WO2021157643A1 - Resin composition, cured film, laminate, production method for cured film, and semiconductor device - Google Patents
Resin composition, cured film, laminate, production method for cured film, and semiconductor device Download PDFInfo
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- WO2021157643A1 WO2021157643A1 PCT/JP2021/004054 JP2021004054W WO2021157643A1 WO 2021157643 A1 WO2021157643 A1 WO 2021157643A1 JP 2021004054 W JP2021004054 W JP 2021004054W WO 2021157643 A1 WO2021157643 A1 WO 2021157643A1
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/5329—Insulating materials
- H01L23/53295—Stacked insulating layers
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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Abstract
Description
このような用途において、硬化膜と金属との密着性に優れた樹脂組成物の提供が望まれている。 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.
In such applications, it is desired to provide a resin composition having excellent adhesion between the cured film and a metal.
<1> ポリイミド、及び、ポリイミド前駆体よりなる群から選ばれた少なくとも1種の樹脂を含み、
固形分中に式(1-1)で表される構造を含む、
樹脂組成物。
式(1-1)中、R1及びR2はそれぞれ独立に、脂肪族基又は芳香族基を表し、上記脂肪族基又は芳香族基の炭素原子又は炭化水素基はヘテロ原子で置換されていてもよく、X1は酸素原子又は硫黄原子を表し、L1は-C(=O)-、又は、-S(=O)2-を表し、*1及び*2はそれぞれ独立に、他の構造との結合部位を表し、R1、R2、*1に結合する構造、及び、*2に結合する構造のうち少なくとも2つが結合して環構造を形成してもよい。
<2> 上記樹脂が、上記式(1-1)で表される構造を含む、<1>に記載の樹脂組成物。
<3> 上記式(1-1)で表される構造を含む化合物であって、上記樹脂とは異なる化合物を更に含む、<1>又は<2>に記載の樹脂組成物。
<4> 上記式(1-1)で表される構造として、下記式(1-2)で表される構造を含む、<1>~<3>のいずれか1つに記載の樹脂組成物。
式(1-2)中、R21及びR22はそれぞれ独立に、脂肪族基又は芳香族基を表し、上記脂肪族基又は芳香族基の炭素原子又は炭化水素基はヘテロ原子で置換されていてもよく、R23は水素原子又は1価の有機基を表し、*は他の構造との結合部位を表し、R21、R22、R23、及び、*に結合する構造のうち少なくとも2つが結合して環構造を形成してもよい。
<5> 樹脂組成物の全固形分に対する、上記式(1-1)で表される構造の含有モル量が0.01~1.0mmol/gである、<1>~<4>のいずれか1つに記載の樹脂組成物。
<6> 光重合開始剤を更に含む、<1>~<5>のいずれか1つに記載の樹脂組成物。
<7> 架橋剤を更に含む、<1>~<6>のいずれか1つに記載の樹脂組成物。
<8> 再配線層用層間絶縁膜の形成に用いられる、<1>~<7>のいずれか1つに記載の樹脂組成物。
<9> <1>~<8>のいずれか1つに記載の樹脂組成物を硬化してなる硬化膜。
<10> <9>に記載の硬化膜を2層以上有し、上記硬化膜同士のいずれかの間に金属層を有する、積層体。
<11> <1>~<8>のいずれか1つに記載の樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。
<12> 上記膜を50~450℃で加熱する工程を含む、<11>に記載の硬化膜の製造方法。
<13> <9>に記載の硬化膜又は<10>に記載の積層体を有する、半導体デバイス。 Examples of typical embodiments of the present invention are shown below.
<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).
Resin composition.
In 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, L 1 may represent -C (= O)-or-S (= O) 2- , and * 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.
<2> The resin composition according to <1>, wherein the resin contains a structure represented by the above formula (1-1).
<3> The resin composition according to <1> or <2>, which is a compound containing a structure represented by the above formula (1-1) and further contains a compound different from the above resin.
<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). ..
In formula (1-2), 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.
<5> Any of <1> to <4>, wherein the molar content of the structure represented by the above formula (1-1) is 0.01 to 1.0 mmol / g with respect to the total solid content of the resin composition. The resin composition according to one.
<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.
<11> 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.
<12> The method for producing a cured film according to <11>, which comprises a step of heating the film at 50 to 450 ° C.
<13> A semiconductor device having the cured film according to <9> or the laminate according to <10>.
本明細書において「~」という記号を用いて表される数値範囲は、「~」の前後に記載される数値をそれぞれ下限値及び上限値として含む範囲を意味する。
本明細書において「工程」との語は、独立した工程だけではなく、その工程の所期の作用が達成できる限りにおいて、他の工程と明確に区別できない工程も含む意味である。
本明細書における基(原子団)の表記において、置換及び無置換を記していない表記は、置換基を有しない基(原子団)と共に置換基を有する基(原子団)をも包含する。例えば、「アルキル基」とは、置換基を有しないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含する。
本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた露光も含む。また、露光に用いられる光としては、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線又は放射線が挙げられる。
本明細書において、「(メタ)アクリレート」は、「アクリレート」及び「メタクリレート」の両方、又は、いずれかを意味し、「(メタ)アクリル」は、「アクリル」及び「メタクリル」の両方、又は、いずれかを意味し、「(メタ)アクリロイル」は、「アクリロイル」及び「メタクリロイル」の両方、又は、いずれかを意味する。
本明細書において、構造式中のMeはメチル基を表し、Etはエチル基を表し、Buはブチル基を表し、Phはフェニル基を表す。
本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の総質量をいう。また本明細書において、固形分濃度とは、組成物の総質量に対する、溶剤を除く他の成分の質量百分率である。
本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、特に述べない限り、ゲル浸透クロマトグラフィ(GPC測定)に従い、ポリスチレン換算値として定義される。本明細書において、重量平均分子量(Mw)及び数平均分子量(Mn)は、例えば、HLC-8220GPC(東ソー(株)製)を用い、カラムとしてガードカラムHZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000、TSKgel Super HZ2000(東ソー(株)製)を用いることによって求めることができる。それらの分子量は特に述べない限り、溶離液としてTHF(テトラヒドロフラン)を用いて測定したものとする。また、GPC測定における検出は特に述べない限り、UV線(紫外線)の波長254nm検出器を使用したものとする。
本明細書において、積層体を構成する各層の位置関係について、「上」又は「下」と記載したときには、注目している複数の層のうち基準となる層の上側又は下側に他の層があればよい。すなわち、基準となる層と上記他の層の間に、更に第3の層や要素が介在していてもよく、基準となる層と上記他の層は接している必要はない。また、特に断らない限り、基材に対し層が積み重なっていく方向を「上」と称し、又は、感光層がある場合には、基材から感光層へ向かう方向を「上」と称し、その反対方向を「下」と称する。なお、このような上下方向の設定は、本明細書中における便宜のためであり、実際の態様においては、本明細書における「上」方向は、鉛直上向きと異なることもありうる。
本明細書において、特段の記載がない限り、組成物は、組成物に含まれる各成分として、その成分に該当する2種以上の化合物を含んでもよい。また、特段の記載がない限り、組成物における各成分の含有量とは、その成分に該当する全ての化合物の合計含有量を意味する。
本明細書において、特に述べない限り、温度は23℃、気圧は101,325Pa(1気圧)、相対湿度は50%RHである。
本明細書において、好ましい態様の組み合わせは、より好ましい態様である。 Hereinafter, main embodiments of the present invention will be described. However, the present invention is not limited to the specified embodiments.
In the present specification, 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.
In the present specification, 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.
In the notation of a group (atomic group) in the present specification, 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). For example, 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).
Unless otherwise specified, the term "exposure" as used herein 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.
As used herein, "(meth) acrylate" means both "acrylate" and "methacrylate", or either, and "(meth) acrylic" means both "acrylic" and "methacrylic", or , And "(meth) acryloyl" means both "acryloyl" and "methacrylic", or either.
In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the total solid content means the total mass of all the components of the composition excluding the solvent. Further, in the present specification, the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
In the present specification, 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. In the present specification, for 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). Unless otherwise specified, their molecular weights shall be measured using THF (tetrahydrofuran) as an eluent. Further, unless otherwise specified, the detection in the GPC measurement shall be performed by using a detector having a wavelength of 254 nm of UV rays (ultraviolet rays).
In the present specification, when the positional relationship of each layer constituting the laminated body is described as "upper" or "lower", the other layer is on the upper side or the lower side of the reference layer among the plurality of layers of interest. All you need is. That is, a third layer or element may be further interposed between the reference layer and the other layer, and the reference layer and the other layer need not be in contact with each other. Unless otherwise specified, 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". It should be noted that such a vertical setting is for convenience in the present specification, and in an actual embodiment, the "upward" direction in the present specification may be different from the vertical upward direction.
Unless otherwise specified in the present specification, the composition may contain, as each component contained in the composition, two or more compounds corresponding to the component. Unless otherwise specified, the content of each component in the composition means the total content of all the compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature is 23 ° C., the atmospheric pressure is 101,325 Pa (1 atm), and the relative humidity is 50% RH.
In the present specification, the combination of preferred embodiments is a more preferred embodiment.
本発明の樹脂組成物(以下、単に「本発明の組成物」ともいう。)は、ポリイミド、及び、ポリイミド前駆体よりなる群から選ばれた少なくとも1種の樹脂を含み、固形分中に式(1-1)で表される構造を含む。
以下、ポリイミド、及び、ポリイミド前駆体よりなる群から選ばれた少なくとも1種の樹脂を「特定樹脂」ともいう。 (Resin composition)
The resin composition of the present invention (hereinafter, also simply referred to as “the 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).
Hereinafter, at least one resin selected from the group consisting of polyimide and a polyimide precursor is also referred to as "specific resin".
式(1-1)中、R1及びR2はそれぞれ独立に、脂肪族基又は芳香族基を表し、上記脂肪族基又は芳香族基の炭素原子又は炭化水素基はヘテロ原子で置換されていてもよく、X1は酸素原子又は硫黄原子を表し、L1は-C(=O)-、又は、-S(=O)2-を表し、*1及び*2はそれぞれ独立に、他の構造との結合部位を表し、R1、R2、*1に結合する構造、及び、*2に結合する構造のうち少なくとも2つが結合して環構造を形成してもよい。
In 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, L 1 may represent -C (= O)-or-S (= O) 2- , and * 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.
上記硬化膜は、例えば、様々なデバイスにおいて、絶縁膜、封止材の材料、保護膜、フレキシブル基板のベースフィルム、カバーレイ等の用途に用いられている。
このような金属層上に形成された硬化膜において、金属層から硬化膜が剥離しにくい、すなわち、金属層と硬化膜との密着性に優れることが求められている。
本発明者らは鋭意検討した結果、上記樹脂組成物において、固形分中に式(1-1)で表される構造を含むことにより、金属層と硬化膜との密着性が向上することを見出した。
上記効果が得られるメカニズムは定かではないが、上記樹脂組成物により形成される硬化膜に含まれる構造と、金属層に含まれる金属とが相互作用するためであると推測されるが、定かではない。
また、上記相互作用により、本発明の樹脂組成物によれば、上記硬化膜及び上記金属層を加熱(例えば、175℃で1,000時間加熱)した場合であっても、硬化膜と金属層との密着性に優れると考えられる。 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.
In 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.
As a result of diligent studies, 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.
Further, according to 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.
以下、本発明の樹脂組成物について詳細に説明する。 Here, Patent Document 1 does not describe or suggest a resin composition containing a structure represented by the formula (1-1) in the solid content.
Hereinafter, the resin composition of the present invention will be described in detail.
式(1-1)で表される構造は、樹脂組成物の固形分中に含まれればよく、例えば、特定樹脂の構造中に式(1-1)で表される構造が含まれていてもよいし、樹脂組成物が、上記式(1-1)で表される構造を含む化合物であって、上記樹脂とは異なる化合物(以下、「特定化合物」ともいう。)を含んでもよい。
また、樹脂組成物が、式(1-1)で表される構造を有する樹脂を含み、かつ、特定化合物を含んでもよい。 <Structure represented by equation (1-1)>
The structure represented by the formula (1-1) may be contained in the solid content of the resin composition. For example, the structure represented by the formula (1-1) is included in the structure of the specific resin. Alternatively, 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.
式(1-1)中、R1及びR2はそれぞれ独立に、脂肪族基又は芳香族基を表し、脂肪族炭化水素基又は芳香族炭化水素基が好ましく、脂肪族炭化水素基がより好ましい。
上記脂肪族炭化水素基としては、炭素数1~20の飽和脂肪族炭化水素基が好ましく、炭素数3~10の飽和脂肪族炭化水素基がより好ましく、炭素数3~6の飽和脂肪族炭化水素基が更に好ましく、イソプロピル基又はシクロへキシル基がより好ましい。
上記脂肪族炭化水素基は公知の置換基を有していてもよいが、置換基を有しないことも本発明の好ましい態様の一つである。
上記芳香族炭化水素基としては、炭素数6~20の芳香族炭化水素基が好ましく、フェニル基又はナフチル基がより好ましく、フェニル基が更に好ましい。
上記芳香族炭化水素基は公知の置換基を有していてもよく、置換基としてはアルキル基が挙げられる。上記アルキル基としては、炭素数1~10のアルキル基が好ましく、炭素数3~10の分岐アルキル基、又は、炭素数5~10の環状アルキル基がより好ましく、炭素数3~6の分岐アルキル基が更に好ましく、イソプロピル基が特に好ましい。
上記置換基の数は特に限定されないが、1~5であることが好ましく、1~3であることがより好ましく、2であることが更に好ましい。
また、R1及びR2における脂肪族基又は芳香族基の炭素原子又は炭化水素基はヘテロ原子で置換されていてもよい。ヘテロ原子としては、酸素原子、窒素原子、硫黄原子等が挙げられる。具体的には、脂肪族基又は芳香族基の内部に-O-、-NRN-、-N=、-S-等の構造を含んでいてもよい。上記RNは水素原子又は炭化水素基を表し、水素原子、アルキル基又はアリール基がより好ましく、水素原子又はアルキル基が更に好ましく、水素原子が特に好ましい。 [R 1 and R 2 ]
In the formula (1-1), 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. ..
As the 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.
As 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. As the 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.
Further, 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. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and the like. Specifically, a structure such as -O-, -NR N- , -N =, -S- may be contained inside the aliphatic group or the aromatic group. 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.
式(1-1)中、X1は酸素原子又は硫黄原子を表し、酸素原子が好ましい。 [X 1 ]
In the formula (1-1), X 1 represents an oxygen atom or a sulfur atom, and an oxygen atom is preferable.
式(1-1)中、L1は-C(=O)-、又は、-S(=O)2-を表し、-C(=O)-が好ましい。 [L 1 ]
In the formula (1-1), L 1 represents -C (= O)-or-S (= O) 2- , and -C (= O)-is preferable.
式(1-1)中、R1、R2、*1に結合する構造、及び、*2に結合する構造のうち少なくとも2つが結合して環構造を形成してもよい。形成される環構造としては、ヒダントイン環、N-アシルイミダゾリジノン環等が挙げられるが、これらに限定されるものではない。
また、本発明において、R1、R2、*1に結合する構造、及び、*2に結合する構造のいずれもが環構造を形成しない態様も好ましい態様の一つである。 [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. Examples of the ring structure formed include, but are not limited to, a hydantoin ring, an N-acylimidazolidinone ring, and the like.
Further, in the present invention, 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.
本発明の樹脂組成物は、式(1-1)で表される構造として、下記式(1-2)で表される構造を含むことが好ましい。
式(1-2)中、R21及びR22はそれぞれ独立に、脂肪族基又は芳香族基を表し、上記脂肪族基又は芳香族基の炭素原子又は炭化水素基はヘテロ原子で置換されていてもよく、R23は水素原子又は1価の有機基を表し、*は他の構造との結合部位を表し、R21、R22、R23、及び、*に結合する構造のうち少なくとも2つが結合して環構造を形成してもよい。 <Structure represented by equation (1-2)>
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).
In formula (1-2), 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.
式(1-2)中、R21及びR22はそれぞれ、式(1-1)中のR1及びR2と同義であり、好ましい態様も同様である。 [R 21 and R 22 ]
In formula (1-2), 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.
式(1-2)中、R23は水素原子又は1価の有機基を表し、水素原子、脂肪族炭化水素基又は芳香族炭化水素基が好ましく、水素原子が更に好ましい。
上記脂肪族炭化水素基又は芳香族炭化水素基としては、上述のR1における脂肪族炭化水素基又は芳香族炭化水素基が挙げられ、好ましい態様も同様である。 [R 23 ]
In the formula (1-2), 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.
式(1-2)中、R21、R22、R23、及び、*に結合する構造のうち少なくとも2つが結合して環構造を形成してもよい。形成される環構造としては、ヒダントイン環、N-アシルイミダゾリジノン環等が挙げられるが、これらに限定されるものではない。
また、本発明において、R21、R22、R23、及び、*に結合する構造のいずれもが環構造を形成しない態様も好ましい態様の一つである。 [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. Examples of the ring structure formed include, but are not limited to, a hydantoin ring, an N-acylimidazolidinone ring, and the like.
Further, in the present invention, one of the preferred embodiments is that none of the structures bonded to R 21 , R 22 , R 23, and * form a ring structure.
密着性を向上する観点から、樹脂組成物の全固形分に対する、式(1-1)で表される構造の含有モル量は、0.01~1.0mmol/gであることが好ましく、0.01~0.85mmol/gであることがより好ましく、0.015~0.75mmol/gであることが更に好ましい。
上記含有モル量が上記下限値以下であれば、金属との密着性に優れた硬化膜が得られやすいと考えられる。
また、上記含有モル量が上記上限値以下であれば、例えばポリイミド前駆体の環化が抑制される、特定樹脂の主鎖の切断が抑制されるなど、組成物の保存安定性に優れた硬化膜が得られやすいと考えられる。
上記含有量の測定方法としては、特に限定されるものではないが、例えば、後述する実施例における測定方法が挙げられる。
上記全固形分の測定方法としては、特に限定されるものではないが、例えば、後述する実施例における測定方法が挙げられ、樹脂組成物を、溶剤以外の揮発成分がないことを確認しながら温度及び気圧を設定して乾燥する方法が挙げられる。ただし、全固形分の測定方法としては、全固形分として樹脂組成物中の溶剤以外の成分の含有量を決定することができる方法であればよく、これに限定されるものではない。
上記含有量は、樹脂組成物の全固形分に対する式(1-1)で表される構造の含有モル量であり、例えば、樹脂組成物が式(1-1)で表される構造を有する樹脂を含み、かつ、特定化合物を含む場合、樹脂に含まれる式(1-1)で表される構造と、特定化合物に含まれる式(1-1)で表される構造との合計量が上記範囲内であることが好ましい。 〔Content〕
From the viewpoint of improving the adhesion, 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.
When 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.
Further, when 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. However, 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. For example, the resin composition has a structure represented by the formula (1-1). When the resin is contained and the specific compound is contained, 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.
本発明の樹脂組成物は、ポリイミド、及び、ポリイミド前駆体よりなる群から選ばれた少なくとも1種の樹脂(特定樹脂)を含む。
本発明の樹脂組成物は、特定樹脂としてポリイミド前駆体を含むことが好ましい。
また、特定樹脂はラジカル重合性基を有することが好ましい。
特定樹脂がラジカル重合性基を有する場合、樹脂組成物は、重合開始剤として後述のラジカル重合開始剤を含むことが好ましく、感光剤として後述のラジカル重合開始剤を含み、かつ、後述のラジカル架橋剤を含むことがより好ましく、重合開始剤として後述のラジカル重合開始剤を含み、後述のラジカル架橋剤を含み、かつ、後述の増感剤を含むことが更に好ましい。このような樹脂組成物からは、例えば、ネガ型感光層が形成される。
また、特定樹脂は、酸分解性基等の極性変換基を有していてもよい。
特定樹脂が酸分解性基を有する場合、樹脂組成物は、後述の光酸発生剤を含むことが好ましい。このような樹脂組成物からは、例えば、化学増幅型であるポジ型感光層又はネガ型感光層が形成される。 <Resin>
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.
Further, the specific resin preferably has a radically polymerizable group.
When the specific resin has a radical 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. It is more preferable to include an agent, and it is further preferable to include a radical polymerization initiator described later as a polymerization initiator, a radical cross-linking agent described later, and a sensitizer described later. From such a resin composition, for example, a negative type photosensitive layer is formed.
Further, the specific resin may have a polarity converting group such as an acid-decomposable group.
When the specific resin has 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.
式(1-1)で表される構造の好ましい態様は上述の通りである。
特定樹脂が式(1-1)で表される構造を含む場合、特定樹脂は、式(1-1)で表される構造を主鎖に有してもよいが、側鎖に有することが好ましい。
本明細書において、「主鎖」とは、樹脂を構成する高分子化合物の分子中で相対的に最も長い結合鎖をいい、「側鎖」とはそれ以外の結合鎖をいう。
特定樹脂が式(1-1)で表される構造を含む場合、特定樹脂は後述する式(2-1)で表される繰返し単位を含むか、又は、末端に後述する式(2-2)で表される構造を含むことが好ましい。
また、樹脂組成物は、式(1-1)で表される構造を含む特定樹脂と、式(1-1)で表される構造を含まない特定樹脂とを含んでもよい。 Further, 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.
When the specific resin contains a structure represented by the formula (1-1), the specific resin may have a structure represented by the formula (1-1) in the main chain, but may have a structure represented by the side chain. preferable.
In the present specification, 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.
When 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.
Further, 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).
本発明で用いるポリイミド前駆体は、その種類等特に定めるものではないが、下記式(2)で表される繰り返し単位を含むことが好ましい。
式(2)中、A1及びA2は、それぞれ独立に、酸素原子又はNHを表し、R111は、2価の有機基を表し、R115は、4価の有機基を表し、R113及びR114は、それぞれ独立に、水素原子又は1価の有機基を表す。 [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).
In 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, and R 113. And R 114 independently represent a hydrogen atom or a monovalent organic group.
式(2)におけるR111は、2価の有機基を表す。2価の有機基としては、直鎖又は分岐の脂肪族基、環状の脂肪族基及び芳香族基を含む基が例示され、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数6~20の環状の脂肪族基、炭素数6~20の芳香族基、又は、これらの組み合わせからなる基が好ましく、炭素数6~20の芳香族基を含む基がより好ましい。本発明の特に好ましい実施形態として、-Ar-L-Ar-で表される基であることが例示される。但し、Arは、それぞれ独立に、芳香族基であり、Lは、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-CO-、-S-、-SO2-又はNHCO-、あるいは、上記の2つ以上の組み合わせからなる基である。これらの好ましい範囲は、上述のとおりである。 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. Examples of 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. As a particularly preferable embodiment of the present invention, a group represented by -Ar-L-Ar- is exemplified. However, 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. These preferred ranges are as described above.
具体的には、炭素数2~20の直鎖又は分岐の脂肪族基、炭素数6~20の環状の脂肪族基、炭素数6~20の芳香族基、又は、これらの組み合わせからなる基を含むジアミンであることが好ましく、炭素数6~20の芳香族基からなる基を含むジアミンであることがより好ましい。芳香族基の例としては、下記が挙げられる。 R 111 is preferably derived from diamine. Examples of 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:
式中、*は他の構造との結合部位を表す。
In the formula, * represents the binding site with other structures.
式(51)
式(51)中、R50~R57は、それぞれ独立に、水素原子、フッ素原子又は1価の有機基であり、R50~R57の少なくとも1つは、フッ素原子、メチル基又はトリフルオロメチル基である。
R50~R57の1価の有機基としては、炭素数1~10(好ましくは炭素数1~6)の無置換のアルキル基、炭素数1~10(好ましくは炭素数1~6)のフッ化アルキル基等が挙げられる。
式(61)中、R58及びR59は、それぞれ独立に、フッ素原子又はトリフルオロメチル基である。
式(51)又は(61)の構造を与えるジアミン化合物としては、2,2’-ジメチルベンジジン、2,2’-ビス(トリフルオロメチル)-4,4’-ジアミノビフェニル、2,2’-ビス(フルオロ)-4,4’-ジアミノビフェニル、4,4’-ジアミノオクタフルオロビフェニル等が挙げられる。これらは1種で又は2種以上を組み合わせて用いてもよい。 Further, R 111 is preferably a divalent organic group represented by the following formula (51) or formula (61) from the viewpoint of i-ray transmittance. In particular, from the viewpoint of i-ray transmittance and availability, 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.
In formula (61), 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.
式(5)又は式(6)中、*は他の構造との結合部位を表す。
式(5)
式(5)中、R112は、単結合、又は、フッ素原子で置換されていてもよい炭素数1~10の脂肪族炭化水素基、-O-、-CO-、-S-、-SO2-、及びNHCO-、ならびに、これらの組み合わせから選択される基であることが好ましく、単結合、フッ素原子で置換されていてもよい炭素数1~3のアルキレン基、-O-、-CO-、-S-及びSO2-から選択される基であることがより好ましく、-CH2-、-C(CF3)2-、-C(CH3)2-、-O-、-CO-、-S-及びSO2-からなる群から選択される2価の基であることが更に好ましい。 R 115 in the formula (2) represents a tetravalent organic group. As the 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.
In formula (5) or formula (6), * represents a binding site with another structure.
Equation (5)
In formula (5), 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-.
テトラカルボン酸二無水物は、下記式(O)で表されることが好ましい。
式(O)
式(O)中、R115は、4価の有機基を表す。R115の好ましい範囲は式(2)におけるR115と同義であり、好ましい範囲も同様である。 Specific examples of 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.
エチレン性不飽和結合を有する基としては、ビニル基、(メタ)アリル基、下記式(III)で表される基などが挙げられ、下記式(III)で表される基が好ましい。 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. preferable. As the 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. Specific examples of the polymerizable group 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. As the radically polymerizable group contained in the polyimide precursor or the like, 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.
式(III)において、R201は、炭素数2~12のアルキレン基、-CH2CH(OH)CH2-又はポリアルキレンオキシ基を表す。
好適なR201の例は、エチレン基、プロピレン基、トリメチレン基、テトラメチレン基、1,2-ブタンジイル基、1,3-ブタンジイル基、ペンタメチレン基、ヘキサメチレン基、オクタメチレン基、ドデカメチレン基、-CH2CH(OH)CH2-、ポリアルキレンオキシ基が挙げられ、エチレン基、プロピレン基、トリメチレン基、-CH2CH(OH)CH2-、ポリアルキレンオキシ基がより好ましく、硬化膜において式(1)又は式(2)を満たしやすくする観点からは、ポリアルキレンオキシ基が更に好ましい。
本発明において、ポリアルキレンオキシ基とは、アルキレンオキシ基が2以上直接結合した基をいう。ポリアルキレンオキシ基に含まれる複数のアルキレンオキシ基におけるアルキレン基は、それぞれ同一であっても異なっていてもよい。
ポリアルキレンオキシ基が、アルキレン基が異なる複数種のアルキレンオキシ基を含む場合、ポリアルキレンオキシ基におけるアルキレンオキシ基の配列は、ランダムな配列であってもよいし、ブロックを有する配列であってもよいし、交互等のパターンを有する配列であってもよい。
上記アルキレン基の炭素数(アルキレン基が置換基を有する場合、置換基の炭素数を含む)は、2以上であることが好ましく、2~10であることがより好ましく、2~6であることがより好ましく、2~5であることが更に好ましく、2~4であることが一層好ましく、2又は3であることが特に好ましく、2であることが最も好ましい。
また、上記アルキレン基は、置換基を有していてもよい。好ましい置換基としては、アルキル基、アリール基、ハロゲン原子等が挙げられる。
また、ポリアルキレンオキシ基に含まれるアルキレンオキシ基の数(ポリアルキレンオキシ基の繰り返し数)は、2~20が好ましく、2~10がより好ましく、2~6が更に好ましい。
ポリアルキレンオキシ基としては、溶剤溶解性及び耐溶剤性の観点からは、ポリエチレンオキシ基、ポリプロピレンオキシ基、ポリトリメチレンオキシ基、ポリテトラメチレンオキシ基、又は、複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基が好ましく、ポリエチレンオキシ基又はポリプロピレンオキシ基がより好ましく、ポリエチレンオキシ基が更に好ましい。上記複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基において、エチレンオキシ基とプロピレンオキシ基とはランダムに配列していてもよいし、ブロックを形成して配列していてもよいし、交互等のパターン状に配列していてもよい。これらの基におけるエチレンオキシ基等の繰り返し数の好ましい態様は上述の通りである。 In formula (III), R200 represents a hydrogen atom or a methyl group, and a hydrogen atom is preferable.
In formula (III), 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. , -CH 2 CH (OH) CH 2- , polyalkyleneoxy group, and ethylene group, propylene group, trimethylene group, -CH 2 CH (OH) CH 2- , polyalkyleneoxy group are more preferable, and the cured film. From the viewpoint of facilitating the filling of the formula (1) or the formula (2), the polyalkyleneoxy group is more preferable.
In the present invention, 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.
When the polyalkyleneoxy group contains a plurality of types of alkyleneoxy groups having different alkylene groups, 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.
Moreover, the said alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms and the like.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repetitions of the polyalkyleneoxy group) is preferably 2 to 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. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, 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.
R113又はR114が、水素原子、2-ヒドロキシベンジル、3-ヒドロキシベンジル及び4-ヒドロキシベンジルであることもより好ましい。 R 113 and R 114 are independently hydrogen atoms or monovalent organic groups. Examples of 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.
アルキル基の炭素数は1~30が好ましい。アルキル基は直鎖、分岐、環状のいずれであってもよい。直鎖又は分岐のアルキル基としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、オクタデシル基、イソプロピル基、イソブチル基、sec-ブチル基、t-ブチル基、1-エチルペンチル基、2-エチルヘキシル基2-(2-(2-メトキシエトキシ)エトキシ)エトキシ基、2-(2-(2-エトキシエトキシ)エトキシ)エトキシ)エトキシ基、2-(2-(2-(2-メトキシエトキシ)エトキシ)エトキシ)エトキシ基、及び2-(2-(2-(2-エトキシエトキシ)エトキシ)エトキシ)エトキシ基が挙げられる。環状のアルキル基は、単環の環状のアルキル基であってもよく、多環の環状のアルキル基であってもよい。単環の環状のアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基及びシクロオクチル基が挙げられる。多環の環状のアルキル基としては、例えば、アダマンチル基、ノルボルニル基、ボルニル基、カンフェニル基、デカヒドロナフチル基、トリシクロデカニル基、テトラシクロデカニル基、カンホロイル基、ジシクロヘキシル基及びピネニル基が挙げられる。中でも、高感度化との両立の観点から、シクロヘキシル基が最も好ましい。また、芳香族基で置換されたアルキル基としては、後述する芳香族基で置換された直鎖アルキル基が好ましい。
芳香族基としては、具体的には、置換又は無置換のベンゼン環、ナフタレン環、ペンタレン環、インデン環、アズレン環、ヘプタレン環、インダセン環、ペリレン環、ペンタセン環、アセナフテン環、フェナントレン環、アントラセン環、ナフタセン環、クリセン環、トリフェニレン環、フルオレン環、ビフェニル環、ピロール環、フラン環、チオフェン環、イミダゾール環、オキサゾール環、チアゾール環、ピリジン環、ピラジン環、ピリミジン環、ピリダジン環、インドリジン環、インドール環、ベンゾフラン環、ベンゾチオフェン環、イソベンゾフラン環、キノリジン環、キノリン環、フタラジン環、ナフチリジン環、キノキサリン環、キノキサゾリン環、イソキノリン環、カルバゾール環、フェナントリジン環、アクリジン環、フェナントロリン環、チアントレン環、クロメン環、キサンテン環、フェノキサチイン環、フェノチアジン環又はフェナジン環である。ベンゼン環が最も好ましい。 From the viewpoint of solubility in an organic solvent, 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. Examples of the linear or branched alkyl group 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-ethoxyethoxy) ethoxy) 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.
Specific examples of the aromatic group 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. Ring, naphthacene ring, chrysen ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indridin ring. , Indol ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinoline ring, quinoline ring, phthalazine ring, naphthylidine ring, quinoxalin ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthrene ring, acrydin ring, phenanthrene ring, It is a thianthrene ring, a chromene ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring or a phenazine ring. The benzene ring is most preferable.
酸分解性基の具体例としては、tert-ブトキシカルボニル基、イソプロポキシカルボニル基、テトラヒドロピラニル基、テトラヒドロフラニル基、エトキシエチル基、メトキシエチル基、エトキシメチル基、トリメチルシリル基、tert-ブトキシカルボニルメチル基、トリメチルシリルエーテル基などが挙げられる。露光感度の観点からは、エトキシエチル基、又は、テトラヒドロフラニル基が好ましい。 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.
Specific examples of the acid-degradable group 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.
式(2-A)
式(2-A)中、A1及びA2は、酸素原子を表し、R111及びR112は、それぞれ独立に、2価の有機基を表し、R113及びR114は、それぞれ独立に、水素原子又は1価の有機基を表し、R113及びR114の少なくとも一方は、重合性基を含む基であり、両方が重合性基であることが好ましい。 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.
R112は、式(5)におけるR112と同義であり、好ましい範囲も同様である。 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.
式(2-1)中、R111は、2価の有機基を表し、R115は、4価の有機基を表し、RX1及びRX2は、それぞれ独立に、式(1-1)で表される構造を含む基又は下記式(R-1)で表される基を表し、RX1及びRX2の少なくとも一方が、式(1-1)で表される構造を含む基を表す。
式(R-1)中、A3は酸素原子又はNHを表し、RX3は、それぞれ独立に、水素原子又は1価の有機基を表し、*はR115との結合部位を表す。 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).
In the formula (2-1), R 111 represents a divalent organic group, R 115 represents a tetravalent organic group, and 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).
In formula (R-1), A 3 represents an oxygen atom or NH, RX 3 independently represents a hydrogen atom or a monovalent organic group, and * represents a binding site with R 115.
上記式(1-1)で表される構造を含む基は、下記式(X-1)で表される基であることが好ましい。
式(X-1)中、R1及びR2はそれぞれ独立に、脂肪族基又は芳香族基を表し、上記脂肪族基又は芳香族基の炭素原子又は炭化水素基はヘテロ原子で置換されていてもよく、X1は酸素原子又は硫黄原子を表し、L1は-C(=O)-、又は、-S(=O)2-を表し、*はR115との結合部位を表す。
式(X-1)中、R1、R2、X1及びL1は式(1-1)中のR1、R2、X1及びL1と同義であり、好ましい態様も同様である。
式(X-1)中、R3は式(1-2)中のR23と同義であり、好ましい態様も同様である。 In formula (2-1), 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 a group represented by the following formula (X-1).
In 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. Alternatively, X 1 represents an oxygen atom or a sulfur atom, L 1 represents -C (= O)-or -S (= O) 2- , and * represents a bonding site with R 115.
In formula (X-1), 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 ..
In formula (X-1), R 3 has the same meaning as R 23 in formula (1-2), and the preferred embodiment is also the same.
式(R-1)中、A3及びRX3は、それぞれ、式(2)中のA2及びR113と同義であり、好ましい態様も同様である。 In formula (2-1), one of RX1 and RX2 may be a group represented by formula (R-1).
In formula (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.
ポリイミド前駆体における式(X-1)で表される基の含有量は、例えば、0.01~1.0mmol/gであることが好ましく、0.01~0.85mmol/gであることがより好ましい。 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.
上記ポリイミド前駆体の分子量の分散度は、2.5以上が好ましく、2.7以上がより好ましく、2.8以上であることが更に好ましい。ポリイミド前駆体の分子量の分散度の上限値は特に定めるものではないが、例えば、4.5以下が好ましく、4.0以下がより好ましく、3.8以下が更に好ましく、3.2以下が一層好ましく、3.1以下がより一層好ましく、3.0以下が更に一層好ましく、2.95以下が特に好ましい。
本明細書において、分子量の分散度とは、重量平均分子量/数平均分子量により算出される値である。 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.
In the present specification, the degree of molecular weight dispersion is a value calculated by weight average molecular weight / number average molecular weight.
本発明に用いられるポリイミドは、アルカリ可溶性ポリイミドであってもよく、有機溶剤を主成分とする現像液に対して可溶なポリイミドであってもよい。
本明細書において、アルカリ可溶性ポリイミドとは、100gの2.38質量%テトラメチルアンモニウム水溶液に対し、23℃で0.1g以上溶解するポリイミドをいい、パターン形成性の観点からは、0.5g以上溶解するポリイミドであることが好ましく、1.0g以上溶解するポリイミドであることが更に好ましい。上記溶解量の上限は特に限定されないが、100g以下であることが好ましい。
また、ポリイミドは、得られる硬化膜の膜強度及び絶縁性の観点からは、複数個のイミド構造を主鎖に有するポリイミドであることが好ましい。
本明細書において、「主鎖」とは、樹脂を構成する高分子化合物の分子中で相対的に最も長い結合鎖をいい、「側鎖」とはそれ以外の結合鎖をいう。 [Polyimide]
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.
In the present specification, 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.
Further, 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.
In the present specification, 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.
得られる硬化膜の膜強度の観点からは、ポリイミドは、フッ素原子を有することが好ましい。
フッ素原子は、例えば、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131にフッ化アルキル基として含まれることがより好ましい。
ポリイミドの全質量に対するフッ素原子の量は、1~50mol/gであることが好ましく、5~30mol/gであることがより好ましい。 -Fluorine atom-
From the viewpoint of the film strength of the obtained cured film, 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.
得られる硬化膜の膜強度の観点からは、ポリイミドは、ケイ素原子を有することが好ましい。
ケイ素原子は、例えば、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR131に後述する有機変性(ポリ)シロキサン構造として含まれることがより好ましい。
また、上記ケイ素原子又は上記有機変性(ポリ)シロキサン構造はポリイミドの側鎖に含まれていてもよいが、ポリイミドの主鎖に含まれることが好ましい。
ポリイミドの全質量に対するケイ素原子の量は、0.01~5mol/gであることが好ましく、0.05~1mol/gであることがより好ましい。 -Silicon atom-
From the viewpoint of the film strength of the obtained cured film, 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.
得られる硬化膜の膜強度の観点からは、ポリイミドは、エチレン性不飽和結合を有することが好ましい。
ポリイミドは、エチレン性不飽和結合を主鎖末端に有していてもよいし、側鎖に有していてもよいが、側鎖に有することが好ましい。
上記エチレン性不飽和結合は、ラジカル重合性を有することが好ましい。
エチレン性不飽和結合は、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131にエチレン性不飽和結合を有する基として含まれることがより好ましい。
これらの中でも、エチレン性不飽和結合は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましく、後述する式(4)で表される繰返し単位におけるR131にエチレン性不飽和結合を有する基として含まれることがより好ましい。
エチレン性不飽和結合を有する基としては、ビニル基、アリル基、ビニルフェニル基等の芳香環に直接結合した、置換されていてもよいビニル基を有する基、(メタ)アクリルアミド基、(メタ)アクリロイルオキシ基、下記式(IV)で表される基などが挙げられる。 -Ethylene unsaturated bond-
From the viewpoint of the film strength of the obtained cured film, 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. 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 a group having an ethylenically unsaturated bond.
Of these, 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).
式(R1)~(R3)中、Lは単結合、又は、炭素数2~12のアルキレン基、炭素数2~30の(ポリ)アルキレンオキシ基若しくはこれらを2以上結合した基を表し、Xは酸素原子又は硫黄原子を表し、*は他の構造との結合部位を表し、●は式(III)中のR201が結合する酸素原子との結合部位を表す。
式(R1)~(R3)中、Lにおける炭素数2~12のアルキレン基、又は、炭素数2~30の(ポリ)アルキレンオキシ基の好ましい態様は、上述のR21における、炭素数2~12のアルキレン基、又は、炭素数2~30の(ポリ)アルキレンオキシ基の好ましい態様と同様である。
式(R1)中、Xは酸素原子であることが好ましい。
式(R1)~(R3)中、*は式(IV)中の*と同義であり、好ましい態様も同様である。
式(R1)で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、イソシアナト基及びエチレン性不飽和結合を有する化合物(例えば、2-イソシアナトエチルメタクリレート等)とを反応することにより得られる。
式(R2)で表される構造は、例えば、カルボキシ基を有するポリイミドと、ヒドロキシ基及びエチレン性不飽和結合を有する化合物(例えば、2-ヒドロキシエチルメタクリレート等)とを反応することにより得られる。
式(R3)で表される構造は、例えば、フェノール性ヒドロキシ基等のヒドロキシ基を有するポリイミドと、グリシジル基及びエチレン性不飽和結合を有する化合物(例えば、グリシジルメタクリレート等)とを反応することにより得られる。
ポリアルキレンオキシ基としては、溶剤溶解性及び耐溶剤性の観点からは、ポリエチレンオキシ基、ポリプロピレンオキシ基、ポリトリメチレンオキシ基、ポリテトラメチレンオキシ基、又は、複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基が好ましく、ポリエチレンオキシ基又はポリプロピレンオキシ基がより好ましく、ポリエチレンオキシ基が更に好ましい。上記複数のエチレンオキシ基と複数のプロピレンオキシ基とが結合した基において、エチレンオキシ基とプロピレンオキシ基とはランダムに配列していてもよいし、ブロックを形成して配列していてもよいし、交互等のパターン状に配列していてもよい。これらの基におけるエチレンオキシ基等の繰り返し数の好ましい態様は上述の通りである。 Among these, 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).
In the formulas (R1) to (R3), 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, and X. Indicates an oxygen atom or a sulfur atom, * represents a bond site with another structure, and ● represents a bond site with an oxygen atom to which R 201 in the formula (III) is bonded.
In the formulas (R1) to (R3), 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.
In formula (R1), X is preferably an oxygen atom.
In formulas (R1) to (R3), * 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). can get.
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. In the group in which the plurality of ethyleneoxy groups and the plurality of propyleneoxy groups are bonded, 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.
ポリイミドは、エチレン性不飽和結合以外の架橋性基を有していてもよい。
エチレン性不飽和結合以外の架橋性基としては、エポキシ基、オキセタニル基等の環状エーテル基、メトキシメチル基等のアルコキシメチル基、メチロール基等が挙げられる。
エチレン性不飽和結合以外の架橋性基は、例えば、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましい。
ポリイミドの全質量に対するエチレン性不飽和結合以外の架橋性基の量は、0.05~10mol/gであることが好ましく、0.1~5mol/gであることがより好ましい。また、製造適性の観点では、ポリイミドの全質量に対するエチレン性不飽和結合以外の架橋性基の量は、0.0001~0.1mol/gであることが好ましく、0.001~0.05mol/gであることがより好ましい。 -Crosslinkable groups other than ethylenically unsaturated bonds-
The polyimide may have a crosslinkable group other than the ethylenically unsaturated bond.
Examples of 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.
ポリイミドは、酸分解性基等の極性変換基を有していてもよい。ポリイミドにおける酸分解性基は、上述の式(2)におけるR113及びR114において説明した酸分解性基と同様であり、好ましい態様も同様である。 -Polarity converter-
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.
ポリイミドがアルカリ現像に供される場合、現像性を向上する観点からは、ポリイミドの酸価は、30mgKOH/g以上であることが好ましく、50mgKOH/g以上であることがより好ましく、70mgKOH/g以上であることが更に好ましい。
また、上記酸価は500mgKOH/g以下であることが好ましく、400mgKOH/g以下であることがより好ましく、200mgKOH/g以下であることが更に好ましい。
また、ポリイミドが有機溶剤を主成分とする現像液を用いた現像(例えば、後述する「溶剤現像」)に供される場合、ポリイミドの酸価は、2~35mgKOH/gが好ましく、3~30mgKOH/gがより好ましく、5~20mgKOH/gが更に好ましい。
上記酸価は、公知の方法により測定され、例えば、JIS K 0070:1992に記載の方法により測定される。
また、ポリイミドに含まれる酸基としては、保存安定性及び現像性の両立の観点から、pKaが0~10である酸基が好ましく、3~8である酸基がより好ましい。
pKaとは、酸から水素イオンが放出される解離反応を考え、その平衡定数Kaをその負の常用対数pKaによって表したものである。
このような酸基として、ポリイミドは、カルボキシ基、及び、フェノール性ヒドロキシ基よりなる群から選ばれた少なくとも1種を含むことが好ましく、フェノール性ヒドロキシ基を含むことがより好ましい。 -Acid value-
When the polyimide is subjected to alkaline development, 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.
When the polyimide is subjected to development using a developing solution containing an organic solvent as a main component (for example, "solvent development" described later), 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.
Further, as the acid group contained in the polyimide, 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.
As such an acid group, 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.
アルカリ現像液による現像速度を適切なものとする観点からは、ポリイミドは、フェノール性ヒドロキシ基を有することが好ましい。
ポリイミドは、フェノール性ヒドロキシ基を主鎖末端に有してもよいし、側鎖に有してもよい。
フェノール性ヒドロキシ基は、例えば、後述する式(4)で表される繰返し単位におけるR132、又は、後述する式(4)で表される繰返し単位におけるR131に含まれることが好ましい。
ポリイミドの全質量に対するフェノール性ヒドロキシ基の量は、0.1~30mol/gであることが好ましく、1~20mol/gであることがより好ましい。 -Phenolic hydroxy group-
From the viewpoint of making the development speed with an alkaline developer appropriate, 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.
式(4)
式(4)中、R131は、2価の有機基を表し、R132は、4価の有機基を表す。
重合性基を有する場合、重合性基は、R131及びR132の少なくとも一方に位置していてもよいし、下記式(4-1)又は式(4-2)に示すようにポリイミドの末端に位置していてもよい。
式(4-1)中、R133は重合性基であり、他の基は式(4)と同義である。
R134及びR135の少なくとも一方は重合性基であり、重合性基でない場合は有機基であり、他の基は式(4)と同義である。 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.
In formula (4-1), 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).
R131は、2価の有機基を表す。2価の有機基としては、式(2)におけるR111と同様のものが例示され、好ましい範囲も同様である。
また、R131としては、ジアミンのアミノ基の除去後に残存するジアミン残基が挙げられる。ジアミンとしては、脂肪族、環式脂肪族又は芳香族ジアミンなどが挙げられる。具体的な例としては、ポリイミド前駆体の式(2)中のR111の例が挙げられる。 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.
例えば、R115として例示される4価の有機基の4つの結合子が、上記式(4)中の4つの-C(=O)-の部分と結合して縮合環を形成する。 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.
For example, four conjugates of a tetravalent organic group exemplified as R 115 combine with four −C (= O) − moieties in the above formula (4) to form a fused ring.
式(2-2)中、R131は2価の有機基を表し、R132は4価の有機基を表し、RX1及びRX2はそれぞれ独立に、式(1-1)で表される構造を含む基又は有機基を表し、RX1及びRX2のうち少なくとも一方が式(1-1)で表される構造を含む基である。
式(2-2)中、R131及びR132はそれぞれ式(4)中のR131及びR132と同義であり、好ましい態様も同様である。
式(2-1)中、RX1及びRX2の少なくとも一方が、式(1-1)で表される構造を含む基を表す。
上記式(1-1)で表される構造を含む基は、上述の式(X-1)で表される基であることが好ましい。 When the polyimide contains a structure represented by the formula (1-1), 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). ..
In the formula (2-2), R 131 represents a divalent organic group, R 132 represents a tetravalent organic group, and RX1 and RX2 are independently represented by the formula (1-1). It represents a group containing a structure or an organic group, and at least one of RX1 and RX2 is a group containing a structure represented by the formula (1-1).
Wherein (2-2), R 131 and R 132 have the same meanings as R 131 and R 132, respectively formula (4), preferred embodiments are also the same.
In formula (2-1), 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).
ポリイミドが式(2-1)で表される構造を含む場合、式(2-1)におけるRX1及びRX2の少なくとも一方は、閉環してイミド環を形成していてもよい。 Further, when the polyimide contains a structure represented by the formula (1-1), the polyimide may include a structure represented by the above formula (2-1).
When including a structure polyimide is represented by the formula (2-1), at least one of R X1 and R X2 in formula (2-1) may also form an imide ring cyclization.
ポリイミドのイミド化率(「閉環率」ともいう)は、得られる硬化膜の膜強度、絶縁性等の観点からは、70%以上であることが好ましく、80%以上であることがより好ましく、90%以上であることがより好ましい。
上記イミド化率の上限は特に限定されず、100%以下であればよい。
上記イミド化率は、例えば下記方法により測定される。
ポリイミドの赤外吸収スペクトルを測定し、イミド構造由来の吸収ピークである1377cm-1付近のピーク強度P1を求める。次に、そのポリイミドを350℃で1時間熱処理した後、再度、赤外吸収スペクトルを測定し、1377cm-1付近のピーク強度P2を求める。得られたピーク強度P1、P2を用い、下記式に基づいて、ポリイミドのイミド化率を求めることができる。
イミド化率(%)=(ピーク強度P1/ピーク強度P2)×100 -Immidization rate (ring closure rate)-
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. for 1 hour, and then the infrared absorption spectrum is measured again to obtain a peak intensity P2 in the vicinity of 1377 cm -1. Using the obtained peak intensities P1 and P2, the imidization rate of polyimide can be determined based on the following formula.
Imidization rate (%) = (peak intensity P1 / peak intensity P2) × 100
ポリイミドの市販品としては、Durimide(登録商標)284(富士フイルム(株)製)、Matrimide5218(HUNTSMAN(株)製)が例示される。 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 method of reacting a diamine compound with an anhydride or a monoacid chloride compound or a terminal capping agent which is a monoactive ester compound), a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then diamine (partly monoamine) is obtained. A method of reacting in the presence of a condensing agent with (replaced with an end-capping agent), a diester is obtained by tetracarboxylic acid dianhydride and alcohol, and then the remaining dicarboxylic acid is acid-chlorided to diamine (partly monoamine). 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. Can be done.
Examples of commercially available polyimide products include Durimide (registered trademark) 284 (manufactured by FUJIFILM Corporation) and Matrimide 5218 (manufactured by HUNTSMAN Corporation).
ポリイミド前駆体等は、ジカルボン酸又はジカルボン酸誘導体とジアミンとを反応させて得られる。好ましくは、ジカルボン酸又はジカルボン酸誘導体を、塩化チオニル等のハロゲン化剤を用いてハロゲン化させた後、ジアミンと反応させて得られる。 [Manufacturing method of polyimide precursor, etc.]
A polyimide precursor or the like is obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably, 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.
有機溶剤としては、原料に応じて適宜定めることができるが、ピリジン、ジエチレングリコールジメチルエーテル(ジグリム)、N-メチルピロリドン及びN-エチルピロリドンが例示される。
ポリイミドは、ポリイミド前駆体を合成してから、熱イミド化、化学イミド化(例えば、触媒を作用させることによる環化反応の促進)等の方法により環化させて製造してもよいし、直接、ポリイミドを合成してもよい。 In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. 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.
ポリイミド前駆体等の製造方法に際し、保存安定性をより向上させるため、酸無水物、モノカルボン酸、モノ酸クロリド化合物、モノ活性エステル化合物などの末端封止剤で、ポリイミド前駆体等の末端を封止することが好ましい。末端封止剤としては、モノアミンを用いることがより好ましく、モノアミンの好ましい化合物としては、アニリン、2-エチニルアニリン、3-エチニルアニリン、4-エチニルアニリン、5-アミノ-8-ヒドロキシキノリン、1-ヒドロキシ-7-アミノナフタレン、1-ヒドロキシ-6-アミノナフタレン、1-ヒドロキシ-5-アミノナフタレン、1-ヒドロキシ-4-アミノナフタレン、2-ヒドロキシ-7-アミノナフタレン、2-ヒドロキシ-6-アミノナフタレン、2-ヒドロキシ-5-アミノナフタレン、1-カルボキシ-7-アミノナフタレン、1-カルボキシ-6-アミノナフタレン、1-カルボキシ-5-アミノナフタレン、2-カルボキシ-7-アミノナフタレン、2-カルボキシ-6-アミノナフタレン、2-カルボキシ-5-アミノナフタレン、2-アミノ安息香酸、3-アミノ安息香酸、4-アミノ安息香酸、4-アミノサリチル酸、5-アミノサリチル酸、6-アミノサリチル酸、2-アミノベンゼンスルホン酸、3-アミノベンゼンスルホン酸、4-アミノベンゼンスルホン酸、3-アミノ-4,6-ジヒドロキシピリミジン、2-アミノフェノール、3-アミノフェノール、4-アミノフェノール、2-アミノチオフェノール、3-アミノチオフェノール、4-アミノチオフェノールなどが挙げられる。これらを2種以上用いてもよく、複数の末端封止剤を反応させることにより、複数の異なる末端基を導入してもよい。 -End sealant-
In order to further improve the storage stability in the method for producing a polyimide precursor, etc., 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-. Hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-amino Naphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy -6-Aminonaphthalene, 2-carboxy-5-Aminonaphthalene, 2-Aminobenzoic acid, 3-Aminobenzoic acid, 4-Aminobenzoic acid, 4-Aminosalicylic acid, 5-Aminosalicylic acid, 6-Aminosalicylic acid, 2- Aminobenzene sulfonic acid, 3-aminobenzene sulfonic acid, 4-aminobenzene sulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol , 3-Aminothiophenol, 4-Aminothiophenol and the like. Two or more of these may be used, and a plurality of different end groups may be introduced by reacting a plurality of end sealants.
ポリイミド前駆体等の製造に際し、固体を析出する工程を含んでいてもよい。具体的には、反応液中のポリイミド前駆体等を、水中に沈殿させ、テトラヒドロフラン等のポリイミド前駆体等が可溶な溶剤に溶解させることによって、固体析出することができる。
その後、ポリイミド前駆体等を乾燥して、粉末状のポリイミド前駆体等を得ることができる。 -Solid precipitation-
A step of precipitating a solid may be included in the production of the polyimide precursor or the like. Specifically, 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.
Then, the polyimide precursor or the like can be dried to obtain a powdery polyimide precursor or the like.
特定樹脂が式(1-1)で表される構造を含む場合、上記特定樹脂は、例えば、下記(1)又は(2)に記載の方法により合成される。
(1)上記ポリイミド前駆体の製造方法においてカルボジイミド化合物を非ハロゲン系触媒として用い、反応時間、反応温度、カルボジイミド化合物の添加タイミングを適宜調整する。
(2)上記ポリイミド前駆体の製造方法により得られたポリイミド前駆体又はポリイミドとカルボジイミド化合物とを溶剤中で反応させる。
これらの方法の具体例としては、後述する合成例に記載の方法が挙げられるが、これらに限定されるものではない。 -Introduction of the structure represented by equation (1-1)-
When 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.
(1) In the method for producing a polyimide precursor, 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.
(2) 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.
本発明の組成物における特定樹脂の含有量は、組成物の全固形分に対し20質量%以上であることが好ましく、30質量%以上であることがより好ましく、40質量%以上であることが更に好ましく、50質量%以上であることが一層好ましい。また、本発明の組成物における樹脂の含有量は、組成物の全固形分に対し、99.5質量%以下であることが好ましく、99質量%以下であることがより好ましく、98質量%以下であることが更に好ましく、97質量%以下であることが一層好ましく、95質量%以下であることがより一層好ましい。
本発明の樹脂組成物は、特定樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。 〔Content〕
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.
本発明の樹脂組成物は、上記式(1-1)で表される構造を含む化合物であって、上記樹脂とは異なる化合物(特定化合物)を含むことが好ましい。 <Specific compound>
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.
具体的には、特定化合物の分子量は、75~1,000であることが好ましく、100~800であることがより好ましく、150~500であることが更に好ましい。 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.
式(3-1)中、R1及びR2はそれぞれ独立に、脂肪族基又は芳香族基を表し、上記脂肪族基又は芳香族基の炭素原子又は炭化水素基はヘテロ原子で置換されていてもよく、X1は酸素原子又は硫黄原子を表し、L1は-C(=O)-、又は、-S(=O)2-を表し、R3は水素原子又は1価の有機基を表し、R4は1価の有機基を表し、R1、R2、R3及びR4のうち少なくとも2つが結合して環構造を形成してもよい。 The specific compound is preferably a compound represented by the following formula (3-1).
In 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, L 1 may represent -C (= O)-or-S (= O) 2- , and 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.
式(3-2)中、R3は式(1-2)中のR23と同義であり、好ましい態様も同様である。 In the formula (3-1), respectively 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.
In formula (3-2), R 3 has the same meaning as R 23 in formula (1-2), and the preferred embodiment is also the same.
上記炭化水素基としては、脂肪族炭化水素基又は芳香族炭化水素基が好ましく、芳香族炭化水素基がより好ましい。
上記脂肪族炭化水素基としては、炭素数1~20の飽和脂肪族炭化水素基が好ましく、炭素数3~10の飽和脂肪族炭化水素基がより好ましい。
上記芳香族炭化水素基としては、炭素数6~20の芳香族炭化水素基が好ましく、フェニル基又はナフチル基がより好ましく、フェニル基が更に好ましい。
R4における1価の有機基は置換基を有していてもよく、置換基としては、アルキル基、アルキルオキシカルボニル基、アリールオキシカルボニル基等があげられる。
これらの中でも、R4としては、フェニル基、アルキルフェニル基、又は、アルキルオキシカルボニルフェニル基が好ましく、フェニル基、t-ブチルフェニル基、又は、アルキル基の炭素数が1~4のアルキルオキシカルボニルフェニル基がさらに好ましい。 In the formula (3-1), R 4 is a monovalent organic group, preferably a hydrocarbon group.
As the hydrocarbon group, an aliphatic hydrocarbon group or an aromatic hydrocarbon group is preferable, and an aromatic hydrocarbon group is more preferable.
As the aliphatic hydrocarbon group, 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.
As 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.
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.
Among these, as 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.
また、本発明において、R1、R2、R3及びR4のいずれもが環構造を形成しない態様も好ましい態様の一つである。 In formula (3-1), at least two of R 1 , R 2 , R 3 and R 4 may be combined to form a ring structure. Examples of the ring structure formed include, but are not limited to, a hydantoin ring, an N-acylimidazolidinone ring, and the like.
Further, in the present invention, a mode in which none of R 1 , R 2 , R 3 and R 4 forms a ring structure is also a preferable mode.
また、樹脂組成物が特定化合物を含有する場合、その含有量は、例えば、本発明の樹脂組成物の全固形分に対して0.01~1.0質量%であることが好ましく、0.01~0.85質量%であることがより好ましく、0.015~0.75質量%であることが更に好ましい。
特定化合物は1種を単独で用いてもよいが、2種以上を用いてもよい。2種以上を併用する場合にはその合計量が上記の範囲となることが好ましい。 When the resin composition contains a specific compound, 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.
When the resin composition contains a specific compound, 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.
As 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.
本発明の樹脂組成物は、溶剤を含有する。溶剤は、公知の溶剤を任意に使用できる。溶剤は有機溶剤が好ましい。有機溶剤としては、エステル類、エーテル類、ケトン類、環式炭化水素類、スルホキシド類、アミド類、ウレア類、アルコール類などの化合物が挙げられる。 <Solvent>
The resin composition of the present invention contains a solvent. As the solvent, a known solvent can be arbitrarily used. The solvent is preferably an organic solvent. Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
本発明の組成物は、上述した特定樹脂以外に、特定樹脂とは異なる、他の樹脂(以下、単に「他の樹脂」ともいう。)を更に含んでもよい。
他の樹脂としては、ポリアミドイミド、ポリアミドイミド前駆体、フェノール樹脂、ポリアミド、エポキシ樹脂、ポリシロキサン、シロキサン構造を含む樹脂、アクリル樹脂等が挙げられる。
例えば、アクリル樹脂を更に加えることにより、塗布性に優れた組成物が得られ、また、耐溶剤性に優れた硬化膜が得られる。
例えば、後述する重合性化合物に代えて、又は、後述する重合性化合物に加えて、重量平均分子量が20,000以下の重合性基価の高いアクリル系樹脂を組成物に添加することにより、組成物の塗布性、硬化膜の耐溶剤性等を向上させることができる。 <Other resins>
In addition to the above-mentioned specific resin, the composition of the present invention may further contain another resin (hereinafter, also simply referred to as “other resin”) different from the specific resin.
Examples of other resins include polyamide-imide, polyamide-imide precursor, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, and acrylic resin.
For example, 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.
For example, 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.
また、本発明の組成物における、他の樹脂の含有量は、組成物の全固形分に対し、80質量%以下であることが好ましく、75質量%以下であることがより好ましく、70質量%以下であることが更に好ましく、60質量%以下であることが一層好ましく、50質量%以下であることがより一層好ましい。
また、本発明の組成物の好ましい一態様として、他の樹脂の含有量が低含有量である態様とすることもできる。上記態様において、他の樹脂の含有量は、組成物の全固形分に対し、20質量%以下であることが好ましく、15質量%以下であることがより好ましく、10質量%以下であることが更に好ましく、5質量%以下であることが一層好ましく、1質量%以下であることがより一層好ましい。上記含有量の下限は特に限定されず、0質量%以上であればよい。
本発明の組成物は、他の樹脂を1種のみ含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合、合計量が上記範囲となることが好ましい。 When the composition of the present invention contains another resin, 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.
Further, as a preferable aspect of the composition of the present invention, the content of the other resin may be low. In the above embodiment, 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.
本発明の樹脂組成物は、重合開始剤を含むことが好ましい。
重合開始剤としては、光重合開始剤が好ましい。 <Polymerization initiator>
The resin composition of the present invention preferably contains a polymerization initiator.
As the polymerization initiator, a photopolymerization initiator is preferable.
本発明の樹脂組成物は、光重合開始剤を含むことが好ましい。
光重合開始剤は、光ラジカル重合開始剤であることが好ましい。光ラジカル重合開始剤としては、特に制限はなく、公知の光ラジカル重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する光ラジカル重合開始剤が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよい。 [Photopolymerization initiator]
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. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet region to the visible region is preferable. Further, it may be an activator that produces an active radical by causing some action with the photoexcited sensitizer.
また、下記の構造のオキシム化合物を用いることもできる。
Further, an oxime compound having the following structure can also be used.
本発明の樹脂組成物は、重合開始剤として熱重合開始剤を含んでもよく、特に熱ラジカル重合開始剤を含んでもよい。熱ラジカル重合開始剤は、熱のエネルギーによってラジカルを発生し、重合性を有する化合物の重合反応を開始又は促進させる化合物である。熱ラジカル重合開始剤を添加することによって、後述する加熱工程において、特定樹脂及び重合性化合物の重合反応を進行させることもできるので、より耐薬品性を向上できる。 [Thermal polymerization initiator]
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.
また、本発明の組成物は、光酸発生剤を含んでもよい。
光酸発生剤を含有することで、例えば、組成物層の露光部に酸が発生して、上記露光部の現像液(例えば、アルカリ水溶液)に対する溶解性が増大し、露光部が現像液により除去されるポジ型のパターンを得ることができる。
また、組成物が、光酸発生剤と、後述するラジカル重合性化合物以外の重合性化合物とを含有することにより、例えば、露光部に発生した酸により上記重合性化合物の架橋反応が促進され、露光部が非露光部よりも現像液により除去されにくくなる態様とすることもできる。このような態様によれば、ネガ型のパターンを得ることができる。 [Photoacid generator]
In addition, the composition of the present invention may contain a photoacid generator.
By containing the 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.
Further, when 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.
上記ナフトキノンジアジド化合物としては、例えば、1,2-ナフトキノン-2-ジアジド-5-スルホン酸又は1,2-ナフトキノン-2-ジアジド-4-スルホン酸、これらの化合物の塩又はエステル化合物等が挙げられる。 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.
オキシムスルホネート化合物は、オキシムスルホネート基を有していれば特に制限はないが、下記式(OS-1)、後述する式(OS-103)、式(OS-104)、又は、式(OS-105)で表されるオキシムスルホネート化合物であることが好ましい。 The photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as “oxime sulfonate compound”).
The 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).
式(OS-1)中、m3は、0~3の整数を表し、0又は1が好ましい。m3が2又は3であるとき、複数のX3は同一でも異なっていてもよい。
式(OS-1)中、R34は、アルキル基又はアリール基を表し、炭素数1~10のアルキル基、炭素数1~10のアルコキシル基、炭素数1~5のハロゲン化アルキル基、炭素数1~5のハロゲン化アルコキシル基、Wで置換されていてもよいフェニル基、Wで置換されていてもよいナフチル基又はWで置換されていてもよいアントラニル基であることが好ましい。Wは、ハロゲン原子、シアノ基、ニトロ基、炭素数1~10のアルキル基、炭素数1~10のアルコキシル基、炭素数1~5のハロゲン化アルキル基又は炭素数1~5のハロゲン化アルコキシル基、炭素数6~20のアリール基、炭素数6~20のハロゲン化アリール基を表す。 Wherein (OS-1), 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 alkyl group in the above X 3, 1 to 4 carbon atoms, straight-chain or branched alkyl group is preferable. The alkoxyl group represented by X 3, preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom in the X 3, a chlorine atom or a fluorine atom is preferable.
In the formula (OS-1), 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.
In the formula (OS-1), 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.
式(OS-103)~式(OS-105)中、Rs1で表されるアルキル基(炭素数1~30が好ましい)、アリール基(炭素数6~30が好ましい)又はヘテロアリール基(炭素数4~30が好ましい)は、置換基Tを有していてもよい。 In formulas (OS-103) to (OS-105), R s1 represents an alkyl group, an aryl group or a heteroaryl group, and R s2, which may be present in a plurality of R s2, independently represents a hydrogen atom, an alkyl group and an aryl 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, and Xs represents O or S. Represents, ns represents 1 or 2, ms represents an integer of 0-6.
In formulas (OS-103) to (OS-105), an alkyl group represented by R s1 (preferably having 1 to 30 carbon atoms), an aryl group (preferably having 6 to 30 carbon atoms) or a heteroaryl group (carbon). (Preferably numbers 4 to 30) may have a substituent T.
式(OS-103)、式(OS-104)、又は、式(OS-105)中、XsはO又はSを表し、Oであることが好ましい。上記式(OS-103)~(OS-105)において、Xsを環員として含む環は、5員環又は6員環である。 In formulas (OS-103) to (OS-105), 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. Of the 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.
In the formula (OS-103), the formula (OS-104), or the formula (OS-105), Xs represents O or S, and is preferably O. In the above formulas (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
式(OS-103)~式(OS-105)中、Rs6で表されるアルキル基(炭素数1~30が好ましい)及びアルキルオキシ基(炭素数1~30が好ましい)は、置換基を有していてもよい。
式(OS-103)~式(OS-105)中、msは0~6の整数を表し、0~2の整数であることが好ましく、0又は1であることがより好ましく、0であることが特に好ましい。 In formulas (OS-103) to (OS-105), 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.
In the formulas (OS-103) to (OS-105), the alkyl group represented by R s6 (preferably having 1 to 30 carbon atoms) and the alkyloxy group (preferably having 1 to 30 carbon atoms) have substituents. You may have.
In the formulas (OS-103) to (OS-105), 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.
式(OS-106)~式(OS-111)中、Rt7は、水素原子又は臭素原子を表し、水素原子であることが好ましい。 In formulas (OS-106) to (OS-111), R t1 represents an alkyl group, an aryl group or a heteroaryl group, R t7 represents a hydrogen atom or a bromine atom, and 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, and R t2 represents a hydrogen atom or a methyl group.
In formulas (OS-106) to (OS-111), R t7 represents a hydrogen atom or a bromine atom, and is preferably a hydrogen atom.
Rt2は、水素原子又はメチル基を表し、水素原子であることが好ましい。
また、上記オキシムスルホネート化合物において、オキシムの立体構造(E,Z)については、いずれか一方であっても、混合物であってもよい。
上記式(OS-103)~式(OS-105)で表されるオキシムスルホネート化合物の具体例としては、特開2011-209692号公報の段落番号0088~0095、特開2015-194674号公報の段落番号0168~0194に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。 In formulas (OS-106) to (OS-111), 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.
Further, in the above-mentioned oxime sulfonate compound, 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.
式(OS-101)又は式(OS-102)中、Ru2aは、アルキル基又はアリール基を表す。
式(OS-101)又は式(OS-102)中、Xuは、-O-、-S-、-NH-、-NRu5-、-CH2-、-CRu6H-又はCRu6Ru7-を表し、Ru5~Ru7はそれぞれ独立に、アルキル基又はアリール基を表す。 In formula (OS-101) or formula (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. The embodiment in which 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.
In formula (OS-101) or formula (OS-102), Ru2a represents an alkyl or aryl group.
In formula (OS-101) or formula (OS-102), Xu is -O-, -S-, -NH- , -NR u5-, -CH 2- , -CR u6 H- or CR u6 R u7. Represents −, and R u5 to R u7 independently represent an alkyl group or an aryl group.
また、上記オキシムスルホネート化合物において、オキシムやベンゾチアゾール環の立体構造(E,Z等)についてはそれぞれ、いずれか一方であっても、混合物であってもよい。
式(OS-101)で表される化合物の具体例としては、特開2011-209692号公報の段落番号0102~0106、特開2015-194674号公報の段落番号0195~0207に記載の化合物が例示され、これらの内容は本明細書に組み込まれる。
上記化合物の中でも、b-9、b-16、b-31、b-33が好ましい。
その他、光酸発生剤としては市販品を使用してもよい。市販品としては、WPAG-145、WPAG-149、WPAG-170、WPAG-199、WPAG-336、WPAG-367、WPAG-370、WPAG-443、WPAG-469、WPAG-638、WPAG-699(いずれも富士フイルム和光純薬(株)製)、Omnicat 250、Omnicat 270(いずれもIGM Resins B.V.社製)、Irgacure 250、Irgacure 270、Irgacure 290(いずれもBASF社製)、MBZ-101(みどり化学(株)製)等が挙げられる。 The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
Further, in the above-mentioned oxime sulfonate compound, 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.
Among the above compounds, b-9, b-16, b-31, and b-33 are preferable.
In addition, a commercially available product may be used as the photoacid generator. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-376, WPAG-370, WPAG-443, WPAG-469, WPAG-638, and WPAG-69 (any of which). Also manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 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) (Made by Midori Chemical Industries, Ltd.) and the like.
より好適には、少なくとも一つのモノ、ジ、又はトリハロゲン置換メチル基がs-トリアジン環に結合したs-トリアジン誘導体、具体的には、例えば、2,4,6-トリス(モノクロロメチル)-s-トリアジン、2,4,6-トリス(ジクロロメチル)-s-トリアジン、2,4,6-トリス(トリクロロメチル)-s-トリアジン、2-メチル-4,6-ビス(トリクロロメチル)-s-トリアジン、2―n-プロピル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(α,α,β-トリクロロエチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-フェニル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-メトキシフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(3,4-エポキシフェニル)-4、6-ビス(トリクロロメチル)-s-トリアジン、2-(p-クロロフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-〔1-(p-メトキシフェニル)-2,4-ブタジエニル〕-4,6-ビス(トリクロロメチル)-s-トリアジン、2-スチリル-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-メトキシスチリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(p-i-プロピルオキシスチリル)-4、6-ビス(トリクロロメチル)-s-トリアジン、2-(p-トリル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-(4-ナトキシナフチル)-4,6-ビス(トリクロロメチル)-s-トリアジン、2-フェニルチオ-4,6-ビス(トリクロロメチル)-s-トリアジン、2-ベンジルチオ-4,6-ビス(トリクロロメチル)-s-トリアジン、2,4,6-トリス(ジブロモメチル)-s-トリアジン、2,4,6-トリス(トリブロモメチル)-s-トリアジン、2-メチル-4,6-ビス(トリブロモメチル)-s-トリアジン、2-メトキシ-4,6-ビス(トリブロモメチル)-s-トリアジン等が挙げられる。 As the photoacid generator, an organic halogenated compound can also be applied. Specific examples of 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. The compounds described in Hutt “Jurnal of Heterocyclic Chemistry” 1 (No. 3), (1970) and the like can be mentioned, and in particular, an oxazole compound substituted with a trihalomethyl group: an S-triazine compound can be mentioned.
More preferably, an s-triazine derivative in which at least one mono, di, or trihalogen-substituted methyl group is attached to the s-triazine ring, specifically, for example, 2,4,6-tris (monochromomethyl)-. s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl)- s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine , 2-Phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4-epoxy) Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-Butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine , 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s- Examples thereof include triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine and the like.
式(RI-I)中、Ar11は置換基を1~6有していても良い炭素数20以下のアリール基を表し、好ましい置換基としては炭素数1~12のアルキル基、炭素数1~12のアルケニル基、炭素数1~12のアルキニル基、炭素数1~12のアリール基、炭素数1~12のアルコキシ基、炭素数1~12のアリーロキシ基、ハロゲン原子、炭素数1~12のアルキルアミノ基、炭素数1~12のジアルキルアミノ基、炭素数1~12のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシル基、シアノ基、スルホニル基、炭素数1~12のチオアルキル基、炭素数1~12のチオアリール基が挙げられる。Z11-は1価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオンが好ましい。式(RI-II)中、Ar21、Ar22は各々独立に置換基を1~6有していても良い炭素数20以下のアリール基を表し、好ましい置換基としては炭素数1~12のアルキル基、炭素数1~12のアルケニル基、炭素数1~12のアルキニル基、炭素数1~12のアリール基、炭素数1~12のアルコキシ基、炭素数1~12のアリーロキシ基、ハロゲン原子、炭素数1~12のアルキルアミノ基、炭素数1~12のジアルキルアミノ基、炭素数1~12のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシル基、シアノ基、スルホニル基、炭素数1~12のチオアルキル基、炭素数1~12のチオアリール基が挙げられる。Z21 -は1価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。式(RI-III)中、R31、R32、R33は各々独立に置換基を1~6有していても良い炭素数20以下のアリール基又はアルキル基、アルケニル基、アルキニル基を表し、好ましくは反応性、安定性の面から、アリール基であることが望ましい。好ましい置換基としては炭素数1~12のアルキル基、炭素数1~12のアルケニル基、炭素数1~12のアルキニル基、炭素数1~12のアリール基、炭素数1~12のアルコキシ基、炭素数1~12のアリーロキシ基、ハロゲン原子、炭素数1~12のアルキルアミノ基、炭素数1~12のジアルキルアミノ基、炭素数1~12のアルキルアミド基又はアリールアミド基、カルボニル基、カルボキシル基、シアノ基、スルホニル基、炭素数1~12のチオアルキル基、炭素数1~12のチオアリール基が挙げられる。Z31-は1価の陰イオンを表し、ハロゲンイオン、過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、チオスルホン酸イオン、硫酸イオンであり、安定性、反応性の面から過塩素酸イオン、ヘキサフルオロホスフェートイオン、テトラフルオロボレートイオン、スルホン酸イオン、スルフィン酸イオン、カルボン酸イオンが好ましい。 Examples of the onium salt include onium salts represented by the following general formulas (RI-I) to (RI-III).
In the formula (RI-I), 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. An alkenyl group having 12 to 12, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, and 1 to 12 carbon atoms. Alkylamino group, dialkylamino group having 1 to 12 carbon atoms, alkylamide group or arylamide group having 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, thioalkyl group having 1 to 12 carbon atoms, Examples thereof include a thioaryl group having 1 to 12 carbon atoms. 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. In the formula (RI-II), 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. Alkyl group, alkenyl group having 1 to 12 carbon atoms, alkynyl group having 1 to 12 carbon atoms, aryl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryloxy group having 1 to 12 carbon atoms, halogen atom , Alkylamino group with 1 to 12 carbon atoms, dialkylamino group with 1 to 12 carbon atoms, alkylamide group or arylamide group with 1 to 12 carbon atoms, carbonyl group, carboxyl group, cyano group, sulfonyl group, 1 carbon number Examples thereof include a thioalkyl group having up to 12 and a thioaryl group having 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. In formula (RI-III), 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. , Preferably 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. Allyloxy group having 1 to 12 carbon atoms, halogen atom, alkylamino group having 1 to 12 carbon atoms, dialkylamino group having 1 to 12 carbon atoms, alkylamide group or arylamide group having 1 to 12 carbon atoms, carbonyl group, carboxyl 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.
本発明の組成物は、熱酸発生剤を含んでもよい。
熱酸発生剤は、加熱により酸を発生し、ヒドロキシメチル基、アルコキシメチル基又はアシルオキシメチル基を有する化合物、エポキシ化合物、オキセタン化合物及びベンゾオキサジン化合物から選ばれる少なくとも1種の化合物の架橋反応を促進させる効果がある。 <Thermal acid generator>
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.
熱分解開始温度は、熱酸発生剤を耐圧カプセル中5℃/分で500℃まで加熱した場合に、最も温度が低い発熱ピークのピーク温度として求められる。
熱分解開始温度を測定する際に用いられる機器としては、Q2000(TAインスツルメント社製)等が挙げられる。 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).
本発明の樹脂組成物は、オニウム塩を更に含んでもよい。
特に、本発明の樹脂組成物が特定樹脂としてポリイミド前駆体を含む場合、オニウム塩を含むことが好ましい。
オニウム塩の種類等は特に定めるものではないが、アンモニウム塩、イミニウム塩、スルホニウム塩、ヨードニウム塩又はホスホニウム塩が好ましく挙げられる。
これらの中でも、熱安定性が高い観点からはアンモニウム塩又はイミニウム塩が好ましく、ポリマーとの相溶性の観点からはスルホニウム塩、ヨードニウム塩又はホスホニウム塩が好ましい。 <Onium salt>
The resin composition of the present invention may further contain an onium salt.
In particular, when 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.
Among these, an ammonium salt or an iminium salt is preferable from the viewpoint of high thermal stability, and a sulfonium salt, an iodonium salt or a phosphonium salt is preferable from the viewpoint of compatibility with a polymer.
すなわち、オニウム塩は、同一の分子構造内に、カチオン部と、アニオン部と、を有する分子内塩であってもよいし、それぞれ別分子であるカチオン分子と、アニオン分子と、がイオン結合した分子間塩であってもよいが、分子間塩であることが好ましい。また、本発明の樹脂組成物において、上記カチオン部又はカチオン分子と、上記アニオン部又はアニオン分子と、はイオン結合により結合されていてもよいし、解離していてもよい。
オニウム塩におけるカチオンとしては、アンモニウムカチオン、ピリジニウムカチオン、スルホニウムカチオン、ヨードニウムカチオン又はホスホニウムカチオンが好ましく、テトラアルキルアンモニウムカチオン、スルホニウムカチオン及びヨードニウムカチオンよりなる群から選択される少なくとも1種のカチオンがより好ましい。 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.
As the cation in the onium salt, 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.
熱塩基発生剤とは、加熱により塩基を発生する化合物をいい、例えば、40℃以上に加熱すると塩基を発生する化合物等が挙げられる。
オニウム塩としては、例えば、国際公開第2018/043262号の段落0122~0138に記載のオニウム塩等が挙げられる。また、その他、ポリイミド前駆体の分野で使用されるオニウム塩を、特に制限なく使用することが可能である。 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. In addition, onium salts used in the field of polyimide precursors can be used without particular limitation.
オニウム塩は、1種又は2種以上を用いることができる。2種以上を用いる場合は、合計量が上記範囲であることが好ましい。 When the resin composition of the present invention contains an onium salt, 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.
As 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.
本発明の樹脂組成物は、熱塩基発生剤を更に含んでもよい。
特に、本発明の樹脂組成物が特定樹脂としてポリイミド前駆体を含む場合、熱塩基発生剤を含むことが好ましい。
他の熱塩基発生剤は、上述のオニウム塩に該当する化合物であってもよいし、上述のオニウム塩以外の熱塩基発生剤であってもよい。
上述のオニウム塩以外の熱塩基発生剤としては、ノニオン系熱塩基発生剤が挙げられる。
ノニオン系熱塩基発生剤としては、式(B1)又は式(B2)で表される化合物が挙げられる。
The resin composition of the present invention may further contain a thermal base generator.
In particular, 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.
Examples of the thermobase generator other than the above-mentioned onium salt include nonionic thermobase generators.
Examples of the nonionic thermobase generator include compounds represented by the formula (B1) or the formula (B2).
Rb13はアルキル基(炭素数1~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アルケニル基(炭素数2~24が好ましく、2~18がより好ましく、3~12が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)であり、本発明の効果を奏する範囲で置換基を有していてもよい。中でも、Rb13はアリールアルキル基が好ましい。 In the formula, 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.
Rb15及びRb16は水素原子、アルキル基(炭素数1~12が好ましく、1~6がより好ましく、1~3が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~6がより好ましく、2~3が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~10が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~11が更に好ましい)であり、水素原子又はメチル基が好ましい。
Rb17はアルキル基(炭素数1~24が好ましく、1~12がより好ましく、3~8が更に好ましい)、アルケニル基(炭素数2~12が好ましく、2~10がより好ましく、3~8が更に好ましい)、アリール基(炭素数6~22が好ましく、6~18がより好ましく、6~12が更に好ましい)、アリールアルキル基(炭素数7~23が好ましく、7~19がより好ましく、7~12が更に好ましい)であり、中でもアリール基が好ましい。 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). ~ 19 is more preferable, and 7 to 11 is more preferable), and a hydrogen atom or a methyl group is preferable.
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.
本発明の樹脂組成物は、架橋剤を含むことが好ましい。
架橋剤としては、ラジカル架橋剤、又は、他の架橋剤が挙げられる。 <Crosslinking agent>
The resin composition of the present invention preferably contains a cross-linking agent.
Examples of the cross-linking agent include radical cross-linking agents and other cross-linking agents.
本発明の樹脂組成物は、ラジカル架橋剤を更に含むことが好ましい。
ラジカル架橋剤は、ラジカル重合性基を有する化合物である。ラジカル重合性基としては、エチレン性不飽和結合を含む基が好ましい。上記エチレン性不飽和結合を含む基としては、ビニル基、アリル基、ビニルフェニル基、(メタ)アクリロイル基などのエチレン性不飽和結合を有する基が挙げられる。
これらの中でも、上記エチレン性不飽和結合を含む基としては、(メタ)アクリロイル基が好ましく、反応性の観点からは、(メタ)アクリロキシ基がより好ましい。 <Radical cross-linking agent>
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. As the radically polymerizable group, a group containing an ethylenically unsaturated bond is preferable. Examples of 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.
Among these, 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.
エチレン性不飽和結合を2個有する化合物は、上記エチレン性不飽和結合を含む基を2個有する化合物であることが好ましい。
また、得られるパターン(硬化膜)の膜強度の観点からは、本発明の樹脂組成物は、ラジカル架橋剤として、エチレン性不飽和結合を3個以上有する化合物を含むことが好ましい。上記エチレン性不飽和結合を3個以上有する化合物としては、エチレン性不飽和結合を3~15個有する化合物が好ましく、エチレン性不飽和結合を3~10個有する化合物がより好ましく、3~6個有する化合物が更に好ましい。
また、上記エチレン性不飽和結合を3個以上有する化合物は、上記エチレン性不飽和結合を含む基を3個以上有する化合物であることが好ましく、3~15個有する化合物であることがより好ましく、3~10個有する化合物であることが更に好ましく、3~6個有する化合物であることが特に好ましい。
また、得られるパターン(硬化膜)の膜強度の観点からは、本発明の樹脂組成物は、エチレン性不飽和結合を2個有する化合物と、上記エチレン性不飽和結合を3個以上有する化合物とを含むことも好ましい。 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.
Further, from the viewpoint of the film strength of the obtained pattern (cured film), the resin composition of the present invention preferably contains a compound having three or more ethylenically unsaturated bonds as a radical cross-linking agent. As 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.
Further, from the viewpoint of the film strength of the obtained pattern (cured film), 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.
また、パターン(硬化膜)の弾性率制御に伴う反り抑制の観点から、ラジカル架橋剤として、単官能ラジカル架橋剤を好ましく用いることができる。単官能ラジカル架橋剤としては、n-ブチル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、カルビトール(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、フェノキシエチル(メタ)アクリレート、N-メチロール(メタ)アクリルアミド、グリシジル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート等の(メタ)アクリル酸誘導体、N-ビニルピロリドン、N-ビニルカプロラクタム等のN-ビニル化合物類、アリルグリシジルエーテル、ジアリルフタレート、トリアリルトリメリテート等のアリル化合物類等が好ましく用いられる。単官能ラジカル架橋剤としては、露光前の揮発を抑制するため、常圧下で100℃以上の沸点を持つ化合物も好ましい。 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 having urethane bonds can be used. can. If necessary, two or more of these can be mixed and used. For example, the PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula of about 200.
Further, from the viewpoint of suppressing warpage associated with the control of the elastic modulus of the pattern (cured film), 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. As 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.
本発明の樹脂組成物は、上述したラジカル架橋剤とは異なる、他の架橋剤を含むことが好ましい。
本発明において、他の架橋剤とは、上述したラジカル架橋剤以外の架橋剤をいい、上述の感光剤の感光により、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が促進される基を分子内に複数個有する化合物であることが好ましく、組成物中の他の化合物又はその反応生成物との間で共有結合を形成する反応が酸又は塩基の作用によって促進される基を分子内に複数個有する化合物が好ましい。
上記酸又は塩基は、露光工程において、感光剤から発生する酸又は塩基であることが好ましい。
他の架橋剤としては、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも一種の基を有する化合物が好ましく、メチロール基及びアルコキシメチル基よりなる群から選ばれた少なくとも一種の基が窒素原子に直接結合した構造を有する化合物がより好ましい。
他の架橋剤としては、例えば、メラミン、グリコールウリル、尿素、アルキレン尿素、ベンゾグアナミンなどのアミノ基含有化合物にホルムアルデヒド又はホルムアルデヒドとアルコールを反応させ、上記アミノ基の水素原子をメチロール基又はアルコキシメチル基で置換した構造を有する化合物が挙げられる。これらの化合物の製造方法は特に限定されず、上記方法により製造された化合物と同様の構造を有する化合物であればよい。また、これらの化合物のメチロール基同士が自己縮合してなるオリゴマーであってもよい。
上記のアミノ基含有化合物として、メラミンを用いた架橋剤をメラミン系架橋剤、グリコールウリル、尿素又はアルキレン尿素を用いた架橋剤を尿素系架橋剤、アルキレン尿素を用いた架橋剤をアルキレン尿素系架橋剤、ベンゾグアナミンを用いた架橋剤をベンゾグアナミン系架橋剤という。
これらの中でも、本発明の樹脂組成物は、尿素系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことが好ましく、後述するグリコールウリル系架橋剤及びメラミン系架橋剤よりなる群から選ばれた少なくとも1種の化合物を含むことがより好ましい。 <Other cross-linking agents>
The resin composition of the present invention preferably contains another cross-linking agent different from the above-mentioned radical cross-linking agent.
In the present invention, 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.
As the other cross-linking agent, 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.
As another cross-linking agent, for example, 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.
As the above amino group-containing compound, 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, and 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.
Among these, 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.
ビスメトキシメチル尿素、ビスエトキシメチル尿素、ビスプロポキシメチル尿素、ビスブトキシメチル尿素等の尿素系架橋剤、
モノヒドロキシメチル化エチレン尿素又はジヒドロキシメチル化エチレン尿素、モノメトキシメチル化エチレン尿素、ジメトキシメチル化エチレン尿素、モノエトキシメチル化エチレン尿素、ジエトキシメチル化エチレン尿素、モノプロポキシメチル化エチレン尿素、ジプロポキシメチル化エチレン尿素、モノブトキシメチル化エチレン尿素、又は、ジブトキシメチル化エチレン尿素などのエチレン尿素系架橋剤、
モノヒドロキシメチル化プロピレン尿素、ジヒドロキシメチル化プロピレン尿素、モノメトキシメチル化プロピレン尿素、ジメトキシメチル化プロピレン尿素、モノジエトキシメチル化プロピレン尿素、ジエトキシメチル化プロピレン尿素、モノプロポキシメチル化プロピレン尿素、ジプロポキシメチル化プロピレン尿素、モノブトキシメチル化プロピレン尿素、又は、ジブトキシメチル化プロピレン尿素などのプロピレン尿素系架橋剤、
1,3-ジ(メトキシメチル)4,5-ジヒドロキシ-2-イミダゾリジノン、1,3-ジ(メトキシメチル)-4,5-ジメトキシ-2-イミダゾリジノンなどが挙げられる。 Specific examples of the urea-based cross-linking agent include monohydroxymethylated glycol uryl, dihydroxymethylated glycol uryl, trihydroxymethylated glycol uryl, tetrahydroxymethylated glycol uryl, monomethoxymethylated glycol uryl, and dimethoxymethylated glycol uryl. , Trimethoxymethylated glycol uryl, tetramethoxymethylated glycol uryl, monomethoxymethylated glycol uryl, dimethoxymethylated glycol uryl, trimethoxymethylated glycol uryl, tetraethoxymethylated glycol uryl, monopropoxymethylated glycol uryl, di Propoxymethylated glycol uryl, tripropoxymethylated glycol uryl, tetrapropoxymethylated glycol uryl, monobutoxymethylated glycol uryl, dibutoxymethylated glycol uryl, tributoxymethylated glycol uryl, or tetrabutoxymethylated glycol uryl, etc. Glycoluryl-based cross-linking agent;
Urea-based cross-linking agents 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, monopropoxymethylated propylene urea, dipropoxy A propylene urea-based cross-linking agent such as methylated propylene urea, monobutoxymethylated propylene urea, or dibutoxymethylated propylene urea,
Examples thereof include 1,3-di (methoxymethyl) 4,5-dihydroxy-2-imidazolidinone and 1,3-di (methoxymethyl) -4,5-dimethoxy-2-imidazolidinone.
このような化合物の具体例としては、ベンゼンジメタノール、ビス(ヒドロキシメチル)クレゾール、ビス(ヒドロキシメチル)ジメトキシベンゼン、ビス(ヒドロキシメチル)ジフェニルエーテル、ビス(ヒドロキシメチル)ベンゾフェノン、ヒドロキシメチル安息香酸ヒドロキシメチルフェニル、ビス(ヒドロキシメチル)ビフェニル、ジメチルビス(ヒドロキシメチル)ビフェニル、ビス(メトキシメチル)ベンゼン、ビス(メトキシメチル)クレゾール、ビス(メトキシメチル)ジメトキシベンゼン、ビス(メトキシメチル)ジフェニルエーテル、ビス(メトキシメチル)ベンゾフェノン、メトキシメチル安息香酸メトキシメチルフェニル、ビス(メトキシメチル)ビフェニル、ジメチルビス(メトキシメチル)ビフェニル、4,4’,4’’-エチリデントリス[2,6-ビス(メトキシメチル)フェノール]、5,5’-[2,2,2‐トリフルオロ‐1‐(トリフルオロメチル)エチリデン]ビス[2‐ヒドロキシ‐1,3‐ベンゼンジメタノール]、3,3’,5,5’-テトラキス(メトキシメチル)-1,1’-ビフェニル-4,4’-ジオール等が挙げられる。 In addition, as 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. , Bis (hydroxymethyl) biphenyl, dimethylbis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) Benzophenone, methoxymethylphenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethylbis (methoxymethyl) biphenyl, 4,4', 4''-ethylidentris [2,6-bis (methoxymethyl) phenol], 5 , 5'-[2,2,2-trifluoro-1- (trifluoromethyl) ethylidene] bis [2-hydroxy-1,3-benzenedimethanol], 3,3', 5,5'-tetrakis ( Examples thereof include methoxymethyl) -1,1'-biphenyl-4,4'-diol.
エポキシ化合物としては、一分子中にエポキシ基を2以上有する化合物であることが好ましい。エポキシ基は、200℃以下で架橋反応し、かつ、架橋に由来する脱水反応が起こらないため膜収縮が起きにくい。このため、エポキシ化合物を含有することは、樹脂組成物の低温硬化及び反りの抑制に効果的である。 [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.
オキセタン化合物としては、一分子中にオキセタン環を2つ以上有する化合物、3-エチル-3-ヒドロキシメチルオキセタン、1,4-ビス{[(3-エチル-3-オキセタニル)メトキシ]メチル}ベンゼン、3-エチル-3-(2-エチルヘキシルメチル)オキセタン、1,4-ベンゼンジカルボン酸-ビス[(3-エチル-3-オキセタニル)メチル]エステル等を挙げることができる。具体的な例としては、東亞合成(株)製のアロンオキセタンシリーズ(例えば、OXT-121、OXT-221、OXT-191、OXT-223)が好適に使用することができ、これらは単独で、又は2種以上混合してもよい。 [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. As a specific example, 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.
ベンゾオキサジン化合物は、開環付加反応に由来する架橋反応のため、硬化時に脱ガスが発生せず、更に熱収縮を小さくして反りの発生が抑えられることから好ましい。 [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.
本発明の樹脂組成物は、更にマイグレーション抑制剤を含むことが好ましい。マイグレーション抑制剤を含むことにより、金属層(金属配線)由来の金属イオンが樹脂組成物層内へ移動することを効果的に抑制可能となる。 <Migration inhibitor>
The resin composition of the present invention preferably further contains 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.
本発明の樹脂組成物は、重合禁止剤を含むことが好ましい。 <Polymerization inhibitor>
The resin composition of the present invention preferably contains a polymerization inhibitor.
本発明の樹脂組成物は、電極や配線などに用いられる金属材料との接着性を向上させるための金属接着性改良剤を含むことが好ましい。金属接着性改良剤としては、シランカップリング剤、アルミニウム系接着助剤、チタン系接着助剤、スルホンアミド構造を有する化合物及びチオウレア構造を有する化合物、リン酸誘導体化合物、βケトエステル化合物、アミノ化合物等などが挙げられる。 <Metal adhesion improver>
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. Examples of 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, β-ketoester compounds, amino compounds and the like. And so on.
他のシランカップリング剤としては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、3-グリシドキシプロピルトリエトキシシラン、p-スチリルトリメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-アクリロキシプロピルトリメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-トリエトキシシリル-N-(1,3-ジメチル-ブチリデン)プロピルアミン 、N-フェニル-3-アミノプロピルトリメトキシシラン、トリス-(トリメトキシシリルプロピル)イソシアヌレー、3-ウレイドプロピルトリアルコキシシラン、3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-イソシアネートプロピルトリエトキシシラン、3-トリメトキシシリルプロピルコハク酸無水物が挙げられる。これらは1種単独または2種以上を組み合わせて使用することができる。
Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycid. Xipropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxy Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2 -(Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-Phyl-3-aminopropyltrimethoxysilane, Tris- (trimethoxysilylpropyl) isocyanure, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanuppropyl Examples thereof include triethoxysilane and 3-trimethoxysilylpropyl succinate anhydride. These can be used alone or in combination of two or more.
アルミニウム系接着助剤としては、例えば、アルミニウムトリス(エチルアセトアセテート)、アルミニウムトリス(アセチルアセトネート)、エチルアセトアセテートアルミニウムジイソプロピレート等を挙げることができる。 [Aluminum-based adhesive aid]
Examples of the aluminum-based adhesive aid include aluminum tris (ethylacetacetate), aluminumtris (acetylacetoneate), ethylacetacetate aluminum diisopropirate, and the like.
本発明の樹脂組成物は、本発明の効果が得られる範囲で、必要に応じて、各種の添加物、例えば、増感剤、連鎖移動剤、界面活性剤、高級脂肪酸誘導体、無機粒子、硬化剤、硬化触媒、充填剤、酸化防止剤、紫外線吸収剤、凝集防止剤等を配合することができる。これらの添加剤を配合する場合、その合計配合量は樹脂組成物の固形分の3質量%以下とすることが好ましい。 <Other additives>
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. 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.
本発明の樹脂組成物は、増感剤を含んでいてもよい。増感剤は、特定の活性放射線を吸収して電子励起状態となる。電子励起状態となった増感剤は、熱硬化促進剤、熱ラジカル重合開始剤、光ラジカル重合開始剤などと接触して、電子移動、エネルギー移動、発熱などの作用が生じる。これにより、熱硬化促進剤、熱ラジカル重合開始剤、光ラジカル重合開始剤は化学変化を起こして分解し、ラジカル、酸又は塩基を生成する。
増感剤としては、例えば、ミヒラーズケトン、4,4’-ビス(ジエチルアミノ)ベンゾフェノン、2,5-ビス(4’-ジエチルアミノベンザル)シクロペンタン、2,6-ビス(4’-ジエチルアミノベンザル)シクロヘキサノン、2,6-ビス(4’-ジエチルアミノベンザル)-4-メチルシクロヘキサノン、4,4’-ビス(ジメチルアミノ)カルコン、4,4’-ビス(ジエチルアミノ)カルコン、p-ジメチルアミノシンナミリデンインダノン、p-ジメチルアミノベンジリデンインダノン、2-(p-ジメチルアミノフェニルビフェニレン)-ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)ベンゾチアゾール、2-(p-ジメチルアミノフェニルビニレン)イソナフトチアゾール、1,3-ビス(4’-ジメチルアミノベンザル)アセトン、1,3-ビス(4’-ジエチルアミノベンザル)アセトン、3,3’-カルボニル-ビス(7-ジエチルアミノクマリン)、3-アセチル-7-ジメチルアミノクマリン、3-エトキシカルボニル-7-ジメチルアミノクマリン、3-ベンジロキシカルボニル-7-ジメチルアミノクマリン、3-メトキシカルボニル-7-ジエチルアミノクマリン、3-エトキシカルボニル-7-ジエチルアミノクマリン、N-フェニル-N’-エチルエタノールアミン、N-フェニルジエタノールアミン、N-p-トリルジエタノールアミン、N-フェニルエタノールアミン、4-モルホリノベンゾフェノン、ジメチルアミノ安息香酸イソアミル、ジエチルアミノ安息香酸イソアミル、2-メルカプトベンズイミダゾール、1-フェニル-5-メルカプトテトラゾール、2-メルカプトベンゾチアゾール、2-(p-ジメチルアミノスチリル)ベンズオキサゾール、2-(p-ジメチルアミノスチリル)ベンズチアゾール、2-(p-ジメチルアミノスチリル)ナフト(1,2-d)チアゾール、2-(p-ジメチルアミノベンゾイル)スチレン、ジフェニルアセトアミド、ベンズアニリド、N-メチルアセトアニリド、3‘,4’-ジメチルアセトアニリド等が挙げられる。
増感剤としては、増感色素を用いてもよい。
増感色素の詳細については、特開2016-027357号公報の段落0161~0163の記載を参酌でき、この内容は本明細書に組み込まれる。 [Sensitizer]
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. As a result, the thermosetting accelerator, the thermal radical polymerization initiator, and the photoradical polymerization initiator undergo a chemical change and decompose to generate radicals, acids, or bases.
Examples of the sensitizer include Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 2,5-bis (4'-diethylaminobenzal) cyclopentane, and 2,6-bis (4'-diethylaminobenzal). Cyclohexanone, 2,6-bis (4'-diethylaminobenzal) -4-methylcyclohexanone, 4,4'-bis (dimethylamino) chalcone, 4,4'-bis (diethylamino) chalcone, p-dimethylaminocinnamyl Denindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylbiphenylene) -benzothiazole, 2- (p-dimethylaminophenylvinylene) benzothiazole, 2- (p-dimethylaminophenylvinylene) iso Naftthiazole, 1,3-bis (4'-dimethylaminobenzal) acetone, 1,3-bis (4'-diethylaminobenzal) acetone, 3,3'-carbonyl-bis (7-diethylaminocoumarin), 3 -Acetone-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylamino Kumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, Np-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercapto Benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzthiazole, 2- (p-dimethylaminostyryl) ) Naft (1,2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3', 4'-dimethylacetanilide and the like.
As the sensitizer, a sensitizing dye may be used.
For details of the sensitizing dye, the description in paragraphs 0161 to 0163 of JP-A-2016-0273557 can be referred to, and this content is incorporated in the present specification.
本発明の樹脂組成物は、連鎖移動剤を含有してもよい。連鎖移動剤は、例えば高分子辞典第三版(高分子学会編、2005年)683-684頁に定義されている。連鎖移動剤としては、例えば、分子内にSH、PH、SiH、及びGeHを有する化合物群が用いられる。これらは、低活性のラジカルに水素を供与して、ラジカルを生成するか、若しくは、酸化された後、脱プロトンすることによりラジカルを生成しうる。特に、チオール化合物を好ましく用いることができる。 [Chain transfer agent]
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. In particular, a thiol compound can be preferably used.
本発明の樹脂組成物には、塗布性をより向上させる観点から、各種類の界面活性剤を添加してもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種類の界面活性剤を使用できる。また、下記界面活性剤も好ましい。下記式中、主鎖の繰返し単位を示す括弧は各繰返し単位の含有量(モル%)を、側鎖の繰返し単位を示す括弧は各繰返し単位の繰り返し数をそれぞれ表す。
また、界面活性剤は、国際公開第2015/199219号の段落0159~0165に記載の化合物を用いることもできる。
フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する含フッ素重合体をフッ素系界面活性剤として用いることもできる。具体例としては、特開2010-164965号公報の段落0050~0090および段落0289~0295に記載された化合物、例えばDIC(株)製のメガファックRS-101、RS-102、RS-718K等が挙げられる。 [Surfactant]
Each type of surfactant may be added to the resin composition of the present invention from the viewpoint of further improving the coatability. As 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. In the following formula, the parentheses indicating the repeating unit of the main chain represent the content (mol%) of each repeating unit, and the parentheses indicating the repeating unit of the side chain represent the number of repetitions of each repeating unit.
Further, as the surfactant, the compound described in paragraphs 0159 to 0165 of International Publication No. 2015/199219 can also be used.
As the 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.
本発明の樹脂組成物は、酸素に起因する重合阻害を防止するために、ベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体を添加して、塗布後の乾燥の過程で樹脂組成物の表面に偏在させてもよい。 [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.
本発明の樹脂組成物は、無機粒子を含んでもよい。無機粒子として、具体的には、炭酸カルシウム、リン酸カルシウム、シリカ、カオリン、タルク、二酸化チタン、アルミナ、硫酸バリウム、フッ化カルシウム、フッ化リチウム、ゼオライト、硫化モリブデン、ガラス等を含むことができる。 [Inorganic particles]
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.
上記無機粒子の平均粒子径を多量に含有させることによって、上記硬化膜の機械特性が劣化することがある。また、上記無機粒子の平均粒子径が2.0μmを超えると、露光光の散乱によって解像度が低下することがある。 The average particle size of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, further preferably 0.03 to 1.0 μm, and 0.04 to 0.5 μm. Especially preferable.
By containing a large amount of the average particle size of the inorganic particles, the mechanical properties of the cured film may deteriorate. Further, if the average particle size of the inorganic particles exceeds 2.0 μm, the resolution may decrease due to scattering of exposure light.
本発明の組成物は、紫外線吸収剤を含んでいてもよい。紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、トリアジン系などの紫外線吸収剤を使用することができる。
サリシレート系紫外線吸収剤の例としては、フェニルサリシレート、p-オクチルフェニルサリシレート、p-t-ブチルフェニルサリシレートなどが挙げられ、ベンゾフェノン系紫外線吸収剤の例としては、2,2’-ジヒドロキシ-4-メトキシベンゾフェノン、2,2’-ジヒドロキシ-4,4’-ジメトキシベンゾフェノン、2,2’,4,4’-テトラヒドロキシベンゾフェノン、2-ヒドロキシ-4-メトキシベンゾフェノン、2,4-ジヒドロキシベンゾフェノン、2-ヒドロキシ-4-オクトキシベンゾフェノンなどが挙げられる。また、ベンゾトリアゾール系紫外線吸収剤の例としては、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-ブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-tert-アミル-5’-イソブチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-メチルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’-イソブチル-5’-プロピルフェニル)-5-クロロベンゾトリアゾール、2-(2’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェニル)ベンゾトリアゾール、2-(2’-ヒドロキシ-5’-メチルフェニル)ベンゾトリアゾール、2-[2’-ヒドロキシ-5’-(1,1,3,3-テトラメチル)フェニル]ベンゾトリアゾールなどが挙げられる。 [UV absorber]
The composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, an ultraviolet absorber such as salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, or triazine-based can be used.
Examples of salicylate-based ultraviolet absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate and the like, and examples of 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. Examples of benzotriazole-based ultraviolet absorbers include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3). '-Tert-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2-( 2'-Hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2 -(2'-Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5' -(1,1,3,3-tetramethyl) phenyl] benzotriazole and the like can be mentioned.
本発明の組成物は、紫外線吸収剤を含んでも含まなくてもよいが、含む場合、紫外線吸収剤の含有量は、本発明の組成物の全固形分質量に対して、0.001質量%以上1質量%以下であることが好ましく、0.01質量%以上0.1質量%以下であることがより好ましい。 In the present invention, 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.
本実施形態の樹脂組成物は、有機チタン化合物を含有してもよい。樹脂組成物が有機チタン化合物を含有することにより、低温で硬化した場合であっても耐薬品性に優れる樹脂層を形成できる。 [Organic titanium compound]
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.
有機チタン化合物の具体例を、以下のI)~VII)に示す:
I)チタンキレート化合物:中でも、ネガ型感光性樹脂組成物の保存安定性がよく、良好な硬化パターンが得られることから、アルコキシ基を2個以上有するチタンキレート化合物がより好ましい。具体的な例は、チタニウムビス(トリエタノールアミン)ジイソプロポキサイド、チタニウムジ(n-ブトキサイド)ビス(2,4-ペンタンジオネート、チタニウムジイソプロポキサイドビス(2,4-ペンタンジオネート)、チタニウムジイソプロポキサイドビス(テトラメチルヘプタンジオネート)、チタニウムジイソプロポキサイドビス(エチルアセトアセテート)等である。
II)テトラアルコキシチタン化合物:例えば、チタニウムテトラ(n-ブトキサイド)、チタニウムテトラエトキサイド、チタニウムテトラ(2-エチルヘキソキサイド)、チタニウムテトライソブトキサイド、チタニウムテトライソプロポキサイド、チタニウムテトラメトキサイド、チタニウムテトラメトキシプロポキサイド、チタニウムテトラメチルフェノキサイド、チタニウムテトラ(n-ノニロキサイド)、チタニウムテトラ(n-プロポキサイド)、チタニウムテトラステアリロキサイド、チタニウムテトラキス[ビス{2,2-(アリロキシメチル)ブトキサイド}]等である。
III)チタノセン化合物:例えば、ペンタメチルシクロペンタジエニルチタニウムトリメトキサイド、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロフェニル)チタニウム、ビス(η5-2,4-シクロペンタジエン-1-イル)ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)フェニル)チタニウム等である。
IV)モノアルコキシチタン化合物:例えば、チタニウムトリス(ジオクチルホスフェート)イソプロポキサイド、チタニウムトリス(ドデシルベンゼンスルホネート)イソプロポキサイド等である。
V)チタニウムオキサイド化合物:例えば、チタニウムオキサイドビス(ペンタンジオネート)、チタニウムオキサイドビス(テトラメチルヘプタンジオネート)、フタロシアニンチタニウムオキサイド等である。
VI)チタニウムテトラアセチルアセトネート化合物:例えば、チタニウムテトラアセチルアセトネート等である。
VII)チタネートカップリング剤:例えば、イソプロピルトリドデシルベンゼンスルホニルチタネート等である。 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) and the like.
II) 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.
III) Titanosen compounds: for example, pentamethylcyclopentadienyl titanium trimethoxide, bis (η5-2,4-cyclopentadiene-1-yl) bis (2,6-difluorophenyl) titanium, bis (η5-2, 2). 4-Cyclopentadiene-1-yl) bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium and the like.
IV) Monoalkoxytitanium compound: For example, titanium tris (dioctyl phosphate) isopropoxyside, titanium tris (dodecylbenzene sulfonate) isopropoxide, and the like.
V) Titanium oxide compound: For example, titanium oxide bis (pentanionate), titanium oxide bis (tetramethylheptandionate), phthalocyanine titanium oxide and the like.
VI) Titanium tetraacetylacetone compound: For example, titanium tetraacetylacetone.
VII) Titanate Coupling Agent: For example, isopropyltridodecylbenzenesulfonyl titanate and the like.
本発明の組成物は、酸化防止剤を含んでいてもよい。添加剤として酸化防止剤を含有することで、硬化後の膜の伸度特性や、金属材料との密着性を向上させることができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位(オルト位)に置換基を有する化合物が好ましい。前述の置換基としては炭素数1~22の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス[2-[[2,4,8,10-テトラキス(1,1-ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル]オキシ]エチル]アミン、トリス[2-[(4,6,9,11-テトラ-tert-ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン-2-イル)オキシ]エチル]アミン、亜リン酸エチルビス(2,4-ジ-tert-ブチル-6-メチルフェニル)などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ AO-20、アデカスタブ AO-30、アデカスタブ AO-40、アデカスタブ AO-50、アデカスタブ AO-50F、アデカスタブ AO-60、アデカスタブ AO-60G、アデカスタブ AO-80、アデカスタブ AO-330(以上、(株)ADEKA製)などが挙げられる。また、酸化防止剤は、特許第6268967号公報の段落番号0023~0048に記載された化合物を使用することもできる。また、本発明の組成物は、必要に応じて、潜在酸化防止剤を含有してもよい。潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、100~250℃で加熱するか、又は酸/塩基触媒存在下で80~200℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては、国際公開第2014/021023号、国際公開第2017/030005号、特開2017-008219号公報に記載された化合物が挙げられる。潜在酸化防止剤の市販品としては、アデカアークルズGPA-5001((株)ADEKA製)等が挙げられる。好ましい酸化防止剤の例としては、2,2-チオビス(4-メチル-6-t-ブチルフェノール)、2,6-ジ-t-ブチルフェノールおよび一般式(3)で表される化合物が挙げられる。 〔Antioxidant〕
The composition of the present invention may contain 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. Examples of the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like. As 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. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Further, as the antioxidant, a compound having a phenol group and a phosphite ester group in the same molecule is also preferable. Further, as the antioxidant, a phosphorus-based antioxidant can also be preferably used. As 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. Commercially available products of 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. Further, as the antioxidant, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used. In addition, 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. Examples of preferred antioxidants include 2,2-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds represented by the general formula (3).
本発明の樹脂組成物の水分含有量は、塗布面性状の観点から、5質量%未満が好ましく、1質量%未満がより好ましく、0.6質量%未満が更に好ましい。水分の含有量を維持する方法としては、保管条件における湿度の調整、収容容器の空隙率低減などが挙げられる。 <Restrictions on other contained substances>
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.
ハロゲン原子の含有量を調節する方法としては、イオン交換処理などが好ましく挙げられる。 Considering the use as a semiconductor material, 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. Examples of 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.
As a method for adjusting the content of halogen atoms, ion exchange treatment and the like are preferably mentioned.
本発明の樹脂組成物は、再配線層用層間絶縁膜の形成に用いられることが好ましい。
また、その他、半導体デバイスの絶縁膜の形成、又は、ストレスバッファ膜の形成等にも用いることができる。 <Use of resin composition>
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.
本発明の樹脂組成物は、上記各成分を混合して調製することができる。混合方法は特に限定はなく、従来公知の方法で行うことができる。 <Preparation of resin composition>
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.
フィルターを用いたろ過の他、吸着材を用いた不純物の除去処理を行ってもよい。フィルターろ過と吸着材を用いた不純物除去処理とを組み合わせてもよい。吸着材としては、公知の吸着材を用いることができる。例えば、シリカゲル、ゼオライトなどの無機系吸着材、活性炭などの有機系吸着材が挙げられる。 Further, it is preferable to perform filtration using a filter for the purpose of removing foreign substances such as dust and fine particles in the resin composition. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, 5 μm or less is preferable, 3 μm or less is more preferable, and 1 μm 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. When using a plurality of types of filters, filters having different pore diameters or materials may be used in combination. Moreover, you may filter various materials a plurality of times. 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. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
次に、硬化膜、積層体、半導体デバイス、及びそれらの製造方法について説明する。 (Cured film, laminate, semiconductor device, and manufacturing method thereof)
Next, a cured film, a laminate, a semiconductor device, and a method for manufacturing them will be described.
本発明の硬化膜の製造方法は、上記膜形成工程、並びに、上記膜を露光する露光工程及び上記膜を現像する現像工程を含むことが好ましい。
また、本発明の硬化膜の製造方法は、上記膜形成工程、及び、必要に応じて上記現像工程を含み、かつ、上記膜を50~450℃で加熱する加熱工程を含むことがより好ましい。
具体的には、以下の(a)~(d)の工程を含むことも好ましい。
(a)樹脂組成物を基材に適用して膜(樹脂組成物層)を形成する膜形成工程
(b)膜形成工程の後、膜を露光する露光工程
(c)露光された上記膜を現像する現像工程
(d)現像された上記膜を50~450℃で加熱する加熱工程
上記加熱工程において加熱することにより、露光で硬化した樹脂層を更に硬化させることができる。この加熱工程で、例えば上述の熱塩基発生剤が分解し、十分な硬化性が得られる。 The method for producing a cured film of the present invention (hereinafter, also simply referred to as "the method for producing 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.
Further, 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).
(A) Film forming step of applying the resin composition to the substrate to form a film (resin composition layer) (b) Exposure step of exposing the film after the film forming step (c) The exposed film Development step for developing (d) Heating step for heating the developed film at 50 to 450 ° C. By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the above-mentioned thermal base generator is decomposed to obtain sufficient curability.
本発明の好ましい実施形態に係る製造方法は、樹脂組成物を基材に適用して膜(層状)にする、膜形成工程(層形成工程)を含む。 <Film formation process (layer formation process)>
The production method according to a preferred embodiment of the present invention includes a film forming step (layer forming step) in which the resin composition is applied to a substrate to form a film (layered).
がより好ましい。
また、これらの基材にはヘキサメチルジシラザン(HMDS)等による密着層や酸化層などの層が表面に設けられていてもよい。
また、基材としては、例えば板状の基材(基板)が用いられる。
基材の形状は特に限定されず、円形状であっても矩形状であってもよいが、矩形状であることが好ましい。
基材のサイズとしては、円形状であれば、例えば直径が100~450mmであり、好ましくは200~450mmである。矩形状であれば、例えば短辺の長さが100~1000mmであり、好ましくは200~700mmである。 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.
Further, 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.
Further, as 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.
また、あらかじめ仮支持体上に上記付与方法によって付与して形成した塗膜を、基材上に転写する方法を適用することもできる。
転写方法に関しては特開2006-023696号公報の段落0023、0036~0051や、特開2006-047592号公報の段落0096~0108に記載の作製方法を本発明においても好適に用いることができる。
また、基材の端部において余分な膜の除去を行なう工程を行なってもよい。このような工程の例には、エッジビードリンス(EBR)、エアナイフ、バックリンスなどが挙げられる。
また樹脂組成物を基材に塗布する前に基材を種々の溶剤を塗布し、基材の濡れ性を向上させた後に樹脂組成物を塗布するプリウェット工程を採用しても良い。 Specifically, as the applicable means, the dip coating method, the air knife coating method, the curtain coating method, the wire bar coating method, the gravure coating method, the extrusion coating method, the spray coating method, the spin coating method, the slit coating method, etc. And 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. For a circular base material such as a wafer, 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. In the case of 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. Further, in order to obtain the uniformity of the film thickness, 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.
本発明の製造方法は、上記膜(樹脂組成物層)を形成後、膜形成工程(層形成工程)の後に、溶剤を除去するために乾燥する工程を含んでいてもよい。好ましい乾燥温度は50~150℃で、70℃~130℃がより好ましく、90℃~110℃が更に好ましい。乾燥時間としては、30秒~20分が例示され、1分~10分が好ましく、3分~7分がより好ましい。 <Drying process>
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.
本発明の製造方法は、上記膜(樹脂組成物層)を露光する露光工程を含んでもよい。露光量は、樹脂組成物を硬化できる限り特に定めるものではないが、例えば、波長365nmでの露光エネルギー換算で100~10,000mJ/cm2照射することが好ましく、200~8,000mJ/cm2照射することがより好ましい。 <Exposure process>
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.
また取り扱いと生産性の観点では、高圧水銀灯のブロード(g,h,i線の3波長)光源や半導体レーザー405nmも好適である。 In relation to the light source, 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. Line (wavelength 405 nm), i-line (wavelength 365 nm), broad (3 wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer Examples thereof include a laser (wavelength 157 nm), (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, and the like. 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. As a result, particularly high exposure sensitivity can be obtained.
From the viewpoint of handling and productivity, 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.
本発明の製造方法は、露光された膜(樹脂組成物層)に対して、現像を行う(上記膜を現像する)現像工程を含んでもよい。現像を行うことにより、露光されていない部分(非露光部)が除去される。現像方法は、所望のパターンを形成できれば特に制限は無く、例えばノズルからの現像液の吐出、スプレー噴霧、基材の現像液浸漬などが挙げられ、ノズルからの吐出が好ましく利用される。現像工程には、現像液が連続的に基材に供給され続ける工程、基材上で現像液が略静止状態で保たれる工程、現像液を超音波等で振動させる工程およびそれらを組み合わせた工程などが採用可能である。 <Development process>
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.
現像液としては、有機溶剤を含む現像液、又は、アルカリ水溶液を用いることができる。 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.
現像液の供給方法は、所望のパターンを形成できれば特に制限は無く、基材を現像液に浸漬する方法、基材上にノズルを用いて現像液を供給しパドル現像、または、現像液を連続供給する方法がある。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
現像液の浸透性、非画像部の除去性、製造上の効率の観点から、現像液をストレートノズルで供給する方法、又はスプレーノズルにて連続供給する方法が好ましく、画像部への現像液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。
また、現像液をストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去し、スピン乾燥後に再度ストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去する工程を採用してもよく、この工程を複数回繰り返しても良い。
また現像工程における現像液の供給方法としては、現像液が連続的に基材に供給され続ける工程、基材上で現像液が略静止状態で保たれる工程、基材上で現像液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。 [Method of supplying developer]
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. From the viewpoint of permeability, 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.
現像液の供給方法は、所望のパターンを形成できれば特に制限は無く、基材を現像液に浸漬する方法、基材上にノズルを用いて現像液を供給しパドル現像、または、現像液を連続供給する方法がある。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
現像液の浸透性、非画像部の除去性、製造上の効率の観点から、現像液をストレートノズルで供給する方法、又はスプレーノズルにて連続供給する方法が好ましく、画像部への現像液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。
また、現像液をストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去し、スピン乾燥後に再度ストレートノズルにて連続供給後、基材をスピンし現像液を基材上から除去する工程を採用してもよく、この工程を複数回繰り返しても良い。
また現像工程における現像液の供給方法としては、現像液が連続的に基材に供給され続ける工程、基材上で現像液が略静止状態で保たれる工程、基材上で現像液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。 [Method of supplying developer]
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. From the viewpoint of permeability, 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.
リンスは、現像液とは異なる溶剤で行うことが好ましい。例えば、樹脂組成物に含まれる溶剤を用いてリンスすることができる。
現像液が有機溶剤を含む現像液である場合、リンス液としては、PGMEA(プロピレングリコールモノエチルエーテルアセテート)、IPA(イソプロパノール)などが挙げられ、好ましくはPGMEAである。また、アルカリ水溶液を含む現像液による現像に対するリンス液としては、水が好ましい。
リンス時間は、10秒~10分間が好ましく、20秒~5分間がより好ましく、5秒~1分が好ましい。リンス時のリンス液の温度は、特に定めるものではないが、好ましくは、10~45℃、より好ましくは、18℃~30℃で行うことができる。 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.
When the developer is a developer containing an organic solvent, examples of the rinse solution include PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropanol), and the like, preferably PGMEA. Further, 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.
他の成分としては、例えば、公知の界面活性剤や公知の消泡剤等が挙げられる。 The rinse solution may further contain other components.
Examples of other components include known surfactants and known defoamers.
リンス液の供給方法は、所望のパターンを形成できれば特に制限は無く、基材をリンス液に浸漬する方法、基材上でのパドル現像、基材にリンス液をシャワーで供給する方法、基材上にストレートノズル等の手段により現像液を連続供給する方法がある。
リンス液の浸透性、非画像部の除去性、製造上の効率の観点から、リンス液をシャワーノズル、ストレートノズル、スプレーノズルなどで供給する方法があり、スプレーノズルにて連続供給する方法が好ましく、画像部へのリンス液の浸透性の観点からは、スプレーノズルで供給する方法がより好ましい。ノズルの種類は特に制限は無く、ストレートノズル、シャワーノズル、スプレーノズル等が挙げられる。
すなわち、リンス工程は、リンス液を上記露光後の膜に対してストレートノズルにより供給、又は、連続供給する工程であることが好ましく、リンス液をスプレーノズルにより供給する工程であることがより好ましい。
またリンス工程におけるリンス液の供給方法としては、リンス液が連続的に基材に供給され続ける工程、基材上でリンス液が略静止状態で保たれる工程、基材上でリンス液を超音波等で振動させる工程及びそれらを組み合わせた工程などが採用可能である。 [Supplying method of rinse liquid]
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. There is a method of continuously supplying the developing solution by means such as a straight nozzle on the top.
From the viewpoint of the permeability of the rinse liquid, the removability of non-image areas, and the efficiency of manufacturing, there is a method of supplying the rinse liquid with a shower nozzle, a straight nozzle, a spray nozzle, etc., and a method of continuously supplying the rinse liquid with a spray nozzle is preferable. From the viewpoint of the permeability of the rinse liquid into the image portion, 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.
Further, as a method of supplying the rinse liquid in the rinsing step, 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.
本発明の製造方法は、現像された上記膜を50~450℃で加熱する工程(加熱工程)を含むことが好ましい。
加熱工程は、膜形成工程(層形成工程)、乾燥工程、及び現像工程の後に含まれることが好ましい。加熱工程では、例えば上述の熱塩基発生剤が分解することにより塩基が発生し、特定樹脂である前駆体の環化反応が進行する。また、本発明の樹脂組成物は特定樹脂である前駆体以外のラジカル重合性化合物を含んでいてもよいが、未反応の特定樹脂である前駆体以外のラジカル重合性化合物の硬化などもこの工程で進行させることができる。加熱工程における層の加熱温度(最高加熱温度)としては、50℃以上であることが好ましく、80℃以上であることがより好ましく、140℃以上であることが更に好ましく、150℃以上であることが一層好ましく、160℃以上であることがより一層好ましく、170℃以上であることが更に一層好ましい。上限としては、500℃以下であることが好ましく、450℃以下であることがより好ましく、350℃以下であることが更に好ましく、250℃以下であることが一層好ましく、220℃以下であることがより一層好ましい。 <Heating process>
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. In the heating step, for example, the above-mentioned thermal base generator decomposes to generate a base, and the cyclization reaction of the precursor, which is a specific resin, proceeds. Further, 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.
加熱手段としては、特に限定されないが、例えばホットプレート、赤外炉、電熱式オーブン、熱風式オーブンなどが挙げられる。 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.
本発明の製造方法は、現像後の膜(樹脂組成物層)の表面に金属層を形成する金属層形成工程を含むことが好ましい。 <Metal layer forming process>
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).
本発明の製造方法は、更に、積層工程を含むことが好ましい。 <Laminating process>
The production method of the present invention preferably further includes a laminating step.
また、積層工程における各層は、組成、形状、膜厚等が同一の層であってもよいし、異なる層であってもよい。 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.
本発明の積層体の製造方法は、上記金属層および感光性樹脂組成物層の少なくとも一部を表面活性化処理する、表面活性化処理工程を含んでもよい。
表面活性化処理工程は、通常、金属層形成工程の後に行うが、上記露光現像工程の後、感光性樹脂組成物層に表面活性化処理工程を行ってから、金属層形成工程を行ってもよい。
表面活性化処理は、金属層の少なくとも一部のみに行ってもよいし、露光後の感光性樹脂組成物層の少なくとも一部のみに行ってもよいし、金属層および露光後の感光性樹脂組成物層の両方について、それぞれ、少なくとも一部に行ってもよい。表面活性化処理は、金属層の少なくとも一部について行うことが好ましく、金属層のうち、表面に感光性樹脂組成物層を形成する領域の一部または全部に表面活性化処理を行うことが好ましい。このように、金属層の表面に表面活性化処理を行うことにより、その表面に設けられる樹脂層との密着性を向上させることができる。
また、表面活性化処理は、露光後の感光性樹脂組成物層(樹脂層)の一部または全部についても行うことが好ましい。このように、感光性樹脂組成物層の表面に表面活性化処理を行うことにより、表面活性化処理した表面に設けられる金属層や樹脂層との密着性を向上させることができる。
表面活性化処理としては、具体的には、各種原料ガス(酸素、水素、アルゴン、窒素、窒素/水素混合ガス、アルゴン/酸素混合ガスなど)のプラズマ処理、コロナ放電処理、CF4/O2、NF3/O2、SF6、NF3、NF3/O2によるエッチング処理、紫外線(UV)オゾン法による表面処理、塩酸水溶液に浸漬して酸化皮膜を除去した後にアミノ基とチオール基を少なくとも一種有する化合物を含む有機表面処理剤への浸漬処理、ブラシを用いた機械的な粗面化処理から選択され、プラズマ処理が好ましく、特に原料ガスに酸素を用いた酸素プラズマ処理が好ましい。コロナ放電処理の場合、エネルギーは、500~200,000J/m2が好ましく、1000~100,000J/m2がより好ましく、10,000~50,000J/m2が最も好ましい。 (Surface activation treatment process)
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. .. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion to the resin layer provided on the surface can be improved.
Further, it is preferable that the surface activation treatment is performed on a part or all of the photosensitive resin composition layer (resin layer) after exposure. By performing the surface activating treatment on the surface of the photosensitive resin composition layer in this way, it is possible to improve the adhesion to the metal layer or the resin layer provided on the surface of the surface activating treatment.
Specifically, 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. For corona discharge treatment, 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.
〔ピロメリット酸二無水物、4,4’-ジアミノジフェニルエーテルおよび2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-1)の合成〕
14.06g(64.5ミリモル)のピロメリット酸二無水物(140℃で12時間乾燥したもの)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4gのピリジン(258ミリモル)と、100gのダイグライム(ジエチレングリコールジメチルエーテル)を混合し、60℃の温度で18時間撹拌して、ピロメリット酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、反応混合物を-10℃に冷却し、温度を-10±4℃に保ちながら16.12g(135.5ミリモル)のSOCl2を10分かけて加えた。SOCl2を加えている間、粘度が増加した。50mLのN-メチルピロリドンで希釈した後、反応混合物を室温で2時間撹拌した。次いで、100mLのN-メチルピロリドンに11.08g(58.7ミリモル)の4,4’-ジアミノジフェニルエーテルを溶解させた溶液を、-5~0℃で20分かけて反応混合物に滴下した。次いで、反応混合物を0℃で1時間反応させたのち、エタノールを70g加えて、室温で1晩撹拌した。次いで、5リットルの水の中でポリイミド前駆体を沈殿させ、水-ポリイミド前駆体混合物を5,000rpm(revolutions per minute)の速度で15分間撹拌した。ポリイミド前駆体をろ過して取得し、4リットルの水の中で再度30分間撹拌し再びろ過した。次いで、得られたポリイミド前駆体を減圧下で、45℃で3日間乾燥し、ポリイミド前駆体A-1を得た。このポリイミド前駆体A-1の重量平均分子量は、19,000であった。得られたポリイミド前駆体A-1は、下記式(A-1)で表される繰り返し単位を含むと推測される。
[Synthesis of polyimide precursor (A-1) from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]
14.06 g (64.5 mmol) of pyromellitic dianhydride (dried at 140 ° C. for 12 hours), 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, 20.4 g of pyridine (258 mmol) and 100 g of diglyme (diethylene glycol dimethyl ether) were mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. The 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. Then, a solution prepared by dissolving 11.08 g (58.7 mmol) of 4,4′-diaminodiphenyl ether in 100 mL of N-methylpyrrolidone was added dropwise to the reaction mixture at −5 to 0 ° C. over 20 minutes. Then, the reaction mixture was reacted at 0 ° C. for 1 hour, 70 g of ethanol was added, and the mixture was stirred at room temperature overnight. The polyimide precursor was then precipitated in 5 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, 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).
〔3,3’,4,4’-ビフェニルテトラカルボン酸無水物、4,4’-ジアミノジフェニルエーテル及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-2)の合成〕
20.0g(64.5ミリモル)の3,3’,4,4’-ビフェニルテトラカルボン酸無水物(140℃で12時間乾燥したもの)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4g(258ミリモル)のピリジンと、100gのダイグライムとを混合し(含水率88ppm)、60℃の温度で18時間撹拌して、3,3’,4,4’-ビフェニルテトラカルボン酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOCl2により塩素化した後、合成例1と同様の方法で4,4’-ジアミノジフェニルエーテルでポリイミド前駆体に変換し、合成例1と同様の方法でポリイミド前駆体A-2を得た。このポリイミド前駆体A-2の重量平均分子量は、20,000であった。得られたポリイミド前駆体A-2は、下記式(A-2)で表される繰り返し単位を含むと推測される。
式(A-2)で表される繰返し単位には、3,3’,4,4’-ビフェニルテトラカルボン酸無水物に由来するビフェニル構造に含まれる単結合と、3,3’,4,4’-ビフェニルテトラカルボン酸無水物、及び、2-ヒドロキシエチルメタクリレートにより形成されるエステル構造とが、ベンゼン環上のメタ位に存在する場合と、パラ位に存在する場合(例えば、下記式(A-2-2)で表される繰返し単位等)とがあり、ポリイミド前駆体A-2にはこれらの構造が混在していると考えられる。
同様に、以下、合成例における、酸二無水物として3,3’,4,4’-ビフェニルテトラカルボン酸無水物又は4,4’-オキシジフタル酸無水物を用いた場合に製造されるポリイミド前駆体に含まれる繰返し単位を示す化学式において、3,3’,4,4’-ビフェニルテトラカルボン酸無水物に由来するビフェニル構造に含まれる単結合、又は、4,4’-オキシジフタル酸無水物に含まれるエーテル結合と、各繰返し単位に含まれるベンゼン環に結合するエステル結合及びアミド結合とのベンゼン環上の位置関係は、化学式として記載した構造に限定されず、上記位置関係が異なるものも混在しているものとする。
[Synthesis of polyimide precursor (A-2) from 3,3', 4,4'-biphenyltetracarboxylic acid anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]
20.0 g (64.5 mmol) of 3,3', 4,4'-biphenyltetracarboxylic dianhydride (dried at 140 ° C. for 12 hours) and 16.8 g (129 mmol) of 2-hydroxyethyl Methacrylate, 0.05 g of hydroquinone, 20.4 g (258 mmol) of pyridine, and 100 g of diglime were mixed (moisture content: 88 ppm) and stirred at a temperature of 60 ° C. for 18 hours to produce 3,3', Diesters of 4,4'-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate were prepared. Next, 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. I got -2. 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, When the 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.
Similarly, hereinafter, 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. In the chemical formula indicating the repeating unit contained in the body, the single bond contained in the biphenyl structure derived from 3,3', 4,4'-biphenyltetracarboxylic acid anhydride, or 4,4'-oxydiphthalic acid anhydride. 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.
〔4,4’-オキシジフタル酸無水物、4,4’-ジアミノジフェニルエーテルおよび2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-3)の合成〕
20.0g(64.5ミリモル)の4,4’-オキシジフタル酸無水物(140℃で12時間乾燥したもの)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4gのピリジン(258ミリモル)と、100gのダイグライムとを混合し、60℃の温度で18時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOCl2により塩素化した後、合成例1と同様の方法で4,4’-ジアミノジフェニルエーテルでポリイミド前駆体に変換し、合成例1と同様の方法でポリイミド前駆体を得た。このポリイミド前駆体の重量平均分子量は、18,000であった。得られたポリイミド前駆体A-3は、下記式(A-3)で表される繰り返し単位を含むと推測される。
[Synthesis of polyimide precursor (A-3) from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether 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. Hydroquinone, 20.4 g of pyridine (258 mmol) and 100 g of diglyme are mixed and stirred at a temperature of 60 ° C. for 18 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. did. Next, 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).
〔4,4’-オキシジフタル酸無水物、4,4’-ジアミノ-2,2’-ジメチルビフェニル(オルトトリジン)及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A-4)の合成〕
20.0g(64.5ミリモル)の4,4’-オキシジフタル酸無水物(140℃で12時間乾燥したもの)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4gのピリジン(258ミリモル)と、100gのダイグライムとを混合し(含水率67ppm)、60℃の温度で18時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをSOCl2により塩素化した後、合成例1と同様の方法で4,4’-ジアミノ-2,2’-ジメチルビフェニルでポリイミド前駆体に変換し、合成例1と同様の方法でポリイミド前駆体A-4を得た。このポリイミド前駆体A-4の重量平均分子量は、19,000であった。得られたポリイミド前駆体A-4は、下記式(A-4)で表される繰り返し単位を含むと推測される。
[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. Hydroquinone, 20.4 g of pyridine (258 mmol), and 100 g of diglime were mixed (water content 67 ppm) and stirred at a temperature of 60 ° C. for 18 hours to 4,4'-oxydiphthalic acid and 2-hydroxyethyl. A methacrylate diester was produced. Next, the obtained diester was chlorinated with SOCL 2 and then converted into a polyimide precursor with 4,4'-diamino-2,2'-dimethylbiphenyl in the same manner as in Synthesis Example 1, and the same as in Synthesis Example 1. A polyimide precursor A-4 was obtained by the above method. The weight average molecular weight of this polyimide precursor A-4 was 19,000. It is presumed that the obtained polyimide precursor A-4 contains a repeating unit represented by the following formula (A-4).
〔4,4’-オキシジフタル酸無水物、4,4’-ジアミノジフェニルエーテルおよび2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A”-5)の合成〕
20.0g(64.5ミリモル)の4,4’-オキシジフタル酸無水物(140℃で12時間乾燥したもの)と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4gのピリジン(258ミリモル)と、200gのγ-ブチロラクトンとを混合し、室温で36時間撹拌して、4,4’-オキシジフタル酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。
次に、氷冷下、ジシクロヘキシルカルボジイミド(DCC)26.6gを25gのγ―ブチロラクトンに溶解した溶液を攪拌しながら滴下した。続いて4,4’-ジアミノジフェニルエーテル12.0gをγ-ブチロラクトン45mlに懸濁したものとDCC 3.8gを10gのγ-ブチロラクトンに溶解させた溶液を攪拌しながら60分かけて同時に加えた。更に室温で2時間攪拌した後、エチルアルコール30mlを加えて1時間攪拌し、次に、γ-ブチロラクトン100mlを加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。次いで、3リットルの水の中でポリイミド前駆体を沈殿させ、水-ポリイミド前駆体混合物を5,000rpm(revolutions per minute)の速度で15分間撹拌した。ポリイミド前駆体をろ過して取得し、300mLのテトラヒドロフランに溶解後、2リットルの水の中で再度ポリイミド前駆体を沈殿物として得た。得られたポリイミド前駆体を減圧下で、45℃で3日間乾燥し、ポリイミド前駆体A”-5を得た。このポリイミド前駆体A”-5の重量平均分子量は、22,000であった。 <Synthesis example 5>
[Synthesis of polyimide precursor (A "-5) from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether 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. Hydroquinone, 20.4 g of pyridine (258 mmol) and 200 g of γ-butyrolactone were mixed and stirred at room temperature for 36 hours to produce a diester of 4,4'-oxydiphthalic acid and 2-hydroxyethyl methacrylate. ..
Next, under ice-cooling, a solution prepared by dissolving 26.6 g of dicyclohexylcarbodiimide (DCC) in 25 g of γ-butyrolactone was added dropwise with stirring. Subsequently, 12.0 g of 4,4'-diaminodiphenyl ether suspended in 45 ml of γ-butyrolactone and a solution of 3.8 g of DCC dissolved in 10 g of γ-butyrolactone were added simultaneously over 60 minutes with stirring. After further stirring at room temperature for 2 hours, 30 ml of ethyl alcohol was added and the mixture was stirred for 1 hour, and then 100 ml of γ-butyrolactone was added. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. 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. ..
〔ピロメリット酸二無水物、4,4’-ジアミノジフェニルエーテルおよび2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A”-6)の合成〕
14.1g(64.5ミリモル)のピロメリット酸二無水物と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4g(258ミリモル)のピリジンと、200gのγ―ブチロラクトンとを混合し、室温で36時間攪拌して、3,3’,4,4’-ビフェニルテトラカルボン酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをDCCを用いて合成例5と同様の方法で4,4’-ジアミノジフェニルエーテルでポリイミド前駆体に変換し、合成例5と同様の方法でポリイミド前駆体A”-6を得た。このポリイミド前駆体A”-6の重量平均分子量は、20,000であった。 <Synthesis example 6>
[Synthesis of polyimide precursor (A "-6) from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate]
14.1 g (64.5 mmol) of pyromellitic dianhydride, 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 20.4 g (258 mmol) of pyridine. , 200 g of γ-butyrolactone was mixed and stirred at room temperature for 36 hours to prepare a diester of 3,3', 4,4'-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was 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 "-6 was obtained in the same manner as in Synthesis Example 5. The weight average molecular weight of this polyimide precursor A "-6 was 20,000.
〔3,3’,4,4’-ビフェニルテトラカルボン酸無水物、4,4’-ジアミノジフェニルエーテル及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A”-7)の合成〕
19.0g(64.5ミリモル)の3,3’,4,4’-ビフェニルテトラカルボン酸無水物と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4g(258ミリモル)のピリジンと、200gのγ―ブチロラクトンとを混合し、室温で36時間撹拌して、3,3’,4,4’-ビフェニルテトラカルボン酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをDCCを用いて合成例5と同様の方法で4,4’-ジアミノジフェニルエーテルでポリイミド前駆体に変換し、合成例5と同様の方法でポリイミド前駆体A”-7を得た。このポリイミド前駆体A”-7の重量平均分子量は、21,000であった。 <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 γ-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.
〔4,4’-オキシジフタル酸無水物、4,4’-ジアミノ-2,2’-ジメチルビフェニル(オルトトリジン)及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体(A”-8)の合成〕
19.0g(64.5ミリモル)の4,4’-オキシジフタル酸無水物と、16.8g(129ミリモル)の2-ヒドロキシエチルメタクリレートと、0.05gのハイドロキノンと、20.4g(258ミリモル)のピリジンと、200gのγ―ブチロラクトンとを混合し、室温で36時間攪拌して、3,3’,4,4’-ビフェニルテトラカルボン酸と2-ヒドロキシエチルメタクリレートのジエステルを製造した。次いで、得られたジエステルをDCCを用いて合成例5と同様の方法で4,4’-ジアミノ-2,2’-ジメチルビフェニル(オルトトリジン)でポリイミド前駆体に変換し、合成例5と同様の方法でポリイミド前駆体A”-8を得た。このポリイミド前駆体A”-8の重量平均分子量は、19,000であった。 <Synthesis Example 8>
[Synthesis of polyimide precursor (A "-8) from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotrizine) and 2-hydroxyethyl methacrylate]
19.0 g (64.5 mmol) of 4,4'-oxydiphthalic anhydride, 16.8 g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05 g of hydroquinone, and 20.4 g (258 mmol). Pyridine and 200 g of γ-butyrolactone were mixed and stirred at room temperature for 36 hours to prepare a diester of 3,3', 4,4'-biphenyltetracarboxylic acid and 2-hydroxyethyl methacrylate. Next, the obtained diester was converted into a polyimide precursor using 4,4'-diamino-2,2'-dimethylbiphenyl (orthotrizine) using DCC in the same manner as in Synthesis Example 5, and the same as in Synthesis Example 5. The polyimide precursor A "-8 was obtained by the method. The weight average molecular weight of the polyimide precursor A" -8 was 19,000.
〔ピロメリット酸二無水物、4,4’-ジアミノジフェニルエーテルおよび2-ヒドロキシエチルメタクリレートからのポリイミド前駆体A-1の変性(ポリイミド前駆体A’-1の合成)〕
合成例1で得られたポリイミド前駆体A-1 20gをテトラフドロフラン200gに溶解した。次いで氷冷下、DCC13.0gを50gのテトラヒドロフランに溶解した溶液を撹拌しながら滴下した。氷冷下で2時間撹拌を続けた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。次いで、3リットルの水の中でポリイミド前駆体を沈殿させ、水-ポリイミド前駆体混合物を5,000rpm(revolutions per minute)の速度で15分間撹拌した。ポリイミド前駆体をろ過して取得し、得られたポリイミド前駆体を減圧下で、45℃で3日間乾燥し、ポリイミド前駆体A’-1を得た。このポリイミド前駆体A’-1の重量平均分子量は、20,500であった。ポリイミド前駆体A’-1は、下記式(A’-1)で表される構造の繰り返し単位を含むと推測される。
[Modification of polyimide precursor A-1 from pyromellitic acid dianhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (synthesis of polyimide precursor A'-1)]
20 g of the polyimide precursor A-1 obtained in Synthesis Example 1 was dissolved in 200 g of tetrafudrofuran. Then, under ice-cooling, a solution prepared by dissolving 13.0 g of DCC in 50 g of tetrahydrofuran was added dropwise with stirring. Stirring was continued for 2 hours under ice cooling. The precipitate formed in the reaction mixture was removed by filtration to obtain a reaction solution. 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).
〔3,3’,4,4’-ビフェニルテトラカルボン酸無水物、4,4’-ジアミノジフェニルエーテル及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体A-2の変性(ポリイミド前駆体A’-2の合成)〕
合成例1-1において、ポリイミド前駆体A-1に代えて、合成例2で得られたポリイミド前駆体A-2 20gを用いた以外は合成例1-1と同様の方法にて、変性ポリイミド前駆体であるポリイミド前駆体A’-2を得た。このポリイミド前駆体A’-2の重量平均分子量は、21,200であった。ポリイミド前駆体A’-2は、下記式(A’-2)で表される構造の繰り返し単位を含むと推測される。
[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'-2 Synthetic)]
Modified polyimide in the same manner as in Synthesis Example 1-1 except that 20 g of the polyimide precursor A-2 obtained in Synthesis Example 2 was used instead of the polyimide precursor A-1 in Synthesis Example 1-1. A polyimide precursor A'-2, which is a precursor, was obtained. The weight average molecular weight of this polyimide precursor A'-2 was 21,200. It is presumed that the polyimide precursor A'-2 contains a repeating unit having a structure represented by the following formula (A'-2).
〔4,4’-オキシジフタル酸無水物、4,4’-ジアミノジフェニルエーテルおよび2-ヒドロキシエチルメタクリレートからのポリイミド前駆体A-3の変性(ポリイミド前駆体A’-3の合成)〕
合成例1-1において、ポリイミド前駆体A-1に代えて、合成例3で得られたポリイミド前駆体A-3 20gを用いた以外は合成例1-1と同様の方法にて、変性ポリイミド前駆体であるポリイミド前駆体A’-3を得た。このポリイミド前駆体A’-3の重量平均分子量は、18,500であった。ポリイミド前駆体A’-3は、下記式(A’-3)で表される構造の繰り返し単位を含むと推測される。
[Modification of polyimide precursor A-3 from 4,4'-oxydiphthalic anhydride, 4,4'-diaminodiphenyl ether and 2-hydroxyethyl methacrylate (synthesis of polyimide precursor A'-3)]
Modified polyimide in the same manner as in Synthesis Example 1-1 except that 20 g of the polyimide precursor A-3 obtained in Synthesis Example 3 was used instead of the polyimide precursor A-1 in Synthesis Example 1-1. A polyimide precursor A'-3, which is a precursor, was obtained. The weight average molecular weight of this polyimide precursor A'-3 was 18,500. It is presumed that the polyimide precursor A'-3 contains a repeating unit having a structure represented by the following formula (A'-3).
〔4,4’-オキシジフタル酸無水物、4,4’-ジアミノ-2,2’-ジメチルビフェニル(オルトトリジン)及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体A-4の変性(ポリイミド前駆体A’-4の合成)〕
合成例1-1において、ポリイミド前駆体A-1に代えて、合成例4で得られたポリイミド前駆体A-4 20gを用いた以外は合成例1-1と同様の方法にて、変性ポリイミド前駆体A’-4を得た。このポリイミド前駆体A’-4の重量平均分子量は、20,500であった。ポリイミド前駆体A’-4は、下記式(A’-4)で表される構造の繰り返し単位を含むと推測される。
Modification of polyimide precursor A-4 from 4,4'-oxydiphthalic anhydride, 4,4'-diamino-2,2'-dimethylbiphenyl (orthotrizine) and 2-hydroxyethyl methacrylate (polyimide precursor A' -4 synthesis)]
Modified polyimide in the same manner as in Synthesis Example 1-1 except that 20 g of the polyimide precursor A-4 obtained in Synthesis Example 4 was used instead of the polyimide precursor A-1 in Synthesis Example 1-1. Precursor A'-4 was obtained. The weight average molecular weight of this polyimide precursor A'-4 was 20,500. It is presumed that the polyimide precursor A'-4 contains a repeating unit having a structure represented by the following formula (A'-4).
〔3,3’,4,4’-ビフェニルテトラカルボン酸無水物、4,4’-ジアミノジフェニルエーテル及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体A-2の変性(ポリイミド前駆体A’-5の合成)〕
合成例1-1において、ポリイミド前駆体A-1に代えて、合成例2で得られたポリイミド前駆体A-2 20gを用いて、DCCに代えてジイソプロピルカルボジイミド(DIC)を用いた以外は合成例1-1と同様の方法にて、変性ポリイミド前駆体A’-5を得た。このポリイミド前駆体A’-5の重量平均分子量は、21,000であった。ポリイミド前駆体A’-5は、下記式(A’-5)で表される構造の繰り返し単位を含むと推測される。
[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)]
In 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).
〔3,3’,4,4’-ビフェニルテトラカルボン酸無水物、4,4’-ジアミノジフェニルエーテル及び2-ヒドロキシエチルメタクリレートからのポリイミド前駆体A-2の変性(ポリイミド前駆体A’-6の合成)〕
合成例1-1において、ポリイミド前駆体A-1に代えて、合成例2で得られたポリイミド前駆体A-2 20gを用いて、DCCに代えて(2,6-ジイソプロピルフェニル)カルボジイミド(DIPC)を用いた以外は合成例1-1と同様の方法にて、変性ポリイミド前駆体A’-6を得た。このポリイミド前駆体A’-6の重量平均分子量は、21,500であった。ポリイミド前駆体A’-6は、下記式(A’-6)で表される構造の繰り返し単位を含むと推測される。
[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'-6 Synthetic)]
In Synthesis Example 1-1, 20 g of the polyimide precursor A-2 obtained in Synthesis Example 2 was used instead of the polyimide precursor A-1, and (2,6-diisopropylphenyl) carbodiimide (DIPC) was used instead of DCC. ) Was used to obtain a modified polyimide precursor A'-6 in the same manner as in Synthesis Example 1-1. The weight average molecular weight of this polyimide precursor A'-6 was 21,500. It is presumed that the polyimide precursor A'-6 contains a repeating unit having a structure represented by the following formula (A'-6).
〔4,4’-オキシジフタル酸無水物、4,4’-ジアミノジフェニルエーテルおよび2-ヒドロキシエチルメタクリレートからのポリイミド前駆体A-3の変性(ポリイミド前駆体A’-7の合成)〕
合成例1-1において、ポリイミド前駆体A-1に代えて、合成例3で得られたポリイミド前駆体A-3 20gを用い、DCCに代えてDICを用いた以外は合成例1-1と同様の方法にて、変性ポリイミド前駆体A’-7を得た。このポリイミド前駆体A’-7の重量平均分子量は、19,000であった。ポリイミド前駆体A’-7は、下記式(A’-7)で表される構造の繰り返し単位を含むと推測される。
[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)]
In 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).
〔ポリイミドP-1の合成)〕
コンデンサー及び撹拌機を取り付けたフラスコに、水分を除去しながら、下記式(a-1)で表される無水物(a-1) 11.4g(25ミリモル)をN-メチルピロリドン(NMP) 33.1gに溶解した。次いで、1,3-フェニレンジアミン(東京化成工業(株)製) 2.70g(25ミリモル)を添加し、25℃で3時間撹拌し、45℃で更に3時間撹拌した。次いで、ピリジン7.50g(94.8ミリモル)、無水酢酸6.38g(62ミリモル)、N-メチルピロリドン(NMP)20.0g添加し、80℃で、3時間撹拌し、N-メチルピロリドン(NMP)50gを加え、希釈した。
この反応液を、1.2リットルのメタノールの中で沈殿させ、3,000rpmの速度で15分間撹拌した。樹脂を濾過して取得し、1リットルのメタノールの中で再度30分間撹拌し再び濾過した。得られた樹脂を減圧下で、40℃で1日乾燥し、閉環型ポリイミドP-1を得た。P-1の分子量は、重量平均分子量(Mw)=74,300、数平均分子量(Mn)=30,100であった。
P-1の構造は下記式(P-1)により表される構造であると推測される。
<Synthesis Example 8-1>
[Synthesis of Polyimide P-1]
In a flask equipped with a condenser and a stirrer, while removing water, 11.4 g (25 mmol) of anhydride (a-1) represented by the following formula (a-1) was added to N-methylpyrrolidone (NMP) 33. Dissolved in 1 g. Next, 2.70 g (25 mmol) of 1,3-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 25 ° C. for 3 hours and further at 45 ° C. for 3 hours. Then, 7.50 g (94.8 mmol) of pyridine, 6.38 g (62 mmol) of acetic anhydride, and 20.0 g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80 ° C. for 3 hours to obtain N-methylpyrrolidone (N-methylpyrrolidone (NMP). NMP) 50 g was added and diluted.
The reaction was precipitated in 1.2 liters of methanol and stirred at a rate of 3,000 rpm for 15 minutes. The resin was obtained by filtration, stirred again in 1 liter of methanol for 30 minutes and filtered again. The obtained resin was dried under reduced pressure at 40 ° C. for 1 day to obtain a ring-closed polyimide P-1. The molecular weight of P-1 was weight average molecular weight (Mw) = 74,300 and number average molecular weight (Mn) = 30,100.
The structure of P-1 is presumed to be the structure represented by the following formula (P-1).
三口フラスコ中でジシクロヘキシルカルボジイミド 41.3g(0.20mol)とテトラヒドロフラン 200mLを混合した。次いで、テトラヒドロフラン 200mLに安息香酸 24.4g(0.02mol)を溶解させた溶液を滴下ロートで室温下30分かけてフラスコ中に滴下した。滴下終了後、室温下で30分反応を続けた後24時間静置させた。析出物をろ過し、ろ液を回収した。回収したろ液(THF溶液)を濃縮後、再結晶操作により白色粉体として化合物H-1を得た。化合物H-1の構造は、後述する式(H-1)で表される構造であると推測される。 <Synthesis Example H-1>
41.3 g (0.20 mol) of dicyclohexylcarbodiimide and 200 mL of tetrahydrofuran were mixed in a three-necked flask. Then, a solution prepared by dissolving 24.4 g (0.02 mol) of benzoic acid in 200 mL of tetrahydrofuran was added dropwise to the flask over 30 minutes at room temperature with a dropping funnel. After completion of the dropping, the reaction was continued at room temperature for 30 minutes and then allowed to stand for 24 hours. The precipitate was filtered and the filtrate was collected. After concentrating the recovered filtrate (THF solution), compound H-1 was obtained as a white powder by a recrystallization operation. The structure of compound H-1 is presumed to be the structure represented by the formula (H-1) described later.
合成例H-1において、安息香酸に代えてフタル酸モノメチル 36.0g(0.2mol)を使用した以外は合成例H-1と同様の方法により、化合物H-2を得た。化合物H-2の構造は、後述する式(H-2)で表される構造であると推測される。 <Synthesis Example H-2>
Compound H-2 was obtained in the same manner as in Synthesis Example H-1 except that 36.0 g (0.2 mol) of monomethyl phthalate was used instead of benzoic acid in Synthesis Example H-1. The structure of compound H-2 is presumed to be the structure represented by the formula (H-2) described later.
合成例H-1において、ジシクロヘキシルカルボジイミドを1,3-ジ-p-トリルカルボジイミド44.5g(0.2mol)に、安息香酸を4-tert-ブチル安息香酸35.2g(0.2mol)にそれぞれ変更した以外は合成例H-1と同様の方法により、化合物H-3を得た。化合物H-3の構造は、後述する式(H-3)で表される構造であると推測される。 <Synthesis Example H-3>
In Synthesis Example H-1, dicyclohexylcarbodiimide was added to 44.5 g (0.2 mol) of 1,3-di-p-tolylcarbodiimide, and benzoic acid was added to 35.2 g (0.2 mol) of 4-tert-butylbenzoic acid. Compound H-3 was obtained by the same method as in Synthesis Example H-1 except that it was changed. The structure of compound H-3 is presumed to be the structure represented by the formula (H-3) described later.
合成例H-1において、ジシクロヘキシルカルボジイミドを1,3-ジ-p-トリルカルボジイミド 44.5g(0.2mol)に、安息香酸をフタル酸モノメチル 36.0g(0.2mol)にそれぞれ変更した以外は合成例H-1と同様の方法により、化合物H-4を得た。化合物H-4の構造は、後述する式(H-4)で表される構造であると推測される。 <Synthesis Example H-4>
In Synthesis Example H-1, dicyclohexylcarbodiimide was changed to 44.5 g (0.2 mol) of 1,3-di-p-tolylcarbodiimide, and benzoic acid was changed to 36.0 g (0.2 mol) of monomethylphthalate. Compound H-4 was obtained by the same method as in Synthesis Example H-1. The structure of compound H-4 is presumed to be the structure represented by the formula (H-4) described later.
合成例H-1において、ジシクロヘキシルカルボジイミドをビス(2,6-ジイソプロピルフェニル)カルボジイミド 72.5g(0.2mol)に変更した以外は合成例H-1と同様の方法にて化合物H-5を得た。化合物H-5の構造は、後述する式(H-5)で表される構造であると推測される。 <Synthesis Example H-5>
Compound H-5 was obtained in the same manner as in Synthesis Example H-1 except that dicyclohexylcarbodiimide was changed to bis (2,6-diisopropylphenyl) carbodiimide 72.5 g (0.2 mol) in Synthesis Example H-1. rice field. The structure of compound H-5 is presumed to be the structure represented by the formula (H-5) described later.
合成例H-1で使用したジシクロヘキシルカルボジイミドを1,3-ジ-p-トリルカルボジイミド 44.5g(0.2mol)に、安息香酸をフタル酸モノブチル 44.4g(0.2mol)にそれぞれ変更した以外は合成例H-1と同様の方法にて化合物H-6を得た。化合物H-6の構造は、後述する式(H-6)で表される構造であると推測される。 <Synthesis example H-6>
Except that the dicyclohexylcarbodiimide used in Synthesis Example H-1 was changed to 44.5 g (0.2 mol) of 1,3-di-p-tolylcarbodiimide, and benzoic acid was changed to 44.4 g (0.2 mol) of monobutyl phthalate. Obtained compound H-6 by the same method as in Synthesis Example H-1. The structure of compound H-6 is presumed to be the structure represented by the formula (H-6) described later.
三口フラスコ中で5,5-ジメチルヒダントイン 10.0g(78mmol)とピリジン40mLを混合した。塩化ベンゾイル 11.0g(78mmol)を室温下でフラスコ中に30分かけて滴下した。滴下終了後、170℃で15時間反応させた。反応終了後、減圧濃縮した後、酢酸エチルで希釈した。シリカゲルを用いて濾過を行った後、酢酸エチル/ヘキサン(酢酸エチルとヘキサンとを酢酸エチル:ヘキサン=1:9(体積比)で混合した溶媒)を用いて再結晶し、白色粉末として化合物H-7を得た。化合物H-7の構造は、後述する式(H-7)で表される構造であると推測される。 <Synthesis Example H-7>
10.0 g (78 mmol) of 5,5-dimethylhydantoin and 40 mL of pyridine were mixed in a three-necked flask. 11.0 g (78 mmol) of benzoyl chloride was added dropwise to the flask at room temperature over 30 minutes. After completion of the dropping, the reaction was carried out at 170 ° C. for 15 hours. After completion of the reaction, the mixture was concentrated under reduced pressure and then diluted with ethyl acetate. After filtration using silica gel, recrystallization was performed using ethyl acetate / hexane (a solvent in which ethyl acetate and hexane were mixed at an ethyl acetate: hexane = 1: 9 (volume ratio)), and compound H was obtained as a white powder. I got -7. The structure of compound H-7 is presumed to be the structure represented by the formula (H-7) described later.
三口フラスコ中でジイソプロピルカルボジイミド 1.26g(10mmol)とテトラヒドロフラン 100mL、塩化ベンゾイル 1.41g(10mmol)を混合した。室温下で撹拌を48時間続けた。次に1,3-ジメチルチオウレア 1.04g(10mmol)を加え、さらに12時間撹拌を続けた。反応液を減圧濃縮し、酢酸エチル/ヘキサン(酢酸エチルとヘキサンとを酢酸エチル:ヘキサン=1:9(体積比)で混合した溶媒)を用いてシリカゲルカラムクロマトグラフィにより精製し、白色固体として化合物H-8を得た。化合物H-8の構造は、後述する式(H-8)で表される構造であると推測される。
1.26 g (10 mmol) of diisopropylcarbodiimide, 100 mL of tetrahydrofuran, and 1.41 g (10 mmol) of benzoyl chloride were mixed in a three-necked flask. Stirring was continued for 48 hours at room temperature. Next, 1.04 g (10 mmol) of 1,3-dimethylthiourea was added, and stirring was continued for another 12 hours. The reaction mixture was concentrated under reduced pressure and purified by silica gel column chromatography using ethyl acetate / hexane (a solvent in which ethyl acetate and hexane were mixed in an ethyl acetate: hexane = 1: 9 (volume ratio)) to prepare Compound H as a white solid. I got -8. The structure of compound H-8 is presumed to be the structure represented by the formula (H-8) described later.
各実施例及び比較例において、それぞれ、下記表1に記載の成分を混合し、樹脂組成物又は比較用組成物を得た。
表1に記載の溶剤以外の各成分の欄における数値は、各成分の含有量(質量部)を表す。
得られた樹脂組成物及び比較用組成物を、細孔の幅0.8μmのポリテトラフルオロエチレン製フィルターを通して加圧ろ過した。
また、表1中、「-」の記載は該当する成分を組成物が含有していないことを示している。 <Examples and Comparative Examples>
In each Example and Comparative Example, 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 μm.
Further, in Table 1, the description of "-" indicates that the composition does not contain the corresponding component.
・A-1~A-4、A”-5~A”-8、A’-1~A’-7、P-1:上述の合成例で合成したポリイミド前駆体A-1~A-4、ポリイミド前駆体A”-5~A”-8、、ポリイミド前駆体A’-1~A’-7、ポリイミドP-1 〔resin〕
-A-1 to A-4, A "-5 to A" -8, A'-1 to A'-7, P-1: Polyimide precursors A-1 to A-4 synthesized in the above synthesis example. , Polyimide precursor A "-5 to A" -8 ,, Polyimide precursor A'-1 to A'-7, Polyimide P-1
・B-1~B-5:下記式(B-1)~式(B-5)で表される化合物
B-1 to B-5: Compounds represented by the following formulas (B-1) to (B-5)
・C-1:IRGACURE OXE 01(BASF社製)
・C-2:IRGACURE OXE 02(BASF社製)
・C-3:IRGACURE 369(BASF社製) [Radical polymerization initiator]
・ C-1: IRGACURE OXE 01 (manufactured by BASF)
・ C-2: IRGACURE OXE 02 (manufactured by BASF)
・ C-3: IRGACURE 369 (manufactured by BASF)
・D-1:A-DPH(新中村化学工業(株)製)
・D-2:SR-209(サートマー社製、下記構造の化合物)
・D-3:A-TMMT(新中村化学工業(株)製)
・ 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.)
・E-1:2-ニトロソー1-ナフトール(東京化成工業(株)製)
・E-2:パラベンゾキノン(東京化成工業(株)製)
・E-3:パラメトキシフェノール(東京化成工業(株)製) [Polymerization inhibitor]
・ E-1: 2-Nitrosaw 1-Naphthol (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ E-2: Parabenzoquinone (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ E-3: Paramethoxyphenol (manufactured by Tokyo Chemical Industry Co., Ltd.)
・F-1~F-4:下記構造の化合物
-F-1 to F-4: Compounds with the following structure
・G-1~G-4:下記構造の化合物。以下の構造式中、Etはエチル基を表す。
-G-1 to G-4: Compounds having the following structures. In the following structural formula, Et represents an ethyl group.
・H-1~H-8:上述の化合物H-1~H-8 [Specific compound]
H-1 to H-8: The above-mentioned compounds H-1 to H-8.
・J-1:下記式(J-1)で表される化合物
・J-2:N-フェニルジエタノールアミン
-J-1: Compound represented by the following formula (J-1) -J-2: N-Phenyldiethanolamine
・I-1:N-メチル-2-ピロリドン
・I-2:乳酸エチル
・I-3:γ-ブチロラクトン:ジメチルスルホキシド=80質量%:20質量%の混合溶剤 〔solvent〕
-I-1: N-methyl-2-pyrrolidone-I-2: Ethyl lactate-I-3: γ-butyrolactone: Dimethyl sulfoxide = 80% by mass: 20% by mass mixed solvent
〔特定構造の定量〕
添加剤(化合物H-1~H-8)として添加した場合とポリマーに結合している場合の特定構造の含有量の定量方法は以下の通りである。 <Evaluation>
[Quantification of specific structure]
The method for quantifying the content of a specific structure when added as an additive (Compounds H-1 to H-8) and when bonded to a polymer is as follows.
調製した組成物をd6-DMSO(ジメチルスルホキシド-d6)にてNMR解析によりポリマーと添加剤のモル比を算出した。次に組成物をテトラヒドロフランで希釈後、水:アセトン=50質量%:50質量%の混合溶媒を添加し、析出物をろ過し、得られたろ過物を乾燥させた。乾燥質量を算出することでポリマーの質量とした。ポリマー/添加剤のモル比とポリマー質量から添加剤の含有量を定量した。
-ポリマーに結合している場合-
組成物をテトラヒドロフランで希釈後、水:アセトン=50質量%:50質量%の混合溶媒を添加し、析出物をろ過し、得られたろ過物を乾燥させた。乾燥質量を算出することでポリマーの質量とした。得られたポリマーをd6-DMSOにてNMR解析によりポリマーと添加剤のモル比を算出した。ポリマー質量とモル比から特定構造の含有量を定量した。
また、樹脂組成物の全固形分は、70℃/0.1Torr/3時間の条件で溶剤を乾燥し、乾燥残渣の質量を全固形分とした。1Torrは1気圧の760分の1を示す値であり、133.322Paとする。上記乾燥において、溶剤以外の揮発成分がないことを揮発成分の1H-NMR(溶媒としてDMSO(ジメチルスルホキシド)-d6を使用した)により確認した。
上記方法により、樹脂組成物の全固形分に対する式(1-1)で表される構造の含有量(mol/g)を定量し、定量結果を表1の「特定構造の含有量」の欄に記載した。 -When added as an additive-
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. Next, the composition was diluted with tetrahydrofuran, a mixed solvent of water: acetone = 50% by mass: 50% by mass was added, the precipitate was filtered, and the obtained filtered product was dried. The dry mass was calculated to obtain the mass of the polymer. The additive content was quantified from the polymer / additive molar ratio and polymer mass.
-When bonded to a polymer-
After diluting the composition with tetrahydrofuran, a mixed solvent of water: acetone = 50% by mass: 50% by mass was added, the precipitate was filtered, and the obtained filtered product was dried. The dry mass was calculated to obtain the mass of the polymer. The molar ratio of the polymer to the additive was calculated by NMR analysis of the obtained polymer with d6-DMSO. The content of the specific structure was quantified from the polymer mass and molar ratio.
For the total solid content of the resin composition, the solvent was dried under the conditions of 70 ° C./0.1Torr / 3 hours, and the mass of the dried residue was taken as the total solid content. 1 Torr is a value indicating 1/760 of 1 atm, and is 133.322 Pa. In the above drying, it was confirmed by 1 H-NMR (using DMSO (dimethyl sulfoxide) -d6 as a solvent) of the volatile component that there was no volatile component other than the solvent.
By the above method, 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.
各実施例及び比較例において調製した樹脂組成物及び比較用組成物について、それぞれ、調製直後にE型粘度計を用いて粘度を測定した。このとき測定された粘度の値を「粘度(0日)」とした。その後、各実施例及び比較例における樹脂組成物及び比較用組成物を密閉容器中、遮光、25℃の条件下で14日間静置した後、再度E型粘度計を用いて粘度を測定した。このとき測定された粘度の値を「粘度(14日)」とした。以下の式から、粘度変動率を算出した。
上記粘度変動率から、下記評価基準に従って評価を行った。評価結果は表2の「保存安定性」の欄に記載した。
上記粘度変動率が低ければ低い程、保存安定性が高いといえる。
粘度変動率=|100×{1-(粘度(14日)/粘度(0日))}|
粘度の測定は25℃で行い、その他の測定条件はJIS Z 8803:2011に準拠した。
-評価基準-
A:粘度変動率が5%以下であった。
B:粘度変動率が5%を超えた。 [Evaluation of storage stability]
Immediately after the preparation, the viscosities of the resin composition and the comparative composition prepared in each Example and Comparative Example were measured using an E-type viscometer. The value of the viscosity measured at this time was defined as "viscosity (0 days)". Then, the resin composition and the comparative composition in each Example and Comparative Example were allowed to stand in a closed container under the conditions of light shielding and 25 ° C. for 14 days, and then the viscosity was measured again using an E-type viscometer. The value of the viscosity measured at this time was defined as "viscosity (14 days)". The viscosity volatility was calculated from the following formula.
Based on the above viscosity volatility, evaluation was performed according to the following evaluation criteria. The evaluation results are shown in the "Storage stability" column of Table 2.
It can be said that the lower the viscosity fluctuation rate, the higher the storage stability.
Viscosity volatility = | 100 × {1- (viscosity (14 days) / viscosity (0 days))} |
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%.
各実施例及び比較例において調製した樹脂組成物又は比較用組成物を、それぞれ、銅基板上にスピンコート法により層状に適用して、樹脂組成物層又は比較用組成物層を形成した。得られた樹脂組成物層又は比較用組成物層を形成した銅基板をホットプレート上で、100℃で5分間乾燥し、銅基板上に20μmの均一な厚さの樹脂組成物層又は比較用組成物層とした。銅基板上の樹脂組成物層又は比較用組成物層を、ステッパー(Nikon NSR 2005 i9C)を用いて、500mJ/cm2の露光エネルギーで100μm四方の正方形状の非マスク部が形成されたフォトマスクを使用してi線により露光し、その後シクロペンタノンで60秒間現像して、100μm四方の正方形状の樹脂層を得た。さらに、窒素雰囲気下で230℃で3時間加熱して樹脂層(パターン)を形成した。
銅基板上の100μm四方の正方形状の樹脂層に対して、25℃、65%相対湿度(RH)の環境下にて、ボンドテスター(XYZTEC社製、CondorSigma)を用いて、せん断力を測定し、下記評価基準に従って評価した。評価結果は表2の「密着性」の欄に記載した。せん断力が大きければ大きいほど硬化膜の金属密着性(銅密着性)に優れるといえる。
-評価基準-
A:せん断力が40gfを超えた。
B:せん断力が35gfを超えて40gf以下であった。
C:せん断力が25gfを超えて35gf以下であった。
D:せん断力が25gf以下であった。
また、1gfは0.00980665Nである。 [Evaluation of adhesion]
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 μm or for comparison was placed on the copper substrate. It was used as a composition layer. A photomask in which a 100 μm square non-masked portion is formed by using a stepper (Nikon NSR 2005 i9C) to form a resin composition layer or a comparative composition layer on a copper substrate with an exposure energy of 500 mJ / cm 2. Was exposed to i-rays using the above, and then developed with cyclopentanone for 60 seconds to obtain a 100 μm square resin layer. Further, 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 μm square resin layer on a copper substrate in an environment of 25 ° C. and 65% relative humidity (RH) using a bond tester (CondorSigma, manufactured by XYZTEC). , Evaluated according to the following evaluation criteria. The evaluation results are described in the "Adhesion" column of Table 2. It can be said that the larger the shearing force, the better the metal adhesion (copper adhesion) of the cured film.
-Evaluation criteria-
A: The shearing force exceeded 40 gf.
B: The shearing force was more than 35 gf and 40 gf or less.
C: The shearing force was more than 25 gf and 35 gf or less.
D: The shearing force was 25 gf or less.
Further, 1 gf is 0.00980665N.
各実施例又は比較例において、上述の密着性の評価において230℃で3時間加熱して樹脂層を形成した後に、樹脂層を175℃の恒温槽で1,000時間経過させてからせん断力の測定を行った以外は、上述の密着性の評価における評価方法と同様の評価方法及び評価基準に従って、加熱後の金属密着性の評価を行った。評価結果は表2の「信頼性」の欄に記載した。せん断力が大きければ大きいほど硬化膜の金属密着性(銅密着性)に優れるといえる。 [Evaluation of reliability (metal adhesion after heating)]
In each Example or Comparative Example, in the above-mentioned evaluation of adhesion, after heating at 230 ° C. for 3 hours to form a resin layer, the resin layer is allowed to elapse in a constant temperature bath at 175 ° C. for 1,000 hours, and then the shearing force is applied. Except for the measurement, the metal adhesion after heating was evaluated according to the same evaluation method and evaluation criteria as the evaluation method in the above-mentioned evaluation of adhesion. The evaluation results are listed in the "Reliability" column of Table 2. It can be said that the larger the shearing force, the better the metal adhesion (copper adhesion) of the cured film.
比較例1~比較例3に記載の比較用組成物は、固形分中に式(1-1)で表される構造を含まない。このような比較用組成物から得られる硬化膜は、金属層との密着性に劣ることがわかる。 From the above results, 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.
実施例1において使用した樹脂組成物を、表面に銅薄層が形成された樹脂基材の銅薄層の表面にスピンコート法により層状に適用して、100℃で5分間乾燥し、膜厚20μmの樹脂組成物層を形成した後、ステッパー((株)ニコン製、NSR1505 i6)を用いて露光した。露光はマスク(パターンが1:1ラインアンドスペースであり、線幅が10μmであるバイナリマスク)を介して、波長365nmの光を照射して行った。露光の後、シクロペンタノンで30秒間現像し、PGMEAで20秒間リンスし、層のパターンを得た。
次いで、230℃で3時間加熱し、再配線層用層間絶縁膜を形成した。この再配線層用層間絶縁膜は、絶縁性に優れていた。
また、これらの再配線層用層間絶縁膜を使用して半導体デバイスを製造したところ、問題なく動作することを確認した。 <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 μm 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 μm). After exposure, it was developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 20 seconds to obtain a layer pattern.
Then, it was heated at 230 ° C. for 3 hours to form an interlayer insulating film for the rewiring layer. 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.
Claims (13)
- ポリイミド、及び、ポリイミド前駆体よりなる群から選ばれた少なくとも1種の樹脂を含み、
固形分中に式(1-1)で表される構造を含む、
樹脂組成物。
式(1-1)中、R1及びR2はそれぞれ独立に、脂肪族基又は芳香族基を表し、前記脂肪族基又は芳香族基の炭素原子又は炭化水素基はヘテロ原子で置換されていてもよく、X1は酸素原子又は硫黄原子を表し、L1は-C(=O)-、又は、-S(=O)2-を表し、*1及び*2はそれぞれ独立に、他の構造との結合部位を表し、R1、R2、*1に結合する構造、及び、*2に結合する構造のうち少なくとも2つが結合して環構造を形成してもよい。 Contains 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).
Resin composition.
In 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, L 1 may represent -C (= O)-or-S (= O) 2- , and * 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. - 前記樹脂が、前記式(1-1)で表される構造を含む、請求項1に記載の樹脂組成物。 The resin composition according to claim 1, wherein the resin contains a structure represented by the formula (1-1).
- 前記式(1-1)で表される構造を含む化合物であって、前記樹脂とは異なる化合物を更に含む、請求項1又は2に記載の樹脂組成物。 The resin composition according to claim 1 or 2, which is a compound having a structure represented by the formula (1-1) and further contains a compound different from the resin.
- 前記式(1-1)で表される構造として、下記式(1-2)で表される構造を含む、請求項1~3のいずれか1項に記載の樹脂組成物。
式(1-2)中、R21及びR22はそれぞれ独立に、脂肪族基又は芳香族基を表し、前記脂肪族基又は芳香族基の炭素原子又は炭化水素基はヘテロ原子で置換されていてもよく、R23は水素原子又は1価の有機基を表し、*は他の構造との結合部位を表し、R21、R22、R23、及び、*に結合する構造のうち少なくとも2つが結合して環構造を形成してもよい。 The resin composition according to any one of claims 1 to 3, wherein the structure represented by the formula (1-1) includes a structure represented by the following formula (1-2).
In formula (1-2), 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. - 樹脂組成物の全固形分に対する、前記式(1-1)で表される構造の含有モル量が0.01~1.0mmol/gである、請求項1~4のいずれか1項に記載の樹脂組成物。 The method according to any one of claims 1 to 4, wherein the molar content of the structure represented by the formula (1-1) is 0.01 to 1.0 mmol / g with respect to the total solid content of the resin composition. Resin composition.
- 光重合開始剤を更に含む、請求項1~5のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 5, further comprising a photopolymerization initiator.
- 架橋剤を更に含む、請求項1~6のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 6, further comprising a cross-linking agent.
- 再配線層用層間絶縁膜の形成に用いられる、請求項1~7のいずれか1項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 7, which is used for forming an interlayer insulating film for a rewiring layer.
- 請求項1~8のいずれか1項に記載の樹脂組成物を硬化してなる硬化膜。 A cured film obtained by curing the resin composition according to any one of claims 1 to 8.
- 請求項9に記載の硬化膜を2層以上有し、前記硬化膜同士のいずれかの間に金属層を有する、積層体。 A laminated body having two or more layers of the cured film according to claim 9, and having a metal layer between any of the cured films.
- 請求項1~8のいずれか1項に記載の樹脂組成物を基板に適用して膜を形成する膜形成工程を含む、硬化膜の製造方法。 A method for producing a cured film, which comprises a film forming step of applying the resin composition according to any one of claims 1 to 8 to a substrate to form a film.
- 前記膜を50~450℃で加熱する工程を含む、請求項11に記載の硬化膜の製造方法。 The method for producing a cured film according to claim 11, which comprises a step of heating the film at 50 to 450 ° C.
- 請求項9に記載の硬化膜又は請求項10に記載の積層体を有する、半導体デバイス。 A semiconductor device having the cured film according to claim 9 or the laminate according to claim 10.
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WO2023112573A1 (en) * | 2021-12-14 | 2023-06-22 | 富士フイルム株式会社 | Method for producing cured product, method for producing laminate , method for producing semiconductor device, and treatment liquid |
WO2024095885A1 (en) * | 2022-10-31 | 2024-05-10 | 富士フイルム株式会社 | Resin composition, cured object, layered object, method for producing cured object, method for producing layered object, method for producing semiconductor device, and semiconductor device |
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WO2024095885A1 (en) * | 2022-10-31 | 2024-05-10 | 富士フイルム株式会社 | Resin composition, cured object, layered object, method for producing cured object, method for producing layered object, method for producing semiconductor device, and semiconductor device |
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