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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/21—Urea; Derivatives thereof, e.g. biuret
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • 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
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/094—Multilayer resist systems, e.g. planarising layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/20—Exposure; Apparatus therefor
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
• • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W20/00—Interconnections in chips, wafers or substrates
  • H10W20/01—Manufacture or treatment
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W20/00—Interconnections in chips, wafers or substrates
  • H10W20/40—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes
  • H10W20/45—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes characterised by their insulating parts
  • H10W20/47—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes characterised by their insulating parts comprising two or more dielectric layers having different properties, e.g. different dielectric constants

Definitions

• the present invention relates to a resin composition, a cured film, a laminate, a method for producing a cured film, and a semiconductor device.
• Polyimide is applied to various applications because it has excellent heat resistance and insulating properties.
• the above application is not particularly limited, and examples of a semiconductor device for mounting include use as a material for an insulating film and a sealing material, or as a protective film. It is also used as a base film and coverlay for flexible substrates.
• polyimide is used in the form of a resin composition containing polyimide itself or a resin composition containing a polyimide precursor (also referred to as "polyimide precursor").
• a cured resin can be formed on the base material by applying such a resin composition to the base material by, for example, coating, and then exposing, developing, heating, etc., if necessary. Since the resin composition can be applied by a known coating method or the like, it has excellent manufacturing adaptability, for example, a high degree of freedom in designing the shape, size, application position, etc. of the applied resin composition. It can be said that.
• industrial application development of a resin composition containing polyimide or a polyimide precursor is expected more and more.
• Patent Document 1 describes a polyimide precursor having a specific structural unit: 100 parts by mass, (B) a photopolymerization initiator: 1 to 20 parts by mass, and (C) a compound having a specific structure, or a weight thereof.
• a cured film is formed on a metal layer using a resin composition containing at least one resin selected from the group consisting of polyimide and a polyimide precursor.
• a resin composition containing at least one resin selected from the group consisting of polyimide and a polyimide precursor.
• it is desired to provide a resin composition having excellent adhesion between the cured film and a metal.
• the present invention relates to a resin composition capable of obtaining a cured film having excellent adhesion to a metal, a cured film obtained by curing the resin composition, a laminate containing the cured film, a method for producing the cured film, and a method for producing the cured film.
• An object of the present invention is to provide a semiconductor device including the cured film or the laminate.
• ⁇ 1> Containing at least one resin selected from the group consisting of polyimide and polyimide precursors.
• the solid content contains the structure represented by the formula (1-1).
• R 1 and R 2 independently represent an aliphatic group or an aromatic group, and the carbon atom or hydrocarbon group of the aliphatic group or aromatic group is substituted with a hetero atom.
• X 1 may represent an oxygen atom or a sulfur atom
• * 1 and * 2 may be independent of each other.
• a ring structure may be formed by bonding at least two of a structure that binds to R 1 , R 2 , * 1 and a structure that binds to * 2.
• ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, which comprises the structure represented by the following formula (1-2) as the structure represented by the above formula (1-1). ..
• R 21 and R 22 independently represent an aliphatic group or an aromatic group, and the carbon atom or hydrocarbon group of the aliphatic group or aromatic group is substituted with a hetero atom.
• R 23 may represent a hydrogen atom or a monovalent organic group, * represents a bonding site with another structure, and at least 2 of the structures bonded to R 21 , R 22 , R 23, and *.
• the groups may be combined to form a ring structure.
• ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, further comprising a photopolymerization initiator.
• ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, further comprising a cross-linking agent.
• ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, which is used for forming an interlayer insulating film for a rewiring layer.
• ⁇ 9> A cured film obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 8>.
• ⁇ 10> A laminate having two or more cured films according to ⁇ 9> and having a metal layer between any of the cured films.
• a method for producing a cured film which comprises a film forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 8> to a substrate to form a film.
• the method for producing a cured film according to ⁇ 11> which comprises a step of heating the film at 50 to 450 ° C.
• a resin composition capable of obtaining a cured film having excellent adhesion to a metal, a cured film obtained by curing the resin composition, a laminate containing the cured film, a method for producing the cured film, and the like. And a semiconductor device including the cured film or the laminate is provided.
• the present invention is not limited to the specified embodiments.
• the numerical range represented by the symbol "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value, respectively.
• the term "process” means not only an independent process but also a process that cannot be clearly distinguished from other processes as long as the desired action of the process can be achieved.
• the notation not describing substitution and non-substitution includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
• the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• exposure includes not only exposure using light but also exposure using particle beams such as an electron beam and an ion beam. Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
• (meth) acrylate means both “acrylate” and “methacrylate”, or either
• (meth) acrylic means both “acrylic” and “methacrylic", or
• (meth) acryloyl means both “acryloyl” and “methacrylic", or either.
• Me in the structural formula represents a methyl group
• Et represents an ethyl group
• Bu represents a butyl group
• Ph represents a phenyl group.
• the total solid content means the total mass of all the components of the composition excluding the solvent.
• the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values according to gel permeation chromatography (GPC measurement) unless otherwise specified.
• GPC measurement gel permeation chromatography
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) for example, HLC-8220GPC (manufactured by Tosoh Corporation) is used, and guard columns HZ-L, TSKgel Super HZM-M, and TSKgel are used as columns. It can be obtained by using Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation).
• the direction in which the layers are stacked on the base material is referred to as "upper", or if there is a photosensitive layer, the direction from the base material to the photosensitive layer is referred to as “upper”.
• the opposite direction is referred to as "down”.
• the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component.
• the content of each component in the composition means the total content of all the compounds corresponding to the component.
• the temperature is 23 ° C.
• the atmospheric pressure is 101,325 Pa (1 atm)
• the relative humidity is 50% RH.
• the combination of preferred embodiments is a more preferred embodiment.
• the resin composition of the present invention contains at least one resin selected from the group consisting of polyimide and a polyimide precursor, and the formula is contained in the solid content. Includes the structure represented by (1-1).
• at least one resin selected from the group consisting of polyimide and a polyimide precursor is also referred to as "specific resin”.
• R 1 and R 2 independently represent an aliphatic group or an aromatic group, and the carbon atom or hydrocarbon group of the aliphatic group or aromatic group is substituted with a hetero atom.
• X 1 may represent an oxygen atom or a sulfur atom
• * 1 and * 2 may be independent of each other.
• a ring structure may be formed by bonding at least two of a structure that binds to R 1 , R 2 , * 1 and a structure that binds to * 2.
• a cured film is formed on a metal layer using a resin composition containing at least one resin selected from the group consisting of polyimide and a polyimide precursor.
• the cured film is used in various devices, for example, as an insulating film, a material for a sealing material, a protective film, a base film for a flexible substrate, a coverlay, and the like.
• the cured film formed on such a metal layer it is required that the cured film is not easily peeled off from the metal layer, that is, the adhesion between the metal layer and the cured film is excellent.
• the present inventors have found that the adhesion between the metal layer and the cured film is improved by including the structure represented by the formula (1-1) in the solid content of the above resin composition. I found it.
• the mechanism by which the above effect is obtained is not clear, but it is presumed that this is because the structure contained in the cured film formed by the resin composition interacts with the metal contained in the metal layer, but it is not clear. do not have.
• the resin composition of the present invention due to the above interaction, even when the cured film and the metal layer are heated (for example, heated at 175 ° C. for 1,000 hours), the cured film and the metal layer are heated. It is considered to have excellent adhesion to.
• Patent Document 1 does not describe or suggest a resin composition containing a structure represented by the formula (1-1) in the solid content.
• the resin composition of the present invention will be described in detail.
• the structure represented by the formula (1-1) may be contained in the solid content of the resin composition.
• the structure represented by the formula (1-1) is included in the structure of the specific resin.
• the resin composition may contain a compound having a structure represented by the above formula (1-1) and different from the above resin (hereinafter, also referred to as “specific compound”). Further, the resin composition may contain a resin having a structure represented by the formula (1-1) and may contain a specific compound.
• R 1 and R 2 independently represent an aliphatic group or an aromatic group, preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably an aliphatic hydrocarbon group. ..
• aliphatic hydrocarbon group a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, a saturated aliphatic hydrocarbon group having 3 to 10 carbon atoms is more preferable, and a saturated aliphatic hydrocarbon group having 3 to 6 carbon atoms is preferable.
• a hydrogen group is more preferable, and an isopropyl group or a cyclohexyl group is more preferable.
• the above-mentioned aliphatic hydrocarbon group may have a known substituent, but it is also one of the preferred embodiments of the present invention that the aliphatic hydrocarbon group does not have a substituent.
• the aromatic hydrocarbon group an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is further preferable.
• the aromatic hydrocarbon group may have a known substituent, and examples of the substituent include an alkyl group.
• an alkyl group having 1 to 10 carbon atoms is preferable, a branched alkyl group having 3 to 10 carbon atoms or a cyclic alkyl group having 5 to 10 carbon atoms is more preferable, and a branched alkyl group having 3 to 6 carbon atoms is preferable.
• the group is more preferable, and the isopropyl group is particularly preferable.
• the number of the substituents is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3, and even more preferably 2.
• the carbon atom or hydrocarbon group of the aliphatic group or aromatic group in R 1 and R 2 may be substituted with a hetero atom.
• hetero atom examples include an oxygen atom, a nitrogen atom, a sulfur atom and the like.
• the RN represents a hydrogen atom or a hydrocarbon group, and a hydrogen atom, an alkyl group or an aryl group is more preferable, a hydrogen atom or an alkyl group is further preferable, and a hydrogen atom is particularly preferable.
• X 1 represents an oxygen atom or a sulfur atom, and an oxygen atom is preferable.
• Ring structure In the formula (1-1), at least two of the structure bonded to R 1 , R 2 , * 1 and the structure bonded to * 2 may be combined to form a ring structure.
• the ring structure formed include, but are not limited to, a hydantoin ring, an N-acylimidazolidinone ring, and the like.
• one of the preferred embodiments is that none of the structure bonded to R 1 , R 2 , * 1 and the structure bonded to * 2 forms a ring structure.
• the resin composition of the present invention preferably contains a structure represented by the following formula (1-2) as a structure represented by the formula (1-1).
• R 21 and R 22 independently represent an aliphatic group or an aromatic group, and the carbon atom or hydrocarbon group of the aliphatic group or aromatic group is substituted with a hetero atom.
• R 23 may represent a hydrogen atom or a monovalent organic group, * represents a bonding site with another structure, and at least 2 of the structures bonded to R 21 , R 22 , R 23, and *.
• the groups may be combined to form a ring structure.
• R 21 and R 22 are synonymous with R 1 and R 2 in formula (1-1), respectively, and the preferred embodiments are also the same.
• R 23 represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably a hydrogen atom.
• examples of the aliphatic hydrocarbon group or an aromatic hydrocarbon group include aliphatic hydrocarbon group or an aromatic hydrocarbon group for R 1 described above, preferred embodiment is also the same.
• Ring structure In formula (1-2), at least two of the structures bonded to R 21 , R 22 , R 23 , and * may be bonded to form a ring structure.
• the ring structure formed include, but are not limited to, a hydantoin ring, an N-acylimidazolidinone ring, and the like.
• one of the preferred embodiments is that none of the structures bonded to R 21 , R 22 , R 23, and * form a ring structure.
• the molar content of the structure represented by the formula (1-1) with respect to the total solid content of the resin composition is preferably 0.01 to 1.0 mmol / g, and is 0. It is more preferably 0.01 to 0.85 mmol / g, and even more preferably 0.015 to 0.75 mmol / g.
• the molar content is not more than the above lower limit value, it is considered that a cured film having excellent adhesion to a metal can be easily obtained.
• the molar content is not more than the above upper limit value, for example, cyclization of the polyimide precursor is suppressed, cleavage of the main chain of the specific resin is suppressed, and curing of the composition is excellent in storage stability. It is considered that a film is easily obtained.
• the method for measuring the content is not particularly limited, and examples thereof include the measuring method in the examples described later.
• the method for measuring the total solid content is not particularly limited, and examples thereof include the measuring method in Examples described later, in which the temperature of the resin composition is measured while confirming that there are no volatile components other than the solvent. And a method of setting the atmospheric pressure and drying.
• the method for measuring the total solid content is not limited to any method as long as it can determine the content of components other than the solvent in the resin composition as the total solid content.
• the above-mentioned content is the molar amount of the structure represented by the formula (1-1) with respect to the total solid content of the resin composition.
• the resin composition has a structure represented by the formula (1-1).
• the total amount of the structure represented by the formula (1-1) contained in the resin and the structure represented by the formula (1-1) contained in the specific compound is It is preferably within the above range.
• the resin composition of the present invention contains at least one resin (specific resin) selected from the group consisting of polyimide and a polyimide precursor.
• the resin composition of the present invention preferably contains a polyimide precursor as a specific resin.
• the specific resin preferably has a radically polymerizable group.
• the resin composition preferably contains a radical polymerization initiator described below as a polymerization initiator, contains a radical polymerization initiator described below as a photosensitizer, and radically crosslinkeds described below.
• the specific resin may have a polarity converting group such as an acid-decomposable group.
• the resin composition preferably contains a photoacid generator described later. From such a resin composition, for example, a chemically amplified positive type photosensitive layer or a negative type photosensitive layer is formed.
• the specific resin preferably contains a structure represented by the formula (1-1).
• the preferred embodiment of the structure represented by the formula (1-1) is as described above.
• the specific resin may have a structure represented by the formula (1-1) in the main chain, but may have a structure represented by the side chain. preferable.
• the "main chain” refers to the relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the "side chain” refers to other binding chains.
• the specific resin contains a structure represented by the formula (1-1)
• the specific resin contains a repeating unit represented by the formula (2-1) described later, or ends with the formula (2-2) described later. ) Is preferably included.
• the resin composition may contain a specific resin containing a structure represented by the formula (1-1) and a specific resin not containing the structure represented by the formula (1-1).
• polyimide precursor The type of the polyimide precursor used in the present invention is not particularly specified, but it is preferable that the polyimide precursor contains a repeating unit represented by the following formula (2).
• a 1 and A 2 independently represent an oxygen atom or NH
• R 111 represents a divalent organic group
• R 115 represents a tetravalent organic group
• R 113 represents a tetravalent organic group
• R 114 independently represent a hydrogen atom or a monovalent organic group.
• a 1 and A 2 in the formula (2) independently represent an oxygen atom or NH, and an oxygen atom is preferable.
• R 111 in the formula (2) represents a divalent organic group.
• the divalent organic group include a linear or branched aliphatic group, a cyclic aliphatic group and a group containing an aromatic group, and a linear or branched aliphatic group having 2 to 20 carbon atoms and a carbon number of carbon atoms.
• a cyclic aliphatic group of 6 to 20, an aromatic group having 6 to 20 carbon atoms, or a group composed of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
• a group represented by -Ar-L-Ar- is exemplified.
• Ar is an aromatic group independently
• L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, ⁇ CO ⁇ , —S—. , -SO 2- or NHCO-, or a group consisting of a combination of two or more of the above.
• R 111 is preferably derived from diamine.
• the diamine used for producing the polyimide precursor include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one kind of diamine may be used, or two or more kinds of diamines may be used. Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a group consisting of a combination thereof. It is preferably a diamine containing, and more preferably a diamine containing a group consisting of an aromatic group having 6 to 20 carbon atoms. Examples of aromatic groups include:
• diamine examples include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; 1,2- or 1 , 3-Diaminocyclopentane, 1,2-, 1,3- or 1,4-diaminocyclohexane, 1,2-, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis- (4-) Aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4,4'-diamino-3,3'-dimethylcyclohexylmethane and isophoronediamine; m- or p-phenylenediamine, diaminotoluene, 4,4'- Or 3,3'-diaminobiphenyl, 4,4'-diaminodiphenyl;
• diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/0385898 are also preferable.
• a diamine having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/0385898 is also preferably used.
• R 111 is preferably represented by —Ar—L—Ar— from the viewpoint of the flexibility of the obtained cured film.
• Ar is an aromatic group independently, and L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, ⁇ CO ⁇ , —S—. , -SO 2- or NHCO-, or a group consisting of a combination of two or more of the above.
• Ar is a phenylene group is preferably, L is an aliphatic hydrocarbon group having a fluorine atom are carbon atoms and optionally 1 or substituted by 2, -O -, - CO - , - S- or SO 2 - are preferred.
• 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) from the viewpoint of i-ray transmittance.
• a divalent organic group represented by the formula (61) is more preferable.
• Equation (51) In formula (51), R 50 to R 57 are independently hydrogen atoms, fluorine atoms or monovalent organic groups, and at least one of R 50 to R 57 is a fluorine atom, methyl group or trifluoro. It is a methyl group.
• the monovalent organic group of R 50 to R 57 includes an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) and 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). Examples thereof include an alkyl fluoride group.
• R 58 and R 59 are independently fluorine atoms or trifluoromethyl groups, respectively.
• Examples of the diamine compound giving the structure of the formula (51) or (61) include 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-. Examples thereof include bis (fluoro) -4,4'-diaminobiphenyl and 4,4'-diaminooctafluorobiphenyl. These may be used alone or in combination of two or more.
• diamines can also be preferably used.
• R 115 in the 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.
• * represents a binding site with another structure.
• R 112 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be replaced with a single bond or a fluorine atom, —O—, —CO ⁇ , —S—, —SO.
• 2- , NHCO-, and a group selected from a combination thereof are preferable, and a single bond, an alkylene group having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -CO. More preferably, it is a group selected from-, -S- and SO 2- , -CH 2- , -C (CF 3 ) 2- , -C (CH 3 ) 2-, -O-, -CO. It is more preferably a divalent group selected from the group consisting of-, -S- and SO 2-.
• R 115 include tetracarboxylic acid residues remaining after removal of the acid anhydride group from the tetracarboxylic dianhydride. Only one type of tetracarboxylic dianhydride may be used, or two or more types may be used.
• the tetracarboxylic dianhydride is preferably represented by the following formula (O). Equation (O) In formula (O), R 115 represents a tetravalent organic group.
• a preferred range of R 115 has the same meaning as R 115 in formula (2), and preferred ranges are also the same.
• tetracarboxylic dianhydride examples include pyromellitic dianhydride (PMDA), 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-.
• PMDA pyromellitic dianhydride
• 3,3', 4,4'-biphenyltetracarboxylic dianhydride 3,3', 4,4'-.
• tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International Publication No. 2017/038598 are also mentioned as preferable examples.
• R 111 and R 115 has an OH group. More specifically, as R 111 , a residue of a bisaminophenol derivative can be mentioned.
• R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, and it is preferable that at least one of R 113 and R 114 contains a polymerizable group, and both contain a polymerizable group.
• a radically polymerizable group is preferable because it is a group capable of undergoing a cross-linking reaction by the action of heat, radicals and the like.
• 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, a methylol group and an amino.
• the group is mentioned.
• a group having an ethylenically unsaturated bond is preferable.
• Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
• R200 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
• R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2 CH (OH) CH 2- or a polyalkyleneoxy group. Examples of suitable R 201 are ethylene group, propylene group, trimethylene group, tetramethylene group, 1,2-butandyl group, 1,3-butandyl group, pentamethylene group, hexamethylene group, octamethylene group, dodecamethylene group.
• the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
• the alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
• the sequence of the alkyleneoxy groups in the polyalkyleneoxy group may be a random sequence or a sequence having a block. It may be an array having a pattern such as alternating.
• the carbon number of the alkylene group (including the carbon number of the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6. Is more preferable, 2 to 5 is more preferable, 2 to 4 is more preferable, 2 or 3 is particularly preferable, and 2 is most preferable.
• the said alkylene group may have a substituent.
• Preferred substituents include alkyl groups, aryl groups, halogen atoms and the like.
• the number of alkyleneoxy groups contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
• the polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance.
• a group in which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable.
• the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.
• R 113 and R 114 are independently hydrogen atoms or monovalent organic groups.
• the monovalent organic group include an aromatic group and an aralkyl group in which an acidic group is bonded to one, two or three carbons constituting the aryl group, preferably one.
• Specific examples thereof include an aromatic group having an acidic group having 6 to 20 carbon atoms and an aralkyl group having an acidic group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group can be mentioned.
• the acidic group is preferably an OH group. It is also more preferable that R 113 or R 114 is a hydrogen atom, 2-hydroxybenzyl, 3-hydroxybenzyl and 4-hydroxybenzyl.
• R 113 or R 114 is preferably a monovalent organic group.
• the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and an alkyl group substituted with an aromatic group is more preferable.
• the alkyl group preferably has 1 to 30 carbon atoms.
• the alkyl group may be linear, branched or cyclic.
• linear or branched alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a tetradecyl group and an octadecyl group.
• Isobutyl group isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, 2-ethylhexyl group 2- (2- (2-methoxyethoxy) ethoxy) ethoxy group, 2- (2- (2) -Ethoxyethoxy) ethoxy) ethoxy) ethoxy group, 2- (2- (2- (2-methoxyethoxy) ethoxy) ethoxy) ethoxy group, and 2- (2- (2- (2- (2-ethoxyethoxy) ethoxy) ethoxy) Ethoxy group is mentioned.
• the cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group.
• Examples of the monocyclic cyclic alkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group.
• Examples of the polycyclic cyclic alkyl group include an adamantyl group, a norbornyl group, a bornyl group, a phenyl group, a decahydronaphthyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a camphoroyl group, a dicyclohexyl group and a pinenyl group. Can be mentioned. Of these, the cyclohexyl group is most preferable from the viewpoint of achieving both high sensitivity. Further, as the alkyl group substituted with an aromatic group, a linear alkyl group substituted with an aromatic group described later is preferable.
• aromatic group examples include substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, inden ring, azulene ring, heptalene ring, indacene ring, perylene ring, pentacene ring, acenaphthene ring, phenanthrene ring, and anthracene.
• the benzene ring is most preferable.
• R 113 is a hydrogen atom or R 114 is a hydrogen atom
• R 113 is a hydrogen atom
• R 114 is a hydrogen atom
• the polyimide precursor forms a salt with a tertiary amine compound having an ethylenically unsaturated bond.
• the tertiary amine compound having such an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
• At least one of R 113 and R 114 may be a polar converting group such as an acid-degradable group.
• the acid-degradable group is not particularly limited as long as it is decomposed by the action of an acid to produce an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but is not particularly limited, but is an acetal group, a ketal group, a silyl group, or a silyl ether group.
• a tertiary alkyl ester group or the like is preferable, and an acetal group is more preferable from the viewpoint of exposure sensitivity.
• the acid-degradable group examples include tert-butoxycarbonyl group, isopropoxycarbonyl group, tetrahydropyranyl group, tetrahydrofuranyl group, ethoxyethyl group, methoxyethyl group, ethoxymethyl group, trimethylsilyl group and tert-butoxycarbonylmethyl.
• examples include a group, a trimethylsilyl ether group and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferable.
• the polyimide precursor has a fluorine atom in the structural unit.
• the fluorine atom content in the polyimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
• the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
• the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
• the repeating unit represented by the formula (2) is preferably the repeating unit represented by the formula (2-A). That is, it is preferable that at least one of the polyimide precursors used in the present invention is a precursor having a repeating unit represented by the formula (2-A). With such a structure, the width of the exposure latitude can be further widened. Equation (2-A) In formula (2-A), A 1 and A 2 represent oxygen atoms, R 111 and R 112 each independently represent a divalent organic group, and R 113 and R 114 each independently. Representing a hydrogen atom or a monovalent organic group , at least one of R 113 and R 114 is a group containing a polymerizable group, and it is preferable that both are polymerizable groups.
• 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 preferred ranges are also the same .
• R 112 has the same meaning as R 112 in formula (5), and preferred ranges are also the same.
• the polyimide precursor may contain one type of repeating structural unit represented by the formula (2), but may contain two or more types. Further, it may contain a structural isomer of a repeating unit represented by the formula (2). Needless to say, the polyimide precursor may contain other types of repeating structural units in addition to the repeating unit of the above formula (2).
• polyimide precursor in the present invention a polyimide precursor in which 50 mol% or more of all repeating units, further 70 mol% or more, particularly 90 mol% or more is a repeating unit represented by the formula (2) is used. Illustrated.
• the polyimide precursor When the polyimide precursor has a structure represented by the formula (1-1), the polyimide precursor preferably contains a repeating unit represented by the following formula (2-1).
• R 111 represents a divalent organic group
• R 115 represents a tetravalent organic group
• RX1 and RX2 are independently represented by the formula (1-1). It represents a group containing a structure represented or a group represented by the following formula (R-1), and at least one of RX1 and RX2 represents a group containing a structure represented by the formula (1-1).
• a 3 represents an oxygen atom or NH
• RX 3 independently represents a hydrogen atom or a monovalent organic group
• * represents a binding site with R 115.
• R 111 and R 115 are synonymous with R 111 and R 115 in formula (2), respectively, and the preferred embodiments are also the same.
• RX1 and RX2 represents a group containing the structure represented by formula (1-1).
• the group containing the structure represented by the above formula (1-1) is preferably a group represented by the following formula (X-1).
• R 1 and R 2 independently represent an aliphatic group or an aromatic group, and the carbon atom or hydrocarbon group of the aliphatic group or aromatic group is substituted with a hetero atom.
• X 1 represents an oxygen atom or a sulfur atom
• * represents a bonding site with R 115.
• R 1, R 2, X 1 and L 1 have the same meanings as R 1, R 2, X 1 and L 1 in the formula (1-1), preferable embodiments thereof are also the same .
• R 3 has the same meaning as R 23 in formula (1-2), and the preferred embodiment is also the same.
• RX1 and RX2 may be a group represented by formula (R-1).
• R-1 A 3 and RX 3 are synonymous with A 2 and R 113 in formula (2), respectively, and the preferred embodiments are also the same.
• the content of the repeating unit represented by the formula (2-1) in the polyimide precursor is not particularly limited, and the molar content of the structure represented by the formula (1-1) with respect to the total solid content of the resin composition. May be appropriately adjusted as the amount within the above range.
• the content of the group represented by the formula (X-1) in the polyimide precursor is preferably, for example, 0.01 to 1.0 mmol / g, and preferably 0.01 to 0.85 mmol / g. More preferred.
• the weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 to 30,000, more preferably 20,000 to 27,000, and even more preferably 22,000 to 25,000.
• the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and even more preferably 9,200 to 11,200.
• the degree of dispersion of the molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and further preferably 2.8 or more.
• the upper limit of the dispersity of the molecular weight of the polyimide precursor is not particularly defined, but for example, 4.5 or less is preferable, 4.0 or less is more preferable, 3.8 or less is further preferable, and 3.2 or less is further preferable. Preferably, 3.1 or less is even more preferable, 3.0 or less is even more preferable, and 2.95 or less is particularly preferable.
• the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
• the polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide that is soluble in a developing solution containing an organic solvent as a main component.
• the alkali-soluble polyimide means a polyimide that dissolves 0.1 g or more at 23 ° C. in 100 g of a 2.38 mass% tetramethylammonium aqueous solution, and 0.5 g or more from the viewpoint of pattern forming property.
• a polyimide that dissolves is preferable, and a polyimide that dissolves 1.0 g or more is more preferable.
• the upper limit of the dissolution amount is not particularly limited, but is preferably 100 g or less.
• the polyimide is preferably a polyimide having a plurality of imide structures in the main chain from the viewpoint of the film strength and the insulating property of the obtained cured film.
• the "main chain” refers to the relatively longest binding chain among the molecules of the polymer compound constituting the resin, and the “side chain” refers to other binding chains.
• the polyimide preferably has a fluorine atom.
• the fluorine atom is preferably contained in, for example, R 132 in the repeating unit represented by the formula (4) described later, or R 131 in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula (4) described later. It is more preferable that R 132 in the repeating unit represented by 4) or R 131 in the repeating unit represented by the formula (4) described later is contained as an alkyl fluoride group.
• the amount of fluorine atoms with respect to the total mass of the polyimide is preferably 1 to 50 mol / g, and more preferably 5 to 30 mol / g.
• the polyimide preferably has a silicon atom.
• the silicon atom is preferably contained in R 131 in the repeating unit represented by the formula (4) described later, and is organically modified (poly ) in R 131 in the repeating unit represented by the formula (4) described later. ) It is more preferable that it is contained as a siloxane structure. Further, the silicon atom or the organically modified (poly) siloxane structure may be contained in the side chain of the polyimide, but is preferably contained in the main chain of the polyimide.
• the amount of silicon atoms with respect to the total mass of the polyimide is preferably 0.01 to 5 mol / g, more preferably 0.05 to 1 mol / g.
• the polyimide preferably has an ethylenically unsaturated bond.
• the polyimide may have an ethylenically unsaturated bond at the end of the main chain or at the side chain, but it is preferably provided at the side chain.
• the ethylenically unsaturated bond preferably has radical polymerization property.
• the ethylenically unsaturated bond is preferably contained in R 132 in the repeating unit represented by the formula (4) described later or R 131 in the repeating unit represented by the formula (4) described later, and is preferably contained in the formula described later.
• R 132 in the repeating unit represented by (4) or R 131 in the repeating unit represented by the formula (4) described later is contained as a group having an ethylenically unsaturated bond.
• ethylenically unsaturated bond ethylene R 131 in the repeating unit represented by the preferably contained in R 131 in the repeating unit represented by the formula (4) described later, which will be described later Equation (4) It is more preferably contained as a group having a sex unsaturated bond.
• Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted, which is directly bonded to an aromatic ring such as a vinyl group, an allyl group and a vinylphenyl group, a (meth) acrylamide group, and a (meth) group.
• Examples thereof include an acryloyloxy group and a group represented by the following formula (IV).
• R 20 represents a hydrogen atom or a methyl group, and a methyl group is preferable.
• a (poly) alkyleneoxy group having 2 to 30 carbon atoms the alkylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3; the number of repetitions is preferably 1 to 12 and 1 ⁇ 6 is more preferable, and 1 to 3 are particularly preferable), or a group in which two or more of these are combined is represented.
• R 21 is preferably a group represented by any of the following formulas (R1) to (R3), and more preferably a group represented by the formula (R1).
• L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) alkyleneoxy group having 2 to 30 carbon atoms, or a group in which two or more of these are bonded
• X Indicates an oxygen atom or a sulfur atom
• * represents a bond site with another structure
• ⁇ represents a bond site with an oxygen atom to which R 201 in the formula (III) is bonded.
• a preferred embodiment of the alkylene group having 2 to 12 carbon atoms in L or the (poly) alkyleneoxy group having 2 to 30 carbon atoms is the above-mentioned R 21 having 2 to 12 carbon atoms. This is the same as the preferred embodiment of 12 alkylene groups or (poly) alkyleneoxy groups having 2 to 30 carbon atoms.
• X is preferably an oxygen atom.
• * is synonymous with * in formula (IV), and the preferred embodiment is also the same.
• the structure represented by the formula (R1) comprises, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group and a compound having an isocyanato group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate). Obtained by reacting.
• the structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxy group with a compound having a hydroxy group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate).
• the structure represented by the formula (R3) is obtained by reacting, for example, a polyimide having a hydroxy group such as a phenolic hydroxy group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate).
• a polyimide having a hydroxy group such as a phenolic hydroxy group
• a compound having a glycidyl group and an ethylenically unsaturated bond for example, glycidyl methacrylate.
• the polyalkyleneoxy group includes a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a plurality of ethyleneoxy groups and a plurality of propylenes from the viewpoint of solvent solubility and solvent resistance.
• a group in which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is further preferable.
• the ethyleneoxy groups and the propyleneoxy groups may be randomly arranged or may be arranged by forming a block. , Alternate or the like may be arranged in a pattern. The preferred embodiment of the number of repetitions of the ethyleneoxy group and the like in these groups is as described above.
• * represents a binding site with another structure, and is preferably a binding site with the main chain of polyimide.
• the amount of the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g. From the viewpoint of production suitability, the amount of ethylenically unsaturated bonds with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, and preferably 0.0005 to 0.05 mol / g. More preferred.
• the polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.
• the crosslinkable group other than the ethylenically unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a methylol group.
• the crosslinkable group other than the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by the formula (4) described later, for example.
• the amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.05 to 10 mol / g, more preferably 0.1 to 5 mol / g. From the viewpoint of production suitability, the amount of the crosslinkable group other than the ethylenically unsaturated bond with respect to the total mass of the polyimide is preferably 0.0001 to 0.1 mol / g, preferably 0.001 to 0.05 mol / g. It is more preferably g.
• the polyimide may have a polarity converting group such as an acid-decomposable group.
• the acid-decomposable group in the polyimide is the same as the acid-decomposable group described in R 113 and R 114 in the above formula (2), and the preferred embodiment is also the same.
• the acid value of the polyimide is preferably 30 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 mgKOH / g or more from the viewpoint of improving the developability. Is more preferable.
• the acid value is preferably 500 mgKOH / g or less, more preferably 400 mgKOH / g or less, and even more preferably 200 mgKOH / g or less.
• the acid value of the polyimide is preferably 2 to 35 mgKOH / g, and 3 to 30 mgKOH. / G is more preferable, and 5 to 20 mgKOH / g is even more preferable.
• the acid value is measured by a known method, for example, by the method described in JIS K 0070: 1992.
• an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable, from the viewpoint of achieving both storage stability and developability.
• the 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.
• the polyimide preferably contains at least one selected from the group consisting of a carboxy group and a phenolic hydroxy group, and more preferably contains a phenolic hydroxy group.
• the polyimide preferably has a phenolic hydroxy group.
• the polyimide may have a phenolic hydroxy group at the end of the main chain or at the side chain.
• the phenolic hydroxy group is preferably contained in, for example, R 132 in the repeating unit represented by the formula (4) described later, or R 131 in the repeating unit represented by the formula (4) described later.
• the amount of the phenolic hydroxy group with respect to the total mass of the polyimide is preferably 0.1 to 30 mol / g, and more preferably 1 to 20 mol / g.
• the polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but preferably contains a repeating unit represented by the following formula (4), and is represented by the formula (4). More preferably, it is a compound containing a repeating unit and having a polymerizable group.
• Equation (4) In formula (4), R 131 represents a divalent organic group and R 132 represents a tetravalent organic group. When having a polymerizable group, the polymerizable group may be located at at least one of R 131 and R 132 , or may be located at the end of the polyimide as shown in the following formula (4-1) or formula (4-2). It may be located in.
• R133 is a polymerizable group, and the other groups are synonymous with formula (4).
• At least one of R 134 and R 135 is a polymerizable group, and if it is not a polymerizable group, it is an organic group, and the other group is synonymous with the formula (4).
• the polymerizable group has the same meaning as the polymerizable group described in the above-mentioned polymerizable group possessed by the polyimide precursor and the like.
• R 131 represents a divalent organic group. Examples of the divalent organic group include those similar to R 111 in the formula (2), and the preferred range is also the same. Further, as R 131 , a diamine residue remaining after removal of the amino group of diamine can be mentioned. Examples of the diamine include aliphatic, cyclic aliphatic or aromatic diamines. Specific examples include the example of R 111 in the formula (2) of the polyimide precursor.
• R 131 is a diamine residue having at least two alkylene glycol units in the main chain from the viewpoint of more effectively suppressing the occurrence of warpage during firing. More preferably, it is a diamine residue containing two or more ethylene glycol chains, one or both of propylene glycol chains in one molecule, and even more preferably, it is a diamine residue containing no aromatic ring.
• diamines containing two or more ethylene glycol chains and / or both of propylene glycol chains in one molecule include Jeffamine® KH-511, ED-600, ED-900, ED-2003, and EDR. -148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name, manufactured by HUNTSMAN Co., Ltd.), 1- (2- (2- (2-aminopropoxy) ethoxy) Examples thereof include, but are not limited to, propoxy) propane-2-amine and 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine.
• R 132 represents a tetravalent organic group.
• examples of the tetravalent organic group include those similar to R 115 in the formula (2), and the preferred range is also the same.
• R 132 includes a tetracarboxylic acid residue remaining after removal of the acid anhydride group from the tetracarboxylic dianhydride.
• Specific examples include an example of R 115 in the polyimide precursor formula (2).
• R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
• R 131 and R 132 has an OH group. More specifically, as R 131 , 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2,2- Bis (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the above (DA-1) to (DA-18) are preferable examples. As R 132 , the above (DAA-1) to (DAA-5) are more preferable examples.
• the structure represented by the formula (1-1) may be located at the end of the polyimide as shown in the following formula (2-2). ..
• R 131 represents a divalent organic group
• R 132 represents a tetravalent organic group
• RX1 and RX2 are independently represented by the formula (1-1). It represents a group containing a structure or an organic group
• at least one of RX1 and RX2 is a group containing a structure represented by the formula (1-1).
• R 131 and R 132 have the same meanings as R 131 and R 132, respectively formula (4), preferred embodiments are also the same.
• at least one of RX1 and RX2 represents a group containing the structure represented by formula (1-1).
• the group containing the structure represented by the above formula (1-1) is preferably the group represented by the above formula (X-1).
• RX1 and RX2 may be a group represented by the above formula (R-1).
• the polyimide may include a structure represented by the above formula (2-1).
• the polyimide may include a structure represented by the above formula (2-1).
• at least one of R X1 and R X2 in formula (2-1) may also form an imide ring cyclization.
• the polyimide has a fluorine atom in the structural unit.
• the content of fluorine atoms in the polyimide is preferably 10% by mass or more, and preferably 20% by mass or less.
• the polyimide may be copolymerized with an aliphatic group having a siloxane structure.
• the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
• the main chain end of polyimide may be sealed with an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound.
• an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound or monoactive ester compound.
• monoamine acid anhydride
• monocarboxylic acid monoacid chloride compound or monoactive ester compound.
• monoactive ester compound preferable.
• monoamine it is more preferable to use monoamine, and preferred compounds of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, and 1-hydroxy-7.
• the imidization rate (also referred to as “ring closure rate”) of the polyimide is preferably 70% or more, more preferably 80% or more, from the viewpoint of film strength, insulating property, etc. of the obtained cured film. More preferably, it is 90% or more.
• the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
• the imidization rate is measured by, for example, the following method. The infrared absorption spectrum of the polyimide is measured to determine the peak intensity P1 near 1377 cm -1, which is the absorption peak derived from the imide structure. Next, the polyimide is heat-treated at 350 ° C.
• the polyimide may contain repeating structural units of the above formula (4), all containing one type of R 131 or R 132, and the above formula (4) containing two or more different types of R 131 or R 132. May include repeating units of. Further, the polyimide may contain other types of repeating structural units in addition to the repeating unit of the above formula (4).
• Polyimide is, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound (partially replaced with a terminal encapsulant which is monoamine) at a low temperature, or a tetracarboxylic acid dianhydride (partly an acid) at a low temperature.
• a polyimide precursor is obtained by using a method such as a method of reacting with an end-capping agent (replaced with an end-capping agent), and the polyimide precursor is completely imidized by using a known imidization reaction method, or an imide in the middle.
• Synthesis using a method of stopping the conversion reaction and introducing a partially imidized structure and further, a method of introducing a partially imidized structure by blending a completely imidized polymer with its polyimide precursor.
• a method of introducing a partially imidized structure by blending a completely imidized polymer with its polyimide precursor.
• Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by HUNTSMAN Corporation).
• the weight average molecular weight (Mw) of the polyimide is 4,000 to 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and 10,000 to 30,000. More preferred. By setting the weight average molecular weight to 5,000 or more, the breakage resistance of the film after curing can be improved. In order to obtain a cured film having excellent mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more kinds of polyimides are contained, it is preferable that the weight average molecular weight of at least one kind of polyimide is in the above range.
• a polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine.
• the dicarboxylic acid or the dicarboxylic acid derivative is obtained by halogenating it with a halogenating agent such as thionyl chloride and then reacting it with a diamine.
• non-halogen catalyst a known amidation catalyst containing no halogen atom can be used without particular limitation.
• a boroxin compound, an N-hydroxy compound, a tertiary amine, a phosphoric acid ester, or an amine can be used.
• carbodiimide compounds such as salts and urea compounds.
• the carbodiimide compound include N, N'-diisopropylcarbodiimide, N, N'-dicyclohexylcarbodiimide, and (2,6-diisopropylphenyl) carbodiimide.
• the organic solvent may be one kind or two or more kinds.
• the organic solvent can be appropriately determined depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone.
• the polyimide may be produced by synthesizing a polyimide precursor and then cyclizing it by a method such as thermal imidization or chemical imidization (for example, promotion of cyclization reaction by acting a catalyst), or directly. , Polyimide may be synthesized.
• the end of the polyimide precursor or the like is used as an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, or a monoactive ester compound. It is preferable to seal. It is more preferable to use monoamine as the terminal encapsulant, and preferred compounds of monoamine are aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-.
• a step of precipitating a solid may be included in the production of the polyimide precursor or the like.
• the polyimide precursor or the like in the reaction solution can be precipitated in water, and the polyimide precursor or the like such as tetrahydrofuran can be dissolved in a soluble solvent to precipitate a solid.
• the polyimide precursor or the like can be dried to obtain a powdery polyimide precursor or the like.
• the specific resin contains a structure represented by the formula (1-1)
• the specific resin is synthesized by, for example, the method described in (1) or (2) below.
• a carbodiimide compound is used as a non-halogen catalyst, and the reaction time, reaction temperature, and addition timing of the carbodiimide compound are appropriately adjusted.
• the polyimide precursor or polyimide obtained by the above method for producing a polyimide precursor is reacted with a carbodiimide compound in a solvent. Specific examples of these methods include, but are not limited to, the methods described in the synthetic examples described later.
• the content of the specific resin in the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and more preferably 40% by mass or more, based on the total solid content of the composition. More preferably, it is more preferably 50% by mass or more.
• the resin content in the 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 composition. It is more preferably 97% by mass or less, and even more preferably 95% by mass or less.
• 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 kinds are included, the total amount is preferably in the above range.
• the resin composition of the present invention is a compound containing a structure represented by the above formula (1-1), and preferably contains a compound (specific compound) different from the above resin.
• the specific compound is not particularly limited except that it contains a structure represented by the formula (1-1), but is preferably a small molecule compound. Specifically, the molecular weight of the specific compound is preferably 75 to 1,000, more preferably 100 to 800, and even more preferably 150 to 500.
• the specific compound is preferably a compound represented by the following formula (3-1).
• R 1 and R 2 independently represent an aliphatic group or an aromatic group, and the carbon atom or hydrocarbon group of the aliphatic group or aromatic group is substituted with a hetero atom.
• X 1 may represent an oxygen atom or a sulfur atom
• R 3 may be a hydrogen atom or a monovalent organic group.
• R 4 represents a monovalent organic group, and at least two of R 1 , R 2 , R 3 and R 4 may be bonded to form a ring structure.
• R 1, R 2, X 1 and L 1 have the same meanings as R 1, R 2, X 1 and L 1 in the formula (1-1), preferred embodiments are also same Is.
• R 3 has the same meaning as R 23 in formula (1-2), and the preferred embodiment is also the same.
• R 4 is a monovalent organic group, preferably a hydrocarbon group.
• a hydrocarbon group an aliphatic hydrocarbon group or an aromatic hydrocarbon group is preferable, and an aromatic hydrocarbon group is more preferable.
• a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, and a saturated aliphatic hydrocarbon group having 3 to 10 carbon atoms is more preferable.
• an aromatic hydrocarbon group an aromatic hydrocarbon group having 6 to 20 carbon atoms is preferable, a phenyl group or a naphthyl group is more preferable, and a phenyl group is further preferable.
• Monovalent organic group for R 4 may have a substituent, examples of the substituent include an alkyl group, an alkyloxycarbonyl group, an aryloxy carbonyl group.
• substituents include an alkyl group, an alkyloxycarbonyl group, an aryloxy carbonyl group.
• R 4 a phenyl group, alkylphenyl group, or preferably an alkyl oxycarbonyl phenyl group, a phenyl group, t- butyl phenyl group, or, alkyloxycarbonyl having 1 to 4 carbon atoms in the alkyl group A phenyl group is more preferred.
• R 1 , R 2 , R 3 and R 4 may be combined to form a ring structure.
• the ring structure formed include, but are not limited to, a hydantoin ring, an N-acylimidazolidinone ring, and the like.
• a mode in which none of R 1 , R 2 , R 3 and R 4 forms a ring structure is also a preferable mode.
• the content thereof is not particularly limited, and the molar content of the structure represented by the formula (1-1) with respect to the total solid content of the resin composition is within the above range.
• the amount may be adjusted as appropriate.
• the content thereof is preferably, for example, 0.01 to 1.0% by mass with respect to the total solid content of the resin composition of the present invention. It is more preferably 01 to 0.85% by mass, and further preferably 0.015 to 0.75% by mass.
• the specific compound one kind may be used alone, or two or more kinds may be used. When two or more types are used in combination, the total amount is preferably in the above range.
• the resin composition of the present invention contains a solvent.
• a solvent a known solvent can be arbitrarily used.
• the solvent is preferably an organic solvent.
• the organic solvent include compounds such as esters, ethers, ketones, 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, and ⁇ -butyrolactone.
• alkylalkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl ethoxyacetate, etc.)
• 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) (eg, methyl 3-methoxypropionate, 3-methoxypropionate, etc.) Ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)
• 2-alkyloxypropionate alkyl esters eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, ethyl 2-alkyl
• ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol.
• Suitable examples include monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.
• ketones for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone 3-heptanone and the like are preferable.
• cyclic hydrocarbons for example, aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene are preferable.
• sulfoxides for example, dimethyl sulfoxide is preferable.
• N, N, N', N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone and the like are preferable.
• Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, Diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, Examples thereof include ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
• the solvent is preferably a mixture of two or more types from the viewpoint of improving the properties of the coated surface.
• the mixed solvent to be mixed is preferable.
• the combined use of dimethyl sulfoxide and ⁇ -butyrolactone is particularly preferred.
• a combination of N-methyl-2-pyrrolidone and ethyl lactate, N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and ⁇ -butyrolactone is also preferable.
• the content of the solvent is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, and is preferably 5 to 75% by mass. More preferably, the amount is 10 to 70% by mass, more preferably 40 to 70% by mass.
• the solvent content may be adjusted according to the desired thickness of the coating film and the coating method.
• the solvent may contain only one type, or may contain two or more types. When two or more kinds of solvents are contained, the total is preferably in the above range.
• the composition of the present invention may further contain another resin (hereinafter, also simply referred to as “other resin”) different from the specific resin.
• other resins include polyamide-imide, polyamide-imide precursor, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, and acrylic resin.
• acrylic resin by further adding an acrylic resin, a composition having excellent coatability can be obtained, and a cured film having excellent solvent resistance can be obtained.
• the composition is formed by adding an acrylic resin having a weight average molecular weight of 20,000 or less and having a high polymerizable base value to the composition in place of the polymerizable compound described later or in addition to the polymerizable compound described later. It is possible to improve the coatability of an object, the solvent resistance of a cured film, and the like.
• the content of the other resin is preferably 0.01% by mass or more, preferably 0.05% by mass or more, based on the total solid content of the composition. More preferably, it is more preferably 1% by mass or more, further preferably 2% by mass or more, further preferably 5% by mass or more, further preferably 10% by mass or more. ..
• the content of the other resin in the 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 composition. It is more preferably less than or equal to, more preferably 60% by mass or less, and even more preferably 50% by mass or less.
• the content of the other resin may be low.
• the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and preferably 10% by mass or less, based on the total solid content of the composition. More preferably, it is more preferably 5% by mass or less, and even more preferably 1% by mass or less.
• the lower limit of the content is not particularly limited, and may be 0% by mass or more.
• the composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more kinds are included, the total amount is preferably in the above range.
• the resin composition of the present invention preferably contains a polymerization initiator.
• a polymerization initiator a photopolymerization initiator is preferable.
• the resin composition of the present invention preferably contains a photopolymerization initiator.
• the photopolymerization initiator is preferably a photoradical polymerization initiator.
• the photoradical polymerization initiator is not particularly limited and may be appropriately selected from known photoradical polymerization initiators.
• a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable.
• it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
• the photoradical polymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol -1 ⁇ cm -1 within the range of about 300 to 800 nm (preferably 330 to 500 nm). Is preferable.
• the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
• a known compound can be arbitrarily used as the photoradical polymerization initiator.
• halogenated hydrocarbon derivatives for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
• acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives and the like.
• paragraphs 0165 to 0182 of JP2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015/199219 can be referred to, and the contents thereof are incorporated in the present specification.
• Examples of the ketone compound include the compounds described in paragraph 0087 of JP-A-2015-087611, the contents of which are incorporated in the present specification.
• KayaCure DETX manufactured by Nippon Kayaku Co., Ltd.
• Nippon Kayaku Co., Ltd. is also preferably used.
• a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used as the photoradical polymerization initiator. More specifically, for example, the aminoacetophenone-based initiator described in JP-A-10-291969 and the acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used.
• IRGACURE 184 (IRGACURE is a registered trademark)
• DAROCUR 1173 As the hydroxyacetophenone-based initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (trade names: all manufactured by BASF) can be used.
• aminoacetophenone-based initiator commercially available products IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all manufactured by BASF) can be used.
• the compound described in JP-A-2009-191179 in which the absorption maximum wavelength is matched with a wavelength light source such as 365 nm or 405 nm, can also be used.
• acylphosphine-based initiator examples include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide. Further, commercially available products such as IRGACURE-819 and IRGACURE-TPO (trade names: both manufactured by BASF) can be used.
• metallocene compound examples include IRGACURE-784 (manufactured by BASF).
• the photoradical polymerization initiator is more preferably an oxime compound.
• the exposure latitude can be improved more effectively.
• the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also acts as a photocuring accelerator.
• the compound described in JP-A-2001-233842 the compound described in JP-A-2000-080068, and the compound described in JP-A-2006-342166 can be used.
• Preferred oxime compounds include, for example, compounds having the following structures, 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxy. Iminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one , And 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.
• an oxime compound (oxime-based photopolymerization initiator) as the photoradical polymerization initiator.
• IRGACURE OXE 01 IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (above, manufactured by BASF), ADEKA PUTMER N-1919 (manufactured by ADEKA Corporation, Japanese Patent Application Laid-Open No. 2012-014052).
• a radical polymerization initiator 2) is also preferably used.
• TR-PBG-304 manufactured by Changshu Powerful Electronics New Materials Co., Ltd.
• ADEKA ARCLUDS NCI-831 ADEKA ARCULDS NCI-930
• DFI-091 manufactured by Daito Chemix Co., Ltd.
• an oxime compound having the following structure can also be used.
• an oxime compound having a fluorene ring can also be used.
• Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081.
• an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
• Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.
• an oxime compound having a fluorine atom examples include compounds described in JP-A-2010-262028, compounds 24, 36-40 described in paragraph 0345 of JP-A-2014-500852, and JP-A-2013. Examples thereof include the compound (C-3) described in paragraph 0101 of JP-A-164471.
• Examples of the most preferable oxime compound include an oxime compound having a specific substituent shown in JP-A-2007-269779 and an oxime compound having a thioaryl group shown in JP-A-2009-191061.
• the photoradical polymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triaryl.
• More preferable photoradical polymerization initiators are trihalomethyltriazine compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds and acetophenone compounds.
• At least one compound selected from the group consisting of trihalomethyltriazine compounds, ⁇ -aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferable, and metallocene compounds or oxime compounds are even more preferable, and oxime compounds are even more preferable. Is even more preferable.
• the photoradical polymerization initiator is N, N'-tetraalkyl-4,4'-diaminobenzophenone, 2-benzyl such as benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler ketone).
• 2-benzyl such as benzophenone
• benzoin ether compounds such as benzoin alkyl ether
• benzoin compounds such as benzoin and alkyl benzoin
• benzyl derivatives such as benzyl dimethyl ketal.
• a compound represented by the following formula (I) can also be used.
• RI00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, and the like.
• R I01 is a group represented by formula (II), the same as R I00 It is a group, and R I02 to R I04 are independently alkyl having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen.
• R I05 to R I07 are the same as R I 02 to R I 04 of the above formula (I).
• the compounds described in paragraphs 0048 to 0055 of International Publication No. 2015/1254669 can also be used.
• the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , More preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more kinds of photopolymerization initiators are contained, the total is preferably in the above range.
• the resin composition of the present invention may contain a thermal polymerization initiator as the polymerization initiator, and may particularly contain a thermal radical polymerization initiator.
• a thermal radical polymerization initiator is a compound that generates radicals by heat energy to initiate or accelerate the polymerization reaction of a polymerizable compound. By adding the thermal radical polymerization initiator, the polymerization reaction of the specific resin and the polymerizable compound can be allowed to proceed in the heating step described later, so that the chemical resistance can be further improved.
• thermal radical polymerization initiator examples include the compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554.
• the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition of the present invention. , More preferably 5 to 15% by mass. Only one type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more types of thermal polymerization initiators are contained, the total is preferably in the above range.
• the composition of the present invention may contain a photoacid generator.
• a photoacid generator for example, acid is generated in the exposed portion of the composition layer, the solubility of the exposed portion in the developing solution (for example, an alkaline aqueous solution) is increased, and the exposed portion is affected by the developing solution. A positive pattern to be removed can be obtained.
• the composition contains a photoacid generator and a polymerizable compound other than the radically polymerizable compound described later, for example, the acid generated in the exposed portion promotes the cross-linking reaction of the polymerizable compound.
• the exposed portion may be more difficult to be removed by the developing solution than the non-exposed portion. According to such an aspect, a negative type pattern can be obtained.
• the photoacid generator is not particularly limited as long as it generates an acid by exposure, but is an onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime.
• onium salt compound such as a quinonediazide compound, a diazonium salt, a phosphonium salt, a sulfonium salt, or an iodonium salt, an imide sulfonate, and an oxime.
• examples thereof include sulfonate compounds such as sulfonate, diazodisulfone, disulfone, and o-nitrobenzyl sulfonate.
• the quinonediazide compound includes a polyhydroxy compound in which quinonediazide sulfonic acid is ester-bonded, a polyamino compound in which quinonediazide sulfonic acid is conjugated with a sulfonamide, and a polyhydroxypolyamino compound in which quinonediazide sulfonic acid is ester-bonded and a sulfonamide bond.
• Examples thereof include those bonded by at least one of the above. In the present invention, for example, it is preferable that 50 mol% or more of all the functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide.
• the quinone diazide either a 5-naphthoquinone diazidosulfonyl group or a 4-naphthoquinone diazidosulfonyl group is preferably used.
• the 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
• the 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
• a 4-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed.
• a naphthoquinone diazidosulfonyl ester compound having a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group may be contained in the same molecule, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound may be contained. It may be contained.
• the naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxy group and a quinone diazido sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.
• Examples of the naphthoquinone diazide compound include 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and salts or ester compounds of these compounds. Be done.
• Examples of the onium salt compound or the sulfonate compound include the compounds described in paragraphs 0064 to 0122 of JP-A-2008-013646.
• the photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as “oxime sulfonate compound”).
• oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but the following formula (OS-1), the formula (OS-103) described later, the formula (OS-104), or the formula (OS-) It is preferably an oxime sulfonate compound represented by 105).
• X 3 is an alkyl group, an alkoxyl group, or a halogen atom. If X 3 there are a plurality, each be the same or may be different. Alkyl group and an alkoxyl group represented by X 3 may have a substituent.
• the halogen atom in the X 3, a chlorine atom or a fluorine atom is preferable.
• m3 represents an integer of 0 to 3, and 0 or 1 is preferable. When m3 is 2 or 3, a plurality of X 3 may be the same or different.
• R 34 represents an alkyl group or an aryl group, which is an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms, and carbon. It is preferably an alkoxyl group of numbers 1 to 5, a phenyl group optionally substituted with W, a naphthyl group optionally substituted with W or an anthranyl group optionally substituted with W.
• W is a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, an alkyl halide group having 1 to 5 carbon atoms or an alkoxyl halide having 1 to 5 carbon atoms. It represents a group, an aryl group having 6 to 20 carbon atoms, and an aryl halide group having 6 to 20 carbon atoms.
• oxime sulfonate compound represented by the formula (OS-1) are described in paragraphs 0064 to 0068 of JP2011-209692A and paragraph numbers 0158 to 0167 of JP2015-194674A. The following compounds are exemplified and their contents are incorporated herein.
• R s1 represents an alkyl group, an aryl group or a heteroaryl group
• R s6 which represents a group or a halogen atom and may be present in a plurality, independently represents a halogen atom, an alkyl group, an alkyloxy group, a sulfonic acid group, an aminosulfonyl group or an alkoxysulfonyl group
• Xs represents O or S.
• ns represents 1 or 2
• ms represents an integer of 0-6.
• an alkyl group represented by R s1 preferably having 1 to 30 carbon atoms
• an aryl group preferably having 6 to 30 carbon atoms
• a heteroaryl group carbon
• numbers 4 to 30 may have a substituent T.
• R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms) or an aryl group (preferably having 6 to 30 carbon atoms). , Hydrogen atom or alkyl group is more preferable.
• R s2 that may be present in two or more in the compound, one or two are preferably an alkyl group, an aryl group or a halogen atom, and one is more preferably an alkyl group, an aryl group or a halogen atom. It is particularly preferable that one is an alkyl group and the rest is a hydrogen atom.
• the alkyl group or aryl group represented by R s2 may have a substituent T.
• Xs represents O or S, and is preferably O.
• the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
• ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is. It is preferably 2.
• the alkyl group represented by R s6 preferably having 1 to 30 carbon atoms
• the alkyloxy group preferably having 1 to 30 carbon atoms
• ms represents an integer of 0 to 6, preferably an integer of 0 to 2, more preferably 0 or 1, and 0. Is particularly preferable.
• the compound represented by the above formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111).
• the compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the above formula (OS-105) is a compound represented by the following formula (OS-105). -108) or a compound represented by the formula (OS-109) is particularly preferable.
• R t1 represents an alkyl group, an aryl group or a heteroaryl group
• R t7 represents a hydrogen atom or a bromine atom
• R t8 represents a hydrogen atom and the number of carbon atoms. 1 to 8 alkyl groups, halogen atoms, chloromethyl groups, bromomethyl groups, bromoethyl groups, methoxymethyl groups, phenyl groups or chlorophenyl groups
• R t9 represents hydrogen atoms, halogen atoms, methyl groups or methoxy groups
• R t2 represents a hydrogen atom or a methyl group.
• R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
• R t8 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, or a phenyl group.
• it represents a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. It is more preferable to have a methyl group, and it is particularly preferable to have a methyl group.
• R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and is preferably a hydrogen atom.
• R t2 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
• the three-dimensional structure (E, Z) of the oxime may be either one or a mixture.
• Specific examples of the oxime sulfonate compound represented by the above formulas (OS-103) to (OS-105) include paragraph numbers 008 to 0995 of JP2011-209692A and paragraphs of JP2015-194674A.
• the compounds of Nos. 0168 to 0194 are exemplified and their contents are incorporated herein.
• oxime sulfonate compound containing at least one oxime sulfonate group include compounds represented by the following formulas (OS-101) and (OS-102).
• Ru9 is a hydrogen atom, an alkyl group, an alkenyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, Represents an aryl group or a heteroaryl group.
• R u9 is a cyano group or an aryl group is more preferable, and the embodiment in which R u9 is a cyano group, a phenyl group or a naphthyl group is further preferable.
• Ru2a represents an alkyl or aryl group.
• Xu is -O-, -S-, -NH- , -NR u5-, -CH 2- , -CR u6 H- or CR u6 R u7.
• Ru1 to Ru4 are independently hydrogen atom, halogen atom, alkyl group, alkenyl group, alkoxyl group, amino group, alkoxycarbonyl group and alkylcarbonyl group, respectively. , Arylcarbonyl group, amide group, sulfo group, cyano group or aryl group. 2 in turn, each may be bonded to each other to form a ring of the R u1 ⁇ R u4. At this time, the ring may be condensed to form a condensed ring together with the benzene ring.
• R u1 ⁇ R u4 a hydrogen atom, preferably a halogen atom or an alkyl group, also aspects to form the at least two aryl groups bonded to each other of R u1 ⁇ R u4 preferred.
• Ru1 to Ru4 are hydrogen atoms. Any of the above-mentioned substituents may further have a substituent.
• the compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
• the three-dimensional structure (E, Z, etc.) of the oxime and the benzothiazole ring may be either one or a mixture.
• Specific examples of the compound represented by the formula (OS-101) include the compounds described in paragraph numbers 0102 to 0106 of JP2011-209692 and paragraph numbers 0195 to 0207 of JP2015-194674. These contents are incorporated herein by reference.
• b-9, b-16, b-31, and b-33 are preferable.
• a commercially available product may be used as the photoacid generator.
• WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-376, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-69 any of which.
• Omnicat 250, Omnicat 270 all manufactured by IGM Resins BV
• Irgacure 250, Irgacure 270, Irgacure 290 all manufactured by BASF
• MBZ-101 all manufactured by BASF
• an organic halogenated compound can also be applied.
• the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, JP-A-46-4605, JP-A. 48-36281, JP-A-55-3270, JP-A-60-239736, JP-A-61-169835, JP-A-61-169837, JP-A-62-58241, JP-A-62- 212401, Japanese Patent Application Laid-Open No. 63-70243, Japanese Patent Application Laid-Open No. 63-298339, M.D. P.
• an oxazole compound substituted with a trihalomethyl group an S-triazine compound
• an organic borate compound can also be applied.
• the organic borate compound include JP-A-62-143044, JP-A-62-150242, JP-A-9-188685, JP-A-9-188686, JP-A-9-188710, and JP-A-2000. -131837, JP-A-2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin "Rad Tech '98. Proceeding Compound 19-22, 1998, Chicago" and the like.
• Specific examples thereof include organic boron transition metal coordination complexes of JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014.
• a disulfone compound can also be applied as a photoacid generator.
• examples of the disulfone compound include compounds described in JP-A-61-166544, Japanese Patent Application Laid-Open No. 2001-132318, and diazodisulfone compounds.
• onium salt compound examples include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18,387 (1974), T.K. S. The diazonium salt described in Bal et al, Polymer, 21,423 (1980), the ammonium salt described in US Pat. No. 4,069,055, JP-A-4-365549, etc., US Pat. No. 4,069, Phosphonium salts described in 055, 4,069,056, European Patents 104, 143, US Patents 339,049, 410,201, JP-A-2. -150848, Iodonium salt described in JP-A-2-296514, European Patent Nos.
• onium salts examples include onium salts represented by the following general formulas (RI-I) to (RI-III).
• Ar 11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferred substituents are an alkyl group having 1 to 12 carbon atoms and 1 carbon number.
• Z11 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, surface stability
• Perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion are preferable.
• Ar 21 and Ar 22 each represent an aryl group having 20 or less carbon atoms which may independently have 1 to 6 substituents, and preferred substituents have 1 to 12 carbon atoms.
• Z 21 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, From the viewpoint of reactivity, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
• R 31 , R 32 , and R 33 each represent an aryl group or an alkyl group, an alkenyl group, or an alkynyl group having 20 or less carbon atoms which may independently have 1 to 6 substituents.
• an aryl group from the viewpoint of reactivity and stability.
• Preferred substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms.
• Examples thereof include a group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms.
• Z31 - represents a monovalent anion, a halogen ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfonate ion, sulfate ion, stability, reaction From the viewpoint of properties, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonic acid ion, sulfinate ion and carboxylate ion are preferable.
• the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the composition of the present invention. It is more preferably 2 to 15% by mass. Only one type of photoacid generator may be contained, or two or more types may be contained. When two or more photoacid generators are contained, the total is preferably in the above range.
• the composition of the present invention may contain a thermoacid generator.
• the thermoacid generator generates an acid by heating and promotes a cross-linking reaction of at least one compound selected from a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound. It has the effect of making it.
• the thermal decomposition start temperature of the thermal acid generator is preferably 50 ° C. to 270 ° C., more preferably 50 ° C. to 250 ° C. Further, no acid is generated during drying (pre-baking: about 70 to 140 ° C.) after the composition is applied to the substrate, and during final heating (cure: about 100 to 400 ° C.) after patterning by subsequent exposure and development. It is preferable to select an acid-generating agent as the thermal acid generator because it can suppress a decrease in sensitivity during development.
• the thermal decomposition start temperature is obtained as the peak temperature of the exothermic peak, which is the lowest temperature when the thermoacid generator is heated to 500 ° C. at 5 ° C./min in a pressure-resistant capsule. Examples of the device used for measuring the thermal decomposition start temperature include Q2000 (manufactured by TA Instruments).
• the acid generated from the thermoacid generator is preferably a strong acid, for example, aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid, or trifluoromethane.
• aryl sulfonic acid such as p-toluene sulfonic acid and benzene sulfonic acid
• alkyl sulfonic acid such as methane sulfonic acid, ethane sulfonic acid and butane sulfonic acid
• haloalkyl sulfonic acid such as sulfonic acid is preferable.
• thermoacid generator include those described in paragraph 0055 of JP2013-072935A.
• alkylsulfonic acid having 1 to 4 carbon atoms or haloalkylsulfonic acid having 1 to 4 carbon atoms are more preferable, and methanesulfonic acid is more preferable, from the viewpoint that there is little residue in the cured film and it is difficult to deteriorate the physical properties of the cured film.
• thermoacid generator the compound described in paragraph 0059 of JP2013-167742A is also preferable as the thermoacid generator.
• the content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin.
• the content of the thermoacid generator is preferably 0.01 part by mass or more, and more preferably 0.1 part by mass or more with respect to 100 parts by mass of the specific resin.
• 0.01 part by mass or more the cross-linking reaction is promoted, so that the mechanical properties and solvent resistance of the cured film can be further improved.
• 20 parts by mass or less is preferable, 15 parts by mass or less is more preferable, and 10 parts by mass or less is further preferable.
• the resin composition of the present invention may further contain an onium salt.
• the resin composition of the present invention contains a polyimide precursor as a specific resin, it preferably contains an onium salt.
• the type of onium salt and the like are not particularly specified, but ammonium salt, iminium salt, sulfonium salt, iodonium salt and phosphonium salt are preferably mentioned.
• an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability
• a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.
• the onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bonded via a covalent bond. .. That is, the onium salt may be an intramolecular salt having a cation portion and an anion portion in the same molecular structure, or a cation molecule and an anion molecule, which are separate molecules, are ionically bonded. It may be an intermolecular salt, but it is preferably an intermolecular salt. Further, in the resin composition of the present invention, the cation portion or the cation molecule and the anion portion or the anion molecule may be bonded or dissociated by an ionic bond.
• an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation is preferable, and at least one cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation is more preferable.
• the onium salt used in the present invention may be a thermobase generator described later.
• the thermal base generator refers to a compound that generates a base by heating, and examples thereof include a compound that generates a base when heated to 40 ° C. or higher.
• Examples of the onium salt include the onium salt described in paragraphs 0122 to 0138 of International Publication No. 2018/043262.
• onium salts used in the field of polyimide precursors can be used without particular limitation.
• the content of the onium salt is preferably 0.1 to 50% by mass with respect to the total solid content of the resin composition of the present invention.
• the lower limit is more preferably 0.5% by mass or more, further preferably 0.85% by mass or more, and even more preferably 1% by mass or more.
• the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less, further preferably 10% by mass or less, 5% by mass or less, or 4% by mass or less.
• the onium salt one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
• the resin composition of the present invention may further contain a thermal base generator.
• a thermal base generator when the resin composition of the present invention contains a polyimide precursor as a specific resin, it preferably contains a thermal base generator.
• the other thermobase generator may be a compound corresponding to the above-mentioned onium salt, or may be a thermobase generator other than the above-mentioned onium salt.
• the thermobase generator other than the above-mentioned onium salt include nonionic thermobase generators.
• the nonionic thermobase generator include compounds represented by the formula (B1) or the formula (B2).
• Rb 1 , Rb 2 and Rb 3 are independently organic groups, halogen atoms or hydrogen atoms having no tertiary amine structure. However, Rb 1 and Rb 2 do not become hydrogen atoms at the same time. Further, none of Rb 1 , Rb 2 and Rb 3 has a carboxy group.
• the tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to a hydrocarbon-based carbon atom. Therefore, this does not apply when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when an amide group is formed together with a nitrogen atom.
• Rb 1 , Rb 2 and Rb 3 contains a cyclic structure, and it is more preferable that at least two of them contain a cyclic structure.
• the cyclic structure may be either a monocyclic ring or a condensed ring, and a fused ring in which two monocyclic rings or two monocyclic rings are condensed is preferable.
• the single ring is preferably a 5-membered ring or a 6-membered ring, and preferably a 6-membered ring.
• a cyclohexane ring and a benzene ring are preferable, and a cyclohexane ring is more preferable.
• Rb 1 and Rb 2 are hydrogen atoms, alkyl groups (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), and alkenyl groups (preferably 2 to 24 carbon atoms). , 2-18 is more preferred, 3-12 is more preferred), aryl groups (6-22 carbons are preferred, 6-18 are more preferred, 6-10 are more preferred), or arylalkyl groups (7 carbons). ⁇ 25 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable). These groups may have substituents as long as the effects of the present invention are exhibited. Rb 1 and Rb 2 may be coupled to each other to form a ring.
• Rb 1 and Rb 2 are particularly linear, branched, or cyclic alkyl groups that may have substituents (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12). It is more preferably a cycloalkyl group which may have a substituent (preferably 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms) and having a substituent.
• a cyclohexyl group which may be used is more preferable.
• an alkyl group preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms
• an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 6.
• alkoxy group (2 to 24 carbon atoms are preferable, 2 to 12 is more preferable, 2 to 6 is more preferable
• arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable).
• an arylalkenyl group (8 to 24 carbon atoms is preferable, 8 to 20 is more preferable, 8 to 16 is more preferable), and an alkoxyl group (1 to 24 carbon atoms is preferable, 2 to 2 to 24).
• 18 is more preferable, 3 to 12 is more preferable), an aryloxy group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), or an arylalkyloxy group (7 to 12 carbon atoms is more preferable).
• 23 is preferable, 7 to 19 is more preferable, and 7 to 12 is even more preferable).
• a cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an arylalkenyl group, and an arylalkyloxy group are preferable.
• Rb 3 may further have a substituent as long as the effects of the present invention are exhibited.
• the compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
• Rb 11 and Rb 12 , and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in the formula (B1), respectively.
• Rb 13 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, further preferably 3 to 12 carbon atoms) and an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and a substituent may be provided as long as the effects of the present invention are exhibited. Of these, Rb 13 is preferably an arylalkyl group.
• Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
• Rb 33 and Rb 34 independently have a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms).
• 2 to 8 are more preferable, 2 to 3 are more preferable
• aryl groups (6 to 22 carbon atoms are preferable, 6 to 18 are more preferable, 6 to 10 are more preferable
• 23 is preferable, 7 to 19 is more preferable, and 7 to 11 is even more preferable), and a hydrogen atom is preferable.
• Rb 35 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 10 carbon atoms). 8 is more preferable), aryl group (6 to 22 carbon atoms is preferable, 6 to 18 is more preferable, 6 to 12 is more preferable), arylalkyl group (7 to 23 carbon atoms is preferable, 7 to 19 is more preferable). , 7-12 is more preferable), and an aryl group is preferable.
• the compound represented by the formula (B1-1) is also preferable.
• Rb 11 and Rb 12 have the same meanings as Rb 11 and Rb 12 in the formula (B1-1).
• Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, further preferably 1 to 3 carbon atoms), and an alkenyl group (preferably 2 to 12 carbon atoms, 2 to 6 carbon atoms). More preferably, 2 to 3 are more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 10 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, 7).
• Rb 17 has an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, further preferably 3 to 8 carbon atoms) and an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 carbon atoms). Is more preferable), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, further preferably 6 to 12 carbon atoms), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms). 7 to 12 is more preferable), and an aryl group is particularly preferable.
• the molecular weight of the nonionic thermobase generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
• the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
• thermo base generators or specific examples of thermal base generators other than the above-mentioned onium salts include the following compounds.
• the content of the other thermobase generator is preferably 0.1 to 50% by mass with respect to the total solid content of the resin composition of the present invention.
• the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
• the upper limit is more preferably 30% by mass or less, further preferably 20% by mass or less.
• the thermobase generator one kind or two or more kinds can be used. When two or more kinds are used, the total amount is preferably in the above range.
• the resin composition of the present invention preferably contains a cross-linking agent.
• the cross-linking agent include radical cross-linking agents and other cross-linking agents.
• the resin composition of the present invention preferably further contains a radical cross-linking agent.
• the radical cross-linking agent is a compound having a radically polymerizable group.
• a group containing an ethylenically unsaturated bond is preferable.
• the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
• the (meth) acryloyl group is preferable as the group containing the ethylenically unsaturated bond, and the (meth) acryloyl group is more preferable from the viewpoint of reactivity.
• the radical cross-linking agent may be a compound having one or more ethylenically unsaturated bonds, but is more preferably a compound having two or more ethylenically unsaturated bonds.
• the compound having two ethylenically unsaturated bonds is preferably a compound having two groups containing the above ethylenically unsaturated bonds.
• the resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical cross-linking agent.
• the compound having 3 or more ethylenically unsaturated bonds a compound having 3 to 15 ethylenically unsaturated bonds is preferable, and a compound having 3 to 10 ethylenically unsaturated bonds is more preferable, and 3 to 6 compounds are more preferable.
• the compound having is more preferable.
• the compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing the ethylenically unsaturated bond, and more preferably a compound having 3 to 15 ethylenically unsaturated bonds.
• a compound having 3 to 10 is more preferable, and a compound having 3 to 6 is particularly preferable.
• the resin composition of the present invention comprises a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds. It is also preferable to include.
• the molecular weight of the radical cross-linking 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 cross-linking agent is preferably 100 or more.
• radical cross-linking agent examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides, which are preferably unsuitable.
• an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group or a sulfanyl group with a monofunctional or polyfunctional isocyanate or an epoxy, or a monofunctional or polyfunctional group.
• a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
• an addition reaction product of an unsaturated carboxylic acid ester or amide having a parentionic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amines or thiols, and a halogeno group.
• Substitution reaction products of unsaturated carboxylic acid esters or amides having a releasable substituent such as tosyloxy group and monofunctional or polyfunctional alcohols, amines and thiols are also suitable.
• radical cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
• examples are polyethylene glycol di (meth) acrylate, trimethyl ethanetri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol.
• a compound obtained by adding ethylene oxide or propylene oxide to a functional alcohol and then (meth) acrylated, is described in JP-A-48-041708, JP-A-50-006034, and JP-A-51-0371993.
• Urethane (meth) acrylates such as those described in JP-A-48-064183, JP-A-49-043191, and JP-A-52-030490, the polyester acrylates, epoxy resins and (meth) acrylics. Examples thereof include polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products with acids, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970 are also suitable.
• a polyfunctional (meth) acrylate obtained by reacting a polyfunctional carboxylic acid with a cyclic ether group such as glycidyl (meth) acrylate and a compound having an ethylenically unsaturated bond can also be mentioned.
• a preferable radical cross-linking agent other than the above it has a fluorene ring and has an ethylenically unsaturated bond, which is described in JP-A-2010-160418, JP-A-2010-129825, Patent No. 4364216 and the like.
• Compounds having two or more groups and cardo resins can also be used.
• dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.) ), A-TMMT: Shin-Nakamura Chemical Industry Co., Ltd.), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) ) Acrylate (commercially available KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth) acryloyl groups are mediated by ethylene glycol residues or propylene glycol residues. A structure that is bonded together is preferable
• SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmer
• SR-209 manufactured by Sartmer which is a bifunctional methacrylate having four ethyleneoxy chains.
• DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains manufactured by Nippon Kayaku Co., Ltd.
• TPA-330 a trifunctional acrylate having 3 isobutyleneoxy chains
• urethane oligomer UAS-10 are examples of the radical cross-linking agent.
• UAB-140 (manufactured by Nippon Paper Co., Ltd.), NK ester M-40G, NK ester 4G, NK ester M-9300, NK ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (Japan) Chemicals (manufactured by Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blemmer PME400 (manufactured by Nichiyu Co., Ltd.), etc. Can be mentioned.
• radical cross-linking agent examples include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Application Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765.
• Urethane compounds having an ethylene oxide-based structure 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 cross-linking 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, are used. You can also do it.
• the radical cross-linking agent may be a radical cross-linking agent having an acid group such as a carboxy group or a phosphoric acid group.
• the radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid group is obtained by reacting an unreacted hydroxy group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride.
• a radical cross-linking agent provided with is more preferable.
• the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Is a compound.
• examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.
• the preferable acid value of the radical cross-linking agent having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g.
• the acid value of the radical cross-linking agent is within the above range, it is excellent in manufacturing handleability and further excellent in developability. Moreover, the polymerizable property is good.
• the acid value is measured according to the description of JIS K 0070: 1992.
• the resin composition of the present invention preferably uses a bifunctional metal acrylate or acrylate from the viewpoint of pattern resolution and film elasticity.
• Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, and polytetraethylene.
• Glycol diacrylate polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6 hexanediol Dimethacrylate, dimethylol-tricyclodecanediacrylate, dimethylol-tricyclodecanedimethacrylate, EO adduct diacrylate of bisphenol A, EO adduct dimethacrylate of bisphenol A, PO adduct diacrylate of bisphenol A, PO of bisphenol A Additives Dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid-modified dimethacrylate, other bifunctional acrylates having urethane bonds, and bifunctional methacrylates
• the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula of about 200.
• a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent.
• Examples of the monofunctional radical cross-linking agent include n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, and cyclohexyl (meth). ) 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.
• (meth) Acrylic acid derivatives N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam, and allyl compounds such as allylglycidyl ether, diallyl phthalate, and triallyl trimellitate are preferably used.
• the monofunctional radical cross-linking agent a compound having a boiling point of 100 ° C. or higher under normal pressure is also preferable in order to suppress volatilization before exposure.
• the content thereof is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition of the present invention.
• the lower limit is more preferably 5% by mass or more.
• the upper limit is more preferably 50% by mass or less, and further preferably 30% by mass or less.
• One type of radical cross-linking agent may be used alone, or two or more types may be mixed and used. When two or more types are used in combination, the total amount is preferably in the above range.
• the resin composition of the present invention preferably contains another cross-linking agent different from the above-mentioned radical cross-linking agent.
• the other cross-linking agent refers to a cross-linking agent other than the above-mentioned radical cross-linking agent, and a covalent bond is formed with another compound in the composition or a reaction product thereof by exposure to the above-mentioned photosensitizer. It is preferable that the compound has a plurality of groups in the molecule for which the reaction to be formed is promoted, and the reaction of forming a covalent bond with another compound in the composition or a reaction product thereof is the action of an acid or a base.
• a compound having a plurality of groups promoted by the above in the molecule is preferable.
• the acid or base is preferably an acid or base generated from the photosensitizer in the exposure step.
• a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is preferable, and at least one group selected from the group consisting of a methylol group and an alkoxymethyl group is a nitrogen atom.
• a compound having a structure directly bonded to is more preferable.
• an amino group-containing compound such as melamine, glycoluryl, urea, alkylene urea, or benzoguanamine is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is changed to a methylol group or an alkoxymethyl group.
• examples thereof include compounds having a substituted structure.
• 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. Further, it may be an oligomer formed by self-condensing the methylol groups of these compounds.
• the cross-linking agent using melamine is a melamine-based cross-linking agent
• the cross-linking agent using glycoluril, urea or alkylene urea is a urea-based cross-linking agent
• the cross-linking agent using alkylene urea is an alkylene urea-based cross-linking agent.
• a cross-linking agent using an agent or benzoguanamine is called a benzoguanamine-based cross-linking agent.
• the resin composition of the present invention preferably contains at least one compound selected from the group consisting of a urea-based cross-linking agent and a melamine-based cross-linking agent, and is preferably a glycoluril-based cross-linking agent and a melamine-based cross-linking agent described later. More preferably, it contains at least one compound selected from the group consisting of agents.
• melamine-based cross-linking agent examples include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, hexabutoxybutyl melamine and the like.
• urea-based cross-linking agent examples include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol uryl.
• Glycoluryl-based cross-linking agent such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea, Monohydroxymethylated ethylene urea or dihydroxymethylated ethylene urea, monomethoxymethylated ethylene urea, dimethoxymethylated ethylene urea, monoethoxymethylated ethylene urea, diethoxymethylated ethylene urea, monopropoxymethylated ethylene urea, dipropoxymethyl Ethylene urea-based cross-linking agents such as ethylene fluoride, monobutoxymethylated ethylene urea, or dibutoxymethylated ethylene urea, Monohydroxymethylated propylene urea, dihydroxymethylated propylene urea, monomethoxymethylated propylene urea, dimethoxymethylated propylene urea, monodiethoxymethylated propylene urea, diethoxymethylated propylene urea,
• benzoguanamine-based cross-linking agent examples include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated benzoguanamine.
• Tetramethoxymethylated benzoguanamine Tetramethoxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, trimethoxymethylated benzoguanamine, tetraethoxymethylated benzoguanamine, monopropoxymethylated benzoguanamine, dipropoxymethylated benzoguanamine, tripropoxymethylated benzoguanamine, tetrapropoxy Methylated benzoguanamine, monobutoxymethylated benzoguanamine, dibutoxymethylated benzoguanamine, tributoxymethylated benzoguanamine, tetrabutoxymethylated benzoguanamine and the like can be mentioned.
• a compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group at least one selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
• a compound to which a group is directly bonded is 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 commercially available products include 46DMOC, 46DMOEP (all manufactured by Asahi Organic Materials Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP.
• the resin composition of the present invention preferably contains at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a benzoxazine compound as another cross-linking agent.
• Epoxy compound (compound having an epoxy group)
• the epoxy compound is preferably a compound having two or more epoxy groups in one molecule.
• the epoxy group undergoes a cross-linking reaction at 200 ° C. or lower, and the dehydration reaction derived from the cross-linking does not occur, so that film shrinkage is unlikely to occur. Therefore, the inclusion of the epoxy compound is effective in suppressing low-temperature curing and warpage of the resin composition.
• the epoxy compound preferably contains a polyethylene oxide group.
• the polyethylene oxide group means that the number of repeating units of ethylene oxide is 2 or more, and the number of repeating units is preferably 2 to 15.
• epoxy compounds include bisphenol A type epoxy resin; bisphenol F type epoxy resin; propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether. , Trimethylol propantriglycidyl ether and other alkylene glycol type epoxy resins or polyhydric alcohol hydrocarbon type epoxy resins; polypropylene glycol diglycidyl ether and other polyalkylene glycol type epoxy resins; polymethyl (glycidyloxypropyl) siloxane and other epoxy groups Examples include, but are not limited to, containing silicones.
• oxetane compound compound having an oxetanyl group
• examples of the oxetane compound include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, and the like.
• examples thereof include 3-ethyl-3- (2-ethylhexylmethyl) oxetane, 1,4-benzenedicarboxylic acid-bis [(3-ethyl-3-oxetanyl) methyl] ester and the like.
• the Aron Oxetane series manufactured by Toagosei Co., Ltd. (for example, OXT-121, OXT-221, OXT-191, OXT-223) can be preferably used, and these can be used alone. Alternatively, two or more types may be mixed.
• Benzoxazine compound (compound having a benzoxazolyl group) Since the benzoxazine compound is a cross-linking reaction derived from the ring-opening addition reaction, degassing does not occur during curing, and heat shrinkage is further reduced to suppress the occurrence of warpage, which is preferable.
• benzoxazine compound are BA type benzoxazine, Bm type benzoxazine, Pd type benzoxazine, FA type benzoxazine (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.), poly.
• examples thereof include a benzoxazine adduct of a hydroxystyrene resin and a phenol novolac type dihydrobenzoxazine compound. These may be used alone or in combination of two or more.
• the content of the other cross-linking agent 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 of the present invention. It is more preferably 5 to 15% by mass, and particularly preferably 1.0 to 10% by mass.
• the other cross-linking agent may contain only one type, or may contain two or more types. When two or more other cross-linking agents are contained, the total is preferably in the above range.
• the resin composition of the present invention preferably further contains a migration inhibitor.
• a migration inhibitor By including the migration inhibitor, it is possible to effectively suppress the movement of metal ions derived from the metal layer (metal wiring) into the resin composition layer.
• the migration inhibitor is not particularly limited, but has a heterocyclic ring (pyrazole ring, furan ring, thiophene ring, triazole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, etc.
• a heterocyclic ring pyrazole ring, furan ring, thiophene ring, triazole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, etc.
• triazole-based compounds such as 1,2,4-triazole and benzotriazole
• tetrazole-based compounds such as 1H-tetrazole and 5-phenyltetrazole can be preferably used.
• an ion trap agent that traps anions such as halogen ions can also be used.
• Examples of other migration inhibitors include rust preventives described in paragraph 0094 of JP2013-015701, compounds described in paragraphs 0073 to 0076 of JP2009-283711, and JP2011-059656.
• the compounds described in paragraph 0052, the compounds described in paragraphs 0114, 0116 and 0118 of JP2012-194520A, the compounds described in paragraph 0166 of International Publication No. 2015/199219, and the like can be used.
• the migration inhibitor include the following compounds.
• the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, preferably 0.05 to 2% by mass, based on the total solid content of the resin composition. It is more preferably 0.0% by mass, and even more preferably 0.1 to 1.0% by mass.
• the migration inhibitor may be only one type or two or more types. When there are two or more types of migration inhibitors, the total is preferably in the above range.
• the resin composition of the present invention preferably contains a polymerization inhibitor.
• polymerization inhibitor examples include hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1,4-benzoquinone, and diphenyl-p-benzoquinone.
• the content of the polymerization inhibitor is 0.01 to 20.0% by mass with respect to the total solid content of the resin composition of the present invention, which is 0. It is preferably 0.01 to 5% by mass, more preferably 0.02 to 3% by mass, and even more preferably 0.05 to 2.5% by mass.
• the polymerization inhibitor may be only one type or two or more types. When there are two or more types of polymerization inhibitors, the total is preferably in the above range.
• the resin composition of the present invention preferably contains a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
• a metal adhesiveness improving agent for improving the adhesiveness with a metal material used for electrodes, wiring and the like.
• the metal adhesion improver include silane coupling agents, aluminum-based adhesive aids, titanium-based adhesive aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, ⁇ -ketoester compounds, amino compounds and the like. And so on.
• silane coupling agent examples include the compounds described in paragraph 0167 of International Publication No. 2015/199219, the compounds described in paragraphs 0062 to 0073 of JP-A-2014-191002, paragraphs of International Publication No. 2011/080992.
• Examples include the compounds described in paragraph 0055. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of JP2011-128358A. Further, it is also preferable to use the following compounds as the silane coupling agent.
• Et represents an ethyl group.
• silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid.
• Aluminum-based adhesive aid examples include aluminum tris (ethylacetacetate), aluminumtris (acetylacetoneate), ethylacetacetate aluminum diisopropirate, and the like.
• the compounds described in paragraphs 0046 to 0049 of JP2014-186186A and the sulfide compounds described in paragraphs 0032 to 0043 of JP2013-072935 can also be used. ..
• the content of the metal adhesive improving agent is preferably in the range of 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 0. It is in the range of 5 to 5 parts by mass.
• the metal adhesiveness improving agent may be only one kind or two or more kinds. When two or more types are used, the total amount is preferably in the above range.
• the resin composition of the present invention can be used with various additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, an inorganic particle, and a cured product, if necessary, as long as the effects of the present invention can be obtained.
• additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, an inorganic particle, and a cured product, if necessary, as long as the effects of the present invention can be obtained.
• Agents, curing catalysts, fillers, antioxidants, UV absorbers, anti-aggregation agents and the like can be blended. When these additives are blended, the total blending amount is preferably 3% by mass or less of the solid content of the resin composition.
• the resin composition of the present invention may contain a sensitizer.
• the sensitizer absorbs specific active radiation and becomes an electron-excited state.
• the sensitizer in the electron-excited state comes into contact with a thermosetting accelerator, a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and acts such as electron transfer, energy transfer, and heat generation occur.
• a thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases.
• sensitizer examples include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal).
• the content of the sensitizer is preferably 0.01 to 20% by mass with respect to the total solid content of the resin composition of the present invention. It is more preferably 1 to 15% by mass, and even more preferably 0.5 to 10% by mass.
• the sensitizer 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, Third Edition (edited by the Society of Polymer Science, 2005), pp. 683-684.
• As the chain transfer agent for example, a group of compounds having SH, PH, SiH, and GeH in the molecule is used. They can donate hydrogen to low-activity radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
• a thiol compound can be preferably used.
• the content of the chain transfer agent is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the total solid content of the resin composition of the present invention. 10 parts by mass is more preferable, and 1 to 5 parts by mass is further preferable.
• the chain transfer agent may be only one kind or two or more kinds. When there are two or more types of chain transfer agents, the total is preferably in the above range.
• Each type of surfactant may be added to the resin composition of the present invention from the viewpoint of further improving the coatability.
• the surfactant various types of surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants can be used.
• the following surfactants are also preferable.
• the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit
• the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.
• the surfactant the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
• a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant.
• Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP2010-164965, such as Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. Can be mentioned.
• the fluorine content in the fluorine-based 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 property, and has good solubility in the composition.
• silicone-based surfactant examples include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.).
• TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials Co., Ltd.), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Silicone Co., Ltd.) ), BYK307, BYK323, BYK330 (all manufactured by Big Chemie Co., Ltd.) and the like.
• hydrocarbon-based surfactant examples include Pionin A-76, New Calgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, and Pionin.
• Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc.
• organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
• (meth) acrylic acid-based (co) polymer Polyflow No. 75, No. 77, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.
• W001 manufactured by Yusho Co., Ltd.
• anionic surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.
• the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the resin composition of the present invention. , More preferably 0.005 to 1.0% by mass.
• the surfactant may be only one kind or two or more kinds. When there are two or more types of surfactant, the total is preferably in the above range.
• Higher fatty acid derivative In the resin composition of the present invention, in order to prevent polymerization inhibition due to oxygen, a higher fatty acid derivative such as behenic acid or behenic acid amide is added to the surface of the resin composition in the process of drying after application. It may be unevenly distributed.
• the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass with respect to the total solid content of the resin composition of the present invention.
• the higher fatty acid derivative may be only one kind or two or more kinds. When there are two or more higher fatty acid derivatives, the total is preferably in the above range.
• the resin composition of the present invention may contain inorganic particles.
• specific examples of the 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 size of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, further preferably 0.03 to 1.0 ⁇ m, and 0.04 to 0.5 ⁇ m. Especially preferable.
• the mechanical properties of the cured film may deteriorate.
• the average particle size of the inorganic particles exceeds 2.0 ⁇ m, the resolution may decrease due to scattering of exposure light.
• the composition of the present invention may contain an ultraviolet absorber.
• an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
• salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like
• benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-.
• Methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2- Hydroxy-4-octoxybenzophenone and the like can be mentioned.
• benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3).
• Examples of the substituted acrylonitrile-based ultraviolet absorber include ethyl 2-cyano-3,3-diphenylacrylate, 2-ethylhexyl 2-cyano-3,3-diphenylacrylate, and the like.
• the triazine-based ultraviolet absorber 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) )-1,3,5-Triazine, 2- [4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) Mono (hydroxyphenyl) triazine compounds such as -1,3,5-triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin
• the above-mentioned various ultraviolet absorbers may be used alone or in combination of two or more.
• the composition of the present invention may or may not contain an ultraviolet absorber, but when it is contained, the content of the ultraviolet absorber is 0.001% by mass with respect to the total solid content mass of the composition of the present invention. It is preferably 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.
• the resin composition of the present embodiment may contain an organic titanium compound. Since the resin composition contains an organic titanium compound, a resin layer having excellent chemical resistance can be formed even when cured at a low temperature.
• Examples of the organic titanium compound that can be used include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
• Specific examples of the organic titanium compound are shown in I) to VII) below:
• I) Titanium chelate compound Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the negative photosensitive resin composition has good storage stability and a good curing pattern can be obtained.
• Specific examples are titanium bis (triethanolamine) diisopropoxyside, titanium di (n-butoxide) bis (2,4-pentanionate, titanium diisopropoxyside bis (2,4-pentanionate)).
• Titanium diisopropoxyside bis tetramethylheptandionate
• titanium diisopropoxyside bis ethylacetacetate
• Tetraalkoxytitanium compounds For example, titanium tetra (n-butoxide), titanium tetraethoxide, titanium tetra (2-ethylhexoxyside), titanium tetraisobutoxide, titanium tetraisopropoxyside, titanium tetramethoxide.
• Titanium Tetramethoxypropoxyside Titanium Tetramethylphenoxide, Titanium Tetra (n-Noniloxide), Titanium Tetra (n-Propoxide), Titanium Tetrasteeryloxyside, Titanium Tetrakiss [Bis ⁇ 2,2- (Aryloxymethyl) Butokiside ⁇ ] etc.
• Titanosen compounds for example, pentamethylcyclopentadienyl titanium trimethoxide, bis ( ⁇ 5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis ( ⁇ 5-2, 2).
• Titanium oxide compound For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
• Titanium tetraacetylacetone compound For example, titanium tetraacetylacetone.
• Titanate Coupling Agent For example, isopropyltridodecylbenzenesulfonyl titanate and the like.
• the organic titanium compound at least one compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxytitanium compound, and III) titanocene compound has better chemical resistance. It is preferable from the viewpoint of playing.
• -Pyrrole-1-yl) phenyl) titanium is preferred.
• the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the precursor of the cyclized resin. ..
• the blending amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited in the obtained curing pattern, while when it is 10 parts by mass or less, the storage stability of the composition is excellent.
• the composition of the present invention may contain an antioxidant.
• an antioxidant By containing an antioxidant as an additive, it is possible to improve the elongation characteristics of the film after curing and the adhesion with a metal material.
• the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like.
• the phenol compound any phenol compound known as a phenolic antioxidant can be used.
• Preferred phenolic compounds include hindered phenolic compounds.
• a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable.
• a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
• a compound having a phenol group and a phosphite ester group in the same molecule is also preferable.
• a phosphorus-based antioxidant can also be preferably used.
• a phosphorus-based antioxidant tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6 -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like.
• antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like.
• the antioxidant the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used.
• the composition of the present invention may contain a latent antioxidant, if necessary.
• the latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. As a result, a compound in which the protecting group is eliminated and functions as an antioxidant can be mentioned.
• Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
• Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation) and the like.
• preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds represented by the general formula (3).
• R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms
• R 6 represents an alkylene group having 2 or more carbon atoms
• R 7 represents a 1- to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms, an O atom, and an N atom
• k represents an integer of 1 to 4.
• the compound represented by the general formula (3) suppresses oxidative deterioration of aliphatic groups and phenolic hydroxyl groups of the resin.
• metal oxidation can be suppressed by the rust preventive action on the metal material.
• k is more preferably an integer of 2 to 4.
• R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-.
• R7 include an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an arylether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and-.
• Examples thereof include O-, -NH-, -NHNH-, and combinations thereof, and may further have a substituent.
• alkyl ether and -NH- from the viewpoint of solubility in a developing solution and metal adhesion, and -NH- is more preferable from the viewpoint of metal adhesion due to interaction with resin and metal complex formation. preferable.
• Examples of the compound represented by the following general formula (3) include the following, but the compound is not limited to the following structure.
• the amount of the antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to the resin. If the amount added is less than 0.1 parts by mass, it is difficult to obtain the effect of improving the elongation characteristics after reliability and the adhesion to the metal material, and if it is more than 10 parts by mass, it is due to the interaction with the photosensitizer. , There is a risk of lowering the sensitivity of the resin composition. Only one type of antioxidant may be used, or two or more types may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
• the water content of the resin composition of the present invention is preferably less than 5% by mass, more preferably less than 1% by mass, and even more preferably less than 0.6% by mass from the viewpoint of coating surface properties.
• Examples of the method for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container.
• 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.
• the metal include sodium, potassium, magnesium, calcium, iron, chromium, nickel and the like. When a plurality of metals are contained, the total of these metals is preferably in the above range.
• a raw material having a low metal content is selected as a raw material constituting the resin composition of the present invention.
• Examples thereof include a method of filtering the raw materials constituting the product, a method of lining the inside of the device with polytetrafluoroethylene or the like, and performing distillation under conditions in which contamination is suppressed as much as possible.
• the resin composition of the present invention preferably has a halogen atom content of less than 500 mass ppm, more preferably less than 300 mass ppm, and less than 200 mass ppm from the viewpoint of wiring corrosiveness. Is more preferable. Among them, those existing in the state of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
• the halogen atom include a chlorine atom and a bromine atom. It is preferable that the total of chlorine atom and bromine atom, or chlorine ion and bromine ion is in the above range, respectively.
• ion exchange treatment and the like are preferably mentioned.
• a conventionally known storage container can be used as the storage container for the resin composition of the present invention.
• a multi-layer bottle in which the inner wall of the container is composed of 6 types and 6 layers of resin and a 7-layer structure of 6 types of resin are used for the purpose of suppressing impurities from being mixed into the raw material and the resin composition. It is also preferable to use a bottle of plastic. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
• the resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer. In addition, it can also be used for forming an insulating film of a semiconductor device, forming a stress buffer film, and the like.
• the resin composition of the present invention can be prepared by mixing each of the above components.
• the mixing method is not particularly limited, and a conventionally known method can be used.
• the filter pore diameter is preferably 1 ⁇ m or less, more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less. On the other hand, from the viewpoint of productivity, 5 ⁇ m or less is preferable, 3 ⁇ m or less is more preferable, and 1 ⁇ m or less is further preferable.
• the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
• the filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel.
• filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. When filtering a plurality of times, circulation filtration may be used. Moreover, you may pressurize and perform filtration. When pressurizing and filtering, the pressurizing pressure is preferably 0.05 MPa or more and 0.3 MPa or less. On the other hand, from the viewpoint of productivity, 0.01 MPa or more and 1.0 MPa or less is preferable, 0.03 MPa or more and 0.9 MPa or less is more preferable, and 0.05 MPa or more and 0.7 MPa or less is further preferable. In addition to filtration using a filter, impurities may be removed using an adsorbent.
• Filter filtration and impurity removal treatment using an adsorbent may be combined.
• a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
• the cured film of the present invention is a cured film obtained by curing the resin composition of the present invention.
• the film thickness of the cured film of the present invention can be, for example, 0.5 ⁇ m or more, and can be 1 ⁇ m or more. Further, the upper limit value can be 100 ⁇ m or less, and can be 30 ⁇ m or less.
• the cured film of the present invention may be laminated in two or more layers, and further in three to seven layers to form a laminated body. It is preferable that the laminate of the present invention contains two or more cured films and includes a metal layer between any of the cured films. For example, a laminate containing at least a layer structure in which three layers of a first cured film, a metal layer, and a second cured film are laminated in this order is preferable.
• the first cured film and the second cured film are both cured films of the present invention.
• both the first cured film and the second cured film have the resin composition of the present invention.
• a preferred embodiment is a film obtained by curing an object.
• the resin composition of the present invention used for forming the first cured film and the resin composition of the present invention used for forming the second cured film may have the same composition. However, the compositions may have different compositions.
• the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
• Examples of applicable fields of the cured film of the present invention include an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like.
• Other examples include forming a pattern by etching on a sealing film, a substrate material (base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting purposes as described above.
• the cured film in the present invention can also be used for manufacturing plate surfaces such as offset plate surfaces or screen plate surfaces, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, especially in microelectronics.
• the method for producing a cured film of the present invention preferably includes a film forming step of applying the resin composition of the present invention to a substrate to form a film. ..
• the method for producing a cured film of the present invention preferably includes the film forming step, an exposure step for exposing the film, and a developing step for developing the film.
• the method for producing a cured film of the present invention more preferably includes the film forming step and, if necessary, the developing step, and also includes a heating step of heating the film at 50 to 450 ° C. Specifically, it is also preferable to include the following steps (a) to (d).
• the method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film of the present invention.
• the method for producing the laminated body of the present embodiment is the step (a), the steps (a) to (c), or (a) after forming the cured film according to the above-mentioned method for producing the cured film. )-(D).
• a laminated body can be obtained.
• the production method includes a film forming step (layer forming step) in which the resin composition is applied to a substrate to form a film (layered).
• the type of base material can be appropriately determined depending on the application, but semiconductor-made base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical film, ceramic material, and thin-film deposition film, There are no particular restrictions on magnetic film, reflective film, metal substrate such as Ni, Cu, Cr, Fe, paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, plasma display panel (PDP) electrode plate, and the like. Further, these base materials may be provided with a layer such as an adhesion layer or an oxide layer on the surface thereof. In the present invention, a semiconductor-made base material is particularly preferable, and a silicon base material, a Cu base material, and a molded base material are more preferable.
• these substrates may be provided with a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
• a layer such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) or the like on the surface.
• HMDS hexamethyldisilazane
• the base material for example, a plate-shaped base material (board) is used.
• the shape of the base material is not particularly limited, and may be circular or rectangular, but is preferably rectangular.
• the size of the base material is, for example, 100 to 450 mm in diameter, preferably 200 to 450 mm in a circular shape. If it is rectangular, for example, the length of the short side is 100 to 1000 mm, preferably 200 to 700 mm.
• the resin layer or the metal layer serves as a base material.
• Coating is preferable as a means for applying the resin composition to the base material.
• the inkjet method and the like are exemplified. From the viewpoint of the uniformity of the thickness of the resin composition layer, a spin coating method, a slit coating method, a spray coating method, and an inkjet method are more preferable.
• a resin layer having a desired thickness can be obtained by adjusting an appropriate solid content concentration and coating conditions according to the method. Further, the coating method can be appropriately selected depending on the shape of the base material.
• a spin coating method, a spray coating method, an inkjet method, etc. are preferable, and for a rectangular base material, a slit coating method or a spray coating method is used.
• the method, the inkjet method and the like are preferable.
• the spin coating method for example, it can be applied at a rotation speed of 500 to 2,000 rpm for about 10 seconds to 1 minute. Further, depending on the viscosity of the photosensitive resin composition and the film thickness to be set, it is preferable to apply the photosensitive resin composition at a rotation speed of 300 to 3,500 rpm for 10 to 180 seconds.
• a plurality of rotation speeds can be combined and applied. Further, it is also possible to apply a method of transferring a coating film previously formed on a temporary support by the above-mentioned application method onto a substrate. Regarding the transfer method, the production method described in paragraphs 0023, 0036 to 0051 of JP-A-2006-023696 and paragraphs 096 to 0108 of JP-A-2006-047592 can be preferably used in the present invention. Further, a step of removing the excess film at the edge of the base material may be performed. Examples of such a process include edge bead rinse (EBR), air knife, back rinse and the like. Further, a pre-wetting step of applying various solvents to the base material before applying the resin composition to the base material to improve the wettability of the base material and then applying the resin composition may be adopted.
• EBR edge bead rinse
• the production method of the present invention may include a step of forming the film (resin composition layer), followed by a film forming step (layer forming step), and then drying to remove the solvent.
• the preferred drying temperature is 50 to 150 ° C., more preferably 70 ° C. to 130 ° C., still more preferably 90 ° C. to 110 ° C.
• the drying time is exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
• the production method of the present invention may include an exposure step of exposing the film (resin composition layer).
• the exposure amount is not particularly determined as long as the resin composition can be cured, but for example, it is preferable to irradiate 100 to 10,000 mJ / cm 2 in terms of exposure energy at a wavelength of 365 nm, and 200 to 8,000 mJ / cm 2 It is more preferable to irradiate.
• the exposure wavelength can be appropriately determined in the range of 190 to 1,000 nm, preferably 240 to 550 nm.
• the exposure wavelengths are (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-ray (wavelength 436 nm), h.
• the resin composition of the present invention is particularly preferably exposed to a high-pressure mercury lamp, and above all, to be exposed to i-rays.
• a broad (three wavelengths of g, h, and i rays) light source of a high-pressure mercury lamp and a semiconductor laser of 405 nm are also suitable.
• the production method of the present invention may include a developing step of developing the exposed film (resin composition layer) (developing the film). By developing, the unexposed portion (non-exposed portion) is removed.
• the developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection of a developing solution from a nozzle, spray spraying, immersion of a developing solution in a base material, and the like, and ejection from a nozzle is preferably used.
• the developing process includes a process in which the developing solution is continuously supplied to the base material, a step in which the developing solution is kept in a substantially stationary state on the base material, a step in which the developing solution is vibrated by ultrasonic waves or the like, and a combination thereof. Processes can be adopted.
• Development is carried out using a developing solution.
• the developer can be used without particular limitation as long as the unexposed portion (non-exposed portion) is removed.
• As the developing solution a developing solution containing an organic solvent or an alkaline aqueous solution can be used.
• the developer preferably contains an organic solvent having a ClogP value of -1 to 5, and more preferably contains an organic solvent having a ClogP value of 0 to 3.
• the ClogP value can be obtained as a calculated value by inputting a structural formula in ChemBioDraw.
• the organic solvent may be, as esters, for example, ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate.
• alkyl alkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate) , Ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.
• 3-alkyloxypropionate alkyl esters eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.) , 3-Methylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)
• the developer is a developer containing an organic solvent
• cyclopentanone and ⁇ -butyrolactone are particularly preferable, and cyclopentanone is more preferable in the present invention.
• the developing solution contains an organic solvent, one kind or a mixture of two or more kinds of organic solvents can be used.
• the developer is a developer containing an organic solvent
• 50% by mass or more of the developer is preferably an organic solvent
• 70% by mass or more is more preferably an organic solvent
• 90% by mass or more is organic. It is more preferably a solvent.
• the developing solution may be 100% by mass of an organic solvent.
• the method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the developer, the method of supplying the developer on the base material using a nozzle, paddle development, or continuous development. There is a way to supply.
• the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoint of the permeability of the developer, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developer with a straight nozzle or the method of continuously supplying the developer with a spray nozzle is preferable, and the developer is supplied to the image area.
• the method of supplying with a spray nozzle is more preferable. Further, after the developing solution is continuously supplied by the straight nozzle, the base material is spun to remove the developing solution from the base material, and after spin drying, the developing solution is continuously supplied by the straight nozzle again, and then the base material is spun to use the developing solution as the base material. A step of removing from the top may be adopted, and this step may be repeated a plurality of times. Further, as a method of supplying the developer in the developing process, a step in which the developer is continuously supplied to the base material, a step in which the developer is kept in a substantially stationary state on the base material, and a step in which the developer is superposed on the base material. A process of vibrating with a sound wave or the like and a process of combining them can be adopted.
• the developing solution is an alkaline aqueous solution
• examples of the basic compound that the alkaline aqueous solution can contain include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), sodium carbonate and the like, and TMAH is preferable. ..
• TMAH tetramethylammonium hydroxide
• KOH potassium hydroxide
• sodium carbonate sodium carbonate
• TMAH is preferable.
• the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.3 to 3% by mass in the total mass of the developer. Is more preferable.
• the method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the developer, the method of supplying the developer on the base material using a nozzle, paddle development, or continuous development. There is a way to supply.
• the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. From the viewpoint of the permeability of the developer, the removability of the non-image area, and the manufacturing efficiency, the method of supplying the developer with a straight nozzle or the method of continuously supplying the developer with a spray nozzle is preferable, and the developer is supplied to the image area.
• the method of supplying with a spray nozzle is more preferable. Further, after the developing solution is continuously supplied by the straight nozzle, the base material is spun to remove the developing solution from the base material, and after spin drying, the developing solution is continuously supplied by the straight nozzle again, and then the base material is spun to use the developing solution as the base material. A step of removing from the top may be adopted, and this step may be repeated a plurality of times. Further, as a method of supplying the developer in the developing process, a step in which the developer is continuously supplied to the base material, a step in which the developer is kept in a substantially stationary state on the base material, and a step in which the developer is superposed on the base material. A process of vibrating with a sound wave or the like and a process of combining them can be adopted.
• the development time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes.
• the temperature of the developing solution at the time of development is not particularly specified, but it can be usually 10 to 45 ° C, preferably 20 to 40 ° C.
• rinsing After the treatment with the developing solution, further rinsing may be performed. Further, a method such as supplying a rinse liquid before the developer in contact with the pattern is completely dried may be adopted.
• the rinsing is preferably performed with a solvent different from that of the developing solution. For example, it can be rinsed with the solvent contained in the resin composition.
• the rinse solution include PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), and the like, preferably PGMEA.
• water is preferable as the rinsing solution for development with a developing solution containing an alkaline aqueous solution.
• the rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and preferably 5 seconds to 1 minute.
• the temperature of the rinsing liquid at the time of rinsing is not particularly specified, but can be preferably 10 to 45 ° C, more preferably 18 ° C to 30 ° C.
• Examples of the organic solvent when the rinsing solution contains an organic solvent include ethyl acetate, -n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate.
• alkyl alkyloxyacetate eg, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, methoxyacetic acid) E
• toluene, xylene, anisole, limonene and the like dimethyl sulfoxide as sulfoxides, and methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methylisobutylcarbinol, triethylene as alcohols.
• glycols and the like and amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.
• the rinsing liquid contains an organic solvent
• one type or a mixture of two or more types of organic solvent can be used.
• cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA and PGME are particularly preferable, cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, PGMEA and PGME are more preferable, and cyclohexanone and PGMEA are more preferable. More preferred.
• the rinsing liquid contains an organic solvent
• 50% by mass or more of the rinsing liquid is preferably an organic solvent, 70% by mass or more is more preferably an organic solvent, and 90% by mass or more is an organic solvent. Is more preferable.
• the rinse liquid may be 100% by mass of an organic solvent.
• the rinse solution may further contain other components.
• other components include known surfactants and known defoamers.
• the method of supplying the rinse liquid is not particularly limited as long as a desired pattern can be formed, and the method of immersing the base material in the rinse liquid, the paddle development on the base material, the method of supplying the rinse liquid to the base material by a shower, and the base material.
• the method of supplying the rinse liquid with a spray nozzle is more preferable.
• the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle. That is, the rinsing step is preferably a step of supplying the rinsing liquid to the exposed film by a straight nozzle or continuously, and more preferably a step of supplying the rinsing liquid by a spray nozzle.
• a step of continuously supplying the rinse liquid to the base material a step of keeping the rinse liquid in a substantially stationary state on the base material, and a step of superimposing the rinse liquid on the base material.
• a process of vibrating with a sound conditioner or the like and a process of combining them can be adopted.
• the production method of the present invention preferably includes a step (heating step) of heating the developed film at 50 to 450 ° C.
• the heating step is preferably included after the film forming step (layer forming step), the drying step, and the developing step.
• the above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the precursor, which is a specific resin, proceeds.
• the resin composition of the present invention may contain a radically polymerizable compound other than the precursor which is a specific resin, but curing of a radically polymerizable compound other than the precursor which is an unreacted specific resin is also in this step. Can be advanced with.
• the heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ° C. or higher, more preferably 80 ° C. or higher, further preferably 140 ° C. or higher, and 150 ° C. or higher. Is even more preferable, 160 ° C. or higher is even more preferable, and 170 ° C. or higher is even more preferable.
• the upper limit is preferably 500 ° C. or lower, more preferably 450 ° C. or lower, further preferably 350 ° C. or lower, further preferably 250 ° C. or lower, and preferably 220 ° C. or lower. Even more preferable.
• the heating is preferably performed at a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
• a heating rate of 1 to 12 ° C./min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10 ° C./min, and even more preferably 3 to 10 ° C./min.
• the temperature at the start of heating it is preferable to carry out from the temperature at the start of heating to the maximum heating temperature at a heating rate of 1 to 8 ° C./sec, more preferably 2 to 7 ° C./sec, and 3 to 6 ° C. °C / sec is more preferable.
• the temperature at the start of heating is preferably 20 ° C. to 150 ° C., more preferably 20 ° C. to 130 ° C., and even more preferably 25 ° C. to 120 ° C.
• the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature is started.
• the temperature of the film (layer) after drying is, for example, 30 to 200 ° C., which is higher than the boiling point of the solvent contained in the resin composition. It is preferable to gradually raise the temperature from a low temperature.
• the heating time (heating time at the maximum heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, and even more preferably 30 to 240 minutes.
• the heating temperature is preferably 180 ° C. to 320 ° C., more preferably 180 ° C. to 260 ° C. from the viewpoint of adhesion between layers of the cured film. The reason is not clear, but it is considered that the ethynyl groups of the specific resin between the layers are undergoing a cross-linking reaction at this temperature.
• Heating may be performed in stages. As an example, the temperature is raised from 25 ° C. to 180 ° C. at 3 ° C./min and held at 180 ° C. for 60 minutes, the temperature is raised from 180 ° C. to 200 ° C. at 2 ° C./min, and held at 200 ° C. for 120 minutes. , Etc. may be performed.
• the heating temperature as the pretreatment step is preferably 100 to 200 ° C., more preferably 110 to 190 ° C., and even more preferably 120 to 185 ° C. In this pretreatment step, it is also preferable to perform the treatment while irradiating with ultraviolet rays as described in US Pat. No. 9,159,547.
• the pretreatment step is preferably performed in a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
• the pretreatment may be performed in two or more steps.
• the pretreatment step 1 may be performed in the range of 100 to 150 ° C.
• the pretreatment step 2 may be performed in the range of 150 to 200 ° C.
• cooling may be performed after heating, and the cooling rate in this case is preferably 1 to 5 ° C./min.
• the heating step is preferably performed in an atmosphere having a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon from the viewpoint of preventing decomposition of the specific resin.
• the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
• the heating means is not particularly limited, and examples thereof include a hot plate, an infrared furnace, an electric heating oven, and a hot air oven.
• the production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the developed film (resin composition layer).
• metal layer existing metal types can be used without particular limitation, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold and tungsten are exemplified, and copper, aluminum, and these metals are exemplified.
• the alloy containing the above is more preferable, and copper is further preferable.
• the method for forming the metal layer is not particularly limited, and an existing method can be applied.
• the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, and JP-A-2004-101850 can be used.
• photolithography, lift-off, electrolytic plating, electroless plating, etching, printing, and a method combining these can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be mentioned.
• the thickness of the metal layer is preferably 0.01 to 100 ⁇ m, preferably 0.1 to 50 ⁇ m, and more preferably 1 to 10 ⁇ m at the thickest portion.
• the production method of the present invention preferably further includes a laminating step.
• the laminating step means that (a) a film forming step (layer forming step), (b) an exposure step, (c) a developing step, and (d) a heating step are performed again on the surface of the cured film (resin layer) or the metal layer. , A series of steps including performing in this order. However, the mode may be such that only the film forming step (a) is repeated. Further, (d) the heating step may be performed collectively at the end or the middle of the lamination. That is, the steps (a) to (c) may be repeated a predetermined number of times, and then the heating of (d) may be performed to cure the laminated resin composition layers all at once.
• the (c) developing step may be followed by the (e) metal layer forming step, and even if the heating is performed each time (d), the (d) is collectively performed after laminating a predetermined number of times. Heating may be performed. Needless to say, the laminating step may further include the above-mentioned drying step, heating step, and the like as appropriate.
• the surface activation treatment step may be further performed after the heating step, the exposure step, or the metal layer forming step.
• An example of the surface activation treatment is plasma treatment.
• the laminating step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and even more preferably 3 to 5 times. Further, each layer in the laminating step may be a layer having the same composition, shape, film thickness, etc., or may be a different layer.
• a structure having two or more layers and 20 layers or less such as a resin layer / metal layer / resin layer / metal layer / resin layer / metal layer is preferable, and a structure in which the resin layer is 3 layers or more and 7 layers or less is more preferable. More preferably, it has 3 or more layers and 5 or less layers.
• a cured film (resin layer) of the resin composition so as to cover the metal layer after the metal layer is provided.
• Examples thereof include an embodiment in which the steps, (b) exposure steps, (c) development steps, and (e) metal layer forming steps are repeated in this order, and (d) heating steps are collectively provided at the end or in the middle.
• the present invention also discloses a semiconductor device containing the cured film or laminate of the present invention.
• the semiconductor device in which the resin composition of the present invention is used to form the interlayer insulating film for the rewiring layer the description in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-0273557 can be referred to. These contents are incorporated in the present specification.
• the method for producing a laminate of the present invention may include a surface activation treatment step of surface activating at least a part of the metal layer and the photosensitive resin composition layer.
• the surface activating treatment step is usually performed after the metal layer forming step, but it is also possible to perform the surface activating treatment step on the photosensitive resin composition layer after the exposure development step and then perform the metal layer forming step. good.
• the surface activation treatment may be performed on at least a part of the metal layer, on at least a part of the photosensitive resin composition layer after exposure, or on the metal layer and the photosensitive resin after exposure. For both of the composition layers, each may be at least partially.
• the surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the region of the metal layer in which the photosensitive resin composition layer is formed on the surface. ..
• the surface activation treatment is performed on a part or all of the photosensitive resin composition layer (resin layer) after exposure.
• the surface activation treatment includes plasma treatment of various raw material gases (oxygen, hydrogen, argon, nitrogen, nitrogen / hydrogen mixed gas, argon / oxygen mixed gas, etc.), corona discharge treatment, CF 4 / O 2 , NF 3 / O 2 , SF 6 , NF 3 , NF 3 / O 2 , surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove oxide film, then amino group and thiol group It is selected from a dipping treatment in an organic surface treatment agent containing at least one compound and a mechanical roughening treatment using a brush, and a plasma treatment is preferable, and an oxygen plasma treatment using oxygen as a raw material gas is particularly preferable.
• the energy is preferably 500 ⁇ 200,000J / m 2, more preferably 1000 ⁇ 100,000J / m 2, and most preferably 10,000 ⁇ 50,000J / m 2.
• reaction mixture was then cooled to ⁇ 10 ° C. and 16.12 g (135.5 mmol) of SOCL 2 was added over 10 minutes while keeping the temperature at ⁇ 10 ⁇ 4 ° C. Viscosity increased while SOCL 2 was added. After diluting with 50 mL of N-methylpyrrolidone, the reaction mixture was stirred at room temperature for 2 hours.
• the polyimide precursor was obtained by filtration, stirred again in 4 liters of water for 30 minutes and filtered again. Then, the obtained polyimide precursor was dried under reduced pressure at 45 ° C. for 3 days to obtain a polyimide precursor A-1.
• the weight average molecular weight of this polyimide precursor A-1 was 19,000. It is presumed that the obtained polyimide precursor A-1 contains a repeating unit represented by the following formula (A-1).
• the obtained diester is chlorinated with SOCL 2 , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and the polyimide precursor A is converted in the same manner as in Synthesis Example 1.
• the weight average molecular weight of this polyimide precursor A-2 was 20,000. It is presumed that the obtained polyimide precursor A-2 contains a repeating unit represented by the following formula (A-2).
• the repeating unit represented by the formula (A-2) includes a single bond contained in the biphenyl structure derived from 3,3', 4,4'-biphenyltetracarboxylic acid anhydride, and 3,3', 4,
• ester structure formed by 4'-biphenyltetracarboxylic acid anhydride and 2-hydroxyethylmethacrylate is present at the meta position on the benzene ring and when it is present at the para position (for example, the following formula (for example, There is a repeating unit represented by A-2-2)), and it is considered that these structures are mixed in the polyimide precursor A-2.
• a polyimide precursor produced when 3,3', 4,4'-biphenyltetracarboxylic acid anhydride or 4,4'-oxydiphthalic acid anhydride is used as the acid dianhydride in the synthetic example.
• the single bond contained in the biphenyl structure derived from 3,3', 4,4'-biphenyltetracarboxylic acid anhydride, or 4,4'-oxydiphthalic acid anhydride is used as the acid dianhydride in the synthetic example.
• the positional relationship between the contained ether bond and the ester bond and amide bond bonded to the benzene ring contained in each repeating unit is not limited to the structure described as the chemical formula, and some of them have different positional relationships. It is assumed that you are doing.
• the obtained diester is chlorinated with SOCL 2 , converted to a polyimide precursor with 4,4'-diaminodiphenyl ether in the same manner as in Synthesis Example 1, and the polyimide precursor is converted into a polyimide precursor in the same manner as in Synthesis Example 1. Obtained. The weight average molecular weight of this polyimide precursor was 18,000. It is presumed that the obtained polyimide precursor A-3 contains a repeating unit represented by the following formula (A-3).
• ⁇ Synthesis example 4> [Synthesis of polyimide precursor (A-4) from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotrizine) and 2-hydroxyethyl methacrylate] 20.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, and 0.05 g.
• the polyimide precursor was then precipitated in 3 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5,000 rpm (revolutions per minute) for 15 minutes.
• the polyimide precursor was obtained by filtration, dissolved in 300 mL of tetrahydrofuran, and then the polyimide precursor was obtained again as a precipitate in 2 liters of water.
• the obtained polyimide precursor was dried under reduced pressure at 45 ° C. for 3 days to obtain a polyimide precursor A "-5.
• the weight average molecular weight of this polyimide precursor A" -5 was 22,000. ..
• ⁇ Synthesis example 7> [Synthesis of polyimide precursor (A "-7) from 3,3', 4,4'-biphenyltetracarboxylic acid anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate] 19.0 g (64.5 mmol) of 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine and 200 g of ⁇ -butyrolactone were mixed and stirred at room temperature for 36 hours for 3,3', 4,4'-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate.
• diester was produced. Next, the obtained diester is converted into a polyimide precursor using DCC in the same manner as in Synthesis Example 5 with 4,4′-diaminodiphenyl ether, and the polyimide precursor A ”-7 is converted into a polyimide precursor in the same manner as in Synthesis Example 5. The weight average molecular weight of this polyimide precursor A "-7 was 21,000.
• the polyimide precursor was then precipitated in 3 liters of water and the water-polyimide precursor mixture was stirred at a rate of 5,000 rpm (revolutions per minute) for 15 minutes.
• the polyimide precursor was obtained by filtration, and the obtained polyimide precursor was dried at 45 ° C. for 3 days under reduced pressure to obtain a polyimide precursor A'-1.
• the weight average molecular weight of this polyimide precursor A'-1 was 20,500. It is presumed that the polyimide precursor A'-1 contains a repeating unit having a structure represented by the following formula (A'-1).
• Synthesis Example 5-1 [Modification of polyimide precursor A-2 from 3,3', 4,4'-biphenyltetracarboxylic acid anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (polyimide precursor A'-5) Synthetic)]
• Synthesis Example 1-1 synthesis was performed except that 20 g of the polyimide precursor A-2 obtained in Synthesis Example 2 was used in place of the polyimide precursor A-1 and diisopropylcarbodiimide (DIC) was used in place of DCC.
• a modified polyimide precursor A'-5 was obtained in the same manner as in Example 1-1. The weight average molecular weight of this polyimide precursor A'-5 was 21,000. It is presumed that the polyimide precursor A'-5 contains a repeating unit having a structure represented by the following formula (A'-5).
• Synthesis Example 7-1 [Modification of polyimide precursor A-3 from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (synthesis of polyimide precursor A'-7)]
• Synthesis Example 1-1 20 g of the polyimide precursor A-3 obtained in Synthesis Example 3 was used instead of the polyimide precursor A-1, and DIC was used instead of DCC.
• a modified polyimide precursor A'-7 was obtained in the same manner. The weight average molecular weight of this polyimide precursor A'-7 was 19,000. It is presumed that the polyimide precursor A'-7 contains a repeating unit having a structure represented by the following formula (A'-7).
• NMP N-methylpyrrolidone
• P-1 ring-closed polyimide
• Mw weight average molecular weight
• Mn number average molecular weight
• Example 1 ⁇ Examples and Comparative Examples>
• the components shown in Table 1 below were mixed to obtain a resin composition or a comparative composition.
• the numerical value in the column of each component other than the solvent shown in Table 1 represents the content (part by mass) of each component.
• the obtained resin composition and the comparative composition were pressure-filtered through a filter made of polytetrafluoroethylene having a pore width of 0.8 ⁇ m. Further, in Table 1, the description of "-" indicates that the composition does not contain the corresponding component.
• ⁇ D-1 A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
• -D-2 SR-209 (manufactured by Sartmer, compound with the following structure)
• ⁇ D-3 A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)
• the prepared composition was subjected to NMR analysis with d 6- DMSO (dimethyl sulfoxide-d 6 ) to calculate the molar ratio of the polymer to the additive.
• the additive content was quantified from the polymer / additive molar ratio and polymer mass.
• 1 Torr is a value indicating 1/760 of 1 atm, and is 133.322 Pa.
• 1 H-NMR using DMSO (dimethyl sulfoxide) -d6 as a solvent
• the content (mol / g) of the structure represented by the formula (1-1) with respect to the total solid content of the resin composition is quantified, and the quantification result is shown in the column of "content of specific structure" in Table 1. Described in.
• Viscosity volatility
• the viscosity was measured at 25 ° C., and other measurement conditions were in accordance with JIS Z 8803: 2011. -Evaluation criteria- A: The viscosity volatility was 5% or less. B: Viscosity volatility exceeded 5%.
• the resin composition or comparative composition prepared in each Example and Comparative Example was applied in layers on a copper substrate by a spin coating method, respectively, to form a resin composition layer or a comparative composition layer.
• the obtained resin composition layer or the copper substrate on which the comparative composition layer was formed was dried on a hot plate at 100 ° C. for 5 minutes, and the resin composition layer having a uniform thickness of 20 ⁇ m or for comparison was placed on the copper substrate. It was used as a composition layer.
• a stepper Nakon NSR 2005 i9C
• the resin layer (pattern) was formed by heating at 230 ° C. for 3 hours in a nitrogen atmosphere. Shear force was measured on a 100 ⁇ m square resin layer on a copper substrate in an environment of 25 ° C.
• a resin containing at least one resin selected from the group consisting of polyimide and a polyimide precursor according to the present invention and having a structure represented by the formula (1-1) in the solid content It can be seen that when the composition is used, a cured film having excellent adhesion to the metal layer can be obtained.
• the comparative compositions described in Comparative Examples 1 to 3 do not contain the structure represented by the formula (1-1) in the solid content. It can be seen that the cured film obtained from such a comparative composition is inferior in adhesion to the metal layer.
• Example 101 The resin composition used in Example 1 was applied in layers to the surface of the thin copper layer of the resin base material having the thin copper layer formed on the surface by a spin coating method, dried at 100 ° C. for 5 minutes, and the film thickness was increased. After forming a 20 ⁇ m resin composition layer, exposure was performed using a stepper (NSR1505 i6, manufactured by Nikon Corporation). The exposure was performed by irradiating light having a wavelength of 365 nm through a mask (a binary mask having a pattern of 1: 1 line and space and a line width of 10 ⁇ m). After exposure, it was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a layer pattern.
• NSR1505 i6, manufactured by Nikon Corporation a stepper
• the exposure was performed by irradiating light having a wavelength of 365 nm through a mask (a binary mask having a pattern of 1: 1 line and space and a line width of 10 ⁇ m). After exposure, it was
• the interlayer insulating film for the rewiring layer was excellent in insulating properties. Moreover, when a semiconductor device was manufactured using these interlayer insulating films for the rewiring layer, it was confirmed that the semiconductor device operated without any problem.

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