[go: up one dir, main page]

WO2025178103A1 - 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 - Google Patents

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

Info

Publication number
WO2025178103A1
WO2025178103A1 PCT/JP2025/005895 JP2025005895W WO2025178103A1 WO 2025178103 A1 WO2025178103 A1 WO 2025178103A1 JP 2025005895 W JP2025005895 W JP 2025005895W WO 2025178103 A1 WO2025178103 A1 WO 2025178103A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
repeating unit
group
resin
resin composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/005895
Other languages
English (en)
Japanese (ja)
Inventor
大輔 浅川
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 WO2025178103A1 publication Critical patent/WO2025178103A1/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
    • 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
    • C08G73/14—Polyamide-imides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • 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

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, a semiconductor device, and a method for producing a polyamic acid ester.
  • heterocycle-containing polymers 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, or protective films for semiconductor devices used for packaging. They are also used as base films or coverlays for flexible substrates.
  • polyimide is used in the form of a resin composition containing a polyamic acid ester.
  • 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 a known coating method, etc., it can be said that the resin composition has excellent adaptability in manufacturing, for example, there is a high degree of freedom in designing the shape, size, application position, etc. of the applied resin composition when it is applied.
  • heterocycle-containing polymers such as polyimides
  • industrial application development of the above-mentioned resin composition is expected to become increasingly widespread.
  • Patent Document 1 describes a photosensitive resin composition containing (A) 100 parts by mass of a polyimide precursor having a specific structure; (B) 0.5 to 10 parts by mass of a photosensitizer; and (D) 100 to 300 parts by mass of a solvent, wherein the photosensitive resin composition is desolvated to obtain a photosensitive resin layer before exposure, and the peak intensity near 1380 cm-1 in the infrared absorption spectrum measured by the ATR (Attenuated Total Reflection) method is 1500 cm-1 or less.
  • ATR Average Total Reflection
  • the photosensitive resin composition described has an imidization rate b, which is the imidization index of the photosensitive resin layer obtained by dividing the imidization index of the photosensitive resin layer by the imidization index of the cured film obtained by heating and curing the photosensitive resin composition at 350°C, of 15% to 50%, and an imide group concentration a, which is the ratio of imide groups to the molecular weight of repeating units containing structures derived from tetracarboxylic acid and diamine, in the polyimide of the cured polyimide film, of 12 wt% to 30 wt%.
  • an imidization rate b is the imidization index of the photosensitive resin layer obtained by dividing the imidization index of the photosensitive resin layer by the imidization index of the cured film obtained by heating and curing the photosensitive resin composition at 350°C, of 15% to 50%
  • an imide group concentration a which is the ratio of imide groups to the molecular weight of repeating units containing structures derived from tetracarbox
  • the present invention aims to provide a resin composition that can give a cured product having excellent storage stability and excellent insulation reliability, 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 producing a polyamic acid ester that, when used in a resin composition, gives a cured product that has excellent storage stability and insulating reliability.
  • Resin and Contains a solvent, the resin is a polyamic acid ester having an imidization rate of 3 to 45% and an amine value of 0.100 mmol/g or less; Resin composition.
  • 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, and Y2 is a divalent organic group.
  • A3 is —O— or —NR Z —, R Z is a hydrogen atom or a monovalent organic group, R3 is a hydrogen atom or a monovalent organic group, X3 is a tetravalent organic group, and Y3 is a divalent organic group.
  • a 41 and A 42 are each independently —O— or —NR Z —, R Z is a hydrogen atom or a monovalent organic group, R 41 and R 42 are each independently a hydrogen atom or a monovalent organic group, X 4 is a tetravalent organic group, and Y 4 is a divalent organic group.
  • Repeating unit A-2 a repeating unit represented by the formula (1-2) above, in which X 2 is any of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure obtained by removing two or more hydrogen atoms from the structure represented by the following formula (V-4).
  • Repeating unit A-3 a repeating unit represented by the formula (1-3) above, in which X 3 is any of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure obtained by removing two or more hydrogen atoms from the structure represented by the following formula (V-4).
  • Repeating unit A-4 a repeating unit represented by the formula (1-4) above, in which X A repeating unit in which 4 is any of the structures represented by the following formulas (2a) to (2e), or a repeating unit containing a structure in which two or more hydrogen atoms have been removed from a structure represented by the following formula (V-4):
  • L1 and L2 each independently represent a divalent group that is not conjugated with the benzene ring to which they are bonded, or a single bond
  • *1 to *4 represent bonding sites with the carbonyl group shown in formula (1-1), formula (1-2), formula (1-3), or formula (1-4), respectively, and hydrogen atoms in these structures may be substituted with substituents.
  • n1 represents an integer of 1 or more.
  • the resin contains at least one repeating unit selected from the group consisting of the following repeating units B-1, B-2, B-3, and B-4.
  • Repeating unit B-1 a repeating unit represented by the formula (1-1) above, wherein X 1 comprises a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the following formulae (V-1), (V-2), (V-3) and (V-5);
  • Repeating unit B-2 a repeating unit represented by the formula (1-2) above, wherein X 2 comprises a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the following formulae (V-1), (V-2), (V-3) and (V-5);
  • Repeating unit B-3 a repeating unit represented by the formula (1-3) above, wherein X 3 comprises a structure obtained by removing two or more hydrogen atoms from a structure represented by any one of the following formulae (V-1), (V-2), (V-3) and (V-5);
  • Repeating unit B-4 a repeating unit represented by the formula (1-4) above, wherein X 4 is a repeating unit containing a structure in which two or more hydrogen
  • R 1 X2 and R 1 X3 each independently represent a hydrogen atom or a substituent, and R 1 X2 and R 1 X3 may be bonded to form a ring structure.
  • the resin contains at least one repeating unit selected from the group consisting of repeating units represented by formula (1-2) in which R 2 is a monovalent organic group having an ethylenically unsaturated bond, repeating units represented by formula (1-3) in which R 3 is a monovalent organic group having an ethylenically unsaturated bond, and repeating units represented by formula (1-4) in which at least one of R 41 and R 42 is a monovalent organic group having an ethylenically unsaturated bond.
  • each R 1 independently represents a hydrogen atom or a monovalent organic group
  • n1 represents an integer of 0 to 3
  • n2 represents an integer of 0 to 3
  • each R 2 independently represents an alkyl group or a fluoroalkyl group
  • * represents a bonding site to another structure.
  • each R 1 independently represents a hydrogen atom or a monovalent organic group
  • n1 represents an integer of 0 to 3
  • * represents a bonding site to another structure.
  • ⁇ 8> The resin composition according to any one of ⁇ 1> to ⁇ 7>, wherein the imidization rate is 10% or more and 30% or less.
  • ⁇ 9> The resin composition according to any one of ⁇ 1> to ⁇ 8>, wherein the resin is a polyamic acid ester having an acid value of 3.70 to 22.5 mgKOH/g.
  • ⁇ 10> The resin composition according to any one of ⁇ 1> to ⁇ 9>, wherein the resin is a polyamic acid ester having an acidic functional group content of less than 0.1 mgKOH/g at a pH of less than 8.0 and an acidic functional group content of 3.70 to 22.5 mgKOH/g at a pH of 8.0 or more, when titrated under the following conditions: Conditions: 0.300 g of resin was completely dissolved in 80 mL of NMP, and then 5 mL of water was added and the mixture was titrated with a 0.01 mol/L aqueous NaOH solution.
  • ⁇ 11> The resin composition according to any one of ⁇ 1> to ⁇ 10>, wherein the resin is a polyamic acid ester having an absorbance of 0.62 or less at a wavelength of 365 nm in a 0.050% by mass solution.
  • ⁇ 12> The resin composition according to any one of ⁇ 1> to ⁇ 11>, further containing 8-azaadenine.
  • ⁇ 13> The resin composition according to any one of ⁇ 1> to ⁇ 12>, wherein the resin composition is a negative photosensitive resin composition.
  • ⁇ 14> The resin composition according to any one of ⁇ 1> to ⁇ 13>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 15> A cured product obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 14>.
  • ⁇ 16> A laminate comprising two or more layers made of the cured product according to ⁇ 15>, and a metal layer between any two adjacent layers made of the cured product.
  • ⁇ 17> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 14> onto a substrate to form a film.
  • the method for producing a cured product according to ⁇ 17> 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.
  • ⁇ 19> A method for producing a cured product according to ⁇ 17> or ⁇ 18>, comprising a heating step of heating the film at 50 to 450°C.
  • ⁇ 20> A method for producing a laminate, comprising the method for producing a cured product according to any one of ⁇ 17> to ⁇ 19>.
  • ⁇ 21> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of ⁇ 17> to ⁇ 19>.
  • ⁇ 22> A semiconductor device comprising the cured product according to ⁇ 15>.
  • a method for producing a polyolefin polymer comprising a step of polycondensing a dicarboxylic acid and a diamine in the presence of a carbodiimide compound as a condensing agent and an active esterifying agent,
  • a resin composition which can give a cured product having excellent storage stability and excellent insulation reliability, 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.
  • the present invention also provides a method for producing a polyamic acid ester that, when used in a resin composition, gives a cured product that has excellent storage stability and insulating reliability.
  • a numerical range expressed using the symbol "to” means a range that includes the numerical values before and after "to” as the lower and upper limits, respectively.
  • the term “step” includes not only an independent step but also a step that cannot be clearly distinguished from other steps, so long as the intended effect of the step can be achieved.
  • groups (atomic groups) when a notation does not specify whether they are substituted or unsubstituted, it encompasses both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents.
  • alkyl group encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
  • exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation.
  • (meth)acrylate means both or either of “acrylate” and “methacrylate”
  • (meth)acrylic means both or either of “acrylic” and “methacrylic”
  • (meth)acryloyl means both or either of “acryloyl” and “methacryloyl”.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • total solids content refers to the total mass of all components of the composition excluding the solvent
  • solids concentration refers to the mass percentage of the components excluding the solvent relative to the total mass of the composition.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) can be determined, for example, using an HLC-8220GPC (manufactured by Tosoh Corporation) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series.
  • these molecular weights are measured using NMP (N-methyl-2-pyrrolidone) as the eluent.
  • NMP N-methyl-2-pyrrolidone
  • THF tetrahydrofuran
  • detection in GPC measurement is performed using a UV (ultraviolet) ray (ultraviolet) detector with a wavelength of 254 nm.
  • a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact.
  • the direction in which layers are stacked on the substrate is referred to as "up,” or, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as “up,” and the opposite direction is referred to as “down.”
  • the "up" direction in this specification may differ from the vertical upward direction.
  • a composition may contain, as each component contained in the composition, two or more compounds corresponding to that component.
  • the content of each component in the composition means the total content of all compounds corresponding to that component.
  • the temperature is 23° C.
  • the atmospheric pressure is 101,325 Pa (1 atmosphere)
  • the relative humidity is 50% RH.
  • combinations of preferred embodiments are more preferred embodiments.
  • the resin composition of the present invention (hereinafter also simply referred to as "resin composition”) contains a resin and a solvent, and the resin is a polyamic acid ester having an imidization rate of 3 to 45% and an amine value of 0.100 mmol/g or less.
  • a polyamic acid ester having an imidization rate of 3 to 45% and an amine value of 0.100 mmol/g or less will also be simply referred to as a "specific resin.”
  • the resin composition of the present invention is preferably used to form a photosensitive film that is subjected to exposure and development, and more preferably used to form a film that is subjected to exposure and development using a developer containing an organic solvent.
  • the resin composition of the present invention can be used to form, for example, an insulating film for a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, etc., and is preferably used to form an interlayer insulating film for a rewiring layer.
  • the resin composition of the present invention is preferably used for forming a photosensitive film to be subjected to negative development.
  • Such a resin composition to be used for forming a photosensitive film to be subjected to negative development is also called a negative photosensitive resin composition.
  • negative development refers to development in which the unexposed areas are removed by development
  • positive development refers to development in which the exposed areas are removed by development.
  • the exposure method, the developer, and the development method for example, the exposure method described in the exposure step and the developer and development method described in the development step in the description of the method for producing a cured product described below can be used.
  • the resin composition of the present invention has excellent storage stability, and the resulting cured product has excellent insulating reliability.
  • the mechanism by which the above effects are obtained is unknown, but is speculated as follows.
  • the present inventors have found that in the method using a carbodiimide compound, the imidization reaction proceeds in the resin as described above, and although the resulting cured product has excellent mechanical properties such as elongation at break, the active terminals become inactive due to acylurea formation, and the starting diamine may not react sufficiently, resulting in a large amount of aromatic amino groups at the resin terminals.
  • the basicity of the produced resin increases, promoting imidization of the resin in the composition and reducing the storage stability of the composition.
  • the amine value of the specific resin is 0.100 mmol/g or less.
  • the present inventors have found that when the amine value of the specific resin is 0.100 mmol/g or less, imidization is less likely to proceed during curing. Therefore, the present inventors have found that the imidization rate of the specific resin can be increased to a relatively high value of 3 to 45% and that the specific resin is imidized to a certain extent in advance. In this way, it is believed that an increase in the imidization rate in the cured film improves, for example, the heat resistance and moisture resistance of the film, thereby improving the insulation reliability.
  • a polyamic acid ester satisfying the following conditions (a) and (b) can be obtained by a method for producing a polyamic acid ester, which includes a step of polycondensing a dicarboxylic acid and a diamine compound in the presence of a carbodiimide compound as a condensing agent and an active esterifying agent: (a) the imidization rate is 3 to 45%; (b) the amine value is 0.100 mmol/g or less. Furthermore, it has been found that by subjecting the polyamic acid ester obtained by the above process to an ion exchange treatment, the acid value can be increased and storage stability can be further improved.
  • Patent Document 1 does not describe resin compositions containing specific resins.
  • the resin composition of the present invention contains a polyamic acid ester (specific resin) having an imidization rate of 3 to 45% and an amine value of 0.100 mmol/g or less.
  • the specific resin is preferably a polyimide precursor.
  • the polyimide precursor refers to a resin that changes its chemical structure in response to an external stimulus to become a polyimide.
  • a resin that changes its chemical structure in response to heat to become a polyimide is preferred, and a resin that changes its chemical structure in response to heat to become a polyimide by forming a ring structure is more preferred.
  • polyimide refers to a resin having a repeating unit containing an imide group in the molecular chain, and is preferably a resin having a repeating unit containing an imide ring structure in the molecular chain.
  • the polyimide is a linear resin, the polyimide is preferably a resin having a repeating unit containing an imide group in the main chain, and more preferably a resin having a repeating unit containing an imide ring structure in the main chain.
  • the term “main chain” refers to the relatively longest bonding chain in a resin molecule, and the term “side chain” refers to any other bonding chain.
  • the imide ring structure refers to a ring structure containing two carbon atoms and all of the nitrogen atoms in the imide as ring members.
  • the imide ring structure is preferably a five-membered ring.
  • the polyimide may be a so-called polyamideimide, which has an amide group in the molecular chain in addition to an imide group.
  • * represents a bonding site to another structure, preferably a bonding site to a hydrogen atom or a carbon atom, and more preferably a bonding site to a hydrogen atom.
  • the imidization rate of the specific resin is 3 to 45%. From the viewpoint of elongation at break, the imidization rate is preferably 5% or more, more preferably 10% or more, and even more preferably 15% or more. Furthermore, from the viewpoint of resolution, the imidization rate is preferably 40% or less, more preferably less than 40%, even more preferably 35% or less, even more preferably 30% or less, and particularly preferably 25% or less.
  • the imidization rate is a value calculated by the following method.
  • the resin is dissolved in ⁇ -butyrolactone, diluted to a viscosity of 2,000 mPa ⁇ s, and applied to a silicon wafer by spin coating to form a resin layer. If a resin layer cannot be formed due to reasons such as low solubility of the resin in ⁇ -butyrolactone, the solvent may be changed to another solvent. Examples of other solvents include solvents contained in the resin composition, such as NMP. The viscosity may also be adjusted as needed.
  • the silicon wafer to which the resulting resin layer is applied is dried on a hot plate at 110°C for 5 minutes to obtain a resin layer with a uniform thickness of approximately 15 ⁇ m after film formation on the silicon wafer.
  • the film thickness may be adjusted as needed. For example, if the film thickness is 5 ⁇ m or greater, the imidization rate will be approximately the same.
  • the resin layer is measured by the ATR method using a NicoletiS20 (manufactured by Thermofisher) in the measurement range of 4000 to 700 cm ⁇ 1 , with 50 measurements.
  • the amine value of the specific resin is 0.100 mmol/g or less, preferably 0.090 mmol/g or less, and more preferably 0.080 mmol/g or less.
  • the lower limit of the amine value is not particularly limited, and it is sufficient if it is 0.000 mmol/g or more.
  • the amine value is measured by dissolving 0.60 g of resin in 50 mL of diglyme, adding 10 mL of acetic acid to prepare a measurement solution, and titrating the solution with a 0.01 N (0.01 mol/L) perchloric acid solution in acetic acid to detect the neutralization point.
  • the specific resin contains substantially no fluorine atoms.
  • substantially no fluorine atoms means that the amount of fluorine atoms relative to the total mass of the specific resin is less than 5% by mass, preferably less than 1% by mass, more preferably less than 0.1% by mass, and even more preferably less than 0.01% by mass.
  • the amount of fluorine atoms may be 0% by mass.
  • the method for producing the specific resin preferably includes a step of polycondensing a dicarboxylic acid and a diamine in the presence of a carbodiimide compound as a condensing agent and an active esterifying agent (polycondensation step).
  • ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
  • esters include methyl acetate, ethyl acetate, butyl acetate, and diethyl oxalate
  • lactones include ⁇ -butyrolactone
  • ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran
  • halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, chlorobenzene, and o-dichlorobenzene
  • hydrocarbons include hexane, heptane, benzene, toluene, and xylene; etc.
  • the diamine may, for example, be a compound represented by the following formula (DAm-1).
  • Y1 represents a divalent organic group.
  • preferred embodiments of Y 1 are the same as the preferred embodiments of Y 1 in formula (1-1) described above.
  • carbodiimide compound As the carbodiimide compound, dialkylcarbodiimide is preferred, and dicyclohexylcarbodiimide or diisopropylcarbodiimide is more preferred.
  • the amount of the carbodiimide compound used is not particularly limited and may be appropriately determined depending on the raw material. For example, the amount is preferably 1.0 to 5.0 molar equivalents, and more preferably 1.5 to 3.0 molar equivalents, relative to the molar amount of the dicarboxylic acid used as the raw material.
  • Active esterifying agent examples include 1-hydroxybenzotriazole or 1-hydroxy-7-azabenzotriazole, N-hydroxysuccinimide, ethyl cyano(hydroxyimino)acetate (oxyma), and the like, with 1-hydroxybenzotriazole or 1-hydroxy-7-azabenzotriazole being preferred.
  • the amount of the active esterifying agent used is not particularly limited and may be appropriately determined depending on the raw material. For example, the amount is preferably 0.1 to 2.5 molar equivalents, and more preferably 0.2 to 2.2 molar equivalents, relative to the molar amount of the dicarboxylic acid used as the raw material.
  • the above-mentioned dicarboxylic acid is mixed with the above-mentioned carbodiimide compound, preferably under ice cooling, to convert the dicarboxylic acid into a polyacid anhydride intermediate, and then the above-mentioned diamine dissolved in a solvent (preferably the solvent described in the above esterification reaction) is added dropwise to the polyacid anhydride to cause amide polycondensation between the two, thereby obtaining a polyamic acid ester.
  • a solvent preferably the solvent described in the above esterification reaction
  • precipitated by-products may be filtered off as needed, and then a suitable poor solvent (e.g., water, aliphatic lower alcohol, or a mixture thereof) may be added to the solution containing the polyamic acid ester to precipitate the polyamic acid ester. Further, redissolution and reprecipitation procedures may be repeated as needed to purify the polyamic acid ester, followed by vacuum drying to isolate the target polyamic acid ester.
  • a suitable poor solvent e.g., water, aliphatic lower alcohol, or a mixture thereof
  • the method for producing the specific resin preferably includes a step of treating the condensate obtained in the polycondensation step with an ion exchange resin.
  • the ion exchange resin is preferably an amphoteric ion exchange resin or an anion exchange resin.
  • the treatment with an ion exchange resin can be carried out, for example, by passing a solution of the condensate obtained in the polycondensation step (which may be purified, if necessary, by repeating the redissolution and reprecipitation procedures) through a column packed with the ion exchange resin swollen with a solvent (preferably the solvent described in the above-mentioned esterification reaction).
  • the content of the specific resin in the resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total solid content of the resin composition. Also, the content of the specific resin in the resin composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, even more preferably 98% by mass or less, even more preferably 97% by mass or less, and even more preferably 95% by mass or less, based on the total solid content of the resin composition.
  • the resin composition of the present invention may contain only one specific resin or two or more specific resins. When two or more specific resins are contained, the total amount is preferably within the above range.
  • the resin composition of the present invention may contain the above-mentioned specific resin and another resin different from the specific resin (hereinafter, also simply referred to as "another resin").
  • other resins include polyimide precursors that do not fall under the category of specific resins, polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamides that do not fall under the category of polyimide precursors, 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.
  • the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, still more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total solid content of the resin composition.
  • the content of the other resins is preferably 80 mass% or less, more preferably 75 mass% or less, even more preferably 70 mass% or less, still more preferably 60 mass% or less, and even more preferably 50 mass% or less, relative to the total solid content of the resin composition.
  • a preferred embodiment of the resin composition of the present invention may be an embodiment in which the content of the other resin is low.
  • the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition.
  • the lower limit of the content is not particularly limited, and may be 0% by mass or more.
  • the resin composition of the present invention may contain only one type of other resin, or may contain two or more types. When two or more types are contained, the total amount is preferably in the above range.
  • the resin composition of the present invention preferably contains a polymerizable compound.
  • the polymerizable compound may be a radical crosslinking agent or other crosslinking agent.
  • the resin composition of the present invention preferably contains a radical crosslinking agent.
  • the radical crosslinking agent is a compound having a radical polymerizable group.
  • the radical polymerizable group is preferably a group containing an ethylenically unsaturated bond.
  • Examples of the group containing an ethylenically unsaturated bond include a vinyl group, an allyl group, a vinylphenyl group, a (meth)acryloyl group, a maleimide group, and a (meth)acrylamide group.
  • a (meth)acryloyl group, a (meth)acrylamide group, and a vinylphenyl group are preferred, and from the viewpoint of reactivity, a (meth)acryloyl group is more preferred.
  • the radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, more preferably a compound having two or more ethylenically unsaturated bonds, and may also have three or more ethylenically unsaturated bonds.
  • the compound having two or more ethylenically unsaturated bonds is preferably a compound having 2 to 15 ethylenically unsaturated bonds, more preferably a compound having 2 to 10 ethylenically unsaturated bonds, and even more preferably a compound having 2 to 6 ethylenically unsaturated bonds.
  • the resin composition of the present invention contains a compound having two ethylenically unsaturated bonds and the compound having three or more ethylenically unsaturated bonds.
  • the molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less.
  • the lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
  • radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), their esters, and amides.
  • esters of unsaturated carboxylic acids and polyhydric alcohol compounds are esters of unsaturated carboxylic acids and polyamine compounds.
  • addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxy groups, and dehydration condensation reaction products of monofunctional or polyfunctional carboxylic acids.
  • the radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure.
  • Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available products include KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available products include KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available products include KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available products include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)), and structures in which
  • radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate with four ethyleneoxy chains, SR-209, 231, and 239, difunctional methacrylates with four ethyleneoxy chains (all manufactured by Sartomer Corporation), DPCA-60, a hexafunctional acrylate with six pentyleneoxy chains, and TPA-330, a trifunctional acrylate with three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers.
  • SR-494 a tetrafunctional acrylate with four ethyleneoxy chains
  • SR-209, 231, and 239 difunctional methacrylates with four ethyleneoxy chains
  • DPCA-60 a hexafunctional acrylate with six pentyleneoxy chains
  • TPA-330 a trifunctional acrylate with three isobutyleneoxy chains (all manufactured by Nippon Kayaku Co., Ltd.), and urethane oligomers.
  • esters examples include UAS-10 and UAB-140 (manufactured by Nippon Paper Industries Co., Ltd.), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, and UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.), and Blenmar PME400 (manufactured by NOF Corporation).
  • Suitable radical crosslinking agents include urethane acrylates such as those described in JP-B No. 48-041708, JP-A No. 51-037193, JP-B No. 02-032293, and JP-B No. 02-016765, as well as urethane compounds with an ethylene oxide skeleton such as those described in JP-B No. 58-049860, JP-B No. 56-017654, JP-B No. 62-039417, and JP-B No. 62-039418.
  • Compounds with an amino structure or sulfide structure in the molecule such as those described in JP-A Nos. 63-277653, 63-260909, and JP-A No. 01-105238, can also be used as radical crosslinking agents.
  • the 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.
  • 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, in which the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol.
  • examples of commercially available products include polybasic acid-modified acrylic oligomers M-510 and M-520 manufactured by Toagosei Co., Ltd.
  • 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").
  • crosslinking agent U a radical crosslinking agent having at least one selected from the group consisting of a urea bond and a urethane bond.
  • crosslinking agent U examples include compounds described in paragraphs 0133 to 0143 of WO 2023/190064, the contents of which are incorporated herein by reference.
  • a bifunctional methacrylate or acrylate for the resin composition.
  • Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexyl methyl ...
  • Examples of usable surfactants include xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, EO-modified isocyanuric acid diacrylate, EO-modified isocyanuric acid dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having a urethane bond.
  • EO ethylene oxide
  • PO propylene oxide
  • PO propylene oxide
  • PO propylene oxide
  • adduct dimethacrylate of bisphenol A 2-hydroxy-3-acryloyloxyprop
  • PEG200 diacrylate refers to polyethylene glycol diacrylate with a formula weight of about 200 for the polyethylene glycol chain.
  • a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent.
  • Examples of the monofunctional radical crosslinking agent include (meth)acrylic acid derivatives such as n-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate, butoxyethyl(meth)acrylate, carbitol(meth)acrylate, cyclohexyl(meth)acrylate, benzyl(meth)acrylate, phenoxyethyl(meth)acrylate, N-methylol(meth)acrylamide, glycidyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether.
  • (meth)acrylic acid derivatives such as n-butyl(meth)acrylate, 2-ethylhex
  • compounds having a boiling point of 100°C or higher under normal pressure are also preferred as the monofunctional radical crosslinking agent.
  • the bifunctional or higher functional radical crosslinking agent include allyl compounds such as diallyl phthalate and triallyl trimellitate.
  • the content of the radical crosslinking agent is preferably more than 0% by mass and not more than 60% by mass, based on the total solids content of the resin composition.
  • the lower limit is more preferably 5% by mass or more.
  • the upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.
  • a single radical crosslinking agent may be used, or two or more may be used in combination. When two or more types are used in combination, it is preferable that the total amount be within the above range.
  • the resin composition of the present invention preferably contains a crosslinking agent other than the above-mentioned radical crosslinking agent.
  • the other crosslinking agent refers to a crosslinking agent other than the above-mentioned radical crosslinking agent, and is preferably a compound having, in its molecule, a plurality of groups that promote a reaction to form a covalent bond with another compound in the composition or a reaction product thereof upon exposure to light by a photoacid generator or a photobase generator, and is preferably a compound having, in its molecule, a plurality of groups that promote, by the action of an acid or a base, a reaction to form a covalent bond with another compound in the composition or a reaction product thereof.
  • the acid or base is preferably an acid or base generated from a photoacid generator or a photobase generator in the exposure step.
  • Other cross-linking agents include the compounds described in paragraphs 0179 to 0207 of WO 2022/145355, which are incorporated herein by reference.
  • the resin composition of the present invention preferably contains a polymerization initiator.
  • the polymerization initiator may be a thermal polymerization initiator or a photopolymerization initiator, but it is particularly preferable to include a photopolymerization initiator.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • the photoradical polymerization initiator there are no particular limitations on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators.
  • a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible range is preferred.
  • it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.
  • the photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L mol cm in a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm ) .
  • the molar absorption coefficient of the compound can be measured using a known method. For example, it is preferably measured using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.
  • any known compound can be used as the photoradical polymerization initiator.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, ⁇ -aminoketone compounds such as aminoacetophenone, ⁇ -hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, and iron arene complexes.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihal
  • Preferred oxime compounds include, for example, compounds having the following structure: 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropan-1-one, 2-(benzoyloxy(imino))-1-phenylpropan-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropan-1-one.
  • oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, and IRGACURE OXE 04 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA ARCLES NCI-730, NCI-831, and ADEKA ARCLES NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito ChemiX Co., Ltd.), and SpeedCure PDO (SARTOMER Also, an oxime compound having the following structure can be used.
  • Usable sensitizers include benzophenone-based, Michler's ketone-based, coumarin-based, pyrazole azo-based, anilino azo-based, triphenylmethane-based, anthraquinone-based, anthracene-based, anthrapyridone-based, benzylidene-based, oxonol-based, pyrazolotriazole azo-based, pyridone azo-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, and indigo-based compounds.
  • the content of the sensitizer is preferably 0.01 to 20 mass%, more preferably 0.1 to 15 mass%, and even more preferably 0.5 to 10 mass%, based on the total solids content of the resin composition.
  • One type of sensitizer may be used alone, or two or more types may be used in combination.
  • chain transfer agent may be the compound described in paragraphs 0152-0153 of WO 2015/199219, the contents of which are incorporated herein by reference.
  • the resin composition of the present invention contains two or more types of polymerization initiators.
  • the resin composition of the present invention preferably contains a photopolymerization initiator and a thermal polymerization initiator described below, or contains the above-mentioned photoradical polymerization initiator and a photoacid generator.
  • thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of JP 2008-063554 A, the contents of which are incorporated herein by reference.
  • a thermal polymerization initiator is included, its content is preferably 0.1 to 30 mass% of the total solids content of the resin composition, more preferably 0.1 to 20 mass%, and even more preferably 0.5 to 15 mass%.
  • the resin composition may contain only one type of thermal polymerization initiator, or two or more types. If two or more types of thermal polymerization initiators are included, the total amount is preferably within the above range.
  • the base generator is not particularly limited, and known base generators can be used, such as carbamoyl oxime compounds, carbamoyl hydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzyl carbamate compounds, nitrobenzyl carbamate compounds, sulfonamide compounds, imidazole derivative compounds, amine imide compounds, pyridine derivative compounds, ⁇ -aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, ⁇ -lactone ring derivative compounds, amine imide compounds, phthalimide derivative compounds, and acyloxyimino compounds.
  • Specific examples of non-ionic base generators include the compounds described in paragraphs 0249 to 0275 of WO 2022/145355, the disclosures of which are incorporated herein by reference.
  • Base generators include, but are not limited to, the following compounds:
  • the molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less.
  • the lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.
  • Specific preferred compounds for the ionic base generator include, for example, the compounds described in paragraphs 0148 to 0163 of WO 2018/038002.
  • ammonium salts include, but are not limited to, the following compounds:
  • iminium salts include, but are not limited to, the following compounds:
  • the base generator is an amine in which the amino group is protected with a t-butoxycarbonyl group.
  • Amine compounds protected by a t-butoxycarbonyl group include, for example, ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol.
  • the 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 for example, ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone, ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -valerolactone, 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,
  • 2- Suitable examples include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, eth
  • Suitable examples of ethers include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, di
  • ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucosenone, and dihydrolevoglucosenone.
  • Suitable examples of cyclic hydrocarbons include aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.
  • a suitable example of a sulfoxide is dimethyl sulfoxide.
  • Preferred ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.
  • Alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
  • Another preferred embodiment of the present invention is to further add toluene to these combined solvents in an amount of about 1 to 10% by mass, based on the total mass of the solvents.
  • an embodiment in which ⁇ -valerolactone is contained as a solvent is also one of the preferred embodiments of the present invention.
  • the content of ⁇ -valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more.
  • the upper limit of the content is not particularly limited and may be 100% by mass. The content may be determined taking into consideration the solubility of components such as the specific resin contained in the resin composition, etc.
  • the solvent preferably contains 60 to 90% by mass of ⁇ -valerolactone and 10 to 40% by mass of dimethyl sulfoxide, more preferably 70 to 90% by mass of ⁇ -valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of ⁇ -valerolactone and 15 to 25% by mass of dimethyl sulfoxide, relative to the total mass of the solvent.
  • the solvent content is preferably an amount that results in a total solids concentration of the resin composition of the present invention of 5 to 80 mass%, more preferably an amount that results in a total solids concentration of 5 to 75 mass%, even more preferably an amount that results in a total solids concentration of 10 to 70 mass%, and even more preferably an amount that results in a total solids concentration of 20 to 70 mass%.
  • the solvent content may be adjusted depending on the desired thickness of the coating film and the application method. When two or more solvents are used, the total amount is preferably within the above range.
  • the resin composition of the present invention preferably contains a metal adhesion improver from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc.
  • metal adhesion improvers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure, compounds having a thiourea structure, phosphoric acid derivative compounds, ⁇ -ketoester compounds, and amino compounds.
  • silane coupling agent examples include the compounds described in paragraph 0316 of WO 2021/112189 and the compounds described in paragraphs 0067 to 0078 of JP 2018-173573 A, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of JP 2011-128358 A. It is also preferable to use the following compounds as the silane coupling agent. In the following formula, Me represents a methyl group, and Et represents an ethyl group. Furthermore, the following R represents a structure derived from a blocking agent in a blocked isocyanate group.
  • Blocking agents may be selected depending on the desorption temperature, and examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds.
  • caprolactam is preferred from the perspective of achieving a desorption temperature of 160 to 180°C.
  • Commercially available products of such compounds include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl
  • an oligomer type compound having a plurality of alkoxysilyl groups can also be used as the silane coupling agent.
  • Such oligomer-type compounds include compounds containing a repeating unit represented by the following formula (S-1).
  • R 1 S1 represents a monovalent organic group
  • R 1 S2 represents a hydrogen atom, a hydroxy group or an alkoxy group
  • n represents an integer of 0 to 2.
  • R S1 preferably has a structure containing a polymerizable group.
  • Examples of the polymerizable group include a group having an ethylenically unsaturated bond, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, and an amino group.
  • Examples of the group having an ethylenically unsaturated bond include a vinyl group, an allyl group, an isoallyl group, a 2-methylallyl group, a group having an aromatic ring directly bonded to a vinyl group (for example, a vinylphenyl group), a (meth)acrylamide group, and a (meth)acryloyloxy group.
  • a vinylphenyl group, a (meth)acrylamide group, or a (meth)acryloyloxy group is preferred, a vinylphenyl group or a (meth)acryloyloxy group is more preferred, and a (meth)acryloyloxy group is even more preferred.
  • R S2 is preferably an alkoxy group, more preferably a methoxy group or an ethoxy group.
  • n represents an integer of 0 to 2, and is preferably 1.
  • the structures of the repeating units represented by formula (S-1) contained in the oligomer-type compound may be the same.
  • n is 1 or 2 in at least one, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two.
  • commercially available products can be used, and examples of commercially available products include KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Aluminum-based adhesion promoter examples include aluminum tris(ethylacetoacetate), aluminum tris(acetylacetonate), and ethylacetoacetate aluminum diisopropylate.
  • metal adhesion improvers that can be used include the compounds described in paragraphs 0046 to 0049 of JP 2014-186186 A and the sulfide-based compounds described in paragraphs 0032 to 0043 of JP 2013-072935 A, the contents of which are incorporated herein by reference.
  • the content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. By 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 may contain compound X1.
  • Compound X1 is a compound having at least one structure selected from the group consisting of a 1,3-dicarbonyl structure and a ⁇ -hydroxycarbonyl structure, and having a molecular weight of 1,000 or less.
  • the 1,3-dicarbonyl structure refers to a structure represented by the following formula (DC-1)
  • the ⁇ -hydroxycarbonyl structure refers to a structure represented by the following formula (HC-1).
  • the compound X1 does not contain a metal atom in its structure, and the metal atom in this case does not include a metalloid atom such as silica. In addition, it is preferable that the compound X1 is not coordinated to a metal atom in the resin composition.
  • the molecular weight of compound X1 is 1,000 or less, preferably 100 to 500, more preferably 100 to 400, even more preferably 100 to 350, particularly preferably 100 to 300, and even more preferably 100 to 250.
  • compound X1 include, but are not limited to, compounds having the following structures:
  • the content of compound X1 relative to the total solid content of the resin composition of the present invention is preferably 0.01 to 30% by mass.
  • the lower limit is more preferably 0.02% by mass or more, even more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more.
  • the upper limit is more preferably 20% by mass or less, even more preferably 10% by mass or less, and particularly preferably 5% by mass or less.
  • An embodiment in which the content is 1% by mass or less is also one of the preferred embodiments of the present invention.
  • Compound X1 may be used singly or in combination of two or more. When two or more types are used in combination, the total amount thereof is preferably within the above range.
  • the resin composition of the present invention preferably further contains a migration inhibitor.
  • a migration inhibitor for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, migration of metal ions derived from the metal layer (or metal wiring) into the film can be effectively suppressed.
  • the migration inhibitor is not particularly limited, but examples thereof include compounds having a heterocycle (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, 6H-pyran ring, triazine ring), thioureas and compounds having a sulfanyl group, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds.
  • a heterocycle pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring
  • triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole
  • tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole are preferably used.
  • the resin composition of the present invention preferably contains 8-azaadenine.
  • Ion trapping agents that capture anions such as halogen ions can also be used as migration inhibitors.
  • Other migration inhibitors that can be used include the rust inhibitors described in paragraph 0094 of JP 2013-015701 A, the compounds described in paragraphs 0073 to 0076 of JP 2009-283711 A, the compounds described in paragraph 0052 of JP 2011-059656 A, the compounds described in paragraphs 0114, 0116, and 0118 of JP 2012-194520 A, and the compounds described in paragraph 0166 of WO 2015/199219, the contents of which are incorporated herein by reference.
  • migration inhibitors include the following compounds:
  • the content of the migration inhibitor is preferably 0.01 to 5.0 mass%, more preferably 0.05 to 2.0 mass%, and even more preferably 0.1 to 1.0 mass%, relative to the total solids content of the resin composition.
  • the migration inhibitor may be one type or two or more types. If two or more types of migration inhibitors are used, it is preferable that the total amount is within the above range.
  • the resin composition of the present invention 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 resin composition of the present invention may contain at least one compound (hereinafter also referred to as "urea compound, etc.") selected from the group consisting of compounds having a urea bond (urea compound), compounds having a carbodiimide structure (carbodiimide compound), and compounds having an isourea bond (isourea compound).
  • urea compound compounds having a urea bond
  • the resin composition of the present invention further contains a compound having a urea bond.
  • the urea compounds and the like referred to here do not include the above-mentioned polymerizable compounds and compounds corresponding to silane coupling agents. Examples of the urea compound include the compounds described in paragraphs 0334 to 0339 of WO 2022/070730.
  • the total content of the urea compounds and the like is preferably 0.1 to 10.0 parts by mass, more preferably 0.5 to 8.0 parts by mass, and even more preferably 1.0 to 6.0 parts by mass, per 100 parts by mass of the specific resin.
  • the urea compounds and the like may be used alone or in combination of two or more. When two or more bases are used in combination in the base-containing treatment liquid, it is preferable that the total content thereof is within the above range.
  • the resin composition of the present invention also preferably contains a compound (light absorber) that reduces the absorbance of light at the exposure wavelength upon exposure.
  • a compound light absorber
  • Examples of the light absorber include the compounds described in paragraphs 0159 to 0183 of WO 2022/202647 and the compounds described in paragraphs 0088 to 0108 of JP 2019-206689 A. The contents of these compounds are incorporated herein by reference.
  • the total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
  • 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.
  • methods for reducing metal impurities unintentionally contained in the resin composition of the present invention include selecting raw materials with low metal content as the raw materials for constituting the resin composition of the present invention, filtering the raw materials for constituting the resin composition of the present invention, and lining the inside of the apparatus with polytetrafluoroethylene or the like to perform distillation under conditions that minimize contamination as much as possible.
  • the content of halogen atoms is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass from the viewpoint of wiring corrosion.
  • those present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass.
  • Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above range.
  • a preferred method for adjusting the content of halogen atoms is ion exchange treatment.
  • any conventional container known in the art can be used as a container for storing the resin composition of the present invention.
  • a container for storing the resin composition of the present invention For the purpose of preventing impurities from being mixed into the raw materials or the resin composition of the present invention, it is also preferable to use a multi-layer bottle whose inner wall is made up of six layers of six types of resin, or a bottle with a seven-layer structure made up of six types of resin. Examples of such containers include the container described in JP 2015-123351 A.
  • a cured product of the resin composition By curing the resin composition of the present invention, a cured product of the resin composition can be obtained.
  • the cured product of the present invention is a cured product obtained by curing a resin composition.
  • the resin composition is preferably cured by heating, with the heating temperature being more preferably 120°C to 400°C, even more preferably 140°C to 380°C, and particularly preferably 170°C to 350°C.
  • the form of the cured product of the resin composition is not particularly limited, and can be selected according to the application, such as film, rod, sphere, or pellet.
  • the cured product is preferably in the form of a film.
  • the shape of the cured product can be selected according to the application, such as forming a protective film on the wall surface, forming via holes for electrical conduction, adjusting impedance, capacitance, or internal stress, or imparting heat dissipation functionality.
  • the film thickness of the cured product (film made of the cured product) is preferably 0.5 ⁇ m or more and 150 ⁇ m or less.
  • the shrinkage percentage of the resin composition of the present invention when cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less.
  • the imidization reaction rate of the cured product of the resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties.
  • the elongation at break of the cured product of the resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
  • the glass transition temperature (Tg) of the cured product of the resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.
  • the resin composition of the present invention can be prepared by mixing the above-mentioned components.
  • the mixing method is not particularly limited, and can be carried out by a conventionally known method. Examples of the mixing method include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank.
  • the temperature during mixing is preferably 10 to 30°C, more preferably 15 to 25°C.
  • 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. Examples of filters include the filters described in paragraph 0287 of WO 2023/190064. The above content is incorporated herein by reference.
  • 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 film thickness, spin coating, slit coating, spray coating, or inkjet coating is preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred.
  • 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 the substrate is coated with various solvents 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.
  • 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 content of the organic solvent relative to the total weight of the developer is preferably 50% by weight or more, more preferably 70% by weight or more, even more preferably 80% by weight or more, and particularly preferably 90% by weight or more.
  • the above content may also be 100% by weight.
  • the developer may further contain other components.
  • other components include known surfactants and known defoaming agents.
  • 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 include the same organic solvents as those exemplified when the developer contains an organic solvent.
  • the organic solvent contained in the rinse liquid is preferably different from the organic solvent contained in the developer, and more preferably an organic solvent that has a lower solubility for the pattern than the organic solvent contained in the developer.
  • 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 liquid may contain at least one of a basic compound and a base generator.
  • a basic compound and a base generator when the developer contains an organic solvent, one preferred embodiment of the present invention is one in which the rinse liquid contains an organic solvent and at least one of a basic compound and a base generator.
  • the basic compound and base generator contained in the rinse solution include the compounds exemplified as the basic compound and base generator that may be contained in the above-mentioned developer containing an organic solvent, and preferred embodiments are also the same.
  • the basic compound and base generator contained in the rinse solution may be selected in consideration of the solubility in the solvent in the rinse solution.
  • the rinse solution may further contain other ingredients.
  • other components include known surfactants and known defoaming agents.
  • the method of supplying the rinse liquid is not particularly limited as long as it can form a desired pattern, and examples thereof include a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid to the substrate by puddling, a method of supplying the rinse liquid to the substrate by showering, and a method of continuously supplying the rinse liquid onto the substrate by means of a straight nozzle or the like.
  • the rinse liquid can be supplied using a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuously supplying the rinse liquid using a spray nozzle is preferred, and from the viewpoint of the permeability of the rinse liquid into the image areas, the method of supplying the rinse liquid using a spray nozzle is more preferred.
  • the type of nozzle is not particularly limited, and examples include a straight nozzle, a shower nozzle, a spray nozzle, etc.
  • the rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes.
  • the temperature of the rinsing liquid during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.
  • the development process may include a step of contacting the pattern with a processing liquid after treatment with a developer or after washing the pattern with a rinse liquid. It may also be possible to employ a method in which the processing liquid is supplied before the developer or rinse liquid in contact with the pattern has completely dried.
  • 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 specific resin is cyclized to form a polyimide. Furthermore, crosslinking of unreacted crosslinkable groups in the specific resin or in a crosslinking agent other than the specific resin also proceeds.
  • the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, still more preferably 160 to 250°C, and particularly preferably 160 to 230°C.
  • the heating step is preferably a step in which the cyclization reaction of the specific resin within the pattern is promoted by the action of the base generated from the base generator due to heating.
  • the heating step is preferably carried out at a temperature increase rate of 1 to 12°C/min from the temperature at the start of heating to the maximum heating temperature.
  • the temperature increase rate is more preferably 2 to 10°C/min, and even more preferably 3 to 10°C/min.
  • the heating rate from the initial temperature to the maximum heating temperature is preferably 1 to 8°C/sec, more preferably 2 to 7°C/sec, and even more preferably 3 to 6°C/sec.
  • the temperature at the start of heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C.
  • the temperature at the start of heating refers to the temperature at which the process of heating up to the maximum heating temperature begins.
  • this is the temperature of the film (layer) after drying.
  • it is preferable to raise the temperature from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.
  • the heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.
  • the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and particularly preferably 120°C or higher.
  • the upper limit of the heating temperature is preferably 350°C or less, more preferably 250°C or less, and even more preferably 240°C or less.
  • 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 specific resin proceeds due to exposure of a photobase generator to light, or a reaction in which elimination of an acid-decomposable group proceeds due to exposure of a photoacid generator to light, can be promoted.
  • the post-development exposure step it is sufficient that at least a part of the pattern obtained in the development step is exposed, but it is preferable that the entire pattern is exposed.
  • the exposure dose in the post-development exposure step is preferably 50 to 20,000 mJ/cm 2 , 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 pattern obtained by the development step (which is preferably subjected to at least one of the heating step and the post-development exposure step) may be subjected to a metal layer forming step in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer forming step of forming a metal layer on the pattern obtained by the development step (preferably the pattern has been subjected to at least one of a heating step and a post-development exposure step).
  • the metal layer is not particularly limited and any existing metal species can be used, including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals. Copper and aluminum are more preferred, and copper is even more preferred.
  • the method for forming the metal layer is not particularly limited, and existing methods can be applied.
  • the methods described in JP 2007-157879 A, JP 2001-521288 A, JP 2004-214501 A, JP 2004-101850 A, U.S. Patent No. 7,888,181 B2, and U.S. Patent No. 9,177,926 B2 can be used.
  • suitable methods include photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and combinations of these. More specific examples include patterning methods that combine sputtering, photolithography, and etching, and patterning methods that combine photolithography and electroplating.
  • a preferred form of plating is electroplating using a copper sulfate or copper cyanide plating solution.
  • the thickness of the metal layer at its thickest point is preferably 0.01 to 50 ⁇ m, and more preferably 1 to 10 ⁇ m.
  • Examples of fields to which the cured product manufacturing method of the present invention or the cured product can be applied include insulating films for electronic devices, interlayer insulating films for rewiring layers, stress buffer films, etc. Other examples include etching patterns for sealing films, substrate materials (base films, coverlays, and interlayer insulating films for flexible printed circuit boards), and insulating films for packaging applications such as those described above.
  • the method for producing the cured product of the present invention, or the cured product of the present invention can also be used to produce printing plates such as offset printing plates or screen printing plates, to etch molded parts, and to produce protective lacquers and dielectric layers in electronics, particularly microelectronics.
  • the laminate of the present invention refers to a structure having a plurality of layers each made of the cured product of the present invention.
  • the laminate is a laminate including two or more layers made of a cured product, and may be a laminate including three or more layers.
  • at least one is a layer made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product associated with the shrinkage, it is also preferable that all of the layers made of the cured product contained in the laminate are layers made of the cured product of the present invention.
  • the method for producing a laminate of the present invention preferably includes the method for producing a cured product of the present invention, and more preferably includes repeating the method for producing a cured product of the present invention multiple times.
  • the laminate of the present invention preferably includes two or more layers made of a cured product, and a metal layer between any two of the layers made of the cured product.
  • the metal layer is preferably formed by the metal layer-forming step. That is, the method for producing a laminate of the present invention preferably further includes a metal layer-forming step of forming a metal layer on the layer made of the cured product, between the steps for producing a cured product that are performed multiple times. Preferred aspects of the metal layer-forming step are as described above.
  • the laminate for example, a laminate including at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order, can be mentioned as a preferred example. It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention.
  • the resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions.
  • the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
  • the method for producing the laminate of the present invention preferably includes a lamination step.
  • the lamination process is a series of processes including (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) at least one of a heating process and a post-development exposure process, which are carried out again on the surface of the pattern (resin layer) or metal layer in this order.
  • at least one of the (a) film formation process and the (d) heating process and the post-development exposure process may be repeated.
  • the (e) metal layer formation process may be included. It goes without saying that the lamination process may further include the above-mentioned drying process, etc. as appropriate.
  • a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step.
  • An example of a surface activation treatment is plasma treatment. Details of the surface activation treatment will be described later.
  • the lamination step is preferably carried out 2 to 20 times, more preferably 2 to 9 times.
  • a structure of 2 to 20 resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a structure of 2 to 9 resin layers is more preferred.
  • the above layers may be the same or different in composition, shape, film thickness, etc.
  • a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer.
  • a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer.
  • Specific examples include an embodiment in which the following steps are repeated in this order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step; or an embodiment in which the following steps are repeated in this order: (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step.
  • the method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment.
  • the surface activation treatment step is usually performed after the metal layer formation step, but the resin composition layer may be subjected to the surface activation treatment step after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) and then the metal layer formation step may be performed.
  • the surface activation treatment may be performed on at least a portion of the metal layer, or on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the resin composition layer after exposure.
  • the surface activation treatment is preferably performed on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region of the metal layer on which the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, it is possible to improve the adhesion with the resin composition layer (film) provided on the surface.
  • the surface activation treatment is preferably performed on a part or all of the resin composition layer (resin layer) after exposure. By performing the surface activation treatment on the surface of the resin composition layer in this way, it is possible to improve the adhesion with a metal layer or a resin layer provided on the surface that has been surface-activated.
  • the resin composition layer when negative development is performed, for example, if the resin composition layer is cured, it is less susceptible to damage due to the surface treatment, and adhesion is likely to be improved.
  • the surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • the present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention.
  • the present invention also discloses a method for producing a semiconductor device, which includes the method for producing the cured product of the present invention or the method for producing the laminate.
  • semiconductor devices using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer the descriptions in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-027357 can be referred to, and the contents of these can be incorporated into this specification.
  • the method for producing a polyamic acid ester of the present invention includes a step of polycondensing a dicarboxylic acid and a diamine in the presence of a carbodiimide compound as a condensing agent and an active esterifying agent, and the resulting polyamic acid ester satisfies the following conditions (a) and (b): (a) Imidization rate: 3 to 45% (b) Amine value is 0 to 0.10 mmol/g.
  • a preferred embodiment of the method for producing the polyamic acid ester of the present invention is as described above as the method for producing the specific resin.
  • the preferred embodiments of the resulting polyamic acid ester are the same as the preferred embodiments of the specific resin described above.
  • Synthesis Example 1 Synthesis of Resin 4 0.015 g of hydroquinone, 5.11 g of 4,4'-oxydiphthalic dianhydride (ODPA), and 3.23 g of bisphthalic dianhydride (BPDA) were placed in a separable flask, and 7.20 g of 2-hydroxyethyl methacrylate (HEMA) and 24.82 g of ⁇ -butyrolactone were added and stirred at room temperature (25°C). 4.47 g of pyridine was added while stirring, and the mixture was stirred for 16 hours to obtain a reaction mixture.
  • ODPA 4,4'-oxydiphthalic dianhydride
  • BPDA bisphthalic dianhydride
  • the structure of Resin 1 is shown below. It was confirmed by 1 H-NMR that Resin 1 had the following structure. In the structure below, the subscripts in parentheses represent the molar ratio of each repeating unit contained.
  • HOAt is 1-hydroxy-7-azabenzotriazole.
  • amphoteric ion exchange resin for the example described as "amphoteric ion exchange resin" in the ion exchange treatment column, 4.0 g of the powdered resin obtained by vacuum drying was dissolved in 26.7 g of tetrahydrofuran, and then 2.0 g of water was added. 5.0 g of ion exchange resin UP6040 (manufactured by AmberTec) was added and stirred for 4 hours. The ion exchange resin was then removed by filtration, and the resulting polymer solution was added to 163.5 g of water to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45°C for 24 hours to obtain a resin powder.
  • anion exchange resin in the ion exchange treatment column, a resin powder was obtained in the same manner as in the case of using an amphoteric ion exchange resin, except that Amberlyst 15 (manufactured by Sigma-Aldrich) was used instead of the ion exchange resin UP6040. All of the above ion exchange resins were used after washing by the following procedure. 150 g of purchased ion exchange resin was suspended in 450 mL of water and stirred for 30 minutes. The water was removed by decantation, and then 450 mL of tetrahydrofuran was added and stirred for 30 minutes.
  • the ion exchange resin was recovered by filtration, washed with 150 mL of tetrahydrofuran, and air-dried on a Nutsche funnel for 30 minutes to prepare washed ion exchange resin.
  • the structures of resins 2, 3, and 5 to 19 were represented by the above formula (P-A).
  • the structures of resins 20 to 21 were represented by the following formula.
  • the structure of each resin was confirmed by 1 H-NMR. In the structures below, the subscripts in parentheses represent the molar ratio of each repeating unit.
  • Synthesis Example C1 Synthesis of Resin C1 Resin C1 was synthesized in the same manner as in Synthesis Example 2, except that an active esterifying agent was not used. The structure of Resin C1 was represented by the above formula (P-A). The structure of the resin was confirmed by 1 H-NMR.
  • the value obtained by dividing the peak height near 1380 cm ⁇ 1 (1350 to 1450 cm ⁇ 1 , the peak with the largest intensity if multiple peaks exist) by the peak height near 1500 cm ⁇ 1 (1460 to 1550 cm ⁇ 1 , the peak with the largest intensity if multiple peaks exist) was defined as the imidization index A of the resin.
  • the imidization index B was calculated in the same manner, and the value obtained by dividing the imidization index A by the imidization index B was calculated as the imidization rate of the resin.
  • each component shown in the table below was mixed to obtain a resin composition.
  • the components shown in the table below were mixed to obtain a comparative composition.
  • the content (blending amount) of each component shown in the table other than the solvent is the amount (parts by mass) shown in the "parts by mass” column of each column in the table.
  • the solvent contents (amounts blended) were adjusted so that the solid content of the composition was the value (mass %) of "solid content concentration” in the table, and the ratio (mass ratio) of the content of each solvent to the total mass of the solvents was the ratio shown in the "Ratio" column in the table.
  • the resulting resin composition and comparative composition were filtered under pressure using a polytetrafluoroethylene filter with a pore width of 0.8 ⁇ m.
  • "-" indicates that the composition does not contain the corresponding component.
  • Resins 1 to 39 and C1 Resins 1 to 39 and C1 obtained in the above synthesis examples
  • B-1 to B-10 Compounds having the following structure (however, B-5 is a compound that also functions as a migration inhibitor)
  • E-1 to E-6, E-9 to E-15 Compounds having the following structure
  • E-7 Ester of 2,2',3,3'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi(1H-indene)-5,5',6,6',7,7'-hexanol and 1,2-naphthoquinone-(2)-diazo-5-sulfonic acid
  • E-8 The following synthetic product: F-554 (manufactured by DIC Corporation) ⁇ BYK-333 (manufactured by BYK Japan Co., Ltd.)
  • NMP N-methyl-2-pyrrolidone
  • EL ethyl lactate
  • DMSO dimethyl sulfoxide
  • GBL ⁇ -butyrolactone
  • MDMPA KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd.)
  • ⁇ toluene toluene
  • ⁇ CP cyclopentanone
  • ⁇ CH cyclohexanone
  • the resin composition or comparative composition prepared in each Example and Comparative Example was applied in the form of a layer to a copper substrate by spin coating, respectively, to form a resin composition layer or comparative composition layer.
  • the copper substrate on which the resulting resin composition layer or comparative composition layer was formed was dried on a hot plate at 100°C for 5 minutes, resulting in a resin composition layer or comparative composition layer with a uniform thickness of 20 ⁇ m on the copper substrate.
  • the resin composition layer or comparative composition layer on the copper substrate was exposed to light with an exposure wavelength (nm) listed in the "Exposure Wavelength (nm)" column of the table, using a photomask with a 1:1 line-and-space pattern formed in 1 ⁇ m increments from 5 ⁇ m to 25 ⁇ m, and a stepper as the light source, at an exposure energy of 500 mJ/cm2.
  • a direct exposure apparatus ADTECH DE-6UH III
  • laser direct imaging exposure was performed in a 1:1 line and space pattern range of 5 ⁇ m to 25 ⁇ m in 1 ⁇ m increments without using a photomask.
  • the film was developed with cyclopentanone for 60 seconds and rinsed with PGMEA to obtain a square resin layer with a side length of 100 ⁇ m.
  • the exposed resin composition layer was heated at a heating rate of 10°C/min in a nitrogen atmosphere using a hot plate. After reaching the temperature listed in the "Cure temperature (°C)” column in the table, the temperature was maintained for the “Cure time (min)” in the table to obtain a cured product.
  • Evaluation criteria A: The minimum line width of the line and space pattern formed was less than 10 ⁇ m.
  • Viscosity change rate (%)
  • the longitudinal elongation of the peeled cured product (a test piece having a sample width of 3 mm and a sample length of 30 mm) was measured using a tensile tester (Tensilon) at a crosshead speed of 300 mm/min, 25°C, and 65% RH (relative humidity) in accordance with JIS K 6251:2017. Each measurement was performed five times, and the arithmetic average of the elongation at which the test piece broke (elongation at break) in the five measurements was used as the index value. The evaluation was carried out according to the following evaluation criteria, and the evaluation results are shown in the column "Elongation at break" in the table. The larger the index value, the better the film strength of the cured product. -Evaluation criteria- A: The index value was 65% or more. B: The index value was 55% or more and less than 65%. C: The index value was less than 55%.
  • the obtained void area ratio was evaluated according to the following evaluation criteria. The evaluation results are shown in the "Insulation reliability" column in the table. The smaller the void area ratio, the better the adhesion of the cured film after the heat resistance test and the better the insulation reliability. -Evaluation criteria- A: The void area ratio was 0.5% or less. B: The void area ratio exceeded 0.5%.
  • the resin composition of the present invention has excellent storage stability, and that the resin composition of the present invention can give a cured product with excellent insulation reliability.
  • the comparative composition according to Comparative Example 1 does not contain the specific resin, and it is clear that such a comparative composition has poor storage stability.
  • Example 201 The resin composition used in Example 1 was applied in the form of a layer by spin coating onto the surface of the thin copper layer of a resin substrate having a thin copper layer formed on its surface, and dried at 100°C for 5 minutes to form a photosensitive film with a thickness of 20 ⁇ m. This was then exposed using a stepper (Nikon Corporation, NSR1505 i6). The exposure was carried out at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 ⁇ m). After the exposure, the film was developed in cyclopentanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain a layer pattern.
  • the temperature was increased at a rate of 10° C./min in a nitrogen atmosphere, and after reaching 230° C., the temperature was maintained at 230° C. for 180 minutes to form an interlayer insulating film for a rewiring layer.
  • This interlayer insulating film for a rewiring layer had excellent insulating properties. Furthermore, when a semiconductor device was manufactured using this interlayer insulating film for rewiring layer, it was confirmed that it operated without any problems.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne une composition de résine qui contient une résine et un solvant. Ladite résine consiste en un ester d'acide polyamique qui présente un taux d'imidisation compris entre ３ et ４５％, et un indice d'amine inférieur ou égal à ０,１００ｍｍｏｌ／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, un dispositif à semi-conducteurs ainsi qu'un procédé de fabrication de celui-ci, et un procédé de fabrication d'ester d'acide polyamique.
PCT/JP2025/005895 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, dispositif à semi-conducteurs ainsi que procédé de fabrication de celui-ci, et procédé de fabrication d'ester d'acide polyamique Pending WO2025178103A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024025595 2024-02-22
JP2024-025595 2024-02-22

Publications (1)

Publication Number Publication Date
WO2025178103A1 true WO2025178103A1 (fr) 2025-08-28

Family

ID=96847229

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2025/005895 Pending WO2025178103A1 (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, dispositif à semi-conducteurs ainsi que procédé de fabrication de celui-ci, et procédé de fabrication d'ester d'acide polyamique

Country Status (1)

Country Link
WO (1) WO2025178103A1 (fr)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019101439A (ja) * 2017-11-30 2019-06-24 東レ株式会社 ポジ型感光性樹脂組成物、硬化膜、半導体装置および硬化膜のレリーフパターンの製造方法
JP2020091464A (ja) * 2018-04-27 2020-06-11 旭化成株式会社 ネガ型感光性樹脂組成物及びその製造方法
WO2021235469A1 (fr) * 2020-05-20 2021-11-25 富士フイルム株式会社 Composition de résine durcissable, film durci, stratifié, procédé de production de film durci et dispositif semi-conducteur
WO2022044999A1 (fr) * 2020-08-25 2022-03-03 富士フイルム株式会社 Composition de résine durcissable, produit durci, stratifié, procédé de production de produit durci, dispositif à semi-conducteurs ainsi que précurseur polyimide et procédé de production de celui-ci
JP2022050106A (ja) * 2020-09-17 2022-03-30 旭化成株式会社 ネガ型感光性樹脂組成物、硬化膜および化合物
WO2022071329A1 (fr) * 2020-09-30 2022-04-07 昭和電工マテリアルズ株式会社 Composition de résine, procédé de production de dispositif à semi-conducteur, objet durci, dispositif à semi-conducteur et procédé de synthèse d'un précurseur de polyimide
WO2023058385A1 (fr) * 2021-10-05 2023-04-13 東京応化工業株式会社 Copolymère séquencé
WO2023106108A1 (fr) * 2021-12-09 2023-06-15 日産化学株式会社 Composition de résine photosensible
WO2023171014A1 (fr) * 2022-03-09 2023-09-14 Ｈｄマイクロシステムズ株式会社 Matériau de formation de film isolant, procédé de fabrication de dispositif à semi-conducteur et dispositif à semi-conducteur
JP2023134943A (ja) * 2022-03-15 2023-09-28 東レ株式会社 感光性樹脂組成物、硬化物および有機ｅｌディスプレイ
JP2024004837A (ja) * 2022-06-29 2024-01-17 東京応化工業株式会社 ポリアミド樹脂の製造方法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019101439A (ja) * 2017-11-30 2019-06-24 東レ株式会社 ポジ型感光性樹脂組成物、硬化膜、半導体装置および硬化膜のレリーフパターンの製造方法
JP2020091464A (ja) * 2018-04-27 2020-06-11 旭化成株式会社 ネガ型感光性樹脂組成物及びその製造方法
WO2021235469A1 (fr) * 2020-05-20 2021-11-25 富士フイルム株式会社 Composition de résine durcissable, film durci, stratifié, procédé de production de film durci et dispositif semi-conducteur
WO2022044999A1 (fr) * 2020-08-25 2022-03-03 富士フイルム株式会社 Composition de résine durcissable, produit durci, stratifié, procédé de production de produit durci, dispositif à semi-conducteurs ainsi que précurseur polyimide et procédé de production de celui-ci
JP2022050106A (ja) * 2020-09-17 2022-03-30 旭化成株式会社 ネガ型感光性樹脂組成物、硬化膜および化合物
WO2022071329A1 (fr) * 2020-09-30 2022-04-07 昭和電工マテリアルズ株式会社 Composition de résine, procédé de production de dispositif à semi-conducteur, objet durci, dispositif à semi-conducteur et procédé de synthèse d'un précurseur de polyimide
WO2023058385A1 (fr) * 2021-10-05 2023-04-13 東京応化工業株式会社 Copolymère séquencé
WO2023106108A1 (fr) * 2021-12-09 2023-06-15 日産化学株式会社 Composition de résine photosensible
WO2023171014A1 (fr) * 2022-03-09 2023-09-14 Ｈｄマイクロシステムズ株式会社 Matériau de formation de film isolant, procédé de fabrication de dispositif à semi-conducteur et dispositif à semi-conducteur
JP2023134943A (ja) * 2022-03-15 2023-09-28 東レ株式会社 感光性樹脂組成物、硬化物および有機ｅｌディスプレイ
JP2024004837A (ja) * 2022-06-29 2024-01-17 東京応化工業株式会社 ポリアミド樹脂の製造方法

Similar Documents

Publication Publication Date Title
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
WO2025178098A1 (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
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
JP2025151101A (ja) 硬化物、積層体、及び、半導体デバイス
JP2025150683A (ja) 硬化物、積層体、及び、半導体デバイス
WO2025205535A1 (fr) Objet durci, stratifié, et dispositif à semi-conducteurs
JP2025151111A (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
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
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
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
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
WO2025159143A1 (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
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
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
WO2025028346A1 (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
WO2025100200A1 (fr) Composition de résine photosensible et procédé de production de produit durci
WO2025205722A1 (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
JP2025150695A (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
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
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
TW202540291A (zh) 樹脂組成物、硬化物、積層體、硬化物之製造方法、積層體之製造方法、半導體元件之製造方法及半導體元件、以及聚醯胺酸酯之製造方法
WO2025249231A1 (fr) Composition de résine, produit durci, procédé de production de produit durci, procédé de production de stratifié et procédé de production de dispositif à semi-conducteur
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

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: 25758326

Country of ref document: EP

Kind code of ref document: A1