[go: up one dir, main page]

WO2025178106A1 - 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
WO2025178106A1
WO2025178106A1 PCT/JP2025/005909 JP2025005909W WO2025178106A1 WO 2025178106 A1 WO2025178106 A1 WO 2025178106A1 JP 2025005909 W JP2025005909 W JP 2025005909W WO 2025178106 A1 WO2025178106 A1 WO 2025178106A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
group
repeating unit
resin composition
resin
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/JP2025/005909
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 WO2025178106A1 publication Critical patent/WO2025178106A1/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
    • 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
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device.
  • 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.
  • a cured product formed from a resin composition containing polyimide or its precursor is used as an insulating material in a wiring pattern, the mechanical properties of the cured product, such as elongation at break, and the storage stability of a resist liquid are required.
  • the present invention aims to provide a resin composition that gives a cured product with excellent mechanical properties and high storage stability, 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 including the method for producing the cured product, and a semiconductor device including the cured product.
  • Another object of the present invention is to provide a method for synthesizing a novel resin.
  • 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—
  • 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-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.
  • L 1 and L 2 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 represent a bonding site with the carbonyl group shown in formula (1-1), formula (1-2), formula (1-3), or formula (1-4), respectively; hydrogen atoms in these structures may be substituted with substituents;
  • n1 represents an integer of 1 or more.
  • 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).
  • each R and X1 independently represents a hydrogen atom, an alkyl group, or a halogenated alkyl group
  • R X2 and R X3 each independently represent a hydrogen atom or a substituent, and R X2 and R 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.
  • ⁇ 7> The resin composition according to any one of ⁇ 1> to ⁇ 6>, wherein an 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 12 to 40 mass%.
  • U an imide group concentration
  • ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the resin has a weight average molecular weight of 5,000 or more and less than 30,000.
  • ⁇ 9> The resin composition according to any one of ⁇ 1> to ⁇ 8>, wherein the imidization rate of the resin is 55% or more and less than 70%.
  • ⁇ 14> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 11> onto a substrate to form a film.
  • the method for producing a cured product according to ⁇ 14> 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.
  • ⁇ 16> A method for producing a cured product according to ⁇ 14> or ⁇ 15>, comprising a heating step of heating the film at 50 to 450°C.
  • ⁇ 17> A method for producing a laminate, comprising the method for producing a cured product according to any one of ⁇ 14> to ⁇ 16>.
  • 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.
  • 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.
  • 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 acid value of 11.2 mgKOH/g or more and 25.3 mgKOH/g or less.
  • 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 of the present invention a cured product having excellent mechanical properties can be obtained, and the resin composition of the present invention also has good storage stability.
  • the mechanism by which the above effects are obtained is unknown, but is speculated as follows. It is believed that the presence of a closed ring structure at an imidization rate of 40 to 85% adjusts the arrangement of the resin, and furthermore, interaction occurs between the acid groups contained within the above-mentioned acid value range, improving the mechanical properties of the cured product, such as the elongation at break. Furthermore, the high acid value inhibits the progress of imidization, so there is little change in the imidization rate of the resin in the resist liquid, resulting in good storage stability.
  • Patent Document 1 does not describe a resin composition containing a specific resin.
  • 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 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.
  • 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.
  • 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.
  • 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-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.
  • 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 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 and n1 are the same as preferred embodiments of R 1 and n1 in formula (C-1).
  • 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 radical polymerizable group is preferable.
  • 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.
  • 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 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 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).
  • One embodiment of the specific resin of the present invention is one in which 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 greater than 90 mol%.
  • all repeating units in the specific resin, excluding terminal repeating units may be repeating units represented by formula (1-1), formula (1-2), formula (1-3), or formula (1-4).
  • the number average molecular weight (Mn) of the specific resin is preferably 40,000 or less, more preferably 30,000 or less, even more preferably 20,000 or less, and particularly preferably 13,000 or less. Moreover, 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 specific resin preferably has an imide group concentration U of 12 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 12 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 16% by mass or more, more preferably 23% by mass or more, and even more preferably more than 26% by mass.
  • 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 diester with a diamine in the presence of 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.
  • reaction conditions in the step of reacting the polyimide oligomer with the compound represented by formula (A-1) conditions for a known amidation method using an acid halide and an amine can be adopted.
  • formula (A-1) preferred embodiments of A 41 , A 42 , R 41 and R 42 , and X 4 are the same as the preferred embodiments of A 41 , A 42 , R 41 and R 42 , and X 4 in formula (1-4) above.
  • 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 obtained specific resin can be adjusted to 11.2 mgKOH/g or more and 25.3 mgKOH/g or less 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 to carboxy groups.
  • water can be added to the reaction solution of the above 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 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,
  • 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.
  • 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 compound containing a (meth)acryloyl group as the polymerizable compound.
  • the radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxy group or a phosphate group.
  • the radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent in which an acid group is imparted by reacting a non-aromatic carboxylic anhydride with the unreacted hydroxy groups of an aliphatic polyhydroxy compound.
  • 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 mechanism by which the above-mentioned effect is obtained is unknown; however, it is thought that, for example, when curing is performed by heating or the like, a part of the crosslinking agent U is thermally decomposed to generate amines or the like, and the amines or the like promote the cyclization of the precursor of the cyclized resin, such as a polyimide precursor.
  • the crosslinking agent U may have only one urea bond or one urethane bond, may have one or more urea bonds and one or more urethane bonds, may have no urethane bond but two or more urea bonds, or may have no urea bond but two or more urethane bonds.
  • 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 number of radical polymerizable groups in the crosslinking agent U may be one or two or more, and is preferably 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 4.
  • the radical polymerizable group value (mass of compound per mole of radical polymerizable group) of the crosslinking agent U is preferably 150 to 400 g/mol.
  • the lower limit of the radically polymerizable group value is more preferably 200 g/mol or more, even more preferably 210 g/mol or more, still more preferably 220 g/mol or more, even more preferably 230 g/mol or more, still more preferably 240 g/mol or more, and particularly preferably 250 g/mol or more.
  • the upper limit of the radically polymerizable group value is more preferably 350 g/mol or less, even more preferably 330 g/mol or less, and particularly preferably 300 g/mol or less.
  • the polymerizable group value of the crosslinking agent U is preferably 210 to 400 g/mol, and more preferably 220 to 400 g/mol.
  • 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.
  • 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.
  • 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.
  • 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 crosslinking agent U preferably contains an aromatic group.
  • the aromatic group is preferably directly bonded to a urea bond or a urethane bond contained in the crosslinking agent U.
  • the crosslinking agent U contains two or more urea bonds or urethane bonds, it is preferable that one of the urea bonds or urethane bonds is directly bonded to the aromatic group.
  • the aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, or may have a structure in which these form a condensed ring, but is preferably an aromatic hydrocarbon group.
  • 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.
  • 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.
  • 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.
  • 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 content of the base generator is preferably 0.1 to 50 parts by mass relative to 100 parts by mass of the resin in the resin composition.
  • the lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more.
  • the upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.
  • the base generator may be used alone or in combination of two or more. When two or more types are used, the total amount is preferably within the above range.
  • the resin composition of the present invention 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
  • ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.
  • 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.
  • 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.
  • Aluminum-based adhesion promoter examples include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.
  • 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, which can effectively inhibit migration of metal ions derived from the metal layer (or metal wiring) into the film when the resin composition is applied to the metal layer (or metal wiring) to form a film.
  • Ion trapping agents that capture anions such as halogen ions can also be used as migration inhibitors.
  • migration inhibitors include the following compounds:
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 unsubstituted embodiment is also one of the preferred embodiments of the present invention.
  • R 12 is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms.
  • the hydrocarbon group for R 12 may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, with aromatic hydrocarbon groups being preferred.
  • the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, 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.
  • 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.
  • 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.
  • 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.
  • the water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If the water content is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the moisture content include adjusting the humidity during storage and reducing the porosity of the container during storage.
  • the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
  • metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but this does not include metals contained as complexes of organic compounds with metals. When multiple metals are contained, it is preferable that the total amount of these metals is within the above range.
  • 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 cured product of the resin composition of the present invention can have an elongation at break of 40% or more, and the elongation at break of the cured product of the resin composition is preferably 40% or more, more preferably 50% or more, and even more preferably 60% 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.
  • 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.
  • Suitable alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, and triethylene glycol
  • suitable amides include N-methylpyrrolidone, N-ethylpyrrolidone, and dimethylformamide.
  • the organic solvent can be used alone or in combination of two or more.
  • a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, ⁇ -butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.
  • the developer may further contain other components.
  • other components include known surfactants and known defoaming agents.
  • 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.
  • a method of supplying the developer through a straight nozzle or a method of continuously supplying the developer through a spray nozzle is preferred, and from the viewpoint of the permeability of the developer into the image areas, a method of supplying the developer through a spray nozzle is more preferred.
  • a process may be employed in which the developer is continuously supplied through a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is continuously supplied again through a straight nozzle, and the substrate is spun to remove the developer from the substrate, and this process may be repeated multiple times.
  • 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 development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes.
  • the temperature of the developer during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.
  • the pattern may be further washed (rinsed) with a rinse solution.
  • a rinse solution may be supplied before the developer in contact with the pattern has completely dried.
  • Rinse solution When the developer is an alkaline aqueous solution, for example, water can be used as the rinse liquid.
  • the developer is a developer containing an organic solvent, for example, a solvent different from the solvent contained in the developer (for example, water, an organic solvent different from the organic solvent contained in the developer) can be used as the rinse liquid.
  • the organic solvent can be used alone or in combination of two or more.
  • Preferred organic solvents are cyclopentanone, gamma-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME, with cyclopentanone, gamma-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME being more preferred, and cyclohexanone and PGMEA being even more preferred.
  • the organic solvent preferably accounts for 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, of the total mass of the rinse solution.
  • the organic solvent may account for 100% by mass of the total mass of the rinse solution.
  • the rinse solution may further contain other ingredients.
  • other components include known surfactants and known defoaming agents.
  • 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 is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher.
  • the upper limit of the heating temperature is preferably 350°C or less, more preferably 250°C or less, and even more preferably 240°C or less.
  • Heating may be performed in stages. For example, the temperature may be increased from 25°C to 120°C at a rate of 3°C/min, held at 120°C for 60 minutes, increased from 120°C to 180°C at a rate of 2°C/min, and held at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Pat. No. 9,159,547. Such a pretreatment step can improve the film properties.
  • the pretreatment step may be performed for a short period of time, preferably from 10 seconds to 2 hours, more preferably from 15 seconds to 30 minutes.
  • the pretreatment step may be performed in two or more steps.
  • a first pretreatment step may be performed in the range of 100 to 150°C, followed by a second pretreatment step in the range of 150 to 200°C.
  • the material may be cooled, and in this case, the cooling rate is preferably 1 to 5° C./min.
  • the heating step is preferably performed in an atmosphere with a low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon, or by performing the heating step under reduced pressure, etc.
  • the oxygen concentration is preferably 50 ppm (volume ratio) or less, more preferably 20 ppm (volume ratio) or less.
  • the heating means in the heating step is not particularly limited, but examples thereof include a hot plate, an infrared oven, an electric heating oven, a hot air oven, and an infrared oven.
  • the pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a post-development exposure step in which the pattern after the development step is exposed to light, instead of or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step of exposing the pattern obtained by the development step.
  • the method for producing a cured product of the present invention may include both a heating step and a post-development exposure step, or may include only one of the heating step and the post-development exposure step.
  • the post-development exposure step for example, a reaction in which cyclization of a polyimide precursor or the like progresses due to exposure of a photobase generator to light, or a reaction in which elimination of an acid-decomposable group progresses due to exposure of a photoacid generator to light, can be promoted.
  • the exposure dose in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , more preferably 100 to 15,000 mJ/cm 2 , in terms of exposure energy at a wavelength to which the photosensitive compound has sensitivity.
  • the post-development exposure step can be carried out using, for example, the light source used in the exposure step described above, and it is preferable to use broadband light.
  • 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 laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention.
  • the laminate is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers.
  • at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.
  • the method for producing the laminate of the present invention preferably includes 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.
  • 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.
  • resin (A-1) The weight average molecular weight (Mw) of the resulting resin (A-1) was 28,000, and the number average molecular weight (Mn) was 11,500. It was confirmed by 1H-NMR that resin (A-1) has 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) and imidization rate (%) of the resin (A-1) are shown in the table 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. Furthermore, the proportion of structures in the resin that form imide rings is shown in the table below as the imidization rate (%) and imide group concentration. This also applies to the other resins described 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 the ATR method using a Nicolet iS20 (manufactured by ThermoFisher) in a measurement range of 4000 to 700 cm-1, with 50 measurements.
  • the imidization index of the resin was calculated by dividing the peak height near 1380 cm-1 (1350 to 1450 cm-1, the peak with the greatest intensity if multiple peaks are present) by the peak height near 1500 cm-1 (1460 to 1550 cm-1, the peak with the greatest intensity if multiple peaks are present), and 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-16 Resins (A-1) to (A-16) synthesized above AC-1
  • AC-2 Resins (AC-1) and (AC-2) synthesized above A-1 to A-16 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
  • E-1 2-nitroso-1-naphthol (Tokyo Chemical Industry Co., Ltd.)
  • E-2 Parabenzoquinone (Tokyo Chemical Industry Co., Ltd.)
  • E-3 paramethoxyphenol (Tokyo Chemical Industry Co., Ltd.)
  • E-4 Compound having the following structure
  • E-5 Compound having the following structure
  • 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
  • the resin composition or comparative composition was applied to a silicon wafer by spin coating to form a resin composition layer.
  • the silicon wafer to which the resin composition layer was applied was dried on a hot plate at 100°C for 5 minutes to obtain a uniform resin composition layer with a thickness of about 15 ⁇ m on the silicon wafer.
  • the entire surface of the obtained resin composition layer was exposed to i-line light at an exposure energy of 500 mJ/cm 2 using a stepper (Nikon NSR 2005 i9C).
  • Viscosity fluctuation rate (%)
  • 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 specimen prepared above was measured at 25°C to 125°C using a TMA450 (TA Instrument)
  • the temperature rise and fall 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. (4) Allow to cool naturally to room temperature.
  • the elongation (displacement) of the sample was measured during the temperature increase and decrease processes (1) to (4) above, and the thermal expansion coefficient was calculated by dividing the elongation (displacement) of the sample at 25°C and 125°C in process (3) by the temperature.
  • the obtained CTE was evaluated according to the following evaluation criteria, and the evaluation results are shown in the "CTE" column of the table. (Evaluation criteria) A: The CTE was less than 30 ppm/°C.
  • C CTE exceeded 55 ppm/°C.
  • 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.
  • the film thickness of the curable resin composition layer was measured using a reflection spectroscopic film thickness meter (FE-3000, manufactured by Otsuka Electronics), and this value was defined as "film thickness A.” Subsequently, the entire surface of the obtained curable resin composition layer was exposed to i-line light at an exposure energy of 500 mJ/cm 2 using a stepper (Nikon NSR 2005 i9C). The exposed curable resin composition layer (resin layer) was heated at a temperature increase rate of 10°C/min in a nitrogen atmosphere, heated at the temperature and for the time shown in the "Cure temperature (°C)" and “Cure time (min)” columns in the table, and then cooled to 25°C to obtain a cured product.
  • FE-3000 reflection spectroscopic film thickness meter
  • the film thickness of the cured product was measured using a reflection spectroscopic film thickness meter (FE-3000, manufactured by Otsuka Electronics), and this value was taken as "film thickness B.”
  • the evaluation was carried out according to the following evaluation criteria, and the evaluation results are shown in the column of "shrinkage rate" in the table. It can be said that the smaller the shrinkage rate value, the more excellent the curing shrinkage rate of the obtained composition layer. (Evaluation criteria)
  • B The shrinkage rate was 15% or more and less than 30%.
  • C The shrinkage rate was 30% or more.

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials For Photolithography (AREA)

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 son indice d'acide est supérieur ou égal à １１,２ｍｇＫＯＨ／ｇ et inférieur ou égal à ２５,３ｍｇＫＯＨ／ｇ. 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/JP2025/005909 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 WO2025178106A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024025232 2024-02-22
JP2024-025232 2024-02-22

Publications (1)

Publication Number Publication Date
WO2025178106A1 true WO2025178106A1 (fr) 2025-08-28

Family

ID=96847276

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2025/005909 Pending WO2025178106A1 (fr) 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

Country Status (1)

Country Link
WO (1) WO2025178106A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018221457A1 (fr) * 2017-05-31 2018-12-06 富士フイルム株式会社 Composition de résine photosensible, précurseur polymère, film durci, stratifié, procédé de production de film durci et dispositif à semi-conducteur
JP2019123864A (ja) * 2018-01-17 2019-07-25 東レ株式会社 樹脂組成物、硬化膜、硬化膜のレリーフパターンの製造方法、電子部品、半導体装置、電子部品の製造方法、半導体装置の製造方法
WO2023120037A1 (fr) * 2021-12-23 2023-06-29 富士フイルム株式会社 Procédé de production de corps assemblé, corps assemblé, procédé de production de stratifié, stratifié, procédé de production de dispositif, dispositif et composition pour former une partie précurseur contenant du polyimide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018221457A1 (fr) * 2017-05-31 2018-12-06 富士フイルム株式会社 Composition de résine photosensible, précurseur polymère, film durci, stratifié, procédé de production de film durci et dispositif à semi-conducteur
JP2019123864A (ja) * 2018-01-17 2019-07-25 東レ株式会社 樹脂組成物、硬化膜、硬化膜のレリーフパターンの製造方法、電子部品、半導体装置、電子部品の製造方法、半導体装置の製造方法
WO2023120037A1 (fr) * 2021-12-23 2023-06-29 富士フイルム株式会社 Procédé de production de corps assemblé, corps assemblé, procédé de production de stratifié, stratifié, procédé de production de dispositif, dispositif et composition pour former une partie précurseur contenant du polyimide

Similar Documents

Publication Publication Date Title
WO2025178106A1 (fr) 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
WO2025178105A1 (fr) 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
WO2025164673A1 (fr) Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur
WO2025105367A1 (fr) Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur, dispositif à semi-conducteur et procédé de production de résine
WO2025105331A1 (fr) Composition de résine photosensible, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur
WO2025105345A1 (fr) Composition de résine, produit durci, corps stratifié, procédé de production de produit durci, procédé de production de corps stratifié, procédé de production de dispositif semi-conducteur et dispositif semi-conducteur
WO2025126934A1 (fr) Composition de résine photosensible, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur, dispositif à semi-conducteur et résine
WO2025070600A1 (fr) 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
WO2025070605A1 (fr) Composition de résine photosensible, 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
WO2025205548A1 (fr) Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur, et dispositif à semi-conducteur
JP2025150683A (ja) 硬化物、積層体、及び、半導体デバイス
WO2025205735A1 (fr) Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur
WO2025070586A1 (fr) Composition de résine photosensible, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur, dispositif à semi-conducteur, résine, procédé de production de résine et dianhydride d'acide carboxylique
WO2025041754A1 (fr) Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur
WO2025070592A1 (fr) Composition de résine photosensible, produit durci, produit stratifié, procédé de production de produit durci, procédé de production de produit stratifié, procédé de production de dispositif à semi-conducteur, dispositif à semi-conducteur et résine
WO2025057903A1 (fr) Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur, dispositif à semi-conducteur et composé
WO2025170014A1 (fr) Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur
JP2025151101A (ja) 硬化物、積層体、及び、半導体デバイス
WO2025205581A1 (fr) 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
WO2025205567A1 (fr) Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur et dispositif à semi-conducteur
WO2025126958A1 (fr) Composition de résine, produit durci, stratifié, procédé de production de produit durci, procédé de production de stratifié, procédé de production de dispositif à semi-conducteur, dispositif à semi-conducteur et résine
JP2025151111A (ja) 硬化物、積層体、及び、半導体デバイス
JP2025150696A (ja) 樹脂組成物、硬化物、積層体、硬化物の製造方法、積層体の製造方法、半導体デバイスの製造方法、及び、半導体デバイス
WO2025178095A1 (fr) Composition de résine, objet durci ainsi que procédé de fabrication de celui-ci, stratifié ainsi que procédé de fabrication de celui-ci, dispositif à semi-conducteurs ainsi que procédé de fabrication de celui-ci, et procédé de fabrication d'ester d'acide polyamique
WO2025178103A1 (fr) Composition de résine, objet durci ainsi que procédé de fabrication de celui-ci, stratifié ainsi que procédé de fabrication de celui-ci, dispositif à semi-conducteurs ainsi que procédé de fabrication de celui-ci, et procédé de fabrication d'ester d'acide polyamique

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 25758346

Country of ref document: EP

Kind code of ref document: A1