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WO2025205735A1 - 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 - Google Patents

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

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Publication number
WO2025205735A1
WO2025205735A1 PCT/JP2025/011676 JP2025011676W WO2025205735A1 WO 2025205735 A1 WO2025205735 A1 WO 2025205735A1 JP 2025011676 W JP2025011676 W JP 2025011676W WO 2025205735 A1 WO2025205735 A1 WO 2025205735A1
Authority
WO
WIPO (PCT)
Prior art keywords
formula
resin composition
group
cured product
resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/011676
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 WO2025205735A1 publication Critical patent/WO2025205735A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/14—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G73/12—Unsaturated polyimide precursors
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Definitions

  • the present invention relates to a resin composition, a cured product, a laminate, a method for producing a cured product, a method for producing a laminate, a method for producing a semiconductor device, and a semiconductor device.
  • cyclized resins such as polyimides have excellent heat resistance and insulating properties, and are therefore used in a variety of applications.
  • examples of such applications include, but are not limited to, insulating films, sealing materials, and protective films for semiconductor devices used for packaging. They are also used as base films and coverlays for flexible substrates.
  • Patent Document 1 describes an aromatic polyimide precursor having a repeating unit represented by general formula (I) with a partial structure of X, which is a tetravalent aromatic group containing no fluorine atoms, and Y, which is a divalent aromatic group containing no fluorine atoms, and having an amide bond concentration of 1.5 mol/kg or more.
  • a low coefficient of thermal expansion is required for the cured product formed on a substrate to minimize the difference in coefficient of thermal expansion between the substrate and the cured product. Furthermore, when producing a pattern of a cured product by exposing and developing a resin composition containing polyimide or its precursor, there is a demand for cured products with excellent resolution in line with the miniaturization and high integration of devices.
  • the present invention aims to provide a resin composition capable of forming a cured layer with a low coefficient of thermal expansion and excellent resolution, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device including the cured product.
  • a 11 and A 12 each independently represent —O— or —NR Z —, R Z represents a hydrogen atom or a monovalent organic group, R 11 and R 12 each independently represent a hydrogen atom or a monovalent organic group, X is a tetravalent organic group;
  • Y 1 is a divalent group represented by any one of formulas (A-1) to (A-7);
  • * indicates the bonding position with the nitrogen atom
  • Each R 13 is independently a hydrogen atom or a substituent; At least one R 13 is an electron-withdrawing group; two adjacent R 13s may be bonded to each other to form a ring;
  • Each R 14 independently represents a hydrogen atom or a substituent;
  • a 13 is —C( ⁇ O)—, —SO 2 —, or —S( ⁇
  • ⁇ 2> The resin composition according to ⁇ 1>, wherein Y 1 is a divalent group represented by any one of the following formulas (1a) to (1m): ⁇ 3>
  • ⁇ 4> The resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the polyimide precursor has a radical polymerizable group.
  • ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the polyimide precursor contains a repeating unit represented by formula (1-2).
  • a 11 , A 12 , R 11 and R 12 have the same meanings as A 11 , A 12 , R 11 and R 12 in formula (1-1), respectively;
  • X2 is a divalent group represented by any one of the following formulas (2a) to (2d):
  • Y is a divalent organic group;
  • the repeating unit represented by formula (1-2) may be a repeating unit represented by formula (1-1),
  • L1 and L2 each independently represent a divalent group or a single bond that is not conjugated with the benzene ring to which they are attached; *1 to *4 each represent a bonding site with a carbonyl group, The hydrogen atoms in these structures may be substituted with a substituent.
  • ⁇ 14> The resin composition according to any one of ⁇ 1> to ⁇ 4>, further comprising an organometallic complex.
  • ⁇ 15> The resin composition according to any one of ⁇ 1> to ⁇ 4>, which is used for forming an interlayer insulating film for a rewiring layer.
  • ⁇ 16> A cured product obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 4>.
  • ⁇ 17> A laminate comprising two or more layers made of the cured product according to ⁇ 16>, and a metal layer between any two adjacent layers made of the cured product.
  • ⁇ 18> A method for producing a cured product, comprising a film-forming step of applying the resin composition according to any one of ⁇ 1> to ⁇ 4> onto a substrate to form a film.
  • the method for producing a cured product according to ⁇ 18> 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.
  • ⁇ 20> A method for producing a cured product according to ⁇ 18> or ⁇ 19>, comprising a heating step of heating the film at 50 to 450°C.
  • ⁇ 21> A method for producing a laminate, comprising the method for producing a cured product according to any one of ⁇ 18> to ⁇ 20>.
  • ⁇ 22> A method for producing a semiconductor device, comprising the method for producing a cured product according to any one of ⁇ 18> to ⁇ 20>.
  • ⁇ 23> A semiconductor device comprising the cured product according to ⁇ 16>.
  • the present invention provides a resin composition capable of forming a cured layer having a low coefficient of thermal expansion and excellent resolution, a cured product obtained by curing the resin composition, a laminate including the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device including the cured product.
  • a numerical range expressed using the symbol "to” means a range that includes the numerical values before and after "to” as the lower and upper limits, respectively.
  • the term “step” includes not only an independent step but also a step that cannot be clearly distinguished from other steps, as long as the intended effect of the step can be achieved.
  • groups (atomic groups) when a notation does not specify whether they are substituted or unsubstituted, it encompasses both groups (atomic groups) that have no substituents and groups (atomic groups) that have substituents.
  • alkyl group encompasses not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have substituents (substituted alkyl groups).
  • exposure includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation.
  • (meth)acrylate means both or either of “acrylate” and “methacrylate”
  • (meth)acrylic means both or either of “acrylic” and “methacrylic”
  • (meth)acryloyl means both or either of “acryloyl” and “methacryloyl”.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • total solids content refers to the total mass of all components of the composition excluding the solvent
  • solids concentration refers to the mass percentage of the components excluding the solvent relative to the total mass of the composition.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) are values measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) can be determined, for example, using an HLC-8220GPC (manufactured by Tosoh Corporation) and guard columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) connected in series.
  • these molecular weights are measured using NMP (N-methyl-2-pyrrolidone) as the eluent.
  • NMP N-methyl-2-pyrrolidone
  • THF tetrahydrofuran
  • detection in GPC measurement is performed using a UV (ultraviolet) ray (ultraviolet) detector with a wavelength of 254 nm.
  • a third layer or element may be interposed between the reference layer and the other layer, and the reference layer and the other layer do not need to be in contact.
  • the direction in which layers are stacked on the substrate is referred to as "up,” or, if a resin composition layer is present, the direction from the substrate to the resin composition layer is referred to as “up,” and the opposite direction is referred to as “down.”
  • the "up" direction in this specification may differ from the vertical upward direction.
  • a composition may contain, as each component contained in the composition, two or more compounds corresponding to that component.
  • the content of each component in the composition means the total content of all compounds corresponding to that component.
  • the temperature is 23° C.
  • the atmospheric pressure is 101,325 Pa (1 atmosphere)
  • the relative humidity is 50% RH.
  • combinations of preferred embodiments are more preferred embodiments.
  • the resin composition of the present invention is a resin composition containing a polyimide precursor (hereinafter also referred to as a "specific resin") having a repeating unit represented by formula (1-1).
  • the repeating unit represented by formula (1-1) has a divalent group represented by any one of formulas (A-1) to (A-7) described below as a partial structure.
  • 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 may be used to form a photosensitive film to be subjected to negative development, or may be used to form a photosensitive film to be subjected to positive development, but is preferably used to form a photosensitive film to be subjected to negative development.
  • the resin composition of the present invention is preferably used to form a cured product in which at least a portion thereof is in contact with a metal, such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, or an alloy containing these metals, including copper and aluminum or an alloy containing at least one of these metals, with copper or an alloy containing copper being preferred.
  • a metal such as copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, or an alloy containing these metals, including copper and aluminum or an alloy containing at least one of these metals, with copper or an alloy containing copper being preferred.
  • the resin composition of the present invention can be used to form a cured layer that has a low coefficient of thermal expansion and excellent resolution.
  • the mechanism by which the above effects are obtained is unknown, but is speculated as follows.
  • the present inventors have discovered that by using a polyimide precursor having a divalent group represented by any one of formulas (A-1) to (A-7) as a partial structure, it is possible to achieve both a low coefficient of thermal expansion and high resolution.
  • the reason why the above embodiment is effective is unclear, but is speculated as follows.
  • the specific divalent organic group has a hard structure, and the aromatic ring in the structure packs between molecules, thereby realizing high orientation and low thermal expansion coefficient.
  • the above structure has high transparency to the light (i-line (365 nm light)) used for exposure, and the light during exposure reaches the inside of the film, so that curing proceeds throughout the film, and the rectangularity of the pattern is increased, thereby showing excellent resolution.
  • Patent Document 1 does not describe a resin composition containing a polyimide precursor having a repeating unit represented by formula (1-1) having the above specific structure.
  • the resin composition of the present invention will be described in detail below.
  • the resin composition of the present invention contains a polyimide precursor containing a repeating unit represented by formula (1-1).
  • a 11 and A 12 are each independently —O— or —NR Z —, R Z is a hydrogen atom or a monovalent organic group, R 11 and R 12 are each independently a hydrogen atom or a monovalent organic group, X is a tetravalent organic group, and Y 1 is a divalent group represented by any one of formulas (A-1) to (A-7) described below.
  • the polyimide precursor refers to a resin that changes its chemical structure in response to an external stimulus to become a polyimide.
  • a resin that changes its chemical structure in response to heat to become a polyimide is preferred, and a resin that changes its chemical structure in response to heat to become a polyimide by forming a ring structure is more preferred.
  • polyimide refers to a resin having a repeating unit containing an imide group in the molecular chain, and is preferably a resin having a repeating unit containing an imide ring structure in the molecular chain.
  • the polyimide when the polyimide is a linear resin, the polyimide is preferably a resin having a repeating unit containing an imide group in the main chain, and more preferably a resin having a repeating unit containing an imide ring structure in the main chain.
  • the term "main chain” refers to the relatively longest bonding chain in a resin molecule, and the term “side chain” refers to any other bonding chain.
  • the imide ring structure refers to a ring structure containing two carbon atoms and all of the nitrogen atoms in the imide as ring members.
  • the imide ring structure is preferably a five-membered ring.
  • the polyimide may be a so-called polyamideimide, which has an amide group in the molecular chain in addition to an imide group.
  • # represents a bonding site to another structure, preferably a bonding site to a hydrogen atom or a carbon atom, and more preferably a bonding site to a hydrogen atom.
  • the specific resin in the resin composition of the present invention may consist of one type of resin or two or more types of resins.
  • the proportion of unit structures, imidization rate, esterification rate, acid value, amine value, etc. are values calculated or measured by treating the multiple types of resins as one resin.
  • Y1 is a divalent group represented by any one of formulas (A-1) to (A-7). All of these groups have a rigid structure, and the aromatic rings in the structure tend to pack easily between molecules.
  • the resin composition of the present invention has a high degree of orientation of the polyimide structure after curing and a low coefficient of thermal expansion of the cured product.
  • Each R 13 independently represents a hydrogen atom or an arbitrary substituent; At least one R 13 is an electron-withdrawing group; two adjacent R 13s may be bonded to each other to form a ring;
  • Each R 14 independently represents a hydrogen atom or a substituent;
  • a 13 is —C( ⁇ O)—, —SO 2 —, or —S( ⁇ O)—;
  • L is a divalent linking group;
  • a 14 is —C(—R 15 ) 2 —, —C( ⁇ O)—, —SO 2 —, or —S( ⁇ O)—, and R 15 is a hydrogen atom or a substituent.
  • R 13 is each independently a hydrogen atom or a substituent, and at least one of R 13 is an electron-withdrawing group.
  • electron-withdrawing groups include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, an ester group, an amide group, a halogenated alkyl group, an alkylcarbonyl group, an arylcarbonyl group, a formyl group (aldehyde), a carboxyl group, a sulfo group (—SO 3 H), a sulfonyl group (—SO 2 —R: R is a methyl group or the like), and a hydroxyl group.
  • Formulas (A-1) to (A-3) each have at least one electron-withdrawing group as R 13 , and thus the absorption of light used for exposure (i-line (365 nm light))
  • R 13 substituents for R 13 include alkyl groups such as methyl groups.
  • Two adjacent R 13 may be bonded to each other to form a ring.
  • they may be bonded to each other to form an alkylene group such as *-CH 2 -CH 2 -CH 2 -CH 2 -*, or *-O-(C 6 H 4 )-O-*, *-C( ⁇ O)-(C 6 H 4 )-C( ⁇ O)-*, thereby forming a ring together with the carbon atoms to which the two are bonded.
  • * indicates the bonding position
  • -(C 6 H 4 )- is 1,2-phenylene.
  • the formed ring may have a substituent.
  • R 14 is independently a hydrogen atom or an arbitrary substituent.
  • substituent represented by R 14 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a halogenated alkyl group such as a trifluoromethyl group, and an alkyl group such as a methyl group.
  • a 13 is —C( ⁇ O)—, —SO 2 —, or —S( ⁇ O)—, and is preferably —C( ⁇ O)— or —SO 2 —.
  • L is a divalent linking group.
  • L include the following groups: In the following formula, R 14 has the same meaning as above.
  • a 14 is —C(—R 15 ) 2 —, —C( ⁇ O)—, —SO 2 —, or —S( ⁇ O)—, and R 15 is a hydrogen atom or a substituent.
  • R 15 is a hydrogen atom or a substituent. Examples of the substituent represented by R 15 include alkyl groups having 1 to 20 carbon atoms, and linear alkyl groups having 1 to 12 carbon atoms are preferred.
  • a 14 is preferably —CH 2 —.
  • R 11 or R 12 may be a polarity conversion group such as an acid-decomposable group.
  • the acid-decomposable group is not particularly limited as long as it is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxy group or a carboxy group, but an acetal group, a ketal group, a silyl group, a silyl ether group, a tertiary alkyl ester group, etc. are preferred, and from the viewpoint of exposure sensitivity, an acetal group or a ketal group is more preferred.
  • the acid-decomposable group examples include a tert-butoxycarbonyl group, an isopropoxycarbonyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, an ethoxyethyl group, a methoxyethyl group, an ethoxymethyl group, a trimethylsilyl group, a tert-butoxycarbonylmethyl group, a trimethylsilyl ether group, etc. From the viewpoint of exposure sensitivity, an ethoxyethyl group or a tetrahydrofuranyl group is preferred.
  • the specific resin preferably contains a repeating unit represented by formula (1-2).
  • the repeating unit represented by formula (1-2) may be one embodiment of the repeating unit represented by formula (1-1), and may not necessarily correspond to the repeating unit represented by formula (1-1).
  • a 11 , A 12 , R 11 and R 12 have the same meanings as A 11 , A 12 , R 11 and R 12 in formula (1-1), respectively.
  • X2 is a divalent group represented by any one of formulas (2a) to (2d) above.
  • Y is a divalent organic group.
  • the specific resin contains a repeating unit represented by formula (1-2), the following combinations of X2 and Y1 are preferred from the viewpoint of the balance of thermal expansion coefficient, resolution, and mechanical properties. Note that X2 and Y1 may be in the same repeating unit or in different repeating units.
  • Y 1 is a divalent group represented by either formula (A-2) or formula (A-3), and X 2 is a divalent group represented by either formula (2a) or formula (2b); Y 1 is a divalent group represented by formula (A-7), and X 2 is a divalent group represented by formula (2a), formula (2c), or formula (2d); Y 1 is a divalent group represented by formula (A-6), and X 2 is a divalent group represented by formula (2c); Y 1 is a divalent group represented by formula (A-1), and X 2 is a divalent group represented by formula (2c); Y 1 is a divalent group represented by either formula (A-4) or formula (A-5), and X 2 is a divalent group represented by either formula (2a) or formula (2b).
  • the specific resin contains a repeating unit represented by formula (1-2), it is also preferable that the specific resin further contains a repeating unit represented by formula (1-3).
  • the repeating unit represented by formula (1-3) may be one embodiment of the repeating unit represented by formula (1-1), and may not necessarily correspond to the repeating unit represented by formula (1-1).
  • a 11 , A 12 , R 11 and R 12 have the same meanings as A 11 , A 12 , R 11 and R 12 in formula (1-1), respectively, and the preferred ranges are also the same.
  • X3 is a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of formulas (V-1) to (V-4).
  • Y is a divalent organic group and may be the same as or different from Y in formula (1-2).
  • Y in the repeating unit represented by formula (1-2) and the repeating unit represented by formula (1-3) is preferably Y1 . That is, the repeating unit represented by formula (1-2) and the repeating unit represented by formula (1-3) are each preferably a repeating unit represented by formula (1-1).
  • the number of carbon atoms in Y is preferably 4 or more, more preferably 4 to 50, and even more preferably 4 to 40.
  • Examples of Y other than Y1 include groups containing a structure in which two or more hydrogen atoms have been removed from a structure represented by any one of the following formulae (Y-1) to (Y-8).
  • R 1 and X1 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
  • R 1 X2 and R 1 X3 each independently represent a hydrogen atom or a substituent, and R 1 X2 and R 1 X3 may be bonded to form a ring structure.
  • R 1 and X5 each independently represent a hydrogen atom, an alkyl group or a halogenated alkyl group.
  • R and X1 are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group.
  • a halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom has been substituted with a halogen atom.
  • the halogen atom is preferably F or Cl, and more preferably F.
  • R X2 and R X3 each independently represent a hydrogen atom.
  • R X2 and R X3 combine to form a ring structure
  • the structure formed by combining R X2 and R X3 is preferably a single bond, -O-, or -C(R) 2 -, more preferably -O- or -C(R) 2 -, and even more preferably -O-.
  • R represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom.
  • R and X5 are each independently preferably an alkyl group or a halogenated alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms or a halogenated alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a trifluoromethyl group.
  • a halogenated alkyl group refers to an alkyl group in which at least one hydrogen atom has been substituted with a halogen atom.
  • the halogen atom is preferably F or Cl, and more preferably F.
  • Y is a group containing a structure obtained by removing two or more hydrogen atoms from the structure represented by formula (Y-1), Y is preferably a group represented by the following formula (Y-1-2):
  • * represents the bonding site to the two nitrogen atoms, and n1 represents an integer of 0 to 5.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • Y is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (Y-2), Y is preferably a group represented by formula (Y-2-3) or formula (Y-2-4) below, and from the viewpoint of reducing the dielectric constant of the cured product, a group represented by formula (Y-2-4) is preferred.
  • L X1 represents a single bond or —O—
  • * represents the bonding site between Y and the two nitrogen atoms to which it is bonded.
  • R X1 are as described above.
  • the hydrogen atoms may be further substituted with known substituents such as hydrocarbon groups.
  • Y is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (Y-4), Y is preferably a group represented by the following formula (Y-4-2).
  • * represents the bonding site between Y and the two nitrogen atoms to which it is bonded.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • Y is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (Y-5)
  • Y is preferably a group represented by the following formula (Y-5-2).
  • * represents the bonding site between Y and the two nitrogen atoms to which it is bonded.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • Y is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (Y-6), Y is preferably a group represented by formula (Y-6-2) below.
  • * represents the bonding site between Y and the two nitrogen atoms to which it is bonded.
  • R X5 The definition and preferred embodiments of R X5 are as described above.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • Y is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (Y-7)
  • Y is preferably a group represented by the following formula (Y-7-2).
  • * represents the bonding site between Y and the two nitrogen atoms in formula (A-1).
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • Y is a group containing a structure obtained by removing two or more hydrogen atoms from a structure represented by formula (Y-8)
  • Y is preferably a group represented by the following formula (Y-8-2).
  • * represents the bonding site between Y and the two nitrogen atoms to which it is bonded.
  • the hydrogen atoms in the following structure may be further substituted with known substituents such as hydrocarbon groups.
  • Y may be a group represented by the following formula (Y-42) or formula (Y-43).
  • * represents the bonding site between Y and the two nitrogen atoms
  • n1 represents an integer of 0 to 5.
  • An embodiment in which n1 is 0 is also one of the preferred embodiments of the present invention.
  • the hydrogen atoms in the following structures may be further substituted with known substituents such as hydrocarbon groups. Examples of known substituents include alkyl groups, halogenated alkyl groups, and halogen atoms.
  • Y other than Y1 may be a group described in paragraphs 0042 to 0053 of JP-A No. 2023-003421. It is also preferable that Y does not contain an imide structure in its structure. It is also preferable that Y does not contain a urethane bond, a urea bond, or an amide bond in the structure. Furthermore, it is preferable that Y does not contain an ester bond in the structure.
  • Y does not contain an imide structure, a urethane bond, a urea bond, or an amide bond, and it is more preferable that Y does not contain an imide structure, a urethane bond, a urea bond, an amide bond, or an ester bond.
  • the total content of repeating units represented by formula (1-2) is preferably 20 mol% or more of all repeating units, more preferably 30 mol% or more, even more preferably 40 mol% or more, and particularly preferably 50 mol% or more.
  • all repeating units in the specific resin except for terminal repeating units may be repeating units represented by formula (1-2).
  • the repeating units represented by formula (1-2) correspond to the repeating units represented by formula (1-1).
  • the total content of the repeating unit represented by formula (1-3) is preferably 0 to 80 mol %, more preferably 5 to 70 mol %, even more preferably 10 to 60 mol %, and particularly preferably 15 to 50 mol % of all repeating units.
  • the total content of repeating units represented by formula (1-2) and repeating units represented by formula (1-3) in the specific resin of the present invention is preferably 50 mol% or more of all repeating units. This total content is more preferably 70 mol% or more, even more preferably 90 mol% or more, and particularly preferably more than 90 mol%.
  • all repeating units in the specific resin excluding terminal repeating units may be repeating units represented by formula (1-2) or repeating units represented by formula (1-3). In this case, at least one of the repeating units represented by formula (1-2) and the repeating units represented by formula (1-3) corresponds to the repeating unit represented by formula (1-1).
  • the imidization ratio represents the ratio of imide ring structures to the total of amic acid structures, amic acid ester structures, and imide ring structures in a specific resin.
  • the imidization rate of the specific resin is preferably less than 70%, more preferably 60% or less, even more preferably 50% or less, still more preferably 40% or less, and particularly preferably 30% or less.
  • the lower limit of the imidization rate is not particularly limited, and it is sufficient if it is 0% or more.
  • the imidization rate can be 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 amine value of the specific resin is preferably 0.100 mmol/g or less, more preferably 0.0001 to 0.090 mmol/g, and even more preferably 0.001 to 0.080 mmol/g.
  • the lower limit of the amine value is not particularly limited, and may be 0.00 mmol/g.
  • the amine value was measured by dissolving 0.62 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) solution of perchloric acid in acetic acid to detect the neutralization point.
  • Non-halogen catalyst without using the above-mentioned halogenating agent.
  • Any known amidation catalyst that does not contain halogen atoms can be used as the non-halogen catalyst without any particular restrictions.
  • catalysts include boroxine compounds, N-hydroxy compounds, tertiary amines, phosphate esters, amine salts, urea compounds, and carbodiimide compounds.
  • carbodiimide compounds include N,N'-diisopropylcarbodiimide, N,N'-dicyclohexylcarbodiimide, and (2,6-diisopropylphenyl)carbodiimide.
  • the organic solvent may be one type or two or more types.
  • the organic solvent can be appropriately selected depending on the raw materials, and examples thereof include pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone, and N-ethylpyrrolidone.
  • an end-capping agent such as an acid anhydride, a monocarboxylic acid, a monoacid chloride compound, a monoactive ester compound, etc.
  • a monoamine As the end-capping agent, it is more preferable to use a monoamine, and preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-9-aminonaphthalene, 1-carboxy-10-aminonaphthalene, 1-carboxy-11-aminonaphthalene, 1-carboxy-12-aminonaphthalene
  • Examples include 5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple different terminal groups may be introduced by reacting multiple terminal-capping agents.
  • the production of the specific resin may include a step of precipitating a solid. Specifically, the polyimide precursor or the like in the reaction solution is precipitated in water, and then the precipitate is dissolved in a solvent in which the specific resin is soluble, such as tetrahydrofuran, to precipitate a solid. Thereafter, the specific resin is dried to obtain a powdery specific resin or the like.
  • 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.
  • a resin composition with excellent coatability can be obtained, and a pattern (cured product) with excellent solvent resistance can be obtained.
  • a (meth)acrylic resin having a weight average molecular weight of 20,000 or less and a high polymerizable group value for example, the molar amount of polymerizable groups contained in 1 g of resin is 1 ⁇ 10 -3 mol/g or more
  • the resin composition it is possible to improve the coatability of the resin composition and the solvent resistance of the pattern (cured product), etc.
  • the content of the other resins is preferably 0.01% 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 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 can be appropriately selected from known photoradical polymerization initiators.
  • a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible range is preferred.
  • it may be an activator that reacts with a photoexcited sensitizer to generate active radicals.
  • the photoradical polymerization initiator preferably contains at least one compound having a molar absorption coefficient of at least about 50 L mol cm in a wavelength range of about 240 to 800 nm (preferably 330 to 500 nm ) .
  • the molar absorption coefficient of the compound can be measured using a known method. For example, it is preferably measured using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.
  • any known compound can be used as the photoradical polymerization initiator.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.
  • acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, ⁇ -aminoketone compounds such as aminoacetophenone, ⁇ -hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organic boron compounds, and iron arene complexes.
  • halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihal
  • ketone compounds include the compounds described in paragraph 0087 of JP 2015-087611 A, the contents of which are incorporated herein by reference.
  • Kayacure-DETX-S manufactured by Nippon Kayaku Co., Ltd. is also suitable.
  • acylphosphine oxide initiators for example, compounds described in paragraphs 0161 to 0163 of WO 2021/112189 can also be suitably used.
  • the contents of this specification are incorporated herein by reference.
  • a more preferred example of a photoradical polymerization initiator is an oxime compound.
  • an oxime compound By using an oxime compound, it is possible to more effectively improve the exposure latitude.
  • Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also function as a photocuring accelerator.
  • oxime compounds include compounds described in JP 2001-233842 A, compounds described in JP 2000-080068 A, compounds described in JP 2006-342166 A, compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), and compounds described in J. C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.
  • oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04, and IRGACURE OXE 05 (manufactured by BASF), ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in JP 2012-014052 A), TR-PBG-304 and 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 (manufactured by SARTOMER ARKEMA) can also be used.
  • an oxime compound having the following structure can also be used.
  • an oxime compound having a fluorene ring described in paragraphs 0169 to 0171 of WO 2021/112189 an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, or an oxime compound having a fluorine atom can be used.
  • oxime compounds having a nitro group oxime compounds having a benzofuran skeleton, and oxime compounds having a carbazole skeleton to which a substituent having a hydroxy group is bonded, as described in paragraphs 0208 to 0210 of WO 2021/020359, the contents of which are incorporated herein by reference.
  • the content thereof is preferably 0.1 to 30 mass% relative to the total solid content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and even more preferably 1.0 to 10 mass%.
  • Only one type of photopolymerization initiator may be contained, or two or more types may be contained. When two or more types of photopolymerization initiators are contained, it is preferable that the total amount is in the above range.
  • the photopolymerization initiator may also function as a thermal polymerization initiator, the crosslinking by the photopolymerization initiator may be further promoted by heating in an oven, a hot plate, or the like.
  • the content of the thermal polymerization initiator is preferably 20 to 70 mass%, more preferably 30 to 60 mass%, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.
  • 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.
  • chain transfer agents examples include compounds having -S-S-, -SO 2 -S-, -N-O-, SH, PH, SiH, and GeH in the molecule, and dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization. These donate hydrogen to low-activity radicals to generate radicals, or can generate radicals by being oxidized and then deprotonated. Thiol compounds are particularly preferred.
  • chain transfer agent may be the compound described in paragraphs 0152-0153 of WO 2015/199219, the contents of which are incorporated herein by reference.
  • the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the total solids content of the resin composition. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types of chain transfer agents are used, the total amount is preferably within the above range.
  • the resin composition of the present invention 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.
  • radical crosslinking agents other than those mentioned above include the radical polymerizable compounds described in paragraphs 0204 to 0208 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • 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 the above-mentioned photoacid generator or photobase generator, and more 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 content of the other crosslinking agent is preferably 0.1 to 30 mass% of the total solids content of the resin composition, more preferably 0.1 to 20 mass%, even more preferably 0.5 to 15 mass%, and particularly preferably 1.0 to 10 mass%. Only one type of other crosslinking agent may be contained, or two or more types may be contained. When two or more types of other crosslinking agents are contained, the total amount is preferably within the above range.
  • the resin composition of the present invention may contain a base generator.
  • the base generator is a compound that can generate a base by physical or chemical action.
  • Preferred base generators include thermal base generators and photobase generators.
  • a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted, for example, by heating, and the mechanical properties and chemical resistance of the cured product can be improved, resulting in good performance as an interlayer insulating film for a rewiring layer included in, for example, a semiconductor package.
  • the base generator may be an ionic base generator or a nonionic base generator. Examples of the base generated from the base generator include secondary amines and tertiary amines.
  • 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.
  • 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.
  • 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
  • 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, propylene glycol
  • 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.
  • Preferred ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.
  • alcohols examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenyl carbinol, n-amyl alcohol, methyl amyl alcohol, and diacetone alcohol.
  • 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 5 to 75 mass%, even more preferably an amount that results in 10 to 70 mass%, and even more preferably an amount that results in 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.
  • 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.
  • 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.
  • Usable organic titanium compounds include those in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond.
  • Specific examples of the organotitanium compound are shown below as I) to VII):
  • I) Titanium chelate compounds Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability to the resin composition and a good curing pattern.
  • titanium bis(triethanolamine) diisopropoxide titanium di(n-butoxide) bis(2,4-pentanedionate), titanium diisopropoxide bis(2,4-pentanedionate), titanium diisopropoxide bis(tetramethylheptanedionate), and titanium diisopropoxide bis(ethylacetoacetate).
  • Tetraalkoxytitanium compounds for example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearyloxide, titanium tetrakis[bis ⁇ 2,2-(allyloxymethyl)butoxide ⁇ ], etc.
  • Titanocene compounds for example, pentamethylcyclopentadienyltitanium trimethoxide, bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis( ⁇ 5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium, and the like.
  • Monoalkoxytitanium compounds For example, titanium tris(dioctylphosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc.
  • Titanium oxide compounds For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.
  • titanium complex compound as the organotitanium compound or instead of the organotitanium compound
  • examples of the titanium complex compound include a compound represented by the following formula (T-1).
  • T-1 a polyimide precursor having a divalent organic group represented by any one of formulas (A-1) to (A-7) as a partial structure in combination with an organometallic complex such as a titanium complex compound
  • the high-temperature, high-humidity resistance of the cured film can be significantly improved. It is presumed that this is because the formation of a flexible crosslinked structure centered on metal ions in the cured film makes it easier for polyimide molecular chains to align at an appropriate distance, thereby improving the orientation of the polyimide molecular chains.
  • R 12 is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms.
  • the hydrocarbon group for R 12 may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, with aromatic hydrocarbon groups being preferred.
  • the aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred.
  • the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group.
  • R 12 is preferably a monovalent substituent, such as a halogen atom, etc.
  • R 12 is an aromatic hydrocarbon group, it may have an alkyl group as a substituent.
  • R 12 is preferably an unsubstituted phenylene group, and the phenylene group in R 12 is preferably a 1,2-phenylene group.
  • formula (T-1) when m is 2 or more and two or more R 2s are contained, the structures of the two or more R 2s may be the same or different. In formula (T-1), when n is 2 or more and two or more R 3s are contained, the structures of the two or more R 3s may be the same or different.
  • Specific examples of compounds represented by formula (T-1) include, but are not limited to, compounds I-1 and I-2 in the examples.
  • an organotitanium compound is included, its content is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. If the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern will be better, and if it is 10 parts by mass or less, the storage stability of the composition will be superior.
  • the cured product of the present invention may contain an antioxidant.
  • the term "antioxidant” refers to a compound that has the function of preventing oxidation of metals, and examples thereof include phenolic compounds, phosphite ester compounds, and thioether compounds. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound. Preferred phenolic compounds include hindered phenolic compounds. Compounds having a substituent at the position adjacent to the phenolic hydroxy group (ortho position) are preferred. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. Furthermore, compounds having a phenol group and a phosphite ester group in the same molecule are also preferred as antioxidants.
  • the antioxidant prevents oxidation of the metal, and therefore, the cured product containing the antioxidant has excellent adhesion. Furthermore, since the antioxidant inhibits polymerization of the polymerizable compound during storage of the resin composition, it is believed that a resin composition containing an antioxidant has excellent storage stability and excellent resolution of the resulting cured product.
  • the antioxidant preferably has an isocyanuric acid skeleton, and more preferably is a hindered phenol compound having an isocyanuric acid skeleton.
  • the content of the antioxidant is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin.
  • the content of the antioxidant is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin.
  • 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 polymerization inhibitor may be one type only, or two or more types. If two or more types of polymerization inhibitors are used, it is preferable that the total amount is within the above range.
  • the resin composition of the present invention may contain various additives, such as surfactants, higher fatty acid derivatives, inorganic particles, UV absorbers, photoacid generators, anti-aggregation agents, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), as needed, as long as the effects of the present invention are achieved.
  • additives such as surfactants, higher fatty acid derivatives, inorganic particles, UV absorbers, photoacid generators, anti-aggregation agents, phenolic compounds, other polymeric compounds, plasticizers, and other auxiliary agents (e.g., antifoaming agents, flame retardants, etc.), as needed, as long as the effects of the present invention are achieved.
  • auxiliary agents e.g., antifoaming agents, flame retardants, etc.
  • the total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.
  • surfactant various surfactants can be used, such as a fluorine-based surfactant, a silicone-based surfactant, a hydrocarbon-based surfactant, etc.
  • the surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.
  • the liquid properties (particularly fluidity) when the coating liquid composition is prepared are further improved, and the uniformity of the coating thickness and liquid saving can be further improved.
  • the interfacial tension between the surface to be coated and the coating liquid is reduced, improving the wettability of the surface to be coated and the coatability of the surface to be coated. This makes it possible to more effectively form a uniform film with minimal thickness unevenness.
  • silicone surfactants examples include the compounds described in paragraphs 0329 to 0334 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • the surfactant may be used alone or in combination of two or more.
  • the content of the surfactant is preferably from 0.001 to 2.0% by mass, more preferably from 0.005 to 1.0% by mass, based on the total solid content of the composition.
  • 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. Furthermore, from the viewpoints of reducing the effort required to reduce the metal content and improving mechanical properties and adhesion, the lower limit of the metal content in the resin composition is preferably 0.001 ppm by mass or more, and can be set to 0.01 ppm by mass or more.
  • metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, nickel, manganese, aluminum, titanium, cobalt, zinc, tin, and zirconium, but this does not include metals contained as complexes of organic compounds and metals. When multiple metals are contained, the total of these metals is preferably within the above range. Specific examples of metal contents include 0.01 ppm by mass, 0.2 ppm by mass, and 0.9 ppm by mass.
  • 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.
  • the lower limit of halogen atoms in the resin composition can be 0.01 ppm by mass or more, and can also be 0.1 ppm by mass or more.
  • halogen atoms examples include bromine atoms, iodine atoms, chlorine atoms, and bromine atoms. It is preferable that the total of bromine atoms, iodine atoms, chlorine atoms, and bromine atoms, or bromine ions, iodine ions, chlorine ions, and bromine ions, respectively, is within the above-mentioned range.
  • a preferred method for adjusting the content of halogen atoms is ion exchange treatment.
  • halogen atoms include 0.02 mass ppm, 0.5 mass ppm, and 2.5 mass ppm.
  • Specific examples of the amount of halogen ions include 0.02 mass ppm, 0.3 mass ppm, and 2.1 mass ppm.
  • 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 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 the film thickness, spin coating, slit coating, spray coating, or inkjet coating is preferred, and from the viewpoint of uniformity of the film thickness and productivity, spin coating and slit coating are more preferred.
  • the solid content concentration of the resin composition and application conditions depending on the application method, a film of the desired thickness can be obtained.
  • the application method can be appropriately selected depending on the shape of the substrate. For circular substrates such as wafers, spin coating, spray coating, inkjet coating, etc.
  • slit coating for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes.
  • a coating film may be formed by applying the coating to a temporary support in advance using the above-mentioned application method, and then transferred onto the substrate.
  • the transfer method the production methods described in paragraphs 0023 and 0036 to 0051 of JP-A No. 2006-023696 and paragraphs 0096 to 0108 of JP-A No. 2006-047592 can be suitably used.
  • a process for removing excess film from the edge of the substrate may be performed, such as edge bead rinsing (EBR) or back rinsing.
  • EBR edge bead rinsing
  • a pre-wetting step may be employed in which various solvents are applied to the substrate before the resin composition is applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.
  • the film may be subjected to a step (drying step) of drying the formed film (layer) to remove the solvent.
  • the method for producing a cured product of the present invention may include a drying step of drying the film formed in the film forming step.
  • the drying step is preferably carried out after the film-forming step and before the exposure step.
  • the drying temperature of the film in the drying step is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure.
  • the drying time is, for example, 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.
  • the film may be subjected to an exposure step to selectively expose the film to light.
  • the method for producing a cured product may include an exposure step of selectively exposing the film formed in the film formation step to light. Selective exposure means that only a portion of the film is exposed, and selective exposure results in exposed and unexposed areas of the film.
  • the exposure dose is not particularly limited as long as it can cure the resin composition of the present invention, but is preferably 50 to 10,000 mJ/cm 2 and more preferably 200 to 8,000 mJ/cm 2 in terms of exposure energy at a wavelength of 365 nm.
  • the exposure wavelength can be appropriately set in the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.
  • the exposure wavelength in relation to the light source, (1) semiconductor laser (wavelengths 830 nm, 532 nm, 488 nm, 405 nm, 375 nm, 355 nm, etc.), (2) metal halide lamp, (3) high-pressure mercury lamp, g-line (wavelength 436 nm), h-line (wavelength 405 nm), i-line (wavelength 365 nm), broad (three wavelengths of g, h, i-line), (4) excimer laser, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), (5) extreme ultraviolet light; EUV (wavelength 13.6 nm), (6) electron beam, (7) YAG laser second harmonic 532 nm, third harmonic 355 nm, etc.
  • semiconductor laser wavelengths 830 nm, 532 nm, 488 nm, 405 nm
  • exposure with a high-pressure mercury lamp is particularly preferred, and exposure with i-line is more preferred from the viewpoint of exposure sensitivity.
  • the exposure method is not particularly limited as long as it is a method that exposes at least a part of the film made of the resin composition of the present invention, and examples thereof include exposure using a photomask and exposure by laser direct imaging.
  • the film may be subjected to a step of heating after exposure (post-exposure baking step). That is, the method for producing a cured product of the present invention may include a post-exposure baking step in which the film exposed in the exposure step is heated.
  • the post-exposure baking step can be carried out after the exposure step and before the development step.
  • the heating temperature in the post-exposure baking step is preferably 50°C to 140°C, more preferably 60°C to 120°C.
  • the heating time in the post-exposure baking step is preferably from 30 seconds to 300 minutes, more preferably from 1 minute to 10 minutes.
  • the temperature rise rate in the post-exposure heating step from the starting temperature to the maximum heating temperature is preferably 1 to 12° C./min, more preferably 2 to 10° C./min, and even more preferably 3 to 10° C./min.
  • the temperature rise rate may be changed during heating as needed.
  • the heating means in the post-exposure baking step is not particularly limited, and known means such as a hot plate, an oven, and an infrared heater can be used. It is also preferable that the heating be carried out in an atmosphere of low oxygen concentration by flowing an inert gas such as nitrogen, helium, or argon.
  • the film After exposure, the film may be subjected to a development step in which it is developed with a developer to form a pattern. That is, the method for producing a cured product of the present invention may include a development step in which the film exposed in the exposure step is developed with a developer to form a pattern. Development removes either the exposed or unexposed portions of the film, forming a pattern.
  • development in which the non-exposed portions of the film are removed by the development process is called negative development
  • development in which the exposed portions of the film are removed by the development process is called positive development.
  • the developer used in the development step may be an aqueous alkaline solution or a developer containing an organic solvent.
  • examples of basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts.
  • examples of basic compounds include the compounds described in paragraph 0300 of WO 2023/190064. The above content is incorporated herein by reference.
  • the content of the basic compound in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer.
  • 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 rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes.
  • the temperature of the rinse solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.
  • the pattern obtained by the development step (if a rinsing step is performed, the pattern after rinsing) may be subjected to a heating step in which the pattern obtained by the development step is heated. That is, the method for producing a cured product of the present invention may include a heating step of heating the pattern obtained in the development step. The method for producing a cured product of the present invention may also include a heating step of heating a pattern obtained by another method without performing a development step, or a film obtained in the film-forming step. In the heating step, the resin such as the polyimide precursor is cyclized to form a resin such as a polyimide.
  • the heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, still more preferably 160 to 250°C, and particularly preferably 160 to 230°C.
  • the heating step is preferably a step in which the cyclization reaction of the polyimide precursor is promoted within the pattern by the action of the base generated from the base generator due to heating.
  • the 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.
  • 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 for example, a laminate including at least a layer structure in which three layers, a layer made of a first cured product, a metal layer, and a layer made of a second cured product, are laminated in this order, can be mentioned as a preferred example. It is preferable that the layer made of the first cured product and the layer made of the second cured product are both layers made of the cured product of the present invention.
  • the resin composition of the present invention used to form the layer made of the first cured product and the resin composition of the present invention used to form the layer made of the second cured product may have the same composition or different compositions.
  • the metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.
  • the method for producing the laminate of the present invention preferably includes a lamination step.
  • the lamination process is a series of processes including (a) a film formation process (layer formation process), (b) an exposure process, (c) a development process, and (d) at least one of a heating process and a post-development exposure process, which are carried out again on the surface of the pattern (resin layer) or metal layer in this order.
  • at least one of the (a) film formation process and the (d) heating process and the post-development exposure process may be repeated.
  • the (e) metal layer formation process may be included. It goes without saying that the lamination process may further include the above-mentioned drying process, etc. as appropriate.
  • a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step.
  • An example of a surface activation treatment is plasma treatment. Details of the surface activation treatment will be described later.
  • the lamination step is preferably carried out 2 to 20 times, more preferably 2 to 9 times.
  • a structure of 2 to 20 resin layers such as resin layer/metal layer/resin layer/metal layer/resin layer/metal layer, is preferred, and a structure of 2 to 9 resin layers is more preferred.
  • the above layers may be the same or different in composition, shape, film thickness, etc.
  • a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer.
  • a cured product (resin layer) of the resin composition of the present invention is further formed to cover the metal layer.
  • Specific examples include an embodiment in which the following steps are repeated in this order: (a) film formation step, (b) exposure step, (c) development step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step; or an embodiment in which the following steps are repeated in this order: (a) film formation step, (d) at least one of a heating step and a post-development exposure step, and (e) metal layer formation step.
  • the method for producing a laminate of the present invention preferably includes a surface activation treatment step of subjecting at least a portion of the metal layer and the resin composition layer to a surface activation treatment.
  • the surface activation treatment step is usually performed after the metal layer formation step, but the resin composition layer may be subjected to the surface activation treatment step after the above-mentioned development step (preferably after at least one of the heating step and the post-development exposure step) and then the metal layer formation step may be performed.
  • the surface activation treatment may be performed on at least a portion of the metal layer, or on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the resin composition layer after exposure.
  • the surface activation treatment is preferably performed on at least a portion of the metal layer, and it is preferable to perform the surface activation treatment on part or all of the region of the metal layer on which the resin composition layer is formed on the surface. In this way, by performing the surface activation treatment on the surface of the metal layer, it is possible to improve the adhesion with the resin composition layer (film) provided on the surface. It is preferable that the surface activation treatment is also performed on a part or all of the resin composition layer (resin layer) after exposure. In this way, by performing the surface activation treatment on the surface of the resin composition layer, it is possible to improve the adhesion with a metal layer or a resin layer provided on the surface that has been surface-activated.
  • the resin composition layer when negative development is performed, etc., if the resin composition layer is cured, it is less susceptible to damage due to the surface treatment, and adhesion is likely to be improved.
  • the surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of WO 2021/112189, the contents of which are incorporated herein by reference.
  • the present invention also discloses a semiconductor device comprising the cured product or laminate of the present invention.
  • the present invention also discloses a method for producing a semiconductor device, which includes the method for producing the cured product of the present invention or the method for producing the laminate.
  • semiconductor devices using the resin composition of the present invention for forming an interlayer insulating film for a rewiring layer the descriptions in paragraphs 0213 to 0218 and FIG. 1 of JP-A-2016-027357 can be referred to, and the contents of these can be incorporated into this specification.
  • the dried powder was dissolved in 225 g of tetrahydrofuran, and then 40.0 g of ion exchange resin UP6040 (manufactured by AmberTec) was added and stirred for 2 hours. The ion exchange resin was then removed by filtration, and the resulting polymer solution was added to 2,500 g of water to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45 ° C. for 24 hours, yielding 33.6 g of resin P-3.
  • ion exchange resin UP6040 manufactured by AmberTec
  • the structure of the resin was confirmed by 1 H-NMR to be the structure represented by the following formula (P-1):
  • the molecular weight of the resin was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 30,000.
  • Mw weight average molecular weight
  • P-1 has the following repeating units. The same applies to the following synthesis examples, where each resin has a repeating unit consisting of a combination of the described acid anhydride-derived structure and diamine-derived structure.
  • the resin when there are a plurality of either or both of the acid anhydride-derived structure and the diamine-derived structure, the resin has repeating units of all combinations of any one of the acid anhydride-derived structures and any one of the diamine-derived structures according to the molar ratio.
  • a resin having two described acid anhydride-derived structures and two described diamine-derived structures has four types of repeating units.
  • the dried powder was dissolved in 300 g of tetrahydrofuran, and then 40.0 g of ion exchange resin UP6040 (manufactured by AmberTec) was added and stirred for 2 hours. The ion exchange resin was then removed by filtration, and the resulting polymer solution was added to 2,500 g of water to obtain a precipitate. The precipitate was collected by filtration and dried under reduced pressure at 45 ° C. for 24 hours, yielding 33.3 g of resin P-3.
  • ion exchange resin UP6040 manufactured by AmberTec
  • the structure of the resin was confirmed by 1 H-NMR to be the structure represented by the following formula (P-3):
  • the molecular weight of the resin was measured by gel permeation chromatography (standard polystyrene equivalent) to find that the weight average molecular weight (Mw) was 30,000.
  • resin P-21 For resin P-21, by adjusting the equivalent amount of diamine relative to the acid anhydride and the polymerization concentration, resins with Mw of 5,000, 10,000, 12,000, 15,000, 20,000, 22,000, 30,000, 45,000, 75,000, and 150,000 were synthesized.
  • 1 H-NMR confirmed that the structures of resin P-0, resin P-2, and resin P-4 to resin P-21 were respectively represented by the following formulas (P-0), (P-2), and (P-4) to (P-21).
  • the imidization rate of all was 0%.
  • ⁇ solvent ⁇ MDMPA KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd.)
  • NMP N-methyl-2-pyrrolidone
  • EL Ethyl lactate
  • DMSO Dimethyl sulfoxide
  • GBL ⁇ -butyrolactone
  • GVL ⁇ -valerolactone
  • toluene Toluene
  • CP Cyclopentanone
  • CH Cyclohexanone
  • a resin composition layer was formed by spin-coating the resin composition or comparative composition onto a silicon wafer.
  • the silicon wafer to which the resin composition layer was applied was dried on a hot plate at 110°C for 5 minutes, yielding a resin composition layer having a uniform thickness of 19.2 ⁇ m after film formation on the silicon wafer.
  • the obtained resin composition layer was exposed using a dumbbell-shaped mask with an Ushio exposure machine (light source: 500 W/m 2 ultra-high pressure mercury lamp) at an exposure energy of 400 mJ/cm 2 .
  • the dumbbell shape was a dumbbell No. 7 shape described in JIS K 6251:2017.
  • the CTE of the test specimen prepared above was measured at 25°C to 125°C using a TMA450 (TA Instrument)
  • the temperature rise and fall conditions during evaluation were as follows (1) to (4). (1) The temperature was increased from room temperature to 130°C at a rate of 5°C/min. (2) The temperature was lowered from 130°C to 10°C at a rate of 5°C/min. (3) The temperature was increased from 10°C to 300°C at a rate of 5°C/min. (4) Allow to cool naturally to room temperature.
  • the elongation (displacement) of the sample was measured during the temperature increase and decrease processes (1) to (4) above, and the thermal expansion coefficient was calculated by dividing the elongation (displacement) of the sample at 25°C and 125°C in process (3) by the temperature.
  • CTE was less than 30 ppm/°C.
  • B CTE was 30 ppm/°C or more and less than 45 ppm/°C.
  • C CTE was 45 ppm/°C or more and less than 55 ppm/°C.
  • D CTE was 55 ppm/°C or more.
  • 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, forming 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 19.2 ⁇ m on the copper substrate.
  • 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.
  • the resin film obtained in each example was heated at a heating rate of 10°C/min in a nitrogen atmosphere using an infrared lamp heating device (RTP-6, manufactured by Advance Riko Co., Ltd.).
  • 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.
  • B The void area ratio was more than 0.5% and 2% or less.
  • C The void area ratio exceeded 2%.

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  • Medicinal Chemistry (AREA)
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  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

La présente invention concerne : une composition de résine contenant un précurseur de polyimide comprenant un motif récurrent représenté par la formule (1-1) dans laquelle A11 et A12 représentent chacun indépendamment -O- ou -NRZ-, RZ représente un atome d'hydrogène ou un groupe organique monovalent, R11 et R12 représentent chacun indépendamment un atome d'hydrogène ou un groupe organique monovalent, X représente un groupe organique tétravalent, et Y1 représente un groupe divalent représenté par l'une quelconque des formules (A-1) à (A-7) ; un stratifié comprenant un produit durci de celui-ci ; un procédé de production du produit durci ; un procédé de production du stratifié ; un procédé de production d'un dispositif à semi-conducteur, le procédé comprenant ledit procédé de production du produit durci ; et un dispositif à semi-conducteur comprenant le produit durci.
PCT/JP2025/011676 2024-03-28 2025-03-25 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 Pending WO2025205735A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08199150A (ja) * 1995-01-25 1996-08-06 Mitsui Toatsu Chem Inc 耐熱性接着剤
CN107189436A (zh) * 2017-07-20 2017-09-22 中国科学院长春应用化学研究所 一种聚酰亚胺纳米泡沫及其制备方法
CN111944312A (zh) * 2020-08-20 2020-11-17 吉林大学 一种可响应性导热聚酰亚胺前驱体凝胶及其制备方法、一种可响应性导热聚酰亚胺蜂窝结构
WO2022019254A1 (fr) * 2020-07-22 2022-01-27 富士フイルム株式会社 Composition de résine, film, filtre optique, élément d'imagerie à l'état solide, dispositif d'affichage d'images, résine, et composé
WO2022044998A1 (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
CN116789965A (zh) * 2022-03-18 2023-09-22 常州力得尔电子新材料有限公司 聚酰亚胺前驱体、光刻胶组合物及其应用

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08199150A (ja) * 1995-01-25 1996-08-06 Mitsui Toatsu Chem Inc 耐熱性接着剤
CN107189436A (zh) * 2017-07-20 2017-09-22 中国科学院长春应用化学研究所 一种聚酰亚胺纳米泡沫及其制备方法
WO2022019254A1 (fr) * 2020-07-22 2022-01-27 富士フイルム株式会社 Composition de résine, film, filtre optique, élément d'imagerie à l'état solide, dispositif d'affichage d'images, résine, et composé
CN111944312A (zh) * 2020-08-20 2020-11-17 吉林大学 一种可响应性导热聚酰亚胺前驱体凝胶及其制备方法、一种可响应性导热聚酰亚胺蜂窝结构
WO2022044998A1 (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
CN116789965A (zh) * 2022-03-18 2023-09-22 常州力得尔电子新材料有限公司 聚酰亚胺前驱体、光刻胶组合物及其应用

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