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WO2023190063A1 - Procédé de production d'un produit durci, procédé de production d'un dispositif à semi-conducteur, liquide de traitement et composition de résine - Google Patents

Procédé de production d'un produit durci, procédé de production d'un dispositif à semi-conducteur, liquide de traitement et composition de résine Download PDF

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Publication number
WO2023190063A1
WO2023190063A1 PCT/JP2023/011592 JP2023011592W WO2023190063A1 WO 2023190063 A1 WO2023190063 A1 WO 2023190063A1 JP 2023011592 W JP2023011592 W JP 2023011592W WO 2023190063 A1 WO2023190063 A1 WO 2023190063A1
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WO
WIPO (PCT)
Prior art keywords
group
formula
cured product
film
carbon atoms
Prior art date
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Ceased
Application number
PCT/JP2023/011592
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English (en)
Japanese (ja)
Inventor
裕樹 奈良
和也 尾田
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Fujifilm Corp
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Fujifilm Corp
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Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Priority to KR1020247032371A priority Critical patent/KR20240157714A/ko
Priority to JP2024512288A priority patent/JPWO2023190063A1/ja
Priority to CN202380031626.6A priority patent/CN118946611A/zh
Publication of WO2023190063A1 publication Critical patent/WO2023190063A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • C08F290/145—Polyamides; Polyesteramides; Polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers

Definitions

  • the present invention relates to a method for producing a cured product, a method for producing a semiconductor device, a treatment liquid, and a resin composition.
  • Resins such as polyimide have excellent heat resistance and insulation properties, so they are used in a variety of applications.
  • the above-mentioned uses include, but are not limited to, using patterns containing these resins as materials for insulating films and sealing materials, or as protective films, for example in semiconductor devices for mounting. . Patterns containing these resins are also used as base films and coverlays for flexible substrates.
  • a cyclized resin such as polyimide is used in the form of a resin composition containing a precursor of the cyclized resin such as a polyimide precursor.
  • a resin composition containing a precursor of the cyclized resin such as a polyimide precursor.
  • a cyclized resin for example, a resin in which a polyimide precursor is imidized
  • the resin composition can be applied using known coating methods, etc., and can be developed to form fine patterns, patterns with complex shapes, etc., so it has great flexibility in manufacturing, such as a high degree of freedom in designing the cured product. It can be said to be excellent.
  • Patent Document 1 describes the steps of (a) coating a substrate with a film containing a polyamic acid ester whose ester substituent has a crosslinkable functional group and a photoinitiator; (c) developing the image; (d) contacting the coating with a base; and (e) heating the coating to cause crosslinking.
  • a method for forming a polyimide negative image on a substrate is described, which includes the step of imidizing the polyamic acid ester.
  • the obtained cured product has excellent elongation at break and that the coefficient of thermal expansion (coefficient of linear thermal expansion, CTE) of the obtained cured product is small.
  • the present invention relates to a method for producing a cured product that has excellent elongation at break and a small CTE, a method for producing a semiconductor device containing the cured product, a processing liquid used in the method for producing the cured product, and the cured product.
  • An object of the present invention is to provide a resin composition used in a method for manufacturing products.
  • R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R 1 and R 2 is a monovalent organic group having an ethylenically unsaturated bond. It is.
  • X 1 is a group containing a structure represented by the following formula (X-1), and Y 1 is a divalent organic group represented by the following general formula (Y-1).
  • R 3 to R 10 are each independently a hydrogen atom or a monovalent group, and at least one of R 3 to R 10 may have a fluorine atom or a substituent. It is an alkyl group, a substituent having a fluorine atom, or an alkoxy group which may have a substituent, and R 5 and R 7 and R 6 and R 8 may be bonded to form a ring structure, and * is each , represents the bonding site with the nitrogen atom in formula (1).
  • X 1 in formula (1) has a structure represented by the following formula (X-2).
  • R represents an aromatic hydrocarbon group that may have or a hydrocarbon group that may be substituted with a halogen atom
  • two R X1 may be bonded to form a ring structure
  • R X2 is represents a halogen atom
  • each # represents a bonding site with a carbonyl group in formula (1).
  • X 1 in formula (1) has a structure represented by the following formula (X-3).
  • R represents an aromatic hydrocarbon group that may have or a hydrocarbon group that may be substituted with a halogen atom
  • two R X1 may be bonded to form a ring structure
  • R X2 is represents a halogen atom
  • each # represents a bonding site with a carbonyl group in formula (1).
  • the base contained in the treatment liquid is a secondary amine or a tertiary amine, and the base generator is a compound that generates a secondary amine or a tertiary amine, ⁇ 1> to ⁇ 4>.
  • ⁇ 6> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 5>, wherein the base and base generator contained in the treatment liquid are compounds having an amide group.
  • ⁇ 7> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 6>, wherein the base or base generator contained in the treatment liquid is a compound having an acrylamide group or a methacrylamide group.
  • ⁇ 8> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 7>, wherein the heating temperature in the heating step is 180° C. or less, and the heating time is 3 hours or less.
  • an exposure step of selectively exposing the film and a development step of developing the exposed film with a developer to form a patterned film.
  • the method for producing a cured product according to any one of ⁇ 1> to ⁇ 8> including the step.
  • ⁇ 10> The method for producing a cured product according to ⁇ 9>, wherein the treatment step is a rinsing step of cleaning the patterned film with the treatment liquid.
  • ⁇ 11> The method for producing a cured product according to ⁇ 9>, wherein the treatment step is performed after cleaning the patterned film by contacting it with a rinsing liquid.
  • ⁇ 12> Between the film forming step and the processing step, there is an exposure step of selectively exposing the film, and the processing step develops the film using the processing solution as a developer to form a pattern.
  • the method for producing a cured product according to any one of ⁇ 1> to ⁇ 8> which is a step of forming a film having a shape.
  • ⁇ 13> The method for producing a cured product according to any one of ⁇ 9> to ⁇ 12>, wherein the development is negative development.
  • the curing according to any one of ⁇ 1> to ⁇ 13> including a heating and cooling step of heating the film at a temperature of 80 to 120° C. and cooling it. How things are manufactured.
  • ⁇ 15> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 14>, wherein the resin composition contains a photopolymerization initiator.
  • ⁇ 16> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 15>, wherein the obtained cured product has a linear thermal expansion coefficient of 50 ppm/K or less in the range of 25° C. to 125° C.
  • ⁇ 17> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 16>, wherein the resulting cured product has an elongation at break of 50% or more.
  • the absolute value of the viscosity change rate expressed by the following formula of the viscosity of the resin composition after storage at 23 ° C. for 14 days after preparation with respect to the viscosity of the resin composition on the day of preparation is 10% or less.
  • Viscosity change rate (%) ⁇ (Viscosity of the resin composition on the day of preparation) - (Viscosity of the resin composition after storage as described above) ⁇ /(Viscosity of the resin composition on the day of preparation) x 100 ⁇ 19>
  • a method for manufacturing a semiconductor device comprising the method for manufacturing a cured product according to any one of ⁇ 1> to ⁇ 18>.
  • a treatment liquid used in a method for producing a cured product including a contacting treatment step and a heating step of heating the film after the treatment step,
  • R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R 1 and R 2 is a monovalent organic group having an ethylenically unsaturated bond. It is.
  • X 1 is a group containing a structure represented by the following formula (X-1), and Y 1 is a divalent organic group represented by the following general formula (Y-1).
  • R 3 to R 10 are each independently a hydrogen atom or a monovalent group, and at least one of R 3 to R 10 may have a fluorine atom or a substituent. It is an alkyl group, a substituent having a fluorine atom, or an alkoxy group which may have a substituent, and R 5 and R 7 and R 6 and R 8 may be bonded to form a ring structure, and * is each , represents the bonding site with the nitrogen atom in formula (1).
  • the treatment liquid contains at least one compound selected from the group consisting of a basic compound and a base generator.
  • R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R 1 and R 2 is a monovalent organic group having an ethylenically unsaturated bond. It is.
  • X 1 is a group containing a structure represented by the following formula (X-1), and Y 1 is a divalent organic group represented by the following general formula (Y-1).
  • R 3 to R 10 are each independently a hydrogen atom or a monovalent group, and at least one of R 3 to R 10 may have a fluorine atom or a substituent. It is an alkyl group, a substituent having a fluorine atom, or an alkoxy group which may have a substituent, and R 5 and R 7 and R 6 and R 8 may be bonded to form a ring structure, and * is each , represents the bonding site with the nitrogen atom in formula (1).
  • a method for producing a cured product that provides a cured product with excellent elongation at break and a small CTE a method for producing a semiconductor device including the cured product, a processing liquid used in the method for producing the cured product, and A resin composition used in the above method for producing a cured product is provided.
  • a numerical range expressed using the symbol " ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as the lower limit and upper limit, respectively.
  • the term “step” includes not only independent steps but also steps that cannot be clearly distinguished from other steps as long as the intended effect of the step can be achieved.
  • substitution or unsubstitution includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • alkyl group includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • (meth)acrylate means both “acrylate” and “methacrylate”, or either “(meth)acrylate”
  • (meth)acrylic means both “acrylic” and “methacrylic”
  • (meth)acryloyl means either or both of "acryloyl” and “methacryloyl.”
  • 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 refers to the total mass of all 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.
  • weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC), and are defined as polystyrene equivalent values.
  • weight average molecular weight (Mw) and number average molecular weight (Mn) are expressed using, for example, HLC-8220GPC (manufactured by Tosoh Corporation) and guard column HZ-L, TSKgel Super HZM-M, TSKgel.
  • THF tetrahydrofuran
  • NMP N-methyl-2-pyrrolidone
  • a detector with a wavelength of 254 nm of UV rays is used for detection in the GPC measurement.
  • each layer constituting a laminate when the positional relationship of each layer constituting a laminate is described as "upper” or “lower", there is another layer above or below the reference layer among the plurality of layers of interest. It would be good if there was. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact with each other.
  • the direction in which layers are stacked relative to the base material is referred to as "top”, or if there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as "top”. , the opposite direction is called "down".
  • the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component. Further, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component.
  • the temperature is 23° C.
  • the atmospheric pressure is 101,325 Pa (1 atm)
  • the relative humidity is 50% RH. In this specification, combinations of preferred aspects are more preferred aspects.
  • the method for producing a cured product of the present invention includes a film forming step of forming a film by applying a polyimide precursor containing a repeating unit represented by formula (1) and a resin composition containing a solvent onto a base material; A treatment step of bringing a treatment liquid into contact with the membrane, and a heating step of heating the membrane after the treatment step, wherein the treatment liquid is selected from the group consisting of a basic compound and a base generator. Contains at least one compound.
  • R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R 1 and R 2 is a monovalent organic group having an ethylenically unsaturated bond. It is.
  • X 1 is a group containing a structure represented by the following formula (X-1), and Y 1 is a divalent organic group represented by the following general formula (Y-1).
  • R 3 to R 10 are each independently a hydrogen atom or a monovalent group, and at least one of R 3 to R 10 may have a fluorine atom or a substituent. It is an alkyl group, a substituent having a fluorine atom, or an alkoxy group which may have a substituent, and R 5 and R 7 and R 6 and R 8 may be bonded to form a ring structure, and * is each , represents the bonding site with the nitrogen atom in formula (1).
  • the polyimide precursor contains a specific repeating unit represented by formula (1)
  • elongation at break is improved. This is presumably because X 1 in formula (1) has a structure that is easily bent within the molecular chain.
  • Y 1 of the repeating units represented by formula (1) has a rigid structure, a rigid structure remains in the final cured product.
  • the resin also has a rigid structure, which is thought to reduce the coefficient of thermal expansion of the resin.
  • any of R 3 to R 10 in formula (Y-1) has a fluorine atom or a substituent having a fluorine atom, the coefficient of thermal expansion tends to decrease.
  • the repeating unit represented by formula (1) has a structure containing an ethylenically unsaturated bond in at least one of R 1 and R 2 , it is possible to create a bond between resins or between a resin and another polymerizable compound. It is thought that polymerization progresses and the coefficient of thermal expansion decreases. Furthermore, by including the treatment step, at least one of the base and the base generator permeates into the membrane. This promotes cyclization of the polyimide precursor during the heating process, and is therefore considered to provide even better elongation at break.
  • the polyimide precursor containing the specific repeating unit represented by formula (1) has a rigid structure as described above, it is difficult to imidize when it is cured by heating, and it is less likely to progress when heated than conventional polyimide precursors. There is a tendency for the subsequent imidization rate to become low. Therefore, by using a polyimide precursor containing a specific repeating unit represented by formula (1) and including the above-mentioned treatment steps to promote cyclization of the polyimide precursor, the imidization rate after heating can be improved.
  • the composition of the composition can be made free of base-generating compounds, so it is considered that the composition has excellent storage stability.
  • Patent Document 1 does not describe a method for producing a cured product using a resin composition containing a polyimide precursor containing a specific repeating unit represented by formula (1) and including a treatment step. Not yet. Hereinafter, the method for producing a cured product of the present invention will be explained in detail.
  • the method for producing a cured product of the present invention includes a film forming step of forming a film by applying a polyimide precursor containing a repeating unit represented by formula (1) and a resin composition containing a solvent onto a base material.
  • a film forming step of forming a film by applying a polyimide precursor containing a repeating unit represented by formula (1) and a resin composition containing a solvent onto a base material. include. Details of the resin composition used in the present invention will be described later.
  • the type of base material can be appropriately determined depending on the purpose and is not particularly limited.
  • the base material include semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposited films, magnetic films, reflective films, Ni, Cu,
  • a metal base material such as Cr or Fe (for example, a base material formed from a metal or a base material on which a metal layer is formed by, for example, plating or vapor deposition), paper, SOG (Spin On Examples include glass), TFT (thin film transistor) array substrates, mold substrates, and electrode plates for plasma display panels (PDP).
  • the base material is particularly preferably a semiconductor production base material, and more preferably a silicon base material, a Cu base material, and a mold base material. These base materials may be provided with a layer such as an adhesive layer or an oxidized layer made of hexamethyldisilazane (HMDS) or the like on the surface.
  • the shape of the base material is not particularly limited, and may be circular or rectangular. As for the size of the base material, if it is circular, the diameter is preferably 100 to 450 mm, more preferably 200 to 450 mm. If it is rectangular, the length of the short side is preferably 100 to 1000 mm, more preferably 200 to 700 mm.
  • a plate-shaped, preferably panel-shaped base material (substrate) is used as the base material.
  • the resin layer or metal layer serves as the base material.
  • Coating is preferred as a means for applying the resin composition onto the substrate.
  • the methods to be applied include dip coating method, air knife coating method, curtain coating method, wire bar coating method, gravure coating method, extrusion coating method, spray coating method, spin coating method, slit coating method, Examples include the inkjet method. From the viewpoint of uniformity of film thickness, spin coating method, slit coating method, spray coating method, or inkjet method is preferable, and from the viewpoint of uniformity of film thickness and productivity, spin coating method and slit coating method are preferable. A coating method is more preferred. A film with a desired thickness can be obtained by adjusting the solid content concentration and application conditions of the resin composition depending on the means to be applied.
  • the coating method can be appropriately selected depending on the shape of the substrate, and for circular substrates such as wafers, spin coating, spray coating, inkjet methods, etc. are preferable, and for rectangular substrates, slit coating, spray coating, etc. method, inkjet method, etc. are preferred.
  • spin coating it can be applied, for example, at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. It is also possible to apply a method in which a coating film that has been previously formed on a temporary support by the above-mentioned application method is transferred onto a base material.
  • the transfer method the production method described in paragraphs 0023, 0036 to 0051 of JP-A No.
  • 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used. Further, a step of removing excess film may be performed at the end of the base material. Examples of such processes include edge bead rinsing (EBR), back rinsing, and the like.
  • EBR edge bead rinsing
  • a pre-wet process may be employed in which various solvents are applied to the base material before the resin composition is applied to the base material to improve the wettability of the base material, and then the resin composition is applied.
  • the film may be subjected to a step of drying the formed film (layer) (drying step) in order to remove the solvent.
  • the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.
  • the drying step is preferably performed after the film forming step and before the exposure step.
  • the drying temperature of the membrane in the drying step is preferably from 50 to 150°C, more preferably from 70°C to 130°C, even more preferably from 90°C to 110°C.
  • drying may be performed under reduced pressure.
  • the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 2 minutes to 7 minutes.
  • the method for producing a cured product of the present invention includes a treatment step of bringing a treatment liquid into contact with the above-mentioned film.
  • the treatment liquid used in the treatment step contains at least one compound selected from the group consisting of a basic compound and a base generator. Moreover, the treatment liquid of the present invention is a treatment liquid used in the method for producing a cured product of the present invention.
  • the base and base generator contained in the treatment liquid are preferably compounds having an amide group. That is, the treatment liquid preferably contains at least one compound selected from the group consisting of a basic compound having an amide group and a base generator having an amide group. That is, it is preferable that the basic compound is a basic compound having an amide group, and the base generator is a base generator having an amide group. Further, the base and base generator contained in the treatment liquid are preferably compounds having an acrylamide group or a methacrylamide group. That is, the treatment liquid preferably contains at least one compound selected from the group consisting of a basic compound having an acrylamide group or a methacrylamide group, and a base generator having an acrylamide group or a methacrylamide group.
  • the treatment liquid of the present invention preferably contains a basic compound having an amide group with a low boiling point.
  • R N represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.
  • Each of the above * represents a bonding site with a carbon atom.
  • the number of amide groups in the basic compound having an amide group is not particularly limited, but is preferably from 1 to 10, more preferably from 1 to 4, even more preferably from 1 or 2, and from 1 to 10. It is particularly preferable that The number of amide groups in the base generator having an amide group is not particularly limited, but is preferably from 1 to 10, more preferably from 1 to 4, even more preferably from 1 or 2, and from 1 to 10. It is particularly preferable that
  • the basic compound having an amide group preferably includes an acrylamide group or a methacrylamide group as the structure containing the amide group.
  • the base generator having an amide group preferably includes an acrylamide group or a methacrylamide group as the structure containing the amide group.
  • the base generator having an amide group contains an acrylamide group or a methacrylamide group as the structure containing the above amide group, the acrylamide group or methacrylamide group may exist in a structure that becomes a basic compound to be generated, although it may exist in a structure that remains after the basic compound is generated, it is preferably present on the side of the generated basic compound.
  • the acrylamide or methacrylamide group and the resin or polymerizable compound are combined. It is considered that a chemical reaction such as polymerization occurs between the polymerizable group and the outgassing amount of the treatment liquid in some cases.
  • the basic compound is preferably an amine, more preferably a secondary amine or a tertiary amine.
  • the base generator is preferably a compound that generates an amine, and more preferably a compound that generates a secondary amine or a tertiary amine.
  • amine refers to a compound in which the hydrogen atom of ammonia is substituted with a hydrocarbon group or an aromatic atomic group. If the number of substitutions is one, it is a primary amine, if there are two, it is a secondary amine, and if there are three, it is a primary amine. If so, it is called a tertiary amine.
  • the number of amino groups in the basic compound is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, and 1 or 2. is more preferable, and 1 is particularly preferable.
  • the number of amino groups in the basic compound is not particularly limited, but it is preferably 1 to 10, more preferably 1 to 4. It is preferably 1 or 2, more preferably 1, and particularly preferably 1.
  • the basic compound having an amide group used in the present invention is preferably a compound having a structure represented by the following formula (1-1).
  • R 1 and R 2 each independently represent a hydrogen atom or a monovalent organic group
  • R 1 and R 2 may be combined to form a ring structure
  • L 1 is It represents a divalent linking group
  • L 1 and at least one of R 1 and R 2 may be combined to form a ring structure
  • R N represents a hydrogen atom or a monovalent organic group
  • R 3 Represents a monovalent organic group.
  • R 1 and R 2 are each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group.
  • the hydrocarbon group or alkyl group in R 1 and R 2 preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 4 carbon atoms.
  • R 1 and R 2 when simply describing a hydrocarbon group, an alkyl group, an alkylene group, etc., it shall include any structure represented by a linear, branched, cyclic, or a bond thereof.
  • at least one of R 1 and R 2 is preferably a monovalent organic group, and more preferably both are monovalent organic groups.
  • R 1 and R 2 may be combined to form a ring structure.
  • the ring structure formed may be an aromatic ring structure or an aliphatic ring structure. Moreover, it is preferable that the ring structure formed is a 5-membered ring structure or a 6-membered ring structure. Furthermore, in formula (1-1), an embodiment in which R 1 and R 2 are not bonded to form a ring structure can also be used.
  • a group represented by a bond with at least one selected structure is preferable, and a hydrocarbon group is more preferable.
  • the above R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom.
  • the bonding sites between L 1 and the two nitrogen atoms are both hydrocarbon groups.
  • the hydrocarbon group in L 1 is preferably an alkylene group.
  • the number of carbon atoms in the hydrocarbon group in L 1 is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 4.
  • L 1 and at least one of R 1 and R 2 may be bonded to form a ring structure.
  • the ring structure formed may be an aromatic ring structure or an aliphatic ring structure.
  • it is preferable that the ring structure formed is a 5-membered ring structure or a 6-membered ring structure.
  • formula (1-1) an embodiment in which L 1 and none of R 1 and R 2 are bonded to form a ring structure can also be used.
  • R N represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, a hydrogen atom or a methyl More preferably, it is a group.
  • R 3 represents a monovalent organic group, preferably a hydrocarbon group, more preferably an alkyl group or an alkenyl group.
  • the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, even more preferably 1 to 4.
  • the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 4 carbon atoms.
  • R 3 is a vinyl group or a 2-methylvinyl group is also one of the preferred embodiments of the present invention.
  • the basic compound having an amide group may be a polymer compound.
  • the polymer compound which is a basic compound having an amide group include a polymer compound having a repeating unit having an amide group and an amino group.
  • the amino group is preferably a secondary amino group or a tertiary amino group.
  • the polymer compound include a polymer compound containing a repeating unit represented by the following formula (1-2).
  • R 1 and R 2 each independently represent a hydrogen atom or a monovalent organic group
  • R 1 and R 2 may be combined to form a ring structure
  • L 1 is Represents a divalent linking group
  • L 1 and at least one of R 1 and R 2 may be bonded to form a ring structure
  • R N represents a hydrogen atom or a monovalent organic group
  • R 4 Represents a hydrogen atom or a monovalent organic group.
  • R 1 , R 2 , R N and L 1 have the same meanings as R 1 , R 2 , R N and L 1 in formula (1-1), and preferred embodiments are also the same. It is.
  • R 4 is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a methyl group.
  • the molecular weight of the basic compound having an amide group is not particularly limited, but it is preferably as small as possible. For example, it is preferably 500 or less, more preferably 200 or less. Further, when the basic compound having an amide group is a polymer compound, the weight average molecular weight of the polymer compound is preferably as small as possible, for example, preferably 2,000 or less.
  • the boiling point at 1 atm of the basic compound having an amide group is not particularly limited, but is preferably 200°C or lower, more preferably 180°C or lower, and even more preferably 160°C or lower.
  • the melting point of the basic compound having an amide group at 1 atmosphere is not particularly limited, but it is preferably a compound that is liquid at room temperature (23° C.).
  • the boiling point of the basic compound having an amide group at 1 atm is preferably higher than the boiling point of the solvent contained in the treatment liquid at 1 atm minus 20°C; It is more preferable that the boiling point is higher than the boiling point of the solvent contained in the liquid at 1 atmosphere.
  • the basic compound having an amide group preferably has a boiling point of 80°C or higher at 1 atm, and it is preferable that the boiling point at 1 atm is 100°C or higher. More preferred.
  • the pKa of the conjugate acid of the basic compound having an amide group is not particularly limited, but is preferably 0 or more, more preferably 3 or more, and even more preferably 6 or more.
  • the upper limit of the pKa of the conjugate acid is not particularly limited, but is preferably 30 or less.
  • pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is expressed by its negative common logarithm pKa.
  • pKa is a value calculated by ACD/ChemSketch (registered trademark) unless otherwise specified.
  • ACD/ChemSketch registered trademark
  • the conjugate acid has a plurality of pKas, it is preferable that at least one of them is within the above range.
  • Examples of the basic compound having an amide group include, but are not limited to, the following compounds.
  • the treatment liquid may contain, as the basic compound, a basic compound that does not have an amide group (also referred to as "another basic compound").
  • a basic compound that does not have an amide group also referred to as "another basic compound”
  • organic bases are preferred from the viewpoint of reliability when remaining in the cured film (adhesion to the substrate when the cured product is further heated).
  • a basic compound having an amino group is preferable, and primary amines, secondary amines, tertiary amines, ammonium salts, tertiary amides, etc.
  • tertiary amines are preferable, but since they promote the imidization reaction, are preferably primary amines, secondary amines, tertiary amines or ammonium salts, more preferably secondary amines, tertiary amines or ammonium salts, even more preferably secondary amines or tertiary amines, and especially tertiary amines. preferable.
  • primary amines secondary amines, tertiary amines or ammonium salts, more preferably secondary amines, tertiary amines or ammonium salts, even more preferably secondary amines or tertiary amines, and especially tertiary amines.
  • the residual amount is not easily reduced before heating.
  • the boiling point of the other basic compound is preferably from 30°C to 350°C, more preferably from 80°C to 270°C, and preferably from 100°C to 230°C at normal pressure (101,325 Pa). is even more preferable.
  • the boiling point of the other basic compound is preferably higher than the boiling point of the organic solvent contained in the treatment liquid minus 20°C, and more preferably higher than the boiling point of the organic solvent contained in the treatment liquid. .
  • the basic compound used preferably has a boiling point of 80°C or higher, more preferably 100°C or higher.
  • other basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane) , N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diaminopentane, N-methylhe
  • the content of the basic compound is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the treatment liquid. Further, the lower limit of the content is not particularly limited, but is preferably 0.1% by mass or more. Further, the content of the basic compound may be 70 to 100% by mass based on the total mass of the treatment liquid.
  • the treatment liquid may contain only one kind of basic compound, or may contain two or more kinds of basic compounds. When there are two or more types of basic compounds, it is preferable that the total is within the above range.
  • the base generator having an amide group used in the present invention among the base generators used in the resin composition according to the present invention described below, those having an amide group can be used without particular limitation. Further, the base generator having an amide group may be a photobase generator or a thermal base generator, but is preferably a thermal base generator.
  • Preferred embodiments of the physical properties such as molecular weight, boiling point, melting point, pKa, etc. of the base generated from the base generator having an amide group are the same as the above-mentioned preferred embodiments of each physical property of the base having an amide group.
  • Examples of the base generator having an amide group include, but are not limited to, the following compounds.
  • the treatment liquid may contain, as the base generator, a base generator that does not have an amide group (also referred to as "another base generator").
  • a base generator that does not have an amide group
  • other base generators among the base generators used in the resin composition according to the present invention described later, those having no amide group can be used without particular limitation.
  • the other base generator may be a photobase generator or a thermal base generator, but is preferably a thermal base generator.
  • the content of the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the treatment liquid. Moreover, it is preferable that the said content is 0.1 mass % or more.
  • the treatment liquid may contain only one kind of base generator, or may contain two or more kinds of base generators. When there are two or more types of base generators, it is preferable that the total is within the above range.
  • the treatment liquid may further contain a polymerization inhibitor.
  • the treatment liquid in the present invention contains at least one compound selected from the group consisting of a basic compound having an acrylamide group or a methacrylamide group, and a base generator having an acrylamide group or a methacrylamide group, and Embodiments that include inhibitors are also one of the preferred embodiments of the invention.
  • polymerization inhibitors include, but are not limited to, phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds. Can be mentioned.
  • Specific compounds of the polymerization inhibitor include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenyl Hydroxyamine cerous salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2, 6-di-tert-butyl-4-methylphenol, 5-
  • the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, and preferably 0.02 to 15% by mass, based on the total solid content of the treatment solution. It is more preferable that the amount is 0.05 to 10% by mass.
  • the number of polymerization inhibitors may be one, or two or more. When there are two or more types of polymerization inhibitors, it is preferable that the total is within the above range.
  • the treatment liquid may contain a solvent.
  • the solvent include water and organic solvents, with organic solvents being preferred.
  • organic solvents include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ - Butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, alkyloxyacetate (e.g.
  • methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate e.g. methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate) , ethyl ethoxy acetate, etc.
  • 3-alkyloxypropionate alkyl esters e.g. methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • Preferred examples include glycol, methylisobutylcarbinol, triethylene glycol, etc., and amides such as N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.
  • the above-mentioned basic compound for example, an organic base
  • the above-mentioned basic compound can be used as a solvent and a basic compound.
  • the solvent contained in the treatment liquid preferably contains at least one selected from the group consisting of an amide group-containing solvent, propylene glycol monomethyl ether acetate, and ⁇ -butyrolactone.
  • the solvent having an amide group include N-methyl-2-pyrrolidone, N-ethylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.
  • the content of the solvent relative to the total mass of the treatment liquid is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. preferable.
  • the content of the organic solvent with respect to the total weight of the treatment liquid is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more. It is even more preferable that there be.
  • the number of solvents may be one, or two or more. When there are two or more types of solvents, it is preferable that the total is within the above range.
  • the treatment liquid may further contain other components.
  • Other components include, for example, known surfactants and known antifoaming agents.
  • the treatment step is a step of bringing the patterned film obtained in the development step into contact with a treatment liquid.
  • the method of supplying the treatment liquid is not particularly limited as long as the treatment liquid can be brought into contact with the film, but examples include a method of supplying the treatment liquid onto the film obtained in the film formation step, a method of supplying the treatment liquid onto the film obtained in the film formation step, and a method of supplying the treatment solution after the exposure step described below. Examples include a method of supplying the processing liquid onto a patterned film, and a method of supplying the processing liquid onto a patterned film.
  • the above-mentioned supply method including immersing the substrate in the treatment liquid, supplying with a paddle (liquid mound) on the substrate, supplying the treatment liquid onto the substrate with a shower, and applying the treatment liquid onto the substrate.
  • a method of continuously supplying the processing liquid using means such as a straight nozzle. From the viewpoint of the permeability of the processing liquid to the image area, the removability of the non-image area, and manufacturing efficiency, there are methods of supplying the processing liquid using a shower nozzle, straight nozzle, spray nozzle, etc., and continuous supply using a nozzle is available.
  • a method is preferred, and from the viewpoint of permeability of the processing liquid into the image area, a method in which the processing liquid supplied through a nozzle is maintained on the substrate is more preferable.
  • the above processing liquid supply methods (for example, a combination of supply using a paddle and supply using a shower, supply using a paddle and supply using a straight nozzle) may be used in combination.
  • paddle supply has the effect of swelling the membrane and making it easier for subsequent processing liquid to penetrate
  • shower supply and spray supply have the effect of increasing the removability of non-image areas.
  • the treatment liquid may be used in at least one of the combined methods.
  • the treatment step using the treatment liquid may be performed.
  • the method for supplying the treatment liquid containing neither the basic compound having an amide group nor the base generator having an amide group onto the pattern is not particularly limited, but may include supply using a paddle.
  • the method for supplying the treatment liquid onto the pattern in the above embodiment is not particularly limited, but preferable examples include supply using a shower, supply using a straight nozzle, and the like.
  • a processing liquid that does not contain either a basic compound having an amide group or a base generator having an amide group By supplying a processing liquid that does not contain either a basic compound having an amide group or a base generator having an amide group through a paddle, the pattern swells and contains the amide group in the processing liquid that is subsequently supplied. It is thought that at least one compound selected from the group consisting of a basic compound and a base generator having an amide group can more easily penetrate into the pattern, making it easier to obtain effects such as improving elongation at break.
  • methods for supplying the treatment liquid in the treatment process include a process in which the treatment liquid is continuously supplied to the substrate, a process in which the treatment liquid is kept in a substantially stationary state on the substrate, and a process in which the treatment liquid is kept in a substantially stationary state on the substrate.
  • a process of vibrating with a sound wave or the like, a process of combining these, etc. can be adopted.
  • the treatment step is preferably a step in which the treatment liquid is supplied to the pattern after development by a method of widely irradiating the developed pattern, such as by spraying or showering, or in which it is continuously supplied. Further, it is also preferable that the development in the development step is performed by paddle development, and that the processing liquid in the processing step is supplied at least once by a shower or by continuous supply by a straight nozzle or the like.
  • the pattern swells due to paddle development, at least one compound selected from the group consisting of a basic compound and a base generator in the processing solution easily permeates into the pattern, thereby reducing elongation at break. It is thought that it will be easier to obtain effects such as improvement.
  • the treatment time in the treatment step (that is, the time during which the treatment liquid is in contact with the pattern) is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
  • the temperature of the treatment liquid during the treatment step is not particularly limited, but it is preferably carried out at 10 to 45°C, more preferably 18 to 30°C.
  • the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed in the film forming step.
  • Selectively exposing means exposing a portion of the film.
  • an exposed area (exposed area) and an unexposed area (unexposed area) are formed in the film.
  • the exposure amount is not particularly limited as long as it can cure the resin composition of the present invention, but for example, it is preferably 50 to 10,000 mJ/cm 2 and more preferably 200 to 8,000 mJ/cm 2 in terms of exposure energy at a wavelength of 365 nm. preferable.
  • the exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
  • the exposure wavelength is: (1) semiconductor laser (wavelength: 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, G-line (wavelength) 436 nm), h line (wavelength 405 nm), i line (wavelength 365 nm), broad (three wavelengths of g, h, i line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc.
  • semiconductor laser wavelength: 830 nm, 532 nm, 488 nm, 405 nm, 375 nm,
  • the resin composition of the present invention exposure using a high-pressure mercury lamp is particularly preferred, and from the viewpoint of exposure sensitivity, exposure using i-line is more preferred.
  • the method of exposure is not particularly limited, and may be any method as long as at least a portion of the film made of the resin composition of the present invention is exposed to light, and examples thereof include exposure using a photomask, exposure using a laser direct imaging method, etc. .
  • the film may be subjected to a heating step after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the film exposed in the exposure step.
  • the post-exposure heating step can be performed after the exposure step and before the development step.
  • the heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.
  • the heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
  • the temperature increase rate in the post-exposure heating step is preferably 1 to 12°C/min, more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min from the temperature at the start of heating to the maximum heating temperature. Further, the temperature increase rate may be changed as appropriate during heating.
  • the heating means in the post-exposure heating step is not particularly limited, and a known hot plate, oven, infrared heater, etc. can be used, and heating with a hot plate is preferred. It is also preferable that the heating be performed in an atmosphere with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon.
  • the exposed film may be subjected to a development step of developing a pattern using a developer. That is, the method for producing a cured product of the present invention may include a development step of developing the film exposed in the exposure step using a developer to form a pattern. By performing development, one of the exposed and non-exposed areas of the film is removed and a pattern is formed.
  • development in which the non-exposed portions of the film are removed in the developing step is referred to as negative development
  • development in which the exposed portions of the film are removed in the development step is referred to as positive development.
  • Examples of the developer used in the development step include an alkaline aqueous solution or a developer containing an organic solvent.
  • basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
  • TMAH tetramethylammonium hydroxide
  • potassium hydroxide sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine , dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, Butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammoni
  • the compound described in paragraph 0387 of International Publication No. 2021/112189 can be used as the organic solvent.
  • alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene glycol, etc.
  • Amides include N-methylpyrrolidone, N-ethylpyrrolidone, Dimethylformamide and the like are also suitable.
  • the developer contains an organic solvent
  • one type of organic solvent or a mixture of two or more types can be used.
  • a developer containing at least one member selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred.
  • a developer containing at least one selected from the group consisting of and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.
  • the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more. is more preferable, and particularly preferably 90% by mass or more. Moreover, the said content may be 100 mass %.
  • the developer may contain at least one compound selected from the group consisting of a basic compound and a base generator.
  • the processing solution used in the above-mentioned processing steps may be used.
  • a preferred embodiment of the present invention is one in which the developing solution does not contain either a basic compound or a base generator. According to the above aspect, variations in pattern shape may be suppressed.
  • preferred compounds as at least one compound selected from the group consisting of basic compounds and base generators include preferred compounds of the basic compounds and base generators contained in the above-mentioned treatment liquid.
  • the developer may further contain other components.
  • other components include known surfactants and known antifoaming agents.
  • the method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and methods include immersing the base material on which the film is formed in the developer, and supplying the developer to the film formed on the base material using a nozzle.
  • a method of supplying with a spray nozzle is more preferable.
  • the base material is spun to remove the developer from the base material, and after spin drying, the developer is continuously supplied again using the straight nozzle, then the base material is spun and the developer is applied to the base material.
  • a process of removing from above may be adopted, or this process may be repeated multiple times.
  • Methods for supplying the developer in the development process include a process in which the developer is continuously supplied to the base material, a process in which the developer is kept in a substantially stationary state on the base material, and a process in which the developer is applied to the base material using ultrasonic waves. Examples include a step of vibrating with the like, and a step of combining these.
  • the development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
  • the temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.
  • the treatment liquid is a rinsing liquid.
  • the rinsing liquid is a liquid used for cleaning a film, for example, a liquid used for cleaning a patterned film after exposure and development.
  • the treatment step is a rinsing step of cleaning the membrane with the treatment liquid.
  • the rinsing step is preferably a rinsing step in which the patterned film after the exposure step and the development step is washed with the treatment liquid.
  • a method such as supplying a processing liquid before the developer in contact with the pattern is completely dried may be adopted. Specifically, by supplying the processing liquid onto the patterned film after the development step using the processing liquid supply method described above, the patterned film can be cleaned with the processing liquid.
  • the treatment step after cleaning the patterned film obtained by the development step by contacting it with a rinsing liquid. That is, in the above aspect A, it is also preferable to further include a rinsing step of bringing a rinsing liquid into contact with the patterned film between the developing step and the treatment step.
  • the rinsing liquid may be a composition corresponding to the above-mentioned treatment liquid, or may be a rinsing liquid that does not contain a base or a compound corresponding to a base generator.
  • a method may be adopted such as supplying the processing liquid before the rinsing liquid in contact with the pattern is completely dry.
  • Examples of the rinsing liquid that does not contain a base or a compound corresponding to a base generator include a rinsing liquid that contains an organic solvent.
  • Examples of the organic solvent contained in the rinsing liquid include the same organic solvents as those exemplified in the case where the above-mentioned developer contains an organic solvent.
  • the organic solvent contained in the rinsing liquid is preferably an organic solvent different from the organic solvent contained in the developer, and more preferably an organic solvent in which the pattern has a lower solubility than the organic solvent contained in the developer.
  • the organic solvent can be used alone or in a mixture of two or more.
  • the organic solvent is preferably cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, PGMEA, or PGME, and cyclohexanone or PGMEA. More preferred.
  • the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the rinsing liquid. Moreover, the organic solvent may be 100% by mass with respect to the total mass of the rinsing liquid.
  • the rinse solution may further contain other components.
  • other components include known surfactants and known antifoaming agents.
  • Examples of the method for supplying the rinsing liquid include the same method as the above-mentioned method for supplying the processing liquid.
  • the method for producing a cured product of the present invention includes an exposure step of selectively exposing the film between the film forming step and the processing step, and the processing step includes developing the processing solution. It is also preferable that the process is a step of developing the film as a liquid to form a patterned film.
  • an embodiment in which the film forming step, the exposure step, and the developing step of developing the film using a processing solution as a developer to form a patterned film will also be referred to as embodiment B.
  • the exposure step in the above aspect B is the same as the exposure step in the above aspect A, and the preferred embodiments are also the same.
  • the developing step in the above embodiment B is the same as the developing step in the above embodiment A, except that a processing liquid is used as the developer, and the preferred embodiments are also the same.
  • the development in the development step in aspect B is preferably negative development.
  • Embodiment B above further includes a second treatment step of contacting a second treatment liquid with the patterned film after the treatment step (development step), wherein the second treatment liquid contains a basic compound, It is also preferable that at least one compound selected from the group consisting of a base generator and a base generator is included. Preferred embodiments of the second treatment liquid are the same as those of the treatment liquid described above. Further, it is also preferable that the second processing liquid is a rinsing liquid. Further, it is preferable that the second treatment step is a rinsing step of cleaning the patterned film with the treatment liquid.
  • the heating and cooling process can dry the solvent in the treatment liquid.
  • the heating temperature in the heating and cooling step is preferably 80 to 120°C, more preferably 90 to 110°C.
  • the heating time in the heating and cooling step is preferably 10 seconds to 300 seconds, more preferably 30 seconds to 180 seconds.
  • the heating means in the heating and cooling step is not particularly limited, and a known hot plate, oven, infrared heater, etc. can be used, and heating with a hot plate is preferred.
  • the temperature of the film after cooling in the heating and cooling step is preferably, for example, 10 to 50°C, more preferably 15 to 40°C.
  • the cooling means is not particularly limited and any known cooling means may be used, including natural cooling (natural heat dissipation), cooling using a known cooling device such as a device using a Peltier element, and the like. Further, during cooling, it is also preferable to perform the cooling in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.
  • the method for producing a cured product of the present invention includes a heating step of heating the pattern obtained by the developing step.
  • the method for producing a cured product of the present invention may include a heating step of heating a pattern obtained by another method without performing a developing step, or a film obtained by a film forming step.
  • a resin such as a polyimide precursor is cyclized to become a resin such as polyimide.
  • crosslinking of unreacted crosslinkable groups in the specific resin or a crosslinking agent other than the specific resin also progresses.
  • the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, particularly 160 to 230°C. preferable. Furthermore, it is particularly preferable that the heating temperature in the heating step is 180° C. or lower and the heating time is 3 hours or less. In the above embodiment, the heating temperature is preferably as low as possible from the viewpoint of suppressing deformation of the base material, etc., but from the viewpoint of the imidization rate of polyimide in the cured product, it is preferably 150°C to 180°C, and 160°C to 180°C. More preferably, the temperature is from °C to 180 °C.
  • the shorter the heating time the better from the viewpoint of suppressing deformation of the base material, etc., but from the viewpoint of the imidization rate of polyimide in the cured product, it is preferably 1 to 3 hours, and 2 to 3 hours. It is more preferable that there be.
  • the heating step is preferably a step of promoting the cyclization reaction of the polyimide precursor within the pattern by heating and the action of a base generated from the base generator.
  • Heating in the heating step is preferably carried out at a temperature increase rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature.
  • the temperature increase rate is 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, 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, for example, 30°C higher than the boiling point of the solvent contained in the resin composition. It is preferable to raise the temperature from a lower temperature by ⁇ 200°C.
  • the heating time (heating time at the highest heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
  • the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher.
  • the upper limit of the heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.
  • Heating may be performed in stages. As an example, the temperature is raised from 25°C to 120°C at a rate of 3°C/min, held at 120°C for 60 minutes, and the temperature is raised from 120°C to 180°C at a rate of 2°C/min, and held at 180°C for 120 minutes. , etc. may be performed. It is also preferable to perform the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such pretreatment steps can improve the properties of the film. The pretreatment step is preferably carried out for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
  • the pretreatment may be performed in two or more steps, for example, the first pretreatment step may be performed at a temperature of 100 to 150°C, followed by the second pretreatment step at a temperature of 150 to 200°C. good. Furthermore, cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5° C./min.
  • the heating step is preferably performed in an atmosphere with a low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium, or argon, or under reduced pressure, from the viewpoint of preventing decomposition of the specific resin.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
  • the heating means in the heating step is not particularly limited, and includes, for example, a hot plate, an infrared oven, an electric oven, a hot air oven, an infrared oven, and the like.
  • the pattern obtained in the development step (in the case of performing the rinsing step, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern after the development step is exposed.
  • the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained in the development step.
  • the method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
  • the post-development exposure step for example, a reaction in which cyclization of a polyimide precursor etc.
  • the post-development exposure step at least a portion of the pattern obtained in the development step may be exposed, but it is preferable that the entire pattern be exposed.
  • the exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , more preferably 100 to 15,000 mJ/cm 2 in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive.
  • the post-development exposure step can be performed, for example, using the light source used in the above-mentioned exposure step, and it is preferable to use broadband light.
  • the pattern obtained by the development process (preferably one that has been subjected to at least one of a heating process and a post-development exposure process) may be subjected to a metal layer forming process of forming a metal layer on the pattern. That is, the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on the pattern obtained by the development step (preferably one that has been subjected to at least one of the heating step and the post-development exposure step). It is preferable.
  • metal layer existing metal species can be used without particular limitation, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. copper and aluminum are more preferred, and copper is even more preferred.
  • the method for forming the metal layer is not particularly limited, and existing methods can be applied.
  • the methods described in JP 2007-157879, JP 2001-521288, JP 2004-214501, JP 2004-101850, US Patent No. 7888181B2, and US Patent No. 9177926B2 are used. can do.
  • photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and a combination thereof can be used.
  • a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating can be mentioned.
  • a preferred embodiment of plating includes electrolytic plating using copper sulfate or copper cyanide plating solution.
  • the thickness of the metal layer is preferably 0.01 to 50 ⁇ m, more preferably 1 to 10 ⁇ m at the thickest part.
  • Fields to which the method for producing a cured product of the present invention or the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, and the like. Other methods include forming a pattern by etching a sealing film, a substrate material (a base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above.
  • a substrate material a base film or coverlay of a flexible printed circuit board, an interlayer insulating film
  • an insulating film for mounting purposes as described above.
  • the method for producing a cured product of the present invention or the cured product of the present invention can be used for producing plates such as offset plates or screen plates, for etching molded parts, and for use in protective lacquers and dielectric layers in electronics, particularly microelectronics. It can also be used for manufacturing.
  • the laminate of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
  • the laminate is a laminate including two or more layers made of cured material, and may be a laminate in which three or more layers are laminated. At least one of the two or more layers made of the cured product contained in the laminate is a layer made of the cured product of the present invention, and shrinkage of the cured product or deformation of the cured product due to the shrinkage, etc. From the viewpoint of suppression, it is also preferable that all the layers made of the cured product contained in the above-mentioned laminate are layers made of the cured product of the present invention.
  • the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.
  • the laminate of the present invention preferably includes two or more layers made of a cured product and includes a metal layer between any of the layers made of the cured product.
  • the metal layer is preferably formed by the metal layer forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on the layer made of the cured product during the method for producing the cured product which is performed multiple times. A preferred embodiment of the metal layer forming step is as described above.
  • the resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product have the same composition. It may be a product or a composition having a different composition.
  • the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
  • the method for manufacturing a laminate of the present invention includes a lamination step.
  • the lamination process refers to (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process and development on the surface of the pattern (resin layer) or metal layer again. This is a series of steps including performing at least one of the post-exposure steps in this order.
  • an embodiment may be adopted in which at least one of the (a) film forming step and (d) heating step and post-development exposure step is repeated.
  • a (e) metal layer forming step may be included.
  • the lamination step may further include the above-mentioned drying step and the like as appropriate.
  • a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer forming step.
  • Plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.
  • the above lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
  • the above layers may have the same composition, shape, thickness, etc., or may have different compositions, shapes, thicknesses, etc.
  • a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer.
  • the following steps are repeated in the following order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of the heating step and post-development exposure step, and (e) metal layer formation step.
  • an embodiment may be mentioned in which (a) a film forming step, (d) at least one of a heating step and a post-development exposure step, and (e) a metal layer forming step are repeated in this order.
  • the method for producing a laminate of the present invention preferably includes a surface activation treatment step of surface activation treatment of at least a portion of the metal layer and the resin composition layer.
  • the surface activation treatment step is usually performed after the metal layer forming step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer is subjected to the surface activation treatment. After performing this step, the metal layer forming step may be performed.
  • the surface activation treatment may be performed on at least a portion of the metal layer, or may be performed on at least a portion of the resin composition layer after exposure, or the surface activation treatment may be performed on at least a portion of the metal layer and the resin composition layer after exposure.
  • the surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable that the surface activation treatment is performed on a part or all of the region of the metal layer on which the resin composition layer is to be formed.
  • the surface activation treatment is also performed on part or all of the resin composition layer (resin layer) after exposure.
  • the resin composition layer when the resin composition layer is hardened, such as when performing negative development, it is less likely to be damaged by surface treatment and adhesion is likely to be improved.
  • the surface activation treatment can be performed, for example, by the method described in paragraph 0415 of International Publication No. 2021/112189. This content is incorporated herein.
  • the present invention also discloses a semiconductor device containing the cured product or laminate of the present invention.
  • the present invention also discloses a method for manufacturing a semiconductor device, including a method for manufacturing a cured product or a method for manufacturing a laminate according to the present invention.
  • a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer the descriptions in paragraphs 0213 to 0218 of JP 2016-027357A and the description in FIG. 1 can be referred to, Their contents are incorporated herein.
  • the resin composition is a resin composition used in the method of manufacturing a cured product of the present invention, the method of manufacturing a laminate of the present invention, or the method of manufacturing a semiconductor device of the present invention.
  • the resin composition of the present invention includes a polyimide precursor (hereinafter also referred to as "specific resin") containing a repeating unit represented by formula (1).
  • R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R 1 and R 2 is a monovalent organic group having an ethylenically unsaturated bond. It is.
  • X 1 is a group containing a structure represented by the following formula (X-1), and Y 1 is a divalent organic group represented by the following general formula (Y-1).
  • R 3 to R 10 are each independently a hydrogen atom or a monovalent group, and at least one of R 3 to R 10 may have a fluorine atom or a substituent. It is an alkyl group, a substituent having a fluorine atom, or an alkoxy group which may have a substituent, and R 5 and R 7 and R 6 and R 8 may be bonded to form a ring structure, and * is each , represents the bonding site with the nitrogen atom in formula (1).
  • R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, and at least one of R 1 and R 2 is a monovalent organic group having an ethylenically unsaturated bond. be.
  • An embodiment in which both R 1 and R 2 are monovalent organic groups having an ethylenically unsaturated bond is also one of the preferred embodiments of the present invention.
  • Examples of the monovalent organic group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinyl phenyl group, etc.), ( A group having a meth)acrylamide group, a (meth)acryloyloxy group, or a group having a group represented by the following formula (III) is preferred, and a group having a group represented by the following formula (III) is more preferred. Further, an embodiment in which the monovalent organic group having an ethylenically unsaturated bond is a group represented by the following formula (III) is also one of the preferred embodiments of the present invention.
  • R 200 represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, and preferably a hydrogen atom or a methyl group.
  • * represents a bonding site with another structure.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH(OH)CH 2 -, a cycloalkylene group or a polyalkyleneoxy group.
  • R 201 examples include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1, Examples include 3-butanediyl group, -CH 2 CH (OH) CH 2 -, polyalkyleneoxy group, alkylene groups such as ethylene group and propylene group, -CH 2 CH (OH) CH 2 -, cyclohexyl group, polyalkylene group.
  • An oxy group is more preferred, and an alkylene group such as an ethylene group or a propylene group, or a polyalkyleneoxy group is even more preferred.
  • a 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 arrangement or an arrangement having blocks. Alternatively, an arrangement having an alternating pattern or the like may be used.
  • the number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6.
  • the 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, and even more preferably 2 to 6.
  • polyalkyleneoxy groups include polyethyleneoxy groups, polypropyleneoxy groups, polytrimethyleneoxy groups, polytetramethyleneoxy groups, or multiple ethyleneoxy groups and multiple propyleneoxy groups.
  • a group bonded to an oxy group is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is even more preferable.
  • the ethyleneoxy groups and propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in an alternating pattern. Preferred embodiments of the repeating number of ethyleneoxy groups, etc. in these groups are as described above.
  • the specific resin when R 1 is a hydrogen atom or when R 2 is a hydrogen atom, the specific resin may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond.
  • a tertiary amine compound having such an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.
  • one of R 1 and R 2 may be a monovalent organic group having no ethylenically unsaturated bond.
  • a group represented by a combination with -S-, -SO 2 - or -NR N - is preferred, a group represented by a hydrocarbon group or a combination of a hydrocarbon group and -O- is more preferred, and an alkyl group, aromatic hydrocarbon group or polyalkyleneoxy group are more preferred.
  • the alkyl group when simply described as an alkyl group, the alkyl group includes any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group.
  • alkylene groups aliphatic hydrocarbon groups, etc.
  • X 1 is a group containing a structure represented by the following formula (X-1).
  • Ar 1 and Ar 2 may be aromatic hydrocarbon ring structures or aromatic heterocyclic structures, but are preferably aromatic hydrocarbon ring structures.
  • the aromatic hydrocarbon ring structure is preferably an aromatic hydrocarbon ring structure having 6 to 20 carbon atoms, more preferably a benzene ring structure or a naphthalene ring structure, and even more preferably a naphthalene ring structure.
  • Examples of the heteroatom in the aromatic heterocyclic structure include an oxygen atom, a nitrogen atom, and a sulfur atom, with a nitrogen atom being preferred.
  • the aromatic heterocyclic structure may be any of a 5-membered ring structure, a 6-membered ring structure, and a fused ring structure thereof, but a 6-membered ring structure is preferable.
  • R X1 each independently represents a hydrogen atom, an aromatic hydrocarbon group that may have a substituent, or a hydrocarbon group that may be substituted with a halogen atom, and at least one of them is Preferably, it is a hydrocarbon group which may be optional.
  • the aromatic hydrocarbon group which may have a substituent a phenyl group is preferably mentioned.
  • Examples of the hydrocarbon group which may be substituted with a halogen atom include an alkyl group and a halogenated alkyl group, and a methyl group or a trifluoromethyl group is more preferable.
  • Two R X1s may be combined to form a ring structure, and the ring structure formed is preferably a 6-membered ring structure.
  • R X2 represents a halogen atom, preferably a fluorine atom.
  • n represents an integer of 1 or more, preferably 1 to 4, more preferably 1 or 2.
  • m represents an integer of 1 or more, preferably 1 to 4, more preferably 1 or 2.
  • X 1 in formula (1) has a structure represented by the following formula (X-2).
  • R represents an aromatic hydrocarbon group that may have or a hydrocarbon group that may be substituted with a halogen atom
  • two R X1 may be bonded to form a ring structure
  • R X2 is represents a halogen atom
  • each # represents a bonding site with a carbonyl group in formula (1).
  • preferred embodiments of X, R X1 and R X2 are the same as the preferred embodiments of X, R X1 and R X2 in formula (X-1) above.
  • Preferred embodiments of the structure represented by formula (X-2) include, but are not limited to, the following structures.
  • * has the same meaning as # in formula (X-2).
  • X 1 in formula (1) has a bisphenol structure including the structure represented by the above formula (X-1).
  • a bisphenol structure has a structure in which Ar 1 and Ar 2 in formula (1) are benzene ring structures, n and m are 1 or more, and Ar 1 and Ar 2 are directly bonded to -O-.
  • the bisphenol structure formed by this is mentioned.
  • X 1 in formula (1) has a structure represented by formula (X-3) below.
  • R represents an aromatic hydrocarbon group that may have or a hydrocarbon group that may be substituted with a halogen atom
  • two R X1 may be bonded to form a ring structure
  • R X2 is It represents a halogen atom
  • each # represents a bonding site with a carbonyl group in formula (1).
  • preferred embodiments of X, R X1 and R X2 are the same as the preferred embodiments of X, R X1 and R X2 in formula (X-1) above.
  • Y 1 is a divalent organic group represented by formula (Y-1).
  • R 3 to R 10 is preferably an alkyl group, a fluorine atom, or a perfluoroalkyl group, and more preferably a fluorine atom or a trifluoromethyl group.
  • the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
  • the above perfluoroalkyl group is preferably a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a trifluoromethyl group.
  • the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group.
  • R 5 and R 7 and R 6 and R 8 may be combined to form a ring structure.
  • the ring structure formed is not particularly limited, but a hydrocarbon ring is preferred.
  • the ring structure formed is preferably a 5-membered ring structure or a 6-membered ring structure, and more preferably a 5-membered ring structure.
  • Y 1 is a divalent organic group represented by formula (Y-2).
  • R 5 and R 8 are each independently an alkyl group, a fluorine atom, or a trifluoromethyl group, and * each represents a bonding site with the nitrogen atom in formula (1).
  • R 5 and R 8 are preferably each independently a fluorine atom or a trifluoromethyl group.
  • the alkyl group for R 5 and R 8 is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
  • divalent organic group represented by formula (Y-1) examples include structures represented by the following formula, but the present invention is not limited thereto.
  • * has the same meaning as * in formula (Y-1).
  • Y 1 is a group represented by formula (Y-3).
  • Y-3 an embodiment in which the specific resin has a repeating unit in which Y 1 is represented by formula (Y-1) and a repeating unit in which Y 1 is represented by formula (Y-2) is also mentioned. It will be done.
  • R 12 to R 15 are each independently a hydrogen atom, a halogen atom, or a monovalent organic group, and * each represents a bonding site with the nitrogen atom in formula (1). represent.
  • R 12 to R 15 in formula (Y-3) are all hydrogen atoms is also one of the preferred embodiments of the present invention.
  • the halogen atom in R 12 to R 15 is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom or a chlorine atom, and even more preferably a fluorine atom.
  • examples of the monovalent organic group for R 12 to R 15 include a hydrocarbon group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyloxy group, and an arylcarbonyl group.
  • Examples include an oxy group, a poly(alkyleneoxy) group, a poly(aryleneoxy) group, a poly(alkyleneoxycarbonyl) group, a poly(aryleneoxycarbonyl) group, a hydroxy group, and a cyano group.
  • Y 1 may have the same structure as R 111 in formula (2) described below.
  • the specific resin further contains a repeating unit represented by the following formula (3).
  • Z 2 is a tetravalent organic group represented by any of the following formulas (2a) to (2d), Y 2 is a divalent organic group, and A 1 and A 2 are each independently an oxygen atom or -NR Z -, R Z is a hydrogen atom or a monovalent organic group, R 1 and R 2 are each independently a hydrogen atom or a monovalent organic group, At least one of R 1 and R 2 is a monovalent organic group having an ethylenically unsaturated bond.
  • Z 2 in formula (3) is preferably a tetravalent organic group represented by formula (2a) or formula (2d); It is more preferable that In formulas (2a) to (2d), L 1 and L 2 are each independently a divalent group or a single bond that is not conjugated with the benzene ring to which they are bonded, and *1 to *4 are each represented by the formula (3) represents the bonding site with the carbonyl group in (3).
  • L 1 and L 2 are each independently preferably -C(R C ) 2 -, -Si(R S ) 2 -, -O-, or a single bond, and -C More preferably, it is (R C ) 2 -, -Si(R S ) 2 -, or -O-. Also. It is preferable that at least one of L 1 and L 2 is -C(R C ) 2 - or -Si(R S ) 2 -.
  • R C is each independently a hydrogen atom or a hydrocarbon group, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group.
  • R C 's may be combined to form a ring structure.
  • R S is each independently a hydrocarbon group, preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group. Furthermore, two R S may be combined to form a ring structure.
  • one of *1 or *2 is bonded to the carbonyl group bonded to A 1 in formula (3), and the other is a group other than the repeating unit represented by formula (3).
  • One of *3 or *4 is bonded to the carbonyl group bonded to the structure of A2 in formula (3), and the other is bonded to NH described in formula (3). It is preferable to bond with a carbonyl group.
  • hydrogen atoms in the ring structures described in formulas (2a) to (2d) may be substituted with known substituents.
  • substituents include an alkyl group, a halogen atom, an alkyl group in which a hydrogen atom is substituted with a halogen atom, and the like.
  • Y 2 , A 1 , A 2 , R 1 and R 2 are the same as those of Y 1 , A 1 , A 2 , R 1 and R 2 in formula (1). It is.
  • the specific resin further includes a repeating unit represented by the following formula (2) as a repeating unit different from both the repeating unit represented by the above formula (1) and the repeating unit represented by the formula (3). But that's fine.
  • the repeating unit that corresponds to the repeating unit represented by formula (1) and the repeating unit represented by formula (3) do not correspond to the repeating unit represented by formula (2) below. shall be taken as a thing.
  • a 1 and A 2 each independently represent an oxygen atom or -NR z -
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group.
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group
  • R z represents a hydrogen atom or a monovalent organic group.
  • a 1 and A 2 in formula (2) each independently represent an oxygen atom or -NR z -, and preferably an oxygen atom.
  • Rz represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.
  • R 111 in formula (2) represents a divalent organic group.
  • divalent organic groups include groups containing straight-chain or branched aliphatic groups, cyclic aliphatic groups, and aromatic groups, including straight-chain or branched aliphatic groups having 2 to 20 carbon atoms, A group consisting of a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
  • the hydrocarbon group in the chain may be substituted with a group containing a hetero atom, and in the above cyclic aliphatic group and aromatic group, the hydrocarbon group in the chain may be substituted with a hetero atom. may be substituted with a group containing.
  • R 111 in formula (2) include groups represented by -Ar- and -Ar-L-Ar-, with a group represented by -Ar-L-Ar- being preferred.
  • Ar is each independently an aromatic group
  • L is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO -, -S-, -SO 2 -, -NHCO-, or a combination of two or more of the above.
  • R 111 is derived from a diamine.
  • diamines used for producing the specific resin include linear or branched aliphatic, cyclic aliphatic, and aromatic diamines.
  • One type of diamine may be used, or two or more types may be used.
  • R 111 is a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or any of these.
  • a diamine containing a combination of groups is preferable, and a diamine containing an aromatic group having 6 to 20 carbon atoms is more preferable.
  • the above-mentioned straight-chain or branched aliphatic group may have a hydrocarbon group in the chain substituted with a group containing a hetero atom.
  • the above-mentioned cyclic aliphatic group and aromatic group may have a ring member hydrocarbon group substituted with a hetero atom-containing group. may be substituted with a group containing.
  • groups containing aromatic groups include the following.
  • diamine specifically, 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane or 1,6-diaminohexane; 1,2- or 1,3-diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis(aminomethyl)cyclohexane , bis-(4-aminocyclohexyl)methane, bis-(3-aminocyclohexyl)methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- or 3,3'-diaminobiphenyl, 4,4'-diaminodipheny
  • diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598.
  • diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 are also preferably used.
  • R 111 is preferably represented by -Ar-L-Ar-.
  • Ar is each independently an aromatic group
  • L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- , -SO 2 -, -NHCO-, or a combination of two or more of the above.
  • Ar is preferably a phenylene group
  • L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms optionally substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 - .
  • the aliphatic hydrocarbon group here is preferably an alkylene group.
  • R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61).
  • a divalent organic group represented by formula (61) is more preferable.
  • R 50 to R 57 are each independently a hydrogen atom, a fluorine atom, or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group, or a trifluoro It is a methyl group, and each * independently represents a bonding site with the nitrogen atom in formula (2).
  • the monovalent organic groups R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples include fluorinated alkyl groups.
  • R 58 and R 59 each independently represent a fluorine atom, a methyl group, or a trifluoromethyl group, and * each independently represents a bonding site with the nitrogen atom in formula (2). represent.
  • Examples of the diamine giving the structure of formula (51) or formula (61) include 2,2'-dimethylbenzidine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2'- Bis(fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminoctafluorobiphenyl, and the like. These may be used alone or in combination of two or more.
  • R 115 in formula (2) represents a tetravalent organic group.
  • a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or formula (6) is more preferable.
  • * each independently represents a bonding site with another structure.
  • R 112 is a single bond or a divalent linking group, and is a single bond or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with a fluorine atom, -O-, A group selected from -CO-, -S-, -SO 2 -, -NHCO-, and combinations thereof is preferable, and the number of carbon atoms optionally substituted with a single bond or a fluorine atom is preferable.
  • it is a group selected from 1 to 3 alkylene groups, -O-, -CO-, -S- and -SO 2 -, including -CH 2 -, -C(CF 3 ) 2 -, - More preferably, it is a divalent group selected from the group consisting of C(CH 3 ) 2 -, -O-, -CO-, -S- and -SO 2 -.
  • R 115 include a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride.
  • the specific resin may contain only one type of tetracarboxylic dianhydride residue, or may contain two or more types of tetracarboxylic dianhydride residues as the structure corresponding to R115 .
  • the tetracarboxylic dianhydride is represented by the following formula (O).
  • R 115 represents a tetravalent organic group.
  • the preferred range of R 115 is the same as R 115 in formula (2), and the preferred range is also the same.
  • tetracarboxylic dianhydride examples include pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'- Diphenylsulfidetetracarboxylic 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 dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,3,
  • preferred examples include tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598.
  • R 111 and R 115 may have an OH group. More specifically, R 111 includes a residue of a bisaminophenol derivative.
  • R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
  • the monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
  • at least one of R 113 and R 114 contains a polymerizable group, and it is more preferable that both of them contain a polymerizable group.
  • the polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, radicals, etc., and a radically polymerizable group is preferable.
  • the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. It will be done.
  • the radically polymerizable group contained in the specific resin is preferably a group having an ethylenically unsaturated bond.
  • groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (for example, vinyl phenyl groups, etc.), and (meth)acrylamide groups.
  • (meth)acryloyloxy group a group represented by the above formula (III), and the like, with the group represented by the above formula (III) being preferred.
  • the specific resin when R 113 is a hydrogen atom, or when R 114 is a hydrogen atom, the specific resin may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond.
  • a tertiary amine compound having such an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.
  • R 113 and R 114 may be a polarity converting group such as an acid-decomposable group.
  • the acid-decomposable group is not particularly limited as long as it decomposes under the action of an acid to produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but examples include an acetal group, a ketal group, a silyl group, and a silyl ether group. , a tertiary alkyl ester group, etc. are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.
  • acid-decomposable groups include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group, tert-butoxycarbonylmethyl group. group, trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, ethoxyethyl group or tetrahydrofuranyl group is preferred.
  • the specific resin has a fluorine atom in its structure.
  • the fluorine atom content in the specific resin is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, and even more preferably 5 to 20% by mass.
  • the specific resin may be copolymerized with an aliphatic group having a siloxane structure for the purpose of improving adhesion to the substrate.
  • examples include embodiments in which bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are used as the diamine.
  • the repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, it is preferable that at least one of the specific resins used in the present invention is a precursor having a repeating unit represented by formula (2-A). When the specific resin contains a repeating unit represented by formula (2-A), it becomes possible to further widen the exposure latitude.
  • a 1 and A 2 represent an oxygen atom
  • R 111 and R 112 each independently represent a divalent organic group
  • R 113 and R 114 each independently, It represents a hydrogen atom or a monovalent organic group
  • at least one of R 113 and R 114 is a group containing a polymerizable group, and preferably both are groups containing a polymerizable group.
  • a 1 , A 2 , R 111 , R 113 and R 114 each independently have the same meaning as A 1 , A 2 , R 111 , R 113 and R 114 in formula (2), and their preferred ranges are also the same.
  • R 112 has the same meaning as R 112 in formula (5), and the preferred ranges are also the same.
  • the specific resin may contain one type of repeating unit represented by formula (2), or may contain two or more types. Furthermore, it may contain structural isomers of the repeating unit represented by formula (2). In addition to the repeating unit of the above formula (2), the specific resin may also contain other types of repeating units.
  • the specific resin may further contain other repeating units different from the repeating units represented by formulas (1) to (3).
  • Examples of other repeating units include a repeating unit represented by the following formula (PAI-2).
  • R 117 represents a trivalent organic group
  • R 111 represents a divalent organic group
  • a 2 represents an oxygen atom or -NH-
  • R 113 represents a hydrogen atom or a monovalent organic group. represents an organic group.
  • R 117 is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or a single bond or a linking group that binds these two groups.
  • the above-linked groups include linear aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
  • An aromatic group having 6 to 20 carbon atoms, or a group having 6 to 20 carbon atoms combined with a single bond or a connecting group is preferable. A group combining two or more of these is more preferable.
  • the group is preferably a group such as -O-, -S-, an alkylene group, a halogenated alkylene group, an arylene group, or a linking group in which two or more of these are bonded together.
  • the alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
  • the above halogenated alkylene group is preferably a halogenated alkylene group having 1 to 20 carbon atoms, more preferably a halogenated alkylene group having 1 to 10 carbon atoms, and more preferably a halogenated alkylene group having 1 to 4 carbon atoms.
  • examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, with a fluorine atom being preferred.
  • the halogenated alkylene group may have a hydrogen atom or all of the hydrogen atoms may be substituted with a halogen atom, but it is preferable that all of the hydrogen atoms are substituted with a halogen atom.
  • examples of preferred halogenated alkylene groups include (ditrifluoromethyl)methylene groups and the like.
  • the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and even more preferably a 1,3-phenylene group or a 1,4-phenylene group.
  • R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated.
  • a tricarboxylic acid compound a compound having three carboxy groups is referred to as a tricarboxylic acid compound. Two of the three carboxy groups of the tricarboxylic acid compound may be converted into acid anhydrides.
  • the optionally halogenated tricarboxylic acid compound used in the production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic, or aromatic tricarboxylic acid compounds. These tricarboxylic acid compounds may be used alone or in combination of two or more.
  • the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 3 to 20 carbon atoms.
  • a tricarboxylic acid compound containing an aromatic group having 6 to 20 carbon atoms or a combination of two or more of these through a single bond or a connecting group is preferred;
  • a tricarboxylic acid compound containing a combination of two or more aromatic groups of 6 to 20 is more preferred.
  • tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid. (or phthalic anhydride) and benzoic acid have a single bond, -O-, -CH 2 -, -C(CH 3 ) 2 -, -C(CF 3 ) 2 -, -SO 2 - or a phenylene group. Examples include linked compounds. These compounds may be compounds in which two carboxyl groups are anhydrides (for example, trimellitic anhydride), or compounds in which at least one carboxyl group is halogenated (for example, trimellitic anhydride). There may be.
  • R 111 , A 2 and R 113 have the same meanings as R 111 , A 2 and R 113 in formula (2) above, respectively, and preferred embodiments are also the same.
  • One embodiment of the specific resin includes an aspect in which the content of the repeating unit represented by formula (1) and the repeating unit represented by formula (3) is 50 mol% or more of the total repeating units.
  • the total content is more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably more than 90 mol%.
  • the upper limit of the total content is not particularly limited, and all repeating units in the specific resin excluding the terminal may be repeating units represented by formula (1), or repeating units represented by formula (1) It may be a repeating unit or a repeating unit represented by formula (3).
  • the repeating unit represented by formula (1) and the repeating unit represented by formula (3) are The content of the repeating unit represented by formula (1) is preferably 5 to 70 mol%, more preferably 20 to 50 mol%, with respect to the total molar content of repeating units.
  • the weight average molecular weight (Mw) of the specific resin is preferably 5,000 to 200,000, more preferably 10,000 to 100,000, and even more preferably 40,000 to 85,000.
  • the number average molecular weight (Mn) of the specific resin is preferably 1,000 to 100,000, more preferably 3,000 to 50,000, and even more preferably 10,000 to 40,000.
  • the molecular weight dispersity of the specific resin is preferably 4.0 or less, more preferably 3.0 or less, and even more preferably 2.0 or less. In this specification, the molecular weight dispersity is a value calculated by weight average molecular weight/number average molecular weight.
  • the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of specific resin are within the above ranges. Further, it is also preferable that the weight average molecular weight, number average molecular weight, and degree of dispersion calculated by considering the plurality of types of specific resins as one resin are each within the above ranges.
  • the specific resin can be synthesized, for example, by the method described in the Examples below, but is not limited thereto. Specifically, for example, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature to obtain a polyamic acid, and a method of reacting a polyamic acid with a condensing agent or an alkylating agent.
  • a method in which a diester is obtained from a tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is acid-halogenated using a halogenating agent and reacted with a diamine is more preferable.
  • the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, Examples include N'-disuccinimidyl carbonate and trifluoroacetic anhydride.
  • alkylating agent examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.
  • halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride, and the like.
  • an organic solvent In the method for producing the specific resin, it is preferable to use an organic solvent during the reaction. The number of organic solvents may be one or two or more.
  • the organic solvent can be determined as appropriate depending on the raw material, and examples include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, ⁇ -butyrolactone, etc. is exemplified.
  • a basic compound In the method for producing the specific resin, it is preferable to add a basic compound during the reaction.
  • the number of basic compounds may be one or two or more.
  • the basic compound can be determined as appropriate depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-amino Examples include pyridine.
  • -Terminal sealing agent- In the method for producing the specific resin, in order to further improve the storage stability, it is preferable to seal the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the terminal end of the specific resin.
  • examples of the terminal capping agent include monoalcohol, phenol, thiol, thiophenol, monoamine, etc. From the viewpoint of properties, it is more preferable to use monoalcohols, phenols, and monoamines.
  • Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol, secondary alcohols such as 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantane alcohol.
  • primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, furfuryl alcohol, and isopropanol.
  • 2-butanol cyclohexyl alcohol
  • Preferred phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalen-1-ol, naphthalen-2-ol, and hydroxystyrene.
  • Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6- Aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminona
  • sealing agents for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic anhydrides, and sulfonic acid carboxylic acid anhydrides, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. preferable.
  • Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like.
  • Preferred carboxylic acid chloride compounds include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexane carbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantane carbonyl chloride. , heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.
  • the method for producing the specific resin may include a step of precipitating a solid. Specifically, after removing the water-absorbed by-products of the dehydration condensation agent coexisting in the reaction solution by filtration as necessary, the obtained product is added to a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof. By adding a polymer component and precipitating the polymer component, the specific resin can be obtained by precipitating it as a solid and drying it. In order to improve the degree of purification, operations such as redissolution, reprecipitation, and drying of the specific resin may be repeated. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.
  • the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more based on the total solid content of the resin composition. It is even more preferable that the amount is 50% by mass or more. Further, the content of the specific resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, and 98% by mass or less based on the total solid content of the resin composition. It is more preferably at most 97% by mass, even more preferably at most 95% by mass.
  • the resin composition of the present invention may contain only one type of specific resin, or may contain two or more types of specific resin. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention preferably contains a metal complex (also referred to as "specific metal complex") having a ⁇ -conjugated site containing a nitrogen atom.
  • a metal complex also referred to as "specific metal complex” having a ⁇ -conjugated site containing a nitrogen atom.
  • the type of metal atom contained in the specific metal complex is not particularly limited, but Group 4 metal atoms are preferable, titanium atoms, zirconium atoms, or hafnium atoms are more preferable, and from the viewpoint of storage stability, titanium atoms is even more preferable. This is presumed to be because the stability of the compound is improved because titanium atoms have a small atomic radius.
  • the number of the metal atoms contained in the specific metal complex is not particularly limited, but may be 1 or more, more preferably 1 to 4, even more preferably 1 or 2, and 1. is particularly preferred.
  • the types of the above metal atoms may be the same or different. For example, when the specific metal complex contains two of the above metal atoms, it may contain two titanium atoms, or it may contain a titanium atom and a zirconium atom.
  • the specific metal complex has a ⁇ -conjugated site containing a nitrogen atom.
  • the nitrogen atom is directly bonded to a metal atom in the specific metal complex.
  • the above bond is not particularly limited, but is preferably a coordinate bond.
  • the ⁇ -conjugated site may have only one nitrogen atom, or may have two or more nitrogen atoms. When there are two or more, it is preferable that one of them is directly bonded to the metal atom in the specific metal complex.
  • the specific metal complex may have only one ⁇ -conjugated site containing the nitrogen atom, or may have two or more, but preferably has one to two.
  • the ⁇ -conjugated site containing a nitrogen atom preferably has a structure represented by the following formula (T1-1).
  • At least two structures bonded to * may be bonded to form a ring structure.
  • the specific metal complex is preferably a compound having a ⁇ -conjugated site containing a nitrogen atom and at least one group selected from the group consisting of a hydroxy group, a mercapto group, and a carboxy group on the same ligand.
  • the specific metal complex may further have another structure different from the ⁇ -conjugated site containing a nitrogen atom.
  • Other structures are not particularly limited, and structures consisting of known ligands can be used.
  • Examples of the above-mentioned ligands include monodentate alkoxide ligands, monodentate aryloxide ligands, polydentate aryloxide ligands, cyclopentadienyl ligands, etc., and these ligands may be further substituted. It may have a group. From the viewpoint of stability of the specific metal complex, substituted or unsubstituted cyclopentadienyl ligands are preferred.
  • the specific metal complex is preferably a compound represented by the following formula (2-1).
  • M is titanium, zirconium or hafnium
  • l1 is an integer of 0 to 2
  • l2 is 0 or 1
  • l1 + l2 ⁇ 2 is an integer of 0 to 2
  • m is an integer of 0 to 4
  • n is an integer of 0 to 2
  • l1 + l2 + m + n x 2 4
  • R 11 is each independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group , or a substituted or unsubstituted phenoxy group
  • R 12 is a substituted or unsubstituted hydrocarbon group
  • R 2 are each independently a group containing a structure represented by the following formula (2-2).
  • each R 3 is independently a group containing a structure represented by the following formula (2-2), and each X A is independently an oxygen atom or a sulfur atom.
  • M is preferably titanium from the viewpoint of storage stability of the composition.
  • l1 and l2 are 0 is also one of the preferred embodiments of the present invention.
  • m is preferably 2 or 4, more preferably 2.
  • n is preferably 1 or 2, more preferably 1.
  • l1 and l2 are 0, and m is 0, 2 or 4.
  • R 11 is preferably a substituted or unsubstituted cyclopentadienyl ligand. Furthermore, although the cyclopentadienyl group, alkoxy group, and phenoxy group in R 11 may be substituted, an embodiment in which they are unsubstituted is also one of the preferred embodiments of the present invention.
  • R 12 is preferably a hydrocarbon group having 1 to 20 carbon atoms, more preferably a hydrocarbon group having 2 to 10 carbon atoms.
  • the hydrocarbon group for R 12 may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aromatic hydrocarbon group is preferable.
  • the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group.
  • the substituent for R 12 is preferably a monovalent substituent, such as a halogen atom. Further, when R 12 is an aromatic hydrocarbon group, it may have an alkyl group as a substituent. Among these, R 12 in formula (2-1) is preferably an unsubstituted phenylene group. Further, the phenylene group in R 12 is preferably a 1,2-phenylene group.
  • formula (2-1) preferred embodiments of the structure represented by formula (2-2) contained in R 2 and R 3 are the same as the preferred embodiments of formula (T1-1) above.
  • formula (2-1) when m is 2 or more and two or more R 2 are included, the structures of the two or more R 2 may be the same or different.
  • formula (2-1) when n is 2 or more and two or more R 3 are included, the structures of the two or more R 3 may be the same or different.
  • R 2 in formula (2-1) represents a binding site with X A in formula (2-1), and # represents a binding site with M in formula (2-1).
  • R 3 in formula (2-1) are described below, but the invention is not limited thereto.
  • * represents a binding site with X A in formula (2-1)
  • # represents a binding site with M in formula (2-1).
  • an embodiment in which the specific metal complex does not have any monodentate ligand other than cyclopentadienyl is also one of the preferred embodiments of the present invention.
  • the specific metal complex generates an amine when heated at 250°C.
  • the temperature is preferably 230°C, more preferably 200°C, and even more preferably 180°C.
  • a specific metal complex is defined as generating an amine at X° C. when the amine is generated in an amount of 10 mol % or more based on the total molar amount.
  • the pKa of the conjugate acid of the amine is preferably 3 or more, more preferably 6 or more.
  • the upper limit of the pKa of the conjugate acid is not particularly limited, it is preferably 30 or less.
  • the pKa of the conjugate acid of the specific metal complex itself is preferably less than 3, preferably -5 or less, and more preferably -10 or less.
  • pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is expressed by its negative common logarithm pKa.
  • pKa is a value calculated by ACD/ChemSketch (registered trademark) unless otherwise specified.
  • the SP (solubility parameter) value is preferably 9 or more, more preferably 10 or more.
  • the upper limit of the SP value is not particularly limited, and may be, for example, 30 or less.
  • the SP value is determined by the Hoy method (HL. Hoy Journal of Painting, 1970, Vol. 42, 76-118).
  • the unit for the SP value is omitted, the unit is cal 1/2 cm -3/2 .
  • the molecular weight of the specific metal complex is preferably 200 to 2,000, more preferably 250 to 1,500, and even more preferably 300 to 1,000.
  • the specific metal complex can be synthesized, for example, by reacting titanium alkoxide with a compound having an alkoxy group or a carboxyl group. Further, it may be synthesized using other known synthesis methods, and the synthesis method is not particularly limited.
  • specific metal complexes include, but are not limited to, J-1 to J-4 used in Examples.
  • the content of the specific metal complex based on the total solid content of the resin composition of the present invention is preferably 0.05 to 20% by mass.
  • the lower limit is more preferably 0.10% by mass or more, further preferably 0.2% by mass or more, particularly preferably 0.5% by mass or more, and most preferably 1% by mass or more.
  • the upper limit is more preferably 15% by mass or less, even more preferably 10% by mass or less, and particularly preferably 8% by mass or less.
  • One type of specific metal complex may be used alone, or two or more types may be used in combination. When two or more types are used together, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter also simply referred to as "other resin").
  • Other resins include polyimide precursors that do not fall under the specific resin (for example, polyimide precursors that do not contain the repeating unit represented by formula (1) and contain the repeating unit represented by formula (2)), Polybenzoxazole precursor, polyamideimide precursor, polyimide, polybenzoxazole, polyamideimide, phenolic resin, polyamide, epoxy resin, polysiloxane, resin containing siloxane structure, (meth)acrylic resin, (meth)acrylamide resin, urethane Examples include resins, butyral resins, styryl resins, polyether resins, polyester resins, and the like.
  • a resin composition with excellent coating properties can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained.
  • a polymerizable group having a high polymerizable group value with a weight average molecular weight of 20,000 or less for example, the molar amount of polymerizable groups contained in 1 g of resin
  • a (meth)acrylic resin having a concentration of 1 ⁇ 10 -3 mol/g or more
  • it is possible to improve the coating properties of the resin composition, the solvent resistance of the pattern (cured product), etc. can.
  • the content of the other resins is preferably 0.01% by mass or more, and 0.05% by mass or more based on the total solid content of the resin composition. It is more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more. More preferred.
  • the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, and 70% by mass based on the total solid content of the resin composition. It is more preferably at most 60% by mass, even more preferably at most 50% by mass.
  • the content of other resins 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 resin composition. is more preferable, even more preferably 5% by mass or less, 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 resin composition of the present invention may contain only one type of other resin, or may contain two or more types of other resins. When two or more types are included, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention contains a polymerizable compound.
  • the polymerizable compound include radical crosslinking agents and other crosslinking agents.
  • the resin composition of the present invention contains a radical crosslinking agent.
  • a radical crosslinking agent is a compound having a radically polymerizable group.
  • the radically polymerizable group a group containing an ethylenically unsaturated bond is preferable.
  • the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinyl phenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
  • (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferable, and from the viewpoint of reactivity, (meth)acryloyl group is more preferable.
  • the radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds.
  • the radical crosslinking agent may have three or more ethylenically unsaturated bonds.
  • the compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and more preferably a compound having 2 to 6 ethylenically unsaturated bonds. More preferred are compounds having the following.
  • the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above ethylenically unsaturated bonds. It is also preferable.
  • the molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
  • radical crosslinking agents include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. These are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds.
  • addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxy groups, amino groups, and sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxies, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
  • the radical crosslinking agent is also preferably a compound having a boiling point of 100°C or higher under normal pressure.
  • Examples of the compound having a boiling point of 100° C. or higher under normal pressure include the compounds described in paragraph 0203 of International Publication No. 2021/112189. This content is incorporated herein.
  • Preferred radical crosslinking agents other than those mentioned above include radically polymerizable compounds described in paragraphs 0204 to 0208 of International Publication No. 2021/112189. This content is incorporated herein.
  • radical crosslinking agents examples include dipentaerythritol triacrylate (commercially available product: KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available product: KAYARAD D-320 (made by Nippon Kayaku Co., Ltd.) Co., Ltd.), A-TMMT (Shin Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (Nippon Kayaku Co., Ltd.)), dipenta Erythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and these (meth)acryloyl groups are ethylene glyco
  • radical crosslinking agents include, for example, SR-494, which is a tetrafunctional acrylate with four ethyleneoxy chains, and SR-209, 231, and 239, which are difunctional methacrylates with four ethyleneoxy chains (all of which are sold by Sartomer Co., Ltd.). (manufactured by Nippon Kayaku Co., Ltd.), DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, TPA-330, a trifunctional acrylate with three isobutyleneoxy chains (manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers.
  • SR-494 which is a tetrafunctional acrylate with four ethyleneoxy chains
  • SR-209, 231, and 239 which are difunctional methacrylates with four ethyleneoxy chains (all of which are sold by Sartomer Co., Ltd.).
  • DPCA-60 a hexafunctional acrylate with six penty
  • urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Publication No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765, Urethane compounds having an ethylene oxide 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.
  • radical crosslinking agent compounds having an amino structure or a sulfide structure in the molecule, which are described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, can also be used. can.
  • the radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphoric acid group.
  • the radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and the unreacted hydroxy group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group.
  • a radical crosslinking agent having the following is more preferable.
  • the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. It is a compound that is Commercially available products include, for example, polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd., such as M-510 and M-520.
  • the acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, more preferably 1 to 100 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, it will have excellent handling properties during production and excellent developability. Moreover, it has good polymerizability. The above acid value is measured in accordance with the description of JIS K 0070:1992.
  • a radical crosslinking agent (hereinafter also referred to as "crosslinking agent U") having at least one type of structure selected from the group consisting of a urea bond, a urethane bond, and an amide bond is also preferable.
  • the crosslinking agent U may have only one urea bond, urethane bond, or amide bond, or may have two or more structures of one or more types selected from the group consisting of urea bond, urethane bond, and amide bond. good.
  • the total number of urea bonds, urethane bonds, and amide bonds in crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2. .
  • the radical polymerizable group in the crosslinking agent U is not particularly limited, but examples include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, a maleimide group, and the like.
  • a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred.
  • the crosslinking agent U has two or more radically polymerizable groups, the structures of each radically polymerizable group may be the same or different.
  • the number of radically polymerizable groups in the crosslinking agent U may be only one or two or more, preferably 1 to 10, more preferably 1 to 6, particularly preferably 1 to 4.
  • the radically polymerizable group value (mass of compound per mole of radically polymerizable group) in crosslinking agent U is preferably 150 to 400 g/mol.
  • the lower limit of the radically polymerizable group value is more preferably 200 g/mol or more, still more preferably 210 g/mol or more, and preferably 220 g/mol or more. More preferably, it is 230 g/mol or more, even more preferably 240 g/mol or more, and particularly preferably 250 g/mol or more.
  • the upper limit of the radically polymerizable group value is more preferably 350 g/mol or less, still more preferably 330 g/mol or less, and particularly preferably 300 g/mol or less.
  • the polymerizable group value of crosslinking agent U is preferably 210 to 400 g/mol, more preferably 220 to 400 g/mol.
  • the crosslinking agent U preferably has a structure represented by the following formula (U-1), for example.
  • R U1 is a hydrogen atom or a monovalent organic group
  • A is a single bond, -O- or -NR N -
  • R N is a hydrogen atom or a monovalent organic group.
  • Z U1 is an m-valent organic group
  • Z U2 is a single bond or an n+1-valent organic group
  • X is a radically polymerizable group
  • n is an integer of 1 or more
  • m is an integer of 1 or more. is an integer.
  • R U1 is preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
  • R N is preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
  • the hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and still more preferably a hydrocarbon group having 16 or less carbon atoms.
  • Examples of the hydrocarbon group include a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group represented by a bond thereof.
  • R N represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.
  • Examples of the hydrocarbon group include those listed in Z U1 , and preferred embodiments are also the same.
  • X is not particularly limited, but examples include vinyl group, allyl group, (meth)acryloyl group, (meth)acryloxy group, (meth)acrylamide group, vinylphenyl group, maleimide group, etc. )
  • An acrylamide group, a vinylphenyl group, or a maleimide group is preferable, and a (meth)acryloxy group is more preferable.
  • n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, even more preferably 1 or 2, and particularly preferably 1.
  • m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, and even more preferably 1 or 2.
  • the crosslinking agent U has at least one of a hydroxy group, an alkyleneoxy group, and a cyano group.
  • the hydroxy group may be an alcoholic hydroxy group or a phenolic hydroxy group, but is preferably an alcoholic hydroxy group.
  • the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, and an alkyleneoxy group having 2 to 4 carbon atoms.
  • An oxy group is more preferred, an ethylene group or a propylene group is even more preferred, and an ethylene group is particularly preferred.
  • the alkyleneoxy group may be included in the crosslinking agent U as a polyalkyleneoxy group.
  • the number of repeating alkyleneoxy groups is preferably 2 to 10, more preferably 2 to 6.
  • the crosslinking agent U has two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (a polyalkyleneoxy group when forming a polyalkyleneoxy group), and a cyano group in the molecule. However, it is also preferable to have only one in the molecule.
  • the above hydroxy group, alkyleneoxy group, and cyano group may be present at any position of the crosslinking agent U, but from the viewpoint of chemical resistance, the crosslinking agent U is more preferable than the above hydroxy group, alkyleneoxy group, and cyano group.
  • At least one group selected from the group consisting of: and at least one radically polymerizable group contained in the crosslinking agent U are a linking group containing a urea bond, a urethane bond, or an amide bond (hereinafter also referred to as "linking group L2-1"). ) is also preferable.
  • the crosslinking agent U contains only one radically polymerizable group
  • the radically polymerizable group contained in the crosslinking agent U and at least one selected from the group consisting of a hydroxy group, an alkyleneoxy group, and a cyano group It is preferable that they be connected by a linking group containing a urea bond, a urethane bond, or an amide bond (hereinafter also referred to as "linking group L2-2").
  • an alkyleneoxy group (However, when constituting a polyalkyleneoxy group, a polyalkyleneoxy group) and has the above linking group L2-1 or the above linking group L2-2, an alkyleneoxy group (However, when constituting a polyalkyleneoxy group, the structure bonded to the side opposite to the connecting group L2-1 or the connecting group L2-2 is not particularly limited, but may be a hydrocarbon group, A group represented by a radically polymerizable group or a combination thereof is preferred.
  • the hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and still more preferably a hydrocarbon group having 16 or less carbon atoms.
  • hydrocarbon group examples include a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a group represented by a bond thereof.
  • preferred embodiments of the radically polymerizable group are the same as those of the radically polymerizable group in the above-mentioned crosslinking agent U.
  • the crosslinking agent U has a hydroxyl group.
  • the crosslinking agent U preferably contains an aromatic group from the viewpoint of compatibility with the specific resin. It is preferable that the aromatic group is directly bonded to a urea bond, urethane bond, or amide bond contained in the crosslinking agent U. When the crosslinking agent U contains two or more urea bonds, urethane bonds, or amide bonds, it is preferable that one of the urea bonds, urethane bonds, or amide bonds is directly bonded to the aromatic group.
  • the aromatic group may be an aromatic hydrocarbon group, an aromatic heterocyclic group, or a structure in which these groups form a condensed ring, but it is preferably an aromatic hydrocarbon group.
  • the aromatic hydrocarbon group mentioned above is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and has two or more hydrogen atoms removed from the benzene ring structure. More preferred are groups.
  • the aromatic heterocyclic group is preferably a 5-membered or 6-membered aromatic heterocyclic group. Examples of the aromatic heterocycle in such an aromatic heterocyclic group include pyrrole, imidazole, triazole, tetrazole, pyrazole, furan, thiophene, oxazole, isoxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, triazine, etc. .
  • the heteroatom contained in the aromatic heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
  • the above-mentioned aromatic group is, for example, a linking group that connects two or more radically polymerizable groups and includes a urea bond, a urethane bond, or an amide bond, or a linking group selected from the group consisting of the above-mentioned hydroxy group, alkyleneoxy group, and cyano group. and at least one radically polymerizable group contained in the crosslinking agent U.
  • the number of atoms (linked chain length) between the urea bond, urethane bond, or amide bond and the radically polymerizable group in crosslinking agent U is not particularly limited, but is preferably 30 or less, and preferably 2 to 20. More preferably, it is 2 to 10.
  • the crosslinking agent U contains a total of two or more urea bonds, urethane bonds, or amide bonds, or contains two or more radically polymerizable groups, or contains two or more urea bonds, urethane bonds, or amide bonds, and is radically polymerizable.
  • the minimum number of atoms (linked chain length) between the urea bond, urethane bond, or amide bond and the radically polymerizable group may be within the above range.
  • “the number of atoms between the urea bond, urethane bond, or amide bond and the polymerizable group (linkage chain length)” refers to the atoms on the path connecting two atoms or atomic groups to be linked. Among chains, it refers to the chain that connects these connected objects in the shortest way (minimum number of atoms). For example, in the structure represented by the following formula, the number of atoms (linked chain length) between the urea bond and the radically polymerizable group (methacryloyloxy group) is two.
  • the crosslinking agent U is a compound having a structure without an axis of symmetry.
  • the crosslinking agent U does not have an axis of symmetry, it means that it does not have an axis that produces molecules identical to the original molecule by rotating the entire compound, and is a left-right asymmetric compound.
  • the structural formula of crosslinking agent U is written on paper, the fact that crosslinking agent U does not have an axis of symmetry means that the structural formula of crosslinking agent U cannot be written in a form that has an axis of symmetry. say. It is thought that since the crosslinking agent U does not have an axis of symmetry, aggregation of the crosslinking agents U is suppressed in the composition film.
  • the molecular weight of the crosslinking agent U is preferably from 100 to 2,000, preferably from 150 to 1,500, and more preferably from 200 to 900.
  • the method for producing crosslinking agent U is not particularly limited, but, for example, it can be obtained by reacting a radically polymerizable compound and a compound having an isocyanate group with a compound having at least one of a hydroxy group or an amino group.
  • crosslinking agent U examples include the following compounds and M-8 to M-13 in Examples described below, but the crosslinking agent U is not limited thereto.
  • bifunctional methacrylate or acrylate as the resin composition from the viewpoint of pattern resolution and film stretchability.
  • Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, and PEG 600 diacrylate.
  • PEG200 diacrylate refers to polyethylene glycol diacrylate in which the formula weight of polyethylene glycol chains is about 200.
  • a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent from the viewpoint of suppressing warpage of the pattern (cured product).
  • monofunctional radical crosslinking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, and cyclohexyl (meth)acrylate.
  • acrylate benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc.
  • Acrylic acid derivatives, N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, allyl glycidyl ether, and the like are preferably used.
  • the monofunctional radical crosslinking agent a compound having a boiling point of 100° C. or higher at normal pressure is also preferred in order to suppress volatilization before exposure.
  • examples of the radical crosslinking agent having two or more functionalities include allyl compounds such as diallyl phthalate and triallyl trimellitate.
  • the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less based on the total solid content of the resin composition.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
  • One type of radical crosslinking agent may be used alone, or a mixture of two or more types may be used. When two or more types are used together, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention contains another crosslinking agent different from the above-mentioned radical crosslinking agent.
  • Other crosslinking agents refer to crosslinking agents other than the above-mentioned radical crosslinking agents, and the above-mentioned photoacid generators or photobase generators can be used to interact with other compounds in the composition or their reaction products.
  • the compound has a plurality of groups in its molecule that promote the reaction of forming a covalent bond between the two, and the reaction of forming a covalent bond with other compounds in the composition or the reaction product thereof is preferably a compound that has a plurality of groups in the molecule.
  • the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
  • the other crosslinking agent is preferably a compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group.
  • a compound having a structure in which at least one group selected from the group consisting of groups is directly bonded to a nitrogen atom is more preferable.
  • crosslinking agents include, for example, reacting an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, benzoguanamine with formaldehyde or formaldehyde and alcohol to convert the hydrogen atom of the amino group into an acyloxymethyl group, methylol group, etc.
  • Examples include compounds having a structure substituted with an ethylol group or an alkoxymethyl group.
  • the method for producing these compounds is not particularly limited, and any compound having the same structure as the compound produced by the above method may be used. An oligomer formed by self-condensation of the methylol groups of these compounds may also be used.
  • a crosslinking agent using melamine is a melamine crosslinking agent
  • a crosslinking agent using glycoluril, urea or alkylene urea is a urea crosslinking agent
  • a crosslinking agent using alkylene urea is an alkylene urea crosslinking agent.
  • a crosslinking agent using benzoguanamine is called a benzoguanamine-based crosslinking agent.
  • the resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based crosslinking agent and a melamine-based crosslinking agent, and a glycoluril-based crosslinking agent and a melamine-based crosslinking agent described below. It is more preferable to include at least one compound selected from the group consisting of agents.
  • the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group has an alkoxymethyl group or an acyloxymethyl group substituted directly on an aromatic group, a nitrogen atom of the urea structure shown below, or on a triazine.
  • Examples of the structure include the following compounds.
  • the alkoxymethyl group or acyloxymethyl group possessed by the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
  • the total number of alkoxymethyl groups and acyloxymethyl groups possessed by the above compound is preferably 1 to 10, more preferably 2 to 8, particularly preferably 3 to 6.
  • the molecular weight of the above compound is preferably 1,500 or less, more preferably from 180 to 1,200.
  • R 100 represents an alkyl group or an acyl group.
  • R 101 and R 102 each independently represent a monovalent organic group, and may be bonded to each other to form a ring.
  • Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted with an aromatic group include compounds represented by the following general formula.
  • R 4 is each independently, It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 5 represents a group that is eliminated by the action of an acid.
  • R 105 each independently represents an alkyl group or an alkenyl group
  • a, b and c each independently represent 1 to 3
  • d represents 0 to 4
  • e represents 0 to 3
  • f represents 0 to 3.
  • a+d is 5 or less
  • b+e is 4 or less
  • c+f is 4 or less.
  • R 5 in a group that decomposes under the action of an acid to produce an alkali-soluble group a group that leaves under the action of an acid, and a group represented by -C(R 4 ) 2 COOR 5 , for example, -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), and -C(R 01 )(R 02 )(OR 39 ).
  • R 36 to R 39 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.
  • R 36 and R 37 may be combined with each other to form a ring.
  • the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms.
  • the alkyl group may be linear or branched.
  • the above-mentioned cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, more preferably a cycloalkyl group having 3 to 8 carbon atoms.
  • the above cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.
  • the above aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, and more preferably a phenyl group.
  • the aralkyl group is preferably an aralkyl group having 7 to 20 carbon atoms, more preferably an aralkyl group having 7 to 16 carbon atoms.
  • the above aralkyl group is intended to be an aryl group substituted with an alkyl group, and the preferred embodiments of these alkyl groups and aryl groups are the same as the preferred embodiments of the alkyl group and aryl group described above.
  • the above alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms. These groups may further have known substituents.
  • R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.
  • Preferable examples of the group that decomposes under the action of an acid to produce an alkali-soluble group, or the group that leaves the group under the action of an acid include a tertiary alkyl ester group, an acetal group, a cumyl ester group, and an enol ester group. More preferred are tertiary alkyl ester groups and acetal groups.
  • the compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group may include at least one group selected from the group consisting of a urea bond and a urethane bond.
  • Compounds having the following are also preferred.
  • a preferred embodiment of the above-mentioned compound is the above-mentioned crosslinked compound, except that the polymerizable group is not a radically polymerizable group but is at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, an ethylol group, and an alkoxymethyl group. This is the same as the preferred embodiment of agent U.
  • the compound having at least one group selected from the group consisting of an acyloxymethyl group, a methylol group, and an ethylol group include the following structures.
  • Examples of the compound having an acyloxymethyl group include the following compounds in which the alkoxymethyl group is changed to an acyloxymethyl group.
  • Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
  • the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group a commercially available compound may be used, or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted on an aromatic ring or triazine ring are preferred.
  • melamine-based crosslinking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutylmelamine, and the like.
  • urea-based crosslinking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, and dimethoxymethylated glycoluril.
  • uril trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monoethoxymethylated glycoluril, diethoxymethylated glycoluril, triethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril , dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril
  • Glycoluril crosslinking agents such as uril, Urea-based crosslinking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea, Monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxymethylated
  • benzoguanamine-based crosslinking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
  • tetramethoxymethylated benzoguanamine monoethoxymethylated benzoguanamine, diethoxymethylated benzoguanamine, triethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetra Examples include propoxymethylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, and tetrabutoxymethylated benzoguanamine.
  • a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is added to an aromatic ring (preferably a benzene ring).
  • aromatic ring preferably a benzene ring
  • compounds in which species groups are directly bonded are also preferably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, and hydroxymethylphenyl hydroxymethylbenzoate.
  • suitable commercial products include 46DMOC, 46DMOEP (manufactured by Asahi Yokuzai Kogyo Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP.
  • the resin composition of the present invention contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another crosslinking agent.
  • Epoxy compounds compounds with epoxy groups
  • the epoxy compound is preferably a compound having two or more epoxy groups in one molecule. Epoxy groups undergo a crosslinking reaction at 200° C. or lower, and no dehydration reaction due to crosslinking occurs, so membrane shrinkage is less likely to occur. Therefore, containing an epoxy compound is effective in curing the resin composition at low temperatures and suppressing warpage.
  • the epoxy compound contains a polyethylene oxide group. This further reduces the elastic modulus and suppresses warpage.
  • the polyethylene oxide group means one in which the number of ethylene oxide repeating units 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; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, and hexamethylene glycol diglycidyl ether.
  • alkylene glycol type epoxy resin or polyhydric alcohol hydrocarbon type epoxy resin such as trimethylolpropane triglycidyl ether
  • polyalkylene glycol type epoxy resin such as polypropylene glycol diglycidyl ether
  • epoxy group such as polymethyl (glycidyloxypropyl) siloxane Examples include, but are not limited to, silicone containing silicone.
  • n is an integer of 1 to 5
  • m is an integer of 1 to 20.
  • n is preferably 1 to 2 and m is preferably 3 to 7 in order to achieve both heat resistance and elongation improvement.
  • Oxetane compounds 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, Examples include 3-ethyl-3-(2-ethylhexylmethyl)oxetane and 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester.
  • the Aronoxetane series (for example, OXT-121, OXT-221) manufactured by Toagosei Co., Ltd. can be suitably used, and these may be used alone or in combination of two or more. good.
  • the benzoxazine compound is preferable because it does not generate outgassing during curing due to the crosslinking reaction derived from the ring-opening addition reaction, and furthermore, it reduces thermal shrinkage and suppresses the occurrence of warping.
  • benzoxazine compounds include P-d type benzoxazine, F-a type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adduct of polyhydroxystyrene resin, and phenol novolak type dihydrobenzo. Examples include oxazine compounds. These may be used alone or in combination of two or more.
  • the content of other crosslinking agents is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and 0.5 to 15% by mass based on the total solid content of the resin composition. It is more preferably 1.0 to 10% by weight, particularly preferably 1.0 to 10% by weight. Only one type of other crosslinking agent may be contained, or two or more types thereof may be contained. When two or more types of other crosslinking agents are contained, it is preferable that the total amount is within the above range.
  • the resin composition of the present invention preferably contains a polymerization initiator.
  • the polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator.
  • the photopolymerization initiator is preferably a radical photopolymerization initiator.
  • the radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators. For example, a photoradical polymerization initiator that is sensitive to light in the ultraviolet to visible range is preferred. Alternatively, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.
  • the photoradical polymerization initiator contains at least one compound having a molar absorption coefficient of at least about 50 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 within the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). It 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).
  • any known compound can be used.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc.
  • ketone compound examples include compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated herein.
  • Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd. is also suitably used.
  • ⁇ -hydroxyketone initiators examples include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE -2959 and IRGACURE 127 (manufactured by BASF) can be used.
  • ⁇ -aminoketone initiators examples include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, and IRGACURE 3. 69, and IRGACURE 379 (manufactured by BASF) can be used.
  • aminoacetophenone initiator the acylphosphine oxide initiator, and the metallocene compound, for example, the compounds described in paragraphs 0161 to 0163 of International Publication No. 2021/112189 can also be suitably used. This content is incorporated herein.
  • photoradical polymerization initiator include oxime compounds.
  • an oxime compound By using an oxime compound, it becomes possible to improve exposure latitude more effectively.
  • Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.
  • oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A 2000-080068, compounds described in JP-A 2006-342166, J. C. S. Perkin II (1979, pp. 1653-1660); C. S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000 - Compounds described in Publication No. 066385, Compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2017-019766, compounds described in Patent No. 6065596, compounds described in International Publication No. 2015/152153, International Publication No.
  • Preferred oxime compounds include, for example, compounds with the following structures, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy( imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino)) -1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, 5-(4-isopropylphenylthio)-1,2-indanedione, 2-(O- Examples include acetyl)oxime and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one.
  • oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF), Omnirad 1312 (manufactured by IGM Resins B.V.), and Adeka Optomer N- 1919 (manufactured by ADEKA Co., Ltd., photoradical polymerization initiator 2 described in JP-A-2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronics New Materials Co., Ltd.), ADEKA Arcles Examples include NCI-730, NCI-831, ADEKA Arkles NCI-930 (manufactured by ADEKA Co., Ltd.), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure PDO (manufactured by SARTOMER ARKEMA). Moreover, oxime compounds having the following structures can also be
  • Examples of the photoradical polymerization initiator include oxime compounds having a fluorene ring described in paragraphs 0169 to 0171 of International Publication No. 2021/112189, and oximes having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring.
  • Compounds, oxime compounds having a fluorine atom can also be used.
  • oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a substituent having a hydroxy group bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of International Publication No. 2021/020359 can also be used. . Their contents are incorporated herein.
  • oxime compound OX an oxime compound having an aromatic ring group Ar OX1 (hereinafter also referred to as oxime compound OX) in which an electron-withdrawing group is introduced into the aromatic ring.
  • Examples of the electron-withdrawing group possessed by the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group,
  • An acyl group and a nitro group are preferred, an acyl group is more preferred because a film with excellent light resistance can be easily formed, and a benzoyl group is even more preferred.
  • the benzoyl group may have a substituent.
  • substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, and more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclicoxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group. More preferably, it is a sulfanyl group or an amino group.
  • the oxime compound OX is preferably at least one selected from a compound represented by formula (OX1) and a compound represented by formula (OX2), and more preferably a compound represented by formula (OX2). preferable.
  • R X3 to R X14 each independently represent a hydrogen atom or a substituent. However, at least one of R X10 to R X14 is an electron-withdrawing group.
  • R X12 is preferably an electron-withdrawing group
  • R X10 , R X11 , R X13 , and R X14 are preferably hydrogen atoms.
  • oxime compound OX examples include compounds described in paragraph numbers 0083 to 0105 of Japanese Patent No. 4,600,600, the contents of which are incorporated herein.
  • Particularly preferable oxime compounds include oxime compounds having a specific substituent group as shown in JP-A No. 2007-269779, and oxime compounds having a thioaryl group as shown in JP-A No. 2009-191061. Incorporated herein.
  • photoradical polymerization initiators include trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and triaryl compounds. selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds.
  • Compounds such as
  • the photoradical polymerization initiator is a trihalomethyltriazine compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, an acetophenone compound, At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferred, and metallocene compounds or oxime compounds are even more preferred.
  • a difunctional, trifunctional or more functional photoradical polymerization initiator may be used as the photoradical polymerization initiator.
  • a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained.
  • the crystallinity decreases and the solubility in solvents improves, making it difficult to precipitate over time, thereby improving the stability of the resin composition over time.
  • Specific examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include those listed in Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
  • the resin composition contains a photopolymerization initiator
  • its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and 0.5% by mass based on the total solid content of the resin composition. It is more preferably from 1.0 to 10% by weight, and even more preferably from 1.0 to 10% by weight.
  • the photopolymerization initiator may contain only one type, or may contain two or more types. When containing two or more types of photopolymerization initiators, it is preferable that the total amount is within the above range. Note that since the photopolymerization initiator may also function as a thermal polymerization initiator, crosslinking by the photopolymerization initiator may be further promoted by heating with an oven, a hot plate, or the like.
  • the resin composition may contain a sensitizer.
  • the sensitizer absorbs specific actinic radiation and becomes electronically excited.
  • the sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, etc., and effects such as electron transfer, energy transfer, and heat generation occur.
  • the thermal radical polymerization initiator and the photo radical polymerization initiator undergo a chemical change and are decomposed to generate radicals, acids, or bases.
  • Usable sensitizers include benzophenone series, Michler's ketone series, coumarin series, pyrazole azo series, anilinoazo series, triphenylmethane series, anthraquinone series, anthracene series, anthrapyridone series, benzylidene series, oxonol series, and pyrazolotriazole azo series.
  • pyridone azo type cyanine type, phenothiazine type, pyrrolopyrazole azomethine type, xanthene type, phthalocyanine type, benzopyran type, indigo type, and other compounds can be used.
  • sensitizer examples include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl Denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso Naphthothiazole, 1,3-
  • the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. More preferably 0.5 to 10% by mass.
  • the sensitizers may be used alone or in combination of two or more.
  • the resin composition of the present invention may contain a chain transfer agent.
  • Chain transfer agents are defined, for example, in the Polymer Dictionary, 3rd edition (edited by the Society of Polymer Science and Technology, 2005), pages 683-684.
  • Examples of chain transfer agents include compounds having -S-S-, -SO 2 -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and RAFT (Reversible Addition Fragmentation chain Transfer).
  • Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used in polymerization are used. These can generate radicals by donating hydrogen to low-activity radicals, or can generate radicals by being oxidized and then deprotonated.
  • thiol compounds can be preferably used.
  • the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, and 0.1 to 10 parts by mass based on 100 parts by mass of the total solid content of the resin composition. More preferably, 0.5 to 5 parts by mass is even more preferred.
  • the number of chain transfer agents may be one, or two or more. When there are two or more types of chain transfer agents, it is preferable that the total is within the above range.
  • the resin composition of the present invention may also contain a base generator.
  • the base generator is a compound that can generate a base by physical or chemical action.
  • Preferred base generators include thermal base generators and photobase generators.
  • the resin composition contains a thermal base generator, the cyclization reaction of the precursor can be promoted by heating, for example, and the cured product has good mechanical properties and chemical resistance. The performance as an interlayer insulating film for wiring layers is improved.
  • an embodiment in which the resin composition does not contain a compound that generates a base is also one of the preferred embodiments of the present invention.
  • the content of the base generator is preferably 0.1% by mass or less, more preferably 0.01% by mass or less, based on the total mass of the resin composition.
  • the above content may be 0% by mass.
  • the base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
  • the base generator is not particularly limited, and any known base generator can be used.
  • Known base generators include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amine imides. compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, ⁇ -lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, acyloxyimino compounds, and the like.
  • Specific examples of the nonionic base generator include compounds represented by formula (B1), formula (B2), or formula (B3).
  • Rb 1 , Rb 2 and Rb 3 each independently represent an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. Moreover, 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 carbon atom of a hydrocarbon group. Therefore, when the carbon atom bonded to the trivalent nitrogen atom is a carbon atom constituting a carbonyl group, that is, when it forms an amide group with the nitrogen atom, it is not a tertiary amine structure.
  • Rb 1 , Rb 2 and Rb 3 preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure.
  • the cyclic structure may be either a single ring or a condensed ring, and preferably a monocycle or a condensed ring in which two monocycles are condensed.
  • the monocyclic ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring.
  • the monocyclic ring is preferably a cyclohexane ring or a benzene ring, and more preferably a cyclohexane ring.
  • Rb 1 and Rb 2 are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms). , more preferably 2 to 18, still more preferably 3 to 12), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 10 carbon atoms), or an arylalkyl group (carbon atoms 7 -25 is preferred, 7-19 is more preferred, and 7-12 is even more preferred). These groups may have a substituent.
  • Rb 1 and Rb 2 may be bonded to each other to form a ring.
  • the ring formed is preferably a 4- to 7-membered nitrogen-containing heterocycle.
  • Rb 1 and Rb 2 are linear, branched, or cyclic alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) that may have a substituent. is preferable, and is more preferably a cycloalkyl group (having preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms) which may have a substituent, and has a substituent. Further preferred is a cyclohexyl group which may be optionally substituted.
  • Rb 3 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 -10 are more preferable), alkenyl groups (preferably 2-24 carbon atoms, more preferably 2-12 carbon atoms, even more preferably 2-6 carbon atoms), arylalkyl groups (preferably 7-23 carbon atoms, more preferably 7-19 carbon atoms), (preferably 7 to 12 carbon atoms), arylalkenyl group (preferably 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, even more preferably 8 to 16 carbon atoms), alkoxyl group (preferably 1 to 24 carbon atoms, 2 to 16 carbon atoms) 18 is more preferable, 3 to 12 are even more preferable), an aryloxy group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms,
  • 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.
  • 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 Formula (B1), respectively.
  • Rb 13 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms), 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 has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 12 carbon atoms), an arylalkyl group (preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms), 7 to 12 are more preferred) and may have a substituent.
  • Rb 13 is preferably an arylalkyl group.
  • Rb 33 and Rb 34 each independently represent a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 3 carbon atoms), or an alkenyl group (preferably 2 to 12 carbon atoms). , more preferably 2 to 8, still more preferably 2 to 3), aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 10 carbon atoms), arylalkyl group (carbon atoms 7 to 10), 23 is preferred, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom is preferred.
  • Rb 35 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, even more 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) 8 is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more 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 are more preferred), and an aryl group is preferred.
  • the compound represented by formula (B1-1) is preferably a compound represented by formula (B1-1a).
  • Rb 11 and Rb 12 have the same meanings as Rb 11 and Rb 12 in formula (B1-1).
  • Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 3 carbon atoms), alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms) more preferably 2 to 3 carbon atoms), aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 10 carbon atoms), arylalkyl group (preferably 7 to 23 carbon atoms, 7 carbon atoms to 19 are more preferable, and 7 to 11 are even more preferable), and a hydrogen atom or a methyl group is preferable.
  • Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, even more 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 has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, even more preferably 6 to 12 carbon atoms), an arylalkyl group (preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms), 7 to 12 are more preferred), and aryl groups are particularly preferred.
  • an alkyl group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, even more 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
  • an aryl group preferably has 6 to
  • L is a divalent hydrocarbon group having a saturated hydrocarbon group on the path of a connecting chain connecting adjacent oxygen atoms and carbon atoms, and the number of atoms on the path of the connecting chain is Represents a hydrocarbon group of 3 or more.
  • R N1 and R N2 each independently represent a monovalent organic group.
  • connection chain refers to an atomic chain on a path connecting two atoms or atomic groups to be connected, which connects these objects in the shortest possible length (minimum number of atoms).
  • L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group
  • the connecting chain is composed of four carbon atoms
  • the path of the connecting chain is The number of atoms (that is, the number of atoms constituting the connected chain, hereinafter also referred to as "connected chain length" or "connected chain length”) is 4.
  • the number of carbon atoms in L in formula (B3) is preferably 3 to 24.
  • the upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less.
  • the lower limit is more preferably 4 or more.
  • the upper limit of the length of the linking chain of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and 5 The following is particularly preferable.
  • the chain length of L is preferably 4 or 5, most preferably 4.
  • Specific preferred compounds of the base generator include, for example, the compounds described in paragraph numbers 0102 to 0168 of WO 2020/066416, and the compounds described in paragraph numbers 0143 to 0177 of WO 2018/038002. Can be mentioned.
  • the base generator contains a compound represented by the following formula (N1).
  • R N1 and R N2 each independently represent a monovalent organic group
  • R C1 represents a hydrogen atom or a protective group
  • L represents a divalent linking group
  • L is a divalent linking group, preferably a divalent organic group.
  • the linking chain length of the linking group is preferably 1 or more, more preferably 2 or more.
  • the upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less.
  • the linking chain length is the number of atoms present in the atomic arrangement that provides the shortest path between two carbonyl groups in the formula.
  • R N1 and R N2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms), and a hydrocarbon group ( It is preferably an aliphatic hydrocarbon group (having preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 10 carbon atoms), specifically an aliphatic hydrocarbon group (preferably having 1 to 24 carbon atoms, 1 to 12 carbon atoms). (more preferably 1 to 10 carbon atoms); Groups are preferred. It is preferable to use aliphatic hydrocarbon groups as R N1 and R N2 because the generated base has high basicity.
  • the aliphatic hydrocarbon group and aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and aromatic hydrocarbon group may have substituents in the aliphatic hydrocarbon chain or aromatic ring,
  • the substituent may have an oxygen atom.
  • an embodiment in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.
  • Examples of the aliphatic hydrocarbon group constituting R N1 and R N2 include a straight or branched chain alkyl group, a cyclic alkyl group, a group containing a combination of a chain alkyl group and a cyclic alkyl group, and a group containing an oxygen atom in the chain.
  • Examples include alkyl groups having .
  • the linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and even more preferably 3 to 12 carbon atoms.
  • Straight chain or branched chain alkyl groups include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, isopropyl group. group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group, and the like.
  • the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
  • cyclic alkyl group examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.
  • the group containing a combination of a chain alkyl group and a cyclic alkyl group preferably has 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms.
  • Examples of the group containing a combination of a chain alkyl group and a cyclic alkyl group include a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group.
  • the alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
  • the alkyl group having an oxygen atom in the chain may be linear or cyclic, linear or branched.
  • R N1 and R N2 are preferably alkyl groups having 5 to 12 carbon atoms, from the viewpoint of increasing the boiling point of the decomposition product base described below.
  • a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
  • R N1 and R N2 may be connected to each other to form a cyclic structure.
  • the cyclic structure may have an oxygen atom or the like in the chain.
  • the cyclic structure formed by R N1 and R N2 may be a monocyclic ring or a condensed ring, but a monocyclic ring is preferable.
  • the cyclic structure formed is preferably a 5-membered ring or a 6-membered ring containing a nitrogen atom in formula (N1), such as a pyrrole ring, an imidazole ring, a pyrazole ring, a pyrroline ring, a pyrrolidine ring, an imidazolidine ring, Examples include a pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring, and preferred examples include a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, and a morpholine ring.
  • R C1 represents a hydrogen atom or a protective group, and preferably a hydrogen atom.
  • the protecting group a protecting group that is decomposed by the action of an acid or a base is preferable, and a protecting group that is decomposed by an acid is preferably mentioned.
  • Specific examples of the protecting group include a chain or cyclic alkyl group or a chain or cyclic alkyl group having an oxygen atom in the chain. Examples of the chain or cyclic alkyl group include methyl group, ethyl group, isopropyl group, tert-butyl group, and cyclohexyl group.
  • Examples of the chain alkyl group having an oxygen atom in the chain include an alkyloxyalkyl group, and methyloxymethyl (MOM) group, ethyloxyethyl (EE) group, etc. are preferable.
  • Examples of the cyclic alkyl group having an oxygen atom in the chain include an epoxy group, a glycidyl group, an oxetanyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl (THP) group.
  • the divalent linking group constituting L is not particularly limited, but is preferably a hydrocarbon group, and more preferably an aliphatic hydrocarbon group.
  • the hydrocarbon group may have a substituent and may have atoms other than carbon atoms in the hydrocarbon chain.
  • the divalent linking group is more preferably a divalent hydrocarbon linking group that may have an oxygen atom in its chain, and a divalent aliphatic linking group that may have an oxygen atom in its chain.
  • the divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms.
  • the divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
  • the divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • the group containing a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18 carbon atoms, and has 7 to 10 carbon atoms. is even more preferable.
  • the linking group L includes a linear or branched chain alkylene group, a cyclic alkylene group, a group containing a combination of a chain alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, and a straight chain alkylene group.
  • a chain or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, and an arylene alkylene group are preferred.
  • the linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
  • the cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
  • the group containing a combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
  • the alkylene group having an oxygen atom in the chain may be linear or cyclic, linear or branched.
  • the alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • the linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 3 carbon atoms.
  • the number of C ⁇ C bonds is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.
  • the cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
  • the number of C ⁇ C bonds in the cyclic alkenylene group is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 2.
  • the arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • the arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
  • linear alkylene groups, cyclic alkylene groups, alkylene groups having an oxygen atom in the chain, linear alkenylene groups, arylene groups, and arylene alkylene groups are preferred, and 1,2-ethylene groups, propanediyl groups (especially 1, 3-propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cisvinylene group), phenylene group (1,2-phenylene group), phenylenemethylene group (especially 1,2-phenylene group) methylene group) and ethyleneoxyethylene group (especially 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.
  • Examples of the base generator include, but are not limited to, the following compounds.
  • the molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
  • the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
  • Specific preferred compounds of the ionic base generator include, for example, the compounds described in paragraph numbers 0148 to 0163 of International Publication No. 2018/038002.
  • ammonium salts include, but are not limited to, the following compounds.
  • iminium salts include, but are not limited to, the following compounds.
  • the content of the base generator is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the resin in the resin composition.
  • the lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
  • the upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.
  • One type or two or more types of base generators can be used. When two or more types are used, the total amount is preferably within the above range.
  • the resin composition of the present invention preferably contains a solvent. Any known solvent can be used as the solvent.
  • the solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
  • esters 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, ⁇ -butyrolactone.
  • alkyloxyacetate e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, 3-alkyloxypropionate alkyl esters (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.), 3-alkyloxypropionate alkyl esters (e.g., methyl 3-methoxypropionate, 3-methoxypropionate), ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-alkyloxypropionate alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl), 2-alkyloxypropionate alkyl esters (e.g
  • ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol Suitable examples include monobutyl ether acetate
  • Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone, and the like.
  • Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.
  • Suitable examples of sulfoxides include dimethyl sulfoxide.
  • Amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, Preferred examples include 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.
  • Suitable ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.
  • 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 include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
  • the content of the solvent is preferably such that the total solids concentration of the resin composition of the present invention is 5 to 80% by mass, and preferably 5 to 75% by mass. More preferably, the amount is 10 to 70% by mass, and even more preferably 20 to 70% by mass.
  • the solvent content may be adjusted depending on the desired thickness of the coating and the application method. When two or more types of solvents are contained, it is preferable that the total amount is within the above range.
  • the resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used for electrodes, wiring, etc.
  • metal adhesion improvers include silane coupling agents having alkoxysilyl groups, aluminum adhesion aids, titanium adhesion aids, compounds having a sulfonamide structure and thiourea structure, phosphoric acid derivative compounds, and ⁇ -keto esters. compounds, amino compounds, etc.
  • silane coupling agent examples include the compounds described in paragraph 0316 of International Publication No. 2021/112189 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573, the contents of which are not included herein. Incorporated. Furthermore, it is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP-A-2011-128358. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group and Et represents an ethyl group. Further, the following R may be a structure derived from a blocking agent in a blocked isocyanate group.
  • the blocking agent may be selected depending on the desorption temperature, and includes alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, active methylene compounds, and the like. For example, from the viewpoint of desiring a desorption temperature of 160 to 180°C, caprolactam and the like are preferred. Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • silane coupling agents examples include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropylmethyldimethoxysilane.
  • an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent.
  • examples of such oligomer type compounds include compounds containing a repeating unit represented by the following formula (S-1).
  • R S1 represents a monovalent organic group
  • R S2 represents a hydrogen atom, a hydroxy group, or an alkoxy group
  • n represents an integer of 0 to 2.
  • R S1 preferably has a structure containing a polymerizable group.
  • Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group.
  • groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (for example, vinyl phenyl groups, etc.), and (meth)acrylamide groups.
  • R S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
  • n represents an integer from 0 to 2, preferably 1.
  • n is 1 or 2 in at least one of the plurality of repeating units represented by formula (S-1) contained in the oligomer type compound, and n is 1 or 2 in at least two. More preferably, n is 2, and even more preferably n is 1 in at least two cases.
  • Commercially available products can be used as such oligomer type compounds, and examples of the commercially available products include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Aluminum-based adhesion aid examples include aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.
  • the content of the metal adhesion improver is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the specific resin.
  • the content of the metal adhesion improver is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the specific resin.
  • the resin composition of the present invention further contains a migration inhibitor.
  • a migration inhibitor for example, when a resin composition is applied to a metal layer (or metal wiring) to form a film, metal ions derived from the metal layer (or metal wiring) may migrate into the film. can be effectively suppressed.
  • Migration inhibitors are not particularly limited, but include heterocycles (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenol compounds , salicylic acid derivative compounds, and hydrazide derivative compounds.
  • heterocycles pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring
  • triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
  • an ion trapping agent that traps anions such as halogen ions can also be used.
  • Other migration inhibitors include, for example, the rust inhibitors described in paragraph 0094 of JP-A No. 2013-015701, and the rust inhibitors described in paragraphs 0073 to 0076 of JP-A-2009-283711.
  • migration inhibitors include the following compounds.
  • the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, and 0.01 to 5.0% by mass based on the total solid content of the resin composition.
  • the amount is more preferably 0.05 to 2.0% by weight, and even more preferably 0.1 to 1.0% by weight.
  • Only one type of migration inhibitor may be used, or two or more types may be used. When there are two or more types of migration inhibitors, it is preferable that the total is within the above range.
  • the resin composition of the present invention preferably contains a polymerization inhibitor.
  • the polymerization inhibitor include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.
  • Specific compounds of the polymerization inhibitor include the compound described in paragraph 0310 of International Publication No. 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1- Examples include oxyl free radical, phenoxazine, tris(2,6-dimethyl-3-hydroxy-4-tert-butyl-benzyl) isocyanurate, and the like. This content is incorporated herein.
  • the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, and 0.02 to 20% by mass based on the total solid content of the resin composition. It is more preferably 15% by mass, and even more preferably 0.05 to 10% by mass.
  • Only one type of polymerization inhibitor may be used, or two or more types may be used. When there are two or more types of polymerization inhibitors, it is preferable that the total is within the above range.
  • the resin composition of the present invention preferably contains an acid scavenger in order to reduce performance changes over time from exposure to heating.
  • the acid scavenger refers to a compound that can capture generated acid by being present in the system, and is preferably a compound with low acidity and high pKa.
  • the acid scavenger is preferably a compound having an amino group, preferably a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, etc. are preferred, and secondary amines, tertiary amines, and ammonium salts are more preferred.
  • acid scavengers include compounds having an imidazole structure, diazabicyclo structure, onium structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives having a hydroxyl group and/or ether bond, aniline having a hydroxyl group and/or ether bond. Preferred examples include derivatives.
  • the acid scavenger has an onium structure, is a salt having a cation selected from ammonium, diazonium, iodonium, sulfonium, phosphonium, pyridinium, etc., and an anion of an acid less acidic than the acid generated by the acid generator. It is preferable.
  • Examples of the acid scavenger having an imidazole structure include imidazole, 2,4,5-triphenylimidazole, benzimidazole, and 2-phenylbenzimidazole.
  • Examples of acid scavengers having a diazabicyclo structure include 1,4-diazabicyclo[2,2,2]octane, 1,5-diazabicyclo[4,3,0]non-5-ene, and 1,8-diazabicyclo[5,4 , 0] undecar-7-ene and the like.
  • acid scavengers having an onium structure include tetrabutylammonium hydroxide, triarylsulfonium hydroxide, phenacylsulfonium hydroxide, sulfonium hydroxide having a 2-oxoalkyl group, specifically triphenylsulfonium hydroxide, tris( Examples include t-butylphenyl)sulfonium hydroxide, bis(t-butylphenyl)iodonium hydroxide, phenacylthiophenium hydroxide, and 2-oxopropylthiophenium hydroxide.
  • Examples of the acid scavenger having a trialkylamine structure include tri(n-butyl)amine and tri(n-octyl)amine.
  • Examples of the acid scavenger having an aniline structure include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline.
  • Examples of the acid scavenger having a pyridine structure include pyridine and 4-methylpyridine.
  • Examples of the alkylamine derivatives having a hydroxyl group and/or ether bond include ethanolamine, diethanolamine, triethanolamine, N-phenyldiethanolamine, and tris(methoxyethoxyethyl)amine.
  • Examples of the aniline derivative having a hydroxyl group and/or an ether bond include N,N-bis(hydroxyethyl)aniline and the like.
  • preferred acid scavengers include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N , N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine, N-methyldicyclohexyl
  • One type of acid scavenger may be used alone, or two or more types may be used in combination.
  • the composition according to the present invention may or may not contain an acid scavenger, but if it does, the content of the acid scavenger is 0.001 to 10% by mass based on the total solid content of the composition. %, more preferably 0.01 to 5% by mass.
  • the acid generator/acid scavenger (mole ratio) is preferably 5.0 to 200, more preferably 7.0 to 150.
  • the resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, etc., as long as the effects of the present invention can be obtained. It may contain organic titanium compounds, antioxidants, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (for example, antifoaming agents, flame retardants, etc.). By appropriately containing these components, properties such as film physical properties can be adjusted. These components are described, for example, in paragraphs 0183 and after of JP-A-2012-003225 (corresponding paragraph 0237 of U.S. Patent Application Publication No.
  • surfactant various surfactants such as fluorine surfactants, silicone surfactants, and hydrocarbon surfactants can be used.
  • the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
  • the liquid properties (especially fluidity) when preparing a coating liquid composition are further improved, and the uniformity of coating thickness and liquid saving are further improved. can do. That is, when forming a film using a coating solution containing a surfactant, the interfacial tension between the surface to be coated and the coating solution is reduced, improving the wettability of the surface to be coated, and making it easier to coat the surface. Improves sex. Therefore, a uniform film with small thickness unevenness can be more suitably formed.
  • fluorine-based surfactant examples include compounds described in paragraph 0328 of International Publication No. 2021/112189, the content of which is incorporated herein.
  • a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a (meth) having 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group) are used.
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and examples thereof include the following compounds.
  • the weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond in its side chain can also be used as the fluorine-based surfactant.
  • Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, the contents of which are incorporated herein.
  • Commercially available products include, for example, Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.
  • the fluorine content in the fluorine surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid saving, and has good solubility in the composition.
  • Silicone surfactants, hydrocarbon surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants are each described in paragraphs 0329 to 0334 of International Publication No. 2021/112189. compounds, the contents of which are incorporated herein.
  • the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
  • Higher fatty acid derivative In order to prevent polymerization inhibition caused by oxygen, higher fatty acid derivatives such as behenic acid and behenic acid amide are added to the resin composition of the present invention during the drying process after application. It may be unevenly distributed on the surface.
  • the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass based on the total solid content of the resin composition.
  • thermal polymerization initiator examples include thermal radical polymerization initiators.
  • a thermal radical polymerization initiator is a compound that generates radicals using thermal energy and initiates or accelerates the polymerization reaction of a compound having polymerizability. By adding a thermal radical polymerization initiator, the polymerization reaction between the resin and the polymerizable compound can be advanced, so that the solvent resistance can be further improved. Further, a photopolymerization initiator may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
  • thermal radical polymerization initiator examples include compounds described in paragraphs 0074 to 0118 of JP-A No. 2008-063554, the contents of which are incorporated herein.
  • thermal polymerization initiator When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition. More preferably, the amount is .5 to 15% by mass.
  • the thermal polymerization initiator may contain only one type, or may contain two or more types. When containing two or more types of thermal polymerization initiators, it is preferable that the total amount is within the above range.
  • inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
  • the average particle diameter of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, even more preferably 0.03 to 1.0 ⁇ m, and particularly preferably 0.04 to 0.5 ⁇ m. .
  • the above average particle diameter of the inorganic particles is a primary particle diameter and a volume average particle diameter.
  • the volume average particle diameter can be measured, for example, by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, measurement can also be performed by centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method.
  • UV absorber examples include salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers.
  • Specific examples of ultraviolet absorbers include compounds described in paragraphs 0341 to 0342 of International Publication No. 2021/112189, the contents of which are incorporated herein.
  • One type of ultraviolet absorber may be used alone, or two or more types may be used in combination.
  • the content of the ultraviolet absorber is preferably 0.001% by mass or more and 1% by mass or less, and 0.01% by mass or less, based on the total solid mass of the resin composition. More preferably, the amount is 0.1% by mass or more and 0.1% by mass or less.
  • organic titanium compounds examples include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond. Specific examples of organic titanium compounds are shown in I) to VII) below:
  • I) Titanium chelate compound A titanium chelate compound having two or more alkoxy groups is more preferred because the resin composition has good storage stability and a good curing pattern can be obtained. Specific examples include titanium bis(triethanolamine) diisopropoxide, titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate).
  • Tetraalkoxytitanium compounds for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , titanium tetramethoxypropoxide, titanium tetramethyl phenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis ⁇ 2,2-(allyloxymethyl)] butoxide ⁇ ], etc.
  • Titanocene compounds for example, pentamethylcyclopentadienyl titanium trimethoxide, bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis( ⁇ 5-2, 4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.
  • Monoalkoxytitanium compounds For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and the like.
  • Titanium oxide compound For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.
  • the organic titanium compound is at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds, from the viewpoint of better chemical resistance. It is preferable that there be.
  • titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H -pyrrol-1-yl)phenyl)titanium is preferred.
  • an organic titanium compound When an organic titanium compound is included, its content is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, based on 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the resulting cured pattern has better heat resistance and chemical resistance, and when the content is 10 parts by mass or less, the storage stability of the composition is better.
  • antioxidants include phenol compounds, phosphite compounds, thioether compounds, and the like. Specific examples of antioxidants include compounds described in paragraphs 0348 to 0357 of International Publication No. 2021/112189, the contents of which are incorporated herein.
  • the content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin.
  • the addition amount is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin.
  • anti-aggregation agents examples include sodium polyacrylate.
  • the anti-aggregation agents may be used alone or in combination of two or more.
  • the content of the anti-aggregation agent is preferably 0.01% by mass or more and 10% by mass or less, and 0.02% by mass or less, based on the total solid mass of the resin composition. It is more preferable that the amount is 5% by mass or more and 5% by mass or less.
  • One type of phenol compound may be used alone, or two or more types may be used in combination.
  • the content of the phenolic compound is preferably 0.01% by mass or more and 30% by mass or less, and 0.02% by mass or less, based on the total solid mass of the resin composition. It is more preferable that the amount is from % by mass to 20% by mass.
  • polymeric compounds include siloxane resins, (meth)acrylic polymers copolymerized with (meth)acrylic acid, novolac resins, resol resins, polyhydroxystyrene resins, and copolymers thereof.
  • Other polymer compounds may be modified products into which crosslinking groups such as methylol groups, alkoxymethyl groups, and epoxy groups are introduced.
  • One type of other polymer compounds may be used alone, or two or more types may be used in combination.
  • the content of the other polymer compounds is preferably 0.01% by mass or more and 30% by mass or less based on the total solid mass of the resin composition. , more preferably 0.02% by mass or more and 20% by mass or less.
  • the viscosity of the resin composition of the present invention can be adjusted by adjusting the solid content concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and 2,500 mm 2 /s to 8,000 mm. 2 /s is more preferable. Within the above range, it becomes easy to obtain a coating film with high uniformity.
  • the absolute value of the viscosity change rate expressed by the following formula of the viscosity of the resin composition after storage at 23 ° C. for 14 days after preparation with respect to the viscosity of the resin composition on the day of preparation is 10% or less. It is preferably 8% or less, more preferably 5% or less.
  • Viscosity change rate (%) ⁇ (Viscosity of the resin composition on the day of preparation) - (Viscosity of the resin composition after storage above) ⁇ /(Viscosity of the resin composition on the day of preparation) x 100
  • the viscosity of the composition can be measured, for example, using a viscometer (such as Toki Sangyo RE85R) at a temperature adjusted to 25°C.
  • the water content of the resin composition of the present invention is preferably less than 0.5% by mass, more preferably less than 0.3% by mass, and even more preferably less than 0.1% by mass. If it is less than 0.5% by mass, the storage stability of the resin composition will improve.
  • Methods for maintaining the moisture content include adjusting the humidity during storage conditions and reducing the porosity of the storage container during storage.
  • the metal content of the 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 insulation.
  • metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals included as complexes of organic compounds and metals are excluded. When a plurality of metals are included, the total of these metals is preferably within the above range.
  • a method for reducing metal impurities that is unintentionally included in the resin composition of the present invention is to select a raw material with a low metal content as a raw material constituting the resin composition of the present invention.
  • Methods include filtering the raw materials constituting the product, lining the inside of the apparatus with polytetrafluoroethylene, etc., and performing distillation under conditions that suppress contamination as much as possible.
  • the resin composition of the present invention has a halogen atom content of preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and more preferably less than 200 mass ppm from the viewpoint of wiring corrosion. is even more preferable.
  • those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
  • the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atoms and bromine atoms, or the total of chlorine ions and bromine ions, is each within the above range.
  • Preferred methods for adjusting the content of halogen atoms include ion exchange treatment.
  • the storage container may be a multilayer bottle whose inner wall is made of 6 types of 6 layers of resin, or a container with 7 layers of 6 types of resin. It is also preferred to use structured bottles. Examples of such a container include the container described in JP-A No. 2015-123351.
  • a cured product of the resin composition By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.
  • the cured product of the present invention is a cured product obtained by the method for producing a cured product of the present invention.
  • the form of the cured product of the resin composition is not particularly limited, and can be selected depending on the purpose, such as film, rod, sphere, or pellet form.
  • the cured product is preferably in the form of a film.
  • the thickness of the cured product is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
  • the shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
  • the imidization reaction rate of the cured product obtained by the method for producing a cured product of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.
  • the elongation at break of the cured product obtained by the method for producing a cured product of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
  • the glass transition temperature (Tg) of the cured product obtained by the method for producing a cured product of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.
  • the linear thermal expansion coefficient of the cured product obtained by the method for producing a cured product of the present invention is preferably 55 ppm/K or less, more preferably 50 ppm/K or less, and still more preferably 45 ppm/K or less. preferable.
  • the resin composition of the present invention can be prepared by mixing the above components.
  • the mixing method is not particularly limited and can be performed by a conventionally known method. Examples of the mixing method include mixing using a stirring blade, mixing using a ball mill, and mixing using a rotating tank.
  • the temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.
  • the filter pore diameter is, for example, preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, even more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. When the material of the filter is polyethylene, it is more preferably HDPE (high density polyethylene).
  • the filter may be washed in advance with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel. When using multiple types of filters, filters with different pore sizes or materials may be used in combination.
  • connection mode examples include a mode in which an HDPE filter with a pore diameter of 1 ⁇ m is connected in series as the first stage and an HDPE filter with a pore diameter of 0.2 ⁇ m as the second stage. Additionally, various materials may be filtered multiple times. When filtration is performed multiple times, circulation filtration may be used. Alternatively, filtration may be performed under pressure.
  • the pressure to be pressurized is, for example, preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, still more preferably 0.05 MPa or more and 0.7 MPa or less, and 0.01 MPa or more and 0.9 MPa or less, still more preferably 0.05 MPa or more and 0.7 MPa or less, and 0.01 MPa or more and 0.9 MPa or less, and even more preferably 0.05 MPa or more and 0.7 MPa or less. Even more preferably 0.05 MPa or more and 0.5 MPa or less.
  • impurity removal treatment using an adsorbent may be performed.
  • Filter filtration and impurity removal treatment using an adsorbent may be combined.
  • a known adsorbent can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtration using a filter, the resin composition filled in the bottle may be placed under reduced pressure and degassed.
  • polyimide precursor (P-1C) 17.1 g of water and 46.6 g of ion exchange resin UP6040 (manufactured by AmberTec) were added thereto, and the mixture was stirred for 4 hours. Thereafter, the ion exchange resin was removed by filtration, and the resulting polymer solution was added to 5,600 g of water to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45° C. for 24 hours to obtain 45.1 g of polyimide precursor (P-1C).
  • the structure of the polyimide precursor (P-1C) is represented by the following formula (P-1C). The structure of each repeating unit was determined from the 1 H-NMR spectrum. When the molecular weight of the polyimide precursor (P-1) was measured by gel permeation chromatography (standard polystyrene conversion), the weight average molecular weight (Mw) was 20,000.
  • the polyimide precursor (P-2) is a resin having two repeating units represented by the following formula (P-2). The structure of each repeating unit was determined from the 1 H-NMR spectrum.
  • Polyimide precursors (P-3) to (P-15) were synthesized in the same manner as polyimide precursor (P-2), except that the carboxylic dianhydride used was changed as appropriate.
  • Polyimide precursors (P-3) to (P-15) each have a structure in which R X in the following formula (P) is one of formulas (RX-3) to (RX-15). The structure of each repeating unit was determined from the 1 H-NMR spectrum.
  • composition ratio mol% content of repeating units
  • weight average molecular weight mol%
  • number average molecular weight of the polyimide precursors (P-2) to (P-15) are listed in the table below.
  • the resulting reaction solution was added to 3 liters of ethyl alcohol to produce a precipitate consisting 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 dropped into 28 liters of water to precipitate the polymer, and the obtained precipitate was collected by filtration and vacuum dried to obtain a powdery polyimide precursor (P-16C). .
  • the weight average molecular weight (Mw) of this polyimide precursor (P-16C) was measured and found to be 22,600.
  • the polyimide precursor (P-16C) contains a repeating unit with the following structure. The structure of each repeating unit was determined from the 1 H-NMR spectrum.
  • M-9 to M-13 were synthesized in the same manner as the synthesis of M-8, except that the raw materials were changed as appropriate.
  • the structures of M-9 to M-13 are shown in the following formulas (M-9) to (M-13).
  • Examples and comparative examples> In each Example, the components listed in the table below were mixed to obtain each resin composition. In each comparative example, the components listed in the table below were mixed to obtain comparative compositions. Specifically, the content of each component listed in the table was the amount (parts by mass) listed in the "parts by mass” column in each column of the table. The obtained resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter with a pore width of 0.5 ⁇ m. Furthermore, in the table, the description "-" indicates that the composition does not contain the corresponding component.
  • Example or Comparative Example for each resin composition or comparative composition, the following shows the viscosity of the composition after storage at 23°C for 14 days after preparation, relative to the viscosity of the composition on the day of preparation.
  • the viscosity change rate (%) expressed by the formula was measured. The measurement results are listed in the "Storage Stability" column of the table. The unit of numerical values in the table is %.
  • the absolute value of the viscosity change rate is preferably 10% or less.
  • Viscosity change rate (%) ⁇ (Viscosity of the resin composition on the day of preparation) - (Viscosity of the resin composition after storage as described above) ⁇ /(Viscosity of the resin composition on the day of preparation) x 100
  • the viscosity can be measured using, for example, a viscometer RE85R manufactured by Toki Sangyo Co., Ltd. (rotor: 1°34' ⁇ R24) with the temperature adjusted to 25°C.
  • ⁇ C-1 KBM-503 (manufactured by Shin-Etsu Silicone)
  • ⁇ C-2 N-(3-(triethoxysilyl)propyl)maleamic acid
  • ⁇ C-3 to C-4 Compounds with the following structure
  • ⁇ C-5 Tetraethoxysilane
  • ⁇ C-6 X-12- 1293 (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • ⁇ C-7 KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • ⁇ A-1 WPBG-140 (manufactured by Fujifilm Wako Pure Chemical Industries)
  • ⁇ A-2 to A-3 Compounds with the following structure
  • each resin composition or each comparative composition was applied onto a silicon wafer by a spin coating method. Place the silicon wafer coated with the resin composition layer on a hot plate at the temperature listed in the "Soft bake temperature [°C]” column for the time listed in the “Soft bake time [m]” column (unit: was dried in minutes) to form a uniform resin composition layer on the silicon wafer with the thickness indicated in the column of "Film thickness [ ⁇ m]” in the table.
  • the resin composition layer on the silicon wafer was exposed in a pattern (10 mm x 50 mm) at an exposure wavelength of 365 nm and an exposure energy of 500 mJ/cm 2 using a stepper (Nikon NSR 2005 i9C), and heated at 100° C. with a hot plate. After heating for 60 seconds, it was developed with a developer and treated with a rinse solution.
  • the treatment liquid was brought into contact with the pattern after rinsing. The contact was carried out by supplying the treatment liquid to the substrate using a paddle (liquid mound).
  • a processing solution was used in the examples described as “development” in the column of “Step using processing solution” in the table, and cyclopentanone was used in other examples.
  • a treatment liquid was used in the examples in which "rinsing” was described in the column of “Step using treatment liquid” in the table, and PGMEA was used in other examples.
  • the resin layer (cured product) peeled off above was tested using a tensile tester (Tensilon) at a crosshead speed of 300 mm/min at 25°C and 65% relative humidity in the longitudinal (length) direction and width direction of the film.
  • the elongation at break was measured in accordance with JIS-K6251:2017 under an environment of (RH).
  • the elongation at break was measured five times in each of the longitudinal and width directions.
  • the arithmetic mean value of the results of a total of 10 measurements of the elongation at break in the longitudinal direction and the width direction was taken as the index value of the elongation at break.
  • the above index value (%) is listed in the "Elongation at break [%]" column in the table.
  • the resin layer (cured product) was peeled from the silicon wafer by coating, exposing, developing, curing (heating in a nitrogen atmosphere), and hydrofluoric acid treatment in the same manner as in ⁇ Evaluation of elongation at break> described above.
  • the elongation (displacement) of the peeled resin layer (cured product) was measured while changing the temperature using a thermomechanical analysis/thermal expansion coefficient measurement device Discovery TMA manufactured by TA Instruments Japan Co., Ltd. .
  • the temperature raising and lowering conditions during evaluation were as shown in (1) to (4) below. (1) Raise the temperature from room temperature to 130°C at a heating rate of 5°C/min.
  • the cured product produced by the method of the present invention has excellent elongation at break and low CTE.
  • the comparative composition according to Comparative Example 1 does not contain any specific resin. It can be seen that when such a comparative composition is used, the elongation at break is inferior and the CTE is also large. In the method according to Comparative Example 2, no treatment was performed using a treatment liquid. It can be seen that such comparative examples are inferior in elongation at break.

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Abstract

L'invention concerne : un procédé de production d'un produit durci comprenant une étape de formation de film pour l'utilisation d'une composition de résine comprenant un solvant et un précurseur de polyimide qui comprend une unité de répétition représentée par la formule (1) sur un matériau de base pour former un film, une étape de traitement consistant à mettre en contact un liquide de traitement et le film, et une étape de chauffe consistant à faire chauffer le film après l'étape de traitement, le liquide de traitement comprenant au moins un composé choisi dans le groupe constitué d'un composé basique et d'un agent de génération de base ; un procédé de production d'un dispositif à semi-conducteur comprenant le produit durci ; et le liquide de traitement utilisé dans le procédé de production du produit durci.
PCT/JP2023/011592 2022-03-29 2023-03-23 Procédé de production d'un produit durci, procédé de production d'un dispositif à semi-conducteur, liquide de traitement et composition de résine Ceased WO2023190063A1 (fr)

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JP2024512288A JPWO2023190063A1 (fr) 2022-03-29 2023-03-23
CN202380031626.6A CN118946611A (zh) 2022-03-29 2023-03-23 固化物的制造方法、半导体器件的制造方法、处理液及树脂组合物

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WO2025105345A1 (fr) * 2023-11-13 2025-05-22 富士フイルム株式会社 Composition de résine, produit durci, corps stratifié, procédé de production de produit durci, procédé de production de corps stratifié, procédé de production de dispositif semi-conducteur et dispositif semi-conducteur

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WO2022050135A1 (fr) * 2020-09-07 2022-03-10 富士フイルム株式会社 Procédé de fabrication d'objet durci, procédé de fabrication de stratifié, et procédé de fabrication de dispositif à semi-conducteurs
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JP2022110943A (ja) * 2021-01-19 2022-07-29 Ｈｄマイクロシステムズ株式会社 樹脂組成物、積層体の製造方法及び硬化膜
JP7259141B1 (ja) * 2021-08-31 2023-04-17 富士フイルム株式会社 硬化物の製造方法、積層体の製造方法、及び、半導体デバイスの製造方法、並びに、処理液

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JPH08339089A (ja) * 1995-06-12 1996-12-24 Nippon Zeon Co Ltd 感光性ポリイミド用現像液
US20210364919A1 (en) * 2019-01-23 2021-11-25 Microcosm Technology Co., Ltd. Photosensitive resin composition and application thereof
JP2022021937A (ja) * 2020-07-22 2022-02-03 Ｈｄマイクロシステムズ株式会社 感光性樹脂組成物、硬化物、パターン硬化物の製造方法、及び電子部品
WO2022050041A1 (fr) * 2020-09-07 2022-03-10 富士フイルム株式会社 Procédé de fabrication d'objet durci, procédé de fabrication de stratifié, et procédé de fabrication de dispositif électronique
WO2022050135A1 (fr) * 2020-09-07 2022-03-10 富士フイルム株式会社 Procédé de fabrication d'objet durci, procédé de fabrication de stratifié, et procédé de fabrication de dispositif à semi-conducteurs
WO2022070730A1 (fr) * 2020-09-29 2022-04-07 富士フイルム株式会社 Procédé de production de produit durci, procédé de production de corps multicouche, et procédé de production de dispositif à semiconducteur
JP2022110943A (ja) * 2021-01-19 2022-07-29 Ｈｄマイクロシステムズ株式会社 樹脂組成物、積層体の製造方法及び硬化膜
JP7259141B1 (ja) * 2021-08-31 2023-04-17 富士フイルム株式会社 硬化物の製造方法、積層体の製造方法、及び、半導体デバイスの製造方法、並びに、処理液

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Publication number Priority date Publication date Assignee Title
WO2025105345A1 (fr) * 2023-11-13 2025-05-22 富士フイルム株式会社 Composition de résine, produit durci, corps stratifié, procédé de production de produit durci, procédé de production de corps stratifié, procédé de production de dispositif semi-conducteur et dispositif semi-conducteur

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