminated body of the present embodiment is the step (a), the steps (a) to (c), or (a) after forming the cured film according to the above-mentioned method for producing the cured film. )-(D).
  • a laminated body can be obtained.
  • the production method 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 deposition film, There are no particular restrictions on magnetic film, reflective film, metal substrate 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 and a molded resin base material are more preferable.
  • the base material for example, a plate-shaped base material (board) is used.
  • 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 means to be applied include a dip coating method, an air knife coating method, a curtain coating method, a wire bar coating method, a gravure coating method, an extrusion coating method, a spray coating method, a spin coating method, and a slit coating method.
  • 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 base material.
  • a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular base material, a slit coating method or a spray coating method is used.
  • the method, the inkjet method and the like are preferable.
  • the spin coating method for example, application is performed at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds, and at a rotation speed of 500 to 2,000 rpm (revolutions per minute), 10 seconds to 1 minute. Can be applied to some extent. Further, in order to obtain the uniformity of the film thickness, a plurality of rotation speeds can be combined and applied.
  • 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. If the amount of solvent in the composition is large, vacuum drying and heat drying can also be combined.
  • a hot plate, a hot air oven, or the like is used for heat drying, and the heating and drying is not particularly limited.
  • 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.
  • a broad (three wavelengths of g, h, and i rays) light source of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.
  • 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).
  • a developing step of performing a developing process on the exposed film (curable resin composition layer) By developing, for example, in the case of a negative type photosensitive resin composition, an 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 curable resin composition is a negative type curable resin composition
  • the developing solution is such that the unexposed portion (non-exposed portion) of the curable resin composition layer is removed, which is the curability of the present invention.
  • the resin composition is a positive curable resin composition, those from which the exposed portion (exposed portion) is removed can be used without particular limitation.
  • alkaline development the case where an alkaline developer is used as the developer
  • solvent development a developer containing 50% by mass or more of an organic solvent
  • the content of the organic solvent in the developing solution is preferably 10% by mass or less, more preferably 5% by mass or less, and 1% by mass or less with respect to the total mass of the developing solution. Is more preferable, and it is particularly preferable that the organic solvent is not contained.
  • the developing solution in alkaline development is more preferably an aqueous solution having a pH of 9 to 14.
  • Examples of the alkaline compound contained in the developing solution in alkaline development include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, and metasilicate. Examples include potassium silicate, ammonia or amine.
  • amines examples include ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, alkanolamine, dimethylethanolamine, triethanolamine, quaternary ammonium hydroxide, and tetramethylammonium hydroxide.
  • TMAH tetraethylammonium hydroxide
  • tetrabutylammonium hydroxide and the like can be mentioned.
  • an alkaline compound containing no metal is preferable, and an ammonium compound is more preferable.
  • the alkaline compound may be only one kind or two or more kinds. When there are two or more alkaline compounds, the total amount is preferably in the above range.
  • the developer contains 90% by mass 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 solvent examples include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, and ⁇ -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 Tons include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and cyclic hydrocarbons, for example, aromatics such as toluene, xylene, anisole, etc. Hydrocarbons, cyclic terpenes such as limonene, and dimethyl sulfoxides are preferable as sulfoxides.
  • cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable.
  • the developer preferably has 50% by mass or more of an organic solvent, more preferably 70% by mass or more of an organic solvent, and further preferably 90% by mass or more of an organic solvent. Further, the developing solution may be 100% by mass of an organic solvent.
  • the development time is preferably 10 seconds to 5 minutes.
  • the temperature of the developing solution at the time of development is not particularly specified, but is usually 20 to 40 ° C.
  • rinsing is preferably performed using an organic solvent different from the developing solution.
  • an organic solvent different from the developing solution For example, propylene glycol monomethyl ether acetate can be mentioned.
  • the rinsing time is preferably 5 seconds to 5 minutes.
  • a step of applying both a developer and a rinse solution may be included between the development and the rinse.
  • the time of the above step is preferably 1 second to 5 minutes.
  • 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 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 carry out 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 of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by performing it under vacuum, 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.
  • a structure such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer is preferable, and the resin layer is preferably 3 layers or more and 7 layers or less, and more preferably 3 layers or more and 5 layers or less.
  • 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 (b) an exposure step, (c) a development step, and (e) a metal layer forming step are repeated in this order, and (d) a heating step is 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 resin of the present invention preferably has a repeating unit represented by the following formula (1-1).
  • X 1 represents a tetravalent group containing an aromatic hydrocarbon group, and all of the bonding sites with the four carbonyl groups in formula (1-1) in X 1 are aromatic hydrocarbons. It is a hydrogen group
  • Y 1 represents an n + divalent group containing an aromatic hydrocarbon group
  • a 1 represents a group containing a polymerizable group
  • G 1 and G 2 are independent hydrogen atoms or substituents, respectively.
  • the above formula (1-1) has the same meaning as the formula (1-1) in the specific resin, and the preferred embodiment is also the same.
  • the resin of the present invention has the same meaning as the above-mentioned specific resin, and the preferred embodiment is also the same.
  • the resin of the present invention is preferably used as the resin contained in the curable resin composition. Further, in a composition in which a conventional polyimide is used, for example, a composition for an interlayer insulating film, a part or all of the conventional polyimide can be used in place of the resin of the present invention without particular limitation. Since the resin of the present invention has excellent chemical resistance, the resin of the present invention is required to have chemical resistance, for example, a composition for forming an insulating film, a composition for forming a laminate, and the like. It is considered that the composition is preferably used in the composition used for the purpose.
  • the method for producing a resin of the present invention comprises compound A having two nitro groups, at least one reactive group, and an aromatic hydrocarbon group, a group capable of forming a bond with the reactive group, and polymerization.
  • (Production step) and a step of reacting the diamine with a tetravalent carboxylic acid compound having a structure in which all four carboxy groups are bonded to an aromatic hydrocarbon group, or a derivative of the tetravalent carboxylic acid compound.
  • Precursor production step is preferably included. The details of each of the above steps are as described in the method for producing a specific resin, and the preferred embodiments are also the same.
  • reaction solution was diluted with 600 mL of ethyl acetate (CH 3 COOEt), transferred to a separating funnel, and washed with 300 mL of water, 300 mL of saturated aqueous sodium hydrogen carbonate, 300 mL of dilute hydrochloric acid, and saturated brine in that order.
  • the mixture was dried over 30 g of magnesium sulfate, concentrated using an evaporator, and vacuum dried to obtain 61.0 g of a dinitro compound (A-1). It was confirmed from the NMR spectrum that it was a dinitro compound (A-1).
  • the dinitro compound (A-1) was analyzed by 1 1 H-NMR. The results are shown below.
  • a white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature, stirred for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 11.9 g (45 mmol) of diamine (AA-1) was dissolved in 50 mL of NMP. It was added by dropping over time. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours.
  • NMP N-methylpyrrolidone
  • AA-1 diamine
  • the polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes.
  • the polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day.
  • the structure of PI-1 is presumed to be the structure represented by the following formula (PI-1).
  • a white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature, stirred for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 8.9 g (46 mmol) of diamine (AA-2) was dissolved in 50 mL of NMP. It was added by dropping over time. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours.
  • NMP N-methylpyrrolidone
  • AA-2 diamine
  • the polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes.
  • the polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day.
  • the structure of PI-2 is presumed to be the structure represented by the following formula (PI-2).
  • the structure of PI-3 is presumed to be the structure represented by the following formula (PI-3).
  • * represents the binding site with the oxygen atom to which R1 binds.
  • a white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature, stirred for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 12.5 g (45 mmol) of diamine (AA-4) was dissolved in 50 mL of NMP. It was added by dropping over time. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours.
  • NMP N-methylpyrrolidone
  • AA-4 diamine
  • the polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes.
  • the polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day.
  • the structure of PI-4 is presumed to be the structure represented by the following formula (PI-4).
  • the structure of PI-5 is presumed to be the structure represented by the following formula (PI-5).
  • a white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature, stirred for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 10.8 g (45 mmol) of diamine (AA-5) was dissolved in 50 mL of NMP. It was added by dropping over time. The viscosity increased while the diamine was added. Then, 8.67 g (188 mmol) of ethanol and 0.05 g of 2,2,6,6-tetramethylpiperidin 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours.
  • NMP N-methylpyrrolidone
  • AA-5 diamine
  • the polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes.
  • the polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day.
  • the structure of PI-6 is presumed to be the structure represented by the following formula (PI-6).
  • 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 R1 binds.
  • a white precipitate of pyridinium hydrochloride was obtained. Then, the mixture was warmed to room temperature, stirred for 2 hours, 30 mL of N-methylpyrrolidone (NMP) was added, and 14.5 g (45 mmol) of diamine (AA-7) was dissolved in 50 mL of NMP. It was added by dropping over time. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours.
  • NMP N-methylpyrrolidone
  • AA-7 diamine
  • the polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes.
  • the polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day.
  • the structure of PI-9 is presumed to be the structure represented by the following formula (PI-9).
  • a white precipitate of pyridinium hydrochloride was obtained.
  • the mixture was then warmed to room temperature, stirred for 2 hours, then 30 mL of N-methylpyrrolidone (NMP) was added, 7.14 g (27 mmol) of diamine (AA-1), 3.75 g of diamine (AA-6) (AA-6). 18 mmol) was dissolved in 50 mL of NMP and added dropwise over 1 hour. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours.
  • the polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes.
  • the polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day.
  • the structure of PI-10 is presumed to be the structure represented by the following formula (PI-10).
  • a white precipitate of pyridinium hydrochloride was obtained.
  • the mixture was then warmed to room temperature, stirred for 2 hours, then 30 mL of N-methylpyrrolidone (NMP) was added and 8.15 g (46 mmol) of diamine (AA-3) was dissolved in 50 mL of NMP. It was added by dropping over 1 hour. The viscosity increased while the diamine was added. Then, 6.0 g (188 mmol) of methanol and 0.05 g of 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred for 2 hours.
  • the polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes.
  • the polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day.
  • the structure of PI-11 is presumed to be the structure represented by the following formula (PI-11).
  • the polyimide precursor resin was then precipitated in 5 liters of water and the water-polyimide precursor resin mixture was stirred at a rate of 500 rpm for 15 minutes.
  • the polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor resin was dried under reduced pressure at 45 ° C. for 1 day.
  • the structure of PI-12 is presumed to be the structure represented by the following formula (PI-12).
  • molar amount ratio of the G 1 or the G 2 is a group, and an organic group having a polyalkyleneoxy group the ratio of the molar amount of the G 1 or the G 2, described in each table below.
  • the description in the column of item 1 is ethylenically unsaturated with respect to the total molar amount of G 1 and G 2 in all the repeating units represented by the above formula (1-1) contained in the resin.
  • the ratio of the molar amount of the said G 1 or the said G 2 which is a substituent containing a group is shown.
  • the description in the column of item 2 includes heteroatoms with respect to the total molar amount of G 1 and G 2 in all the repeating units represented by the above formula (1-1) contained in the resin.
  • the ratio of the molar amount of the G 1 or the G 2 which is an organic group having 1 to 30 carbon atoms may be shown.
  • the description in the column of item 3 is a polyalkyleneoxy group with respect to the total molar amount of the above G 1 and the above G 2 in all the repeating units represented by the above formula (1-1) contained in the resin.
  • the ratio of the molar amount of the above-mentioned G 1 or the above-mentioned G 2 which is an organic group having is shown. Further, in the table below, the numerical values described in items 1 to 3 are values rounded off to the first decimal place of the numerical values represented by%.
  • 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 (polyimide precursor for comparative example (A-). 1)) was obtained.
  • the weight average molecular weight (Mw) of this polymer A-1 was measured and found to be 20,000.
  • the polyimide precursor (A-1) for comparative example is a resin having no repeating unit represented by the formula (1-1).
  • the polyimide precursor resin (A-2) for comparative example is a resin having no repeating unit represented by the formula (1-1).
  • the polyimide precursor (A-3) for comparative example is a resin in which the content of the repeating unit represented by the formula (1-1) is 10 mol%.
  • the polyimide precursor (A-4) for comparative example is a resin containing no repeating unit represented by the formula (1-1).
  • the structure of the polyimide precursor (A-4) for comparative examples is presumed to be the structure represented by the following formula (A-4).
  • -PI-1 to PI-10 Polyimide precursor resins (PI-1) to (PI-10) synthesized above.
  • -A-1 to A-3 Comparative polyimide precursors (A-1) to (A-3) synthesized above.
  • the temperature was raised at a heating rate of 10 ° C./min under a nitrogen atmosphere, and after reaching the temperature described in the column of "curing conditions" in Table 2, heating was performed for 3 hours.
  • the cured resin composition 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 sample width of 3 mm and a sample length of 30 mm.
  • the elongation rate of the obtained test piece in the longitudinal direction was adjusted to JIS-K6251 using a tensile tester (Tensilon) in an environment with a crosshead speed of 300 mm / min, 25 ° C., and 65% RH (relative humidity). Measured according to. The measurement was carried out 5 times each, and the arithmetic mean value of the elongation rate (breaking elongation rate) when the test piece was broken in each of the 5 measurements was used as an index value. The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in Table 2. It can be said that the larger the index value, the better the film strength of the cured film. -Evaluation criteria- A: The above index value was 60% or more. 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 entirely 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 nitrogen.
  • the cured layer (resin layer) of the curable resin composition layer is heated at a heating rate of 10 ° C./min in an atmosphere at the temperature shown in the “Curing conditions” column of Table 2 for 180 minutes.
  • Got 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 immersion. The dissolution rate (nm / min) was calculated by comparing the film thicknesses of the above.
  • the evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in Table 2. It can be said that the lower the dissolution rate, the better the chemical resistance.
  • -Evaluation criteria A 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.
  • 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, respectively.
  • the silicon wafer after the above application was dried on a hot plate at 100 ° C. for 5 minutes to form a curable resin composition layer having a uniform film thickness of 10 ⁇ m on the silicon wafer.
  • the curable resin composition layer on the silicon wafer was fully exposed using a stepper (Nikon NSR 2005 i9C). The exposure was performed by i-line, and the exposure was performed at a wavelength of 365 nm with an exposure energy of 400 mJ / cm 2. After the exposure, negative development was carried out with cyclopentanone for 60 seconds to obtain a resin layer.
  • This resin layer is heated in a nitrogen atmosphere at the temperature shown in the column of "curing conditions" in Table 2 for 3 hours to form a cured film A, and then the cured film A is scraped from a silicon wafer and infrared spectroscopic measurement is performed. IR measurement) was performed. Further, using each curable resin composition or comparative composition prepared in each Example and Comparative Example, “heating at the temperature described in the" curing conditions "column of Table 2 for 3 hours” was performed at "350 ° C.” A cured film B was prepared by the same method as that of the cured film A except that the temperature was changed to "heating for 3 hours”. The cured film B was also scraped from the silicon wafer and IR measurement was performed.
  • Ring closure rate (%) peak area A / peak area B x 100 -Evaluation criteria-
  • the curable resin composition containing the specific resin according to the present invention has excellent chemical resistance.
  • the comparative compositions according to Comparative Examples 1 to 4 do not contain a specific resin. It can be seen that the comparative compositions according to Comparative Examples 1 to 4 are inferior in chemical resistance.
  • Example 101 The curable resin composition according to Example 1 was spun and applied to the surface of the thin copper layer of the resin base material having the thin copper layer formed on the surface so as to have a film thickness of 20 ⁇ m.
  • the curable resin composition applied to the resin substrate was dried at 100 ° C. for 2 minutes and then exposed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). The exposure was carried out through a mask of a square pattern (square pattern of 100 ⁇ m each in length and width, number of repetitions of 10) at a wavelength of 365 nm and an exposure amount of 400 mJ / cm 2 to prepare a square remaining pattern.

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Abstract

L'invention concerne : une composition de résine durcissable comprenant un photosensibilisateur et une résine qui comprend des motifs de répétition représentés par la formule (1-1), la composition de résine durcissable étant caractérisée en ce que la résine comprend 50 % en moles ou plus de motifs de répétition représentés par la formule (1-1) par rapport à la totalité des motifs de répétition de la résine; un film durci obtenu par durcissement de la composition de résine durcissable; un stratifié comprenant le film durci; un procédé de production du film durci; un dispositif à semi-conducteur comprenant le film durci ou le stratifié; une résine présentant des motifs de répétition représentés par la formule (1-1); et un procédé de production de la résine.
PCT/JP2020/033326 2019-09-05 2020-09-02 Composition de résine durcissable, film durci, stratifié, procédé de production de film durci, dispositif à semi-conducteur, résine, et procédé de production de résine WO2021045126A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022044999A1 (fr) * 2020-08-25 2022-03-03 富士フイルム株式会社 Composition de résine durcissable, produit durci, stratifié, procédé de production de produit durci, dispositif à semi-conducteurs ainsi que précurseur polyimide et procédé de production de celui-ci
WO2022044998A1 (fr) * 2020-08-25 2022-03-03 富士フイルム株式会社 Composition de résine durcissable, produit durci, stratifié, procédé de production de produit durci, dispositif à semi-conducteurs ainsi que précurseur polyimide et procédé de production de celui-ci
WO2024111130A1 (fr) * 2022-11-25 2024-05-30 Ｈｄマイクロシステムズ株式会社 Ester d'acide polyamique, et composition de résine
WO2024185652A1 (fr) * 2023-03-08 2024-09-12 富士フイルム株式会社 Composition de résine, produit durci, corps multicouche, procédé de production d'un produit durci, procédé de production d'un corps multicouche, procédé de production d'un dispositif semiconducteur et dispositif semiconducteur
WO2024195608A1 (fr) * 2023-03-20 2024-09-26 富士フイルム株式会社 Composition de résine photosensible, produit durci, corps multicouche, procédé de production de produit durci, procédé de production de corps multicouche, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur

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JPS57143329A (en) * 1981-03-03 1982-09-04 Nippon Telegr & Teleph Corp <Ntt> Photosensitive resin and its production
JPH03245148A (ja) * 1990-02-23 1991-10-31 Hitachi Chem Co Ltd 感光性樹脂組成物及び感光性エレメント
JPH10239841A (ja) * 1997-02-28 1998-09-11 Toray Ind Inc 感光性ポリイミド前駆体組成物
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JPS57143329A (en) * 1981-03-03 1982-09-04 Nippon Telegr & Teleph Corp <Ntt> Photosensitive resin and its production
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WO2022044999A1 (fr) * 2020-08-25 2022-03-03 富士フイルム株式会社 Composition de résine durcissable, produit durci, stratifié, procédé de production de produit durci, dispositif à semi-conducteurs ainsi que précurseur polyimide et procédé de production de celui-ci
WO2022044998A1 (fr) * 2020-08-25 2022-03-03 富士フイルム株式会社 Composition de résine durcissable, produit durci, stratifié, procédé de production de produit durci, dispositif à semi-conducteurs ainsi que précurseur polyimide et procédé de production de celui-ci
WO2024111130A1 (fr) * 2022-11-25 2024-05-30 Ｈｄマイクロシステムズ株式会社 Ester d'acide polyamique, et composition de résine
WO2024185652A1 (fr) * 2023-03-08 2024-09-12 富士フイルム株式会社 Composition de résine, produit durci, corps multicouche, procédé de production d'un produit durci, procédé de production d'un corps multicouche, procédé de production d'un dispositif semiconducteur et dispositif semiconducteur
WO2024195608A1 (fr) * 2023-03-20 2024-09-26 富士フイルム株式会社 Composition de résine photosensible, produit durci, corps multicouche, procédé de production de produit durci, procédé de production de corps multicouche, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur

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