Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
  • C08F290/145—Polyamides; Polyesteramides; Polyimides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
  • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
  • C08L55/005—Homopolymers or copolymers obtained by polymerisation of macromolecular compounds terminated by a carbon-to-carbon double bond
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/031—Organic compounds not covered by group G03F7/029
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/16—Coating processes; Apparatus therefor
  • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
• • 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
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/03—Use of materials for the substrate
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
  • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
  • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
  • H10P76/2041—Photolithographic processes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

• the present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device.
• the resin material can be used as an insulating film, a sealing material, or a protective film for a semiconductor device to be mounted, although the resin material is not particularly limited thereto. It is also used as a base film or coverlay for a flexible substrate.
• the resin composition can be applied by known coating methods, and therefore has excellent adaptability in manufacturing, for example, allowing for a high degree of freedom in designing the shape, size, application position, etc., of the resin composition when applied. In view of this excellent adaptability in manufacturing, there are high expectations for the development of industrial applications of the above-mentioned resin composition.
• Patent Document 1 describes a photosensitive resin composition characterized by comprising, as essential components, (A) a soluble polyimide containing at least one structural unit of a specific structure, (B) a compound having at least one atom or moiety selected from the group consisting of phosphorus, halogen, and siloxane moieties, and (C) a (meth)acrylic compound having at least one carbon-carbon double bond.
• Patent Document 2 describes a solvent-soluble negative-type photosensitive polyimide composition that contains two or more aromatic diamine components in a polyimide main chain, one of which is an aromatic diamine having photosensitivity and the other of which is an aromatic diamine having a hydrophilic group.
• the present invention aims to provide a resin composition that has excellent resolution when forming a pattern of the cured product, a cured product obtained by curing the composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product, as well as a novel resin.
• ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the resin has a weight average molecular weight of 8,000 or more and less than 30,000.
• ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the resin has a ring structure having 5 or more ring members in a side chain.
• ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the resin is a resin having a structure represented by the following formula (A-1):
• A-1 L A1 represents a single bond or an (m+1)-valent linking group
• each Cy independently represents a ring structure having 5 or more ring members which may have a substituent
• m represents an integer of 1 or more
• * represents a bonding site to another structure.
• A6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the resin has a polymerizable group.
• ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the resin has a repeating unit represented by the following formula (1-1):
• X1 is a tetravalent organic group
• Y1 is an organic group containing a group having an ethylenically unsaturated bond.
• ⁇ 8> The resin composition according to ⁇ 7>, in which a value of the molar amount of oxygen atoms in the resin/weight average molecular weight is 9.7 mmol/g or less.
• Y 1 in the formula (1-1) contains a ring structure having 5 or more ring members.
• each R 1 independently represents an organic group containing a group having an ethylenically unsaturated bond
• n1 represents an integer of 0 to 3
• n2 represents an integer of 0 to 3
• n1+n2 is an integer of 1 to 6, and * represents a bonding site to another structure.
• each R 1 independently represents an organic group containing a group having an ethylenically unsaturated bond
• n1 represents an integer of 0 to 3
• n2 represents an integer of 0 to 3
• n1+n2 is an integer of 1 to 6
• each R 2 independently represents an alkyl group or a fluoroalkyl group
• * represents a bonding site to another structure.
• X2 is a tetravalent organic group
• Y2 is a divalent organic group having no ethylenically unsaturated bond
• at least one of X2 and Y2 contains a group in which two or more hydrogen atoms have been removed from a structure represented by the following formula (C-1):
• Z 1 to Z 3 each independently represent a single bond or a divalent linking group, and the four benzene rings depicted in formula (C-1) may each have a substituent.
• L A1 represents a single bond or an (m+1)-valent linking group
• each Cy independently represents a ring structure having 5 or more ring members which may have a substituent
• m represents an integer of 1 or more
• * represents a bonding site to another structure.
• X3 is a tetravalent organic group
• Y3 is a divalent organic group containing a vinylphenyl group
• Y3 contains a structure represented by formula (B-1) or formula (B-2).
• each R 1 independently represents an organic group containing a group having an ethylenically unsaturated bond
• n1 represents an integer of 0 to 3
• n2 represents an integer of 0 to 3
• n1+n2 is an integer of 1 to 6
• * represents a bonding site to another structure.
• each R 1 independently represents an organic group containing a group having an ethylenically unsaturated bond
• n1 represents an integer of 0 to 3
• n2 represents an integer of 0 to 3
• n1+n2 is an integer of 1 to 6
• each R 2 independently represents an alkyl group or a fluoroalkyl group, and * represents a bonding site to another structure.
• ⁇ 14> The resin composition according to any one of ⁇ 1> to ⁇ 13>, wherein the polymerizable compound is a radically polymerizable compound, and the content of the radically polymerizable compound is 8 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the resin.
• ⁇ 15> The resin composition according to ⁇ 1> or ⁇ 2>, comprising a photoradical polymerization initiator as the polymerization initiator, and comprising a radical polymerizable compound as the polymerizable compound.
• ⁇ 16> The resin composition according to ⁇ 15>, wherein the radical polymerizable compound contains two or more (meth)acryloyl groups.
• ⁇ 17> The resin composition according to ⁇ 15> or ⁇ 16>, comprising an oxime compound as the photoradical polymerization initiator.
• ⁇ 18> The resin composition according to ⁇ 15> or ⁇ 16>, comprising a compound having a ketoxime group as the photoradical polymerization initiator.
• ⁇ 19> The resin composition according to any one of ⁇ 1> to ⁇ 18>, wherein the resin contains a resin having an ethylenically unsaturated bond valence of 0.5 to 2.0 mmol/g or less.
• ⁇ 20> The resin composition according to ⁇ 1> or ⁇ 2>, which is used for forming an interlayer insulating film for a redistribution layer.
• ⁇ 21> A cured product obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 20>.
• ⁇ 22> A laminate comprising two or more layers made of the cured product according to ⁇ 21>, and a metal layer between any two adjacent layers made of the cured product.
• ⁇ 23> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 20> onto a substrate to form a film.
• the method for producing a cured product according to ⁇ 23> comprising: an exposure step of selectively exposing the film to light; and a development step of developing the film with a developer to form a pattern.
• ⁇ 25> A method for producing a cured product according to ⁇ 23> or ⁇ 24>, comprising a heating step of heating the film at 50 to 450° C.
• ⁇ 26> A method for producing a laminate, comprising the method for producing a cured product according to any one of ⁇ 23> to ⁇ 25>.
• ⁇ 27> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of ⁇ 23> to ⁇ 25>.
• ⁇ 28> A semiconductor device comprising the cured product according to ⁇ 21>.
• the present invention provides a resin composition that has excellent resolution when forming a pattern of a cured product, a cured product obtained by curing the composition, a laminate including the cured product, a method for producing the cured product, a method for producing the laminate, a method for producing a semiconductor device including the method for producing the cured product, and a semiconductor device including the cured product.
• a numerical range expressed using the symbol "to” means a range that includes the numerical values before and after "to” as the lower limit and upper limit, respectively.
• the term “process” includes not only an independent process but also a process that cannot be clearly distinguished from other processes, so long as the process can achieve its intended effect.
• groups (atomic groups) when there is no indication of whether they are substituted or unsubstituted, the term encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups).
• an "alkyl group” encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
• exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation.
• (meth)acrylate means both or either of “acrylate” and “methacrylate”
• (meth)acrylic means both or either of “acrylic” and “methacrylic”
• (meth)acryloyl means both or either of “acryloyl” and “methacryloyl”.
• Me represents a methyl group
• Et represents an ethyl group
• Bu represents a butyl group
• Ph represents a phenyl group.
• the total solid content refers to the total mass of all components of the composition excluding the solvent
• the solid content concentration refers to the mass percentage of the other components excluding the solvent with respect to the total mass of the composition.
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) method, and are defined as polystyrene equivalent values, unless otherwise specified.
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be determined, for example, by using HLC-8220GPC (manufactured by Tosoh Corporation) and using guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series as columns.
• these molecular weights are measured using THF (tetrahydrofuran) as an eluent.
• THF tetrahydrofuran
• NMP N-methyl-2-pyrrolidone
• detection in GPC measurement is performed using a UV (ultraviolet) light detector with a wavelength of 254 nm.
• a third layer or element may be interposed between the reference layer and the other layer, and the reference layer does not need to be in contact with the other layer.
• the direction in which the layers are stacked on the substrate is referred to as "upper", or, in the case of a resin composition layer, the direction from the substrate to the resin composition layer is referred to as “upper”, and the opposite direction is referred to as "lower”. Note that such a vertical direction is set for the convenience of this specification, and in an actual embodiment, the "upper” direction in this specification may be different from the vertical upward direction.
• the composition may contain, as each component contained in the composition, two or more compounds corresponding to that component.
• 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.
• combinations of preferred aspects are more preferred aspects.
• a resin composition according to a first aspect of the present invention (hereinafter, also simply referred to as "first resin composition”) is a resin composition containing at least one resin selected from the group consisting of polyimides and precursors thereof, a polymerizable compound, and a polymerization initiator, and a film having a thickness of 10 ⁇ m obtained from the resin composition has a dissolution rate in cyclopentanone of 0.01 to 0.55 ⁇ m/sec.
• a resin composition according to a second aspect of the present invention is a resin composition containing at least one resin selected from the group consisting of polyimides and precursors thereof, a polymerizable compound, and a polymerization initiator, and the resin contains a resin having a dissolution rate in cyclopentanone of 0.01 to 0.2 ⁇ m/sec when the resin film has a thickness of 10 ⁇ m.
• the resin composition according to the third aspect of the present invention (hereinafter, also simply referred to as the “third resin composition”) contains a resin having a repeating unit represented by formula (1-3) and a structure represented by formula (A-1), a polymerizable compound, and a polymerization initiator.
• the first resin composition, the second resin composition, and the third resin composition will be collectively referred to simply as the "resin composition".
• the polyimide resin having a repeating unit represented by formula (1-2) contained in the first resin composition is also referred to as a "first specific resin.”
• the at least one resin selected from the group consisting of polyimides and precursors thereof contained in the second resin composition is also referred to as a "second specific resin.”
• the at least one resin selected from the group consisting of polyimides and their precursors contained in the third resin composition is also referred to as a "third specific resin.”
• specific resin when the term “specific resin” is simply used, it refers to all of the first specific resin, the second specific resin, and the third specific resin.
• the resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and is preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent.
• the resin composition of the present invention can be used, for example, to form an insulating film for a semiconductor device, an interlayer insulating film for a redistribution layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a redistribution layer.
• the resin composition of the present invention is used for forming an interlayer insulating film for a rewiring layer.
• the resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to negative development.
• negative development refers to a development in which the non-exposed areas are removed by development during exposure and development
• positive development refers to a development in which the exposed areas are removed by development.
• the exposure method, the developer, and the development method for example, the exposure method described in the exposure step and the developer and development method described in the development step in the description of the production method of the cured product described later can be used.
• the resin composition of the present invention has excellent resolution when forming a pattern of the cured product.
• the mechanism by which the above effects are obtained is unclear, but is speculated to be as follows.
• a first resin composition has a dissolution rate in cyclopentanone of 0.01 to 0.55 ⁇ m/sec when a film having a thickness of 10 ⁇ m is obtained from the resin composition.
• a film having low solubility in cyclopentanone is unlikely to swell in the image area (undeveloped area) upon development, and is therefore unlikely to cause opening defects when forming a fine pattern, and is considered to exhibit high resolution.
• the second resin composition contains, as a resin, a resin having a dissolution rate in cyclopentanone of 0.01 to 0.2 ⁇ m/sec when the resin film has a thickness of 10 ⁇ m.
• the third resin composition has a repeating unit represented by formula (1-3) and a structure represented by formula (A-1). It is believed that the film containing such a resin having a specific structure and molecular weight is unlikely to cause swelling of the image area by development, and is unlikely to cause opening defects when forming a fine pattern, and thus exhibits high resolution. As described above, it is believed that the resin composition of the present invention is unlikely to cause swelling of the pattern during development.
• the film has excellent adhesion to the substrate and the pattern collapse due to development is suppressed. Furthermore, when the resin composition of the present invention is used, dissolution of the resin from the pattern during development is suppressed, and it is believed that the resulting pattern is prevented from having a trailing shape (i.e., a shape with a small taper angle).
• Patent Documents 1 and 2 do not describe the first resin composition, the second resin composition, or the third resin composition.
• the dissolution rate of a film having a thickness of 10 ⁇ m obtained from the first resin composition in cyclopentanone is 0.01 to 0.55 ⁇ m/sec.
• the dissolution rate of a film having a thickness of 10 ⁇ m obtained from the second resin composition in cyclopentanone is preferably 0.01 to 0.55 ⁇ m/sec.
• the dissolution rate of a film having a thickness of 10 ⁇ m obtained from the third resin composition in cyclopentanone is preferably 0.01 to 0.55 ⁇ m/sec.
• the lower limit of the dissolution rate of the film is preferably 0.01 ⁇ m/sec or more, and more preferably 0.1 ⁇ m/sec or more.
• the upper limit of the dissolution rate of the film is preferably 0.55 ⁇ m/sec or less, and more preferably 0.40 ⁇ m/sec or less.
• the above-mentioned film can be obtained, for example, by applying the resin composition to a substrate such as a silicon wafer and drying it as necessary. If drying is performed, the film thickness after drying will be 10 ⁇ m.
• a silicon wafer can be used as the substrate. If it is difficult to form a film with a thickness of 10 ⁇ m using a silicon wafer, other substrates with different properties such as surface wettability may be used.
• the method for applying the resin composition to the substrate is not particularly limited as long as it is a method that results in a film thickness of 10 ⁇ m, and spin coating can be used. If it is difficult to form a film with a thickness of 10 ⁇ m using spin coating, a suitable method may be selected from known methods such as dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, slit coating, and inkjet coating.
• the drying is preferably carried out until the amount of the solvent in the film becomes 0.1% by mass or less.
• the drying conditions are not particularly limited, and drying can be performed by heating. If it is difficult to sufficiently dry the material by heating alone, the pressure may be reduced.
• the drying can be carried out in the atmosphere, but when the resin composition contains a component that is easily modified by oxygen, the drying can be carried out under an inert gas such as nitrogen or under vacuum.
• the drying means is not particularly limited, but examples thereof include a hot plate, etc. However, when the above-mentioned reduction in pressure, replacement with an inert gas, etc. are required, an oven equipped with a reduction in pressure function, an oven equipped with a gas replacement function, etc. may also be used.
• the heating temperature can be, for example, 110° C. However, when drying at 110° C. is difficult, the drying temperature may be appropriately changed between 70° C. and 130° C., preferably between 90° C. and 120° C., depending on the type of solvent contained in the resin composition, etc.
• the drying time time to be heated to the above-mentioned temperature
• the temperature rise rate during heating is not particularly limited and can be, for example, 5° C./min. If drying at the above temperature rise rate is difficult, the temperature rise rate may be appropriately changed between 1 to 12° C./min or 2 to 10° C./min depending on the type of solvent contained in the resin composition, etc.
• the dissolution rate of the film in cyclopentanone can be calculated by immersing a silicon wafer on which a film has been formed in cyclopentanone for 15 seconds and measuring the film thickness before and after immersion using an ellipsometer.
• the membrane is immersed in cyclopentanone without being subjected to any heating other than the drying described above.
• the amount of cyclopentanone used for immersion is preferably 30 times the volume of the membrane.
• the temperatures of cyclopentanone, the film and the silicon wafer during immersion are set to 23°C. In cases where the film is completely dissolved or where the film thickness does not change at all, the immersion time may be appropriately changed to calculate the dissolution rate.
• the dissolution rate of the film can be measured by the method described in the Examples below.
• the dissolution rate of the film can be adjusted by the structure and content of the specific resin, polymerizable compound, etc. contained in the resin composition.
• the first resin composition contains at least one resin selected from the group consisting of polyimides and precursors thereof, and preferably contains polyimide.
• the second resin composition contains at least one resin selected from the group consisting of polyimides and precursors thereof, and preferably contains polyimide.
• the polyimide precursor refers to a resin that changes its chemical structure in response to an external stimulus to become a polyimide. A resin that changes its chemical structure in response to heat to become a polyimide is preferred, and a resin that changes its chemical structure in response to heat to become a polyimide by forming a ring structure is more preferred.
• the dissolution rate of the second specific resin film having a thickness of 10 ⁇ m in cyclopentanone is 0.01 to 0.2 ⁇ m/sec.
• the dissolution rate of the first specific resin film having a thickness of 10 ⁇ m in cyclopentanone is preferably 0.01 to 0.2 ⁇ m/sec.
• the dissolution rate of a film of the third specific resin having a thickness of 10 ⁇ m in cyclopentanone is preferably 0.01 to 0.2 ⁇ m/sec.
• the lower limit of the dissolution rate is preferably 0.02 ⁇ m/sec or more, and more preferably 0.05 ⁇ m/sec or more.
• the upper limit of the dissolution rate is preferably 0.2 ⁇ m/sec or less, and more preferably 0.15 ⁇ m/sec or less.
• the film used to measure the dissolution rate of a specific resin is obtained, for example, by preparing a solution in which the specific resin is dissolved in a solvent, applying the solution to a substrate such as a silicon wafer, and drying as necessary. If drying is performed, the film thickness after drying will be 10 ⁇ m.
• the solvent for dissolving the specific resin used in preparing the solution may be ⁇ -butyrolactone. If it is difficult to carry out the process because the specific resin does not dissolve in ⁇ -butyrolactone, the solvent may be changed to a solvent that dissolves the specific resin, such as N-methyl-2-pyrrolidone or dimethyl sulfoxide.
• the content of the specific resin in the solution can be 30% by mass relative to the total mass of the solvent. However, in cases where it is difficult to form a 10 ⁇ m film at the above content, or the solubility of the specific resin is low and preparation is not possible, the content may be appropriately set between, for example, 10 and 60% by mass.
• the above-mentioned substrate, the method of applying the solution to the substrate, the drying method, the method of measuring the dissolution rate, etc. can be performed in the same manner as for the dissolution rate of the film obtained from the above-mentioned resin composition, and the preferred embodiments are also the same.
• the dissolution rate of the specific resin film can be measured by the method described in the examples below. Specifically, for example, it is measured by the following method.
• a solution of a specific resin in GBL ( ⁇ -butyrolactone) is prepared, and the solution is applied onto a silicon wafer by spin coating or spin coating, followed by heating at 110° C. for 5 minutes or 120° C. for 5 minutes to form a resin layer (film) having a thickness of 10 ⁇ m on the silicon wafer.
• the silicon wafer on which the resin layer was formed was immersed in cyclopentanone for 15 seconds, and after immersion, the wafer was rotated at 2000 rpm for 10 seconds.
• the thickness of the resin composition layer after immersion was measured at 10 points on the coating surface using an ellipsometer (KT-22 manufactured by Foothill Corporation) and calculated as the arithmetic average value.
• the dissolution rate ( ⁇ m/sec) was calculated from the measured thickness and the thickness of the layer before immersion, which was 10 ⁇ m.
• the influence of the variation in dissolution rate depending on the film thickness is quite small for films of 10 ⁇ m or more, when a film of 10 ⁇ m cannot be obtained, even if a film of a thickness exceeding 10 ⁇ m is formed and measured, it can be considered that the same dissolution rate is obtained as when the film thickness is 10 ⁇ m.
• the weighted average value of the dissolution rates of those resins based on the content mass ratio is preferably 0.01 to 0.2 ⁇ m/sec, more preferably 0.05 to 0.20 ⁇ m/sec, and even more preferably 0.05 to 0.15 ⁇ m/sec.
• an embodiment in which the above-mentioned dissolution rate is 0.01 to 0.2 ⁇ m/sec for all of the specific resins contained in the first resin composition or the second resin composition is also one of the preferred embodiments of the present invention.
• the first specific resin and the second specific resin are preferably resins having a ring structure with 5 or more ring members in the side chain.
• the main chain of a resin refers to the relatively longest bond chain in a resin molecule.
• the atoms contained as ring members in the ring structure are atoms contained in the main chain.
• the side chain of the resin refers to a molecular chain bonded to the main chain, and the molecular chain may or may not have a repeating unit. That is, the molecular chain may or may not include a repeating structure.
• the molecular chain is preferably a molecular chain composed of 6 or more atoms, more preferably a molecular chain composed of 10 or more atoms, and even more preferably a molecular chain composed of 15 or more atoms.
• the upper limit of the number of atoms contained in the molecular chain is not particularly limited, but is preferably 1,000 or less, and more preferably 500 or less, for example.
• the side chains in the first specific resin and the second specific resin are preferably bonded to a carbon atom contained in the main chain, and when the side chain is represented by R, the side chain R is preferably bonded to the carbon atom C of the main chain as C-R. In other words, it is preferable that one side chain has only one bond with the main chain.
• ring structure having 5 or more ring members a ring structure having 5 to 20 ring members is preferable, and a ring structure having 5 to 12 ring members is more preferable.
• the ring structure having 5 or more ring members may be either an aromatic ring or an aliphatic ring, is preferably an aromatic ring or an aliphatic hydrocarbon ring, and is more preferably an aromatic ring.
• the aromatic ring may be either an aromatic hydrocarbon ring or a heteroaromatic ring, but is preferably an aromatic hydrocarbon ring or a heteroaromatic ring containing a nitrogen atom as a ring member.
• the aromatic hydrocarbon ring is preferably an aromatic hydrocarbon ring having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and even more preferably a benzene ring.
• the heteroaromatic ring include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, an oxazole ring, a pyridine ring, a pyridazine ring, a pyrazine ring, a triazine ring, an indole ring, an indazole ring, a benzimidazole ring, and a purine ring.
• the aliphatic ring examples include an aliphatic hydrocarbon ring having 5 to 20 carbon atoms, a pyrrolidine ring, a pyrroline ring, a pyrazolidine ring, an imidazolidine ring, a tetrahydrofuran ring, a tetrahydrothiophene ring, a piperidine ring, a piperazine ring, a tetrahydropyran ring, a dioxane ring, and a morpholine ring.
• the ring structure having 5 or more ring members is preferably a benzene ring, a cyclohexane ring, or an adamantane ring, and more preferably a benzene ring.
• a hydrogen atom that is bonded to the ring member by a single bond without a linking group may be substituted.
• substituents include an alkyl group, an aryl group, a halogen atom, and a polymerizable group described later.
• the content of ring structures having 5 or more ring members in the first specific resin and the second specific resin is preferably 0.01 to 5.0 mmol/g, more preferably 0.1 to 4.0 mmol/g, and even more preferably 0.5 to 2.0 mmol/g, per 1 g of the specific resin.
• the first specific resin and the second specific resin preferably contain a structure represented by the following formula (A-1).
• the third specific resin includes a structure represented by the following formula (A-1).
• L A1 represents a single bond or an (m+1)-valent linking group
• each Cy independently represents a ring structure having 5 or more ring members which may have a substituent
• m represents an integer of 1 or more
• * represents a bonding site to another structure.
• L A1 is preferably a linking group having a valence of m+1.
• Preferred embodiments of L A1 are the same as the preferred embodiments of L 1 in formula (R-1) described later.
• preferred embodiments of Cy are the same as the preferred embodiments of the ring structure having 5 or more ring members described above.
• Cy is preferably directly bonded to a polymerizable group described later.
• the direct bond between a certain structure A and another structure B means that the structure A and the structure B are bonded without a linking group therebetween.
• * represents a bonding site to another structure, preferably a bonding site to an atom contained in the main chain of the resin, and more preferably a bonding site to a carbon atom contained in the main chain.
• the carbon atom is preferably a tertiary carbon atom or a quaternary carbon atom. It is preferable that the structure represented by formula (A-1) is not included in the main chain. In addition, it is also one of the preferred embodiments of the present invention that the structure represented by formula (A-1) is a structure represented by formula (R-1) described below.
• the content of the structure represented by formula (A-1) in the specific resin is preferably 0.01 to 5.0 mmol/g, more preferably 0.1 to 4.0 mmol/g, and even more preferably 0.5 to 2.0 mmol/g, per 1 g of the specific resin.
• the first specific resin and the second specific resin preferably have a polymerizable group.
• the polymerizable group may be a cationic polymerizable group, but is preferably a radical polymerizable group.
• examples of the polymerizable group include an epoxy group, an oxetanyl group, an alkoxymethyl group, an acyloxymethyl group, a methylol group, a blocked isocyanate group, and a group containing an ethylenically unsaturated bond, with a group containing an ethylenically unsaturated bond being preferred.
• the group containing an ethylenically unsaturated bond is preferably a radically polymerizable group.
• groups containing an ethylenically unsaturated bond include vinyl groups, vinyl ether groups, allyl groups, isoallyl groups, 2-methylallyl groups, (meth)acrylamide groups, and (meth)acryloyloxy groups. From the viewpoint of low polarity and reducing the dielectric constant of the resulting cured product, vinyl groups and vinyl ether groups are preferred.
• the vinyl group is directly bonded to the above-mentioned ring structure having 5 or more ring members.
• the above-mentioned aromatic ring structure has 5 or more ring members, and that the aromatic ring structure is directly bonded to the vinyl group.
• the polymerizable group value (total molar amount of polymerizable groups per 1 g of specific resin) in the first specific resin and the second specific resin is preferably 0.1 to 10 mmol/g, more preferably 0.2 to 5 mmol/g, and even more preferably 0.5 to 1.5 mmol/g.
• the specific resin preferably has a group in which two or more hydrogen atoms have been removed from a structure represented by the following formula (C-1), and more preferably has a group in which two or more hydrogen atoms have been removed from a structure represented by the following formula (C-2).
• Z 1 to Z 3 each independently represent a single bond or a divalent linking group, and the four benzene rings depicted in formula (C-1) may each have a substituent.
• Z 1 to Z 3 are preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C( ⁇ O)-, -S-, -S( ⁇ O) 2 -, -NHC( ⁇ O)-, or a group consisting of a combination of two or more of these, more preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C( ⁇ O)-, or a group consisting of a combination of two or more of these, and further preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom or -O-.
• Z1 and Z3 are preferably --O--.
• Z2 is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom.
• Z 1 and Z 3 are —O— and Z 2 is —C(CH 3 ) 2 — is also one of the preferred embodiments of the present invention.
• the number of carbon atoms in the aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom is not particularly limited, but is preferably 1 to 6, and more preferably 1 to 4.
• aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom include -CH 2 -, -C(CH 3 ) 2 -, and -C(CF 3 ) 2 -, with -C(CH 3 ) 2 - being preferred.
• substituents on the four benzene rings shown in formula (C-1) include a fluorine atom and a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom.
• An embodiment in which all of the four benzene rings depicted in formula (C-1) are unsubstituted is also one of the preferred embodiments of the present invention.
• the specific resin preferably contains the structure represented by formula (C-1) as X1 or Y1 in formula (1-1) described below , or as R115 or R111 in formula (2). These aspects will be described later.
• the first specific resin and the second specific resin preferably contain a repeating unit represented by formula (1-1).
• X1 is a tetravalent organic group
• Y1 is an organic group containing a group having an ethylenically unsaturated bond.
• -X1- X1 preferably includes a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulae (V-1) to (V-5).
• R 1 and X1 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
• R 1 X2 and R 1 X3 each independently represent a hydrogen atom or a substituent, and R 1 X2 and R 1 X3 may be bonded to form a ring structure.
• R X1 are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and further preferably a methyl group or a trifluoromethyl group.
• the halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom is substituted with a halogen atom. As the halogen atom, F or Cl is preferable, and F is more preferable.
• R 1 X2 and R 1 X3 each independently represent a hydrogen atom.
• R X2 and R X3 are bonded to form a ring structure
• the structure formed by bonding R X2 and R X3 is preferably a single bond, -O- or -C(R) 2 -, more preferably -O- or -C(R) 2 -, and even more preferably -O-.
• R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.
• L 1 is preferably a hydrocarbon group which may have a substituent, more preferably an aromatic hydrocarbon group, and further preferably a phenylene group.
• the hydrocarbon group in L1 may have a substituent. Examples of the substituent include a fluorine atom and a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom.
• X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-1)
• X 1 is preferably a group represented by the following formula (V-1-1).
• * represents a bonding site to the four carbonyl groups to which X 1 in formula (1-1) is bonded
• n1 represents an integer of 0 to 5, and is also preferably an integer of 1 to 5.
• the hydrogen atoms in the following structure may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
• one or more hydrogen atoms may be substituted with a group represented by formula (R-1).
• L1 represents a linking group having a valence of a2+1
• Z1 represents an aromatic group or a cyclic aliphatic group
• A1 represents a polymerizable group
• a1 represents an integer of 0 or more and not exceeding the maximum number of substituents of Z1
• a2 represents an integer of 1 or more
• * represents a bonding site to another structure.
• L1 is preferably a group represented by the following formula (L-1).
• Lx represents a linking group having a valence of a2+1
• a2 represents an integer of 1 or more
• * represents a bonding site with X1 in formula (1-1)
• # represents a bonding site with Z1 in formula (R-1).
• Lx is preferably an alkylene group, more preferably an alkylene group having 1 to 10 carbon atoms, even more preferably an alkylene group having 1 to 4 carbon atoms, and particularly preferably a methylene group.
• the preferred embodiments of a2 in formula (L-1) are the same as the preferred embodiments of a2 in formula (R-1).
• Z1 represents an aromatic group or a cyclic aliphatic group. Preferred embodiments of these groups are the same as the preferred embodiments of the ring structure having 5 or more ring members described above.
• a 1 in formula (R-1) preferably represents a group having an ethylenically unsaturated bond.
• Preferred embodiments of the group having an ethylenically unsaturated bond are the same as the preferred embodiments of the group having an ethylenically unsaturated bond in Y1 described below.
• at least one of A 1 in formula (R-1) is preferably a vinyl group, a (meth)acryloxy group, a vinyl ether group, an allyl group, an epoxy group, or a group containing these, and more preferably a vinyl group or a vinyl ether group.
• a1 is preferably an integer of 0 to 2, and more preferably 0 or 1. Moreover, an embodiment in which a1 is 1 or 2 is also one of the preferred embodiments of the present invention.
• a2 represents an integer of 1 or more, preferably 1 or 2, and more preferably 1.
• the number of ester bonds contained in formula (R-1) is preferably 1 or 0.
• X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-2), X 1 is preferably a group represented by formula (V-2-1) or formula (V-2-2) below, and from the viewpoint of lowering the amine value in the resin, it is preferably a group represented by formula (V-2-2).
• a bond crossing a side of a ring structure means substituting any of the hydrogen atoms in the ring structure.
• L X1 represents a single bond or -O-
• * represents a bonding site with the four carbonyl groups to which X 1 in formula (1-1) is bonded.
• R X1 are as described above.
• the hydrogen atoms in these structures may be further substituted with known substituents such as a hydroxy group and a hydrocarbon group.
• one or more hydrogen atoms may be substituted with a group represented by the above formula (R-1).
• X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-3)
• X 1 is preferably a group represented by formula (V-3-1) or formula (V-3-2) below, and from the viewpoint of lowering the dielectric constant, etc., it is preferably a group represented by formula (V-3-2).
• * represents a bonding site with four carbonyl groups to which X 1 in formula (1-1) is bonded.
• R X2 and R X3 are as described above.
• the hydrogen atoms in these structures may be further substituted with known substituents such as a hydroxy group and a hydrocarbon group.
• one or more hydrogen atoms may be substituted with a group represented by the above formula (R-1).
• X 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-4), X 1 is preferably a group represented by the following formula (V-4-1).
• * represents a bonding site to the four carbonyl groups to which X 1 in formula (1-1) is bonded
• n1 represents an integer of 0 to 5.
• the hydrogen atoms in the following structure may be further substituted with a known substituent such as a hydroxy group or a hydrocarbon group.
• one or more hydrogen atoms may be substituted with a group represented by the above formula (R-1).
• X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-5)
• X1 is preferably a group represented by the following formula (V-5-1), and more preferably a group represented by formula (V-5-2).
• the hydrogen atoms in the following structure may be further substituted with known substituents such as a hydroxy group and a hydrocarbon group.
• one or more hydrogen atoms may be substituted with a group represented by formula (R-1).
• L1 represents a divalent linking group;
• * represents a bonding site with the carbonyl group in formula (1-1); and the two benzene rings depicted in formula (V-5-1) each may have a substituent.
• preferred embodiments of A 4 , A 5 and the substituent on the benzene ring are the same as the preferred embodiments of A 4 , A 5 and the substituent on the benzene ring in formula (V-5) described above.
• R each independently represents a substituent
• n is an integer of 0 to 4
• * represents a bonding site with the carbonyl group in formula (1-1).
• Each R is preferably a fluorine atom or a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted by a fluorine atom, and more preferably a hydrocarbon group having 1 to 10 carbon atoms in which a hydrogen atom may be substituted by a fluorine atom.
• n is an integer of 0 to 2.
• an embodiment in which n is 2 is also one of the preferable embodiments of the present invention.
• X 1 is also preferably a group represented by the following formula (7):
• X 1 is more preferably a group represented by the following formula (7-2):
• Formula (7) is a group in which four hydrogen atoms have been removed from the structure represented by formula (C-1) above
• formula (7-2) is a group in which four hydrogen atoms have been removed from the structure represented by formula (C-2) above.
• a 1 to A 3 each independently represent a single bond or a divalent linking group
• * represents a bonding site with the carbonyl group in formula (1-1)
• each of the four benzene rings described in formula (7) may have a substituent.
• * represents a bonding site with the carbonyl group in formula (1-1).
• preferred embodiments of A 1 to A 3 and the substituents on the benzene ring are the same as the preferred embodiments of Z 1 to Z 3 and the substituents on the benzene ring in formula (C-1) described above.
• X 1 may be a group in which m hydrogen atoms have been removed from a group represented by R 132 in the formula (4) described below.
• X1 does not contain an imide structure in the structure.
• R N is preferably a hydrogen atom, an alkyl group or an aryl group, and more preferably a hydrogen atom.
• Preferred aspects of R N are as described above.
• R N represents a hydrogen atom or a monovalent organic group
• * represents a bonding site with a carbon atom.
• X1 does not contain an ester bond in the structure.
• X 1 does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that X 1 does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.
• Y 1 preferably contains a ring structure having 5 or more ring members. Preferred embodiments of the ring structure having 5 or more ring members are as described above.
• Y1 is a group having an ethylenically unsaturated bond.
• the preferred embodiments of the group having an ethylenically unsaturated bond are as described above.
• the group having an ethylenically unsaturated bond in Y1 is directly bonded to an aromatic group, and it is more preferable that Y1 contains a vinylphenyl group.
• Y 1 in formula (1-1) is preferably a group represented by the following formula (Y-1).
• Y X1 represents an (n+2)-valent organic group
• R Y1 each independently represent a structure represented by formula (R-1) above, in which A 1 in formula (R-1) is a group having an ethylenically unsaturated bond, and n represents an integer of 1 or more.
• Y 1 X1 is preferably a group containing a structure in which 2+n hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-4) above.
• Y 1 X1 is a group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by formula (V-1)
• Y 1 X1 is preferably a group in which n hydrogen atoms have been removed from a group represented by formula (V-1-2) below.
• * represents two bonds possessed by Y 1 in formula (1-1)
• n1 represents an integer of 1 to 5.
• n has the same meaning as n in formula (1-1).
• the hydrogen atoms in the structure below may be further substituted with known substituents such as a hydroxy group and a hydrocarbon group.
• Y 1 X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-2), Y 1 is preferably a group represented by formula (V-2-3) or formula (V-2-4) below, and from the viewpoint of decreasing the dielectric constant, etc., it is preferably a group represented by formula (V-2-4).
• L 1 X1 represents a single bond or -O-, and * represents two bonds possessed by Y 1 in formula (1-1).
• preferred embodiments of R 1 X1 are as described above.
• n are substituted by R 1 Y1 in formula (Y-1). n has the same meaning as n in formula (Y-1).
• the hydrogen atoms in these structures may be further substituted by known substituents such as a hydroxy group and a hydrocarbon group.
• Y 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-3), Y 1 is preferably a group represented by formula (V-3-3) or formula (V-3-4) below, and from the viewpoint of decreasing the dielectric constant, etc., it is preferably a group represented by formula (V-3-3).
• * represents two bonds possessed by Y 1 in formula (1-1).
• preferred embodiments of R X2 and R X3 are as described above.
• n are substituted by R Y1 in formula (Y-1).
• n has the same meaning as n in formula (1-1).
• the hydrogen atoms in these structures may be further substituted by known substituents such as a hydroxy group and a hydrocarbon group.
• Y 1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-4), Y 1 is preferably a group represented by formula (V-4-2) below.
• * represents two bonds possessed by Y 1 in formula (1-1)
• n1 represents an integer of 0 to 5.
• An embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention.
• n are substituted with R Y1 in formula (Y-1).
• n has the same meaning as n in formula (1-1).
• the hydrogen atoms in the structure below may be further substituted with known substituents such as a hydroxy group and a hydrocarbon group.
• R Y1 each independently represents a structure represented by formula (R-1) above, and the same applies to preferred embodiments.
• the description "* represents a bonding site with X1 in formula (1-1)” should be read as “* represents a bonding site with Y Y1 in formula (Y-1).”
• R 111 is also preferably a group represented by the following formula (71): In the above embodiment, R 111 is more preferably a group represented by the following formula (72).
• Formula (71) is a group obtained by removing two hydrogen atoms from the structure represented by formula (C-1) above
• formula (72) is a group obtained by removing two hydrogen atoms from the structure represented by formula (C-2) above.
• n of the hydrogen atoms in the following structure are substituted with R Y1 in formula (Y-1). n has the same meaning as n in formula (Y-1).
• a 1 to A 3 each independently represent a single bond or a divalent linking group, * represents a bonding site with the nitrogen atom in formula (2), and each of the four benzene rings described in formula (71) may have a substituent.
• * represents a bonding site with the nitrogen atom in formula (1-1).
• n is preferably 1 or 2, and more preferably 2.
• Y 1 in formula (1-1) preferably contains a structure represented by the following formula (B-1) or formula (B-2), and more preferably has a structure represented by the following formula (B-1) or formula (B-2).
• each R 1 independently represents an organic group containing a group having an ethylenically unsaturated bond
• n1 represents an integer of 0 to 3
• n2 represents an integer of 0 to 3
• n1+n2 is an integer of 1 to 6
• * represents a bonding site to another structure.
• each R 1 independently represents an organic group containing a group having an ethylenically unsaturated bond
• n1 represents an integer of 0 to 3
• n2 represents an integer of 0 to 3
• n1+n2 is an integer of 1 to 6
• each R 2 independently represents an alkyl group or a fluoroalkyl group
• * represents a bonding site to another structure.
• R1 is preferably a group represented by the above formula (R-1), and Cy is a group that is directly bonded to a group having an ethylenically unsaturated bond that is a polymerizable group.
• R-1 the description "* represents a bonding site with X1 in formula (1-1)” should be read as “* represents a bonding site with the benzene ring in formula (B-1).”
• n1 and n2 each independently are preferably 1 or 2, and more preferably both are 1.
• the preferred embodiments of R 1 are the same as those of R 1 in formula (B-1).
• R 2 is preferably an alkyl group having 1 to 10 carbon atoms or a fluoroalkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms or a fluoroalkyl group having 1 to 4 carbon atoms, more preferably a methyl group, an ethyl group, a trifluoromethyl group, or a pentafluoroethyl group, and particularly preferably a methyl group or a trifluoromethyl group.
• Y1 does not contain an imide structure in its structure. It is also preferred that Y1 does not contain a urethane bond, a urea bond or an amide bond in the structure. Furthermore, it is preferable that Y1 does not contain an ester bond in the structure. Among these, it is preferable that Y1 does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that Y1 does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.
• X 1 in formula (1-1) contains a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the above formulas (V-1) to (V-5), and Y 1 contains a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the above formulas (V-1) to (V-4).
• the specific resin further contains a repeating unit represented by formula (1-2).
• X2 is a tetravalent organic group
• Y2 is a divalent organic group having no ethylenically unsaturated bond
• at least one of X2 and Y2 contains a group in which two or more hydrogen atoms have been removed from the structure represented by formula (C-1) above.
• the preferred embodiments of X2 are the same as the preferred embodiments of X1 in formula (1-1) described above.
• Y2 is more preferably a group represented by the above formula (71), and more preferably a group represented by the above formula (72).
• Preferred embodiments of the formula (C-1), the formula (71) and the formula (72) in Y2 are as described above.
• the third specific resin contains a repeating unit represented by formula (1-3).
• the first specific resin or the second specific resin preferably contains a repeating unit represented by formula (1-3) as the repeating unit represented by formula (1-1).
• X3 is a tetravalent organic group
• Y3 is a divalent organic group containing a vinylphenyl group
• Y3 contains a structure represented by formula (B-1) or (B-2).
• X3 is a tetravalent organic group
• Y3 is a divalent organic group containing a vinylphenyl group
• Y3 contains a structure represented by formula (B-1) or (B-2).
• Y3 is more preferably a structure represented by formula (B-1) or formula (B-2).
• Y3 is preferably a structure containing all of the structure represented by formula (B-1) or (B-2), a vinylphenyl group, and the structure represented by formula (A-1) above.
• Y3 is preferably a structure represented by formula (B-3) or (B-4).
• L A1 each independently represents a single bond or an (m+1) valent linking group
• V 1 represents a vinylphenyl group
• m represents an integer of 1 or more
• n1 represents an integer of 0 to 3
• n2 represents an integer of 0 to 3
• n1+n2 is an integer of 1 to 6
• * represents a bonding site to another structure.
• each L A1 independently represents a single bond or an (m+1) valent linking group
• V 1 represents a vinylphenyl group
• m represents an integer of 1 or more
• n1 represents an integer of 0 to 3
• n2 represents an integer of 0 to 3
• n1+n2 is an integer of 1 to 6
• each R 2 independently represents an alkyl group or a fluoroalkyl group
• * represents a bonding site to another structure.
• L A1 corresponds to L A1 in the above formula (A-1)
• the vinylphenyl group in V 1 corresponds to the structure in which Cy in the above formula (A-1) is a benzene ring substituted with a vinyl group.
• the preferred embodiments of L A1 and m are the same as the preferred embodiments of L A1 and m in formula (A-1) described above.
• preferred embodiments of n1 and n2 are the same as the preferred embodiments of n1 and n2 in formula (B-1) described above.
• the preferred embodiments of L A1 and m are the same as the preferred embodiments of L A1 and m in formula (A-1) described above.
• preferred embodiments of R 2 , n1 and n2 are the same as the preferred embodiments of R 2 , n1 and n2 in formula (B-2) above.
• the first specific resin and the second specific resin contain a repeating unit represented by formula (2-1).
• the third specific resin may further contain a repeating unit represented by formula (2-1).
• A1 and A2 each independently represent an oxygen atom or -NRz-
• X1 represents an organic group having 4 or more carbon atoms
• Y1 represents an organic group having 4 or more carbon atoms
• R113 and R114 each independently represent a hydrogen atom or a monovalent organic group
• Rz represents a hydrogen atom or a monovalent organic group.
• a 1 and A 2 each independently represent an oxygen atom or —NR z —, and preferably an oxygen atom.
• Rz represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.
• R 113 and R 114 in formula (2-1) each independently represent a hydrogen atom or a monovalent organic group.
• the monovalent organic group preferably contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkyleneoxy group.
• at least one of R 113 and R 114 contains two or more polymerizable groups.
• the polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., 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.
• a group having an ethylenically unsaturated bond is preferable.
• Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, a (meth)acryloyloxy group, and a group represented by the following formula (III), and the group represented by the following formula (III) is preferred.
• R 200 represents a hydrogen atom, a methyl group, an ethyl group or a methylol group, and is preferably a hydrogen atom or a methyl group.
• * represents a bonding site with another structure.
• R 201 represents an alkylene group having 2 to 12 carbon atoms, —CH 2 CH(OH)CH 2 —, a cycloalkylene group or a polyalkyleneoxy group.
• R 201 examples include alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-butanediyl group, -CH 2 CH(OH)CH 2 -, and polyalkyleneoxy groups, of which alkylene groups such as ethylene group and propylene group, -CH 2 CH(OH)CH 2 -, cyclohexyl group, and polyalkyleneoxy groups are more preferred, and alkylene groups such as ethylene group and propylene group, or polyalkyleneoxy groups are even more preferred.
• alkylene groups such as ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, and dodecamethylene group, 1,2-butanediyl group, 1,3-but
• the polyalkyleneoxy group refers to a group in which two or more alkyleneoxy groups are directly bonded.
• the alkylene groups in the multiple 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, an arrangement having blocks, or an arrangement having a pattern such as alternating.
• the number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituent, when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, more preferably 2 to 6, even more preferably 2 to 5, still more preferably 2 to 4, still more preferably 2 or 3, and particularly preferably 2.
• the alkylene group may have a substituent, and preferred examples of the substituent include an alkyl group, an aryl group, and a halogen atom.
• the number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2-20, more preferably 2-10, and even more preferably 2-6.
• the polyalkyleneoxy group is preferably a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which multiple ethyleneoxy groups and multiple propyleneoxy groups are bonded, more preferably a polyethyleneoxy group or a polypropyleneoxy group, and even more preferably a polyethyleneoxy group.
• the ethyleneoxy groups and the propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in a pattern such as alternating. The preferred embodiment of the number of repetitions of the ethyleneoxy group in these groups is as described above.
• the second specific resin and the third specific resin may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond.
• a tertiary amine compound having an ethylenically unsaturated bond is 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 carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred.
• the acid-decomposable group examples include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
• the first specific resin and the second specific resin may contain a repeating unit represented by formula (2).
• a repeating unit corresponding to the repeating unit represented by formula (2-1) does not correspond to the repeating unit represented by formula (2).
• A1 and A2 each independently represent an oxygen atom or -NRz-
• R111 represents a divalent organic group not containing a group having an ethylenically unsaturated bond
• R115 represents a tetravalent organic group
• R113 and R114 each independently represent a hydrogen atom or a monovalent organic group
• Rz represents a hydrogen atom or a monovalent organic group.
• the preferred embodiments of R 115 are the same as the preferred embodiments of X 1 in formula (1-1) above.
• preferred aspects of R 111 are the same as the preferred aspects of X 1 in formula (1-1) above, except that it does not contain a group having an ethylenically unsaturated bond. Specifically, it is preferably a structure represented by any one of formulas (V-1) to (V-4) and formula (71) above, in which the bonding site to the group having an ethylenically unsaturated bond is substituted with a hydrogen atom. Preferred aspects of these formulas are as described above.
• preferred embodiments of A 1 , A 2 , R 113 and R 114 are the same as the preferred embodiments of A 1 , A 2 , R 113 and R 114 in formula (2-1) above.
• the content of the repeating unit represented by formula (1-1) relative to the total mass of the second specific resin or the third specific resin is preferably 30 mass% or more, more preferably 40 mass% or more, further preferably 50 mass% or more, and particularly preferably 80 mass% or more.
• the upper limit of the content is not particularly limited, and may be 100 mass%.
• the second specific resin or the third specific resin may contain two or more repeating units represented by formula (1-1) having different structures. In that case, it is preferable that the total amount is within the above range.
• the content of the repeating unit represented by formula (1-3) relative to the total mass of the third specific resin is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more.
• the upper limit of the content is not particularly limited, and may be 100% by mass.
• the third specific resin may contain two or more repeating units represented by formula (1-3) having different structures. In that case, it is preferable that the total amount is within the above range.
• the content of the repeating unit represented by formula (1-2) relative to the total mass of the specific resin is preferably 0 to 90 mass%, more preferably 10 to 80 mass%, even more preferably 20 to 70 mass%, and particularly preferably 30 to 60 mass% or more.
• the specific resin may contain two or more repeating units represented by formula (1-2) having different structures. In that case, it is preferable that the total amount is within the above range.
• the content of the repeating unit represented by formula (1-3) relative to the total mass of the third specific resin is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more.
• the upper limit of the content is not particularly limited, and may be 100% by mass.
• the third specific resin may contain two or more repeating units represented by formula (1-3) having different structures. In that case, it is preferable that the total amount is within the above range.
• the total content of the repeating unit represented by formula (1-1) and the repeating unit represented by formula (1-2) relative to the total mass of the second specific resin or the third specific resin is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, even more preferably 90% by mass or more, and most preferably 99% by mass or more.
• the total content of the repeating unit represented by formula (1-3) and the repeating unit represented by formula (1-2) relative to the total mass of the third specific resin is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, particularly preferably 80% by mass or more, even more preferably 90% by mass or more, and most preferably 99% by mass or more.
• the content of the repeating unit represented by formula (2-1) relative to the total mass of the first specific resin or the second specific resin is preferably 30 mass% or more, more preferably 50 mass% or more, further preferably 70 mass% or more, and particularly preferably 80 mass% or more.
• the upper limit of the content is not particularly limited, and may be 100 mass%.
• the first specific resin or the second specific resin may contain two or more repeating units represented by formula (2-1) having different structures. In that case, it is preferable that the total amount is within the above range.
• the total content of the repeating unit represented by formula (2-1) and the repeating unit represented by formula (2) relative to the total mass of the first specific resin or the second specific resin is preferably 50 mass% or more, more preferably 70 mass% or more, further preferably 80 mass% or more, and particularly preferably 90 mass% or more.
• the upper limit of the content is not particularly limited, and may be 100 mass%.
• the first specific resin or the second specific resin contains a repeating unit represented by formula (2), it may contain two or more repeating units represented by formula (2) having different structures. In that case, it is preferable that the total amount is within the above range.
• the value of the molar amount of oxygen atoms/weight average molecular weight is preferably 9.7 mmol/g or less.
• the lower limit of the value of the molar amount of oxygen atoms/weight average molecular weight is preferably 7.0 mmol/g or more, and more preferably 7.5 mmol/g or more.
• the upper limit of the value of the molar amount of oxygen atoms/weight average molecular weight is preferably 9.2 mmol/g or less, and more preferably 8.8 mmol/g or less.
• the value of the molar amount of oxygen atoms/weight average molecular weight is 9.7 mmol/g or less, the polarity of the resin and the free mobility of the molecules are reduced, and the dissolution rate of the resin itself and the film made of the resin composition in cyclopentanone is reduced, which is thought to suppress swelling of the image area and the occurrence of opening defects.
• the weight average molecular weight (Mw) of the specific polyimide resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, even more preferably 8,000 to 40,000, still more preferably 8,000 or more and less than 30,000, particularly preferably 8,000 to 26,000, and most preferably 10,000 to 25,000.
• Mw weight average molecular weight
• the weight average molecular weight 3,000 or more it is possible to improve the folding resistance of the cured product.
• the weight average molecular weight is particularly preferably 8,000 or more.
• the weight average molecular weight 3,000 or more peeling of the resin from the substrate is suppressed, and the reliability of the cured product (adhesion to the substrate when the cured product is further heated) can be improved.
• the weight average molecular weight is particularly preferably 8,000 or more.
• the weight average molecular weight is particularly preferably less than 30,000.
• the number average molecular weight (Mn) of the specific polyimide resin is preferably from 1,000 to 40,000, more preferably from 2,000 to 30,000, and even more preferably from 5,000 to 20,000.
• the molecular weight dispersity of the specific polyimide resin is preferably 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 polyimide is not particularly specified, but is, for example, 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 dispersity of at least one polyimide are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimides as one resin are each within the above ranges.
• the weight average molecular weight (Mw) is preferably 5,000 to 100,000, more preferably 6,000 to 50,000, even more preferably 7,000 to 40,000, still more preferably 8,000 or more and less than 30,000, particularly preferably 8,000 to 26,000, and most preferably 10,000 to 25,000.
• the number average molecular weight (Mn) is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and even more preferably from 4,000 to 20,000.
• the polyimide precursor has a molecular weight dispersity of preferably 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 polyimide precursor is not particularly limited, but is, for example, preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less.
• the dispersity of molecular weight is a value calculated by weight average molecular weight/number average molecular weight.
• the weight average molecular weight, number average molecular weight, and dispersity of at least one polyimide precursor are within the above ranges. It is also preferable that the weight average molecular weight, number average molecular weight, and dispersity calculated by treating the multiple polyimide precursors as one resin are each within the above ranges.
• the imidization rate (also referred to as "ring closure rate") of the specific polyimide resin is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoints of the film strength, insulating properties, etc. of the resulting organic film.
• the upper limit of the imidization rate is not particularly limited, and may be 100% or less.
• the content of the imide structure in the specific polyimide resin is preferably 3 mmol/g or less, more preferably 2.5 mmol/g or less.
• the lower limit of the content is not particularly limited, but can be, for example, 0.5 mmol/g or more.
• the imidization rate (also referred to as "ring closure rate") of the polyimide precursor is preferably less than 70%, more preferably 50% or less, even more preferably 20% or less, and particularly preferably 10% or less, from the viewpoint of the film strength, insulating properties, etc. of the obtained organic film.
• the lower limit of the imidization rate is not particularly limited, and may be 0% or more.
• the imidization rate is measured, for example, by the following method.
• the infrared absorption spectrum of the specific resin is measured to determine the peak intensity P1 near 1377 cm ⁇ 1 , which is an absorption peak derived from the imide structure.
• the specific resin is heat-treated at 350° C.
• the ethylenically unsaturated bond valence of the specific resin (the molar amount of ethylenically unsaturated bonds per 1 g of the specific resin) is preferably 0.5 mmol/g or more and 2.0 mmol/g or less.
• the lower limit of the ethylenically unsaturated bond valence is not particularly limited, but is preferably 0.6 mmol/g or more, and more preferably 0.7 mmol/g or more.
• the upper limit of the ethylenically unsaturated bond valence is not particularly limited, but is preferably 1.9 mmol/g or less, and more preferably 1.8 mmol/g or less.
• the specific resin can be obtained by, for example, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature, a method of reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid and esterifying it using a condensing agent or an alkylating agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine in the presence of a condensing agent, a method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and reacting it with a diamine, etc.
• the method of obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then acid-halogenating the remaining dicarboxylic acid using a halogenating agent, and reacting it with a diamine is more preferable.
• the condensing agent include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride.
• alkylating agent examples include N,N-dimethylformamide dimethyl acetal, N,N-dimethylformamide diethyl acetal, N,N-dialkylformamide dialkyl acetal, trimethyl orthoformate, and triethyl orthoformate.
• halogenating agent examples include thionyl chloride, oxalyl chloride, phosphorus oxychloride, and the like.
• the resin obtained by the above method can be completely imidized by a known imidization reaction method, or the imidization reaction is stopped midway to partially introduce an imide structure, or further, a completely imidized polymer is blended with a polyimide precursor to partially introduce an imide structure.
• a completely imidized polymer is blended with a polyimide precursor to partially introduce an imide structure.
• Other known methods for synthesizing polyimides can also be applied.
• an organic solvent in the reaction it is preferable to use an organic solvent in the reaction.
• the organic solvent may be one type or two or more types.
• the organic solvent can be appropriately selected depending on the raw material, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and ⁇ -butyrolactone.
• a basic compound may be one type or two or more types.
• the basic compound can be appropriately selected depending on the raw material, and examples thereof include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, and N,N-dimethyl-4-aminopyridine.
• -End-capping agent- In the method for producing the specific resin, in order to further improve storage stability, it is preferable to cap the carboxylic acid anhydride, acid anhydride derivative, or amino group remaining at the resin terminal of the specific resin.
• examples of the terminal capping agent include monoalcohols, phenols, thiols, thiophenols, monoamines, etc., and it is more preferable to use monoalcohols, phenols, or monoamines from the viewpoint of reactivity and film stability.
• Examples of 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; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol.
• primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol
• secondary alcohols such as isopropanol, 2-butanol, cyclo
• Preferred 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, Examples of such an acid include 2-carboxy-7-aminonaphthalene, 2-car
• a plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.
• the amino group at the resin terminal is blocked, it is possible to block it with a compound having a functional group capable of reacting with the amino group.
• Preferred blocking agents for the amino group include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, sulfonic acid carboxylic acid anhydrides, and the like, and more preferred are carboxylic acid anhydrides and carboxylic acid chlorides.
• Preferred compounds of carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, and the like.
• carboxylic acid chloride examples include acetyl chloride, acrylic acid chloride, propionyl chloride, methacrylic acid chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantanecarbonyl chloride, heptafluorobutyryl chloride, stearic acid chloride, and benzoyl chloride.
• the method for producing the specific resin may include a step of precipitating a solid. Specifically, after filtering off the water-absorbing by-product of the dehydration condensation agent coexisting in the reaction liquid as necessary, the obtained polymer component is put into a poor solvent such as water, aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid, and then dried to obtain the specific resin. In order to improve the degree of purification, the specific resin may be repeatedly subjected to operations such as redissolving, reprecipitating, and drying. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.
• Specific examples of the specific resin include polyimides (P-1) to (P-3), (P-5) to (P-17), and polyimide precursor (P-4) in the examples described below, but the present invention is not limited thereto.
• the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition.
• the content of the resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition.
• the resin composition of the present invention may contain only one type of specific resin, or may contain two or more types. When two or more types are contained, it is preferable that the total amount is in the above range.
• the resin composition of the present invention contains at least two types of resins.
• the resin composition of the present invention may contain a total of two or more types of the specific resin and the other resins described below, or may contain two or more types of specific resins, but it is preferable that the resin composition contains two or more types of specific resins.
• the resin composition of the present invention contains two or more specific resins, it is preferable that the resin composition contains, for example, two or more polyimide precursors having different dianhydride-derived structures.
• the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, simply referred to as "another resin").
• the other resin include a polyimide precursor different from the specific resin, a polyimide different from the specific resin, a polybenzoxazole precursor, a polybenzoxazole, a polyamideimide precursor, a polyamideimide, an aromatic polyether, a phenolic resin, a polyamide, an epoxy resin, a polysiloxane, a resin containing a siloxane structure, a (meth)acrylic resin, a (meth)acrylamide resin, a urethane resin, a butyral resin, a styryl resin, a polyether resin, and a polyester resin.
• polyimide precursors include the compounds described in paragraphs 0017 to 0138 of WO 2022/145355. The above descriptions are incorporated herein by reference.
• the aromatic polyether is not particularly limited, but is preferably polyphenylene ether.
• the polyphenylene ether preferably contains a repeating unit represented by the following formula (PE).
• R E1 represents a hydrogen atom or a substituent.
• the substituent include a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an amino group which may have a substituent, a nitro group, and a carboxy group.
• the polyphenylene ether is also preferably a compound having a polymerizable group.
• the polymerizable group is preferably an epoxy group, an oxetanyl group, an oxazolyl group, a methylol group, an alkoxymethyl group, an acyloxymethyl group, a blocked isocyanate group, or a group having an ethylenically unsaturated bond, and more preferably a group having an ethylenically unsaturated bond.
• Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group.
• a vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is preferred, a vinylphenyl group or a (meth)acryloyloxy group is more preferred, and a (meth)acryloyloxy group is even more preferred.
• the polyphenylene ether is a compound having a polymerizable group
• the position of the polymerizable group is not particularly limited, but for example, a structure in which the polymerizable group is introduced at the end of the main chain is preferred.
• the polyphenylene ether may contain other repeating units.
• the content of the other repeating units is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, based on the total mass of the polyphenylene ether.
• the number average molecular weight of the polyphenylene ether is not particularly limited, but is preferably 500 to 50,000.
• the lower limit of the number average molecular weight is preferably 800 or more, more preferably 1,000 or more, and even more preferably 1,500 or more.
• the upper limit of the number average molecular weight is preferably 30,000 or less, more preferably 20,000 or less, and even more preferably 10,000 or less.
• polyphenylene ether examples include, but are not limited to, poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether), copolymers of 2,6-dimethylphenol with other phenols (e.g., 2,3,6-trimethylphenol, 2-methyl-6-butylphenol, etc.), polyphenylene ether copolymers obtained by coupling 2,6-dimethylphenol with biphenols or bisphenols, and polyphenylene ethers having a linear or branched structure obtained by heating poly(2,6-dimethyl-1,4-phenylene ether) or the like with a phenolic compound such as a bisphenol or trisphenol in a toluene solvent in the presence of an organic peroxide to cause a redistribution reaction
• the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, even more preferably 1 mass% or more, still more preferably 2 mass% or more, even more preferably 5 mass% or more, and even more preferably 10 mass% or more, based on the total solid content of the resin composition.
• the content of other resins in the resin composition of the present invention is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, still more preferably 60 mass% or less, and even more preferably 50 mass% or less, based on the total solid content of the resin composition.
• the content of the other resin may be low.
• the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition.
• the lower limit of the content is not particularly limited, and may be 0% by mass or more.
• the resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.
• the resin composition of the present invention contains a polymerizable compound. Moreover, the resin composition of the present invention preferably contains a photoradical polymerization initiator described below as the polymerization initiator, and contains a radically polymerizable compound as the polymerizable compound.
• the polymerizable compound may be a radically polymerizable compound (radical crosslinking agent) or another crosslinking agent.
• the resin composition of the present invention preferably contains a radical crosslinking agent.
• the radical crosslinking agent is a compound having a radical polymerizable group.
• the radical polymerizable group is preferably a group containing an ethylenically unsaturated bond.
• Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
• a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.
• the radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds.
• the radical crosslinking agent may have three or more ethylenically unsaturated bonds.
• a compound having 2 to 15 ethylenically unsaturated bonds is preferable, a compound having 2 to 10 ethylenically unsaturated bonds is more preferable, and a compound having 2 to 6 ethylenically unsaturated bonds is even more preferable.
• the radical crosslinking agent preferably contains two or more (meth)acryloyl groups, more preferably contains 2 to 15 (meth)acryloyl groups, even more preferably contains 2 to 10 (meth)acryloyl groups, and particularly preferably contains 2 to 6 (meth)acryloyl groups.
• the radical crosslinking agent may have a polymerizable group other than the (meth)acryloyl group, but it is also preferable that the radical crosslinking agent does not have a polymerizable group.
• the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the above-mentioned compound having three or more ethylenically unsaturated bonds.
• the molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
• the lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
• radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyvalent amine compounds.
• unsaturated carboxylic acids e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
• esters and amides preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds
• amides of unsaturated carboxylic acids and polyvalent amine compounds amides of unsaturated carboxylic acids and polyvalent amine compounds.
• addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, and sul
• 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 substitution reaction products of unsaturated carboxylic acid esters or amides having eliminable substituents such as halogeno groups and tosyloxy groups with monofunctional or polyfunctional alcohols, amines, and thiols are also suitable.
• the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure.
• Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021/112189, the contents of which are incorporated herein by reference.
• radical crosslinking agents other than those mentioned above include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021/112189, the contents of which are incorporated herein by reference.
• the radical crosslinking agents include ethoxylated glycerin triacrylate (commercially available products are A-GLY-3E, A-GLY-9E, and A-GLY-20E, manufactured by Shin-Nakamura Chemical Co., Ltd.), trimethylolpropane trimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available product is KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (commercially available product is KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.).
• dipentaerythritol penta(meth)acrylate commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in which these (meth)acryloyl groups are bonded via ethylene glycol residues or propylene glycol residues. Oligomer types of these can also be used.
• radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethyleneoxy chains, SR-209, 231, and 239, which are difunctional methacrylates with four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, TPA-330, a trifunctional acrylate with three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), UAS-10 and UAB-140, which are urethane oligomers (both manufactured by Nippon Paper Industries Co., Ltd.), and N Examples include K Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, NK Ester A-BPE-4, NK Ester A-BPE-10, NK Ester A-BPE-20, NK Ester A-BPE-30, and UA-7200 (all manufactured by Shin-Nakamura Chemical Co.
• radical crosslinking agents urethane acrylates such as those described in JP-B-48-041708, JP-A-51-037193, JP-B-02-032293, and JP-B-02-016765, and 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.
• radical crosslinking agents compounds having an amino structure or sulfide structure in the molecule, as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238, can also be used.
• the radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group.
• the radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride.
• a radical crosslinking agent in which an acid group is provided by reacting an unreacted hydroxy group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic anhydride, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol.
• 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 crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, more preferably 1 to 100 mgKOH/g. If the acid value of the radical crosslinking agent is within the above range, the agent has excellent handling properties during manufacturing and developability. In addition, the agent has good polymerizability. The acid value is measured in accordance with the description of JIS K 0070:1992.
• a difunctional methacrylate or acrylate for the resin composition.
• the compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,7-heptanediol
• PEG200 diacrylate refers to polyethylene glycol diacrylate having a formula weight of about 200 for the polyethylene glycol chain.
• a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent.
• the monofunctional radical crosslinking agent a compound having a boiling point of 100° C. or more under normal pressure is also preferred in order to suppress volatilization before exposure.
• the difunctional or higher radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.
• the content of the radical crosslinking agent is preferably more than 0% by mass and not more than 60% by mass based on the total solid content of the resin composition.
• the lower limit is more preferably 5% by mass or more.
• the upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
• the resin composition of the present invention preferably contains a radical crosslinking agent, and the content of the radical polymerizable compound is preferably 8 parts by mass or more and 30 parts by mass or less per 100 parts by mass of the specific resin.
• the radical crosslinking agent may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total amount is within the above range.
• the resin composition of the present invention also preferably contains another crosslinking agent different from the above-mentioned radical crosslinking agent.
• the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by the above-mentioned photoacid generator or photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote, by the action of an acid or a base, a reaction to form a covalent bond with another compound in the composition or a reaction product thereof.
• the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
• Other cross-linking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022/145355, the disclosures of which are incorporated herein by reference.
• the resin composition of the present invention contains a polymerization initiator.
• the polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable that the resin composition contains a photopolymerization initiator.
• the photopolymerization initiator is preferably a photoradical polymerization initiator.
• the photoradical polymerization initiator is not particularly limited and can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays in the ultraviolet to visible regions is preferable. Alternatively, it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.
• the photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 in a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm).
• the molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.
• 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 oxides, hexaarylbiimidazoles
• oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, ⁇ -aminoketone compounds such as aminoacetophenones, ⁇ -hydroxyketone compounds such as hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organic boron compounds, iron arene complexes, etc.
• ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference.
• Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd.
• Nippon Kayaku Co., Ltd. is also preferably used.
• hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. 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, the contents of which are incorporated herein by reference.
• ⁇ -Hydroxyketone initiators that can be used include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF).
• Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.
• aminoacetophenone initiator acylphosphine oxide initiator, and metallocene compound
• aminoacetophenone initiator acylphosphine oxide initiator, and metallocene compound
• the compounds described in paragraphs 0161 to 0163 of WO 2021/112189 can also be suitably used.
• the contents of this specification are incorporated herein.
• the photoradical polymerization initiator it is preferable to include an oxime compound as the photoradical polymerization initiator.
• an oxime compound By using an oxime compound, it is possible to more effectively improve the exposure latitude.
• the oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.
• the resin composition preferably contains a compound having a ketoxime group as a photoradical polymerization initiator.
• oxime compounds include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, the compounds described in JP-A-2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.
• Preferred oxime compounds include, for example, compounds having the following structure, 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one.
• an oxime compound as a photoradical polymerization initiator.
• oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemistry Co., Ltd.), and SpeedCure PDO (SARTOMER Also usable are oxime compounds having the following structure:
• an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of WO 2021/112189 an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, or an oxime compound having a fluorine atom can be used.
• oxime compounds having a nitro group, oxime compounds having a benzofuran skeleton, and oxime compounds having a hydroxyl group-containing substituent bonded to a carbazole skeleton described in paragraphs 0208 to 0210 of WO 2021/020359 can also be used. The contents of these compounds are incorporated herein by reference.
• an oxime compound having an aromatic ring group Ar OX1 in which an electron-withdrawing group is introduced into an aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used.
• the electron-withdrawing group of the aromatic ring group Ar OX1 includes 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.
• the benzoyl group may have a substituent.
• the substituent is preferably a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, 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, and further preferably an alkoxy group, an alkyl
• 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), and more preferably the compound represented by the formula (OX2).
• R X1 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl 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 represents an alkyl group, an alkenyl group, an alkoxy group, an aryl
• R X12 is an electron-withdrawing group
• R X10 , R X11 , R X13 and R X14 are each a hydrogen atom.
• oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, the contents of which are incorporated herein by reference.
• oxime compounds include oxime compounds having specific substituents as disclosed in JP 2007-269779 A and oxime compounds having thioaryl groups as disclosed in JP 2009-191061 A, the contents of which are incorporated herein by reference.
• At least one compound selected from the group consisting of a trihalomethyltriazine compound, an ⁇ -aminoketone compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, or a benzophenone compound is more preferred, and a metallocene compound or an oxime compound is even more preferred.
• a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photoradical polymerization initiator.
• two or more radicals are generated from one molecule of the photoradical polymerization initiator, resulting in good sensitivity.
• crystallinity decreases and solubility in solvents improves, making it less likely to precipitate over time, and improving the stability of the resin composition over time.
• bifunctional or trifunctional or higher functional photoradical polymerization initiators include dimers of oxime compounds described in JP-T-2010-527339, JP-T-2011-524436, WO-2015/004565, WO-2016-532675, paragraphs 0407 to 0412, and WO-2017/033680, paragraphs 0039 to 0055; compound (E) and compound (G) described in WO-T-2013-522445; Examples of such initiators include Cmpd1 to 7 described in Japanese Patent Publication No.
• the content is preferably 0.1 to 30 mass% based on the total solid content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%. Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of 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 caused by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.
• the resin composition may contain a sensitizer.
• the sensitizer absorbs specific active radiation and becomes electronically excited.
• the sensitizer in the electronically excited state comes into contact with a thermal radical polymerization initiator, a photoradical polymerization initiator, or the like, and effects such as electron transfer, energy transfer, and heat generation occur.
• the thermal radical polymerization initiator and the photoradical polymerization initiator undergo a chemical change and are decomposed to generate a radical, an acid, or a base.
• Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based compounds, and the like.
• sensitizer examples include Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamylidene indanone, and p-dimethylaminobenzylidene indanone.
• the content of the sensitizer is preferably 0.01 to 20 mass % relative to the total solid content of the resin composition, more preferably 0.1 to 15 mass %, and even more preferably 0.5 to 10 mass %.
• the sensitizer may be used alone or in combination of two or more types.
• the resin composition of the present invention may contain a chain transfer agent.
• the chain transfer agent is defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684.
• Examples of the chain transfer agent include compounds having -S-S-, -SO 2 -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthates having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization.
• RAFT Reversible Addition Fragmentation Chain Transfer
• chain transfer agent may be the compound described in paragraphs 0152 to 0153 of International Publication No. 2015/199219, the contents of which are incorporated herein by reference.
• the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total solid content of the resin composition.
• the chain transfer agent may be one type or two or more types. When there are two or more types of chain transfer agents, the total is preferably within the above range.
• the polymerization initiator is preferably a photoacid generator, and the photoacid generator is preferably a photoacid generator that generates radicals.
• the photoacid generator is a compound that absorbs light, decomposes to generate radicals, and abstracts hydrogen from a solvent or the acid generator itself to generate an acid.
• Examples of the photoacid generator include quinone diazide compounds, oxime sulfonate compounds, organic halogenated compounds, organic borate compounds, disulfone compounds, and onium salts, with onium salts being preferred.
• Examples of the onium salt include diazonium salts, phosphonium salts, sulfonium salts, and iodonium salts.
• An onium salt is a salt of a cation and an anion having an onium structure, and the cation and anion may or may not be bonded via a covalent bond. That is, the onium salt may be an intramolecular salt having a cationic moiety and an anionic moiety in the same molecular structure, or an intermolecular salt in which a cationic molecule and an anionic molecule, which are separate molecules, are ionic-bonded, but an intermolecular salt is preferable.
• the cationic moiety or cationic molecule and the anionic moiety or anionic molecule may be bonded by an ionic bond or may be dissociated.
• the sulfonium salt means a salt of a sulfonium cation and an anion.
• sulfonium cation As the sulfonium cation, a tertiary sulfonium cation is preferred, and a triarylsulfonium cation is more preferred. Moreover, the sulfonium cation is preferably a cation represented by the following formula (103).
• R 8 to R 10 each independently represent a hydrocarbon group.
• Each of R 8 to R 10 independently represents preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, even more preferably an aryl group having 6 to 12 carbon atoms, and still more preferably a phenyl group.
• R 8 to R 10 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc.
• the substituent is an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and even more preferably a branched alkyl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
• R 8 to R 10 may be the same group or different groups, but from the viewpoint of synthesis suitability, it is preferable that they are the same group.
• the anion is not particularly limited and may be selected taking into consideration the acid to be generated.
• examples of the anion include boron-based anions such as B(C 6 F 5 ) 4 ⁇ and BF 4 ⁇ , phosphorus-based anions such as (Rf) n PF 6-n ⁇ , PF 3 (C 2 F 5 ) 3 ⁇ and PF 6 ⁇ , antimony-based anions such as SbF 6 ⁇ , and other carboxylate anions and sulfonate anions.
• the iodonium salt refers to a salt of an iodonium cation and an anion.
• anion include the same anions as those in the sulfonium salt described above, and preferred embodiments are also the same.
• the iodonium cation is preferably a diaryliodonium cation. Moreover, the iodonium cation is preferably a cation represented by the following formula (104).
• R 11 and R 12 each independently represent a hydrocarbon group.
• R 11 and R 12 are each independently preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, even more preferably an aryl group having 6 to 12 carbon atoms, and even more preferably a phenyl group.
• R 11 and R 12 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc.
• the substituent has an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and further preferably a branched alkyl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
• R 11 and R 12 may be the same group or different groups, but from the viewpoint of synthesis suitability, it is preferable that they are the same group.
• the phosphonium salt refers to a salt of a phosphonium cation and an anion.
• anion include the same anions as those in the sulfonium salt described above, and preferred embodiments are also the same.
• the phosphonium cation is preferably a quaternary phosphonium cation, such as a tetraalkylphosphonium cation or a triarylmonoalkylphosphonium cation. Moreover, the phosphonium cation is preferably a cation represented by the following formula (105).
• R 13 to R 16 each independently represent a hydrogen atom or a hydrocarbon group.
• Each of R 13 to R 16 independently represents preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 12 carbon atoms, even more preferably an aryl group having 6 to 12 carbon atoms, and still more preferably a phenyl group.
• R 13 to R 16 may have a substituent, and examples of the substituent include a hydroxy group, an aryl group, an alkoxy group, an aryloxy group, an arylcarbonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, etc.
• the substituent is an alkyl group or an alkoxy group, more preferably a branched alkyl group or an alkoxy group, and even more preferably a branched alkyl group having 3 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
• R 13 to R 16 may be the same group or different groups, but from the viewpoint of synthesis suitability, it is preferable that they are the same group.
• the content of the photoacid generator is preferably 0.1 to 20 mass%, more preferably 0.5 to 18 mass%, even more preferably 0.5 to 10 mass%, still more preferably 0.5 to 3 mass%, and even more preferably 0.5 to 1.2 mass%, based on the total solid content of the resin composition.
• the photoacid generator may be used alone or in combination of two or more kinds. In the case of using a combination of two or more kinds, the total amount thereof is preferably within the above range. It is also preferable to use a sensitizer in combination in order to impart photosensitivity to a desired light source.
• thermal polymerization initiator examples include a thermal radical polymerization initiator.
• a thermal radical polymerization initiator is a compound that generates radicals by thermal energy and initiates or promotes a 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 promoted, so that the solvent resistance can be further improved.
• thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A, the contents of which are incorporated herein by reference.
• thermal polymerization initiator When a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%. Only one type of thermal polymerization initiator may be included, or two or more types may be included. When two or more types of thermal polymerization initiators are included, it is preferable that the total amount is within the above range.
• the resin composition of the present invention may contain a base generator.
• the base generator is a compound that can generate a base by physical or chemical action.
• Preferred base generators include thermal base generators and photobase generators.
• the resin composition when the resin composition contains a precursor of a cyclized resin, the resin composition preferably contains a base generator.
• the thermal base generator in the resin composition, for example, the cyclization reaction of the precursor can be promoted by heating, and the mechanical properties and chemical resistance of the cured product can be improved, and the performance as an interlayer insulating film for a rewiring layer contained in a semiconductor package can be improved.
• the base generator may be an ionic base generator or a nonionic base generator.
• Examples of the base generated from the base generator include secondary amines and tertiary amines.
• the base generator is not particularly limited, and a known base generator can be used.
• Examples of known base generators include carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, ⁇ -lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds.
• Specific examples of the non-ionic base generator include the compounds described in paragraphs 0249 to 0275 of WO 2022/145355. The above descriptions are incorporated herein by
• Base generators include, but are not limited to, the following compounds:
• the molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
• the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
• Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018/038002.
• ammonium salts include, but are not limited to, the following compounds:
• iminium salts include, but are not limited to, the following compounds:
• the base generator is preferably an amine in which the amino group is protected by a t-butoxycarbonyl group, from the viewpoints of storage stability and generating a base by deprotection during curing.
• Amine compounds protected by a t-butoxycarbonyl group include, for example, ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, Diol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-
• the content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition.
• the lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
• the upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.
• the base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.
• the resin composition of the present invention preferably contains a solvent.
• the solvent may be any known solvent.
• the solvent is preferably an organic solvent.
• Examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
• Esters for example, 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, ⁇ -valerolactone, alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), 3-alkyloxypropionic acid alkyl esters (for example,
• alkyloxypropionic acid alkyl esters include alkyl esters (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc.
• Suitable examples of 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 monobutyl ether acetate, di
• ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.
• cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.
• dimethyl sulfoxide is preferred.
• amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutyramide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.
• ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.
• alcohols examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.
• An embodiment in which toluene is further added to these combined solvents in an amount of about 1 to 10% by mass based on the total mass of the solvent is also one of the preferred embodiments of the present invention.
• an embodiment containing ⁇ -valerolactone as a solvent is one of the preferred embodiments of the present invention.
• the content of ⁇ -valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more.
• the upper limit of the content is not particularly limited and may be 100% by mass.
• the content may be determined taking into consideration the solubility of components such as a specific resin contained in the resin composition, and the like.
• the solvent preferably contains 60 to 90 mass% of ⁇ -valerolactone and 10 to 40 mass% of dimethyl sulfoxide, more preferably 70 to 90 mass% of ⁇ -valerolactone and 10 to 30 mass% of dimethyl sulfoxide, and even more preferably 75 to 85 mass% of ⁇ -valerolactone and 15 to 25 mass% of dimethyl sulfoxide, relative to the total mass of the solvent.
• the content of the solvent is preferably an amount that results in a total solids concentration of the resin composition of the present invention of 5 to 80 mass%, more preferably an amount that results in a total solids concentration of 5 to 75 mass%, even more preferably an amount that results in a total solids concentration of 10 to 70 mass%, and even more preferably an amount that results in a total solids concentration of 20 to 70 mass%.
• the content of the solvent may be adjusted according to the desired thickness of the coating film and the coating method. When two or more types of solvents are contained, the total amount is preferably within the above range.
• the resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc.
• the metal adhesion improver include a silane coupling agent having an alkoxysilyl group, an aluminum-based adhesion aid, a titanium-based adhesion aid, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a ⁇ -ketoester compound, an amino compound, and the like.
• silane coupling agent examples include the compounds described in paragraph 0316 of International Publication No. 2021/112189 and the compounds described in paragraphs 0067 to 0078 of JP-A-2018-173573, the contents of which are incorporated herein.
• Me represents a methyl group
• Et represents an ethyl group.
• the following R includes a structure derived from a blocking agent in a blocked isocyanate group.
• the blocking agent may be selected according to the desorption temperature, and examples thereof include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds.
• examples thereof include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds.
• caprolactam and the like are preferred.
• Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).
• silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl
• an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent.
• examples of such oligomer-type compounds include compounds containing a repeating unit represented by the following formula (S-1).
• R 1 S1 represents a monovalent organic group
• R 1 S2 represents a hydrogen atom, a hydroxyl group or an alkoxy group
• n represents an integer of 0 to 2.
• R S1 is preferably a structure containing a polymerizable group.
• Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group.
• Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (e.g., a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group.
• R S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
• n represents an integer of 0 to 2, and is preferably 1.
• n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and further preferably that n is 1 in at least two.
• oligomer type compounds commercially available products can be used, and an example of a commercially available product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).
• Aluminum-based adhesion promoter examples include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.
• metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A, the contents of which are incorporated herein by reference.
• 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 even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By making the content equal to or greater than the above lower limit, the adhesion between the pattern and the metal layer will be good, and by making the content equal to or less than the above upper limit, the heat resistance and mechanical properties of the pattern will be good. Only one type of metal adhesion improver may be used, or two or more types may be used. When two or more types are used, it is preferable that the total is within the above range.
• the resin composition of the present invention preferably further contains a migration inhibitor.
• a migration inhibitor for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively suppressed.
• the migration inhibitor examples include compounds having a heterocycle (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), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds.
• a heterocycle pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring
• triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole
• tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferably used.
• Ion trapping agents that capture anions such as halogen ions can also be used as migration inhibitors.
• Other migration inhibitors that can be used include the rust inhibitors described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, the compounds described in paragraph 0052 of JP 2011-059656 A, the compounds described in paragraphs 0114, 0116, and 0118 of JP 2012-194520 A, and the compounds described in paragraph 0166 of WO 2015/199219 A, the contents of which are incorporated herein by reference.
• migration inhibitors include the following compounds:
• the content of the migration inhibitor is preferably 0.01 to 5.0 mass %, more preferably 0.05 to 2.0 mass %, and even more preferably 0.1 to 1.0 mass %, based on the total solid content of the resin composition.
• the migration inhibitor may be one type or two or more types. When two or more types of migration inhibitors are used, it is preferable that the total is within the above range.
• the resin composition of the present invention also preferably contains a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure.
• Whether or not a certain compound a contained in a resin composition corresponds to a light absorbent can be determined by the following method. First, a solution of compound a is prepared at the same concentration as that contained in the resin composition, and the molar absorption coefficient of compound a at the wavelength of the exposure light (mol -1 ⁇ L ⁇ cm -1 , also called "molar absorption coefficient 1") is measured. The measurement is carried out quickly so as to reduce the influence of changes such as a decrease in the molar absorption coefficient of compound a.
• the solvent for the solution when the resin composition contains a solvent, that solvent is used, and when the resin composition does not contain a solvent, N-methyl-2-pyrrolidone is used.
• the solution of compound a is irradiated with exposure light, with the cumulative exposure dose being 500 mJ per mole of compound a.
• the molar absorption coefficient (mol ⁇ 1 ⁇ L ⁇ cm ⁇ 1 , also referred to as “molar absorption coefficient 2”) of compound a at the wavelength of the exposure light is measured using the solution of compound a after exposure. From the above molar absorption coefficient 1 and molar absorption coefficient 2, the attenuation rate (%) is calculated based on the following formula.
• compound a is determined to be a compound whose absorbance at the exposure wavelength decreases upon exposure (i.e., a light absorber).
• Extinction rate (%) 1 - molar extinction coefficient 2 / molar extinction coefficient 1 x 100
• the attenuation rate is preferably 10% or more, and more preferably 20% or more. There is no particular lower limit to the attenuation rate, so long as it is 0% or more.
• the wavelength of the exposure light may be any wavelength at which the photosensitive film is exposed.
• the wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition has sensitivity.
• the photopolymerization initiator has sensitivity to a certain wavelength, meaning that the photopolymerization initiator generates a polymerization initiating species when exposed to light of a certain wavelength.
• the wavelength of the exposure light in terms of its light source, may include (1) semiconductor laser (wavelengths 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, and i-lines), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron
• the wavelength of the exposure light may be selected from those to which the photopolymerization initiator has sensitivity, and preferably, h-line (wavelength 405 nm) or i-line (wavelength 365 nm), more preferably i-line (wavelength 365 nm).
• the light absorbent may be a compound that generates radical polymerization initiating species upon exposure to light, but from the viewpoints of resolution and chemical resistance, it is preferable that the light absorbent is a compound that does not generate radical polymerization initiating species upon exposure to light. Whether or not a light absorbent is a compound that generates a radical polymerization initiating species upon exposure to light can be judged by the following method.
• a solution containing a light absorber and a radical crosslinker at the same concentration as those contained in the resin composition is prepared.
• the radical crosslinker in the solution is the same compound as the radical crosslinker contained in the resin composition and at the same concentration.
• the resin composition does not contain a radical crosslinker
• methyl methacrylate is used at a concentration five times that of the light absorber. Thereafter, exposure light is irradiated to an integrated amount of 500 mJ.
• polymerization of the polymerizable compound is determined, for example, by high performance liquid chromatography, and if the ratio of the molar amount of the polymerized polymerizable compound to the total molar amount of the polymerizable compounds is 10% or less, the light absorber is determined to be a compound that does not generate radical polymerization initiating species upon exposure.
• the molar ratio is preferably 5% or less, and more preferably 3% or less.
• the lower limit of the molar ratio is not particularly limited, and may be 0%.
• the wavelength of the exposure light may be any wavelength that exposes the photosensitive film.
• the wavelength of the exposure light is preferably a wavelength to which the photopolymerization initiator contained in the resin composition has sensitivity.
• Examples of the compound that generates a radical polymerization initiating species upon exposure include the same compounds as the above-mentioned photoradical polymerization initiator.
• the composition contains a photoradical polymerization initiator as a light absorber
• the compound that generates the radical species with the lowest polymerization initiation ability is the light absorber, and the rest are the photopolymerization initiators.
• Examples of the compound that does not generate a radical polymerization initiating species upon exposure include a photoacid generator, a photobase generator, and a dye whose absorption wavelength changes upon exposure.
• the light absorbent is preferably a naphthoquinone diazide compound or a dye whose absorbance changes upon exposure to light, and more preferably a naphthoquinone diazide compound.
• a photoacid generator or a photobase generator may be used in combination with a compound whose absorbance at the exposure wavelength decreases depending on the pH.
• the naphthoquinone diazide compound includes a compound which generates indene carboxylic acid upon exposure and has a reduced absorbance at the exposure wavelength, and is preferably a compound having a 1,2-naphthoquinone diazide structure.
• the naphthoquinone diazide compound is preferably a naphthoquinone diazide sulfonic acid ester of a hydroxy compound.
• the hydroxy compound is preferably a compound represented by any one of the following formulas (H1) to (H6).
• R1 and R2 each independently represent a monovalent organic group
• R3 and R4 each independently represent a hydrogen atom or a monovalent organic group
• n1, n2, m1, and m2 each independently represent an integer of 0 to 5
• at least one of m1 and m2 is an integer of 1 to 5.
• Z represents a tetravalent organic group
• L 1 , L 2 , L 3 and L 4 each independently represent a single bond or a divalent organic group
• R 5 , R 6 , R 7 and R 8 each independently represent a monovalent organic group
• n3, n4, n5 and n6 each independently represent an integer from 0 to 3
• m3, m4, m5 and m6 each independently represent an integer from 0 to 2
• at least one of m3, m4, m5 and m6 is 1 or 2.
• R 9 and R 10 each independently represent a hydrogen atom or a monovalent organic group
• L 5 each independently represent a divalent organic group
• n7 represents an integer of 3 to 8.
• L6 represents a divalent organic group
• L7 and L8 each independently represent a divalent organic group containing an aliphatic tertiary or quaternary carbon.
• R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 each independently represent a hydrogen atom, a halogen atom or a monovalent organic group
• L 9 , L 10 and L 11 each independently represent a single bond or a divalent organic group
• m7, m8, m9 and m10 each independently represent an integer of 0 to 2, and at least one of m7, m8, m9 and m10 is 1 or 2.
• R 42 , R 43 , R 44 , and R 45 each independently represent a hydrogen atom or a monovalent organic group
• R 46 and R 47 each independently represent a monovalent organic group
• n16 and n17 each independently represent an integer of 0 to 4
• m11 and m12 each independently represent an integer of 0 to 4
• at least one of m11 and m12 is an integer of 1 to 4.
• R1 and R2 are each preferably independently a monovalent organic group having 1 to 60 carbon atoms, and more preferably a monovalent organic group having 1 to 30 carbon atoms.
• Examples of the monovalent organic group in R1 and R2 include a hydrocarbon group which may have a substituent, such as an aromatic hydrocarbon group which may have a substituent such as a hydroxy group.
• R3 and R4 are each preferably independently a monovalent organic group having 1 to 60 carbon atoms, and more preferably a monovalent organic group having 1 to 30 carbon atoms.
• Examples of the monovalent organic group in R3 and R4 include hydrocarbon groups which may have a substituent, such as a hydroxyl group or the like.
• n1 and n2 each independently are preferably 0 or 1, and more preferably 0. In formula (H1), it is preferable that both m1 and m2 are 1.
• the compound represented by formula (H1) is preferably a compound represented by any one of formulas (H1-1) to (H1-5).
• R 21 , R 22 and R 23 each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and more preferably a hydrogen atom or a group represented by the following formula (R-1):
• R 29 represents a hydrogen atom, an alkyl group or an alkoxy group
• n13 represents an integer of 0 to 2
• * represents a bonding site to another structure.
• n8, n9 and n10 each independently represent an integer of 0 to 2, and are preferably 0 or 1.
• R 24 represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 20 carbon atoms.
• n14, n15, and n16 each independently represent an integer of 0 to 2.
• R 30 represents a hydrogen atom or an alkyl group.
• R 25 , R 26 , R 27 and R 28 each independently represent a monovalent organic group, and are preferably a hydrogen atom, an alkyl group or a group represented by the above formula (R-1).
• n11, n12 and n13 each independently represent an integer of 0 to 2, and preferably 0 or 1.
• the compound represented by formula (H1-1) is preferably a compound represented by any one of the following formulas (H1-1-1) to (H1-1-4).
• the compound represented by formula (H1-2) is preferably a compound represented by the following formula (H1-2-1) or (H1-2-2).
• the compound represented by formula (H1-3) is preferably a compound represented by the following formulas (H1-3-1) to (H1-3-3).
• Z is preferably a tetravalent group having 1 to 20 carbon atoms, and more preferably a group represented by any one of the following formulae (Z-1) to (Z-4):
• * represents a bonding site to other structures.
• L 1 , L 2 , L 3 and L 4 each independently represent a single bond or a methylene group.
• R 5 , R 6 , R 7 and R 8 are preferably each independently an organic group having 1 to 30 carbon atoms.
• n3, n4, n5 and n6 each independently represent an integer of 0 to 2, and more preferably 0 or 1.
• m3, m4, m5 and m6 each independently preferably represent 1 or 2, and more preferably represent 1.
• Examples of the compound represented by formula (H2) include compounds having the following structures:
• R 9 and R 10 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.
• each L5 independently represents a group represented by the following formula (L-1).
• R 30 represents a monovalent organic group having 1 to 20 carbon atoms
• n14 represents an integer of 1 to 5
• * represents a bonding site to another structure.
• n7 is preferably an integer of 4 to 6. Examples of the compound represented by formula (H3) include the following compounds: In the following formula, each n independently represents an integer of 0 to 9.
• L 6 is preferably —C(CF 3 ) 2 —, —S( ⁇ O) 2 — or —C( ⁇ O)—.
• L 7 and L 8 each independently preferably represent a divalent organic group having 2 to 20 carbon atoms. Examples of the compound represented by formula (H4) include the following compounds.
• R11 , R12 , R13 , R14 , R15 , R16 , R17 , R18 , R19 and R20 are each preferably independently a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an allyl group or an acyl group.
• L 9 , L 10 and L 11 each independently represent preferably a single bond, -O-, -S-, -S( ⁇ O) 2 -, -C( ⁇ O)-, -C( ⁇ O)O-, cyclopentylidene, cyclohexylidene, phenylene or a divalent organic group having 1 to 20 carbon atoms, and more preferably a group represented by any of the following formulae (L-2) to (L-4).
• R 31 and R 32 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group
• R 34 , R 35 , R 36 , and R 37 each independently represent a hydrogen atom or an alkyl group
• n15 is an integer of 1 to 5
• R 38 , R 39 , R 40 , and R 41 each independently represent a hydrogen atom or an alkyl group
• * represents a bonding site to another structure.
• Examples of the compound represented by formula (H5) include the following compounds.
• R 42 , R 43 , R 44 , and R 45 each independently represent a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms.
• R 46 and R 47 each independently preferably represent an alkyl group, an alkoxy group or an aryl group, and more preferably an alkyl group.
• n16 and n17 each independently represent preferably an integer of 0 to 2, and more preferably 0 or 1.
• n16 and n17 each independently represent preferably an integer of 1 to 3, and more preferably 2 or 3. Examples of the compound represented by formula (H6) include the following compounds.
• hydroxy compounds include polyhydroxybenzophenones such as 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,4,6,3',4'-pentahydroxybenzophenone, 2,3,4,2',4'-pentahydroxybenzophenone, 2,3,4,2',5'-pentahydroxybenzophenone, 2,4,6,3',4',5'-hexahydroxybenzophenone, and 2,3,4,3',4',5'-hexahydroxybenzophenone; polyhydroxyphenyl alkyl ketones such as 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyphenyl pentyl ketone, and 2,3,4-trihydroxyphenyl hexyl ketone; bis(
• Naphthoquinone diazide sulfonic acids include 6-diazo 5,6-dihydro-5-oxo-1-naphthalene sulfonic acid, 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid, etc., which may be used in combination.
• the method for producing a naphthoquinone diazide sulfonate ester of a hydroxy compound is not particularly limited.
• the ester can be obtained by converting naphthoquinone diazide sulfonic acid into a sulfonyl chloride with chlorosulfonic acid or thionyl chloride, and then subjecting the resulting naphthoquinone diazide sulfonyl chloride to a condensation reaction with the hydroxy compound.
• a hydroxy compound and a predetermined amount of naphthoquinone diazide sulfonyl chloride are reacted in a solvent such as dioxane, acetone, or tetrahydrofuran in the presence of a basic catalyst such as triethylamine to carry out esterification, and the resulting product is washed with water and dried to obtain the compound.
• a solvent such as dioxane, acetone, or tetrahydrofuran
• the esterification rate of the naphthoquinone diazide sulfonic acid ester is not particularly limited, but is preferably 10% or more, and more preferably 20% or more.
• the upper limit of the esterification rate is not particularly limited, and may be 100%.
• the above-mentioned esterification rate can be confirmed by 1 H-NMR or the like as the proportion of esterified groups among the hydroxy groups contained in the hydroxy compound.
• the content of the light absorber relative to the total solid content of the resin composition of the present invention is not particularly limited, but is preferably 0.1 to 20 mass%, more preferably 0.5 to 10 mass%, and even more preferably 1 to 5 mass%.
• the resin composition of the present invention preferably contains a polymerization inhibitor, such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.
• a polymerization inhibitor such as a phenolic compound, a quinone compound, an amino compound, an N-oxyl free radical compound, a nitro compound, a nitroso compound, a heteroaromatic ring compound, or a metal compound.
• polymerization inhibitor examples include the compounds described in paragraph 0310 of WO 2021/112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide, etc.
• the contents of this document are incorporated herein by reference.
• the content of the polymerization inhibitor is preferably 0.01 to 20 mass % relative to the total solid content of the resin composition, more preferably 0.02 to 15 mass %, and even more preferably 0.05 to 10 mass %.
• the polymerization inhibitor may be one type or two or more types. When two or more types of polymerization inhibitors are used, it is preferable that the total is within the above range.
• the resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, photoacid generators, aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope in which the effects of the present invention can be obtained.
• additives such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organic titanium compounds, antioxidants, photoacid generators, aggregation inhibitors, phenolic compounds, other polymer compounds, plasticizers, and other auxiliaries (e.g., defoamers, flame retardants, etc.), as necessary, within the scope in which the effects of the present invention can be obtained.
• auxiliaries e.g., defoamers, flame retardants, etc.
• the total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
• Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
• Specific examples of the organotitanium compound are shown below in I) to VII):
• I) Titanium chelate compounds Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide a resin composition with good storage stability and a good curing pattern.
• 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), etc.
• 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-cyclopentadiene-1-yl)bis(2,6-difluorophenyl)titanium, bis( ⁇ 5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.
• Monoalkoxytitanium compounds For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.
• Titanium oxide compounds For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, and the like.
• the organic titanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds.
• titanium diisopropoxide bis(ethylacetoacetate), titanium tetra(n-butoxide), and bis( ⁇ 5-2,4-cyclopentadiene-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are preferred.
• T-1 a compound represented by the following formula (T-1) as the organotitanium compound or in place of the organotitanium compound.
• M is titanium, zirconium or hafnium
• l1 is an integer of 0 to 2
• l2 is 0 or 1
• l1+l2 ⁇ 2 is an integer of 0 to 2
• m is an integer of 0 to 4
• n is an integer of 0 to 2
• R 12 is a substituted or unsubstituted hydrocarbon group
• R 2 is independently a group containing a structure represented by formula (T-2) below
• R 3 is independently a group containing a structure represented by formula (T-2) below
• X A is independently
• M is preferably titanium.
• l1 and l2 are 0 is also one of the preferred embodiments of the present invention.
• m is preferably 2 or 4, and more preferably 2.
• n is preferably 1 or 2, and more preferably 1.
• l1 and l2 are 0, and m is 0, 2 or 4 in formula (T-1).
• R 11 is preferably a substituted or unsubstituted cyclopentadienyl ligand. Furthermore, the cyclopentadienyl group, alkoxy group and phenoxy group in R 11 may be substituted, but the unsubstituted embodiment is also one of the preferred embodiments of the present invention.
• R 12 is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms.
• the hydrocarbon group for R 12 may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, with aromatic hydrocarbon groups being preferred.
• the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, with a saturated aliphatic hydrocarbon group being preferred.
• the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group.
• R 12 is preferably a monovalent substituent, such as a halogen atom, etc.
• R 12 is an aromatic hydrocarbon group, it may have an alkyl group as a substituent.
• R 12 is preferably an unsubstituted phenylene group, and the phenylene group in R 12 is preferably a 1,2-phenylene group.
• formula (T-1) when m is 2 or more and two or more R 2s are included, the structures of the two or more R 2s may be the same or different. In formula (T-1), when n is 2 or more and two or more R 3s are included, the structures of the two or more R 3s may be the same or different.
• an organotitanium compound When an organotitanium compound is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the specific resin. If the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern will be better, and if it is 10 parts by mass or less, the storage stability of the composition will be superior.
• an organotitanium compound When an organotitanium compound is contained, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the obtained cured pattern become better, and when it is 10 parts by mass or less, the storage stability of the composition becomes more excellent.
• Other additives include compounds described in paragraphs 0316 to 00358 of WO 2022/145355, the disclosures of which are incorporated herein by reference.
• the viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of the 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 even more preferably 2,500 mm 2 /s to 8,000 mm 2 /s. If it is within the above range, it is easy to obtain a coating film with high uniformity.
• the water content of the resin composition of 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 the water content is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.
• the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
• metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, etc., but metals contained as complexes of organic compounds and metals are excluded. When multiple metals are contained, it is preferable that the total of these metals is within the above range.
• methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, filtering the raw materials constituting the resin composition of the present invention, lining the inside of the apparatus with polytetrafluoroethylene or the like and performing distillation under conditions that suppress contamination as much as possible, etc.
• the content of halogen atoms is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm from the viewpoint of wiring corrosion.
• those present in the form of halogen ions are preferably less than 5 mass ppm, more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm.
• Halogen atoms include chlorine atoms and bromine atoms.It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range.
• a preferred method for adjusting the content of halogen atoms is ion exchange treatment.
• a conventionally known container can be used as the container for the resin composition of the present invention.
• the container it is also preferable to use a multi-layer bottle whose inner wall is made of six types of six layers of resin, or a bottle with a seven-layer structure of six types of resin, in order to prevent impurities from being mixed into the raw materials or the resin composition of the present invention.
• An example of such a container is the container described in JP 2015-123351 A.
• a cured product of the resin composition By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.
• the cured product of the present invention is a cured product obtained by curing a resin composition.
• the resin composition is preferably cured by heating, and the heating temperature is more preferably 120°C to 400°C, further preferably 140°C to 380°C, and particularly preferably 170°C to 350°C.
• the form of the cured product of the resin composition is not particularly limited, and can be selected according to the application, such as film-like, rod-like, spherical, pellet-like, etc.
• the cured product is preferably in the form of a film.
• the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming a via hole for conduction, adjusting impedance, electrostatic capacitance or internal stress, and imparting a heat dissipation function.
• 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 percentage of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
• the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.
• the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
• the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180° C. or higher, more preferably 210° C. or higher, and even more preferably 230° C. or higher.
• the resin composition of the present invention can be prepared by mixing the above-mentioned components.
• the mixing method is not particularly limited, and can be a conventionally known method. Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank.
• the temperature during mixing is preferably from 10 to 30°C, more preferably from 15 to 25°C.
• the filter pore size is, for example, preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, even more preferably 0.5 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
• the material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. When the material of the filter is polyethylene, it is more preferable that it is HDPE (high density polyethylene).
• the filter may be used after being washed in advance with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel.
• filters with different pore sizes or materials may be used in combination.
• a connection mode an HDPE filter with a pore size of 1 ⁇ m as the first stage and an HDPE filter with a pore size of 0.2 ⁇ m as the second stage may be connected in series.
• various materials may be filtered multiple times. When filtration is performed multiple times, circulation filtration may be performed. Filtration may also be performed under pressure.
• the pressure to be applied is, for example, preferably 0.01 MPa or more and 1.0 MPa or less, more preferably 0.03 MPa or more and 0.9 MPa or less, even more preferably 0.05 MPa or more and 0.7 MPa or less, and even more preferably 0.05 MPa or more and 0.5 MPa or less.
• impurity removal treatment using an adsorbent may be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined.
• the adsorbent a known adsorbent may be used.
• inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon may be used.
• the resin composition filled in the bottle may be subjected to a degassing step by placing it under reduced pressure.
• the method for producing a cured product of the present invention preferably includes a film formation step of applying the resin composition onto a substrate to form a film. It is more preferable that the method for producing a cured product includes the above-mentioned film formation step, an exposure step of selectively exposing the film formed in the film formation step, and a development step of developing the film exposed in the exposure step with a developer to form a pattern.
• the method for producing a cured product includes the above-mentioned film-forming step, the above-mentioned exposure step, the above-mentioned development step, and at least one of a heating step of heating the pattern obtained by the development step and a post-development exposure step of exposing the pattern obtained by the development step.
• the method for producing a cured product preferably includes the film-forming step and a step of heating the film. Each step will be described in detail below.
• the resin composition of the present invention can be used in a film-forming process in which the resin composition is applied onto a substrate to form a film.
• the method for producing a cured product of the present invention preferably includes a film formation step of applying the resin composition onto a substrate to form a film.
• substrate The type of substrate can be appropriately determined according to the application, and is not particularly limited.
• substrates include semiconductor-prepared substrates 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 in which a metal layer is formed by plating, vapor deposition, etc.), paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, mold substrates, and electrode plates of plasma display panels (PDPs).
• semiconductor-prepared substrates 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 in which a metal layer is formed by plating,
• the substrate is preferably a semiconductor-prepared substrate, more preferably a silicon substrate, a Cu substrate, or a mold substrate. These substrates may have a layer such as an adhesion layer made of hexamethyldisilazane (HMDS) or an oxide layer provided on the surface.
• HMDS hexamethyldisilazane
• the shape of the substrate is not particularly limited, and may be circular or rectangular.
• the size of the substrate is preferably, for example, a diameter of 100 to 450 mm, more preferably 200 to 450 mm, if it is circular, and is preferably, for example, a short side length of 100 to 1000 mm, more preferably 200 to 700 mm, if it is rectangular.
• a plate-shaped substrate preferably a panel-shaped substrate (substrate) is used as the substrate.
• a resin composition When a resin composition is applied to the surface of a resin layer (e.g., a layer made of a cured material) or to the surface of a metal layer to form a film, the resin layer or metal layer serves as the substrate.
• a resin layer e.g., a layer made of a cured material
• a metal layer to form a film
• the resin layer or metal layer serves as the substrate.
• the resin composition is preferably applied to a substrate by coating.
• the 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, and inkjet methods. From the viewpoint of uniformity of the thickness of the film, spin coating, slit coating, spray coating, or inkjet methods are preferred, and from the viewpoint of uniformity of the thickness of the film and productivity, spin coating and slit coating are more preferred.
• a film of a desired thickness can be obtained by adjusting the solid content concentration and coating conditions of the resin composition according to the means to be applied.
• the coating method can be appropriately selected depending on the shape of the substrate, and if the substrate is a circular substrate such as a wafer, spin coating, spray coating, inkjet, etc. are preferred, and if the substrate is a rectangular substrate, slit coating, spray coating, inkjet, etc. are preferred.
• the spin coating method for example, it can be applied for about 10 seconds to 3 minutes at a rotation speed of 500 to 3,500 rpm.
• a coating film formed by applying the coating material to a temporary support in advance using the above-mentioned application method may be transferred onto the substrate.
• the transfer method the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A No.
• 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used.
• a process for removing excess film from the edge of the substrate may be performed, such as edge bead rinse (EBR) and back rinse.
• EBR edge bead rinse
• a pre-wetting step may be employed in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.
• the above-mentioned film may be subjected to a step of drying the formed film (layer) (drying step) in order to remove the solvent.
• the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.
• the drying step is preferably carried out after the film-forming 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., and even more preferably 90 to 120° C. Drying may be performed under reduced pressure.
• the drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.
• the film may be subjected to an exposure step to selectively expose the film to light.
• the method for producing a cured product may include an exposure step of selectively exposing the film formed in the film formation step to light. Selective exposure means that only a portion of the film is exposed, and selective exposure results in exposed and unexposed areas of the film.
• the amount of exposure light is not particularly limited as long as it can cure the resin composition of the present invention, but is preferably 50 to 10,000 mJ/cm 2 , and more preferably 200 to 8,000 mJ/cm 2 , calculated as exposure energy at a wavelength of 365 nm.
• the exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.
• the exposure wavelength may be, in particular, (1) semiconductor laser (wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, (7) second harmonic 532 nm, third harmonic 355 nm, etc.
• semiconductor laser wavelength 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 3
• the exposure method is not particularly limited as long as it is a method that exposes at least a part of the film made of the resin composition of the present invention, and examples of the exposure method 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 baking step). That is, the method for producing a cured product of the present invention may include a post-exposure baking step of heating the film exposed in the exposure step.
• the post-exposure baking step can be carried out after the exposure step and before the development step.
• the heating temperature in the post-exposure baking step is preferably from 50°C to 140°C, and more preferably from 60°C to 120°C.
• the heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, and more preferably from 1 minute to 10 minutes.
• the heating rate in the post-exposure heating step is preferably from 1 to 12° C./min, more preferably from 2 to 10° C./min, and even more preferably from 3 to 10° C./min, from the temperature at the start of heating to the maximum heating temperature.
• the rate of temperature rise may be appropriately changed during heating.
• the heating means in the post-exposure baking step is not particularly limited, and known hot plates, ovens, infrared heaters, etc. can be used. It is also preferable that the heating be performed in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.
• the film may be subjected to a development step in which the film is developed with a developer to form a pattern.
• the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed with a developer to form a pattern. Development removes one of the exposed and unexposed areas of the film to form a pattern.
• development in which the non-exposed portion of the film is removed by the development process is called negative development
• development in which the exposed portion of the film is removed by the development process is called positive development.
• the developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.
• examples of 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 compounds described in paragraph 0387 of WO 2021/112189 can be used as the organic solvent.
• the organic solvent examples include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbinol, and triethylene glycol
• examples of amides that are suitable include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.
• the organic solvent may be used alone 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, a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, and dimethylsulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.
• the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
• the content may be 100% by mass.
• the developer may further contain at least one of a basic compound and a base generator.
• the performance of the pattern such as the breaking elongation, may be improved.
• an organic base is preferred.
• a basic compound having an amino group is preferable, and a primary amine, a secondary amine, a tertiary amine, an ammonium salt, a tertiary amide, or the like is preferable.
• a primary amine, a secondary amine, a tertiary amine, or an ammonium salt is preferable, a secondary amine, a tertiary amine, or an ammonium salt is more preferable, a secondary amine or a tertiary amine is further more preferable, and a tertiary amine is particularly preferable.
• the boiling point of the basic compound is preferably 30°C to 350°C, more preferably 80°C to 270°C, and even more preferably 100°C to 230°C at normal pressure (101,325 Pa).
• the boiling point of the basic compound is preferably higher than the temperature obtained by subtracting 20° C.
• the basic compound used preferably has a boiling point of 80° C. or higher, and more preferably has a boiling point of 100° C. or higher.
• the developer may contain only one kind of basic compound, or may contain two or more kinds of basic compounds.
• basic compounds include ethanolamine, diethanolamine, triethanolamine, ethylamine, diethylamine, triethylamine, hexylamine, dodecylamine, cyclohexylamine, cyclohexylmethylamine, cyclohexyldimethylamine, aniline, N-methylaniline, N,N-dimethylaniline, diphenylamine, pyridine, butylamine, isobutylamine, dibutylamine, tributylamine, dicyclohexylamine, DBU (diazabicycloundecene), DABCO (1,4-diazabicyclo[2.2.2]octane), N,N-diisopropylethylamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylenediamine, butanediamine, 1,5-diamino Examples include pentane, N-methylhexy
• the preferred embodiment of the base generator is the same as the preferred embodiment of the base generator contained in the composition described above.
• the base generator is a thermal base generator.
• the content of the basic compound or the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the developer.
• the lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
• the content of the basic compound or base generator is preferably 70 to 100% by mass based on the total solid content of the developer.
• the developer may contain at least one of a basic compound and a base generator, or may contain two or more of them. When at least one of a basic compound and a base generator is two or more, the total amount of them is preferably within the above range.
• the developer may further comprise other components.
• other components include known surfactants and known defoamers.
• the method of supplying the developer is not particularly limited as long as the desired pattern can be formed, and includes a method of immersing the substrate on which the film is formed in the developer, a paddle development method in which the developer is supplied to the film formed on the substrate using a nozzle, and a method of continuously supplying the developer.
• the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, and a spray nozzle.
• a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, a method of supplying the developer through a spray nozzle is more preferred.
• a process may be adopted in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate. This process may be repeated multiple times.
• Methods of supplying the developer in the development step include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept substantially stationary on the substrate, a step in which the developer is vibrated by ultrasonic waves or the like on the substrate, and a combination of these steps.
• the development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes.
• the temperature of the developer during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18°C to 30°C.
• the pattern may be washed (rinsed) with a rinse solution. Also, a method may be adopted in which a rinse solution is supplied before the developer in contact with the pattern has completely dried.
• the rinse liquid may be, for example, water.
• the rinse liquid may be, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer).
• the organic solvent include the same organic solvents as those exemplified when the developer contains an organic solvent.
• the organic solvent contained in the rinse liquid is preferably different from the organic solvent contained in the developer, and more preferably has a lower solubility for the pattern than the organic solvent contained in the developer.
• the organic solvent may be used alone or in combination of two or more.
• the organic solvent is preferably cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, or PGME, more preferably cyclopentanone, ⁇ -butyrolactone, dimethylsulfoxide, PGMEA, or PGME, and even more preferably cyclohexanone or PGMEA.
• the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, based on the total mass of the rinse solution. Furthermore, the organic solvent may account for 100% by mass, based on the total mass of the rinse solution.
• the rinse liquid may contain at least one of a basic compound and a base generator.
• a basic compound and a base generator when the developer contains an organic solvent, an embodiment in which the rinsing liquid contains an organic solvent and at least one of a basic compound and a base generator is also one of the preferred embodiments of the present invention.
• the basic compound and base generator contained in the rinse solution include the compounds exemplified as the basic compound and base generator that may be contained in the above-mentioned developer containing an organic solvent, and preferred embodiments thereof are also the same.
• the basic compound and base generator contained in the rinse solution may be selected in consideration of the solubility in the solvent in the rinse solution.
• the content of the basic compound or the base generator is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the rinse solution.
• the lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
• the content of the basic compound or base generator is also preferably 70 to 100 mass % based on the total solid content of the rinse liquid.
• the rinse solution may contain only one kind of at least one of the basic compound and the base generator, or may contain two or more kinds.
• the total amount thereof is preferably within the above range.
• the rinse solution may further contain other ingredients.
• other components include known surfactants and known defoamers.
• the method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples of the method include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like.
• the rinse liquid may be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, while from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred.
• the type of nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, etc.
• the rinsing step is preferably a step of supplying a rinsing liquid to the exposed film through a straight nozzle or continuously supplying the rinsing liquid to the exposed film, and more preferably a step of supplying the rinsing liquid through a spray nozzle.
• the method of supplying the rinsing liquid in the rinsing step may be a step in which the rinsing liquid is continuously supplied to the substrate, a step in which the rinsing liquid is kept substantially stationary on the substrate, a step in which the rinsing liquid is vibrated on the substrate by ultrasonic waves or the like, or a combination of these steps.
• the rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes.
• the temperature of the rinsing liquid during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18°C to 30°C.
• the development step may include a step of contacting the pattern with a processing liquid after treatment with a developer or after washing the pattern with a rinse liquid. Also, a method may be employed in which the processing liquid is supplied before the developer or rinse liquid in contact with the pattern is completely dried.
• the treatment liquid includes a treatment liquid containing at least one of water and an organic solvent, and at least one of a basic compound and a base generator.
• Preferred aspects of the organic solvent, and at least one of the basic compound and the base generator are the same as the preferred aspects of the organic solvent, and at least one of the basic compound and the base generator used in the above-mentioned rinse solution.
• the method of supplying the processing liquid to the pattern can be the same as the above-mentioned method of supplying the rinsing liquid, and the preferred embodiments are also the same.
• the content of the basic compound or base generator in the treatment liquid is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the treatment liquid.
• the lower limit of the content is not particularly limited, but is preferably, for example, 0.1% by mass or more.
• the content of the basic compound or base generator is preferably 70 to 100 mass % based on the total solid content of the treatment liquid.
• the treatment liquid may contain only one kind of at least one of the basic compound and the base generator, or may contain two or more kinds.
• the total amount thereof is preferably within the above range.
• the pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the developing step. The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without carrying out a development step, or a film obtained in a film formation step. In the heating step, the resin such as the polyimide precursor is cyclized to become a resin such as a polyimide.
• the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, further preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.
• the heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of the base generated from the base generator through heating.
• the heating step is preferably performed at a temperature rise rate of 1 to 12° C./min from the temperature at the start of heating to the maximum heating temperature.
• the temperature rise rate is more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min.
• the temperature is increased from the starting temperature to the maximum heating temperature at a rate of preferably 1 to 8° C./sec, more preferably 2 to 7° C./sec, and even more preferably 3 to 6° C./sec.
• the temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C.
• the temperature at the start of heating refers to the temperature at which the process of heating to the maximum heating temperature begins.
• the resin composition of the present invention when applied to a substrate and then dried, it is the temperature of the film (layer) after drying, and it is preferable to raise the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.
• the heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
• the heating temperature is preferably 30° C. or higher, more preferably 80° C. or higher, even more preferably 100° C. or higher, and particularly preferably 120° C. or higher.
• the upper limit of the heating temperature is preferably 350° C. or less, more preferably 250° C. or less, and even more preferably 240° C. or less.
• Heating may be performed stepwise. For example, a process may be performed in which the temperature is increased from 25°C to 120°C at 3°C/min, held at 120°C for 60 minutes, increased from 120°C to 180°C at 2°C/min, and held at 180°C for 120 minutes. It is also preferable to treat while irradiating with ultraviolet light as described in U.S. Pat. No. 9,159,547. Such a pretreatment process can improve the properties of the film.
• the pretreatment process may be performed for a short time of about 10 seconds to 2 hours, and more preferably for 15 seconds to 30 minutes.
• the pretreatment process may be performed in two or more steps, for example, a first pretreatment process may be performed in the range of 100 to 150°C, and then a second pretreatment process may be performed in the range of 150 to 200°C. Furthermore, after heating, the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C./min.
• the heating step is preferably performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by performing the heating step under reduced pressure, etc.
• the oxygen concentration is preferably 50 ppm (volume ratio) or less, and more preferably 20 ppm (volume ratio) or less.
• the heating means in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.
• the pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern after the development step is exposed to light instead of or in addition to the heating step. That is, 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 due to the exposure of a photobase generator to light can be promoted.
• the post-development exposure step it is sufficient that at least a part of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed.
• the exposure dose in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , and more preferably 100 to 15,000 mJ/cm 2 , calculated as exposure energy at a wavelength to which the photosensitive compound has sensitivity.
• the post-development exposure step can be carried out, for example, using the light source in the exposure step described above, and it is preferable to use broadband light.
• the pattern obtained by the development step may be subjected to a metal layer forming step in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the development step (preferably subjected to at least one of a heating step and a post-development exposure step).
• the metal layer can be made of any existing metal type without any particular limitations, and examples include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.
• the method for forming the metal layer is not particularly limited, and existing methods can be applied.
• the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used.
• photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electrolytic plating, electroless plating, etching, printing, and combinations of these methods are possible.
• examples of the method include a patterning method that combines sputtering, photolithography, and etching, and a patterning method that combines photolithography and electrolytic plating.
• a preferred embodiment of plating is electrolytic plating using a copper sulfate or copper cyanide plating solution.
• the thickness of the metal layer at its thickest point is preferably 0.01 to 50 ⁇ m, and more preferably 1 to 10 ⁇ m.
• Examples of the field of application of the method for producing the cured product of the present invention or the cured product include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc.
• Other examples include etching patterns of sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or insulating films for mounting applications such as those described above.
• the method for producing the cured product of the present invention or the cured product of the present invention can also be used for producing printing plates such as offset printing plates or screen printing plates, for etching molded parts, and for producing protective lacquers and dielectric layers in electronics, especially microelectronics.
• the laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention.
• the laminate is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers.
• at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of 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 cured product of the present invention multiple times.
• the laminate of the present invention preferably includes two or more layers made of a cured product, and includes a metal layer between any two of the layers made of the cured product.
• the metal layer is preferably formed by the metal layer forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer forming step of forming a metal layer on a layer made of a cured product between the steps for producing a cured product which are performed multiple times.
• a preferred embodiment of the metal layer forming step is as described above.
• a laminate having at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order can be mentioned as a preferred example.
• the layer made of the first cured product and the layer made of the second cured product are preferably layers made of 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 may have the same composition or different compositions.
• the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
• the method for producing the laminate of the present invention preferably includes a lamination step.
• the lamination process is a series of processes including performing at least one of (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) a heating process and a post-development exposure process again on the surface of the pattern (resin layer) or metal layer in this order.
• at least one of (a) the film formation process and (d) the heating process and the post-development exposure process may be repeated.
• a metal layer formation process may be included. It goes without saying that the lamination process may further include the above-mentioned drying process and the like as appropriate.
• a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step.
• An example of the surface activation treatment is a plasma treatment. Details of the surface activation treatment will be described later.
• the lamination step is preferably carried out 2 to 20 times, and 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 preferred, and a structure of 2 to 9 resin layers is more preferred.
• the layers may be the same or different in composition, shape, film thickness, etc.
• a particularly preferred embodiment is one in which, after providing a metal layer, a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.
• a cured product (resin layer) of the resin composition of the present invention is further formed so as to cover the metal layer.
• the following may be repeated in this order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step; or (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step.
• the method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment.
• the surface activation treatment step is usually carried out after the metal layer formation step, but after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step), the resin composition layer may be subjected to a surface activation treatment step before the metal layer formation step is carried out.
• the surface activation treatment may be performed on at least a part of the metal layer, or on at least a part of the resin composition layer after exposure, or on at least a part of both the metal layer and the resin composition layer after exposure.
• the surface activation treatment is preferably performed on at least a part of the metal layer, and it is preferable to perform the surface activation treatment on a part or all of the area of the metal layer on which the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin composition layer (film) provided on the surface can be improved. It is preferable to perform the surface activation treatment on a part or the whole of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion with the metal layer or the resin layer provided on the surface that has been surface-activated.
• the resin composition layer when performing negative development, etc., when the resin composition layer is cured, it is less likely to be damaged by the surface treatment, and the adhesion is likely to be improved.
• the surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of WO 2021/112189, the contents of which are incorporated herein by reference.
• the present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention.
• the present invention also discloses a method for producing a semiconductor device, which includes the method for producing the cured product or the method for producing the laminate of the present invention.
• semiconductor devices using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer the descriptions in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-027357 can be referred to, and the contents of these are incorporated herein by reference.
• the reaction solution was dropped into a mixture of 1.8 liters of methanol and 0.6 liters of water, and the mixture was stirred for 15 minutes, after which the polyimide resin was filtered.
• the resin was reslurried in 1 liter of water, filtered, and then reslurried again in 1 liter of methanol, filtered, and dried under reduced pressure at 40° C. for 8 hours.
• the resin dried above was dissolved in 250 g of tetrahydrofuran, 40 g of ion exchange resin (MB-1: manufactured by Organo Corporation) was added, and the mixture was stirred for 4 hours.
• polyimide (P-1) is a resin having a repeating unit represented by the following formula (P-1).
• the subscripts in parentheses of the following repeating units represent the molar ratio of each repeating unit.
• the structures of the repeating units were determined from 1 H-NMR spectra.
• the ethylenically unsaturated bond valence (mmol/g) and the molar amount of oxygen atoms/weight average molecular weight (mmol/g) of the polyimide (P-1) are shown in the table below.
• the subscripts in parentheses indicate the molar ratio of each structure. Furthermore, the ethylenically unsaturated bond valence (mmol/g) and the molar amount of oxygen atoms/weight average molecular weight (mmol/g) of the polyimides (P-2) to (P-3), the polyimide precursor (P-4), and the polyimides (P-5) to (P-16) are shown in the table below.
• Comparative polyimides (B-1) and (B-2) were synthesized in the same manner as for polyimide (P-1), except that the raw materials used were appropriately changed.
• Comparative polyimides (B-1) to (B-2) are resins having repeating units represented by the following formulas (B-1) to (B-2). The structure of each repeating unit was determined from 1 H-NMR spectrum. In the following structures, the subscripts in parentheses indicate the molar ratio of each structure.
• the weight average molecular weight (Mw) of the comparative polyimide (B-1) was 7,500
• the Mw of the comparative polyimide (B-2) was 50,000.
• Examples and Comparative Examples> In each of the examples, the components shown in the following table were mixed to obtain a resin composition. In each of the comparative examples, the components shown in the following table were mixed to obtain a comparative composition. Specifically, the content of each component shown in the table is the amount (parts by mass) shown in the "parts by mass” column of each column in the table.
• the obtained resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter having a pore width of 0.5 ⁇ m. In the table, "-" indicates that the composition does not contain the corresponding component.
• F-1 Compound having the following structure
• F-2 X-12-967C (manufactured by Shin-Etsu Chemical Co., Ltd.)
• F-3 KBM-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)
• F-4 KBM-1083 (manufactured by Shin-Etsu Chemical Co., Ltd.)
• F-5 KBM-573 (manufactured by Shin-Etsu Chemical Co., Ltd.)
• F-6 KBE-903 (manufactured by Shin-Etsu Chemical Co., Ltd.)
• I-1 Compound having the following structure (titanium compound)
• I-2 Compound having the following structure (titanium compound) ⁇ I-3: TC-750 (manufactured by Matsumoto Fine Chemical)
• I-4 Ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid (NQD (naphthoquinone diazide))
• I-5 Compound having the following structure I-6: Percumyl D (manufactured by NOF Corp.)
• I-7 F-554 (fluorine-based surfactant, manufactured by Shin-Etsu Chemical)
• I-8 KF-6000 (silicon-based surfactant, manufactured by Shin-Etsu Chemical) I-9
• the thickness of the resin composition layer after immersion was measured at 10 points on the coating surface using an ellipsometer (KT-22 manufactured by Foothill Corporation), and the thickness was calculated as the arithmetic average value.
• the dissolution rate ( ⁇ m/sec) was calculated from the film thickness measured above and the film thickness before immersion, which was 10 ⁇ m. The measurement results are shown in the "composition dissolution rate” column in the table.
• a resin layer (film) was formed in a GBL ( ⁇ -butyrolactone) solution in the same manner as above, and the dissolution rate was measured. The measurement results are shown in the "Dissolution rate” column of "Resin” in the table.
• the obtained resin composition layer was exposed to light at each exposure amount in the range of 100 to 800 mJ/ cm2 in 50 mJ/cm2 increments using an i-line stepper (Canon: FPA-3000i5) using a square via mask in which a pattern was formed in 0.5 ⁇ m increments from 0.5 to 10 ⁇ m. Thereafter, the resist was developed with cyclopentanone for 30 seconds by the method described in the "Method" column of the "Development” in the table, and rinsed with PGMEA (propylene glycol monomethyl ether acetate) for 30 seconds.
• PGMEA propylene glycol monomethyl ether acetate
• the minimum opening mask diameter of the obtained cured product was determined by observing the cross section of the opening pattern portion with a scanning microscope S-4800 (manufactured by Hitachi High-Technologies Corporation) and evaluated according to the following evaluation criteria.
• the minimum opening mask diameter was defined as the smallest mask diameter among those in which an opening pattern was formed with at least one of the above exposure doses. The evaluation results are shown in the "Resolution” column in the table. (Evaluation Criteria) A: The minimum opening mask diameter was 3 ⁇ m or less. B: The minimum opening mask diameter was more than 3 ⁇ m and 5 ⁇ m or less. C: The minimum opening mask diameter exceeded 5 ⁇ m.
• the resin composition of the present invention provides excellent resolution when forming a pattern of the cured product.
• the dissolution rate of a film having a thickness of 10 ⁇ m obtained from the composition in cyclopentanone exceeds 0.55 ⁇ m/sec
• the dissolution rate of a film having a thickness of 10 ⁇ m in cyclopentanone of the resin contained therein exceeds 0.2 ⁇ m/sec. It is clear that the resolution is poor in such a comparative example.
• the dissolution rate of a film having a thickness of 10 ⁇ m obtained from the composition in cyclopentanone is less than 0.01 ⁇ m/sec, and the dissolution rate of a film having a thickness of 10 ⁇ m in cyclopentanone of the resin contained therein is also less than 0.01 ⁇ m/sec.
• the resolution is poor.
• Example 101 The resin composition used in Example 1 was applied in a layer by spin coating to the surface of a substrate on which 2 ⁇ m line-and-space copper wiring was formed, and then dried at 110 ° C. for 5 minutes to form a resin composition layer with a film thickness of 5 ⁇ m. The layer was then exposed to light at a wavelength of 365 nm and 300 mJ / cm 2 using an i-line stepper (Canon: FPA-3000i5). The layer was then developed with cyclopentanone for 30 seconds and rinsed with PGMEA for 30 seconds to obtain a layer pattern. The layer was then heated at a heating rate of 10 ° C.
• interlayer insulating film for a rewiring layer had excellent insulation properties. Furthermore, when semiconductor devices were manufactured using these interlayer insulating films for redistribution layers, it was confirmed that they operated without any problems.

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