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WO2025178105A1 - Composition de résine, objet durci ainsi que procédé de fabrication de celui-ci, stratifié ainsi que procédé de fabrication de celui-ci, et dispositif à semi-conducteurs ainsi que procédé de fabrication de celui-ci - Google Patents

Composition de résine, objet durci ainsi que procédé de fabrication de celui-ci, stratifié ainsi que procédé de fabrication de celui-ci, et dispositif à semi-conducteurs ainsi que procédé de fabrication de celui-ci

Info

Publication number
WO2025178105A1
WO2025178105A1 PCT/JP2025/005904 JP2025005904W WO2025178105A1 WO 2025178105 A1 WO2025178105 A1 WO 2025178105A1 JP 2025005904 W JP2025005904 W JP 2025005904W WO 2025178105 A1 WO2025178105 A1 WO 2025178105A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
group
repeating unit
resin
resin composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/005904
Other languages
English (en)
Japanese (ja)
Inventor
倫弘 小川
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of WO2025178105A1 publication Critical patent/WO2025178105A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • cyclized resins such as polyimides have excellent heat resistance and insulating properties, and are therefore used in a variety of applications.
  • examples of such applications include, but are not limited to, insulating films, sealing materials, and protective films for semiconductor devices used for packaging. They are also used as base films and coverlays for flexible substrates.
  • the cyclized resin such as polyimide is used in the form of a resin composition containing the cyclized resin or a precursor thereof.
  • a resin composition is applied to a substrate by, for example, coating to form a photosensitive film, and then, if necessary, exposure, development, heating, etc. are carried out to form a cured product on the substrate.
  • the resin composition can be applied by known coating methods, etc., and therefore can be said to have excellent adaptability in manufacturing, for example, a high degree of freedom in designing the shape, size, application position, etc. of the resin composition when applied.
  • cyclized resins such as polyimides from the viewpoint of such excellent adaptability in manufacturing, there are increasing expectations for the industrial application and development of the above-mentioned resin composition.
  • Patent Document 1 describes a photosensitive resin composition containing: (A) 100 parts by mass of a copolymer resin containing a polyimide and a polyimide precursor; (B) 0.5 to 30 parts by mass of a photopolymerization initiator; and (C) 100 to 1,000 parts by mass of a solvent, wherein the copolymer resin containing a polyimide and a polyimide precursor has a specific structure.
  • the cured product When a cured product formed from a resin composition containing polyimide or its precursor is used as an insulating material in a wiring pattern, the cured product must have a low thermal expansion coefficient to minimize the difference in thermal expansion coefficient with the substrate.
  • the present invention aims to provide a resin composition that can give a cured product with a low thermal expansion coefficient, a cured product obtained by curing the resin 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 that includes the method for producing the cured product, and a semiconductor device that includes the cured product.
  • Another object of the present invention is to provide a method for synthesizing a novel resin.
  • the imidization rate of the resin is 40 to 85%, a resin composition in which the imide group concentration U, which is the mass ratio of imide groups in a polyimide obtained by imidizing 100% of the amic acid structure and amic acid ester structure of the resin, is 16 to 40 mass%.
  • X1 is a tetravalent organic group
  • Y1 is a divalent organic group
  • A2 is —O— or —NR2—
  • R2 is a hydrogen atom or a monovalent organic group
  • R2 is a hydrogen atom or a monovalent organic group
  • X2 is a tetravalent organic group
  • Y2 is a divalent organic group
  • A3 is —O— or —NR Z —
  • R Z is a hydrogen atom or a monovalent organic group
  • R3 is a hydrogen atom or a monovalent organic group
  • X3 is a tetravalent organic group
  • Y3 is a divalent organic group
  • a 41 and A 42 are each independently —O— or —NR Z —
  • R Z is a hydrogen atom or a monovalent organic group
  • R 41 and R 42 are each independently a hydrogen atom or a monovalent organic group
  • X 4 is a a hydrogen atom or a
  • ⁇ 2> The resin composition according to ⁇ 1>, wherein the resin contains at least one repeating unit selected from the group consisting of repeating units A-1, A-2, A-3, and A-4.
  • Repeating unit A-2 A repeating unit represented by formula (1-2), in which X 2 is any of the structures represented by formula (2a) to formula (2g), or a repeating unit represented by formula (1-2), in which X 2 contains a structure in which two or more hydrogen atoms have been removed from a structure represented by any of formula (V-4), formula (V-6), formula (V-7), formula (V-9), and formula (V-10).
  • Repeating unit A-3 A repeating unit represented by formula (1-3), in which X Repeating unit A-4: A repeating unit represented by formula (1-4) in which X 4 is any of the structures represented by formula (2a) to formula (2g), or a repeating unit represented by formula (1-3) in which X 3 has been removed from any of the structures represented by formula (V-4), formula (V-6), formula (V-7), formula (V-9), and formula (V-10) by removing two or more hydrogen atoms.
  • Repeating unit A-5 A repeating unit represented by formula (1-4) in which X 4 is any of the structures represented by formula (2a) to formula (2g), or a repeating unit represented by formula (1-4) in which X 4 has been removed from any of the structures represented by formula (V-4), formula (V-6), formula (V-7), formula (V-9), and formula (V-10) by removing two or more hydrogen atoms.
  • repeating unit B-1 A repeating unit represented by formula (1-1), in which X 1 comprises a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1), (V-2), (V-3), (V-5), and (V-8).
  • Repeating unit B-2 A repeating unit represented by formula (1-2), in which X 2 comprises a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1), (V-2), (V-3), (V-5), and (V-8).
  • Repeating unit B-3 A repeating unit represented by formula (1-3), in which X 3 comprises a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of formulas (V-1), (V-2), (V-3), (V-5), and (V-8).
  • Repeating unit B-4 A repeating unit represented by formula (1-4), in which X 4 is a repeating unit containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1), (V-2), (V-3), (V-5), and (V-8).
  • ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the resin contains at least one repeating unit selected from the group consisting of repeating units represented by formula (1-2), in which R 2 is a monovalent organic group having an ethylenically unsaturated bond; repeating units represented by formula (1-3), in which R 3 is a monovalent organic group having an ethylenically unsaturated bond; and repeating units represented by formula (1-4), in which at least one of R 41 and R 42 is a monovalent organic group having an ethylenically unsaturated bond.
  • ⁇ 6> The resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein the imide group concentration U is 23 to 38 mass%.
  • ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein the resin has an acid value of less than 11.2 mg KOH/g.
  • ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the imidization rate of the resin is 55% or more and less than 70%.
  • ⁇ 9> The resin composition according to any one of ⁇ 1> to ⁇ 8>, wherein the resin composition is a negative photosensitive resin composition.
  • ⁇ 10> The resin composition according to any one of ⁇ 1> to ⁇ 9>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 11> A cured product obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 10>.
  • ⁇ 12> A laminate comprising two or more layers made of the cured product according to ⁇ 11>, and a metal layer between any two adjacent layers made of the cured product.
  • ⁇ 13> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 10> onto a substrate to form a film.
  • the method for producing a cured product according to ⁇ 13> 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.
  • ⁇ 15> A method for producing a cured product according to ⁇ 13> or ⁇ 14>, comprising a heating step of heating the film at 50 to 450°C.
  • ⁇ 16> A method for producing a laminate, comprising the method for producing a cured product according to any one of ⁇ 13> to ⁇ 15>.
  • ⁇ 17> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of ⁇ 13> to ⁇ 15>.
  • ⁇ 18> A semiconductor device comprising the cured product according to ⁇ 11>.
  • a resin composition that can give a cured product with a low thermal expansion coefficient, a cured product obtained by curing the resin 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 that includes the method for producing the cured product, and a semiconductor device that includes the cured product.
  • the present invention also provides a novel method for synthesizing a resin.
  • a numerical range expressed using the symbol "to” means a range that includes the numerical values before and after "to” as the lower and upper limits, respectively.
  • the term “step” includes not only an independent step but also a step that cannot be clearly distinguished from other steps, as long as the intended effect of the step can be achieved.
  • groups (atomic groups) when a notation does not specify whether they are substituted or unsubstituted, it encompasses both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents.
  • 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 typified by excimer lasers, 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.
  • total solids content refers to the total mass of all components of the composition excluding the solvent
  • solids concentration refers to the mass percentage of the components excluding the solvent relative to the total mass of the composition.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) can be determined, for example, using an HLC-8220GPC (manufactured by Tosoh Corporation) and 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.
  • these molecular weights are measured using NMP (N-methyl-2-pyrrolidone) as the eluent.
  • NMP N-methyl-2-pyrrolidone
  • THF tetrahydrofuran
  • detection in GPC measurement is performed using a UV (ultraviolet) ray (ultraviolet) 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 and the other layer do not need to be in contact.
  • the direction in which layers are stacked on the substrate is referred to as "up,” or, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as “up,” and the opposite direction is referred to as “down.”
  • the "up" direction in this specification may differ from the vertical upward direction.
  • a 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 atmospheric pressure is 101,325 Pa (1 atmosphere)
  • the relative humidity is 50% RH.
  • combinations of preferred embodiments are more preferred embodiments.
  • the resin composition of the present invention comprises a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by formula (1-1), a repeating unit represented by formula (1-2), a repeating unit represented by formula (1-3), and a repeating unit represented by formula (1-4), a polymerization initiator, and a solvent,
  • the resin has an imidization rate of 40 to 85% and an imide group concentration U of 16 to 40% by mass.
  • a resin having at least one repeating unit selected from the group consisting of a repeating unit represented by formula (1-1), a repeating unit represented by formula (1-2), a repeating unit represented by formula (1-3), and a repeating unit represented by formula (1-4), and having an imide group concentration U of 16 to 40 mass % is also referred to as a "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 more 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 to form, for example, an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used to form 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.
  • the resin composition used for forming a photosensitive film to be subjected to negative development is referred to as a negative photosensitive resin composition.
  • negative development refers to development in which the unexposed areas are removed by development
  • positive development refers to 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 method for producing a cured product described below can be used.
  • the resin composition of the present invention provides a cured product with a reduced coefficient of thermal expansion.
  • the mechanism by which the above effects are obtained is unknown, but is speculated as follows.
  • the imidization rate of the resin is 40% or more, interactions between imide rings occur during application, resulting in high orientation in the film and making it easier to maintain orientation in the cured film.
  • increasing the imide group concentration that is, reducing the molecular weight of the unit structure (diamine, acid anhydride) and rigidifying it, can suppress thermal expansion of the cured product.
  • the present inventors have also found that the resin composition of the present invention has high storage stability, reduces unevenness during application, and provides high resolution.
  • Patent Document 1 does not describe a resin composition containing a specific resin.
  • the resin composition of the present invention contains a resin (specific resin) having at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (1-1), a repeating unit represented by the following formula (1-2), a repeating unit represented by the following formula (1-3), and a repeating unit represented by the following formula (1-4), wherein the resin has an imidization rate of 40 to 85% and an imide group concentration U of 16 to 40 mass%.
  • X1 is a tetravalent organic group
  • Y1 is a divalent organic group
  • A2 is -O- or -NRz-
  • Rz is a hydrogen atom or a monovalent organic group
  • R2 is a hydrogen atom or a monovalent organic group
  • X2 is a tetravalent organic group
  • Y2 is a divalent organic group
  • A3 is —O— or —NR Z —
  • R Z is a hydrogen atom or a monovalent organic group
  • R3 is a hydrogen atom or a monovalent organic group
  • X3 is a tetravalent organic group
  • Y3 is a divalent organic group
  • a 41 and A 42 are each independently —O— or —NR Z —
  • R Z is a hydrogen atom or a monovalent organic group
  • R 41 and R 42 are each independently a hydrogen atom or a monovalent organic group
  • X 4 is a a hydrogen atom or a
  • the specific resin is preferably a polyimide precursor.
  • 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.
  • polyimide refers to a resin having a repeating unit containing an imide group in the molecular chain, and is preferably a resin having a repeating unit containing an imide ring structure in the molecular chain.
  • the polyimide when the polyimide is a linear resin, the polyimide is preferably a resin having a repeating unit containing an imide group in the main chain, and more preferably a resin having a repeating unit containing an imide ring structure in the main chain.
  • the term "main chain” refers to the relatively longest bonding chain in a resin molecule, and the term “side chain” refers to any other bonding chain.
  • the imide ring structure refers to a ring structure containing two carbon atoms and all of the nitrogen atoms in the imide as ring members.
  • the imide ring structure is preferably a five-membered ring.
  • the polyimide may be a so-called polyamideimide, which has an amide group in the molecular chain in addition to an imide group.
  • # represents a bonding site to another structure, preferably a bonding site to a hydrogen atom or a carbon atom, and more preferably a bonding site to a hydrogen atom.
  • the specific resin preferably has a polymerizable group, and more preferably contains a radically polymerizable group.
  • the resin composition of the present invention preferably contains a radical polymerization initiator as a polymerization initiator. From the viewpoint of resolution, it is also preferable that the resin composition contains both the radical polymerization initiator and a radical crosslinking agent. Furthermore, if necessary, a sensitizer may be contained in these embodiments. From such a resin composition, for example, a negative photosensitive film is formed.
  • the specific resin may also have a polarity conversion group such as an acid-decomposable group. When the specific resin has an acid-decomposable group, the resin composition preferably contains a photoacid generator. From such a resin composition, for example, a chemically amplified positive-working photosensitive film or negative-working photosensitive film is formed.
  • the specific resin has an imidization rate of 40 to 85%.
  • the imidization ratio is a value calculated by the following method, and represents the ratio of imide ring structures to the total of amic acid structures, amic acid ester structures, and imide ring structures in the specific resin.
  • the resin is dissolved in ⁇ -butyrolactone, diluted to a viscosity of 2,000 mPa ⁇ s, and applied to a silicon wafer by spin coating to form a resin layer. If a resin layer cannot be formed due to reasons such as low solubility of the resin in ⁇ -butyrolactone, the solvent may be changed to another solvent. Examples of other solvents include solvents contained in the resin composition, such as NMP.
  • the viscosity may also be adjusted as needed.
  • the silicon wafer to which the resulting resin layer is applied is dried on a hot plate at 110°C for 5 minutes to obtain a resin layer with a uniform thickness of approximately 15 ⁇ m after film formation on the silicon wafer.
  • the film thickness may be adjusted as needed. For example, if the film thickness is 5 ⁇ m or greater, the imidization rate will be approximately the same.
  • the resin layer is measured by the ATR (attenuated total reflection) method using a NicoletiS20 (manufactured by Thermofisher) in the measurement range of 4000 to 700 cm ⁇ 1 , with 50 measurements.
  • the imidization index A of the resin is calculated by dividing the peak height near 1380 cm ⁇ 1 (1350 to 1450 cm ⁇ 1 , the peak with the greatest intensity if there are multiple peaks) by the peak height near 1500 cm ⁇ 1 (1460 to 1550 cm ⁇ 1 , the peak with the greatest intensity if there are multiple peaks).
  • the imidization index B is calculated in the same manner for a film heated at a heating rate of 10°C/min in a nitrogen atmosphere and heated at 350°C for 1 hour, and the imidization index A is divided by the imidization index B to calculate the imidization rate of the resin.
  • the imidization ratio of the specific resin is preferably 45% or more, more preferably 50% or more, and even more preferably 55% or more.
  • the imidization degree of the specific resin is preferably 80% or less, more preferably 75% or less, and even more preferably less than 70%.
  • the specific resin has an imide group concentration U of 16 to 40% by mass.
  • the imide group concentration U is the mass proportion of imide groups in the structure, and for a resin that is a polyimide precursor, it is the mass proportion of imide groups in the polyimide when a polyimide obtained by imidizing 100% of the amic acid structures and amic acid ester structures in the structure is assumed.
  • the imide group concentration can be calculated by the following formula (I) using the molecular weight of the tetracarboxylic dianhydride and the molecular weight of the diamine compound used in preparing the specific resin.
  • Mw(A) represents the molecular weight of the tetracarboxylic dianhydride
  • Mw(B) represents the molecular weight of the diamine.
  • Mw(A) is the average molecular weight calculated from the molecular weight of each tetracarboxylic dianhydride used and the molar ratio used.
  • Mw(B) is the average molecular weight calculated from the molecular weight of each diamine used and the molar ratio used.
  • imide group concentration U reference can also be made to the descriptions in paragraphs 0035 to 0037 of WO 2023/228568.
  • the imide group concentration U can also be determined by calculating, based on NMR measurement results or the like, the proportion of the molecular weight of the imide group to the molecular weight of the repeating unit containing a structure derived from a tetracarboxylic dianhydride and a diamine compound in the polyimide of a cured polyimide film obtained by heat-curing a resin composition under conditions under which 100% of the amic acid structure and amic acid ester structure of the resin are imidized (e.g., at 350°C for 1 hour).
  • the imide group concentration U can be adjusted to 16 to 40% by mass by adjusting the molecular weight of the tetracarboxylic dianhydride and the molecular weight of the diamine compound used in preparing the specific resin.
  • the imide group concentration U of the specific resin is preferably 23% by mass or more, and more preferably more than 26% by mass.
  • the acid value of the specific resin is not particularly limited, and may be, for example, 25.3 mgKOH/g or less, or may be 0.05 to 20.0 mgKOH/g. Even if the specific resin has a low acid value, for example, less than 11.2 mgKOH/g or 5.6 mgKOH/g or less, the specific resin has an imidization rate of 40%, so that it undergoes little change due to imidization and can be stored stably.
  • the acid value is measured by a known method, for example, the method described in JIS K 0070:1992.
  • the acid group contained in the polyimide is preferably an acid group having a pKa of 0 to 10, more preferably an acid group having a pKa of 3 to 8, from the viewpoint of achieving both storage stability and developability.
  • pKa is the equilibrium constant Ka of a dissociation reaction in which a hydrogen ion is released from an acid, expressed as its negative common logarithm pKa.
  • pKa is a value calculated using ACD/ChemSketch (registered trademark) unless otherwise specified.
  • ACD/ChemSketch registered trademark
  • the acid value of the specific resin is substantially derived from carboxy groups, and the content of carboxy groups may be, for example, 25.3 mgKOH/g or less, or 0.05 to 20.0 mgKOH/g or less. For example, it may be less than 11.2 mgKOH/g, or 5.6 mgKOH/g or less.
  • the content of carboxy groups can also be determined from the peak specific to carboxylic acid in 1 H-NMR measurement. 1 H-NMR measurement can be carried out, for example, under the following conditions. ⁇ 1H -NMR (BRUKER, AVANCE NEO 400) ⁇ Analysis software: TopSpin 4.0.7 Solvent: DMSO-d6
  • X1 is a tetravalent organic group
  • Y1 is a divalent organic group
  • A2 is —O— or —NR Z —
  • R Z is a hydrogen atom or a monovalent organic group
  • R 2 is a hydrogen atom or a monovalent organic group
  • X2 is a tetravalent organic group
  • Y2 is a divalent organic group
  • A3 is —O— or —NR Z —
  • R Z is a hydrogen atom or a monovalent organic group
  • R3 is a hydrogen atom or a monovalent organic group
  • X3 is a tetravalent organic group
  • Y3 is a divalent organic group
  • a 41 and A 42 are each independently —O— or —NR Z —
  • R Z is a hydrogen atom or a monovalent organic group
  • X1 preferably has 4 or more carbon atoms, more preferably 4 to 50 carbon atoms, and even more preferably 6 to 40 carbon atoms.
  • X1 preferably contains a structure in which two or more hydrogen atoms have been removed from any of the structures represented by the following formulae (2a) to (2g) or any of the structures represented by the following formulae (V-4), (V-6), (V-7), (V-9), and (V-10), because this provides the following effects: improved chemical resistance and flatness of the cured product, suppression of development residues, lower dielectric constant of the cured product, and reduced thermal expansion coefficient.
  • L1 and L2 each independently represent a divalent group that is not conjugated with the benzene ring to which they are bonded, or a single bond
  • *1 to *4 each represent a bonding site with the carbonyl group described in formula (1-1), and the hydrogen atoms in these structures may be substituted with a substituent.
  • L 1 and L 2 each independently represent —CH 2 — or —O—.
  • the hydrogen atoms in formulas (2a) to (2g) may be substituted with a substituent, and examples of the substituent include an alkyl group, a halogenated alkyl group, etc., and are preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or a trifluoromethyl group.
  • a halogenated alkyl group refers to a group in which at least one hydrogen atom of an alkyl group is substituted with a halogen atom.
  • the halogen atom is preferably F or Cl, and more preferably F.
  • n1 represents an integer of 1 or more.
  • n1 is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, even more preferably 1 or 2, and particularly preferably 1.
  • X 1 is a group containing a structure in which two or more hydrogen atoms have been removed from a structure represented by formula (V-4), X 1 is preferably a group represented by the following formula (V-4-1).
  • * represents the bonding site of X1 in formula (1-1) with the four carbonyl groups
  • n1 represents an integer of 1 to 5.
  • the hydrogen atoms in formula (V-4-1) may be further substituted with a known substituent such as a hydrocarbon group. Examples of known substituents include an alkyl group, a halogenated alkyl group, and a halogen atom. However, it is also preferable that none of the hydrogen atoms in the structure represented by (V-4-1) are substituted.
  • X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-6)
  • X2 is preferably a group represented by the following formula (V-6-1).
  • * represents the bonding site to the four carbonyl groups to which X1 in formula (1-1) is bonded.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-7)
  • X2 is preferably a group represented by the following formula (V-7-1).
  • * represents the bonding site to the four carbonyl groups to which X1 in formula (1-1) is bonded.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-9)
  • X2 is preferably a group represented by the following formula (V-9-1).
  • * represents the bonding site to the four carbonyl groups to which X1 in formula (1-1) is bonded.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-10)
  • X2 is preferably a group represented by the following formula (V-10-1).
  • * represents the bonding site to the four carbonyl groups to which X1 in formula (1-1) is bonded.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • X1 further contains a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1), (V-2), (V-3), (V-5), and (V-8), because the improved transmittance to ultraviolet light provides effects such as making the pattern of the cured product less likely to become tapered and providing a wide tolerance for the exposure dose.
  • a repeating unit represented by formula (1-1), in which X1 contains a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1), (V-2), (V-3), (V-5), and (V-8), is also referred to as a repeating unit B-1.
  • 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 1 and X5 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
  • R and 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 even more preferably a methyl group or a trifluoromethyl group.
  • a halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom has been substituted with a halogen atom.
  • the halogen atom is preferably F or Cl, and more preferably F.
  • 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.
  • R and X5 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 even more preferably a methyl group or a trifluoromethyl group.
  • a halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom has been substituted with a halogen atom.
  • the halogen atom is preferably F or Cl, and more preferably F.
  • X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-1)
  • X2 is preferably a group represented by the following formula (V-1-1).
  • * represents the bonding site to which X2 in formula (1-1) bonds with the four carbonyl groups
  • 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 known substituents such as hydrocarbon groups.
  • X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-2)
  • X2 is preferably a group represented by formula (V-2-1) below.
  • a bond crossing a side of a ring structure means that any of the hydrogen atoms in the ring structure is substituted.
  • L X1 represents a single bond or -O-
  • * represents the bonding site with the four carbonyl groups to which X1 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 hydrocarbon groups.
  • X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-3)
  • X1 is preferably a group represented by formula (V-3-1) or formula (V-3-2) below, and from the viewpoint of reducing the dielectric constant of the cured product, a group represented by formula (V-3-2) is preferred.
  • * represents the bonding site to the four carbonyl groups to which X2 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 hydrocarbon groups.
  • X1 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-5)
  • X2 is preferably a group represented by the following formula (V-5-1).
  • * represents the bonding site to which X2 in formula (1-1) bonds with the four carbonyl groups.
  • the hydrogen atoms in formula (V-5-1) may be further substituted with a known substituent such as a hydrocarbon group. Examples of known substituents include an alkyl group, a halogenated alkyl group, and a halogen atom. However, it is also preferable that none of the hydrogen atoms in the structure represented by formula (V-5-1) are substituted.
  • X2 is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (V-8)
  • X2 is preferably a group represented by the following formula (V-8-1).
  • * represents the bonding site to the four carbonyl groups to which X2 in formula (1-1) is bonded.
  • R X5 The definition and preferred embodiments of R X5 are as described above.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • X 1 may be a tetracarboxylic acid residue remaining after removal of the anhydride groups from the tetracarboxylic acid dianhydride described in paragraphs 0055 to 0057 of JP-A No. 2023-003421.
  • X1 does not contain an imide bond in the structure. Furthermore, it is preferable that X1 does not contain a urethane bond, a urea bond, or an amide bond in the structure.
  • R N is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom.
  • X 1 does not contain an imide bond, a urethane bond, a urea bond, or an amide bond, and it is more preferable that X 1 does not contain an imide bond, a urethane bond, a urea bond, an amide bond, or an ester bond.
  • Y 1 preferably has 4 or more carbon atoms, more preferably 4 to 50 carbon atoms, and even more preferably 6 to 40 carbon atoms.
  • Y1 preferably has a structure containing the structures represented by formulas (C-1) to (C-5).
  • each R 1 independently represents a hydrogen atom or a monovalent organic group
  • n1 represents an integer of 0 to 3
  • n2 represents an integer of 0 to 3
  • * represents a bonding site to another structure.
  • each R 1 independently represents a hydrogen atom or a monovalent organic group, n1 represents an integer of 0 to 3, n2 represents an integer of 0 to 3, each R 2 independently represents an alkyl group or a fluoroalkyl group, and * represents a bonding site to another structure.
  • each R 1 independently represents a hydrogen atom or a monovalent organic group, n1 represents an integer of 0 to 3, and * represents a bonding site to another structure.
  • each R 1 independently represents a hydrogen atom or a monovalent organic group, n1 represents an integer of 0 to 3, and * represents a bonding site to another structure.
  • each R 1 independently represents a hydrogen atom or a monovalent organic group
  • n1 represents an integer of 0 to 3
  • n2 represents an integer of 0 to 3
  • each R 2 independently represents an alkyl group or a fluoroalkyl group
  • * represents a bonding site to another structure.
  • each R 1 is 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 even more preferably a methyl group or a trifluoromethyl group.
  • the halogen atom in the halogenated alkyl group is preferably F or Cl, and more preferably F.
  • n1 is preferably 0 or 1, and more preferably 1.
  • n2 is preferably 0 or 1, and more preferably 1.
  • R 1 , n1 and n2 are the same as the preferred embodiments of R 1 , n1 and n2 in formula (C-1), respectively.
  • An alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms is preferred, and a methyl group or a trifluoromethyl group is more preferred.
  • R 1 and n1 are the same as the preferred embodiments of R 1 and n1 in formula (C-1).
  • R 1 and n1 are the same as preferred embodiments of R 1 and n1 in formula (C-1).
  • R 1 , R 2 , n1 and n2 are the same as preferred embodiments of R 1 , R 2 , n1 and n2 in formula (C-2), respectively.
  • each * represents a bonding site with a nitrogen atom.
  • Y 1 may be a group described in paragraphs 0042 to 0053 of JP-A No. 2023-003421. It is also preferred that Y1 does not contain an imide bond in the 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, Y1 preferably does not contain an imide bond, a urethane bond, a urea bond, or an amide bond, and more preferably does not contain an imide bond, a urethane bond, a urea bond, an amide bond, or an ester bond.
  • -A2- A 2 in formula (1-2) represents an oxygen atom or —NR z —, and is preferably an oxygen atom.
  • Rz represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom.
  • R2 represents 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.
  • R2 contains a polymerizable group.
  • the polymerizable group is a group capable of undergoing a crosslinking reaction by the action of heat, radicals, etc., and a radically polymerizable group is preferable.
  • the polymerizable group examples include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group.
  • the radically polymerizable group contained in the specific resin is 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, 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 to 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.
  • 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 in the substituent when the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, still 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 to 20, more preferably 2 to 10, and even more preferably 2 to 6.
  • a polyethyleneoxy group, a polypropyleneoxy group, a polytrimethyleneoxy group, a polytetramethyleneoxy group, or a group in which a plurality of ethyleneoxy groups and a plurality of propyleneoxy groups are bonded is preferred, a polyethyleneoxy group or a polypropyleneoxy group is more preferred, and a polyethyleneoxy group is even more preferred.
  • 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 embodiments of the number of repetitions of the ethyleneoxy groups etc. in these groups are as described above.
  • the specific resin when R2 is a hydrogen atom, the specific resin may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond.
  • a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.
  • R2 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.
  • a repeating unit represented by formula (1-2) in which X2 contains a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1), (V-2), (V-3), (V-5), and (V-8) above is also referred to as a repeating unit B-2.
  • A3 and R3 in formula (1-3) are the same as preferred embodiments of A2 and R2 in formula (1-2). However, the description of "formula (1-2)" in the explanation of A2 and R2 should be read as “formula (1-3)”.
  • Preferred embodiments of X3 and Y3 in formula (1-3) are the same as preferred embodiments of X1 and Y1 in formula (1-1). However, the description of "formula (1-1)" in the explanation of X1 and Y1 should be read as “formula (1-3)".
  • a repeating unit represented by formula (1-3) in which X3 contains a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1), (V-2), (V-3), (V-5), and (V-8) above is also referred to as repeating unit B-3.
  • a 41 and A 42 in formula (1-4) are the same as the preferred embodiments of A 2 in formula (1-2).
  • Preferred embodiments of R 41 and R 42 in formula (1-4) are the same as the preferred embodiments of R 2 in formula (1-2), except that the description of "formula (1-2)" in the explanation of R 2 should be read as "formula (1-4).”
  • Preferred embodiments of X4 and Y4 in formula (1-4) are the same as preferred embodiments of X1 and Y1 in formula (1-1).
  • a repeating unit represented by formula (1-4) in which X4 contains a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1), (V-2), (V-3), (V-5), and (V-8) above is also referred to as a repeating unit B-2.
  • the specific resin preferably contains at least one repeating unit selected from the group consisting of repeating unit A-1, repeating unit A-2, repeating unit A-3, and repeating unit A-4.
  • the specific resin contains a repeating unit having a structure represented by formula (2a) or formula (2d) as repeating unit A-1, repeating unit A-2, repeating unit A-3, or repeating unit A-4.
  • the repeating unit having a structure represented by formula (2a) or formula (2d) preferably accounts for 5 to 80 mol %, and more preferably 5 to 50 mol %, of the total molar amount of repeating units represented by formula (1-1), formula (1-2), formula (1-3), or formula (1-4) in the specific resin.
  • the specific resin preferably contains at least one repeating unit selected from the group consisting of repeating units B-1, B-2, B-3, and B-4.
  • the specific resin preferably contains at least one repeating unit selected from the group consisting of repeating units A-1, A-2, A-3, and A-4, and at least one repeating unit selected from the group consisting of repeating units B-1, B-2, B-3, and B-4.
  • the specific resin preferably contains at least one repeating unit selected from the group consisting of repeating units represented by the above formula (1-2) in which R 2 is a monovalent organic group having an ethylenically unsaturated bond, repeating units represented by the above formula (1-3) in which R 3 is a monovalent organic group having an ethylenically unsaturated bond, and repeating units represented by the above formula (1-4) in which at least one of R 41 and R 42 is a monovalent organic group having an ethylenically unsaturated bond.
  • the specific resin preferably contains at least one repeating unit selected from the group consisting of repeating units represented by formula (1-1), in which Y1 contains a structure represented by any one of formulas (C-1) to (C-5), repeating units represented by formula (1-2), in which Y2 contains a structure represented by any one of formulas (C-1) to (C-5), repeating units represented by formula (1-3), in which Y3 contains a structure represented by any one of formulas (C-1) to (C-5), and repeating units represented by formula (1-4), in which Y4 contains a structure represented by any one of formulas (C-1) to (C-5).
  • the repeating unit in which Y1 is a structure containing a structure represented by formula (C-1) to formula (C-5) is preferably a repeating unit corresponding to the above-mentioned repeating unit A-1 or repeating unit B-1.
  • the repeating unit in which Y2 is a structure containing a structure represented by formula (C-1) to formula (C-5) is preferably a repeating unit corresponding to the above-mentioned repeating unit A-2 or repeating unit B-2.
  • the repeating unit in which Y3 is a structure containing a structure represented by formula (C-1) to formula (C-5) is preferably a repeating unit corresponding to the above-mentioned repeating unit A-3 or repeating unit B-3.
  • the repeating unit in which Y4 is a structure containing a structure represented by formula (C-1) to formula (C-5) is preferably a repeating unit corresponding to the above-mentioned repeating unit A-4 or repeating unit B-4.
  • the total content of repeating units represented by formula (1-1), formula (1-2), formula (1-3), or formula (1-4) is 50 mol% or more of all repeating units.
  • the total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%.
  • the upper limit of the total content is not particularly limited, and all repeating units in the specific resin except for the terminal repeating units may be repeating units represented by formula (1-1), formula (1-2), formula (1-3), or formula (1-4).
  • Another embodiment of the specific resin of the present invention is one in which the total content of repeating units represented by formula (1-1) or formula (1-4) is 50 mol% or more of all repeating units.
  • This total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%.
  • all repeating units in the specific resin except for the terminal repeating units may be repeating units represented by formula (1-1) or formula (1-4).
  • the specific resin in the present invention has an imidization rate of 40 to 85%, not all repeating units are repeating units represented by formula (1-1) and not all repeating units are repeating units represented by formula (1-4).
  • the total content of repeating units corresponding to repeating unit A-1, repeating unit A-2, repeating unit A-3, or repeating unit A-4 is preferably 20 mol% or more of all repeating units.
  • This total content is more preferably 30 mol% or more, even more preferably 40 mol% or more, and particularly preferably 50 mol% or more.
  • All repeating units in the specific resin except for the terminal repeating units may be repeating unit A.
  • the total content of repeating units corresponding to repeating unit B-1, repeating unit B-2, repeating unit B-3, or repeating unit B-4 is preferably 0 to 80 mol% of all repeating units. This total content is more preferably 5 to 70 mol%, even more preferably 10 to 60 mol%, and particularly preferably 15 to 50 mol%.
  • the total content of repeating unit A and repeating unit B in the specific resin of the present invention is preferably 50 mol% or more of all repeating units.
  • the above total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%.
  • all repeating units in the specific resin excluding the terminal repeating units may be repeating unit A or repeating unit B.
  • the weight average molecular weight (Mw) of the specific resin is preferably 120,000 or less, more preferably 70,000 or less, and even more preferably 60,000 or less.
  • the Mw is preferably 5,000 or more, more preferably 10,000 or more, and even more preferably 15,000 or more.
  • the number average molecular weight (Mn) of the specific resin is preferably 40,000 or less, more preferably 30,000 or less, and even more preferably 25,000 or less.
  • the Mn is preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 4,000 or more.
  • the molecular weight dispersity of the specific 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 specific resin 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 molecular weight dispersity is a value calculated by dividing the weight average molecular weight by the number average molecular weight.
  • the weight-average molecular weight, number-average molecular weight, and dispersity of at least one specific resin are within the above-mentioned ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and dispersity calculated by treating the multiple specific resins as one resin are each within the above-mentioned ranges.
  • the specific resin can be synthesized by known methods for synthesizing polyimides and polyimide precursors.
  • the specific resin can be synthesized by the methods described in (1) to (3) below so that the imidization rate is 40 to 85%.
  • (1) A method for producing a conventional polyimide precursor using a polyimide oligomer having an amino group at its terminal as a diamine component.
  • (2) A method for imidizing a polyimide precursor produced by a conventional method by thermal imidization, chemical imidization, etc. so that the imidization rate is 40 to 85%.
  • (3) A method for synthesizing a polyamic acid, esterifying a portion of the carboxylic acid, and imidizing the unesterified carboxylic acid portion by thermal imidization, chemical imidization, etc.
  • the above (1) comprises a step of synthesizing a polyimide oligomer having an amino group at its terminal; It is preferable to include a step of reacting the polyimide oligomer with a compound represented by the following formula (A-1).
  • a 41 and A 42 each independently represent —O— or —NR Z —
  • R Z represents a hydrogen atom or a monovalent organic group
  • R 41 and R 42 each independently represent a hydrogen atom or a monovalent organic group
  • X 4 represents a tetravalent organic group.
  • the step of synthesizing a polyimide oligomer having an amino group at its terminal is not particularly limited, and any known method can be used.
  • suitable methods include reacting a tetracarboxylic dianhydride with a diamine at low temperature, reacting a tetracarboxylic dianhydride with a diamine at low temperature to obtain a polyamic acid, and then esterifying the polyamic acid using a condensing agent or alkylating agent, obtaining a diester from a tetracarboxylic dianhydride with an alcohol and then reacting the diamine with a condensing agent, and obtaining a diester from a tetracarboxylic dianhydride with an alcohol, then halogenating the remaining dicarboxylic acid with a halogenating agent and reacting the diamine with the polyimide precursor.
  • the polyimide precursor is then imidized by a known thermal or chemical imidization method to synthesize a polyimide oligomer.
  • Step 2 is carried out in an organic solvent containing 400 ppm or more of water.
  • the polyimide may be prepared in a one-step process from a tetracarboxylic dianhydride and a diisocyanate.
  • methods such as using an excess amount of diamine during synthesis or using a compound having an amino group as an end-capping agent can be mentioned.
  • the polyimide oligomer may be a resin having a repeating unit represented by the above formula (1-1) and having an amino group at the terminal.
  • the compound represented by formula (A-1) can be obtained, for example, by preparing a diester from a tetracarboxylic dianhydride and an alcohol, and then subjecting the remaining dicarboxylic acid to acid halogenation using a halogenating agent.
  • a halogenating agent include thionyl chloride, oxalyl chloride, and phosphorus oxychloride.
  • the solvent used in the esterification reaction and the acid halogenation reaction is preferably an organic solvent. One or more organic solvents may be used.
  • the organic solvent can be appropriately determined depending on the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and ⁇ -butyrolactone.
  • the acid value of the resulting specific resin can be adjusted by the amount of water added to the reaction system. For example, by adding water to the reaction solution of the esterification reaction to hydrolyze some of the acid anhydrides, or by adding water at the start or end of the acid halogenation reaction to convert some of the acid halogenated sites into carboxy groups, the acid value can be adjusted to 11.2 mg KOH/g or more and 25.3 mg KOH/g or less.
  • water can be added to the reaction solution of the esterification reaction so that the amount at the start of the esterification reaction is preferably 400 ppm or more, more preferably 500 ppm or more, even more preferably 600 ppm or more, particularly preferably 700 ppm or more, and preferably 5000 ppm or less, more preferably 4000 ppm or less, even more preferably 3000 ppm or less, and particularly preferably 2000 ppm or less.
  • the acid value of the specific resin can be made relatively low (for example, 0.05 KOH/g or more and less than 11.2 mg KOH/g) by using a carbodiimide-based condensing agent as the condensing agent.
  • 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. Also, 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 specific resin or two or more specific resins. When two or more specific resins are contained, the total amount is preferably within the above range.
  • the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as "another resin").
  • other resins include phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing a siloxane structure, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, and polyester resins.
  • phenolic resins polyamides
  • epoxy resins polysiloxanes
  • resins containing a siloxane structure resins containing a siloxane structure
  • (meth)acrylic resins eth)acrylamide resins
  • urethane resins urethane resins
  • butyral resins styryl resins
  • polyether resins e.g., polyether resins
  • polyester resins e.g., polyether resins,
  • a (meth)acrylic resin having a weight average molecular weight of 20,000 or less and a high polymerizable group value for example, the molar amount of polymerizable groups contained in 1 g of resin is 1 ⁇ 10 -3 mol/g or more
  • the resin composition it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product), etc.
  • the content of the other resins is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, and even more preferably 1 mass% or more, based on the total solid content of the resin composition.
  • 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, still 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 it is also preferable that it is 0.01% by mass or less.
  • 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 in the above range.
  • the resin composition of the present invention preferably does not contain a polymerizable compound or contains a polymerizable compound in an amount of less than 15% by mass based on the total solid content, more preferably does not contain a polymerizable compound or contains a polymerizable compound in an amount of 10% by mass or less based on the total solid content, and even more preferably does not contain a polymerizable compound or contains a polymerizable compound in an amount of 5% by mass or less based on the total solid content.
  • the polymerizable compound in an amount of 1 part by mass or more per 100 parts by mass of the specific resin.
  • the content is preferably 2 parts by mass or more, and more preferably 3 parts by mass or more.
  • the content is preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.
  • polymerizable compounds examples include polymerizable compounds having radical polymerizable groups (radical crosslinking agents) and other crosslinking agents.
  • 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.
  • the resin composition of the present invention preferably contains a compound containing a (meth)acryloyl group as the polymerizable compound.
  • 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, and may also have three or more ethylenically unsaturated bonds.
  • the compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds.
  • the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the 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.), their esters, and amides.
  • esters of unsaturated carboxylic acids and polyhydric alcohol compounds are esters of unsaturated carboxylic acids and polyamine compounds.
  • addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxy groups, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids.
  • 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.
  • Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical 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
  • radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethyleneoxy chains, SR-209, 231, and 239, difunctional methacrylates with four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, and TPA-330, a trifunctional acrylate with three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers.
  • SR-494 a tetrafunctional acrylate with four ethyleneoxy chains
  • SR-209, 231, and 239 difunctional methacrylates with four ethyleneoxy chains
  • 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.), and urethane oligomers.
  • esters examples include UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corporation).
  • Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, as well as urethane compounds with an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418.
  • Compounds with an amino structure or sulfide structure in the molecule such as those described in JP-A Nos. 63-277653, 63-260909, and JP-A No. 01-105238, can also be used as radical crosslinking agents.
  • the acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mgKOH/g, and more preferably 1 to 100 mgKOH/g.
  • the acid value of the radical crosslinking agent is within the above range, it provides excellent handling during manufacturing and developability. It also provides good polymerizability.
  • the acid value is measured in accordance with the description of JIS K 0070:1992.
  • the radical crosslinking agent is preferably a radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond (hereinafter also referred to as "crosslinking agent U").
  • the total number of urea bonds and urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
  • the number of urea bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
  • the number of urethane bonds in the crosslinking agent U is 1 or more, preferably 1 to 10, more preferably 1 to 4, and even more preferably 1 or 2.
  • the radical polymerizable group in the crosslinking agent U is not particularly limited, and examples thereof include a vinyl group, an allyl group, a (meth)acryloyl group, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, and a maleimide group. Of these, a (meth)acryloxy group, a (meth)acrylamide group, a vinylphenyl group, or a maleimide group is preferred, and a (meth)acryloxy group is more preferred.
  • the crosslinking agent U has two or more radically polymerizable groups, the structures of the radically polymerizable groups may be the same or different.
  • the crosslinking agent U preferably has a structure represented by the following formula (U-1):
  • R U1 is a hydrogen atom or a monovalent organic group
  • A is —O— or —NR N —
  • R N is a hydrogen atom or a monovalent organic group
  • Z U1 is an m-valent organic group
  • Z U2 is an (n+1)-valent organic group
  • X is a radical polymerizable group
  • n is an integer of 1 or more
  • m is an integer of 1 or more.
  • R U1 is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom.
  • R 1 N is preferably a hydrogen atom, an alkyl group or an aromatic hydrocarbon group, more preferably a hydrogen atom.
  • Z U1 is preferably a hydrocarbon group, —O—, —C( ⁇ O)—, —S—, —S( ⁇ O) 2 —, —NR N —, or a group in which two or more of these are bonded together, and more preferably a hydrocarbon group or a group in which a hydrocarbon group is bonded to at least one group selected from the group consisting of —O—, —C( ⁇ O)—, —S—, —S( ⁇ O) 2 —, and —NR N —.
  • the hydrocarbon group is preferably a hydrocarbon group having 20 or less carbon atoms, more preferably a hydrocarbon group having 18 or less carbon atoms, and even more preferably a hydrocarbon group having 16 or less carbon atoms.
  • Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination thereof.
  • R N represents a hydrogen atom or a monovalent organic group, and is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and even more preferably a hydrogen atom or a methyl group.
  • Z U2 is preferably a hydrocarbon group, —O—, —C( ⁇ O)—, —S—, —S( ⁇ O) 2 —, —NR N —, or a group in which two or more of these are bonded together, and more preferably a hydrocarbon group or a group in which a hydrocarbon group is bonded to at least one group selected from the group consisting of —O—, —C( ⁇ O)—, —S—, —S( ⁇ O) 2 —, and —NR N —.
  • Examples of the hydrocarbon group include the same groups as those listed for ZU1 , and preferred embodiments are also the same.
  • the crosslinking agent U has at least one of a hydroxy group, an alkyleneoxy group, an amide group, and a cyano group.
  • the hydroxy group may be either an alcoholic hydroxy group or a phenolic hydroxy group, but is preferably an alcoholic hydroxy group.
  • the alkyleneoxy group is preferably an alkyleneoxy group having 2 to 20 carbon atoms, more preferably an alkyleneoxy group having 2 to 10 carbon atoms, even more preferably an alkyleneoxy group having 2 to 4 carbon atoms, still more preferably an ethylene group or a propylene group, and particularly preferably an ethylene group.
  • the alkyleneoxy group may be contained as a polyalkyleneoxy group in the crosslinking agent U.
  • the number of repeating alkyleneoxy groups is preferably 2 to 10, and more preferably 2 to 6.
  • R represents a hydrogen atom or a monovalent substituent, preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom, an alkyl group, or an aromatic hydrocarbon group.
  • the crosslinking agent U may have, in the molecule, two or more structures selected from the group consisting of a hydroxy group, an alkyleneoxy group (however, in the case where a polyalkyleneoxy group is constituted, a polyalkyleneoxy group), an amide group, and a cyano group. However, an embodiment in which only one structure is present in the molecule is also preferred.
  • the hydroxy group, alkyleneoxy group, amide group, and cyano group may be present at any position in the crosslinking agent U.
  • the crosslinking agent U is such that at least one selected from the group consisting of the hydroxy group, alkyleneoxy group, amide group, and cyano group is linked to at least one radically polymerizable group contained in the crosslinking agent U via a linking group containing a urea bond or a urethane bond (hereinafter, also referred to as "linking group L2-1").
  • crosslinking agent U contains an alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) and has the linking group L2-1 or the linking group L2-2
  • the structure bonded to the side of the alkyleneoxy group (however, when it constitutes a polyalkyleneoxy group, it is a polyalkyleneoxy group) opposite to the linking group L2-1 or the linking group L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof.
  • crosslinking agent U contains an amide group and has the linking group L2-1 or L2-2
  • the structure bonded to the side of the amide group opposite to the linking group L2-1 or L2-2 is not particularly limited, but is preferably a hydrocarbon group, a radically polymerizable group, or a group represented by a combination thereof.
  • the hydrocarbon group is preferably a hydrocarbon group having 20 or fewer carbon atoms, more preferably a hydrocarbon group having 18 or fewer carbon atoms, and even more preferably a hydrocarbon group having 16 or fewer carbon atoms.
  • Examples of the hydrocarbon group include saturated aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups represented by a combination thereof.
  • Preferred aspects of the radically polymerizable group are the same as those of the radically polymerizable group in crosslinking agent U described above.
  • the carbon atom side of the amide group may be bonded to the linking group L2-1 or L2-2, or the nitrogen atom side of the amide group may be bonded to the linking group L2-1 or L2-2.
  • the crosslinking agent U has a hydroxy group.
  • the "number of atoms (linking chain length) between a urea bond or a urethane bond and a polymerizable group” refers to the chain of atoms on the path connecting the two atoms or groups of atoms to be linked, which links these objects with the shortest length (minimum number of atoms).
  • the number of atoms (linking chain length) between the urea bond and the radical polymerizable group (methacryloyloxy group) is 2.
  • the molecular weight of the crosslinking agent U is preferably 100 to 2,000, more preferably 150 to 1,500, and even more preferably 200 to 900.
  • Examples of usable surfactants include xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, EO-modified isocyanuric acid dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having a urethane bond.
  • EO ethylene oxide
  • PO propylene oxide
  • PO propylene oxide
  • PO propylene oxide
  • adduct dimethacrylate of bisphenol A 2-hydroxy-3-acryloyloxyprop
  • PEG200 diacrylate refers to polyethylene glycol diacrylate with 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.
  • Examples of the monofunctional radical crosslinking agent include (meth)acrylic acid derivatives such as n-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, butoxyethyl(meth)acrylate, carbitol(meth)acrylate, cyclohexyl(meth)acrylate, benzyl(meth)acrylate, phenoxyethyl(meth)acrylate, N-methylol(meth)acrylamide, glycidyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether.
  • (meth)acrylic acid derivatives such as n-butyl(meth)acrylate, 2-ethylhex
  • 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 solids 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.
  • a single radical crosslinking agent may be used, or two or more may be used in combination. When two or more types are used in combination, it is preferable that the total amount be within the above range.
  • the content of the other crosslinking agent is preferably 0.1 to 30 mass% of the total solids content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and particularly preferably 1.0 to 10 mass%. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total amount is preferably within the above range.
  • 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 can be appropriately selected from known photoradical polymerization initiators.
  • a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible range is preferred.
  • 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 cm 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 preferably measured using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.
  • any known compound can be used as the photoradical polymerization initiator.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, ⁇ -aminoketone compounds such as aminoacetophenone, ⁇ -hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, and iron arene complexes.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihal
  • 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. is also suitable.
  • ⁇ -hydroxyketone initiators examples include Omnirad 184, Omnirad 1173, Omnirad 2959, and 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).
  • ⁇ -aminoketone initiators examples include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (all manufactured by IGM Resins B.V.), and IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF).
  • a more preferred example of a photoradical polymerization initiator is an oxime compound.
  • an oxime compound By using an oxime compound, it is possible to more effectively improve the exposure latitude.
  • Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.
  • oxime compounds include compounds described in JP 2001-233842 A, compounds described in JP 2000-080068 A, compounds described in JP 2006-342166 A, compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), and 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.
  • 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 ChemiX Co., Ltd.), and SpeedCure PDO (SARTOMER Also, an oxime compound having the following structure can be used.
  • 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 replaced with 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 in which a substituent having a hydroxy group is bonded to a carbazole skeleton, as described in paragraphs 0208 to 0210 of WO 2021/020359, the contents of which are incorporated herein by reference.
  • the content thereof is preferably 0.1 to 30 mass% relative to 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, it is preferable that the total amount is in the above range.
  • the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.
  • the content of the sensitizer is preferably 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, and even more preferably 0.5 to 10 mass%, based on the total solids content of the resin composition.
  • One type of sensitizer may be used alone, or two or more types may be used in combination.
  • the resin composition of the present invention may contain a chain transfer agent.
  • Chain transfer agents are defined, for example, in the Third Edition of the Polymer Dictionary (edited by the Society of Polymer Science, 2005), pages 683-684.
  • Examples of chain transfer agents include compounds having -S-S-, -SO 2 -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These donate hydrogen to low-activity radicals to generate radicals, or can generate radicals by being oxidized and then deprotonated. Thiol compounds are particularly preferred.
  • chain transfer agent may be the compound described in paragraphs 0152-0153 of WO 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 solids content of the resin composition. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, the total amount is preferably within the above range.
  • the resin composition of the present invention contains two or more types of polymerization initiators.
  • the resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described below, or contains the above-mentioned photoradical polymerization initiator and the above-mentioned photoacid generator.
  • the content of the thermal polymerization initiator is preferably 20 to 70 mass %, more preferably 30 to 60 mass %, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.
  • 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 the polymerization reaction of a polymerizable compound. Addition of the thermal radical polymerization initiator can also promote the polymerization reaction of the resin and the polymerizable compound, thereby further improving solvent resistance.
  • 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.
  • a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass% of the total solids content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%.
  • the resin composition may contain only one type of thermal polymerization initiator, or two or more types. If two or more types of thermal polymerization initiators are included, the total amount is preferably 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, resulting in good performance as an interlayer insulating film for a rewiring layer included in, for example, a semiconductor package.
  • 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 known base generators can be used, such as 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 non-ionic base generators include the compounds described in paragraphs 0249 to 0275 of WO 2022/145355, the disclosures of which are incorporated herein by reference.
  • 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 an amine in which the amino group is protected with a t-butoxycarbonyl group.
  • 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, and 2-amino-1,3-propanediol.
  • the resin composition of the present invention contains a solvent.
  • Any known solvent can be used as the solvent.
  • the solvent is preferably an organic solvent.
  • examples of the organic solvent include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.
  • Esters include, 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, alkyl alkyloxyacetates (for example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (for example, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionates (for example, methyl 3-alkyloxy
  • 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.
  • Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.
  • a suitable example of a sulfoxide is dimethyl sulfoxide.
  • 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.
  • Preferred 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, methyl amyl alcohol, and diacetone alcohol.
  • the solvent content 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 solvent content may be adjusted depending on the desired thickness of the coating film and the application method. When two or more solvents are used, 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.
  • metal adhesion improvers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, ⁇ -ketoester compounds, and amino compounds.
  • silane coupling agent examples include the compounds described in paragraph 0316 of WO 2021/112189 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573 A, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of JP 2011-128358 A. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group. Furthermore, the following R represents a structure derived from a blocking agent in a blocked isocyanate group.
  • Blocking agents may be selected depending on the desorption temperature, and examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds.
  • caprolactam is preferred from the perspective of achieving a desorption temperature of 160 to 180°C.
  • 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.
  • 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 hydroxy group or an alkoxy group
  • n represents an integer of 0 to 2.
  • R S1 preferably has a structure containing a polymerizable group.
  • Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group.
  • 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.
  • 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.
  • the structures of the repeating units represented by formula (S-1) contained in the oligomer-type compound may be the same.
  • n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two.
  • commercially available products can be used, and examples of commercially available products include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • 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 ensuring that the content is above the above lower limit, the adhesion between the pattern and the metal layer will be good, and by ensuring that the content is below 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 amount 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.
  • Migration inhibitors are not particularly limited, but 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, 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,
  • 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 preferred.
  • 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, 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%, relative to the total solids content of the resin composition.
  • the migration inhibitor may be one type or two or more types. If two or more types of migration inhibitors are used, it is preferable that the total amount is within the above range.
  • the resin composition of the present invention also preferably contains a compound (light absorber) that reduces the absorbance of light at the exposure wavelength upon exposure.
  • a compound light absorber
  • Examples of the light absorber include the compounds described in paragraphs 0159 to 0183 of WO 2022/202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of these compounds are incorporated herein by reference.
  • 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 compounds 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, and 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]non-2-ene-N,N-dioxide.
  • the contents of this document are incorporated herein by reference.
  • the content of the polymerization inhibitor is preferably 0.01 to 20 mass%, more preferably 0.02 to 15 mass%, and even more preferably 0.05 to 10 mass%, based on the total solids content of the resin composition.
  • the total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
  • surfactant various surfactants can be used, such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc.
  • the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
  • the liquid properties (particularly fluidity) when the coating liquid composition is prepared are further improved, and the uniformity of the coating thickness and liquid saving can be further improved.
  • the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and the coatability of the surface to be coated. This makes it possible to more effectively form a uniform film with minimal thickness unevenness.
  • fluorosurfactants examples include compounds described in paragraph 0328 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • a fluorine-based surfactant a fluorine-containing polymer compound containing a repeating unit derived from a (meth)acrylate compound having a fluorine atom and a repeating unit derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy groups or propyleneoxy groups) can also be preferably used, and examples thereof include the following compounds.
  • the weight average molecular weight of the compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000.
  • the fluorosurfactant may also be a fluorine-containing polymer having an ethylenically unsaturated group in the side chain. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP 2010-164965 A, the contents of which are incorporated herein by reference.
  • Commercially available products include Megafac RS-101, RS-102, and RS-718K manufactured by DIC Corporation.
  • the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorosurfactants with a fluorine content within this range are effective in terms of uniformity of the coating film thickness and liquid saving, and also have good solubility in the composition.
  • silicone surfactants examples include the compounds described in paragraphs 0329 to 0334 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • the surfactant may be used alone or in combination of two or more.
  • the content of the surfactant is preferably from 0.001 to 2.0% by mass, more preferably from 0.005 to 1.0% by mass, based on the total solid content of the composition.
  • inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.
  • the average particle size of the inorganic particles is preferably from 0.01 to 2.0 ⁇ m, more preferably from 0.02 to 1.5 ⁇ m, even more preferably from 0.03 to 1.0 ⁇ m, and particularly preferably from 0.04 to 0.5 ⁇ m.
  • the above-mentioned average particle size of the inorganic particles is the primary particle size and also the volume average particle size, which can be measured by a dynamic light scattering method using, for example, a Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). When the above measurement is difficult, the measurement can also be performed by a centrifugal sedimentation light transmission method, an X-ray transmission method, or a laser diffraction/scattering method.
  • 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 as I) to VII):
  • I) Titanium chelate compounds Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability to the resin composition 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), and titanium diisopropoxide bis(ethylacetoacetate).
  • 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 ⁇ ], etc.
  • Titanocene compounds for example, pentamethylcyclopentadienyltitanium trimethoxide, bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.
  • 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, etc.
  • the organic titanium compound be 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-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium are particularly preferred.
  • T-1 a compound represented by the following formula (T-1) as the organotitanium compound or in place of the organotitanium compound.
  • M represents titanium, zirconium, or hafnium
  • l1 represents an integer of 0 to 2
  • l2 represents 0 or 1
  • l1 + l2 ⁇ 2 represents an integer of 0 to 2
  • m represents an integer of 0 to 4
  • n represents an integer of 0 to 2
  • R 11 represents independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group
  • R 12 represents a substituted or unsubstituted hydrocarbon group
  • each R 2 represents independently a group containing a structure represented by formula (T-2) below
  • each R 3 represents independently a group containing a structure represented by formula (T-2)
  • R 11 is preferably a substituted or unsubstituted cyclopentadienyl ligand.
  • the cyclopentadienyl group, alkoxy group and phenoxy group in R 11 may be substituted, but an embodiment in which they are unsubstituted is also one of the preferred embodiments of the present invention.
  • R 12 is preferably a hydrocarbon group having 1 to 20 carbon atoms, 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, but a saturated aliphatic hydrocarbon group is preferred.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group.
  • 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 contained, 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 contained, the structures of the two or more R 3s may be the same or different.
  • Specific examples of compounds represented by formula (T-1) include, but are not limited to, compounds I-5 to I-8 in the examples.
  • 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 is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 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.
  • the viscosity of the resin composition of the present invention can be adjusted by the solids concentration of the resin composition. From the viewpoint of coating film thickness, it is preferably 1,000 mm 2 /s to 12,000 mm 2 /s, more preferably 2,000 mm 2 /s to 10,000 mm 2 /s, and even more preferably 2,500 mm 2 /s to 8,000 mm 2 /s. Within the above range, it is easy to obtain a highly uniform coating film.
  • methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with low metal content as the raw materials for constituting the resin composition of the present invention, filtering the raw materials for constituting the resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.
  • the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass from the viewpoint of wiring corrosion.
  • those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
  • Examples of 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.
  • any conventional container known in the art can be used as a container for storing the resin composition of the present invention.
  • a container for storing the resin composition of the present invention For the purpose of preventing impurities from being mixed into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is made up of six layers of six types of resin, or a bottle with a seven-layer structure made up of six types of resin. Examples of such containers include 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, with the heating temperature being more preferably 120°C to 400°C, even more 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, rod, sphere, or pellet.
  • 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 via holes for electrical conduction, adjusting impedance, capacitance, or internal stress, or imparting heat dissipation functionality.
  • 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 carried out by 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 10 to 30°C, more preferably 15 to 25°C.
  • Filtration using a filter is preferably performed to remove foreign matter such as dust and fine particles from the resin composition of the present invention.
  • 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 filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. When the filter material is polyethylene, HDPE (high-density polyethylene) is more preferable.
  • the filter may be pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined.
  • connection mode is a mode in which an HDPE filter with a pore size of 1 ⁇ m is connected in series as the first stage and an HDPE filter with a pore size of 0.2 ⁇ m is connected in series as the second stage.
  • Various materials may also be filtered multiple times. When filtration is performed multiple times, circulating filtration may be used. Filtration may also be performed under pressure. When filtration is 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.
  • impurities may be removed using an adsorbent.
  • Filter filtration and impurity removal using an adsorbent may be combined.
  • Known adsorbents can be used as the adsorbent.
  • the adsorbent include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
  • the method for producing a cured product of the present invention preferably includes a film-forming step of applying the resin composition onto a substrate to form a film.
  • the method for producing a cured product more preferably 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 in the development step and a post-development exposure step of exposing the pattern obtained in the development step.
  • the method for producing a cured product preferably includes the film-forming step and the 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 to a substrate to form a film.
  • the method for producing a cured product of the present invention preferably includes a film-forming step of applying the resin composition onto a substrate to form a film.
  • the type of substrate can be appropriately determined depending on the application and is not particularly limited.
  • substrates include semiconductor production 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 on 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 for plasma display panels (PDPs).
  • semiconductor production 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 on which a metal layer is formed by plating, vapor deposition,
  • the substrate is particularly preferably a semiconductor production substrate, and 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 preferably, 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 film is formed by applying a resin composition to the surface of a resin layer (e.g., a layer made of a cured product) or the surface of a metal layer, the resin layer or metal layer serves as the substrate.
  • a resin layer e.g., a layer made of a cured product
  • the resin layer or metal layer serves as the substrate.
  • the resin composition is preferably applied to a substrate by coating.
  • Specific examples of the application method include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of the film thickness, spin coating, slit coating, spray coating, or inkjet coating is preferred, and from the viewpoint of uniformity of the film thickness and productivity, spin coating and slit coating are more preferred.
  • the solid content concentration of the resin composition and application conditions depending on the application method, a film of the desired thickness can be obtained.
  • the application method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, inkjet coating, etc.
  • slit coating for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
  • a coating film may be formed by applying the coating to a temporary support in advance using the above-mentioned application method, and then 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 rinsing (EBR) or back rinsing.
  • EBR edge bead rinsing
  • 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 film may be subjected to a step (drying step) of drying the formed film (layer) 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 110°C. Drying may also 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 exposure dose 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 in terms of 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 in relation to the light source, (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, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc.
  • semiconductor laser wavelengths 830 nm, 532 nm, 488 nm, 405 nm
  • exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is more preferred from the viewpoint of exposure sensitivity.
  • 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 thereof include exposure using a photomask and exposure by laser direct imaging.
  • 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 in which the film exposed in the exposure step is heated.
  • 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 50°C to 140°C, more preferably 60°C to 120°C.
  • the heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, more preferably from 1 minute to 10 minutes.
  • the temperature rise rate in the post-exposure heating step from the starting temperature to the maximum heating temperature is preferably 1 to 12° C./min, more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min.
  • the temperature rise rate may be changed during heating as needed.
  • the heating means in the post-exposure baking step is not particularly limited, and known means such as a hot plate, an oven, and an infrared heater can be used. It is also preferable to carry out the heating in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.
  • the film After exposure, the film may be subjected to a development step in which it is developed with a developer to form a pattern. That is, 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 either the exposed or unexposed portions of the film, forming a pattern.
  • development in which the non-exposed portions of the film are removed by the development process is called negative development
  • development in which the exposed portions of the film are 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.
  • the method of supplying the developer is not particularly limited as long as it can form a desired pattern, and examples thereof include a method of immersing a substrate on which a film has been formed in the developer, puddle development in which the developer is supplied to a film formed on a 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.
  • Methods for 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 on the substrate by ultrasonic waves or the like, and a step in which these are combined.
  • the rinse liquid can 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, and 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 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 rinse liquid in the rinsing step may include a step of continuously supplying the rinse liquid to the substrate, a step of keeping the rinse liquid substantially stationary on the substrate, a step of vibrating the rinse liquid on the substrate by ultrasonic waves or the like, and 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 rinse solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.
  • 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 development 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 performing a development step, or a film obtained in the film-forming step. In the heating step, the resin such as the polyimide precursor is cyclized to form 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, even more preferably 150 to 250°C, still 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 due to heating.
  • the heating step is preferably carried out at a temperature increase rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature.
  • the temperature increase rate is more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min.
  • the heating rate from the initial temperature to the maximum heating temperature is 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 up to the maximum heating temperature begins.
  • this is the temperature of the film (layer) after drying.
  • 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.
  • 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, 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 (which is preferably subjected to at least one of the heating step and the post-development exposure 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 the pattern has been subjected to at least one of a heating step and a post-development exposure step).
  • the metal layer is not particularly limited and any existing metal species can be used, including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.
  • the method for forming the metal layer is not particularly limited, and existing methods can be applied.
  • the methods described in JP 2007-157879 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.
  • suitable methods include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and combinations of these. More specific examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating.
  • a preferred form of plating is electroplating 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 fields to which the cured product manufacturing method of the present invention or the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include etching patterns for sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), and insulating films for packaging 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 to produce printing plates such as offset printing plates or screen printing plates, to etch molded parts, and to produce protective lacquers and dielectric layers in electronics, particularly 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 a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.
  • the laminate of the present invention preferably includes two or more layers made of a cured product, and 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 the layer made of the cured product, between the steps for producing a cured product that are performed multiple times. Preferred aspects of the metal layer-forming step are as described above.
  • the laminate for example, a laminate including 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. It is preferable that the layer made of the first cured product and the layer made of the second cured product are both 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 (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) at least one of a heating process and a post-development exposure process, which are carried out again on the surface of the pattern (resin layer) or metal layer in this order.
  • at least one of the (a) film formation process and the (d) heating process and the post-development exposure process may be repeated.
  • the (e) metal layer formation process may be included. It goes without saying that the lamination process may further include the above-mentioned drying process, etc. 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 a surface activation treatment is plasma treatment. Details of the surface activation treatment will be described later.
  • the lamination step is preferably carried out 2 to 20 times, more preferably 2 to 9 times.
  • a structure of 2 to 20 resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a structure of 2 to 9 resin layers is more preferred.
  • the above layers may be the same or different in composition, shape, film thickness, etc.
  • a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer.
  • a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer.
  • Specific examples include an embodiment in which the following steps are 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 an embodiment in which the following steps are repeated in this order: (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 performed after the metal layer formation step, but the resin composition layer may be subjected to the surface activation treatment step after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) and then the metal layer formation step may be performed.
  • the surface activation treatment may be performed on at least a portion of the metal layer, or on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the resin composition layer after exposure.
  • the surface activation treatment is preferably performed on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region 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, it is possible to improve the adhesion with the resin composition layer (film) provided on the surface. It is preferable that the surface activation treatment is also performed on a part or all 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 a metal layer or a resin layer provided on the surface that has been surface-activated.
  • the resin composition layer when negative development is performed, etc., if the resin composition layer is cured, it is less susceptible to damage due to the surface treatment, and 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 of the present invention or the method for producing the laminate.
  • 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 can be incorporated into this specification.
  • the weight average molecular weight (Mw) of the resulting resin (A-1) was 38,500, and the number average molecular weight (Mn) was 17,500.
  • Resin (A-1) was confirmed by 1H-NMR to have a structure containing a repeating unit represented by the following formula (A-1). In the following structure, the symbols in parentheses are the values listed in the table below and represent the molar ratio of each structure. The weight average molecular weight (Mw), number average molecular weight (Mn), imidization rate (%), and imide group concentration of the resin (A-1) are shown in the table below.
  • repeating units containing two imidizable moieties (repeating units at m mol % and n mol % below), and structures in which two imidizable moieties form an imide ring (repeating units at k mol % and l mol % below).
  • repeating units in which only one of the two imidizable moieties forms an imide ring and the other does not are also included. This is the same for the resins described below.
  • the molar ratio is based solely on the assumption that only the repeating units described below are present, and in reality, repeating units in which only one forms an imide ring and the other does not may be included, as long as the total amount of imide ring structures remains the same.
  • the proportion of structures in the resin that form imide rings is shown as the imidization rate (%) in the table below. This is also true for the other resins described below.
  • Resin AC-2 Synthesis of Resin (AC-2)> Resin AC-3 was synthesized in the same manner as Resin AC-1, except that the raw material acid anhydride and diamine used in Synthesis Example AC-1 were appropriately changed, the charging ratio, and the amount of water added.
  • Resin (AC-2) had a weight average molecular weight (Mw) of 28,000 and a number average molecular weight (Mn) of 10,800.
  • the resulting reaction mixture was allowed to stand at room temperature for 20 hours, after which the precipitate that formed in the reaction mixture was removed by filtration to obtain a reaction solution.
  • the resulting reaction solution was added to 750 g of ethanol to produce a precipitate consisting of a crude polymer.
  • the produced crude polymer was filtered and dissolved in 250 g of tetrahydrofuran to obtain a crude polymer solution.
  • the resulting crude polymer solution was added dropwise to 5 L of water to precipitate the polymer, and the resulting precipitate was filtered.
  • the resulting resin was then dried under reduced pressure at 45°C for 2 days to obtain resin (A-19).
  • the resulting resin (A-19) had a weight-average molecular weight of 31,200 and a number-average molecular weight (Mn) of 10,900.
  • Resin (A-19) is presumed to have a structure containing a repeating unit represented by the following formula (A-19).
  • the symbols in parentheses are values listed in the table below and represent the molar ratio of each structure contained.
  • the weight-average molecular weight (Mw), number-average molecular weight (Mn), and imidization rate (%) of resin (A-19) are also listed in the table below.
  • Resins A-1 to A-20 were dissolved in gamma-butyrolactone, diluted to 2000 mPa s, and applied to a silicon wafer by spin coating to form a resin layer.
  • the silicon wafer to which the resulting resin layer was applied was dried on a hot plate at 110°C for 5 minutes, yielding a resin layer with a uniform thickness of approximately 15 ⁇ m after film formation on the silicon wafer.
  • the resin layer was measured by ATR using a Nicolet iS20 (manufactured by Thermofisher) over a measurement range of 4000 to 700 cm, with 50 measurements.
  • the imidization index of the resin was calculated by dividing the peak height near 1380 cm (1350 to 1450 cm; if multiple peaks are present, the peak with the greatest intensity) by the peak height near 1500 cm (1460 to 1550 cm; if multiple peaks are present, the peak with the greatest intensity).
  • the imidization rate of the resin was calculated by dividing the value by the imidization index of a film heated at a heating rate of 10°C/min under a nitrogen atmosphere and heated at 350°C for 1 hour.
  • the imide group concentration U was calculated by the following formula (I) using the molecular weight (average molecular weight) (Mw(A)) of the tetracarboxylic dianhydride and the molecular weight (average molecular weight) (Mw(B)) of the diamine compound used in the synthesis of the resin. 70.02 ⁇ 2/[Mw(A)+Mw(B)-36] ⁇ 100 (I)
  • each example the components shown in the table below were mixed to obtain a resin composition.
  • the components shown in the table below were mixed to obtain a comparative composition.
  • 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 amount of solvent used was the amount that would give the solids concentration of the composition as "Solids concentration (% by mass)" in the table, and each solvent was mixed at the mixing ratio (mass ratio) shown in the "Ratio" column.
  • the resulting resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter with a pore size of 0.8 ⁇ m.
  • "-" indicates that the composition does not contain the corresponding component.
  • A-1 to A-20 Resins (A-1) to (A-20) synthesized above AC-1
  • AC-2 Resins (AC-1) and (AC-2) synthesized above A-1 to A-20 are compounds that fall under the category of specific resins.
  • AC-1) and (AC-2) are compounds that do not fall under the category of specific resins.
  • B-1 SR-209 (manufactured by Sartomer)
  • B-2 ADPH: Dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
  • B-3 Compound having the following structure
  • B-4 Compound having the following structure
  • D-1 to D-7 Compounds represented by the following formulas (D-1) to (D-7)
  • G-1 to G-4 Compounds having the following structures: In the following structural formulas, Et represents an ethyl group.
  • H-1 Compound represented by the following formula (H-1)
  • H-2 N-phenyldiethanolamine
  • H-3 Compound having the following structure
  • H-4 Compound having the following structure
  • H-5 Compound having the following structure
  • Titanium compound I-1 TC-750 (manufactured by Matsumoto Fine Chemical Co., Ltd.)
  • I-2 TC-401 (manufactured by Matsumoto Fine Chemical Co., Ltd.)
  • I-3 TC-800 (manufactured by Matsumoto Fine Chemical Co., Ltd.)
  • I-4 TC-810 (manufactured by Matsumoto Fine Chemical Co., Ltd.)
  • I-5 to I-8 Compounds having the following structures
  • J-1 F-554 (manufactured by DIC)
  • J-2 BYK-3760 (manufactured by BYK)
  • J-3 BYK-333 (manufactured by BYK)
  • the dumbbell shape was a dumbbell No. 7 as defined in JIS K 6251:2017.
  • the exposed resin composition layer (resin layer) was developed with the developer listed in the "Developer” column of the table until the unexposed areas were removed, and then rinsed with PGMEA for 30 seconds. The temperature was then increased at a rate of 10°C/min under a nitrogen atmosphere, and the layer was heated to the temperature and time listed in the "Cure Temperature (°C)" and “Cure Time (min)” columns of the table.
  • the cured resin layer (cured product) was immersed in a 4.9% by mass aqueous solution of hydrofluoric acid, and a dumbbell-shaped cured product (test piece) was peeled off from the silicon wafer (sample width 2 mm, sample length 35 mm).
  • the CTE of the test specimens prepared above was measured using a TMA450 (TA Instruments) at 25° C. to 125° C.
  • the heating and cooling conditions during evaluation were as follows (1) to (4). (1) The temperature was increased from room temperature to 130°C at a rate of 5°C/min. (2) The temperature was lowered from 130°C to 10°C at a rate of 5°C/min. (3) The temperature was increased from 10°C to 300°C at a rate of 5°C/min.
  • Viscosity fluctuation rate (%)
  • the resin composition used in each example and each comparative example was applied in the form of a layer by spin coating to the surface of the thin copper layer of a resin substrate having a thin copper layer formed on its surface, and dried at 110°C for 5 minutes to form a resin composition layer having a film thickness shown in the "Film thickness ( ⁇ m)" column in the table.
  • the film was developed with the developer shown in the "Developer” column of the table until the unexposed areas were removed, rinsed with PGMEA for 30 seconds, and then heated at a temperature increase rate of 10°C/min under a nitrogen atmosphere, and heated at the temperature and for the time shown in the "Cure temperature (°C)" and “Cure time (min)” columns of the table.
  • the minimum opening mask diameter of the obtained cured product was determined by observing the cross section of the opening pattern using 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 on which an opening pattern was formed using at least one of the above exposure doses.
  • the evaluation results are shown in the "Resolution" column in the table.
  • Example 1001 A resin composition was prepared in the same manner as in Example 1, except that the polymerizable compound B-1 was not contained and the amount of resin A-1 was changed from 82.5 parts by mass to 91.0 parts by mass. The resin composition was used to evaluate the breaking elongation, storage stability, and coatability in the same manner as in Example 1, and the same results as in Example 1 were obtained in all evaluation items.
  • Example 1002 The resin composition used in Example 1 was applied in the form of a layer by spin coating onto the surface of the thin copper layer of a resin substrate having a thin copper layer formed on its surface, and dried at 100°C for 5 minutes to form a photosensitive film with a thickness of 20 ⁇ m. This was then exposed using a stepper (Nikon Corporation, NSR1505 i6). The exposure was carried out at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 ⁇ m). After the exposure, the film was developed in cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
  • the temperature was increased at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 180 minutes to form an interlayer insulating film for a rewiring layer.
  • This interlayer insulating film for a rewiring layer had excellent insulating properties. Furthermore, when a semiconductor device was manufactured using this interlayer insulating film for rewiring layer, it was confirmed that it operated without any problems.

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Abstract

L'invention concerne une composition de résine qui contient une résine possédant au moins une sorte d'unité de répétition choisie dans un groupe constitué d'une unité de répétition représentée par les formules （１－１） à （１－４）, un initiateur de polymérisation, et un solvant. Le taux d'imidation de ladite résine est compris entre ４０ et ８５％, et sa concentration en groupes imide (U) est comprise entre １６ et ４０% en masse. L'invention concerne également un objet durci ainsi qu'un procédé de fabrication de celui-ci, un stratifié ainsi qu'un procédé de fabrication de celui-ci, et un dispositif à semi-conducteurs ainsi qu'un procédé de fabrication de celui-ci.
PCT/JP2025/005904 2024-02-22 2025-02-20 Composition de résine, objet durci ainsi que procédé de fabrication de celui-ci, stratifié ainsi que procédé de fabrication de celui-ci, et dispositif à semi-conducteurs ainsi que procédé de fabrication de celui-ci Pending WO2025178105A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021235469A1 (fr) * 2020-05-20 2021-11-25 富士フイルム株式会社 Composition de résine durcissable, film durci, stratifié, procédé de production de film durci et dispositif semi-conducteur
WO2022158359A1 (fr) * 2021-01-22 2022-07-28 旭化成株式会社 Composition de résine photosensible, procédé de production de film durci de polyimide l'utilisant et film durci de polyimide
WO2023228568A1 (fr) * 2022-05-23 2023-11-30 旭化成株式会社 Composition de résine photosensible, procédé de production de film durci de polyimide l'utilisant, et film durci de polyimide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021235469A1 (fr) * 2020-05-20 2021-11-25 富士フイルム株式会社 Composition de résine durcissable, film durci, stratifié, procédé de production de film durci et dispositif semi-conducteur
WO2022158359A1 (fr) * 2021-01-22 2022-07-28 旭化成株式会社 Composition de résine photosensible, procédé de production de film durci de polyimide l'utilisant et film durci de polyimide
WO2023228568A1 (fr) * 2022-05-23 2023-11-30 旭化成株式会社 Composition de résine photosensible, procédé de production de film durci de polyimide l'utilisant, et film durci de polyimide

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