WO2023008090A1 - 硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、樹脂組成物、硬化物、積層体、及び、半導体デバイス - Google Patents

硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、樹脂組成物、硬化物、積層体、及び、半導体デバイス Download PDF

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Publication number
WO2023008090A1
WO2023008090A1 PCT/JP2022/026314 JP2022026314W WO2023008090A1 WO 2023008090 A1 WO2023008090 A1 WO 2023008090A1 JP 2022026314 W JP2022026314 W JP 2022026314W WO 2023008090 A1 WO2023008090 A1 WO 2023008090A1
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Prior art keywords
group
formula
cured product
producing
acid
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PCT/JP2022/026314
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English (en)
French (fr)
Japanese (ja)
Inventor
敦靖 野崎
美沙樹 ▲高▼嶋
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to CN202280053079.7A priority Critical patent/CN117751326A/zh
Priority to JP2022568516A priority patent/JP7528260B2/ja
Priority to KR1020247003473A priority patent/KR20240028462A/ko
Publication of WO2023008090A1 publication Critical patent/WO2023008090A1/ja
Priority to JP2023091852A priority patent/JP2023124872A/ja

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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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0387—Polyamides or polyimides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, a resin composition, a cured product, a laminate, and a semiconductor device.
  • Cyclized resins such as polyimide are used in a variety of applications due to their excellent heat resistance and insulating properties.
  • the use is not particularly limited, but in the case of a semiconductor device for mounting, use as a material for an insulating film or a sealing material, or as a protective film can be mentioned. It is also used as a base film or coverlay for flexible substrates.
  • the cyclized resin such as polyimide is used in the form of a resin composition containing at least one of a cyclized resin such as polyimide and a precursor of the cyclized resin.
  • a resin composition is applied to a substrate, for example, by coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are performed to form a cured product on the substrate.
  • a precursor of the cyclized resin such as a polyimide precursor is cyclized, for example, by heating, and becomes a cyclized resin such as polyimide in the cured product.
  • the resin composition can be applied by a known coating method or the like, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the resin composition to be applied. It can be said that it is excellent in sex.
  • cyclized resins such as polyimide, from the viewpoint of such excellent manufacturing adaptability, industrial application and development of the above-mentioned resin compositions are increasingly expected.
  • Patent Document 1 a semiconductor chip, a sealing material covering the semiconductor chip, and a rewiring layer having a larger area than the semiconductor chip in a plan view are provided, and an interlayer insulating film of the rewiring layer is provided.
  • a semiconductor device having a weight reduction rate of 5 to 95% by weight after being heated to 700° C. at 10° C./min in an air atmosphere is disclosed.
  • An object of the present invention is to provide a method for producing a cured product that produces a cured product with little outgassing, and a method for producing a laminate and a method for producing a semiconductor device using the above method for producing a cured product. .
  • the present invention provides a resin composition that generates little outgassing from the obtained cured product, a cured product obtained by curing the resin composition, a laminate and a semiconductor device containing the cured product. aim.
  • ⁇ 3> The method for producing a cured product according to ⁇ 1> or ⁇ 2>, wherein the film after the heating step is a polyimide film and the imidization rate of the film is 90% or more.
  • ⁇ 4> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 3>, further comprising an exposure step of selectively exposing the film between the film forming step and the heating step. .
  • ⁇ 5> The method for producing a cured product according to ⁇ 4>, further comprising, between the exposure step and the heating step, a developing step of developing the exposed film with a developer to form a pattern.
  • ⁇ 6> The method for producing a cured product according to ⁇ 5>, wherein the developer contains an organic solvent.
  • ⁇ 7> The method for producing a cured product according to ⁇ 5> or ⁇ 6>, wherein the developing step is a step of forming a negative pattern.
  • ⁇ 8> The method for producing a cured product according to any one of ⁇ 5> to ⁇ 7>, wherein the developer contains a base.
  • ⁇ 9> The cured product according to any one of ⁇ 5> to ⁇ 8>, including a treatment step of contacting the pattern with a treatment liquid containing a base between the developing step and the heating step. Production method.
  • ⁇ 10> The method for producing a cured product according to any one of ⁇ 1> to ⁇ 9>, wherein the resin composition contains a photosensitizer.
  • the resin composition contains a solvent, and the content of the precursor of the cyclized resin is 70% by mass or more relative to the total solid content of the resin composition.
  • the polymerizable compound having a boiling point of 200°C or higher at 1 atm is a compound having three or more (meth)acrylate groups.
  • the precursor of the cyclized resin is a resin having at least one of a repeating unit represented by the following formula (2) and a repeating unit represented by the formula (PAI-2), ⁇ 1> to ⁇ 14>
  • a 1 and A 2 each independently represent an oxygen atom or —NR z —
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group.
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group, and R z represents a hydrogen atom or a monovalent organic group.
  • R 117 represents a trivalent organic group
  • R 111 represents a divalent organic group
  • a 2 represents an oxygen atom or —NR z —
  • R 113 represents a hydrogen atom or 1 represents a valent organic group
  • Rz represents a hydrogen atom or a monovalent organic group.
  • R 115 in the above formula (2) is represented by any one of the following formulas (X1-1) to (X1-3), or a group containing one or more aliphatic ring structures and R 117 in the above formula (PAI-2) contains a group represented by any one of the following formulas (X2-1) to (X2-3), or one or more aliphatic ring structures
  • the method for producing a cured product according to ⁇ 15> which is a group.
  • R represents a substituent
  • n1 represents an integer of 0 to 2
  • * each represents a binding site to another structure.
  • each R independently represents a substituent, each m1 independently represents an integer of 0 to 3, and each * represents a binding site to another structure.
  • each R independently represents a substituent, each m1 independently represents an integer of 0 to 2
  • R 2 C represents a monovalent organic group
  • * each represents a bonding site with another structure.
  • R represents a substituent
  • n2 represents an integer of 0 to 2
  • each R independently represents a substituent
  • m2 represents an integer of 0 to 3
  • m3 represents an integer of 0 to 4
  • * is each a binding site to another structure represents
  • each R independently represents a substituent
  • m2 represents an integer of 0 to 2
  • m3 represents an integer of 0 to 3
  • L 2 is -CR C 2 -
  • R 2 C represents a monovalent organic group
  • * each represents a bonding site with another structure.
  • R 111 in the above formula (2) is a group represented by any one of the following formulas (W1-1) to (W1-5), or a group containing one or more aliphatic ring structures and R 111 in the above formula (PAI-2) contains a group represented by any one of the following formulas (W1-1) to (W1-3), or one or more aliphatic ring structures
  • R represents a substituent
  • n1 represents an integer of 0 to 4
  • * each represents a binding site to another structure.
  • each R independently represents a substituent
  • each m4 independently represents an integer of 0 to 4
  • each * represents a binding site to another structure.
  • each R independently represents a substituent
  • each m4 independently represents an integer of 0 to 3
  • R C represents a monovalent organic group
  • * each represents a binding site to another structure.
  • each R independently represents a substituent
  • n3 represents an integer of 0 to 6
  • R each independently represents a substituent
  • n4 each independently represents an integer of 0 to 3
  • X 1 and X 2 each independently represent an oxygen atom
  • each R C independently represents a hydrogen atom or a monovalent organic group
  • each * represents a binding site to another structure.
  • Condition 1 The precursor of the cyclized resin is a group in which at least one of —A 2 —R 113 and —A 1 —R 114 in the above formula (2) is represented by the following formula (3-1).
  • the precursor of the cyclized resin contains a repeating unit in which —A 2 —R 113 in formula (PAI-2) is a group represented by formula (3-1) below.
  • Z 1 and Z 2 each independently represent an organic group, Z 1 and Z 2 may combine to form a ring structure, and * is a bonding site with another structure. represents ⁇ 19> A method for producing a laminate, comprising repeating the method for producing a cured product according to any one of ⁇ 1> to ⁇ 18> multiple times.
  • a method for producing a semiconductor device comprising the method for producing a cured product according to any one of ⁇ 1> to ⁇ 18> or the method for producing a laminate according to ⁇ 19>.
  • a resin composition containing a precursor of a cyclized resin A resin composition in which at least one of three films with different thicknesses has a glass transition temperature of 200° C. or higher when the glass transition temperature is measured under the following measurement conditions 1; Measurement condition 1: The resin composition was coated on a silicon substrate to a thickness of 5 ⁇ m, 10 ⁇ m, or 20 ⁇ m, respectively, dried at 100° C. for 5 minutes, heated at 180° C. for 2 hours to obtain a cured product, and returned to 25° C.
  • the glass transition temperature of the cured product is measured using a differential scanning calorimeter.
  • ⁇ 24> A semiconductor device comprising the cured product according to ⁇ 22> or the laminate according to ⁇ 23>.
  • cured material which can obtain hardened
  • a numerical range represented by the symbol "to” means a range including the numerical values before and after "to” as lower and upper limits, respectively.
  • the term "process” is meant to include not only independent processes, but also processes that are indistinguishable from other processes as long as the desired effects of the process can be achieved.
  • a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent.
  • alkyl group includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups).
  • exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified.
  • Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • (meth)acrylate means both or either of “acrylate” and “methacrylate”
  • (meth)acrylic means both “acrylic” and “methacrylic”
  • (meth)acryloyl means either or both of “acryloyl” and “methacryloyl”.
  • Me in the structural formulas represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • total solid content refers to the total mass of all components of the composition excluding the solvent.
  • the solid content concentration is the mass percentage of other components excluding the solvent with respect to the total mass of the composition.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using a gel permeation chromatography (GPC) method, unless otherwise specified, and are defined as polystyrene conversion values.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are, for example, HLC-8220GPC (manufactured by Tosoh Corporation), guard column HZ-L, TSKgel Super HZM-M, TSKgel It can be obtained by connecting Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (manufactured by Tosoh Corporation) in series. Unless otherwise stated, their molecular weights were determined using THF (tetrahydrofuran) as an eluent.
  • THF tetrahydrofuran
  • NMP N-methyl-2-pyrrolidone
  • detection in GPC measurement uses a UV ray (ultraviolet) wavelength detector of 254 nm.
  • UV ray ultraviolet
  • a third layer or element may be 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.
  • the direction in which the layers are stacked with respect to the base material is referred to as "upper", or when there is a resin composition layer, the direction from the base material to the resin composition layer is referred to as “upper”. and the opposite direction is called “down”.
  • the composition may contain two or more compounds corresponding to each component contained in the composition.
  • the content of each component in the composition means the total content of all compounds corresponding to that component.
  • the temperature is 23° C.
  • the pressure is 101,325 Pa (1 atm)
  • the relative humidity is 50% RH unless otherwise specified. Combinations of preferred aspects are more preferred aspects herein.
  • the method for producing a cured product of the present invention includes a film forming step of applying a resin composition containing a precursor of a cyclized resin onto a substrate to form a film, and heating the film at a heating temperature of 180 ° C. or less.
  • a cured product with less outgassing can be obtained.
  • a cured product is obtained using a resin composition containing a precursor of a cyclized resin.
  • the heating temperature in the heating step is 180°C or lower, and the glass transition temperature of the film after the heating step is 200°C or higher.
  • the cyclization rate of the cyclized resin in the film is high. It is believed that the high degree of cyclization when cured at 180° C.
  • the glass transition temperature is considered to correlate with the rigidity of the structure of the polymerizable compound and the reaction rate. That is, when the glass transition temperature is 200° C. or higher, the structure formed by polymerizing the polymerizable compound is relatively rigid, and the amount of unreacted polymerizable compound in the film is small. It is considered that outgassing is more likely to be suppressed when the structure formed by polymerizing the polymerizable compound is a rigid structure.
  • the method for producing a cured product of the present invention includes a film forming step of applying a resin composition containing a cyclized resin precursor onto a substrate to form a film.
  • the details of the resin composition will be described later.
  • the type of base material can be appropriately determined according to the application, and includes semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals, and substrates having metal layers formed by plating, vapor deposition, etc.) ), paper, SOG (Spin On Glass), TFT (Thin Film Transistor) array substrates, mold substrates, plasma display panel (PDP) electrode plates, etc., and are not particularly limited.
  • semiconductor manufacturing base materials such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon, quartz, glass, optical films, ceramic materials, vapor deposition films, Magnetic films, reflective films, metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metals, and substrates having metal layers formed by plating, vapor deposition, etc.
  • a semiconductor fabrication substrate is particularly preferable, and a silicon substrate, a Cu substrate and a mold substrate 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.
  • HMDS hexamethyldisilazane
  • the shape of the substrate is not particularly limited, and may be circular or rectangular.
  • the diameter is, for example, 100 to 450 mm, preferably 200 to 450 mm.
  • the short side length is, for example, 100 to 1000 mm, preferably 200 to 700 mm.
  • the base material for example, a plate-like base material (substrate), preferably a panel-like base material (substrate) is used.
  • the resin layer or metal layer serves as the base material.
  • Coating is preferable as a means of applying the resin composition onto the substrate.
  • Specific means to be applied include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, An inkjet method and the like are exemplified. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet method is more preferable, and spin coating from the viewpoint of uniformity of film thickness and productivity. and slit coating methods are preferred.
  • a film having a desired thickness can be obtained by adjusting the solid content concentration and application conditions of the resin composition according to the method.
  • the coating method can be appropriately selected depending on the shape of the substrate. Spin coating, spray coating, inkjet method, etc.
  • slit coating and spray coating are preferable for rectangular substrates.
  • method, inkjet method, and the like are preferred.
  • the spin coating method for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
  • a method of transferring a coating film, which is formed on a temporary support in advance by the application method described above, onto a base material can be applied.
  • the transfer method the manufacturing methods described in paragraphs 0023 and 0036 to 0051 of JP-A-2006-023696 and paragraphs 0096-0108 of JP-A-2006-047592 can also be preferably used in the present invention.
  • a step of removing excess film at the edge of the substrate may be performed.
  • processes include edge bead rinsing (EBR), back rinsing, and the like.
  • EBR edge bead rinsing
  • a pre-wetting step may also be employed in which the substrate is coated with various solvents before applying the resin composition to the substrate to improve the wettability of the substrate, and then the resin composition is applied.
  • the film may be subjected to a step of drying the formed film (layer) to remove the solvent (drying step) after the film forming step (layer forming step). That is, the method for producing a cured product of the present invention may include a drying step of drying the film formed by the film forming step. Moreover, the drying step is preferably performed after the film formation step and before the exposure step.
  • the drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, even more preferably 90 to 110°C. Moreover, you may dry by pressure reduction.
  • the drying time is exemplified from 30 seconds to 20 minutes, preferably from 1 minute to 10 minutes, more preferably from 2 minutes to 7 minutes.
  • the method for producing a cured product of the present invention includes a heating step of heating the film at a heating temperature of 180° C. or lower.
  • the film in the heating step may be a film (pattern) after development that has undergone an exposure step and a development step, which will be described later, or a film that has undergone an exposure step, which will be described later, but has not undergone a development step.
  • it may be a film formed by the above-described film forming step (and, if necessary, the above-described drying step) without undergoing other steps.
  • the temperature of the film is preferably 180° C. or lower in all steps including the heating step.
  • the temperature of the film is preferably 180° C. or lower in all steps including the heating step. According to the above aspect, it is possible to suppress thermal damage to the material such as the base material.
  • a resin such as a polyimide precursor is cyclized into a resin such as polyimide.
  • cross-linking of unreacted cross-linkable groups in the specific resin described later or in a cross-linking agent other than the specific resin also progresses.
  • the heating temperature (maximum heating temperature) in the heating step is preferably 20°C to 180°C, more preferably 150°C to 180°C, and even more preferably 160°C to 180°C.
  • the film after the heating step is preferably a polyimide film.
  • the resin contained in the film after the heating step is a resin having an imide ring structure in the repeating unit.
  • the heating step is preferably a step of promoting the cyclization reaction of the precursor of the cyclized resin in the film by heating. It is more preferable that the step promotes the cyclization reaction of the precursor of the cyclized resin in the film by the action of the permeated base, the base permeated from the rinsing liquid, or the like. That is, before and after the heating step, it is preferable that the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin in the film after the heating step increases.
  • the cyclization rate (%) of the precursor of the cyclized resin in the film before the heating step is A
  • the ring of the cyclized resin obtained from the precursor of the cyclized resin in the film after the heating step is
  • the cyclization rate (%) is defined as the cyclization rate B
  • the difference in the cyclization rate represented by the following formula is preferably 70% or more, more preferably 80% or more, and 90% or more. It is even more preferable to have
  • Heating in the heating step is preferably carried out at a temperature rising rate of 0.1 to 30° C./min from the temperature at the start of heating to the maximum heating temperature.
  • the rate of temperature increase is more preferably 0.5 to 20°C/min, still more preferably 2 to 10°C/min.
  • the temperature rise rate is more preferably 0.5 to 20°C/min, still more preferably 2 to 10°C/min.
  • the temperature rise rate is preferably increased from the temperature at the start of heating to the maximum heating temperature at a rate of 1 to 30°C/sec, more preferably 2 to 20°C/sec, and 3 to 10°C/sec. °C/sec is more preferred.
  • 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 up to the maximum heating temperature is started.
  • the temperature of the film (layer) after drying is, for example, 30 to 200° C. higher than the boiling point of the solvent contained in the resin composition. It is preferable to raise the temperature from a low temperature.
  • the heating time (heating time at the maximum heating temperature) is preferably 30 minutes to 5 hours, more preferably 1 hour to 3 hours.
  • the temperature fluctuation width when maintaining the maximum heating temperature is preferably 0.1 ° C. to 20 ° C., and 0.1 to 10 ° C. is more preferred, and 0.1°C to 3°C is more preferred.
  • the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, and further preferably 100° C. or higher, from the viewpoint of adhesion between layers. It is particularly preferably above 120°C, most preferably above 150°C.
  • the upper limit of the heating temperature is 180° C. or lower, preferably 170° C. or lower.
  • the method for producing a cured product may include the step of heating at a heating temperature above 180°C, or may not include the step of heating at a heating temperature above 180°C.
  • Heating may be done in stages. As an example, the temperature is raised from 25° C. to 120° C. at 3° C./min, held at 120° C. for 60 minutes, heated from 120° C. to 180° C. at 2° C./min, and held at 180° C. for 120 minutes. , may be performed. It is also preferable to carry out the treatment while irradiating ultraviolet rays as described in US Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film.
  • the pretreatment step is preferably performed for a short time of about 10 seconds to 2 hours, more preferably 15 seconds to 30 minutes.
  • the pretreatment may be performed in two or more steps.
  • the first pretreatment step may be performed in the range of 100 to 150°C, and then the second pretreatment step may be performed in the range of 150 to 180°C. good. Further, 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 carried out in an atmosphere of low oxygen concentration, such as by flowing an inert gas such as nitrogen, helium or argon, or under reduced pressure, in order to prevent decomposition of the specific resin.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
  • the heating in the heating step may be performed under normal pressure or under reduced pressure.
  • the pressure reduction may be completed before the start of heating, the pressure reduction may be completed during the temperature rise from the start of heating, or the pressure reduction may be completed after the maximum heating temperature is reached.
  • the timing of completion of decompression is not particularly limited. Completion of pressure reduction means that the pressure becomes 20 mmHg (volume ratio) or less.
  • the above pressure can be measured with a differential pressure gauge.
  • the membrane is under reduced pressure during the entire time period during which the maximum heating temperature is maintained.
  • the heating means in the heating step is not particularly limited, and examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, an infrared oven and the like.
  • the film before the heating step may be subjected to an exposure step for selectively exposing the film.
  • the method for producing a cured product of the present invention may include an exposure step of selectively exposing the film formed by the film forming step between the film forming step and the heating step.
  • Selectively exposing means exposing a portion of the film.
  • the film is formed with exposed regions (exposed portions) and non-exposed regions (non-exposed portions).
  • the amount of exposure is not particularly defined as long as the resin composition can be cured. For example, it is preferably 50 to 10,000 mJ/cm 2 and more preferably 200 to 8,000 mJ/cm 2 in terms of exposure energy at a wavelength of 365 nm. .
  • the exposure wavelength can be appropriately determined in the range of 190-1,000 nm, preferably 240-550 nm.
  • the exposure wavelength is (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm) ), F2 excimer laser ( wavelength 157 nm), (5) extreme ultraviolet; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc.
  • semiconductor laser wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355
  • the resin composition exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is particularly preferred. Thereby, particularly high exposure sensitivity can be obtained.
  • the method of exposure is not particularly limited as long as at least a part of the film made of the resin composition is exposed. Examples thereof include exposure using a photomask and exposure by a laser direct imaging method.
  • the film may be subjected to a step of heating after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step of heating the exposed film in the exposure step. Before and after the post-exposure heating step, it is also preferred that the cyclization rate of the film after the heating step (that is, the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin) does not substantially increase. Specifically, the above-described difference in cyclization rate is preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less. The upper limit of the cyclization rate is not particularly limited, and may be 0%.
  • the difference in cyclization rate is preferably 30% or less, more preferably 20% or less, and 10% or less. More preferred.
  • the upper limit of the cyclization rate is not particularly limited, and may be 0%.
  • the post-exposure heating step can be performed after the exposure step and before the development step.
  • the heating temperature in the post-exposure heating step is preferably 50°C to 140°C, more preferably 60°C to 120°C.
  • the heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, more preferably 1 minute to 10 minutes.
  • the heating rate in the post-exposure heating step is preferably 1 to 12° C./min, more preferably 2 to 10° C./min, still more preferably 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature. Also, the rate of temperature increase may be appropriately changed during heating.
  • the heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters and the like can be used. Moreover, it is also preferable to carry out the heating in an atmosphere of low oxygen concentration by, for example, flowing an inert gas such as nitrogen, helium or argon.
  • the film after exposure may be subjected to a development step in which the film is developed using a developer to form a pattern.
  • the method for producing a cured product of the present invention may include a development step of developing a film exposed in the exposure step with a developer to form a pattern. By performing development, one of the exposed and non-exposed portions of the film is removed to form a pattern.
  • the development in which the non-exposed portion of the film is removed by the development process is called negative development, and the formed pattern is called negative pattern.
  • development in which the exposed portion of the film is removed by the development process is called positive development, and the formed pattern is called positive pattern.
  • the developing step is preferably a step of forming a negative pattern.
  • Examples of the developer used in the developing step include an aqueous alkaline solution and a developer containing an organic solvent, and the developer containing an organic solvent is preferable.
  • basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
  • TMAH tetramethylammonium hydroxide
  • potassium hydroxide sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine , dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, Butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammoni
  • the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, more preferably 0.3 to 3% by mass, based on the total mass of the developer. is more preferred.
  • the organic solvent may be an ester such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, Methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetate (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
  • 3-alkyloxypropionate alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., 3-methoxy methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.
  • 2-alkyloxypropionate alkyl esters e.g.
  • methyl 2-alkyloxypropionate, 2- ethyl alkyloxypropionate, propyl 2-alkyloxypropionate, etc. e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionic acid ethyl
  • methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate e.g.
  • ethers such as 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 (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene Glycol monoethyl ether acetate
  • the organic solvent can be used singly or in combination of two or more.
  • a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, and cyclopentanone and ⁇ -butyrolactone. and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is most preferred.
  • the content of the organic solvent relative to the total weight of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, and 80% by mass or more. is more preferable, and 90% by mass or more is particularly preferable. Moreover, the content may be 100% by mass. Further, when the developer contains an organic solvent, the content of water relative to the total weight of the developer is preferably 10% by mass or less, more preferably 5% by mass or less, and 1% by mass or less. is more preferable, and 0.1% by mass or less is particularly preferable. The content of water is not particularly limited, and may be 0% by mass.
  • the developer contains at least one compound selected from the group consisting of bases and base generators.
  • the base or base generator in the developer penetrates into the film, and in the subsequent heating step, the base or the base generated from the base generator acts to form a precursor of the cyclized resin. It is thought that the cyclization of is promoted.
  • the developer preferably contains a base.
  • the developer is preferably a developer containing an organic solvent.
  • bases are organic bases from the viewpoint of reliability when remaining in the cured product (adhesion to the substrate when the cured product is further heated).
  • a base having an amino group is preferable, and primary amine, secondary amine, tertiary amine, ammonium salt, tertiary amide, etc. are preferable.
  • secondary amines and tertiary amines are preferred, secondary amines or tertiary amines are more preferred, and tertiary amines are most preferred.
  • the base is preferably one that does not easily remain in the resulting cured product. It is preferable that the remaining amount is difficult to decrease before.
  • the boiling point of the base is preferably 30°C to 350°C, more preferably 80°C to 270°C, even more preferably 100°C to 230°C at normal pressure (101,325 Pa).
  • the boiling point of the base is preferably higher than the boiling point of the organic solvent contained in the developer minus 20° C., and more preferably higher than the boiling point of the organic solvent contained in the developer.
  • the base used preferably has a boiling point of 80° C. or higher, more preferably 100° C. or higher.
  • the pKa of the conjugate acid of the base in DMSO is preferably 1 or more, more preferably 3 or more. Although the upper limit of the pKa is not particularly limited, it is preferably 20 or less. When the conjugate acid of the above base has multiple pKa's in DMSO, at least one of them is preferably within the above range.
  • the above pKa represents the logarithm of the reciprocal of the first dissociation constant of the acid, Determination of Organic Structures by Physical Methods (Author: Brown, H.C., McDaniel, D.H., Hafliger, O., Nachod, F.C.; Compilation: Braude, E.
  • the base contained in the developer include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, dimethylcyclohexylamine, aniline, N-methyl Aniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo [2.2.2] octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, 1,5-diaminopentane, N-methylhexylamine
  • the content of the base relative to the total weight of the developer is preferably 0.1 to 100% by mass, more preferably 0.3 to 30% by mass, and 0.5% by mass. More preferably, it is up to 20% by mass. Also, when the base is not liquid at 10 to 30° C., the content of the base is preferably 0.3 to 30% by mass, more preferably 0.5 to 20% by mass.
  • One type of base may be used alone, or two or more types may be used in combination. When two or more bases are used in the developer, the total content thereof is preferably within the above range.
  • the developer may contain a base generator.
  • the base generator include photobase generators and thermal base generators, with thermal base generators being preferred.
  • the photobase generator or thermal base generator for example, the base generators described below as components contained in the resin composition can be used without particular limitation.
  • the content of the base generator with respect to the total weight of the developer is preferably 0.005 to 100% by mass, more preferably 0.05 to 20% by mass. , more preferably 0.08 to 5% by mass.
  • the base generator may be used singly or in combination of two or more. When two or more base generators are used in the developer, the total content thereof is preferably within the above range.
  • the developer may further contain other components.
  • Other components include, for example, known surfactants and known antifoaming agents.
  • the method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and a method of immersing the substrate on which the film is formed in the developer, and supplying the developer to the film formed on the substrate using a nozzle.
  • the type of nozzle is not particularly limited, and straight nozzles, shower nozzles, spray nozzles and the like can be mentioned. From the viewpoint of permeability of the developer, removability of the non-image area, and efficiency in production, a method of supplying the developer with a straight nozzle or a method of continuously supplying the developer with a spray nozzle is preferable.
  • the method of supplying with a spray nozzle is more preferable.
  • the substrate is spun to remove the developer from the substrate.
  • a step of removing from above may be employed, and this step may be repeated multiple times.
  • the method of supplying the developer in the development process includes a process in which the developer is continuously supplied to the base material, a process in which the developer is kept substantially stationary on the base material, and a process in which the developer exceeds the developer on the base material.
  • a process of vibrating with sound waves or the like and a process of combining them can be employed.
  • the development time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
  • the temperature of the developer during development is not particularly limited, but is preferably 10 to 45°C, more preferably 18 to 30°C.
  • the pattern is brought into contact with a processing solution containing at least one compound selected from the group consisting of bases and base generators between the developing step and the heating step. It is preferable to include a step, and it is more preferable to include, between the developing step and the heating step, a processing step of bringing the pattern into contact with a processing liquid containing a base. According to this aspect, it is considered that at least one compound selected from the group consisting of bases and base generators contained in the processing liquid permeates the pattern after development.
  • the cyclization rate of the cyclized resin obtained from the cyclized resin precursor in the film after the heating step increases, and even when heated at a low temperature of 180° C. or less, the glass transition temperature increases, It is considered that a cured product with little outgassing can be obtained.
  • the treatment step is a rinse step of washing the pattern with the treatment liquid.
  • the treatment liquid is preferably a rinse liquid.
  • the treatment liquid is a rinse liquid
  • the treatment step is a rinse step of washing the pattern with the rinse liquid. That is, the treatment step is preferably a rinse step of washing the pattern (pattern obtained by the development step) with a rinse solution containing at least one compound selected from the group consisting of bases and base generators. .
  • the treatment process may be performed, for example, after "another rinsing process" to be described later.
  • the water content relative to the total mass of the treatment liquid is preferably 50% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, and 5% by mass or less. is more preferable, and 2% by mass or less is particularly preferable.
  • the lower limit of the content of water is not particularly limited, and may be 0% by mass.
  • a solvent contained in the developer and a solvent different from the solvent contained in the developer for example, an organic solvent different from the organic solvent contained in the developer
  • a solvent containing at least one compound selected from the group consisting of can be used.
  • -base- Preferred embodiments of the base contained in the processing liquid are the same as the preferred embodiments of the base contained in the developer described above.
  • a tertiary amine is preferable as the base contained in the treatment liquid.
  • a base that hardly reacts with the solvent (for example, cyclopentanone, etc.) used in the treatment liquid is preferable.
  • the content of the base relative to the total weight of the treatment liquid is preferably 0.1 to 100% by mass, more preferably 0.3 to 30% by mass, and 0.5% by mass. More preferably, it is up to 20% by mass. Also, when the base is not liquid at 10 to 30° C., the content of the base is preferably 0.3 to 30% by mass, more preferably 0.5 to 20% by mass.
  • One type of base may be used alone, or two or more types may be used in combination. When two or more types of bases are used in combination in the treatment liquid, the total content thereof is preferably within the above range.
  • the treatment liquid may contain a base generator.
  • the base generator include photobase generators and thermal base generators, with thermal base generators being preferred.
  • the photobase generator or thermal base generator for example, the photobase generator or thermal base generator described below as a component contained in the resin composition can be used without particular limitation.
  • the content of the base generator relative to the total weight of the treatment liquid is preferably 0.005 to 100% by mass, more preferably 0.05 to 20% by mass. , more preferably 0.08 to 5% by mass.
  • the base generator may be used singly or in combination of two or more. When two or more kinds of base generators are used in combination in the treatment liquid, the total content thereof is preferably within the above range.
  • Organic solvents contained in the treatment liquid include esters such as ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, Ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
  • 3-alkyloxypropionate alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate , ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.
  • 2-alkyloxypropionate alkyl esters e.g.
  • methyl 2-alkyloxypropionate, 2-alkyloxypropionate ethyl acetate, propyl 2-alkyloxypropionate, etc. e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)
  • methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
  • methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and ethers such
  • Glycol, methyl isobutyl carbinol, triethylene glycol and the like, and amides preferably include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide and the like.
  • the base eg, organic base
  • the base described above can be used as the solvent and the base.
  • the organic solvent can be used singly or in combination of two or more.
  • the organic solvent can be used singly or in combination of two or more.
  • cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA and PGME are particularly preferred, cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, PGMEA and PGME are more preferred, and cyclohexanone and PGMEA are more preferred. More preferred.
  • the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and 90% by mass or more of the total mass of the treatment liquid.
  • Organic solvents are more preferred.
  • 100% by mass of the treatment liquid may be an organic solvent.
  • the treatment liquid may further contain other components.
  • Other components include, for example, known surfactants and known antifoaming agents.
  • the method of supplying the processing liquid is not particularly limited as long as the processing liquid can be brought into contact with the pattern obtained in the developing step. be done.
  • the supply method is not particularly limited, and includes a method of immersing the substrate in the processing liquid, a method of supplying the substrate with a paddle (liquid heap), a method of supplying the processing liquid to the substrate by showering, and a method of supplying the processing liquid onto the substrate.
  • a method of continuously supplying the processing liquid using a nozzle is preferable, and the method of supplying the processing liquid to the image area is preferable.
  • a method in which the treatment liquid supplied from the nozzle is kept on the substrate is more preferable.
  • the above treatment liquid supply methods (for example, a combination of paddle supply and shower supply, paddle supply and straight nozzle supply) may be used in combination.
  • paddle feeding has the effect that the membrane swells, making it easier for subsequent treatment liquids to permeate.
  • the treatment liquid may be used in at least one of the combined methods.
  • the treatment process using the treatment liquid may be performed.
  • Preferred aspects of the treatment liquid that does not contain a base and a base generator are the same as preferred aspects of the rinsing solution in other rinsing steps described later.
  • the method of supplying the processing liquid containing no base and base generator onto the pattern in the above embodiment is not particularly limited, but a method of supplying with a paddle can be mentioned.
  • the method of supplying the treatment liquid onto the pattern in the above-described mode is not particularly limited, but preferred examples include supply by a shower, supply by a straight nozzle, and the like.
  • a base-free treatment liquid from the paddle By supplying a base-free treatment liquid from the paddle, the pattern swells, and at least one compound selected from the group consisting of bases and base generators in the treatment liquid to be supplied later easily permeates into the pattern. Therefore, it is considered that the effects such as improvement of elongation at break are more likely to be obtained.
  • the processing liquid from a shower, a straight nozzle, or the like the removability (rinsability) of development scum and the like may be excellent.
  • the method of supplying the processing liquid in the processing step includes a process in which the processing liquid is continuously supplied to the substrate, a process in which the processing liquid is kept in a substantially stationary state on the substrate, and a process in which the processing liquid is kept on the substrate in a substantially stationary state.
  • a process of vibrating with sound waves or the like and a process of combining them can be employed.
  • the processing step is preferably a step of showering or continuously supplying the processing liquid to the pattern after development. It is also preferable that development in the development step is performed by puddle development, and at least one supply of the processing liquid in the processing step is performed by shower supply or continuous supply by a straight nozzle or the like.
  • the puddle development swells the pattern, which facilitates penetration of at least one compound selected from the group consisting of bases and base generators in the processing liquid into the pattern, thereby improving elongation at break and the like. It is considered that the effect of is more likely to be obtained.
  • the treatment time in the treatment step (that is, the time during which the treatment liquid is in contact with the pattern) is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes.
  • the temperature of the treatment solution during the treatment step is not particularly defined, but it is preferably 10 to 45°C, more preferably 18 to 30°C.
  • the method for producing a cured product of the present invention includes a rinsing step (hereinafter also referred to as "another rinsing step") in which the pattern (pattern obtained by the developing step) is washed with a rinsing solution that does not contain a base or a base generator. ) may be included.
  • the method for producing a cured product of the present invention can include other rinsing steps, for example, before the processing steps described above and after the developing steps described above.
  • the method for producing a cured product of the present invention does not include the above-described treatment step, it can be included after the above-described development step and before the above-described heating step.
  • the same liquid as the above-described treatment liquid can be used except that it does not contain a base and a base generator. It is the same as the preferred embodiment of each component other than the base and the base generator contained in the liquid. Also, the rinse liquid can be supplied to the pattern in the same manner as the treatment liquid described above.
  • the pattern obtained by the development step (the pattern after rinsing when the rinsing step is performed) is subjected to a post-development exposure step of exposing the pattern after the development step instead of or in addition to the heating step.
  • the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step.
  • the method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
  • the post-development exposure step for example, a reaction in which cyclization of a polyimide precursor or the like proceeds by exposure of a photobase generator, or a reaction in which elimination of an acid-decomposable group proceeds by exposure of a photoacid generator is promoted. can do.
  • the post-development exposure step at least part of the pattern obtained in the development step may be exposed, but it is preferable that the entire pattern be exposed.
  • the exposure amount in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , more preferably 100 to 15,000 mJ/cm 2 in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive. preferable.
  • the post-development exposure step can be performed using, for example, the light source used in the exposure step described above, and broadband light is preferably used.
  • the pattern obtained by the development step may be subjected to a metal layer forming step of forming a metal layer on the pattern. That is, the method for producing a cured product of the present invention includes a metal layer forming step of forming a metal layer on the pattern obtained by the developing step (preferably subjected to at least one of the heating step and the post-development exposure step). is preferred.
  • the metal layer is not particularly limited, and existing metal species can be used. Examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. copper and aluminum are more preferred, and copper is even more preferred.
  • the method of forming the metal layer is not particularly limited, and existing methods can be applied. For example, use the methods described in JP-A-2007-157879, JP-A-2001-521288, JP-A-2004-214501, JP-A-2004-101850, US Pat. can do.
  • photolithography, PVD (Physical Vapor Deposition), CVD (Chemical Vapor Deposition), lift-off, electroplating, electroless plating, etching, printing, and a combination thereof can be considered. More specifically, a patterning method combining sputtering, photolithography and etching, and a patterning method combining photolithography and electroplating can be used.
  • a preferred embodiment of plating is electroplating using a copper sulfate or copper cyanide plating solution.
  • the thickness of the metal layer is preferably 0.01 to 50 ⁇ m, more preferably 1 to 10 ⁇ m, at the thickest part.
  • the glass transition temperature of the cured product obtained is 200° C. or higher, preferably 220° C. or higher, and more preferably 250° C. or higher.
  • the upper limit of the glass transition temperature is not particularly limited, it is preferably 350° C. or lower.
  • the glass transition temperature is calculated by the method described in Examples.
  • the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin in the film after the heating step is preferably 90% or more, more preferably 95% or more. It is more preferably 98% or more, and particularly preferably 99% or more.
  • the film after the heating step is a polyimide film, and the imidization rate of the polyimide is preferably 90% or more, more preferably 95% or more, even more preferably 98% or more, 99% or more is particularly preferred.
  • the upper limit of the cyclization rate is not particularly limited, and may be 100%. The above cyclization rate is calculated by the following method.
  • the precursor of the cyclized resin is a polyimide precursor or a polyamideimide precursor
  • the infrared absorption spectrum of the film after the heating step is measured, and the peak intensity P1 near 1377 cm -1 which is an absorption peak derived from the imide structure is measured. demand.
  • the infrared absorption spectrum is measured again to obtain the peak intensity P2 near 1377 cm ⁇ 1 .
  • the cyclization rate (imidation rate) can be determined based on the following formula.
  • Imidation rate (%) (peak intensity P1/peak intensity P2) x 100
  • the peak intensity Q1 near 1650 cm ⁇ 1 which is the absorption peak derived from the amide structure of the film after the heating step.
  • normalization is performed by the absorption intensity of the aromatic ring seen around 1490 cm ⁇ 1 .
  • the peak intensity Q2 near 1650 cm ⁇ 1 is obtained, and the aromatic ring seen near 1490 cm ⁇ 1 is measured. Normalize by absorption intensity.
  • the cyclization rate (oxazole conversion rate) can be determined according to the following formula.
  • Oxazolization rate (%) (standardized value of peak intensity Q1/standardized value of peak intensity Q2) x 100
  • the cyclization rate (imidization rate, oxazolization rate) compounds having absorption at a wavelength of 1377 cm -1 or 1377 cm -1 or 1490 cm -1 or 1650 cm -1 in the composition (for example, phthalimide, etc.), the peak intensity derived from this compound may be removed as the background.
  • the form of the cured product of the resin composition is not particularly limited, and can be selected from film-like, rod-like, spherical, pellet-like, etc. according to the application.
  • this cured product is preferably in the form of a film.
  • pattern processing of the resin composition can be used to form protective films on walls, form via holes for conduction, adjust impedance, capacitance or internal stress, and impart heat dissipation functions. You can also choose the shape.
  • the film thickness of the cured product (film made of the cured product) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
  • the shrinkage ratio of the film before and after the heating step is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
  • the shrinkage ratio refers to the percentage of volume change before and after the heating process, and can be calculated from the following formula.
  • Shrinkage rate [%] 100 - (volume after heating process / volume before heating process) x 100
  • the elongation at break of the cured product is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
  • the upper limit of the elongation at break is not particularly limited, it may be, for example, 200% or less.
  • the elongation at break can be measured according to JIS (Japanese Industrial Standards) K 6251:2017.
  • the coefficient of thermal expansion (CTE) of the cured product is preferably 70 ppm/K or less, preferably 60 ppm/K or less, and more preferably 50 ppm/K or less.
  • the lower limit of CTE is not particularly limited, and may be 0 ppm/K.
  • Fields to which the cured product of the present invention can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, and stress buffer films.
  • pattern formation by etching of a sealing film, a substrate material (a base film or coverlay of a flexible printed circuit board, an interlayer insulating film), or an insulating film for mounting as described above may be used.
  • the method for producing the cured product of the present invention or the cured product of the present invention can also be used for the production of plates such as offset plates or screen plates, for etching molded parts, for protective lacquers and dielectrics in electronics, especially microelectronics. It can also be used for the production of layers and the like.
  • resin composition used in the method for producing a cured product of the present invention is described below.
  • the resin composition in the present invention contains a precursor (specific resin) of a cyclized resin.
  • the cyclized resin is preferably a resin containing an imide ring structure or an oxazole ring structure in its main chain structure.
  • the main chain represents the relatively longest connecting chain in the resin molecule.
  • cyclized resins include polyimide, polybenzoxazole, and polyamideimide.
  • a precursor of a cyclized resin is a resin that undergoes a change in chemical structure by an external stimulus to become a cyclized resin, preferably a resin that undergoes a change in chemical structure by heat to become a cyclized resin.
  • a resin that becomes a cyclized resin by forming a ring structure is more preferable.
  • Precursors of the cyclized resin include polyimide precursors, polybenzoxazole precursors, polyamideimide precursors, and the like. That is, the resin composition in the present invention may contain, as the specific resin, at least one resin (specific resin) selected from the group consisting of polyimide precursors, polybenzoxazole precursors, and polyamideimide precursors. preferable.
  • the resin composition in the present invention preferably contains a polyimide precursor as the specific resin.
  • the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
  • the resin composition in the present invention preferably contains a radical polymerization initiator described later, and contains a radical polymerization initiator described later and a radical cross-linking agent described later. is more preferred. Further, if necessary, a sensitizer described later can be included. For example, a negative photosensitive film is formed from the resin composition of the present invention.
  • the specific resin may have a polarity conversion group such as an acid-decomposable group.
  • the resin composition in the invention preferably contains a photoacid generator, which will be described later. For example, a chemically amplified positive photosensitive film or negative photosensitive film is formed from the resin composition of the present invention.
  • the precursor of the cyclized resin is preferably a resin having at least one of a repeating unit represented by formula (2) and a repeating unit represented by formula (PAI-2), which will be described later.
  • R 115 in formula (2) described later is represented by any one of formulas (X1-1) to (X1-3) described later. or a group comprising one or more aliphatic ring structures, wherein R 117 in formula (PAI-2) described later is any of formulas (X2-1) to (X2-3) described later or a group containing one or more aliphatic ring structures.
  • aspect A such an aspect is described as aspect A.
  • R 111 in formula (2) described later is any one of formulas (W1-1) to (W1-5) described later. or a group comprising one or more aliphatic ring structures, wherein R 111 in formula (PAI-2) described later is formula (W1-1) to formula (W1-5) described later or a group containing one or more aliphatic ring structures. Furthermore, in the aspect A, from the viewpoint of suppressing outgassing from the cured product, it is preferable to satisfy at least one of the following conditions 1 and 2.
  • Condition 1 The precursor of the cyclized resin is a group in which at least one of —A 2 —R 113 and —A 1 —R 114 in the above formula (2) is represented by the following formula (3-1). Contains a repeating unit.
  • Condition 2 The precursor of the cyclized resin contains a repeating unit in which —A 2 —R 113 in formula (PAI-2) is a group represented by formula (3-1) below.
  • Condition 1 is satisfied when the cyclized resin precursor does not contain a repeating unit represented by formula (PAI-2), and the cyclized resin precursor contains a repeating unit represented by formula (2). If not, the condition 2 is satisfied, and if the precursor of the cyclized resin contains the repeating unit represented by the formula (2) and the repeating unit represented by the formula (PAI-2), conditions 1 and 2 It is more preferable to satisfy at least one of them.
  • polyimide precursor Although the type of the polyimide precursor used in the present invention is not particularly limited, it preferably contains a repeating unit represented by the following formula (2).
  • a 1 and A 2 each independently represent an oxygen atom or —NR z —
  • R 111 represents a divalent organic group
  • R 115 represents a tetravalent organic group
  • R 113 and R 114 each independently represent a hydrogen atom or a monovalent organic group
  • R z represents a hydrogen atom or a monovalent organic group.
  • a 1 and A 2 in formula (2) each independently represent an oxygen atom or —NR Z —, preferably an oxygen atom.
  • Rz represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom.
  • R Z represents a monovalent organic group
  • preferred embodiments of R Z are the same as preferred embodiments of Z 1 in formula (3-1) described later.
  • R 111 in formula (2) represents a divalent organic group.
  • divalent organic groups include groups containing linear or branched aliphatic groups, cyclic aliphatic groups and aromatic groups, linear or branched aliphatic groups having 2 to 20 carbon atoms, A cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferable, and a group containing an aromatic group having 6 to 20 carbon atoms is more preferable.
  • the hydrocarbon group in the chain may be substituted with a group containing a heteroatom, and in the cyclic aliphatic group and the aromatic group, the ring-membered hydrocarbon group is a heteroatom.
  • Ar is each independently an aromatic group
  • L is a single bond, an aliphatic hydrocarbon group having 1 to 10 carbon atoms optionally 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. Preferred ranges for these are as described above.
  • R 111 is preferably derived from a diamine.
  • Diamines used in the production of polyimide precursors include linear or branched aliphatic, cyclic aliphatic or aromatic diamines. Only one type of diamine may be used, or two or more types may be used. Specifically, a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, an aromatic group having 3 to 20 carbon atoms, or a group consisting of a combination thereof is preferably a diamine containing, more preferably a diamine containing an aromatic group having 6 to 20 carbon atoms. In the straight-chain or branched aliphatic group, the hydrocarbon group in the chain may be substituted with a group containing a heteroatom. may be substituted with a group containing Examples of groups containing aromatic groups include:
  • * represents a binding site with other structures.
  • diamines include 1,2-diaminoethane, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane and 1,6-diaminohexane; ,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 ether, 3, 3,3
  • diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International Publication No. 2017/038598.
  • diamines having two or more alkylene glycol units in the main chain described in paragraphs 0032 to 0034 of International Publication No. 2017/038598 are preferably used.
  • R 111 is preferably represented by -Ar-L-Ar- from the viewpoint of the flexibility of the resulting organic film.
  • Ar is each independently an aromatic group
  • L is an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S- , —SO 2 — or —NHCO—, or a group consisting of a combination of two or more of the above.
  • Ar is preferably a phenylene group
  • L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms optionally substituted with a fluorine atom, -O-, -CO-, -S- or -SO 2 - .
  • the aliphatic hydrocarbon group here is preferably an alkylene group.
  • R 111 is preferably a divalent organic group represented by the following formula (51) or (61).
  • a divalent organic group represented by Formula (61) is more preferable.
  • Equation (51) In formula (51), R 50 to R 57 are each independently a hydrogen atom, a fluorine atom or a monovalent organic group, and at least one of R 50 to R 57 is a fluorine atom, a methyl group or a trifluoro It is a methyl group, and each * independently represents a binding site to the nitrogen atom in formula (2).
  • the monovalent organic groups represented by R 50 to R 57 include unsubstituted alkyl groups having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), A fluorinated alkyl group and the like can be mentioned.
  • R 58 and R 59 are each independently a fluorine atom, a methyl group, or a trifluoromethyl group, and * is each independently a bonding site to the nitrogen atom in formula (2) show.
  • Diamines that give the structure of formula (51) or (61) include 2,2′-dimethylbenzidine, 2,2′-bis(trifluoromethyl)-4,4′-diaminobiphenyl, 2,2′-bis (Fluoro)-4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl and the like. These may be used alone or in combination of two or more.
  • R 111 is a group represented by any one of the following formulas (W1-1) to (W1-5), or one or more aliphatic A group containing a ring structure is also preferred. By including such a structure in R 111 , it is believed that the glass transition temperature of the cured product rises and the generation of outgassing from the cured product is suppressed.
  • R represents a substituent
  • n1 represents an integer of 0 to 4
  • * each represents a binding site with another structure.
  • each R independently represents a substituent
  • each m4 independently represents an integer of 0 to 4, and each * represents a binding site to another structure.
  • each R independently represents a substituent
  • each m4 independently represents an integer of 0 to 3
  • R C represents a monovalent organic group
  • each R independently represents a substituent
  • n3 represents an integer of 0 to 6
  • R each independently represents a substituent
  • n4 each independently represents an integer of 0 to 3
  • X 1 and X 2 each independently represent an oxygen atom
  • each R C independently represents a hydrogen atom or a monovalent organic group
  • the substituent represented by R is not particularly limited, but is an aliphatic hydrocarbon group, an aryl group, an alkoxy group, an alkylcarbonyl group, an alkoxycarbonyl group, an alkylcarbonyloxy group, an aryloxy group, an arylcarbonyl group. , an aryloxycarbonyl group, an arylcarbonyloxy group, a halogen atom, and the like.
  • the aliphatic hydrocarbon group is preferably an alkyl group, more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms.
  • the aryl group is preferably an aromatic hydrocarbon group, more preferably a phenyl group.
  • the alkyl group in the alkoxy group, alkylcarbonyl group, alkoxycarbonyl group, and alkylcarbonyloxy group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms.
  • the above alkyl group may be further substituted with a halogen atom or the like.
  • Such embodiments include a trifluoromethyl group, a pentafluoroethyl group, and the like.
  • aryl group in the aryloxy group, arylcarbonyl group, aryloxycarbonyl group, and arylcarbonyloxy group is preferably an aromatic hydrocarbon group, more preferably a phenyl group.
  • n1 is preferably an integer of 0 to 3, more preferably 0 or 1.
  • Preferred embodiments of R and m4 in formula (W1-2) are the same as preferred embodiments of R and n1 in formula (W1-1), respectively.
  • Preferred embodiments of R in formula (W1-3) are the same as preferred embodiments of R in formula (W1-1).
  • m4 is preferably an integer of 0 to 2, more preferably 0 or 1.
  • Preferred embodiments of R 1 C in formula (W1-3) are the same as preferred embodiments of R in formula (W1-1).
  • Preferred embodiments of R in formula (W1-4) are the same as preferred embodiments of R in formula (W1-1).
  • n3 is preferably an integer of 0-4, more preferably an integer of 0-2.
  • Preferred embodiments of R in formula (W1-5) are the same as preferred embodiments of R in formula (W1-1).
  • n4 is each independently preferably an integer of 0 to 2, more preferably 0 or 1.
  • R 1 C is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom.
  • the alicyclic structure in the group containing one or more alicyclic structures may be either a saturated alicyclic structure or an unsaturated alicyclic structure.
  • the aliphatic ring structure may be a heterocyclic structure, but preferably an aliphatic hydrocarbon ring structure.
  • the aliphatic ring structure in the group containing one or more aliphatic ring structures may be a monocyclic ring or a multicyclic ring such as a condensed ring, a bridged condensed ring, or a spiro ring.
  • Examples of the alicyclic structure in the group containing one or more alicyclic structures include cyclohexane structure, cyclohexene structure, bicyclo[2.2.2]oct-5-ene structure and the like.
  • R 115 in formula (2) represents a tetravalent organic group.
  • a tetravalent organic group containing an aromatic ring is preferable, and a group represented by the following formula (5) or (6) is more preferable.
  • each * independently represents a binding site to another structure.
  • R 112 is a single bond or a divalent linking group, a single bond, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, —O—, -CO-, -S-, -SO 2 -, and -NHCO-, and preferably a group selected from a combination thereof, having 1 to 1 carbon atoms optionally substituted by a single bond or a fluorine atom 3 alkylene group, -O-, -CO-, -S- and -SO 2 -, and -CH 2 -, -C(CF 3 ) 2 -, -C( It is more preferably a divalent group selected from the group consisting of CH 3 ) 2 -, -O-, -CO-, -S- and -SO 2 -.
  • R 115 is a group represented by any one of the following formulas (X1-1) to (X1-3), or one or more aliphatic A group containing a ring structure is also preferred.
  • R represents a substituent
  • n1 represents an integer of 0 to 2
  • * each represents a binding site to another structure.
  • each R independently represents a substituent
  • each m1 independently represents an integer of 0 to 3
  • each * represents a binding site to another structure.
  • each R independently represents a substituent
  • each m1 independently represents an integer of 0 to 3
  • R 2 C represents a monovalent organic group
  • * each represents a bonding site with another structure.
  • R in formula (X1-1) are the same as the preferred embodiments of R in formula (W1-1) described above.
  • n1 is preferably 0 or 1.
  • Preferred embodiments of R in formula (X1-2) are the same as the preferred embodiments of R in formula (W1-1) described above.
  • m1 is preferably 0 or 1.
  • Preferred embodiments of R in formula (X1-3) are the same as preferred embodiments of R in formula (W1-1).
  • m1 is preferably 0 or 1.
  • Preferred embodiments of R 1 C in formula (X1-3) are the same as preferred embodiments of R in formula (W1-1).
  • Preferred embodiments of the alicyclic structure in the group containing one or more alicyclic structures are the same as the preferred embodiments of the alicyclic structure in the group containing one or more alicyclic structures in R 111 described above. be.
  • R 115 specifically includes a tetracarboxylic acid residue remaining after removal of an anhydride group from a tetracarboxylic dianhydride.
  • the polyimide precursor may contain only one type of tetracarboxylic dianhydride residue, or may contain two or more types thereof, as the structure corresponding to R115 .
  • the tetracarboxylic dianhydride is preferably represented by the following formula (O).
  • R 115 represents a tetravalent organic group.
  • the preferred range of R 115 is synonymous with R 115 in formula (2), and the preferred range is also the same.
  • tetracarboxylic dianhydrides include pyromellitic dianhydride (PMDA), 3,3′,4,4′-biphenyltetracarboxylic dianhydride, 3,3′,4,4′- Diphenyl sulfide tetracarboxylic dianhydride, 3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, 3,3′ ,4,4′-diphenylmethanetetracarboxylic dianhydride, 2,2′,3,3′-diphenylmethanetetracarboxylic dianhydride, 2,3,3′,4′-biphenyltetracarboxylic dianhydride, 2,3,3′,4′-benzophenonetetracarboxylic dianhydride, 4,4′-oxydiphthalic dianhydride,
  • tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of WO 2017/038598 are also preferred examples.
  • R 111 and R 115 has an OH group. More specifically, R 111 includes residues of bisaminophenol derivatives.
  • R 113 and R 114 in formula (2) each independently represent a hydrogen atom or a monovalent organic group.
  • the monovalent organic group preferably includes a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
  • At least one of R 113 and R 114 preferably contains a polymerizable group, more preferably both contain a polymerizable group. It is also preferred that at least one of R 113 and R 114 contains two or more polymerizable groups.
  • the polymerizable group is a group capable of undergoing a cross-linking reaction by the action of heat, radicals, or the like, and is preferably a radically polymerizable group.
  • the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group. be done.
  • a group having an ethylenically unsaturated bond is preferred.
  • Groups having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), and a (meth)acrylamide group.
  • a (meth)acryloyloxy group a group represented by the following formula (III), and the like, and a group represented by the following formula (III) is preferable.
  • R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, preferably a hydrogen atom or a methyl group.
  • * represents a binding site with another structure.
  • R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
  • R 201 examples include ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2 —, cyclohexyl group, polyalkylene An oxy group is more preferred, and an alkylene group such as an ethylene group, a propylene group, or a polyalkyleneoxy group is even more preferred.
  • alkylene groups such as dodecamethylene, 1,2-butanediyl, 1, 3-butanediyl group, —CH 2 CH(OH)CH 2 —, polyalkyleneoxy group, ethylene group, alkylene group such as propylene group, —CH 2 CH(OH)CH 2
  • a polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
  • the alkylene groups in the plurality of alkyleneoxy groups contained in the polyalkyleneoxy group may be the same or different.
  • the arrangement of the alkyleneoxy groups in the polyalkyleneoxy group may be a random arrangement or a block arrangement. Alternatively, it may be arranged in a pattern such as an alternating pattern.
  • the number of carbon atoms in the alkylene group (including the number of carbon atoms in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, and 2 to 6.
  • the said alkylene group may have a substituent.
  • Preferred substituents include alkyl groups, aryl groups, and halogen atoms.
  • 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.
  • a group to which an oxy group is bonded is preferable, a polyethyleneoxy group or a polypropyleneoxy group is more preferable, and a polyethyleneoxy group is still more preferable.
  • the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, or may be arranged to form blocks. , may be arranged in a pattern such as alternately. Preferred embodiments of the number of repetitions of ethyleneoxy groups and the like in these groups are as described above.
  • the polyimide precursor when R 113 is a hydrogen atom, or when R 114 is a hydrogen atom, the polyimide precursor may form a tertiary amine compound having an ethylenically unsaturated bond and a counter salt. good.
  • tertiary amine compounds having ethylenically unsaturated bonds include N,N-dimethylaminopropyl methacrylate.
  • R 113 and R 114 may be a polarity conversion group such as an acid-decomposable group.
  • the acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxyl group. , a tertiary alkyl ester group and the like are preferable, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferable.
  • acid-decomposable groups include tert-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, and tert-butoxycarbonylmethyl. groups, trimethylsilyl ether groups, and the like. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
  • At least one of -A 2 -R 113 and -A 1 -R 114 is a repeating unit represented by the following formula (3-1). It is also preferred to include In formula (3-1), Z 1 and Z 2 each independently represent an organic group, Z 1 and Z 2 may combine to form a ring structure, and * is a bonding site with another structure. represents
  • a base is generated from the structure represented by the formula (3-1) during ring closure of the specific resin, and the ring closure is further promoted, so that it was obtained by heating at a low temperature of 180 ° C. or less. Even if it is a cured product, it is considered that the glass transition temperature increases and a cured product with less outgassing is obtained. Further, for example, when a base generator, which will be described later, is used, a residue may remain in the cured product after the base generator generates a base, and volatilization of this residue may cause outgassing. There is a case. However, in the case of a resin having a group represented by formula (3-1), what remains is the resin after ring closure. Therefore, it is considered that the residual low-molecular compound in the film after the heating process is eliminated, and the amount of outgassing is reduced.
  • the specific resin When the specific resin has a group represented by formula (3-1), the specific resin preferably generates a base at any temperature of 120 to 180°C. Further, the specific resin preferably generates a base when heated in the heating step. Whether or not a specific resin generates a base at a certain temperature X°C is judged by the following method. After heating 1 mol of the specific resin under 1 atmospheric pressure in a closed container at the above X° C. for 3 hours, the decomposition amount is quantified by a method such as HPLC (high performance liquid chromatography) to determine whether or not a base is generated. can be done. The amount of the base generated is preferably 0.1 mol or more, more preferably 0.5 mol or more. The upper limit of the amount of generated base is not particularly limited, but it can be, for example, 1000 mol or less.
  • the molecular weight of the base generated from the specific resin is preferably 40-1,000, more preferably 40-500, even more preferably 50-400.
  • the boiling point of the base having a pyridine structure at 1 atm is preferably 50 to 600°C, more preferably 50 to 500°C, even more preferably 50 to 450°C.
  • the generated base preferably has a conjugate acid with a pKa of 0 or more, more preferably 3 or more, and more preferably 6 or more.
  • the upper limit of the pKa of the conjugate acid is not particularly limited, it is preferably 30 or less.
  • the pKa is a dissociation reaction in which hydrogen ions are released from an acid, and its equilibrium constant Ka is represented by its negative common logarithm pKa.
  • pKa is a value calculated by ACD/ChemSketch (registered trademark).
  • RN is as described above.
  • the hydrocarbon group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, preferably an aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group.
  • the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-20, more preferably 1-10, and even more preferably 1-8.
  • the aliphatic hydrocarbon group may have a linear, branched, or cyclic structure, or may have a structure represented by a combination thereof.
  • the aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms, and still more preferably 6 carbon atoms.
  • the hydrocarbon group may have a known substituent as long as the effects of the present invention can be obtained.
  • An embodiment in which at least one of Z 1 and Z 2 has a polymerizable group is also one of preferred embodiments of the present invention.
  • the polymerizable group include a radically polymerizable group, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group and the like, and a radically polymerizable group is preferred.
  • the radically polymerizable group is preferably a group having an ethylenically unsaturated group, such as a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, a maleimide group, a styryl group, a vinyl group, a (meth)allyl group, and the like. mentioned.
  • a (meth)acryloxy group is preferable from the viewpoint of reactivity.
  • These polymerizable groups may be directly bonded to the nitrogen atom in formula (3-1), or may be bonded via a linking group such as a hydrocarbon group (eg, an alkylene group).
  • Z 1 and Z 2 may combine to form a ring structure.
  • the ring structure to be formed may be either an aromatic ring structure or an aliphatic ring structure, preferably an aliphatic ring structure, and more preferably a saturated aliphatic ring structure.
  • the above ring structure is preferably a cyclic amine having 2 to 10 carbon atoms, and examples thereof include a pyrrolidine ring, a piperidine ring, a morpholine ring, an octahydroindole ring, an octahydroisoindole ring, a pyrrole ring and a pyridine ring.
  • a ring, a piperidine ring or a morpholine ring are preferred.
  • the above ring structure may have a substituent within the range in which the effect of the present invention can be obtained.
  • a hydrocarbon group, a halogen atom, etc. are mentioned as a substituent.
  • Examples of the ring structure substituted with a substituent include a dimethylpiperidine ring.
  • the group represented by formula (3-1) is preferably a group represented by formula (3-1-1) or formula (3-1-2) below.
  • Cy represents an aliphatic ring structure or an aromatic ring structure, and * represents a binding site with another structure.
  • Z 3 and Z 4 each independently represent an alkyl group, and * represents a bonding site with another structure.
  • the ring structure represented by Cy is preferably an aliphatic ring structure, more preferably a saturated aliphatic ring structure.
  • the ring structure represented by Cy include pyrrolidine ring, piperidine ring, morpholine ring, octahydroindole ring, octahydroisoindole ring, pyrrole ring, pyridine ring and the like.
  • a ring is preferred.
  • the ring structure represented by Cy may have a substituent as long as the effects of the present invention can be obtained.
  • a hydrocarbon group, a halogen atom, etc. are mentioned as a substituent.
  • Examples of the ring structure substituted with a substituent include a dimethylpiperidine ring.
  • Z 3 and Z 4 each independently represent an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. Alkyl groups of 1 to 8 are more preferred.
  • the alkyl group may have a linear, branched, or cyclic structure, or may have a structure represented by a combination thereof.
  • Formula ( 3 _ _ _ _ _ The ratio of the total molar amount of the groups represented by -1) is preferably 0.1 mol % or more, more preferably 5 mol % or more, and even more preferably 10 mol % or more.
  • the total molar amount of groups represented by can be calculated, for example, by NMR (nuclear magnetic resonance).
  • the ratio of the total molar amount of the group represented by the formula (3-1) to the total molar amount of 113 is preferably 99.9 mol% or less, more preferably 95 mol% or less, and 90 It is more preferably mol % or less, and particularly preferably 80 mol % or less.
  • -A in the formula (2) contained in the specific resin 2 -R 113 and -A 1 -R 114 and the ratio of the molar amount of the group represented by formula (3-1) to the total molar amount of -A 2 -R 113 in formula (PAI-2) described later is preferably 80 mol % or more, more preferably 90 mol % or more, still more preferably 95 mol % or more, and particularly preferably 98 mol % or more.
  • the molar content of the group represented by the formula (3-1) contained in the specific resin relative to the total mass of the specific resin is preferably 0.001 to 10 mmol/g, more preferably 0.01 to 5 mmol/g. and more preferably 0.1 to 3 mmol/g.
  • the content mass of the group represented by formula (3-1) contained in the specific resin with respect to the total mass of the specific resin is preferably 0.1 to 70%, more preferably 0.5 to 40%. is more preferred, and 1 to 20% is even more preferred.
  • the polyimide precursor preferably has a fluorine atom in its structure.
  • the content of fluorine atoms 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.
  • an aliphatic group having a siloxane structure there is an embodiment using bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, or the like as the diamine.
  • the repeating unit represented by formula (2) is preferably a repeating unit represented by formula (2-A). That is, at least one polyimide precursor used in the present invention is preferably a precursor having a repeating unit represented by formula (2-A). By including the repeating unit represented by the formula (2-A) in the polyimide precursor, it becomes possible to further widen the width of the exposure latitude.
  • a 1 and A 2 represent an oxygen atom
  • R 111 and R 112 each independently represent a divalent organic group
  • R 113 and R 114 each independently represents a hydrogen atom or a monovalent organic group
  • at least one of R 113 and R 114 is a group containing a polymerizable group, and both are preferably groups containing a polymerizable group.
  • a 1 , A 2 , R 111 , R 113 and R 114 are each independently synonymous with 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 definition as R 112 in formula (5), and the preferred range is also the same.
  • the polyimide precursor may contain one type of repeating unit represented by formula (2), but may contain two or more types. It may also contain structural isomers of the repeating unit represented by formula (2). It goes without saying that the polyimide precursor may also contain other types of repeating units in addition to the repeating units of formula (2) above.
  • the content of the repeating unit represented by formula (2) is 50 mol% or more of the total repeating units.
  • the total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %.
  • the upper limit of the total content is not particularly limited, and all repeating units in the polyimide precursor excluding terminals may be repeating units represented by formula (2).
  • the weight average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, still more preferably 15,000 to 40,000. Also, the number average molecular weight (Mn) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, still more preferably 4,000 to 20,000.
  • the polyimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. Although the upper limit of the polyimide precursor's molecular weight dispersity is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
  • the molecular weight dispersity is a value calculated by weight average molecular weight/number average molecular weight.
  • the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one polyimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the multiple types of polyimide precursors as one resin are within the ranges described above.
  • polybenzoxazole precursor Although the structure of the polybenzoxazole precursor used in the present invention is not particularly defined, it preferably contains a repeating unit represented by the following formula (3).
  • R 121 represents a divalent organic group
  • R 122 represents a tetravalent organic group
  • R 123 and R 124 each independently represent a hydrogen atom or a monovalent organic group. show.
  • R 123 and R 124 each have the same meaning as R 113 in formula (2), and the preferred ranges are also the same. That is, at least one is preferably a polymerizable group.
  • R 121 represents a divalent organic group.
  • the divalent organic group a group containing at least one of an aliphatic group and an aromatic group is preferred.
  • the aliphatic group a linear aliphatic group is preferred.
  • R 121 is preferably a dicarboxylic acid residue. Only one type of dicarboxylic acid residue may be used, or two or more types may be used.
  • a dicarboxylic acid residue containing an aliphatic group and a dicarboxylic acid residue containing an aromatic group are preferable, and a dicarboxylic acid residue containing an aromatic group is more preferable.
  • the dicarboxylic acid containing an aliphatic group is preferably a dicarboxylic acid containing a linear or branched (preferably linear) aliphatic group, a linear or branched (preferably linear) aliphatic group and two -COOH A dicarboxylic acid consisting of is more preferred.
  • the number of carbon atoms in the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, even more preferably 3 to 20, and 4 to 15 is more preferred, and 5-10 is particularly preferred.
  • the linear aliphatic group is preferably an alkylene group.
  • Dicarboxylic acids containing linear aliphatic groups include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2, 2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberin acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedi
  • Z is a hydrocarbon group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.
  • the dicarboxylic acid containing an aromatic group the following dicarboxylic acid having an aromatic group is preferable, and the following dicarboxylic acid consisting of only a group having an aromatic group and two -COOH is more preferable.
  • A is -CH 2 -, -O-, -S-, -SO 2 -, -CO-, -NHCO-, -C(CF 3 ) 2 -, and -C(CH 3 ) 2 - represents a divalent group selected from the group consisting of * independently represents a binding site to another structure.
  • dicarboxylic acids containing aromatic groups include 4,4'-carbonyl dibenzoic acid, 4,4'-dicarboxydiphenyl ether, and terephthalic acid.
  • R 122 represents a tetravalent organic group.
  • the tetravalent organic group has the same meaning as R 115 in the above formula (2), and the preferred range is also the same.
  • R 122 is also preferably a group derived from a bisaminophenol derivative.
  • bisaminophenol derivatives having the following aromatic groups are preferred.
  • X 1 represents -O-, -S-, -C(CF 3 ) 2 -, -CH 2 -, -SO 2 -, -NHCO-, and * and # respectively represent other structures and represents the binding site of R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group.
  • R 122 is also preferably a structure represented by the above formula.
  • any two of the total four * and # are binding sites with the nitrogen atom to which R 122 in formula (3) binds, and Another two are preferably bonding sites with the oxygen atom to which R 122 in formula (3) is bonded, and two * are bonding sites with the oxygen atom to which R 122 in formula (3) is bonded. and two #s are binding sites to the nitrogen atom to which R 122 in formula (3) binds, or two * are binding sites to the nitrogen atom to which R 122 in formula (3) binds and two #s are more preferably a binding site to the oxygen atom to which R 122 in formula (3) binds, and two * are the oxygen to which R 122 in formula (3) binds. More preferably, it is a bonding site with an atom and two #s are bonding sites with a nitrogen atom to which R 122 in formula (3) is bonded.
  • the bisaminophenol derivative is also preferably a compound represented by formula (As).
  • R 1 is a hydrogen atom, alkylene, substituted alkylene, -O-, -S-, -SO 2 -, -CO-, -NHCO-, a single bond, or the following formula (A- It is an organic group selected from the group of sc).
  • R2 is a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.
  • R3 is a hydrogen atom , a linear or branched alkyl group, an alkoxy group, an acyloxy group, or a cyclic alkyl group, and may be the same or different.
  • R 1 is alkylene or substituted alkylene.
  • alkylene and substituted alkylene for R 1 include linear or branched alkyl groups having 1 to 8 carbon atoms, among which —CH 2 — and —CH(CH 3 ) -, -C(CH 3 ) 2 - have sufficient solubility in solvents while maintaining the effect of high i-line transparency and high cyclization rate when cured at low temperature. It is more preferable in that a polybenzoxazole precursor having excellent properties can be obtained.
  • the polybenzoxazole precursor may contain other types of repeating units in addition to the repeating units of formula (3) above.
  • the polybenzoxazole precursor preferably contains a diamine residue represented by the following formula (SL) as another type of repeating unit in that warping due to ring closure can be suppressed.
  • Z has an a structure and a b structure
  • R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
  • R 2s is a hydrocarbon group having 1 to 10 carbon atoms.
  • At least one of R 3s , R 4s , R 5s and R 6s is an aromatic group, and the rest are hydrogen atoms or organic groups having 1 to 30 carbon atoms, which may be the same or different.
  • Polymerization of a structure and b structure may be block polymerization or random polymerization.
  • the mol % of the Z portion is 5 to 95 mol % for the a structure, 95 to 5 mol % for the b structure, and 100 mol % for a+b.
  • preferred Z include those in which R 5s and R 6s in the b structure are phenyl groups.
  • the molecular weight of the structure represented by formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000.
  • tetracarboxylic acid residues include those of R 115 in formula (2).
  • the weight average molecular weight (Mw) of the polybenzoxazole precursor is, for example, preferably 18,000 to 30,000, more preferably 20,000 to 29,000, still more preferably 22,000 to 28, 000. Also, the number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, still more preferably 9,200 to 11,200.
  • the molecular weight dispersity of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and even more preferably 1.6 or more.
  • the upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly defined, for example, it is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, and 2.3 or less. is more preferable, and 2.2 or less is even more preferable.
  • the resin composition contains a plurality of types of polybenzoxazole precursors as specific resins
  • the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polybenzoxazole precursor are within the above ranges. preferable. It is also preferable that the weight-average molecular weight, the number-average molecular weight, and the degree of dispersion calculated from the plurality of types of polybenzoxazole precursors as one resin are within the ranges described above.
  • the polyamideimide precursor preferably contains a repeating unit represented by the following formula (PAI-2).
  • R 117 represents a trivalent organic group
  • R 111 represents a divalent organic group
  • a 2 represents an oxygen atom or —NR z —
  • R 113 represents a hydrogen atom or 1 represents a valent organic group
  • Rz represents a hydrogen atom or a monovalent organic group.
  • R 117 is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or two
  • the above-linked groups are exemplified, straight-chain aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
  • alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
  • halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
  • the halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • the above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms.
  • preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group and the like.
  • the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
  • R 117 is a group represented by any one of the following formulas (X2-1) to (X2-3), or one or more aliphatic A group containing a ring structure is also preferred.
  • R represents a substituent
  • n2 represents an integer of 0 to 2
  • * each represents a binding site with another structure.
  • each R independently represents a substituent
  • m2 represents an integer of 0 to 3
  • m3 represents an integer of 0 to 4
  • * is each a binding site to another structure represents
  • each R independently represents a substituent
  • m2 represents an integer of 0 to 2
  • m3 represents an integer of 0 to 3
  • L 2 is -CR C 2 -
  • R C represents a monovalent organic group
  • * each represents a binding site to another structure.
  • R in formula (X2-1) are the same as the preferred embodiments of R in formula (W1-1) described above.
  • n2 is preferably 0 or 1.
  • Preferred embodiments of R in formula (X2-2) are the same as the preferred embodiments of R in formula (W1-1) described above.
  • m2 is preferably 0 or 1.
  • m3 is preferably 0 or 1.
  • Preferred embodiments of R in formula (X2-3) are the same as preferred embodiments of R in formula (W1-1).
  • m2 is preferably 0 or 1.
  • m3 is preferably 0 or 1.
  • Preferred embodiments of R 1 C in formula (X2-3) are the same as preferred embodiments of R in formula (W1-1).
  • the specific resin when the specific resin contains a group represented by any one of formulas (X2-1) to (X2-3), the specific resin preferably contains, for example, the following structure.
  • Preferred embodiments of the alicyclic structure in the group containing one or more alicyclic structures are the same as the preferred embodiments of the alicyclic structure in the group containing one or more alicyclic structures in R 111 described above. be.
  • R 117 is preferably derived from a tricarboxylic acid compound in which at least one carboxy group may be halogenated. Chlorination is preferable as the halogenation.
  • a compound having three carboxy groups is called a tricarboxylic acid compound. Two of the three carboxy groups of the tricarboxylic acid compound may be anhydrided.
  • the optionally halogenated tricarboxylic acid compound used in the production of the polyamideimide precursor include branched aliphatic, cyclic aliphatic or aromatic tricarboxylic acid compounds. Only one of these tricarboxylic acid compounds may be used, or two or more thereof may be used.
  • the tricarboxylic acid compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, a cyclic aliphatic group having 3 to 20 carbon atoms, and a Tricarboxylic acid compounds containing 6 to 20 aromatic groups or groups in which two or more of these are combined via a single bond or a linking group are preferred, and aromatic groups having 6 to 20 carbon atoms or carbon atoms via a single bond or linking group are preferred. More preferred are tricarboxylic acid compounds containing groups in which two or more aromatic groups of numbers 6 to 20 are combined.
  • tricarboxylic acid compounds include 1,2,3-propanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, citric acid, trimellitic acid, 2,3,6-naphthalenetricarboxylic acid, and phthalic acid.
  • (or phthalic anhydride) and benzoic acid are a single bond, —O—, —CH 2 —, —C(CH 3 ) 2 —, —C(CF 3 ) 2 —, —SO 2 — or a phenylene group
  • Linked compounds and the like are included.
  • These compounds may be compounds in which two carboxy groups are anhydrided (e.g., trimellitic anhydride), or compounds in which at least one carboxy group is halogenated (e.g., trimellitic anhydride chloride). There may be.
  • R 111 , A 2 , R 113 and R z have the same meanings as R 111 , A 2 , R 113 and R z in formula (2) above, and preferred embodiments are also the same. be.
  • Polyamideimide precursors may further comprise other repeating units.
  • Other repeating units include repeating units represented by the above formula (2) and repeating units represented by the following formula (PAI-1).
  • R 116 represents a divalent organic group and R 111 represents a divalent organic group.
  • R 116 is a linear or branched aliphatic group, a cyclic aliphatic group, an aromatic group, a heteroaromatic group, or two
  • the above-linked groups are exemplified, straight-chain aliphatic groups having 2 to 20 carbon atoms, branched aliphatic groups having 3 to 20 carbon atoms, cyclic aliphatic groups having 3 to 20 carbon atoms, and 6 to 20 carbon atoms.
  • alkylene group is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 4 carbon atoms.
  • halogenated alkylene group a halogenated alkylene group having 1 to 20 carbon atoms is preferable, a halogenated alkylene group having 1 to 10 carbon atoms is more preferable, and a halogenated alkylene group having 1 to 4 carbon atoms is more preferable.
  • the halogen atom in the halogenated alkylene group includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
  • the above halogenated alkylene group may have hydrogen atoms, or all of the hydrogen atoms may be substituted with halogen atoms, but it is preferred that all of the hydrogen atoms be substituted with halogen atoms.
  • preferred halogenated alkylene groups include a (ditrifluoromethyl)methylene group and the like.
  • the arylene group is preferably a phenylene group or a naphthylene group, more preferably a phenylene group, and still more preferably a 1,3-phenylene group or a 1,4-phenylene group.
  • R 116 is preferably derived from a dicarboxylic acid compound or a dicarboxylic acid dihalide compound.
  • a compound having two carboxy groups is called a dicarboxylic acid compound
  • a compound having two halogenated carboxy groups is called a dicarboxylic acid dihalide compound.
  • the carboxy group in the dicarboxylic acid dihalide compound may be halogenated, but is preferably chlorinated, for example. That is, the dicarboxylic acid dihalide compound is preferably a dicarboxylic acid dichloride compound.
  • linear or branched aliphatic, cyclic aliphatic or aromatic dicarboxylic acid compounds or dicarboxylic acids examples include acid dihalide compounds.
  • One of these dicarboxylic acid compounds or dicarboxylic acid dihalide compounds may be used, or two or more thereof may be used.
  • the dicarboxylic acid compound or dicarboxylic acid dihalide compound includes a linear aliphatic group having 2 to 20 carbon atoms, a branched aliphatic group having 3 to 20 carbon atoms, and a cyclic aliphatic group having 3 to 20 carbon atoms.
  • a dicarboxylic acid compound or dicarboxylic acid dihalide compound containing a group, an aromatic group having 6 to 20 carbon atoms, or a group in which two or more of these are combined via a single bond or a linking group is preferable, and an aromatic group having 6 to 20 carbon atoms.
  • dicarboxylic acid compounds include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2- dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecanedioic acid, azelaic acid, sebacic acid, hexadecanedioic acid, 1,9
  • R 111 has the same definition as R 111 in formula (2) above, and preferred embodiments are also the same.
  • the polyamideimide precursor preferably has a fluorine atom in its structure.
  • the content of fluorine atoms in the polyamideimide precursor is preferably 10% by mass or more, and preferably 20% by mass or less.
  • the polyamideimide precursor may be copolymerized with an aliphatic group having a siloxane structure.
  • the diamine component bis(3-aminopropyl)tetramethyldisiloxane, bis(p-aminophenyl)octamethylpentasiloxane, etc. are used.
  • An aspect in which the total content of units is 50 mol % or more of all repeating units is exemplified.
  • the total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %.
  • the upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are the repeating units represented by the formula (PAI-2), represented by the formula (PAI-1).
  • the total content of repeating units represented by formula (PAI-2) and repeating units represented by formula (PAI-1) is An embodiment in which it is 50 mol % or more of all repeating units is mentioned.
  • the total content is more preferably 70 mol % or more, still more preferably 90 mol % or more, and particularly preferably more than 90 mol %.
  • the upper limit of the total content is not particularly limited, and all repeating units in the polyamideimide precursor excluding the terminal are repeating units represented by formula (PAI-2), or represented by formula (PAI-1) may be any of the repeating units provided.
  • the weight average molecular weight (Mw) of the polyamideimide precursor is preferably 2,000 to 500,000, more preferably 5,000 to 100,000, still more preferably 10,000 to 50,000. .
  • the number average molecular weight (Mn) is preferably 800 to 250,000, more preferably 2,000 to 50,000, still more preferably 4,000 to 25,000.
  • the polyamidoimide precursor preferably has a molecular weight distribution of 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more.
  • the upper limit of the molecular weight dispersity of the polyamideimide precursor is not particularly defined, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
  • the weight average molecular weight, number average molecular weight, and degree of dispersion of at least one type of polyamideimide precursor are preferably within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated from the plurality of types of polyamideimide precursors as one resin are within the ranges described above.
  • Polyimide precursors and the like for example, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature, a method of reacting a tetracarboxylic dianhydride and a diamine at a low temperature to obtain a polyamic acid, a condensing agent or an alkylating agent A method of esterification using a tetracarboxylic dianhydride and an alcohol to obtain a diester, followed by a reaction with a diamine in the presence of a condensing agent, a method of reacting a tetracarboxylic dianhydride and an alcohol to obtain a diester, After that, the remaining dicarboxylic acid can be acid-halogenated using a halogenating agent and reacted with a diamine.
  • a more preferable method is to obtain a diester from a tetracarboxylic dianhydride and an alcohol, then acid-halogenate the remaining dicarboxylic acid with a halogenating agent, and react it with a diamine.
  • the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N, N'-disuccinimidyl carbonate, trifluoroacetic anhydride and the like can be mentioned.
  • alkylating agent examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate and triethyl orthoformate.
  • halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride and the like.
  • organic solvent In the method for producing a polyimide precursor or the like, it is preferable to use an organic solvent in the reaction. One type of organic solvent may be used, or two or more types may be used.
  • the organic solvent can be appropriately determined depending on the raw material, but pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, ⁇ -butyrolactone and the like. is exemplified.
  • a basic compound In the method for producing a polyimide precursor or the like, it is preferable to add a basic compound during the reaction.
  • One type of basic compound may be used, or two or more types may be used.
  • the basic compound can be appropriately determined depending on the raw material, but triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, N,N-dimethyl-4-amino Pyridine and the like are exemplified.
  • terminal blocking agents include monoalcohols, phenols, thiols, thiophenols, monoamines, and the like. It is more preferable to use monoalcohols, phenols and monoamines from the viewpoint of their properties.
  • Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol and furfuryl alcohol, and isopropanol. , 2-butanol, cyclohexyl alcohol, cyclopentanol and 1-methoxy-2-propanol, and tertiary alcohols such as t-butyl alcohol and adamantane alcohol.
  • Preferable phenolic compounds include phenols such as phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, and hydroxystyrene.
  • Preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6- aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1- Carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-amin
  • Preferred capping agents for amino groups are carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromide, sulfonic acid chlorides, sulfonic anhydrides, sulfonic acid carboxylic acid anhydrides, etc., more preferably carboxylic acid anhydrides and carboxylic acid chlorides. preferable.
  • Preferred carboxylic anhydride compounds include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, and the like. is mentioned.
  • Preferred compounds of carboxylic acid chlorides include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, and 1-adamantanecarbonyl chloride. , heptafluorobutyryl chloride, stearic acid chloride, benzoyl chloride, and the like.
  • a compound represented by formula (T-1) may also be used as the terminal blocking agent.
  • By blocking the terminal with such a compound it is possible to introduce a structure in which a base is likely to be generated at the terminal, and the cyclization rate of the cyclized resin obtained from the precursor of the cyclized resin even when cured at a low temperature is likely to increase.
  • L T represents a divalent organic group
  • Z 1 and Z 2 each independently represent an organic group
  • Z 1 and Z 2 combine to form a ring structure. good too.
  • L T is preferably a hydrocarbon group and may be either an aromatic hydrocarbon group or an aliphatic hydrocarbon group. It is preferably a hydrocarbon group or a cyclic aliphatic hydrocarbon group.
  • the linking chain length of L T (that is, the minimum number of atoms among the atoms connecting two carbonyl groups bonded to L T ) is preferably 2 to 4, more preferably 2.
  • Z 1 and Z 2 have the same meanings as Z 1 and Z 2 in formula (3-1), and preferred embodiments are also the same.
  • an aspect in which at least one of Z 1 and Z 2 has a polymerizable group is also one of preferred aspects of the present invention.
  • Examples of the polymerizable group include a radically polymerizable group, an epoxy group, an oxetanyl group, a methylol group, an alkoxymethyl group and the like, and a radically polymerizable group is preferred.
  • the radically polymerizable group is preferably a group having an ethylenically unsaturated group, such as a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, a maleimide group, a styryl group, a vinyl group, a (meth)allyl group, and the like. mentioned. Among these, a (meth)acryloxy group is preferable from the viewpoint of reactivity.
  • These polymerizable groups may be directly bonded to the nitrogen atom in formula (T-1), or may be bonded via a linking group such as a hydrocarbon group (eg, an alkylene group).
  • a step of depositing a solid may be included in the production of the polyimide precursor or the like. Specifically, after filtering off the water absorption by-products of the dehydration condensation agent coexisting in the reaction solution as necessary, water, aliphatic lower alcohol, or a poor solvent such as a mixture thereof, the obtained A polyimide precursor or the like can be obtained by adding a polymer component and depositing the polymer component, depositing it as a solid, and drying it. In order to improve the degree of purification, operations such as redissolution, reprecipitation, drying, etc. of the polyimide precursor may be repeated. Furthermore, a step of removing ionic impurities using an ion exchange resin may be included.
  • the content of the specific resin in the resin composition in the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more with respect to the total solid content of the resin composition. more preferably 50% by mass or more, and particularly preferably 70% by mass or more.
  • the resin composition in the present invention contains a solvent, and the content of the precursor of the cyclized resin is 70% by mass with respect to the total solid content of the resin composition.
  • the aspect described above is also one of the preferred aspects of the present invention.
  • the content of the resin in the resin composition in the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, more preferably 98% by mass, based on the total solid content of the resin composition. % or less, more preferably 97 mass % or less, and even more preferably 95 mass % or less.
  • the resin composition in the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition in the present invention contains at least two kinds of resins.
  • the resin composition in the present invention may contain a total of two or more of the specific resin and other resins described later, or may contain two or more of the specific resins. It is preferable to include two or more kinds.
  • the resin composition in the present invention contains two or more specific resins, for example, two or more polyimides that are polyimide precursors and have different dianhydride-derived structures (R 115 in the above formula (2)) It preferably contains a precursor.
  • the resin composition in the present invention may contain the specific resin described above and another resin different from the specific resin (hereinafter also simply referred to as "other resin").
  • Other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins. etc.
  • phenolic resins polyamides
  • epoxy resins polysiloxanes
  • resins containing siloxane structures resins containing siloxane structures
  • (meth)acrylic resins eth)acrylamide resins
  • urethane resins urethane resins
  • butyral resins styryl resins
  • polyether resins e.g., polyether resins, and polyester resins.
  • a high polymerizable group value having a weight average molecular weight of 20,000 or less for example, the molar amount of the polymerizable group in 1 g of the resin is 1 ⁇ 10 ⁇ 3 mol/g or more
  • the coating properties of the resin composition and the solvent resistance of the pattern (cured product) can be improved. can.
  • the content of the other resins is preferably 0.01% by mass or more, and 0.05% by mass or more, relative to the total solid content of the resin composition. More preferably, it is more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and further preferably 10% by mass or more. More preferred.
  • the content of other resins in the resin composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, based on the total solid content of the resin composition. It is more preferably 60% by mass or less, even more preferably 50% by mass or less.
  • the content of other resins may be low.
  • the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, and 10% by mass or less relative to the total solid content of the resin composition. is more preferable, 5% by mass or less is even more preferable, and 1% by mass or less is even more preferable.
  • the lower limit of the content is not particularly limited as long as it is 0% by mass or more.
  • the resin composition in the present invention may contain only one kind of other resin, or may contain two or more kinds thereof. When two or more types are included, the total amount is preferably within the above range.
  • the resin composition in the present invention preferably contains a polymerizable compound.
  • Polymerizable compounds include radical cross-linking agents or other cross-linking agents.
  • the resin composition in the present invention preferably contains a polymerizable compound having a boiling point of 200° C. or higher at 1 atmosphere.
  • the boiling point is preferably 200°C or higher, more preferably 250°C or higher.
  • the upper limit of the boiling point is not particularly limited, and may be, for example, 500° C. or lower. According to the above aspect, the amount of outgas generated can be reduced.
  • the polymerizable compound having a boiling point of 200° C. or higher at 1 atm is preferably a compound having 3 or more polymerizable groups, more preferably a compound having 4 or more polymerizable groups. is more preferably a compound having 5 or more Although the upper limit of the number of polymerizable groups is not particularly limited, it is preferably 20 or less. Further, the polymerizable compound having a boiling point of 200° C. or higher at 1 atm is preferably a compound having 3 or more (meth)acrylate groups, and is preferably a compound having 4 or more (meth)acrylate groups. More preferably, it is a compound having 5 or more (meth)acrylate groups. Although the upper limit of the number of (meth)acrylate groups is not particularly limited, it is preferably 20 or less.
  • polymerizable compound having a boiling point of 200° C. or higher at 1 atm examples include dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethylolpropane tetraacrylate, ethoxylated dipentaerythritol polymethacrylate, and the like. are mentioned.
  • these compounds can be used as long as they have a boiling point of 200° C. or higher whether they are acrylates or methacrylates.
  • Commercially available products may be used as these compounds, for example, those manufactured by Shin-Nakamura Chemical Co., Ltd. may be used.
  • the resin composition preferably contains a polymerizable compound having an alicyclic structure.
  • the polymerizable compound may have only one polymerizable group, but preferably has 2 or more, more preferably 2 to 10, more preferably 2 to 6, more preferably 4 to 6 It is particularly preferred to have one.
  • the alicyclic structure may be either a saturated alicyclic structure or an unsaturated alicyclic structure.
  • the above-mentioned aliphatic ring structure may be a monocyclic ring or a multicyclic ring such as a condensed ring, a bridged condensed ring, or a spiro ring. Examples of the above alicyclic structure include cyclohexane structure, cyclohexene structure, bicyclo[2.2.2]oct-5-ene structure and the like.
  • the resin composition in the present invention preferably contains a radical cross-linking agent.
  • a radical cross-linking agent is a compound having a radically polymerizable group.
  • the radically polymerizable group a group containing an ethylenically unsaturated bond is preferred.
  • Examples of the group containing an ethylenically unsaturated bond include groups containing an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
  • the group containing an ethylenically unsaturated bond is preferably a (meth)acryloyl group, a (meth)acrylamide group, or a vinylphenyl group, and more preferably a (meth)acryloyl group from the viewpoint of reactivity.
  • the radical cross-linking agent is preferably a compound having one or more ethylenically unsaturated bonds, and more preferably a compound having two or more.
  • the radical cross-linking agent may have 3 or more ethylenically unsaturated bonds.
  • the compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and 2 to 6.
  • the resin composition in the present invention contains a compound having two ethylenically unsaturated bonds and a compound having three or more of the above ethylenically unsaturated bonds. It is also preferred 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 (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides. They are esters of saturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds.
  • addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxy group, an amino group, or a sulfanyl group with monofunctional or polyfunctional isocyanates or epoxies, or monofunctional or polyfunctional is also preferably used.
  • addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines, and thiols, and halogeno groups
  • substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as a tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols.
  • paragraphs 0113 to 0122 of JP-A-2016-027357 can be referred to, and the contents thereof are incorporated herein.
  • the radical cross-linking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure.
  • examples include polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol di(meth)acrylate, trimethylolpropane tri(acryloyloxypropyl)ether, tri(acryloyloxyethyl)isocyanurate, glycerin, trimethylolethane, etc.
  • polyfunctional (meth)acrylate obtained by reacting polyfunctional carboxylic acid with a compound having a cyclic ether group such as glycidyl (meth)acrylate and an ethylenically unsaturated bond can also be used.
  • JP-A-2010-160418, JP-A-2010-129825, JP-A-4364216, etc. have a fluorene ring and an ethylenically unsaturated bond. It is also possible to use compounds having two or more groups and cardo resins.
  • JP-B-46-043946 JP-B-01-040337, JP-B-01-040336, and JP-A-02-025493.
  • vinyl phosphonic acid compounds and the like can also be mentioned.
  • Compounds containing perfluoroalkyl groups described in JP-A-61-022048 can also be used.
  • the journal of the Japan Adhesive Association vol. 20, No. 7, pp. 300-308 (1984) as photopolymerizable monomers and oligomers can also be used.
  • dipentaerythritol triacrylate commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.
  • dipentaerythritol tetraacrylate commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd.
  • A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.
  • dipentaerythritol penta(meth)acrylate (as a commercial product, KAYARAD D-310; manufactured by 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 Co., Ltd.)
  • their (meth)acryloyl groups are converted via ethylene glycol residues or propylene glycol residues Structures that are linked together are preferred. These oligomeric types can also be used.
  • radical cross-linking agents examples include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains, manufactured by Sartomer, SR-209, a bifunctional methacrylate having four ethyleneoxy chains, manufactured by Sartomer. 231, 239, Nippon Kayaku Co., Ltd.
  • DPCA-60 a hexafunctional acrylate having 6 pentyleneoxy chains, TPA-330, a trifunctional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10 , UAB-140 (manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Japan Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), Blenmer PME400 (manufactured by NOF Corporation), etc. mentioned.
  • radical cross-linking agents examples include urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, JP-B-02-016765, Urethane compounds having an ethylene oxide skeleton described in JP-B-58-049860, JP-B-56-017654, JP-B-62-039417 and JP-B-62-039418 are also suitable.
  • compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 are used. can also
  • 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.
  • a radical cross-linking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid. is more preferable.
  • the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol is a compound.
  • Examples of commercially available products include polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd. such as M-510 and M-520.
  • the acid value of the radical cross-linking agent having an acid group is preferably 0.1-300 mgKOH/g, particularly preferably 1-100 mgKOH/g. If the acid value of the radical cross-linking agent is within the above range, the handleability in production is excellent, and furthermore the developability is excellent. Moreover, the polymerizability is good. The acid value is measured according to JIS K 0070:1992.
  • the resin composition preferably uses a bifunctional methacrylate or acrylate.
  • Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, and PEG600 diacrylate.
  • PEG200 diacrylate is a polyethylene glycol diacrylate having a polyethylene glycol chain formula weight of about 200.
  • a monofunctional radical cross-linking agent can be preferably used as the radical cross-linking agent from the viewpoint of suppressing warpage associated with the elastic modulus control of the pattern (cured product).
  • Monofunctional radical cross-linking agents include n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, ) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, glycidyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, etc.
  • N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam
  • allyl glycidyl ether 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.
  • Other di- or higher functional radical cross-linking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.
  • a radical cross-linking agent When a radical cross-linking agent is contained, its content is preferably more than 0% by mass and 60% by mass or less with respect to the total solid content of the resin composition in the present invention. More preferably, the lower limit is 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
  • a single radical cross-linking agent may be used alone, or two or more may be used in combination. When two or more are used in combination, the total amount is preferably within the above range.
  • the resin composition in the present invention contains another cross-linking agent different from the radical cross-linking agent described above.
  • the other cross-linking agent refers to a cross-linking agent other than the above-described radical cross-linking agent, and the above-described photoacid generator or photobase generator reacts with other compounds in the composition or reacts with them.
  • the compound has a plurality of groups in the molecule that promote the reaction forming covalent bonds with the product, and covalent bonds are formed with other compounds in the composition or reaction products thereof. Compounds having a plurality of groups in the molecule, the reaction of which is promoted by the action of an acid or base, are preferred.
  • the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
  • compounds having at least one group selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups are preferred, and the compounds are preferably selected from the group consisting of acyloxymethyl groups, methylol groups and alkoxymethyl groups. More preferred is a compound having a structure in which at least one group is directly bonded to a nitrogen atom.
  • cross-linking agents include, for example, an amino group-containing compound such as melamine, glycoluril, urea, alkylene urea, and benzoguanamine, which is reacted with formaldehyde or formaldehyde and alcohol, and the hydrogen atom of the amino group is converted to an acyloxymethyl group, methylol group, or A compound having a structure substituted with an alkoxymethyl group can be mentioned.
  • the method for producing these compounds is not particularly limited as long as they have the same structure as the compounds produced by the above methods. Oligomers formed by self-condensation of methylol groups of these compounds may also be used.
  • a melamine-based crosslinking agent is a melamine-based crosslinking agent
  • a glycoluril, urea or alkyleneurea-based crosslinking agent is a urea-based crosslinking agent
  • an alkyleneurea-based crosslinking agent is an alkyleneurea-based crosslinking agent.
  • a cross-linking agent using benzoguanamine is called a benzoguanamine-based cross-linking agent.
  • the resin composition in the present invention preferably contains at least one compound selected from the group consisting of urea-based cross-linking agents and melamine-based cross-linking agents. More preferably, it contains at least one compound selected from the group consisting of agents.
  • an alkoxymethyl group or an acyloxymethyl group is directly substituted on the nitrogen atom of an aromatic group or the following urea structure, or on a triazine.
  • the alkoxymethyl group or acyloxymethyl group of the above compound preferably has 2 to 5 carbon atoms, preferably 2 or 3 carbon atoms, and more preferably 2 carbon atoms.
  • the total number of alkoxymethyl groups and acyloxymethyl groups in the above compound is preferably 1-10, more preferably 2-8, and particularly preferably 3-6.
  • the molecular weight of the compound is preferably 1500 or less, preferably 180-1200.
  • R 100 represents an alkyl group or an acyl group.
  • R 101 and R 102 each independently represent a monovalent organic group and may combine with each other to form a ring.
  • Examples of compounds in which an alkoxymethyl group or an acyloxymethyl group is directly substituted by an aromatic group include compounds represented by the following general formula.
  • X represents a single bond or a divalent organic group
  • each R 104 independently represents an alkyl group or an acyl group
  • R 103 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group , or a group that decomposes under the action of an acid to produce an alkali-soluble group (e.g., a group that leaves under the action of an acid, a group represented by —C(R 4 ) 2 COOR 5 (R 4 is independently It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R 5 represents a group that leaves under the action of an acid.)).
  • R 105 each independently represents an alkyl group or alkenyl group, a, b and c are each independently 1 to 3, d is 0 to 4, e is 0 to 3, f is 0 to 3 , a+d is 5 or less, b+e is 4 or less, and c+f is 4 or less.
  • R 5 in the group represented by —C(R 4 ) 2 COOR 5 a group that is decomposed by the action of an acid to produce an alkali-soluble group, a group that is eliminated by the action of an acid, and —C(R 36 )(R 37 )(R 38 ), —C(R 36 )(R 37 )(OR 39 ), —C(R 01 )(R 02 )(OR 39 ), and the like.
  • R 36 to R 39 each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group.
  • R 36 and R 37 may combine with each other to form a ring.
  • alkyl group an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
  • the alkyl group may be linear or branched.
  • a cycloalkyl group having 3 to 12 carbon atoms is preferable, and a cycloalkyl group having 3 to 8 carbon atoms is more preferable.
  • the cycloalkyl group may have a monocyclic structure or a polycyclic structure such as a condensed ring.
  • the aryl group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably a phenyl group.
  • an aralkyl group having 7 to 20 carbon atoms is preferable, and an aralkyl group having 7 to 16 carbon atoms is more preferable.
  • the aralkyl group is intended to be an aryl group substituted with an alkyl group, and preferred embodiments of these alkyl and aryl groups are the same as the preferred embodiments of the alkyl and aryl groups described above.
  • the alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms, more preferably an alkenyl group having 3 to 16 carbon atoms. Moreover, these groups may further have a known substituent within the range in which the effects of the present invention can be obtained.
  • R 01 and R 02 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
  • These groups are preferably tertiary alkyl ester groups, acetal ester groups, cumyl ester groups, enol ester groups, and the like. More preferred are tertiary alkyl ester groups and acetal ester groups.
  • compounds having an alkoxymethyl group include the following structures.
  • Examples of the compound having an acyloxymethyl group include compounds obtained by changing the alkoxymethyl group of the following compounds to an acyloxymethyl group.
  • Compounds having an alkoxymethyl group or acyloxymethyl in the molecule include, but are not limited to, the following compounds.
  • the compound containing at least one of an alkoxymethyl group and an acyloxymethyl group a commercially available one or a compound synthesized by a known method may be used. From the viewpoint of heat resistance, compounds in which an alkoxymethyl group or acyloxymethyl group is directly substituted on an aromatic ring or a triazine ring are preferred.
  • melamine-based cross-linking agents include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine.
  • urea-based cross-linking agents include monohydroxymethylated glycoluril, dihydroxymethylated glycoluril, trihydroxymethylated glycoluril, tetrahydroxymethylated glycoluril, monomethoxymethylated glycoluril, and dimethoxymethylated glycol.
  • Uril trimethoxymethylated glycoluril, tetramethoxymethylated glycoluril, monomethoxymethylated glycoluril, dimethoxymethylated glycoluril, trimethoxymethylated glycoluril, tetraethoxymethylated glycoluril, monopropoxymethylated glycoluril, Dipropoxymethylated glycoluril, tripropoxymethylated glycoluril, tetrapropoxymethylated glycoluril, monobutoxymethylated glycoluril, dibutoxymethylated glycoluril, tributoxymethylated glycoluril, or tetrabutoxymethylated glycoluril
  • Glycoluril-based cross-linking agents such as; urea-based cross-linking agents such as bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea; monohydroxymethylated ethyleneurea or dihydroxymethylated ethyleneurea, monomethoxymethylated ethyleneurea, dimethoxy
  • benzoguanamine-based cross-linking agents include monohydroxymethylated benzoguanamine, dihydroxymethylated benzoguanamine, trihydroxymethylated benzoguanamine, tetrahydroxymethylated benzoguanamine, monomethoxymethylated benzoguanamine, dimethoxymethylated benzoguanamine, and trimethoxymethylated 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.
  • the compound having at least one group selected from the group consisting of a methylol group and an alkoxymethyl group includes at least one group selected from the group consisting of a methylol group and an alkoxymethyl group on an aromatic ring (preferably a benzene ring).
  • Compounds to which a seed group is directly attached are also preferably used. Specific examples of such compounds include benzenedimethanol, bis(hydroxymethyl)cresol, bis(hydroxymethyl)dimethoxybenzene, bis(hydroxymethyl)diphenyl ether, bis(hydroxymethyl)benzophenone, hydroxymethylphenyl hydroxymethylbenzoate.
  • suitable commercial products include 46DMOC, 46DMOEP (manufactured by Asahi Organic Chemicals Industry Co., Ltd.), DML-PC, DML-PEP, DML-OC, and DML-OEP.
  • DML-34X DML-PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP -Z, DML-BPC, DMLBisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML -BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (Honshu Chemical Industry Co., Ltd.), Nikalac (registered
  • the resin composition of the present invention preferably contains at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and benzoxazine compounds 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 less and does not undergo a dehydration reaction resulting from the cross-linking, so film shrinkage does not easily occur. Therefore, containing an epoxy compound is effective for low-temperature curing and suppression of warping of the resin composition of the present invention.
  • 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 2-15.
  • 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.
  • alkylene glycol type epoxy resins such as trimethylolpropane triglycidyl ether or polyhydric alcohol hydrocarbon type epoxy resins
  • polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether
  • epoxy groups such as polymethyl (glycidyloxypropyl) siloxane Examples include, but are not limited to, containing silicones and the like.
  • Epiclon (registered trademark) 850-S Epiclon (registered trademark) HP-4032, Epiclon (registered trademark) HP-7200, Epiclon (registered trademark) HP-820, Epiclon (registered trademark) HP-4700, Epiclon (registered trademark) HP-4770, Epiclon (registered trademark) EXA-830LVP, Epiclon (registered trademark) EXA-8183, Epiclon (registered trademark) EXA-8169, Epiclon (registered trademark) N-660, Epiclon (registered trademark) N-665-EXP-S, Epiclon (registered trademark) N-740 (trade name, manufactured by DIC Corporation), Ricaresin (registered trademark) BEO-20E, Jamaicaresin (registered trademark) BEO-60E, Ricaresin (registered trademark) ) HBE-100, Ricaresin (registered trademark) DME-100, Ricaresin (registered trademark)
  • n is an integer of 1-5 and m is an integer of 1-20.
  • n 1 to 2 and m is 3 to 7 from the viewpoint of achieving both heat resistance and elongation improvement.
  • oxetane compound compound having an oxetanyl group
  • the oxetane compounds include compounds having two or more oxetane rings in one molecule, 3-ethyl-3-hydroxymethyloxetane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl)methoxy]methyl ⁇ benzene, 3-ethyl-3-(2-ethylhexylmethyl)oxetane, 1,4-benzenedicarboxylic acid-bis[(3-ethyl-3-oxetanyl)methyl]ester and the like can be mentioned.
  • Aron oxetane series manufactured by Toagosei Co., Ltd. eg, OXT-121, OXT-221
  • OXT-121, OXT-221 can be suitably used, and these can be used alone or in combination of two or more. good.
  • a benzoxazine compound (compound having a benzoxazolyl group)-
  • a benzoxazine compound is preferable because it is a cross-linking reaction derived from a ring-opening addition reaction, so that degassing does not occur during curing, and thermal shrinkage is reduced to suppress the occurrence of warping.
  • benzoxazine compounds include Pd-type benzoxazine, Fa-type benzoxazine (these are trade names, manufactured by Shikoku Kasei Kogyo Co., Ltd.), benzoxazine adducts of polyhydroxystyrene resins, phenol novolac-type dihydrobenzoxazines, oxazine compounds. 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 in the present invention. It is more preferably 5 to 15% by mass, particularly preferably 1.0 to 10% by mass.
  • Other cross-linking agents may be contained alone, or may be contained in two or more. When two or more other cross-linking agents are contained, the total is preferably within the above range.
  • the resin composition in the present invention preferably contains a photosensitizer.
  • Photosensitizers include photopolymerization initiators, photoacid generators, and the like, with photopolymerization initiators being preferred.
  • the resin composition in the present invention preferably contains a polymerization initiator capable of initiating polymerization by light and/or heat.
  • a photopolymerization initiator is preferably a photoradical polymerization initiator.
  • the radical photopolymerization initiator is not particularly limited and can be appropriately selected from known radical photopolymerization initiators.
  • a photoradical polymerization initiator having photosensitivity to light in the ultraviolet region to the visible region is preferred. It may also be an activator that produces an active radical by producing some action with a photoexcited sensitizer.
  • the radical photopolymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 within the wavelength range of about 240 to 800 nm (preferably 330 to 500 nm). is preferred.
  • the molar extinction coefficient of a compound can be measured using known methods. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
  • any known compound can be used as the photoradical polymerization initiator.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime derivatives, etc.
  • ketone compounds include compounds described in paragraph 0087 of JP-A-2015-087611, the content of which is incorporated herein.
  • Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd. is also suitably used.
  • a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be suitably used as the radical photopolymerization initiator. More specifically, for example, aminoacetophenone-based initiators described in JP-A-10-291969 and acylphosphine oxide-based initiators described in Japanese Patent No. 4225898 can be used. incorporated.
  • ⁇ -hydroxyketone initiators include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE -2959 and IRGACURE 127 (trade names: both manufactured by BASF) can be used.
  • ⁇ -aminoketone initiators examples include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (trade names: all BASF company) can be used.
  • the compound described in JP-A-2009-191179 whose absorption maximum wavelength is matched to a wavelength light source such as 365 nm or 405 nm, can also be used, the content of which is incorporated herein.
  • Acylphosphine-based initiators include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), IRGACURE-819 and IRGACURE-TPO (trade names: all manufactured by BASF) can also be used.
  • metallocene compounds examples include IRGACURE-784, IRGACURE-784EG (both manufactured by BASF) and Keycure VIS 813 (manufactured by King Brother Chem).
  • the photoradical polymerization initiator is more preferably an oxime compound.
  • an oxime compound By using an oxime compound, the exposure latitude can be improved more effectively.
  • Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.
  • oxime compound examples include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2006-342166, compounds described in JP-A-2017-019766, compounds described in Patent No. 6065596, International Publication No.
  • 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-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one , and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
  • an oxime compound an oxime-based radical photopolymerization initiator
  • DFI-091 manufactured by Daito Chemix Co., Ltd.
  • SpeedCure PDO manufactured by SARTOMER ARKEMA
  • an oxime compound having the following structure can be used.
  • An oxime compound having a fluorene ring can also be used as the photoradical polymerization initiator.
  • Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466 and compounds described in Japanese Patent No. 06636081, the contents of which are incorporated herein.
  • 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 oxime compounds include compounds described in WO2013/083505, the contents of which are incorporated herein.
  • 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. and compound (C-3) described in paragraph 0101 of JP-A-164471, the contents of which are incorporated herein.
  • An oxime compound having a nitro group can be used as the photopolymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Included are compounds described in paragraphs 0007-0025 of Japanese Patent No. 4223071, the contents of which are incorporated herein.
  • the oxime compound having a nitro group also includes ADEKA Arkles NCI-831 (manufactured by ADEKA Co., Ltd.).
  • An oxime compound having a benzofuran skeleton can also be used as the photoradical polymerization initiator.
  • Specific examples include OE-01 to OE-75 described in WO 2015/036910.
  • an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
  • photoinitiators include compounds such as those described in WO2019/088055, the contents of which are incorporated herein.
  • an oxime compound having an aromatic ring group Ar 2 OX1 in which an electron-withdrawing group is introduced into the aromatic ring (hereinafter also referred to as oxime compound OX) can be used.
  • the electron-withdrawing group possessed by the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group.
  • a benzoyl group may have a substituent.
  • substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group.
  • a sulfanyl group or an amino group is more preferred.
  • the oxime compound OX is preferably at least one selected from the compounds represented by the formula (OX1) and the compounds represented by the formula (OX2), more preferably the compound represented by the formula (OX2). preferable.
  • R X1 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclicoxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl a group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group
  • R X2 is an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group,
  • R X12 is an electron-withdrawing group
  • R X10 , R X11 , R X13 and R X14 are preferably hydrogen atoms.
  • oxime compound OX examples include compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein.
  • oxime compounds having specific substituents shown in JP-A-2007-269779 and oxime compounds having a thioaryl group shown in JP-A-2009-191061. incorporated herein.
  • photoradical polymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl selected from the group consisting of imidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds; are preferred.
  • More preferred radical photopolymerization 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, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is more preferred, and metallocene compounds or oxime compounds are even more preferred. .
  • the photoradical polymerization initiator includes benzophenone, N,N'-tetraalkyl-4,4'-diaminobenzophenone such as N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthraquinones, etc.
  • benzophenone N,N'-tetraalkyl-4,4'-diaminobenzophenone
  • 2-benzyl -aromatic ketones such as 2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1, alkylanthr
  • benzoin ether compounds such as benzoin alkyl ether
  • benzoin compounds such as benzoin and alkylbenzoin
  • benzyl derivatives such as benzyl dimethyl ketal
  • a compound represented by the following formula (I) can also be used.
  • R 100 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, Alternatively, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, a carbon number interrupted by one or more oxygen atoms a phenyl group or a biphenyl group substituted with at least one of an alkyl group having 2 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms, and R I01 is a group represented by formula (II); It is the same group as R 100 , and each of R 102 to R 104 is independently an alkyl group having 1 to 12 carbon atoms
  • R 105 to R 107 are the same as R 102 to R 104 in formula (I) above.
  • radical photopolymerization initiator a difunctional or trifunctional or higher radical photopolymerization initiator may be used.
  • a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained.
  • the crystallinity is lowered, the solubility in a solvent or the like is improved, and precipitation becomes difficult over time, and the stability over time of the resin composition can be improved.
  • Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
  • a photopolymerization initiator When a photopolymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition in the present invention. , more preferably 0.5 to 15% by mass, and still 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 photopolymerization initiators are contained, the total amount is preferably within the above range. In addition, since the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further advanced by heating with an oven, a hot plate, or the like.
  • the resin composition may contain a sensitizer.
  • a sensitizer absorbs specific actinic radiation and enters an electronically excited state.
  • the sensitizer in an electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and causes electron transfer, energy transfer, heat generation, or the like.
  • the thermal radical polymerization initiator and the photoradical polymerization initiator undergo chemical changes and are decomposed to generate radicals, acids or bases.
  • Sensitizers that can be used include benzophenones, Michler's ketones, coumarins, pyrazole azos, anilinoazos, triphenylmethanes, anthraquinones, anthracenes, anthrapyridones, benzylidenes, oxonols, and pyrazolotriazole azos. , pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, penzopyran, and indigo compounds.
  • Sensitizers include, for example, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal) Cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyl denindanone, p-dimethylaminobenzylideneindanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)iso naphthothiazole,
  • the content of the sensitizer is preferably 0.01 to 20% by mass, preferably 0.1 to 15% by mass, based on the total solid content of the resin composition. more preferably 0.5 to 10% by mass.
  • the sensitizers may be used singly or in combination of two or more.
  • the resin composition in the invention may contain a chain transfer agent.
  • the chain transfer agent is defined, for example, in Kobunshi Jiten, 3rd edition (edited by Kobunshi Gakkai, 2005), pp. 683-684.
  • Chain transfer agents include, for example, a group of compounds having —S—S—, —SO 2 —S—, —NO—, SH, PH, SiH, and GeH in the molecule, RAFT (Reversible Addition Fragmentation chain Transfer )
  • Dithiobenzoate, trithiocarbonate, dithiocarbamate, xanthate compounds and the like having a thiocarbonylthio group used for polymerization are used. They can either donate hydrogen to less active radicals to generate radicals, or they can be oxidized and then deprotonated to generate radicals.
  • thiol compounds can be preferably used.
  • chain transfer agent can also use the compounds described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, the contents of which are incorporated herein.
  • the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, based on 100 parts by mass of the total solid content of the resin composition of the present invention. 1 to 10 parts by mass is more preferable, and 0.5 to 5 parts by mass is even more preferable.
  • One type of chain transfer agent may be used, or two or more types may be used. When two or more chain transfer agents are used, the total is preferably within the above range.
  • the resin composition in the present invention may contain a base generator.
  • the base generator is a compound capable of generating a base by physical or chemical action.
  • the base generator as used herein does not include the specific resins described above.
  • Preferred base generators for the resin composition of the present invention include thermal base generators and photobase generators.
  • the resin composition when the resin composition contains a cyclized resin precursor, the resin composition preferably contains a base generator.
  • the base generator may be an ionic base generator or a non-ionic base generator.
  • bases generated from base generators include secondary amines and tertiary amines. There are no particular restrictions on the base generator used in the present invention, and known base generators can be used. Examples of known base generators include carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, and amine imides.
  • Nonionic base generator examples include compounds represented by Formula (B1), Formula (B2), or Formula (B3).
  • Rb 1 , Rb 2 and Rb 3 are each independently an organic group having no tertiary amine structure, a halogen atom or a hydrogen atom. However, Rb 1 and Rb 2 are not hydrogen atoms at the same time. Also, 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, when the bonded carbon atom is a carbon atom forming a carbonyl group, that is, when forming an amide group together with the nitrogen atom, this is not the case.
  • Rb 1 , Rb 2 and Rb 3 preferably contains a cyclic structure, and more preferably at least two of them contain a cyclic structure.
  • the cyclic structure may be either a single ring or a condensed ring, preferably a single ring or a condensed ring in which two single rings are condensed.
  • the monocyclic ring is preferably a 5- or 6-membered ring, preferably a 6-membered ring.
  • the monocyclic ring is preferably a cyclohexane ring and a benzene ring, more preferably a cyclohexane ring.
  • Rb 1 and Rb 2 are a hydrogen atom, an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms). , more preferably 2 to 18, more preferably 3 to 12), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), or an arylalkyl group (7 carbon atoms to 25 are preferred, 7 to 19 are more preferred, and 7 to 12 are even more preferred). These groups may have substituents to the extent that the effects of the present invention are exhibited. Rb 1 and Rb 2 may combine with each other to form a ring.
  • the ring to be formed is preferably a 4- to 7-membered nitrogen-containing heterocyclic ring.
  • Rb 1 and Rb 2 are particularly linear, branched or cyclic alkyl groups (having preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms) which may have a substituent.
  • Rb 3 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, 6 to 10 are more preferred), alkenyl groups (preferably 2 to 24 carbon atoms, more preferably 2 to 12, more preferably 2 to 6), arylalkyl groups (preferably 7 to 23 carbon atoms, more preferably 7 to 19 preferably 7 to 12), arylalkenyl groups (preferably 8 to 24 carbon atoms, more preferably 8 to 20, more preferably 8 to 16), alkoxyl groups (preferably 1 to 24 carbon atoms, 2 to 18 is more preferred, and 3 to 12 are even more preferred), an aryloxy group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or an arylalkyloxy group (preferably 7 to 12 carbon atoms).
  • an aryl group preferably
  • Rb 3 may further have a substituent as long as the effects of the present invention are exhibited.
  • the compound represented by Formula (B1) is preferably a compound represented by Formula (B1-1) or Formula (B1-2) below.
  • Rb 11 and Rb 12 and Rb 31 and Rb 32 are respectively the same as Rb 1 and Rb 2 in formula (B1).
  • Rb 13 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, 3 to 12 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and may have a substituent within the range in which the effects of the present invention are exhibited.
  • Rb 13 is preferably an arylalkyl group.
  • Rb 33 and Rb 34 each independently represents a hydrogen atom, an alkyl group (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms , more preferably 2 to 8, more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), an arylalkyl group (7 to 23 is preferred, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom is preferred.
  • an alkyl group preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms
  • an alkenyl group preferably 2 to 12 carbon atoms , more preferably 2 to 8, more preferably 2 to 3
  • an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10
  • Rb 35 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19 , 7 to 12 are more preferred), and aryl groups are preferred.
  • the compound represented by formula (B1-1) is also preferably the compound represented by formula (B1-1a).
  • Rb 11 and Rb 12 have the same definitions as Rb 11 and Rb 12 in formula (B1-1).
  • Rb 15 and Rb 16 are hydrogen atoms, alkyl groups (preferably 1 to 12 carbon atoms, more preferably 1 to 6, even more preferably 1 to 3), alkenyl groups (preferably 2 to 12 carbon atoms, 2 to 6 more preferably 2 to 3), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, even more preferably 6 to 10), an arylalkyl group (preferably 7 to 23 carbon atoms, 7 to 19 are more preferred, and 7 to 11 are even more preferred), and a hydrogen atom or a methyl group is preferred.
  • Rb 17 is an alkyl group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred), an aryl group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12), an arylalkyl group (preferably 7 to 23 carbon atoms, more preferably 7 to 19, 7 to 12 are more preferable), and aryl groups are particularly preferable.
  • an alkyl group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms
  • an alkenyl group preferably 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, 3 to 8 is more preferred
  • an aryl group preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 12
  • L is a divalent hydrocarbon group having a saturated hydrocarbon group on a linking chain path connecting adjacent oxygen atoms and carbon atoms, wherein the number of atoms on the linking chain path is represents a hydrocarbon group of 3 or more.
  • RN1 and RN2 each independently represent a monovalent organic group.
  • the term “connected chain” refers to the shortest (minimum number of atoms) of atomic chains on a path connecting two atoms or groups of atoms to be connected.
  • L is composed of a phenylene ethylene group, has an ethylene group as a saturated hydrocarbon group
  • the linking chain is composed of four carbon atoms, and on the route of the linking chain
  • the number of atoms of (that is, the number of atoms constituting the linked chain, hereinafter also referred to as "linked chain length" or "linked chain length”) is 4.
  • the number of carbon atoms in L (including carbon atoms other than carbon atoms in the connecting chain) in formula (B3) is preferably 3-24.
  • the upper limit is more preferably 12 or less, still more preferably 10 or less, and particularly preferably 8 or less. More preferably, the lower limit is 4 or more.
  • the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, further preferably 6 or less, and 5 The following are particularly preferred.
  • the linking chain length of L is preferably 4 or 5, most preferably 4.
  • Specific preferred compounds of the base generator include, for example, compounds described in paragraph numbers 0102 to 0168 of WO2020/066416, and compounds described in paragraph numbers 0143 to 0177 of WO2018/038002. mentioned.
  • the base generator preferably contains a compound represented by the following formula (N1).
  • RN1 and RN2 each independently represent a monovalent organic group
  • RC1 represents a hydrogen atom or a protecting group
  • L represents a divalent linking group
  • L is a divalent linking group, preferably a divalent organic group.
  • the linking chain length of the linking group is preferably 1 or more, more preferably 2 or more.
  • the upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less.
  • the linking chain length is the number of atoms present in the atomic arrangement that provides the shortest path between two carbonyl groups in the formula.
  • R N1 and R N2 each independently represent a monovalent organic group (preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms), and a hydrocarbon group (preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms), specifically, an aliphatic hydrocarbon group (preferably 1 to 24 carbon atoms, 1 to 12 is more preferable, 1 to 10 is more preferable) or an aromatic hydrocarbon group (preferably 6 to 22 carbon atoms, more preferably 6 to 18, more preferably 6 to 10), and an aliphatic hydrocarbon groups are preferred.
  • a monovalent organic group preferably 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, more preferably 3 to 12 carbon atoms
  • a hydrocarbon group preferably 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms
  • an aliphatic hydrocarbon group preferably 1 to
  • an aliphatic hydrocarbon group as R N1 and R N2 because the generated base is highly basic.
  • the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent, and the aliphatic hydrocarbon group and the aromatic hydrocarbon group are in the aliphatic hydrocarbon chain or in the aromatic ring, You may have an oxygen atom in the substituent.
  • an aspect in which the aliphatic hydrocarbon group has an oxygen atom in the hydrocarbon chain is exemplified.
  • Aliphatic hydrocarbon groups constituting R N1 and R N2 include linear or branched chain alkyl groups, cyclic alkyl groups, groups related to combinations of chain alkyl groups and cyclic alkyl groups, and oxygen atoms in the chains.
  • Alkyl groups having The linear or branched chain alkyl group preferably has 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, and still more preferably 3 to 12 carbon atoms.
  • Linear or branched chain alkyl groups are, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl group, isobutyl group, secondary butyl group, tertiary butyl group, isopentyl group, neopentyl group, tertiary pentyl group, isohexyl group and the like.
  • the cyclic alkyl group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
  • Cyclic alkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.
  • Groups associated with a combination of a chain alkyl group and a cyclic alkyl group preferably have 4 to 24 carbon atoms, more preferably 4 to 18 carbon atoms, and even more preferably 4 to 12 carbon atoms.
  • Groups related to combinations of chain alkyl groups and cyclic alkyl groups include, for example, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylpropyl group, a methylcyclohexylmethyl group, and an ethylcyclohexylethyl group.
  • the alkyl group having an oxygen atom in the chain preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • An alkyl group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched.
  • R 1 N1 and R 2 N2 are preferably alkyl groups having 5 to 12 carbon atoms.
  • a group having a cyclic alkyl group or an alkyl group having 1 to 8 carbon atoms is preferable.
  • RN1 and RN2 may be linked to each other to form a ring structure.
  • the chain may have an oxygen atom or the like.
  • the cyclic structure formed by R N1 and R N2 may be a monocyclic ring or a condensed ring, but is preferably a monocyclic ring.
  • the cyclic structure to be formed is preferably a 5- or 6-membered ring containing a nitrogen atom in formula (N1), such as pyrrole ring, imidazole ring, pyrazole ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, A pyrazolidine ring, a piperidine ring, a piperazine ring, a morpholine ring and the like can be mentioned, and a pyrroline ring, a pyrrolidine ring, a piperidine ring, a piperazine ring and a morpholine ring are preferably mentioned.
  • N1 nitrogen atom in formula (N1)
  • R C1 represents a hydrogen atom or a protecting group, preferably a hydrogen atom.
  • the protective group is preferably a protective group that is decomposed by the action of an acid or a base, and preferably includes a protective group that is decomposed by an acid.
  • protecting groups include chain or cyclic alkyl groups or chain or cyclic alkyl groups having an oxygen atom in the chain.
  • Chain or cyclic alkyl groups include methyl group, ethyl group, isopropyl group, tert-butyl group, cyclohexyl group and the like.
  • the chain alkyl group having an oxygen atom in the chain specifically includes an alkyloxyalkyl group, more specifically a methyloxymethyl (MOM) group, an ethyloxyethyl (EE) group, and the like. mentioned.
  • Cyclic alkyl groups having an oxygen atom in the chain include epoxy group, glycidyl group, oxetanyl group, tetrahydrofuranyl group, tetrahydropyranyl (THP) group and the like.
  • the divalent linking group constituting L is not particularly defined, but is preferably a hydrocarbon group, more preferably an aliphatic hydrocarbon group.
  • the hydrocarbon group may have substituents and may have atoms of types other than carbon atoms in the hydrocarbon chain. More specifically, it is preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and a divalent aliphatic hydrocarbon which may have an oxygen atom in the chain group, a divalent aromatic hydrocarbon group, or a group related to a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, A divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain is more preferred.
  • the divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms.
  • the divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 2 to 4 carbon atoms.
  • the divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and still more preferably 6 to 10 carbon atoms.
  • a group related to a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and 7 to 10 is more preferred.
  • linking group L specifically, a linear or branched chain alkylene group, a cyclic alkylene group, A group related to a combination of a chain alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched chain alkenylene group, a cyclic alkenylene group, an arylene group, Arylene alkylene groups are preferred.
  • the linear or branched chain alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms.
  • the cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
  • the group associated with the combination of a chain alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12 carbon atoms, and even more preferably 4 to 6 carbon atoms.
  • An alkylene group having an oxygen atom in the chain may be chain or cyclic, and may be linear or branched.
  • the alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 3 carbon atoms.
  • the linear or branched chain alkenylene group preferably has 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 3 carbon atoms.
  • the linear or branched chain alkenylene group preferably has 1 to 10 C ⁇ C bonds, more preferably 1 to 6, even more preferably 1 to 3.
  • the cyclic alkenylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6 carbon atoms.
  • the number of C ⁇ C bonds in the cyclic alkenylene group is preferably 1-6, more preferably 1-4, even more preferably 1-2.
  • the arylene group preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • the arylene alkylene group preferably has 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, and even more preferably 7 to 11 carbon atoms.
  • a chain alkylene group, a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a chain alkenylene group, an arylene group, and an arylene alkylene group are preferable, and a 1,2-ethylene group and a propanediyl group (especially 1, 3-propanediyl group), cyclohexanediyl group (especially 1,2-cyclohexanediyl group), vinylene group (especially cis-vinylene group), phenylene group (1,2-phenylene group), phenylenemethylene group (especially 1,2-phenylene methylene group) and ethyleneoxyethylene group (especially 1,2-ethyleneoxy-1,2-ethylene group) are more preferred.
  • base generators include the following, but the present invention should not be construed as being limited thereto.
  • the molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
  • the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
  • Specific preferred compounds of the ionic base generator include, for example, compounds described in paragraphs 0148 to 0163 of International Publication No. 2018/038002.
  • ammonium salts include the following compounds, but the present invention is not limited thereto.
  • iminium salts include the following compounds, but the present invention is not limited thereto.
  • the content of the base generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin in the resin composition of the present invention.
  • the lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
  • the upper limit is more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and may be 5 parts by mass or less, or may be 4 parts by mass or less.
  • One or two or more base generators can be used. When two or more kinds are used, the total amount is preferably within the above range.
  • a base can also be generated from the specific resin, or a base or a base generator can be contained in the developer or the processing liquid and permeated into the film. Therefore, compared with a conventional resin composition containing a base generator and a cyclized resin or a precursor thereof, it can be designed to reduce the content of the base generator. As a result, the residue after the base generation of the base generator, the undecomposed base generator itself, etc. are less likely to remain in the composition, the amount of outgassing from the cured product is reduced, and the adhesion of the cured product is improved.
  • the content of the base generator it is also preferable to set the content of the base generator to 2% by mass or less with respect to 100 parts by mass of the resin. Further, the content of the base generator is preferably 1% by mass or less, more preferably 0.5% by mass or less, relative to 100 parts by mass of the resin. It is also preferable to set the content of the base generator to 0.1% by mass or less with respect to 100 parts by mass of the resin. In these aspects, the lower limit of the content of the base generator may be 0% by mass.
  • the content of the base generator can be determined in consideration of the type and amount of base generated from the specific resin, the type and amount of base contained in the developer or processing liquid, heating conditions, and the like.
  • the resin composition in the present invention preferably contains a solvent. Any known solvent can be used as the solvent.
  • the solvent is preferably an organic solvent.
  • Organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
  • Esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone , ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkyloxyacetates (e.g. methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g.
  • 3-alkyloxypropionic acid alkyl esters e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc.
  • 2-alkyloxypropionate alkyl esters e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, 2-alkyl propyl oxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)
  • 2-alkyloxy- Methyl 2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.
  • ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol Preferred examples include monobutyl ether acetate
  • Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, dihydrolevoglucosenone and the like.
  • Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.
  • Suitable sulfoxides include, for example, dimethyl sulfoxide.
  • Suitable ureas include N,N,N',N'-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, and the like.
  • Alcohols such as 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, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol and the like.
  • a combination of dimethyl sulfoxide and ⁇ -butyrolactone or a combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly
  • the content of the solvent is preferably an amount such that the total solid concentration of the resin composition in the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass. More preferably, the amount is from 10 to 70% by mass, and even more preferably from 20 to 70% by mass.
  • the solvent content may be adjusted according to the desired thickness of the coating and the method of application.
  • the resin composition in the present invention may contain only one type of solvent, or may contain two or more types. When two or more solvents are contained, the total is preferably within the above range.
  • the resin composition in the present invention preferably contains a metal adhesion improver for improving adhesion to metal materials used for electrodes, wiring, and the like.
  • metal adhesion improvers include alkoxysilyl group-containing silane coupling agents, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, and ⁇ -ketoesters. compounds, amino compounds, and the like.
  • silane coupling agent examples include compounds described in paragraph 0167 of WO 2015/199219, compounds described in paragraphs 0062 to 0073 of JP 2014-191002, and paragraphs of WO 2011/080992.
  • Compounds described in 0063-0071, compounds described in paragraphs 0060-0061 of JP-A-2014-191252, compounds described in paragraphs 0045-0052 of JP-A-2014-041264, International Publication No. 2014/097594 Compounds described in paragraph 0055, compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein.
  • silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, sidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltri Methoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane,
  • Aluminum-based adhesion promoters include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), ethylacetoacetate aluminum diisopropylate, and the like.
  • the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the specific resin. It is in the range of 5 to 5 parts by mass. When it is at least the above lower limit value, the adhesiveness between the pattern and the metal layer is improved, and when it is at most the above upper limit value, the heat resistance and mechanical properties of the pattern are improved.
  • One type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, the total is preferably within the above range.
  • the resin composition in the present invention preferably further contains a migration inhibitor.
  • a migration inhibitor By including the migration inhibitor, it becomes possible to effectively suppress the migration of metal ions derived from the metal layer (metal wiring) into the film.
  • Migration inhibitors are not particularly limited, but heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring and 6H-pyran ring, triazine ring), compounds having thioureas and sulfanyl groups, hindered phenolic compounds , salicylic acid derivative-based compounds, and hydrazide derivative-based compounds.
  • heterocyclic rings pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring,
  • triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 1H-tetrazole, 5- Tetrazole compounds such as phenyltetrazole and 5-amino-1H-tetrazole can be preferably used.
  • an ion trapping agent that traps anions such as halogen ions can be used.
  • Other migration inhibitors include rust inhibitors described in paragraph 0094 of JP-A-2013-015701, compounds described in paragraphs 0073 to 0076 of JP-A-2009-283711, and JP-A-2011-059656.
  • the compound described in paragraph 0052, the compound described in paragraphs 0114, 0116 and 0118 of JP-A-2012-194520, the compound described in paragraph 0166 of WO 2015/199219, etc. can be used, and these The contents are incorporated herein.
  • migration inhibitors include the following compounds.
  • the content of the migration inhibitor is preferably 0.01 to 5.0% by mass with respect to the total solid content of the resin composition in the present invention. , more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass.
  • migration inhibitor Only one type of migration inhibitor may be used, or two or more types may be used. When two or more migration inhibitors are used, the total is preferably within the above range.
  • the resin composition in the present invention preferably contains a polymerization inhibitor.
  • Polymerization inhibitors include phenol compounds, quinone compounds, amino compounds, N-oxyl free radical compound compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, metal compounds and the like.
  • Specific compounds of polymerization inhibitors include p-hydroquinone, o-hydroquinone, o-methoxyphenol, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, p-tert-butylcatechol, 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenyl hydroxylamine cerium salt, N-nitroso-N-phenylhydroxyamine aluminum salt, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2, 6-di-tert-butyl-4-methylphenol,
  • the content of the polymerization inhibitor is preferably 0.01 to 20% by mass with respect to the total solid content of the resin composition in the present invention, It is more preferably 0.02 to 15% by mass, even more preferably 0.05 to 10% by mass.
  • polymerization inhibitor Only one type of polymerization inhibitor may be used, or two or more types may be used. When two or more polymerization inhibitors are used, the total is preferably within the above range.
  • the resin composition in the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, as long as the effects of the present invention can be obtained.
  • additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, as long as the effects of the present invention can be obtained.
  • Organic titanium compounds, antioxidants, anti-agglomerating agents, phenolic compounds, other polymer compounds, plasticizers and other auxiliaries (for example, antifoaming agents, flame retardants, etc.) can be blended. Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No.
  • the total blending amount is preferably 3% by mass or less of the solid content of the resin composition in the present invention.
  • surfactant various surfactants such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants can be used.
  • the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
  • the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving are further improved.
  • a surfactant in the resin composition of the present invention, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid saving are further improved.
  • the interfacial tension between the surface to be coated and the coating liquid is reduced, and the wettability to the surface to be coated is improved.
  • the coatability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with little unevenness in thickness.
  • fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (manufactured by DIC Corporation), Florado FC430, FC431, FC171, Novec FC4430, FC4432 (manufactured by 3M Japan Ltd.), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above , Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), and the like.
  • Fluorinated surfactants compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327, compounds described in paragraphs 0117-0132 of JP-A-2011-132503 can also be used, the contents of which are incorporated herein.
  • a block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090, the contents of which are incorporated herein.
  • the fluorosurfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meta)
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3,000 to 50,000, more preferably 5,000 to 30,000.
  • a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used as a fluorine-based surfactant. Specific examples include compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965, the contents of which are incorporated herein.
  • Commercially available products include Megafac RS-101, RS-102 and RS-718K manufactured by DIC Corporation.
  • the fluorine content in the fluorine-based surfactant is preferably 3-40% by mass, more preferably 5-30% by mass, and particularly preferably 7-25% by mass.
  • a fluorosurfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and saving liquid, and has good solubility in the composition.
  • silicone-based surfactants examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (the above, Toray Dow Corning Co., Ltd. ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF6001, KF6002 (manufactured by Shin-Etsu Silicone Co., Ltd. ), BYK307, BYK323, and BYK330 (manufactured by BYK Chemie Co., Ltd.).
  • Hydrocarbon surfactants include, for example, Pionin A-76, Nucalgen FS-3PG, Pionin B-709, Pionin B-811-N, Pionin D-1004, Pionin D-3104, Pionin D-3605, Pionin D-6112, Pionin D-2104-D, Pionin D-212, Pionin D-931, Pionin D-941, Pionin D-951, Pionin E-5310, Pionin P-1050-B, Pionin P-1028-P, Pionin P-4050-T and the like (manufactured by Takemoto Oil & Fat Co., Ltd.), and the like.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Examples include polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester.
  • cationic surfactants include organosiloxane polymer KP-341 (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.), and the like.
  • anionic surfactants include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and Sandet BL (manufactured by Sanyo Kasei Co., Ltd.).
  • the surfactant content is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition.
  • a higher fatty acid derivative such as behenic acid or behenic acid amide is added in order to prevent polymerization inhibition caused by oxygen. may be unevenly distributed on the surface of the resin composition of the present invention
  • the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the resin composition of the present invention. Only one type of higher fatty acid derivative may be used, or two or more types thereof may be used. When two or more higher fatty acid derivatives are used, the total is preferably within the above range.
  • the resin composition in the present invention may contain a thermal polymerization initiator, particularly a thermal radical polymerization initiator.
  • a thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or accelerates the polymerization reaction of a polymerizable compound. By adding a thermal radical polymerization initiator, the polymerization reaction of the resin and the polymerizable compound can be advanced, so that the solvent resistance can be further improved.
  • the photopolymerization initiator described above may also have a function of initiating polymerization by heat, and may be added as a thermal polymerization initiator.
  • thermal radical polymerization initiators include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063554, the contents of which are incorporated herein.
  • thermal polymerization initiator When a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, based on the total solid content of the resin composition in the present invention. , more preferably 0.5 to 15% by mass.
  • One type of thermal polymerization initiator may be contained, or two or more types may be contained. When two or more thermal polymerization initiators are contained, the total amount is preferably within the above range.
  • the resin composition in the present invention may contain inorganic particles.
  • inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.
  • the average particle diameter of the inorganic particles is preferably 0.01 to 2.0 ⁇ m, more preferably 0.02 to 1.5 ⁇ m, still more preferably 0.03 to 1.0 ⁇ m, and 0.04 to 0.5 ⁇ m. Especially preferred.
  • the average particle size of the inorganic particles is the primary particle size and the volume average particle size.
  • the volume average particle size can be measured by a dynamic light scattering method using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, the centrifugal sedimentation light transmission method, X-ray transmission method, or laser diffraction/scattering method can be used.
  • the resin composition in the present invention may contain an ultraviolet absorber.
  • an ultraviolet absorber As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
  • salicylate-based UV absorbers include phenyl salicylate, p-octylphenyl salicylate, pt-butylphenyl salicylate, and the like.
  • benzophenone-based UV absorbers examples 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- and hydroxy-4-octoxybenzophenone.
  • benzotriazole-based UV absorbers examples 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,
  • Examples of substituted acrylonitrile UV absorbers include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.
  • examples of triazine-based UV absorbers include 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-triazine 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(
  • the above various ultraviolet absorbers may be used singly or in combination of two or more.
  • the resin composition in the present invention may or may not contain an ultraviolet absorber, but when it does, the content of the ultraviolet absorber is 0.001 with respect to the total solid mass of the resin composition in the present invention. It is preferably from 0.01% by mass to 1% by mass, and more preferably from 0.01% by mass to 0.1% by mass.
  • the resin composition of this embodiment may contain an organic titanium compound. By including the organic titanium compound in the resin composition, it is possible to form a resin layer having excellent chemical resistance even when cured at a low temperature.
  • Organotitanium compounds that can be used include those in which organic groups are attached to titanium atoms through covalent or ionic bonds. Specific examples of organotitanium compounds are shown below in I) to VII): I) Titanium chelate compound: Among them, a titanium chelate compound having two or more alkoxy groups is more preferable because the storage stability of the resin composition is good and a good curing pattern can be obtained.
  • titanium bis(triethanolamine) diisopropoxide titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate ), titanium diisopropoxide bis(tetramethylheptanedionate), titanium diisopropoxide bis(ethylacetoacetate), and the like.
  • Tetraalkoxytitanium compounds for example titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide , titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis ⁇ 2,2-(allyloxymethyl) butoxide ⁇ ] and the like.
  • Titanocene compounds for example, pentamethylcyclopentadienyltitanium trimethoxide, bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis( ⁇ 5-2, 4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium and the like.
  • Monoalkoxy titanium compounds for example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, and the like.
  • Titanium oxide compounds for example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide and the like.
  • the organotitanium compound at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds provides better chemical resistance. It is preferable from the viewpoint of performance.
  • titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide) and bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H) -pyrrol-1-yl)phenyl)titanium is preferred.
  • the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin.
  • the amount is 0.05 parts by mass or more, the resulting cured pattern exhibits good heat resistance and chemical resistance more effectively. Excellent.
  • the resin composition in the present invention may contain an antioxidant.
  • an antioxidant By containing an antioxidant as an additive, it is possible to improve the elongation properties of the cured film and the adhesion to metal materials.
  • Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound.
  • Preferred phenolic compounds include hindered phenolic compounds.
  • a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable as the above substituent.
  • the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
  • Phosphorus-based antioxidants can also be suitably used as antioxidants.
  • a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, 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 (manufactured by ADEKA Corporation) and the like.
  • compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967 can also be used, the contents of which are incorporated herein.
  • the resin composition in the present invention may contain a latent antioxidant, if necessary.
  • the latent antioxidant is a compound in which the site functioning as an antioxidant is protected by a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst.
  • a compound that functions as an antioxidant by removing the protective group by the reaction is exemplified.
  • latent antioxidants include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219, the contents of which are incorporated herein.
  • Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
  • Examples of preferred antioxidants include 2,2-thiobis(4-methyl-6-t-butylphenol), 2,6-di-t-butylphenol and compounds of formula (3).
  • R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), and R 6 represents alkylene having 2 or more carbon atoms (preferably 2 to 10 carbon atoms). represents a group.
  • R 7 represents a monovalent to tetravalent organic group containing at least one of an alkylene group having 2 or more carbon atoms (preferably 2 to 10 carbon atoms), an oxygen atom and a nitrogen atom.
  • k represents an integer of 1 to 4;
  • the compound represented by formula (3) suppresses oxidative deterioration of the aliphatic groups and phenolic hydroxyl groups of the resin. In addition, metal oxidation can be suppressed by the antirust action on the metal material.
  • R7 includes an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, -O-, -NH-, -NHNH-, combinations thereof, and the like, which may further have a substituent.
  • Examples of compounds represented by general formula (3) include the following, but are not limited to the structures below.
  • the amount of antioxidant added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, relative to the resin. By making the addition amount 0.1 parts by mass or more, the effect of improving elongation characteristics and adhesion to metal materials can be easily obtained even in a high-temperature and high-humidity environment. The interaction with the agent improves the sensitivity of the resin composition. Only one kind of antioxidant may be used, or two or more kinds thereof may be used. When two or more kinds are used, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present embodiment may contain an anti-aggregation agent as necessary.
  • Anti-aggregating agents include sodium polyacrylate and the like.
  • the aggregation inhibitor may be used alone or in combination of two or more.
  • the resin composition in the present invention may or may not contain an anti-aggregation agent, but when it is included, the content of the anti-aggregation agent is 0.01 with respect to the total solid mass of the resin composition in the present invention. It is preferably from 0.02 mass % to 5 mass %, and more preferably from 0.02 mass % to 5 mass %.
  • the resin composition of the present embodiment may contain a phenolic compound as necessary.
  • phenolic compounds include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, methylenetris-FR-CR, BisRS-26X (these are trade names, manufactured by Honshu Chemical Industry Co., Ltd.), BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F (these are trade names, manufactured by Asahi Organic Chemicals Industry Co., Ltd.) and the like.
  • one type of phenolic compound may be used alone, or two or more types may be used in combination.
  • the resin composition in the present invention may or may not contain a phenolic compound, but when it does, the content of the phenolic compound is 0.01 with respect to the total solid mass of the resin composition in the present invention.
  • the content is preferably from 0.02 mass % to 30 mass %, more preferably from 0.02 mass % to 20 mass %.
  • Other polymer compounds include siloxane resins, (meth)acrylic polymers obtained by copolymerizing (meth)acrylic acid, novolac resins, resole resins, polyhydroxystyrene resins, and copolymers thereof.
  • Other polymer compounds may be modified products into which cross-linking groups such as methylol groups, alkoxymethyl groups and epoxy groups have been introduced.
  • the resin composition in the present invention may or may not contain other polymer compounds, but when it does, the content of the other polymer compound is relative to the total solid mass of the resin composition in the present invention. , preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.02% by mass or more and 20% by mass or less.
  • the viscosity of the resin composition in the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and 2,500 mm 2 /s to 8,000 mm. 2 /s is more preferred. If it is the said range, it will become easy to obtain a coating film with high uniformity. If it is 1,000 mm 2 /s or more , it is easy to apply the film with a film thickness required, for example, as an insulating film for rewiring. A coating is obtained.
  • the water content of the resin composition in the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity in the storage conditions and reducing the porosity of the storage container during storage.
  • the metal content of the resin composition in 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.
  • metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are included, the total of these metals is preferably within 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.
  • the raw material constituting the product is filtered through a filter, or the inside of the apparatus is lined with polytetrafluoroethylene or the like to perform distillation under conditions in which contamination is suppressed as much as possible.
  • the resin composition in the present invention preferably has a halogen atom content of less than 500 ppm by mass, more preferably less than 300 ppm by mass, and less than 200 ppm by mass from the viewpoint of wiring corrosion. is more preferred.
  • those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
  • Halogen atoms include chlorine and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms or chlorine ions and bromine ions is within the above ranges.
  • ion exchange treatment and the like are preferably mentioned.
  • the content of a component having a molecular weight of 1000 or less contained in the resin composition and a component different from the solvent is the total solid content of the resin composition. It is preferably 40% by mass or less with respect to.
  • the molecular weight is preferably 800 or less, more preferably 600 or less.
  • the lower limit of the molecular weight is not particularly limited, it can be, for example, 50 or more.
  • the content is preferably 30% by mass or less, more preferably 10% by mass or less.
  • the lower limit of the content is not particularly limited, and may be 0% by mass.
  • a conventionally known storage container can be used as the storage container for the resin composition in the present invention.
  • the inner wall of the container is a multi-layer bottle made of 6 types and 6 layers of resin, and 6 types of resin are used. It is also preferred to use bottles with a seven-layer structure. Examples of such a container include the container described in JP-A-2015-123351.
  • the resin composition of the present invention is a resin composition containing a precursor of a cyclized resin, At least one of the three films having different thicknesses has a glass transition temperature of 200° C. or higher when the glass transition temperature is measured under the following measurement condition 1.
  • Measurement condition 1 The resin composition was coated on a silicon substrate to a thickness of 5 ⁇ m, 10 ⁇ m, or 20 ⁇ m, respectively, dried at 100° C. for 5 minutes, heated at 180° C. for 2 hours to obtain a cured product, and returned to 25° C.
  • the glass transition temperature of the cured product is measured using a differential scanning calorimeter.
  • the glass transition temperature of at least one of the three films having different thicknesses is 200° C. or higher when the glass transition temperature is measured under the measurement conditions 1 described above.
  • the cyclization rate of the cyclized resin in the cured product is high. It is considered that the high cyclization rate suppresses the generation of outgassing due to further cyclization in the film after curing.
  • the heating for 2 hours under the above measurement condition 1 is performed in a nitrogen atmosphere.
  • the glass transition temperature is measured by the method described in Examples.
  • the cyclization rate of the cured product (cured product before measurement of the glass transition temperature) obtained under the above measurement conditions 1 is preferably 95% or more, more preferably 98% or more, and 99% or more. It is even more preferable to have The upper limit of the cyclization rate is not particularly limited, and may be 100%. Cyclization rate is measured by the method described above. When the cyclization rate is within the above range, the migration of metal ions from the metal layer with the uncyclized portion as the permeation path to the cured product is also suppressed, and the cured product with excellent adhesion to the metal is obtained. It is considered to be obtained.
  • the details of the components contained in the resin composition of the present invention, the properties of the resin composition, etc. are the same as the details of the components, the properties of the resin composition, etc. of the resin composition used in the method for producing the cured product of the present invention described above. and preferred embodiments are also the same.
  • the cured product of the present invention is a cured product obtained by curing the resin composition of the present invention.
  • the details of the cured product of the present invention are the same as the details of the cured product obtained in the above-described method for producing the cured product of the present invention, and preferred embodiments are also the same.
  • the laminate of the present invention refers to a structure having a plurality of layers made of the cured product of the present invention.
  • the laminate of the present invention is a laminate containing two or more layers made of a cured product, and may be a laminate in which three or more layers are laminated. Of the two or more layers of the cured product contained in the laminate, at least one is a layer made of the cured product of the present invention, and the shrinkage of the cured product, or the deformation of the cured product due to the shrinkage, etc. From the viewpoint of suppression, it is also preferable that all the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.
  • the method for producing the laminate of the present invention preferably includes the method for producing the cured product of the present invention, and more preferably includes repeating the method for producing the laminate of the present invention multiple times.
  • the laminate of the present invention includes two or more layers of a cured product obtained by curing a resin composition containing a precursor of a cyclized resin, and at least one of the layers of the cured product is the cured product of the present invention. It is a layer made up of things. Here, it is also one of the preferred embodiments of the present invention that all the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention. It is preferable that the laminate of the present invention includes two or more layers made of the cured product, and a metal layer between any of the layers made of the cured product. The metal layer is preferably formed by the metal layer forming step.
  • the method for producing a laminate of the present invention further includes a metal layer forming step of forming a metal layer on the layer made of the cured product between the methods for producing the cured product that are performed multiple times.
  • a metal layer forming step of forming a metal layer on the layer made of the cured product between the methods for producing the cured product that are performed multiple times.
  • Preferred aspects of the metal layer forming step are as described above.
  • the laminate for example, a laminate containing at least a layer structure in which three layers of a layer made of the first cured product, a metal layer, and a layer made of the second cured product are laminated in this order is preferable. be done. It is preferable that both the layer comprising the first cured product and the layer comprising the second cured product are layers comprising the cured product of the present invention.
  • the resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product have the same composition. It may be a product or a composition having a different composition.
  • the metal layer in the laminate of the present invention is preferably used as a metal wiring such as a rewiring layer.
  • the method for producing a laminate of the present invention includes a lamination step.
  • the lamination step means that the surface of the pattern (resin layer) or metal layer is again subjected to (a) film formation step (layer formation step), (b) exposure step, (c) development step, (d) heating step and development It is a series of steps including performing at least one of the post-exposure steps in this order. However, at least one of (a) the film forming step and (d) the heating step and the post-development exposure step may be repeated. Moreover, after at least one of the (d) heating step and the post-development exposure step, (e) a metal layer forming step may be included. Needless to say, the lamination step may further include the drying step and the like as appropriate.
  • a surface activation treatment process may be further performed.
  • a plasma treatment is exemplified as the surface activation treatment. Details of the surface activation treatment will be described later.
  • the lamination step is preferably performed 2 to 20 times, more preferably 2 to 9 times.
  • a structure of 2 to 20 resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer is preferable, and a structure of 2 to 9 layers is more preferable.
  • Each of the layers described above may have the same composition, shape, film thickness, etc., or may differ from each other.
  • a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after providing the metal layer.
  • the film forming step, (b) the exposure step, (c) the developing step, (d) at least one of the heating step and the post-development exposure step, and (e) the metal layer forming step are repeated in this order.
  • the film forming step, (d) at least one of the heating step and the post-development exposure step, and (e) the metal layer forming step are repeated in this order.
  • the method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least part of the metal layer and the resin composition layer to surface activation treatment.
  • the surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer is subjected to surface activation treatment.
  • the metal layer forming step may be performed.
  • the surface activation treatment may be performed only on at least part of the metal layer, may be performed only on at least part of the resin composition layer after exposure, or may be performed on the metal layer and the resin composition layer after exposure. Both may be done at least partially, respectively.
  • the surface activation treatment is preferably performed on at least part of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the area of the metal layer on which the resin composition layer is formed.
  • the surface of the metal layer By subjecting the surface of the metal layer to the surface activation treatment in this manner, the adhesiveness to the resin composition layer (film) provided on the surface can be improved.
  • the resin composition layer when the resin composition layer is cured, such as in the case of negative development, it is less likely to be damaged by surface treatment, and the adhesion is likely to be improved.
  • Specific examples of the surface activation treatment include plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, and CF 4 /O 2 . , NF 3 /O 2 , SF 6 , NF 3 , NF 3 /O 2 etching treatment, surface treatment by ultraviolet (UV) ozone method, immersion in hydrochloric acid aqueous solution to remove the oxide film, and then amino groups and thiol groups.
  • UV ultraviolet
  • the treatment is selected from immersion treatment in an organic surface treatment agent containing at least one compound and mechanical surface roughening treatment using a brush.
  • Plasma treatment is preferred, and oxygen plasma treatment using oxygen as a raw material gas is particularly preferred.
  • the energy is preferably 500-200,000 J/m 2 , more preferably 1000-100,000 J/m 2 , most preferably 10,000-50,000 J/m 2 .
  • the present invention also discloses a semiconductor device comprising the cured product of the present invention or the laminate of the present invention. Moreover, this invention also discloses the manufacturing method of the semiconductor device containing the manufacturing method of the hardened
  • Specific examples of a semiconductor device using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer can refer to the description of paragraphs 0213 to 0218 of JP-A-2016-027357 and the description of FIG. The contents of which are incorporated herein.
  • SA-1 polyimide precursor
  • SA-2 to SA-7 ⁇ Synthesis of polyimide precursor resins (SA-2 to SA-7)> The types of amine (pyrrolidine in the synthesis of SA-1) and alcohol (2-hydroxyethyl methacrylate in the synthesis of SA-1) and their molar ratios were changed as shown in the table below, and the carboxylic anhydride (SA- 4,4'-biphthalic dianhydride in the synthesis of SA-1) and diamine (4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl in the synthesis of SA-1) were changed as appropriate. , SA-2 to SA-7 were synthesized in the same manner as for SA-1.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of these resins are shown in the Mw and Mn columns of the table below, respectively.
  • the structures of SA-2 to SA-7 are presumed to be structures represented by the following formulas (SA-2) to (SA-7), respectively.
  • subscripts in parentheses representing repeating units represent the molar ratio of each repeating unit.
  • SA-8 polyimide precursor
  • SA-8 polyimide precursor
  • the resulting polyimide precursor SA-8 had a weight average molecular weight of 24,200 and a number average molecular weight of 10,100.
  • SA-8 The structure of SA-8 is presumed to be a structure represented by the following formula (SA-8). In the following formula, subscripts in parentheses representing repeating units represent the molar ratio of each repeating unit.
  • HA-1 is a compound having the following structure. It was confirmed by 1 H-NMR that it was HA-1.
  • the polyimide precursor resin was obtained by filtration, stirred again in 4 liters of water for 30 minutes, filtered again, and dried at 45° C. under reduced pressure for 24 hours. Subsequently, the dried polyimide precursor resin is dissolved in 300 mL of tetrahydrofuran, 50 g of an ion exchange resin is added, and the mixture is stirred for 6 hours. The mixture was stirred for 15 minutes at a speed of 500 rpm. The polyimide precursor resin was collected by filtration and dried at 45° C. for 2 days to obtain a polyamideimide precursor (SA-9).
  • SA-9 polyamideimide precursor
  • SA-9 had a weight average molecular weight of 26,100 and a number average molecular weight of 11,300.
  • the structure of SA-9 is presumed to be a structure represented by the following formula (SA-9).
  • the obtained polyimide precursor A-1 had a weight average molecular weight of 22,100 and a number average molecular weight of 9,400.
  • each resin composition was obtained by mixing the components shown in the table below.
  • the components shown in the table below were mixed to obtain comparative compositions.
  • the content of each component described in the table was the amount (parts by mass) described in the "addition amount” column of each column of the table.
  • the resulting resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter with a pore width of 0.5 ⁇ m.
  • the description of "-" indicates that the composition does not contain the corresponding component.
  • SR-209 (manufactured by Sartomer)
  • A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate)
  • A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd., tricyclodecanedimethanol diacrylate)
  • H-1 N-phenyldiethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • H-2 N-hydroxyphthalimide (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • the curable resin composition layer on the copper substrate is exposed using a stepper (Nikon NSR 2005 i9C) with an exposure energy of 500 mJ/cm 2 using a 100 ⁇ m square photomask for pattern formation, and then the table
  • the film was developed for 60 seconds with the developer described in the column “Developer” and rinsed for 30 seconds with the rinse liquid described in the column “Rinse” in the table to obtain a 100 ⁇ m square resin layer.
  • the temperature was raised at the temperature increase rate described in the "Temperature increase rate” column of the table, and after reaching the temperature described in the "Temperature” column of the “Curing conditions” table, this temperature was maintained for 2 hours to obtain a resin film 2.
  • the glass transition temperature of the resin film 2 was the same as the glass transition temperature of the cured product used in outgassing evaluation.
  • a shear force was measured on a 100 ⁇ m square resin film 2 on a copper substrate using a bond tester (CondorSigma manufactured by XYZTEC) under an environment of 25° C. and 65% relative humidity (RH). The larger the shearing force, the larger the adhesion force, which is a preferable result.
  • the evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the "Adhesion" column of the table. -Evaluation criteria- A: Shearing force exceeded 30 gf. B: Shearing force exceeded 25 gf and was 30 gf or less. C: Shearing force exceeded 20 gf and was 25 gf or less. D: Shearing force was 20 gf or less. Also, 1 gf is 0.00980665N.
  • a resin composition layer was formed by applying the resin composition or the comparative composition onto a silicon wafer by spin coating.
  • the silicon wafer to which the resulting resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to obtain a uniform resin composition layer having a thickness of about 15 ⁇ m on the silicon wafer.
  • the entire surface of the obtained resin composition layer was exposed to i-line at an exposure energy of 500 mJ/cm 2 using a stepper (Nikon NSR 2005 i9C).
  • the film was developed for 60 seconds with the developer described in the "Developer” column of the table, and rinsed for 30 seconds with the rinse liquid described in the "Rinse” column of the table.
  • the resin composition layer (resin layer) after the rinsing was heated in a nitrogen atmosphere at the temperature increase rate described in the "Temperature increase rate” column of the table, and the "Temperature” of the “Curing conditions” in the table was After reaching the temperature indicated in the column, it was heated for 2 hours.
  • the cured resin layer (cured material) was immersed in a 4.9 mass % hydrofluoric acid aqueous solution, and the cured material was separated from the silicon wafer.
  • Weight loss (%) (1 - mass B / mass A) ⁇ 100
  • the evaluation was carried out according to the following evaluation criteria, and the evaluation results are shown in the "outgassing property" column of the table. It can be said that the smaller the mass reduction, the better the outgassing property.
  • D Mass reduction was 7% or more.
  • the cyclization rate (imidization rate) of the cured product obtained in the outgassing evaluation was measured and described in the "imidization rate" column of the table.
  • the imidization rate was calculated by the following method.
  • the peak intensity P1 near 1377 cm ⁇ 1 which is the absorption peak derived from the imide structure, was obtained, and the resin film 2 was heat - treated at 350° C. for 1 hour.
  • a peak intensity P2 near 1 was obtained.
  • the solid content concentration of the composition is diluted to 29% by mass with the solvent (solvent listed in the table) contained in each composition, and the rotation speed in the spin coating method is set to 3000 rpm. applied.
  • Each of the obtained silicon wafers to which the resin composition layer was applied was dried on a hot plate at 100° C. for 5 minutes to form a resin composition layer on the silicon wafer.
  • the resin composition layer was heated in a nitrogen atmosphere at a heating rate of 10° C./min, reaching 180° C., and then maintained at this temperature for 2 hours to obtain a cured product.
  • the cured product was immersed in a 4.9% by mass hydrofluoric acid aqueous solution, and the cured product was peeled off from the silicon wafer.
  • the glass transition temperature of the resulting cured product was measured under the following measurement conditions. ⁇ Measurement conditions> Using a differential scanning calorimeter, in a nitrogen atmosphere, the temperature conditions of the cured product are changed in the order of (1) to (4) below to create a differential scanning calorimetry curve, and the low temperature side in the differential scanning calorimetry curve The glass transition temperature was measured as the temperature at the intersection of a straight line obtained by extending the base line of to the high temperature side and a tangent line drawn at the point where the slope of the stepwise change portion of the glass transition curve becomes maximum.
  • B The minimum value among the glass transition temperatures of the cured products with three thicknesses was less than 250°C and 200°C or higher.
  • C The minimum value among the glass transition temperatures of the cured products with three thicknesses was less than 200°C and 190°C or more.
  • D The minimum value among the glass transition temperatures of the cured products with three thicknesses was less than 190°C.
  • the cured product obtained by the production method of the cured product of the present invention and the cured product composed of the resin composition of the present invention have suppressed generation of outgassing.
  • the obtained cured product has a glass transition temperature of less than 200°C. be. It can be seen that the cured product obtained by the method for producing a cured product according to Comparative Example 1 and the cured product formed from the comparative composition generate a large amount of outgas.
  • Example 101 The resin composition used in Example 1 was applied in a layer by spin coating to the surface of the thin copper layer of the resin base material on which the thin copper layer was formed, and dried at 100° C. for 4 minutes to obtain a film thickness. After forming a resin composition layer of 20 ⁇ m, it was exposed using a stepper (NSR1505 i6 manufactured by Nikon Corporation). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 ⁇ m). After exposure, it was heated at 100° C. for 4 minutes.
  • NSR1505 i6 manufactured by Nikon Corporation
  • the film was developed with cyclohexanone (I-1) for 2 minutes and rinsed with PGMEA (J-1) for 30 seconds to obtain a layer pattern.
  • the temperature was raised at a rate of 10° C./min, and after reaching 180° C., the temperature was maintained at 180° C. for 2 hours to form an interlayer insulating film for a rewiring layer.
  • This interlayer insulating film for rewiring layer was excellent in insulating properties.
  • a semiconductor device was manufactured using these interlayer insulating films for rewiring layers, it was confirmed that the device operated without any problem.

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PCT/JP2022/026314 2021-07-30 2022-06-30 硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、樹脂組成物、硬化物、積層体、及び、半導体デバイス WO2023008090A1 (ja)

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