WO2022102345A1 - 樹脂組成物、硬化膜、絶縁膜または保護膜、アンテナ素子、並びに電子部品、表示装置または半導体装置及びその製造方法 - Google Patents

樹脂組成物、硬化膜、絶縁膜または保護膜、アンテナ素子、並びに電子部品、表示装置または半導体装置及びその製造方法 Download PDF

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Publication number
WO2022102345A1
WO2022102345A1 PCT/JP2021/038380 JP2021038380W WO2022102345A1 WO 2022102345 A1 WO2022102345 A1 WO 2022102345A1 JP 2021038380 W JP2021038380 W JP 2021038380W WO 2022102345 A1 WO2022102345 A1 WO 2022102345A1
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mol
resin
formula
group
resin composition
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PCT/JP2021/038380
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English (en)
French (fr)
Japanese (ja)
Inventor
荘司優
荒木斉
富川真佐夫
小笠原央
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Toray Industries Inc
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Toray Industries Inc
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Priority to CN202180068562.8A priority Critical patent/CN116323755A/zh
Priority to KR1020237012118A priority patent/KR20230104869A/ko
Priority to JP2021564739A priority patent/JPWO2022102345A1/ja
Publication of WO2022102345A1 publication Critical patent/WO2022102345A1/ja
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    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • 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
    • C08G73/22—Polybenzoxazoles
    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Definitions

  • the present invention relates to a resin composition, a cured film, an insulating film or a protective film, an antenna element, an electronic component, a display device or a semiconductor device, and a method for manufacturing the same.
  • polyimide resins and polybenzoxazole resins having excellent heat resistance and mechanical properties have been widely used as surface protective films and interlayer insulating films of semiconductor devices.
  • polyimide and polybenzoxazole are obtained by thermally dehydrating and ring-closing the coating film of these precursors to obtain a thin film having excellent heat resistance and mechanical properties.
  • high-temperature firing at around 350 ° C. is usually required.
  • MRAM Magneticoresistive Random Access Memory
  • sealing resin are vulnerable to high temperatures. Therefore, in order to use it as a surface protective film for such an element and an interlayer insulating film for a fan-out wafer level package that forms a rewiring structure on a sealing resin, it is cured by firing at a low temperature of about 250 ° C. or lower.
  • a polyimide resin or a polybenzoxazole resin that can obtain properties comparable to those obtained by firing a conventional material at a high temperature of about 350 ° C.
  • the film after heat curing remains as a permanent film in the device, so the physical characteristics of the cured film, especially the elongation, are very important. Further, when it is used as an insulating film between wiring layers of a wafer level package, chemical resistance is required to withstand the treatment because the chemical liquid treatment is repeatedly performed at the time of forming the metal wiring.
  • Patent Document 1 a method using a polybenzoxazole precursor having an aliphatic group (Patent Document 1) and a photosensitive resin composition containing a novolak resin having a crosslinkable group has been proposed (Patent Document 1). 2).
  • the cured film of the photosensitive resin composition containing the polybenzoxazole precursor having an aliphatic group described in Patent Document 1 and the novolak resin described in Patent Document 2 is contained in the cured film after the package reliability test. There is a problem that deterioration of the contained resin is observed, the elongation after the reliability test is lowered, and cracks are generated.
  • the present invention relates to the following. That is, the resin composition of the present invention is a resin composition containing (A) a resin and (E) a solvent, and the (A) resin is polyimide, polyamide, polybenzoxazole, or precursors thereof. , And at least one selected from the group consisting of copolymers thereof, and the resin (A) has a structure represented by the formula (1).
  • a is an integer of 0 to 4 independently, b is an integer of 0 to 2 independently, and when b is 0, a single bond is shown in parentheses and n is 1. It is an integer of ⁇ 12.
  • A is an independently single-bonded, -O-, -S-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, or a divalent hydrocarbon group having 1 to 5 carbon atoms.
  • R 1 is independently a halogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenoxy group. * Indicates a chemical bond.
  • the first aspect of the cured film of the present invention is obtained by curing the resin composition of the present invention.
  • a second aspect of the cured film of the present invention is a cured film having a resin (A), wherein the resin (A) is made of polyimide, polyamide, polybenzoxazole, precursors thereof, and copolymers thereof.
  • the resin (A) has a structure represented by the formula (1), including at least one selected from the group.
  • the insulating film or protective film of the present invention has the cured film of the present invention.
  • the method for manufacturing an electronic component, a display device or a semiconductor device of the present invention includes a step of applying the resin composition of the present invention and drying to form a resin film, a step of irradiating the resin film with chemical rays, and a resin film. It includes a step of developing to form a pattern and a step of heat treatment to form a relief pattern layer of a cured film.
  • the first aspect of the electronic component, display device or semiconductor device of the present invention has a relief pattern layer of the cured film of the present invention.
  • the second aspect of the electronic component, display device or semiconductor device of the present invention is that the cured film of the present invention is arranged as an insulating film between wirings.
  • the antenna element of the present invention is an antenna element provided with at least one or more antenna wirings and the cured film of the present invention, and the antenna wirings are a meander-shaped loop antenna, a coil-shaped loop antenna, or a meander-shaped monopole antenna.
  • the area occupied by one antenna portion in the antenna wiring is 1000 mm 2 or less, and the cured film is between the ground and the antenna wiring. It is an insulating film that insulates.
  • IC chip semiconductor element
  • rewiring layer a rewiring layer
  • sealing resin a sealing resin
  • the resin composition of the present invention is a resin composition containing (A) a resin and (E) a solvent, wherein the (A) resin is polyimide, a polyamide, a polybenzoxazole, a precursor thereof, and a precursor thereof.
  • the resin (A) has a structure represented by the formula (1), which comprises at least one selected from the group consisting of the copolymers thereof.
  • a is an integer of 0 to 4 independently, b is an integer of 0 to 2 independently, and when b is 0, a single bond is shown in parentheses and n is 1. It is an integer of ⁇ 12.
  • A is an independently single-bonded, -O-, -S-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, or a divalent hydrocarbon group having 1 to 5 carbon atoms.
  • R 1 is independently a halogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenoxy group. * Indicates a chemical bond.
  • the resin composition of the present invention contains (A) a resin (hereinafter, may be referred to as a component (A)).
  • the resin (A) contains at least one selected from the group consisting of polyimide, polyamide, polybenzoxazole, precursors thereof, and copolymers thereof.
  • the "copolymer thereof” refers to a copolymer obtained by copolymerizing two or more kinds selected from the group consisting of polyimide, polyamide, polybenzoxazole, and precursors thereof.
  • the polyimide is not particularly limited as long as it has an imide ring. Further, the polyimide precursor is not particularly limited as long as it has a structure that becomes a polyimide having an imide ring by dehydrating and closing the ring, and may contain a polyamic acid, a polyamic acid ester, or the like.
  • the polyamide is not particularly limited as long as it has an amide bond.
  • the polybenzoxazole is not particularly limited as long as it has a benzoxazole ring.
  • the polybenzoxazole precursor is not particularly limited as long as it has a structure that becomes a polybenzoxazole having a benzoxazole ring by dehydration closing, and can contain a polyhydroxyamide or the like.
  • the resin (A) is 160 after heat treatment because it is easy to obtain excellent characteristics as a surface protective film for semiconductor elements, an interlayer insulating film, an insulating layer for display devices such as organic light emitting elements, and a flattening film for a TFT substrate. It is preferable that the amount of outgas is small at a high temperature of ° C. or higher. Specifically, it is preferable that the resin (A) contains at least one selected from the group consisting of polyimide, polybenzoxazole, precursors thereof, and copolymers thereof.
  • the resin has a structure represented by the formula (1).
  • a is an integer of 0 to 4 independently, b is an integer of 0 to 2 independently, and when b is 0, a single bond is shown in parentheses and n is 1. It is an integer of ⁇ 12.
  • A is an independently single-bonded, -O-, -S-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, or a divalent hydrocarbon group having 1 to 5 carbon atoms.
  • R 1 is independently a halogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenoxy group. * Indicates a chemical bond.
  • a is preferably an integer of 1 to 4 independently.
  • A is preferably a single bond, —O—, —S—, —CO—, ⁇ COO ⁇ , —OCO ⁇ , —NHCO ⁇ , —CONH ⁇ .
  • n is preferably 4 or more, and more preferably 6 or more.
  • Examples of the method for obtaining the resin (A) include a method of polycondensing a dicarboxylic acid, a dicarboxylic acid derivative, an acid dianhydride, a diamine, a diisocyanate and the like having a structure represented by the formula (1).
  • Specific examples of the dicarboxylic acid derivative having the structure represented by the formula (1) include, but are not limited to, active amide compounds such as dicarboxylic acid dichloride, hydroxybenzotriazole and imidazole. Since polymerization can be carried out under mild conditions, when the resin (A) having the structure represented by the formula (1) is obtained by polycondensation, it is preferable to use a diamine having the structure represented by the formula (1).
  • the resin is (a-1) an alkali-soluble resin, and (B-1) a compound that generates an acid by light (hereinafter, (B-). 1) It may be referred to as a component) and (C-1) a heat-crosslinking agent (hereinafter, may be referred to as a component (C-1)) are preferably contained.
  • the resin composition can be imparted with photosensitivity.
  • photosensitivity By adding the component (C-1), it is possible to improve the mechanical properties of the cured film. By imparting photosensitivity, it is possible to rationalize the work process when forming through holes or the like in an interlayer insulating film or the like.
  • the alkali solubility in the present invention will be described.
  • a solution in which a resin is dissolved in ⁇ -butyrolactone is applied onto a silicon wafer and prebaked at 120 ° C. for 4 minutes to form a prebaked film having a film thickness of 10 ⁇ m ⁇ 0.5 ⁇ m.
  • the prebaked film is immersed in an alkaline aqueous solution selected from any of 2.38 mass% tetramethylammonium hydroxide aqueous solution, 1 mass% potassium hydroxide aqueous solution, and 1 mass% sodium hydroxide aqueous solution at 23 ⁇ 1 ° C. for 1 minute.
  • a resin having a dissolution rate of 50 nm / min or more of the prebake film is defined as being alkaline-soluble.
  • a second preferred embodiment of the resin composition of the present invention further comprises (B-2) a photopolymerization initiator (hereinafter, may be referred to as a component (B-2)), and (C-2). It preferably contains a compound having two or more ethylenically unsaturated bonds (hereinafter, may be referred to as a component (C-2)). Photosensitivity can be imparted to the resin composition by containing the component (B-2) and the component (C-2).
  • a third preferred embodiment of the resin composition of the present invention is a resin composition further containing (B-2) a photopolymerization initiator, wherein the (A) resin has an ethylenically unsaturated bond. It is preferable to have. Photosensitivity can be imparted to the resin composition by containing the resin (A) having an ethylenically unsaturated bond and the component (B-2).
  • a method for introducing an organic group having an ethylenically unsaturated bond for example, a tetracarboxylic acid dianhydride is reacted with alcohols having an ethylenically unsaturated bond to form a tetracarboxylic acid diester, which is then polyvalent amine.
  • examples thereof include a method of introducing by an amide polycondensation reaction with a compound.
  • Other methods include, for example, a method of obtaining a polyamic acid from an acid dianhydride and a diamine, and then reacting trifluoroacetic acid and alcohols having an ethylenically unsaturated bond with the polyamic acid.
  • the above-mentioned acid dianhydride and alcohol can be reacted as they are in a solvent, but it is preferable to use a reaction activator from the viewpoint of reactivity.
  • the reaction activator include tertiary amines such as pyridine, dimethylaminopyridine, triethylamine, N-methylmorpholine and 1,8-diazabicycloundecene.
  • the amount of the reaction activator added is preferably 3 mol parts or more and 300 mol parts or less, and more preferably 20 mol parts or more and 150 mol parts or less with respect to 100 mol parts of the acid anhydride group to be reacted.
  • Examples of the alcohols having an ethylenically unsaturated bond include alcohols having an ethylenically unsaturated bond and one hydroxyl group, and alcohols having two or more ethylenically unsaturated bonds and one hydroxyl group.
  • alcohols having one ethylenically unsaturated bond and one hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 1- (meth) acryloyl.
  • alcohols having 2 or more ethylenically unsaturated bonds and 1 hydroxyl group include glycerin-1,3-di (meth) acrylate, glycerin-1,2-di (meth) acrylate, and trimethylolpropanedi (meth).
  • Alcohols may be used at the same time when the acid anhydride and alcohols having an ethylenically unsaturated bond are reacted.
  • Other alcohols can be appropriately selected according to various purposes such as adjustment of exposure sensitivity and adjustment of solubility in an organic solvent. Specific examples thereof include aliphatic alcohols and monoalcohols derived from alkylene oxides.
  • Fatty alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, i-butanol, t-butanol, 1-pentanol, 2-pentanol, 3-pentanol, i. -Examples include pentanol.
  • Examples of monoalcohol derived from alkylene oxide include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, and triethylene glycol monoethyl ether.
  • an ionic bond may be used as a method for introducing an organic group having an ethylenically unsaturated bond.
  • a method for introducing an organic group having an ethylenically unsaturated bond by an ionic bond for example, a method of reacting a polyamic acid obtained by a reaction between an acid dianhydride and a diamine with a tertiary amine having an ethylenically unsaturated bond.
  • the tertiary amine having an ethylenically unsaturated bond include a compound represented by the following formula (8).
  • R 20 represents a hydrogen atom or a methyl group.
  • R 21 and R 22 independently indicate either a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an s-butyl group, a t-butyl group or a phenyl group.
  • z represents an integer from 1 to 10.
  • dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate tend to increase the exposure sensitivity. preferable.
  • Other methods for introducing an organic group having an ethylenically unsaturated bond include a method of reacting a hydroxyl group and / or a carboxy group in a resin with a compound having an ethylenically unsaturated double bond group, and an ethylenically unsaturated group. Examples thereof include a method of obtaining a resin by polymerization using a monomer having a saturated bond.
  • the compound having an ethylenically unsaturated double bond group an electrophilic compound having an ethylenically unsaturated double bond group is preferable from the viewpoint of reactivity.
  • electrophilic compound examples include isocyanate compounds, isothiocyanate compounds, epoxy compounds, aldehyde compounds, thioaldehyde compounds, ketone compounds, thioketone compounds, acetate compounds, carboxylated compounds, carboxylic acid anhydrides, and carboxylic acid active ester compounds. , Carboxylic acid compound, alkyl halide compound, alkyl azide compound, trifurate alkyl compound, mesylate alkyl compound, tosylate alkyl compound, alkyl cyanide compound and the like.
  • isocyanate compounds, epoxy compounds, aldehyde compounds, ketone compounds and carboxylic acid anhydrides are preferable, and isocyanate compounds, epoxy compounds and carboxylic acid anhydrides are more preferable, from the viewpoint of reactivity and compound availability.
  • the resin composition of the present invention may contain a polymerization inhibitor.
  • a polymerization inhibitor By containing the polymerization inhibitor, it is possible to easily prevent the ethylenically unsaturated bond site from being crosslinked during the reaction.
  • the polymerization inhibitor include phenol compounds such as hydroquinone, 4-methoxyphenol, t-butylpyrocatechol, and bis-t-butylhydroxytoluene.
  • the content of the polymerization inhibitor is preferably 0.1 mol or more and 5 mol or less of the phenolic hydroxyl group of the polymerization inhibitor with respect to 100 mol by mole of the ethylenically unsaturated bond of the alcohol.
  • b is an integer of 1 to 2 and 1 to 2 of R 1 are hydroxyl groups in the above formula (1).
  • b is 1 in the above formula (1).
  • the resin (A) is one or more selected from the group consisting of the structural unit represented by the formula (2), the structural unit represented by the formula (3), and the structural unit represented by the formula (4). It is preferable to have the structural unit of.
  • R 2 represents a tetravalent organic group having 4 to 40 carbon atoms.
  • the tetravalent organic group having 4 to 40 carbon atoms include a structure in which a carboxyl group is removed from an aromatic tetracarboxylic acid, a structure in which a carboxyl group is removed from an aliphatic tetracarboxylic acid, and the like.
  • the aliphatic tetracarboxylic acid preferably contains an alicyclic tetracarboxylic acid.
  • aromatic tetracarboxylic acid examples include pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-diphenyl ether tetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, 2,2', 3,3'- Benzophenone tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) propane, 1,1-bis (3,4-dicarboxyphenyl) ) Etan, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3
  • aliphatic tetracarboxylic acid examples include cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid and the like. Of these, pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 3,3', 4,4'-diphenyl ether tetracarboxylic acid, 2,2-bis (3,4-di) are preferred. Carboxyphenyl) Hexafluoropropane. Two or more kinds of structures in which the carboxyl group is removed from these tetracarboxylic acids may be contained.
  • R 3 indicates a structural unit when b is 1 or 2 in the structure represented by the above formula (1).
  • R 4 represents a 2- to 8-valent organic group having 4 to 40 carbon atoms.
  • R 5 indicates a structural unit when b is 1 or 2 in the structure represented by the above formula (1).
  • R 6 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.
  • q and r represent integers in the range of 0 ⁇ q ⁇ 4 and 0 ⁇ r ⁇ 4. When q and r are 0, (OH) q and (COOR 6 ) r represent a hydrogen atom. q and r indicate integers satisfying 0 ⁇ q + r ⁇ 6.
  • R 7 indicates a structural unit when b is 0 in the structure represented by the formula (1).
  • R 8 represents a divalent organic group having 4 to 40 carbon atoms.
  • R 4 and R 8 have a structure obtained by condensing a carboxylic acid having two or more carboxyl groups, excluding a portion derived from the two carboxyl groups.
  • R4 has a structure in which 0 to 6 hydrogen atoms are further substituted with OH and / or COOR 6 , so that it becomes a base of 2 to 8 valences.
  • carboxylic acids having two or more carboxyl groups include aromatic dicarboxylic acids, aromatic tricarboxylic acids, aromatic tetracarboxylic acids, alicyclic dicarboxylic acids, and aliphatic tetracarboxylic acids.
  • aromatic dicarboxylic acids examples include terephthalic acid, isophthalic acid, diphenyletherdicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyldicarboxylic acid, benzophenonedicarboxylic acid, triphenyldicarboxylic acid and the like.
  • aromatic tricarboxylic acids examples include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid and the like.
  • aromatic tetracarboxylic acid examples include pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, 2,2', 3,3.
  • Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid.
  • aliphatic tetracarboxylic acid examples include cyclobutane tetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid.
  • diphenyl ether dicarboxylic acid bis (carboxyphenyl) hexafluoropropane, pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 3,3', 4,4'-diphenyl ether tetracarboxylic acid are preferred.
  • Acid 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane.
  • R 4 and R 8 may contain two or more types of structures obtained by condensing a carboxylic acid having two or more of these carboxyl groups, excluding a portion derived from the two carboxyl groups.
  • Curing of the resin composition by containing the resin (A) having the structure represented by the formula (1) in the structural unit represented by the formula (2), the formula (3) or the formula (4). High elongation in the membrane, deterioration of elongation after the reliability test is less likely to occur, and high crack resistance is easily obtained.
  • the structural unit represented by the formula (3) has a carboxy group or a carboxyester group at the ortho position of the aromatic amide group, and for example, an imide ring structure can be formed by dehydration ring closure.
  • R5 in the formula ( 3 ) has an aromatic group and a hydroxyl group at the ortho position of the aromatic amide group, for example, benzoxazole by dehydration ring closure.
  • a ring structure can be formed.
  • the total content of the structural unit represented by the formula (2), the structural unit represented by the formula (3), and the structural unit represented by the formula (4) is (A) the structural unit 100 of the entire resin.
  • it is preferably 10 mol% or more and 80 mol% or less, more preferably 30 mol% or more and 80 mol% or less, and most preferably 50 mol% or more and 80 mol% or less.
  • R 1 is independently a halogen atom, a monovalent hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenoxy group.
  • the total content of the structural unit represented by the formula (2), the structural unit represented by the formula (3), and the structural unit represented by the formula (4) is (A) the structural unit 100 of the entire resin. It is preferably 10 mol% or more and 20 mol% or less in mol%.
  • a is an integer of 1 to 4 independently, and 1 to 2 of R 1 are hydroxyl groups, and the structural unit represented by the formula (2), the formula (3).
  • the total content of the structural unit represented by) and the structural unit represented by the formula (4) is 10 mol% or more and 100 mol% or less in (A) 100 mol% of the structural unit of the whole resin. It is more preferably 50 mol% or more and 100 mol% or less, and most preferably 80 mol% or more and 100 mol% or less.
  • the resin (A) can be used as a polyimide or polybenzoxazole by dehydration ring closure, but it may also be used as a precursor polyamide, and it is not always necessary to dehydrate and ring closure.
  • R 3 , R 5 , and R 7 can be obtained from a diamine residue having a structure represented by the formula (1), but can be obtained from a diamine residue other than the diamine having a structure represented by the formula (1).
  • the structural units may be copolymerized.
  • Specific examples of the diamine constituting a diamine residue other than the diamine having the structure represented by the formula (1) include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and 3,4'-.
  • an aliphatic group having a siloxane structure may be copolymerized as long as the heat resistance is not lowered. By copolymerizing such groups, the adhesiveness with the substrate can be improved.
  • the diamine component include those obtained by copolymerizing 1 to 15 mol% of bis (3-aminopropyl) te-lamethyldisi-mouth xan, bis (p-aminophenyl) octamethylpentasiloxane, and the like.
  • the copolymerizing by 1 mol% or more is preferable in terms of improving the adhesiveness with a substrate such as a silicon wafer.
  • the copolymerization is carried out in an amount of 15 mol% or less, it is preferable in that the solubility in the Al-Rikiri solution is not lowered.
  • the resin (A) preferably has a structure represented by the formula (6) and / or a structure represented by the formula (7). Having such a structure makes it easy to reduce the rate of change in elongation at break point after the reliability test.
  • R 16 and R 17 each represent a monovalent organic group or hydroxyl group having 1 to 5 carbon atoms
  • v and w each represent an integer of 0 to 4
  • m represents an integer of 0 to 2.
  • Indicated, * indicates a chemical bond. However, those included in the structural unit represented by the formula (1) are excluded.
  • R 18 and R 19 each represent a monovalent organic group or hydroxyl group having 1 to 5 carbon atoms
  • x and y each represent an integer of 0 to 4
  • * represents a chemical bond.
  • diamine component having the structure represented by the formula (6) and / or the structure represented by the formula (7) include m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, and 2 , 6-naphthalenediamine, benzidine, 3,3'-dihydroxybenzidine, bis (4-aminophenoxy) biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4 '-Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2', 3,3'-tetramethyl-4, 4'-diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-d
  • Examples of the dicarboxylic acid having the structure represented by the formula (6) and / or the structure represented by the formula (7) include terephthalic acid, isophthalic acid, biphenyldicarboxylic acid, triphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid and Examples thereof include those derivatives or compounds in which at least a part of the hydrogen atom of these aromatic rings is replaced with an alkyl group or a halogen atom.
  • Examples of the tetracarboxylic acid dianhydride having the structure represented by the formula (6) and / or the structure represented by the formula (7) include acid dianhydride having the structure shown below.
  • it is preferably 10 mol% or more and 80 mol% or less, more preferably 10 mol% or more and 65 mol% or less, and most preferably 10 mol% or more and 50 mol% or less. ..
  • the resin (A) has a main chain end of a terminal encapsulant such as monoamine, acid anhydride, monocarboxylic acid, monoacid kutolide compound, monoactive ester compound and the like. It is preferable to seal with. Further, by sealing the end of the resin (A) with an end-capping agent having a hydroxyl group, a force ruboxyl group, a sulfonic acid group, a thiol group, a vinyl group, an ethynyl group or an allyl group, the dissolution rate of the resin in an alkaline solution The mechanical properties of the obtained cured film can be easily adjusted to a preferable range.
  • a terminal encapsulant such as monoamine, acid anhydride, monocarboxylic acid, monoacid kutolide compound, monoactive ester compound and the like. It is preferable to seal with. Further, by sealing the end of the resin (A) with an end-capping agent having a hydroxyl group, a force rub
  • the introduction ratio of the terminal encapsulant is preferably 0.1 mol because the molecular weight of the resin (A) becomes high and the solubility in an alkaline solution is suppressed with respect to 100 mol parts of the total amine component. More than a portion, particularly preferably 5 mol parts or more. Further, in order to suppress the deterioration of the mechanical properties of the obtained cured film by lowering the molecular weight of the resin (A), the introduction ratio of the terminal encapsulant is preferably 60 mol parts or less, particularly preferably 50 mol parts or less. be. A plurality of different end groups may be introduced by reacting a plurality of terminal encapsulants.
  • the compounds described in Patent Nos. 6740903 [0038] to [0042] can be used as the monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, and monoactive ester compound.
  • the terminal encapsulant introduced into the resin (A) is gask mouth measurement (GC), pyrolysis gask mouth measurement graph (PGC), infrared spectrum and / or NMR measurement. Can be easily detected with.
  • the resin (A) preferably has a weight average molecular weight of 10,000 or more and 100,000 or less.
  • the weight average molecular weight is 10,000 or more, the mechanical properties of the cured film after curing can be improved. More preferably, the weight average molecular weight is 20,000 or more.
  • the weight average molecular weight is 100,000 or less, the developability with various developing solutions can be improved, and if the weight average molecular weight is 50,000 or less, the developability with an alkaline solution can be improved. It is preferable because it can be done.
  • the weight average molecular weight (Mw) can be confirmed by using GPC (gel permeation chromatography).
  • the developing solvent can be measured as N-methyl-2-pyrrolidone (hereinafter, may be abbreviated as NMP) and determined in terms of polystyrene.
  • NMP N-methyl-2-pyrrolidone
  • the weight average molecular weight of at least one kind may be within the above range.
  • the resin can be produced by a known method.
  • A When the resin is a polyimide precursor, for example, a polyamic acid or a polyamic acid ester, for example, as a first method, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound at a low temperature may be mentioned.
  • a diester is obtained from a tetracarboxylic acid dianhydride and an alcohol. Then, a method of reacting with an amine in the presence of a condensing agent can be mentioned.
  • a diester is obtained from a tetracarboxylic acid dianhydride and an alcohol. After that, a method of synthesizing the remaining dicarboxylic acid by acid chloride formation and reaction with an amine can be mentioned.
  • examples of the production method include a method of condensing a bisaminophenol compound with a dicarboxylic acid.
  • Examples thereof include a method of dropping a solution of dicarboxylic acid dichloride.
  • the resin when it is polyimide, it can be obtained, for example, by dehydrating and closing the ring of the polyimide precursor obtained by the above-mentioned method by heat treatment or chemical treatment with an acid or a base.
  • polybenzoxazole for example, it can be obtained by dehydrating and closing the ring of the polybenzoxazole precursor obtained by the above-mentioned method by heat treatment or chemical treatment such as acid or base.
  • the resin composition of the present invention preferably contains (B-1) a compound that generates an acid by light.
  • the resin composition can be imparted with photosensitivity.
  • (B-1) The compound that generates an acid by light generates an acid in the light-irradiated portion of the resin composition.
  • the solubility of the light-irradiated portion in the alkaline developer is increased, so that a positive pattern in which the light-irradiated portion is dissolved can be obtained.
  • Examples of the compound that generates an acid by the above-mentioned (B-1) light include a quinonediazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, and an iodonium salt.
  • the resin composition of the present invention may further contain a sensitizer or the like, if necessary.
  • quinone diazide compound a compound in which a sulfonic acid of naphthoquinone diazide is ester-bonded to a compound having a phenolic hydroxyl group is preferable.
  • Compounds having a phenolic hydroxyl group include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, and BisP.
  • naphthoquinone diazide sulfonic acid examples include 4-naphthoquinone diazido sulfonic acid and 5-naphthoquinone diazido sulfonic acid.
  • the dissolution rate ratio between the exposed portion and the unexposed portion of the composition can be increased, and a pattern can be obtained with high resolution.
  • a resin composition can be obtained.
  • the component (B-1) may be contained alone or in combination of two or more, and a photosensitive resin composition having high sensitivity can be obtained.
  • any of 5-naphthoquinone diazidosulfonyl group and 4-naphthoquinone diazidosulfonyl group is preferably used.
  • the 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure and all-wavelength exposure.
  • the 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
  • a naphthoquinone diazidosulfonyl ester compound containing a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group in the same molecule.
  • a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound can also be used in combination.
  • the quinone diazide compound can be synthesized by a known method by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazido sulfonic acid compound.
  • the resolution, sensitivity, and residual film ratio are further improved by using the quinone diazide compound.
  • the molecular weight of the component (B-1) is preferably 300 or more, more preferably 350 or more, preferably 3,000 or less, more preferably 3,000 or less, from the viewpoint of heat resistance, mechanical properties and adhesiveness of the film obtained by heat treatment. Is less than 1,500.
  • a sulfonium salt, a phosphonium salt, and a diazonium salt are preferable because they appropriately stabilize the acid component generated by exposure.
  • the sulfonium salt is preferable.
  • the content of the component (B-1) is preferably 0.1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the resin (A).
  • the photosensitivity can be imparted while maintaining the heat resistance, chemical resistance and mechanical properties of the film after heat treatment. can.
  • the content of the component (B-1) is more preferably 1 part by mass or more and further preferably 3 parts by mass or more with respect to 100 parts by mass of the resin (A). preferable. Further, 100 parts by mass or less is more preferable, and 80 parts by mass or less is further preferable. When the amount is 1 part by mass or more and 100 parts by mass or less, the photosensitivity can be imparted while maintaining the heat resistance, chemical resistance and mechanical properties of the film after the heat treatment.
  • the content of the component (B-1) is 0.1 part by mass or more with respect to 100 parts by mass of the resin (A).
  • 1 part by mass or more is more preferable, and 3 parts by mass or more is particularly preferable.
  • 100 parts by mass or less is more preferable, 80 parts by mass or less is further preferable, and 50 parts by mass or less is particularly preferable.
  • the photosensitivity can be imparted while maintaining the heat resistance, chemical resistance and mechanical properties of the film after the heat treatment.
  • the resin composition of the present invention preferably contains (C-1) a thermal cross-linking agent.
  • the thermal cross-linking agent contains at least two or more groups selected from the group consisting of an acrylic group, a methacrylic group, an epoxy group, an oxetanyl group, a benzoxazine structure, an alkoxymethyl group and a methylol group. It is a compound.
  • the content of the component (C-1) is preferably 10 parts by mass or less with respect to 100 parts by mass of the resin (A). Within such a range, it is possible to appropriately facilitate a wide range of designs for improving the sensitivity and the mechanical properties of the cured film.
  • the (C-1) thermal cross-linking agent preferably contains a compound having at least two alkoxymethyl groups or methylol groups.
  • "having at least two alkoxymethyl groups or methylol groups” means having two or more alkoxymethyl groups, having two or more methylol groups, and having a total of two or more alkoxymethyl groups and methylol groups. Represents one of the things. By having at least two of these groups, a crosslinked structure can be formed by a condensation reaction with a resin and a homologous molecule. By including the compound having at least two alkoxymethyl groups or methylol groups together with the component (B-1), a wider range of designs can be made for improving the sensitivity and the mechanical properties of the cured film.
  • Preferred examples of compounds having at least two alkoxymethyl or methylol groups include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML-.
  • OCHP DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DMLBisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), NIKARAC (registered trademark) ) MX-290, NIKALAC
  • the content of the compound having at least two alkoxymethyl groups or methylol groups is preferably 10 parts by mass or less with respect to 100 parts by mass of the resin (A). Within this range, a wide range of designs for improving sensitivity and mechanical properties of the cured film can be made more appropriately.
  • the resin composition of the present invention preferably contains (B-2) a photopolymerization initiator.
  • the (B-2) photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals upon exposure, but is an alkylphenone compound, an aminobenzophenone compound, a diketone compound, a ketoester compound, a phosphine oxide compound, an oxime ester compound, and a scent. Acid ester compounds are preferable because they are excellent in sensitivity, stability, and ease of synthesis.
  • an alkylphenone compound and an oxime ester compound are preferable from the viewpoint of sensitivity, and an oxime ester compound is particularly preferable. Further, in the case of a thick film having a processed film thickness of 5 ⁇ m or more, a phosphine oxide compound is preferable from the viewpoint of resolution.
  • alkylphenone compound examples include ⁇ -aminoalkylphenone compound, ⁇ -hydroxyalkylphenone compound, ⁇ -alkoxyalkylphenone compound and the like.
  • the ⁇ -aminoalkylphenone compound is preferable because of its high sensitivity.
  • Examples of ⁇ -aminoalkylphenone compounds are 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1-. (4-Morphorin-4-yl-phenyl) -butane-1-one and the like can be mentioned.
  • Examples of the ⁇ -hydroxyalkylphenone compound include 1-hydroxycyclohexyl-phenylketone, benzoin and the like.
  • Examples of the ⁇ -alkoxyalkylphenone compound include 4-benzoyl-4-methylphenylketone, 2,3-diethoxyacetophenone and the like.
  • Examples of the phosphine oxide compound include 6-trimethylbenzoylphenylphosphine oxide.
  • Examples of the oxime ester compound include 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (0-acetyloxime), 2-octanedione, 1-. [4- (Phenylthio) -2- (O-benzoyloxime)], NCI-831, NCI-930 (above, trade name, manufactured by ADEKA Co., Ltd.), "Irgacure (registered trademark)" OXE-03, OXE- 04 (above, trade name, manufactured by BASF Co., Ltd.) can be mentioned.
  • aminobenzophenone compound examples include 4,4-bis (dimethylamino) benzophenone.
  • diketone compound examples include benzyl and the like.
  • ketoester compound examples include methyl benzoylate.
  • benzoic acid ester compound examples include methyl o-benzoyl benzoate and ethyl p-dimethylaminobenzoate.
  • photopolymerization initiator examples include benzophenone, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, fluorenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 2-. Hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propanolinium chloride, anthraquinone, triphenylphosphine, carbon tetrabromide And so on.
  • the content of the (B-2) photopolymerization initiator is 100 parts by mass when the sum of the contents of the resin (A) and the compound having two or more ethylenically unsaturated bonds contained as needed is 100 parts by mass.
  • 0.5 parts by mass or more and 20 parts by mass or less are preferable because sufficient sensitivity can be obtained and the amount of degassing during thermal curing can be suppressed. Above all, 1.0 part by mass or more and 10 parts by mass or less are more preferable.
  • the resin composition of the present invention may contain a sensitizer.
  • a sensitizer By containing the sensitizer, the function of the (B-2) photopolymerization initiator can be further enhanced, the sensitivity can be improved, and the photosensitive wavelength can be adjusted.
  • the sensitizer include bis (dimethylamino) benzophenone, bis (diethylamino) benzophenone, diethylthioxanthone, N-phenyldiethanolamine, N-phenylglycine, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-4-methyl. Examples include, but are not limited to, coumarin, N-phenylmorpholine and derivatives thereof.
  • the resin composition of the present invention preferably further contains a compound (C-2) having two or more ethylenically unsaturated bonds.
  • Photosensitivity can be imparted by containing the component (C-2). Further, since the crosslink density at the time of exposure is improved, the exposure sensitivity is further improved, which can contribute to the reduction of the exposure amount and the reduction of the developing film.
  • the component (C-2) a polyfunctional (meth) acrylate compound can be contained.
  • polyfunctional (meth) acrylate compound examples include diethylene glycol di (meth) acrylate, trimethyl propanetri (meth) acrylate, 1,3-butanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate, 1.
  • Examples of other polyfunctional (meth) acrylate compounds include epoxy (meth) acrylates obtained by reacting a polyfunctional epoxy compound with (meth) acrylic acid.
  • the content of the component (C-2) is preferably 5 parts by mass or more and 100 parts by mass or less, and more preferably 10 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin (A). By setting the content of the component (C-2) in such a range, it is possible to easily maintain the mechanical properties while improving the sensitivity.
  • the resin composition of the present invention preferably further contains a compound represented by the formula (D) (5) (hereinafter, may be abbreviated as the component (D)).
  • R 9 represents an alkyl group having 1 or more and 15 or less carbon atoms
  • R 10 represents an alkylene group having 2 or more and 10 or less carbon atoms
  • R 11 has an alkyl group having 1 to 20 carbon atoms, an alkylene group having 1 to 20 carbon atoms, or a 1 to 4 valence having 1 to 20 carbon atoms containing at least one of an O atom, an S atom and an N atom.
  • k represents an integer of 1 to 4.
  • R 11 examples include a quaternary carbon group, a tertiary carbon group, a secondary carbon group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group and an aryl ether group.
  • Examples thereof include a carboxy group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, —O—, —NH—, —NHNH— and a combination thereof, and may further have a substituent.
  • an alkyl ether group or -NH- is preferable from the viewpoint of solubility in a developing solution and metal adhesion, and -NH- is preferable from the viewpoint of (A) interaction with a resin and metal adhesion due to metal complex formation. More preferred.
  • the component (D) By including the component (D), it becomes easy to suppress the oxidative deterioration of the aliphatic group and the hydroxyl group of the resin (A). In addition, the rust preventive action on the metal material makes it easier to suppress the metal oxidation caused by moisture or a photosensitive agent from the outside and the accompanying peeling between the cured film and the metal material. That is, it is possible to easily suppress the deterioration of the device characteristics after the device reliability test.
  • Specific examples of the component (D) include, but are not limited to, other compounds may be used.
  • the amount of the component (D) added is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the resin (A).
  • the addition amount is 0.1 part by mass or more, the adhesion to the metal material is improved and peeling is suppressed. Further, when the addition amount is 10 parts by mass or less, the sensitivity of the resin composition can be maintained.
  • the resin composition of the present invention may contain an adhesion improver.
  • adhesion improver include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, and the like.
  • silane coupling agents such as 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, aromatic amine compounds and alkoxy groups. Examples thereof include a compound obtained by reacting a silicon compound. Two or more of these may be contained.
  • the adhesion improver By containing the adhesion improver, it is possible to improve the adhesion to a base material such as a silicon wafer, ITO, SiO 2 , or silicon nitride when developing a resin film. In addition, it is possible to increase the resistance to oxygen plasma and UV ozone treatment used for cleaning and the like.
  • the content of the adhesion improver in the resin composition is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin (A). Within such a range, it is possible to provide a resin composition having high adhesion after development and excellent resistance to oxygen plasma and UV ozone treatment.
  • the resin composition of the present invention may contain a compound having a phenolic hydroxyl group from the viewpoint of easily supplementing the alkali developability. Since the resin composition contains a compound having a phenolic hydroxyl group, it hardly dissolves in an alkaline developer before exposure and easily dissolves in an alkaline developer when exposed, so that film loss due to development is small and short. Development becomes easier in time. Therefore, the sensitivity is likely to be improved.
  • Examples of the compound having a phenolic hydroxyl group selected from this point include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, and BisP.
  • the resin composition of the present invention may contain a compound having a phenolic hydroxyl group as long as the shrinkage residual film ratio after curing is not reduced from the viewpoint of shortening the developing time.
  • Examples of the compound having a phenolic hydroxyl group selected from this point include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, and BisP.
  • the resin composition of the present invention may contain a surfactant, if necessary.
  • a surfactant By containing the surfactant, the wettability with the substrate can be improved and the film thickness uniformity of the coating film can be improved.
  • the surfactant a commercially available compound can be used. Specifically, as silicone-based surfactants, Toshiba Dow Corning Silicone's SH series, SD series, ST series, Big Chemie Japan's BYK series, Shinetsu Silicone's KP series, Nippon Oil &Fats' disform series, etc. Examples include the TSF series manufactured by Toshiba Silicone.
  • Fluorine-based surfactants include Dainippon Ink Industry's "Megafuck” (registered trademark) series, Sumitomo 3M's Florard series, Asahi Glass's “Surflon” (registered trademark) series, and "Asahi Guard” (registered). Trademarks) series, Shin-Akita Kasei's EF series, Omniova Solution's Polyfox series, etc.
  • Examples of the surfactant obtained from the acrylic and / or methacrylic polymer include, but are not limited to, the Polyflow series of Kyoeisha Chemical Co., Ltd. and the "Disparon” (registered trademark) series of Kusumoto Kasei Co., Ltd.
  • the content of the surfactant is preferably 0.001 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of the resin (A).
  • the wettability between the resin composition and the substrate and the film thickness uniformity of the coating film can be improved without causing problems such as air bubbles and pinholes.
  • the resin composition of the present invention contains (E) a solvent (hereinafter, may be referred to as a component (E)).
  • a solvent hereinafter, may be referred to as a component (E)).
  • the solvent N-methyl-2-pyrrolidone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1,3- Polar aprotonic solvents such as dimethyl-2-imidazolidinone, N, N'-dimethylpropylene urea, N, N-dimethylisobutyric acid amide, methoxy-N, N-dimethylpropionamide, tetrahydrofuran, dioxane, propylene glycol monomethyl Ethers such as ethers and propylene glycol monoethyl ethers, ketones such as acetone, methyl ethyl
  • esters such as ethyl lactate, methyl lactate, diacetone alcohol, alcohols such as 3-methyl-3-methoxybutanol, aromatic hydrocarbons such as toluene and xylene, and the like. Two or more of these may be contained.
  • the content of the solvent (E) is preferably 100 parts by mass or more from the viewpoint that the composition can be easily dissolved with respect to 100 parts by mass of the resin (A).
  • the content of the solvent (E) is preferably 1,500 parts by mass or less because it is easy to form a coating film having a film thickness of 1 ⁇ m or more.
  • the component (B) is a general term for the component (B-1) and the component (B-2).
  • the component (C) is a general term for the component (C-1) and the component (C-2).
  • the melting method examples include heating and stirring.
  • the heating temperature is preferably set within a range that does not impair the performance of the resin composition, and is usually 25 ° C to 80 ° C.
  • the dissolution order of each component is not particularly limited, and examples thereof include a method of sequentially dissolving compounds having low solubility.
  • the rotation speed is preferably set within a range that does not impair the performance of the resin composition, and is usually 200 rpm to 2000 rpm. It may be agitated or heated as needed, and is usually 25 ° C to 80 ° C.
  • components that tend to generate bubbles during stirring and dissolution such as surfactants and some adhesion improvers, by dissolving other components and then adding them last, the other components are poorly dissolved due to the generation of bubbles. Can be prevented.
  • the viscosity of the resin composition of the present invention is preferably 2 to 5,000 mPa ⁇ s at 25 ° C. By adjusting the solid content concentration so that the viscosity is 2 mPa ⁇ s or more, it becomes easy to obtain a desired film thickness. On the other hand, when the viscosity is 5,000 mPa ⁇ s or less, it becomes easy to obtain a highly uniform coating film.
  • the viscosity measurement here is a measurement using a former E-type viscometer / DVE-type viscometer of TVE-25 type viscometer (manufactured by Toki Sangyo Co., Ltd.), and 1.1 mL of the resin composition of the present invention is collected. And pour into the sample cup.
  • the torque is selected in the range of 65 to 6000 ⁇ N ⁇ m, and the measurement is performed in the range of the rotation speed of 0.5 to 100 rpm.
  • the resin composition of the present invention having such a viscosity has the content of the component (A) in 100% by mass of the resin composition of the present invention, and if contained, the component (B) and the component (C) combined. Can be easily obtained by setting the content to 5 to 60% by mass.
  • the solid content concentration means a component other than the solvent.
  • the obtained resin composition is filtered using a filtration filter to remove dust and particles.
  • the filter hole diameter is, for example, 0.5 ⁇ m, 0.2 ⁇ m, 0.1 ⁇ m, 0.05 ⁇ m, 0.02 ⁇ m, and the like, but is not limited thereto.
  • the material of the filtration filter includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE) and the like, but polyethylene and nylon are preferable.
  • the first aspect of the cured film of the present invention is obtained by curing the resin composition of the present invention.
  • the cured film is excellent in heat resistance, mechanical properties and chemical resistance.
  • a second aspect of the cured film of the present invention is a cured film having (A) a resin, wherein the resin is made of polyimide, polyamide, polybenzoxazole, precursors thereof, and copolymers thereof.
  • the resin (A) has a structure represented by the formula (1), including at least one selected from the group.
  • a is an integer of 0 to 4 independently, b is an integer of 0 to 2 independently, and when b is 0, a single bond is shown in parentheses and n is 1. It is an integer of ⁇ 12.
  • A is an independently single-bonded, -O-, -S-, -CO-, -COO-, -OCO-, -NHCO-, -CONH-, or a divalent hydrocarbon group having 1 to 5 carbon atoms.
  • R 1 is independently a halogen atom, a hydroxyl group, a monovalent hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenoxy group. * Indicates a chemical bond.
  • the components (A) and the structure represented by the formula (1) are the same as those described in the above composition.
  • the cured film of the present invention does not show any decrease in elongation even after the package reliability test, has high crack resistance, and can improve the reliability of the semiconductor device, electronic component, and display device of the present invention. ..
  • the cured film of the present invention can be produced, for example, by the following method.
  • the resin composition of the present invention is applied onto a substrate and dried to obtain a resin film.
  • the cured film of the present invention can be obtained by heat-treating the resin film.
  • the heat treatment of the resin film may be carried out by raising the temperature stepwise or while continuously raising the temperature.
  • the heat treatment is preferably carried out for 5 minutes to 5 hours.
  • the heat treatment temperature is preferably 140 ° C. or higher and 400 ° C. or lower.
  • the heat treatment temperature is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, in order to remove the solvent in the resin film.
  • the heat treatment temperature is preferably 400 ° C. or lower, more preferably 350 ° C. or lower.
  • the insulating film or protective film of the present invention has the cured film of the present invention.
  • Specific examples of the insulating film or the protective film include a semiconductor passive film, a surface protective film of a semiconductor element, an interlayer insulating film, an interlayer insulating film of a multilayer wiring for high-density mounting, an insulating layer of an organic electric field light emitting element, and the like. , Not limited to this, and various structures can be mentioned.
  • the insulating film or protective film of the present invention has high mechanical properties at the time of curing and maintains the mechanical properties even after the reliability test as compared with that before the reliability test. Therefore, it is a highly reliable semiconductor exhibiting high crack resistance. Equipment can be provided.
  • the method for manufacturing an electronic component, a display device or a semiconductor device of the present invention includes a step of applying the resin composition of the present invention and drying to form a resin film, a step of irradiating the resin film with chemical rays, and a resin film. It includes a step of developing to form a pattern and a step of heat treatment to form a relief pattern layer of a cured film.
  • the resin composition of the present invention is applied to a substrate to obtain a coating film of the resin composition.
  • the substrate include, but are not limited to, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and those on which circuit constituent materials are arranged.
  • Examples of the coating method include a spin coating method, a slit coating method, a dip coating method, a spray coating method, and a printing method.
  • the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 150 ⁇ m.
  • the base material to which the resin composition is applied may be pretreated with the above-mentioned adhesion improver.
  • the adhesion improver is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate by 0.5 to 20 mass by mass.
  • % Examples thereof include a method of treating the surface of the substrate by a method such as spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment using the dissolved solution.
  • a vacuum drying treatment may be performed, if necessary. Further, after that, the reaction between the base material and the adhesion improver may be allowed to proceed by heat treatment at 50 ° C. to 280 ° C.
  • the coating film of the resin composition is dried to form a resin film. Drying is preferably carried out in the range of 50 ° C. to 140 ° C. for 1 minute to 2 hours using an oven, a hot plate, infrared rays or the like.
  • the chemical rays are irradiated and exposed through a mask having a desired pattern on the photosensitive resin film.
  • Chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, g-rays (436 nm), h-rays (405 nm), or i-rays (365 nm), which are common exposure wavelengths, are used. It is preferable to use a chemical line containing.
  • the method for manufacturing an electronic component, a display device, or a semiconductor device of the present invention may include a post-exposure bake (PEB) step, if necessary.
  • the PEB step is preferably carried out on the exposed resin film in the range of 50 ° C. to 150 ° C. for 1 minute to 2 hours using an oven, a hot plate, infrared rays or the like.
  • the developing solution used in the step of developing the resin film to form a pattern includes tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, and carbonic acid.
  • An aqueous solution of an alkaline compound such as potassium, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylenediamine and hexamethylenediamine is preferable.
  • polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, ⁇ -butyrolactone, and dimethylacrylamide may be added to the aqueous solution of these alkaline compounds.
  • Add one or more alcohols such as methanol, ethanol and isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone. May be good.
  • the developer is preferably a good solvent for the resin composition or a combination of the good solvent and a poor solvent.
  • the good solvent include N-methylpyrrolidone, N, N-dimethylacetamide, cyclopentanone, cyclohexanone, ⁇ -butyrolactone and the like.
  • the poor solvent include toluene, xylene, ethanol, isopropyl alcohol, ethyl lactate, propylene glycol methyl ether acetate, water and the like.
  • each solvent for example, several kinds can be used in combination.
  • it is generally rinsed with an organic solvent or water.
  • alcohols such as ethanol and isopropyl alcohol
  • esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added for rinsing treatment.
  • Dry etching may be used as a pattern forming method for the resin composition.
  • the irradiation conditions of the UV laser are not particularly limited, but usually an excimer laser such as ArF (193 nm), KrF (248 nm), XeCl (308 nm), XeCl (351 nm), or YAG laser (355 nm) light is used. ..
  • the carbon dioxide laser is inferior in resolution to the UV laser, the carbon dioxide laser may be used in applications that do not require high definition because the equipment cost is low and the economy is excellent.
  • the method for manufacturing an electronic component, a display device, or a semiconductor device of the present invention includes a step of heat-treating to form a relief pattern layer of a cured film.
  • the preferred conditions for the heat treatment are the same as the heat treatment conditions for the resin film in the above-mentioned ⁇ cured film>.
  • a method for manufacturing a semiconductor device using a re-division layer (RDL) first step is shown.
  • a barrier metal such as Ti is formed on a support substrate such as a glass substrate or a silicon wafer by a sputtering method, a Cu seed (seed layer) is further formed on the barrier metal by a sputtering method, and then an electrode pad made of Cu is formed by a plating method. do.
  • the resin composition of the present invention is applied to the entire surface of the support substrate on which the electrode pad is formed and dried to form a resin film.
  • the obtained resin film is irradiated with chemical rays at an exposure amount of 100 to 2000 mJ / cm 2 using an i-line stepper, a broadband aligner, or the like.
  • the developer is discharged onto the exposed resin film to dissolve and remove the exposed portion for development, and a line & space or a square or hole-shaped pattern is formed.
  • the heat treatment is performed to form a relief pattern layer of the cured film.
  • This relief pattern layer serves as an insulating film.
  • the seed layer is formed again by the sputtering method, and the metal wiring (rewiring) made of Cu is formed by the plating method. After that, the process of forming the metal wiring is repeated from the process of the seed layer to form the multilayer wiring structure.
  • the resin composition of the present invention is applied again, a pattern is formed using the chemical beam irradiation step, an insulating film is formed by heat treatment and curing, and then the insulating film is formed on the metal wiring at the opening of the insulating film.
  • a Cu post is formed using a plating method.
  • the pitch of the Cu post and the pitch of the conductive portion of the semiconductor chip are made equal to each other. That is, the pitch of the conductive portion of the semiconductor chip is finer than the pitch of the electrode pad, and each rewiring layer constituting the multilayer wiring structure is wired from the electrode pad to the Cu post while gradually becoming a fine pitch. Is multi-layered.
  • the thickness of the adjacent insulating film in the multilayer wiring structure also becomes the same or thinner as it approaches the semiconductor chip.
  • the semiconductor chip is connected to the Cu post via the solder bump.
  • the electrode pad and the semiconductor chip are electrically connected via the metal wiring and the solder bump.
  • the semiconductor chip is sealed with a sealing resin to form a semiconductor package, and then the support substrate and the rewiring layer are peeled off to separate the semiconductor package. In this way, a semiconductor device having a multi-layer wiring structure using the RDL first process can be obtained.
  • the first aspect of the electronic component, display device or semiconductor device of the present invention has a relief pattern layer of the cured film of the present invention.
  • the relief pattern layer of the cured film of the present invention it is possible to obtain a highly reliable electronic component, display device or semiconductor device in which cracks do not occur in the relief pattern layer even after the package reliability test.
  • the electronic component, display device or semiconductor device described in JP-A-2020-66651 can be mentioned.
  • the second aspect of the electronic component, display device or semiconductor device of the present invention is that the cured film of the present invention is arranged as an insulating film between wirings.
  • the cured film of the present invention is arranged as an insulating film between wirings.
  • a package having a multi-layer wiring structure has a problem that a strong stress is applied to the insulating film and cracks occur after the package reliability test.
  • the insulating film made of a cured product of the resin composition of the present invention is used. Therefore, it is possible to obtain a highly reliable package in which cracks do not occur even after the package reliability test.
  • There is no upper limit to the number of layers in the multi-layer wiring structure but those with 10 or less layers are often used.
  • examples of the semiconductor device include, for example, a chip-first fan-out wafer level package or a chip-first fan-out panel level package.
  • a chip-first fan-out wafer level package or a chip-first fan-out panel level package is a chip-first fan-out panel level package in which an expansion portion is provided around a semiconductor chip using a sealing resin such as epoxy resin, and rewiring is performed from the electrode on the semiconductor chip to the expansion portion. It is a semiconductor package that secures the required number of terminals by applying solder balls to the expansion part.
  • wiring is installed so as to straddle the boundary line formed by the main surface of the semiconductor chip and the main surface of the encapsulating resin, and the cured film is between the wirings. It is arranged as an insulating film.
  • the antenna element of the present invention is an antenna element provided with at least one or more antenna wirings and the cured film of the present invention, and the antenna wirings are a meander-shaped loop antenna, a coil-shaped loop antenna, or a meander-shaped monopole antenna.
  • the area occupied by one antenna portion in the antenna wiring is 1000 mm 2 or less, and the cured film is between the ground and the antenna wiring. It is an insulating film that insulates.
  • FIG. 1 is a schematic diagram of an example of a coplanar-fed microstrip antenna, which is a type of planar antenna.
  • 1a is a cross-sectional view and 1b is a top view.
  • the forming method will be described.
  • the resin composition of the present invention is applied onto a copper foil and prebaked.
  • the copper foil is laminated and heat-cured to form a cured film having the copper foil on both sides.
  • an antenna element having the antenna pattern of the copper wiring of the microstrip line (MSL) shown in FIG. 1 is obtained.
  • MSL microstrip line
  • the antenna pattern of FIG. 1 will be described.
  • 15 indicates the ground (entire surface)
  • 16 indicates the insulating film used as the substrate of the antenna.
  • 11 to 13 of the upper layer show the cross section of the antenna wiring obtained by the patterning.
  • the ground wiring thickness J and the antenna wiring thickness K can have any thickness depending on the impedance design, but are generally 2 to 20 ⁇ m.
  • 11 is an antenna unit
  • 12 is a matching circuit
  • 13 is an MSL feeding line
  • 14 is a feeding point.
  • the width W and the length L of the antenna portion 11 are designed to have a length of 1 / 2 ⁇ r.
  • the antenna portion length L may be 1 / 2 ⁇ r or less depending on the impedance design.
  • the electronic component of the present invention is an electronic component including at least a semiconductor element, a rewiring layer, a sealing resin, and a semiconductor package including antenna wiring, and is an insulating layer of the rewiring layer and / or the encapsulation. It is preferable that the resin contains the cured film of the present invention, and the sealing resin is between the ground and the antenna wiring.
  • the electronic component of the present invention is an electronic component including an antenna wiring and an antenna element obtained by laminating the cured film of the present invention, and the height of the antenna wiring is 50 to 200 ⁇ m, and the cured film is provided.
  • the thickness of the antenna is preferably 80 to 300 ⁇ m.
  • FIG. 2 is a schematic view of a cross section of a semiconductor package including an IC chip (semiconductor element), a rewiring layer, a sealing resin, and an antenna element.
  • a rewiring layer (copper 2 layer, insulating film 3 layer) is formed on the electrode pad 202 of the IC chip 201 by the copper wiring 209 and the insulating film 210 formed by the cured film of the present invention.
  • Barrier metal 211 and solder bump 212 are formed on the pads of the rewiring layer (copper wiring 209 and insulating film 210).
  • a first sealing resin 208 made of the cured film of the present invention is formed, and a copper wiring 209 serving as a ground for an antenna is further formed on the first sealing resin 208.
  • the first via wiring 207 connecting the ground 206 and the rewiring layer (copper wiring 209 and the insulating film 210) is formed through the via hole formed in the first sealing resin 208.
  • a second sealing resin 205 made of the cured film of the present invention is formed on the first sealing resin 208 and the ground wiring 206, and a flat antenna wiring 204 is formed on the second sealing resin 205.
  • a second via wiring connecting the flat antenna wiring 204 and the rewiring layer (copper wiring 209 and insulating film 210) via the via holes formed in the first sealing resin 208 and the second sealing resin 205. 203 is formed.
  • the thickness of the insulating film 210 per layer is preferably 10 to 20 ⁇ m, and the first sealing resin and the second sealing resin are preferably 50 to 200 ⁇ m and 100 to 400 ⁇ m, respectively. Since the cured film of the present invention has little deterioration after the reliability test, the obtained semiconductor package including the antenna element can obtain a highly reliable package in which cracks do not occur even after the package reliability test.
  • the resin composition in the examples was evaluated by the following method.
  • a resin composition hereinafter referred to as varnish
  • a 1 ⁇ m polytetrafluoroethylene filter manufactured by Sumitomo Electric Industries, Ltd.
  • the wafer was taken out and immersed in 45% by mass of hydrofluoric acid for 1 minute to peel off the cured film from the wafer.
  • This film is cut into strips with a width of 1.5 cm and a length of 5 cm, and using Tensilon RTM-100 (manufactured by Orientec Co., Ltd.), the tensile speed is 23.0 ° C at room temperature and 45.0% RH in humidity.
  • the elongation at the breaking point was measured by pulling at 5 mm / min. The measurement was performed on 10 strips per sample, and the average value of the top 5 points was obtained from the results.
  • a breaking point elongation value of 30% or more was regarded as very good (3), a breaking point elongation value of 15% or more and less than 30% was regarded as good (2), and a breaking point elongation value of less than 15% was regarded as defective (1).
  • the wafer was taken out, the wafer with a cured film was placed in an oven (Clean Oven DE42 manufactured by Yamato Scientific Co., Ltd.), and then heat-treated at 175 ° C. for 200 hours in the atmosphere. After the heat treatment was completed, the wafer was taken out and immersed in 45% by mass of hydrofluoric acid for 1 minute to peel off the cured film from the wafer.
  • This film is cut into strips with a width of 1.5 cm and a length of 5 cm, and using Tensilon RTM-100 (manufactured by Orientec Co., Ltd.), the tensile speed is 23.0 ° C at room temperature and 45.0% RH in humidity.
  • the elongation at the breaking point was measured by pulling at 5 mm / min. The measurement was performed on 10 strips per sample, and the average value of the top 5 points was obtained from the results and used as the breaking point elongation (%) after HTS.
  • the rate of change in fracture point elongation after the reliability test (HTS) is
  • the varnish was applied onto the evaluation substrate by a spin coating method using a coating and developing device ACT-8 (manufactured by Tokyo Electron Limited) so that the film thickness after heat treatment at 120 ° C. for 3 minutes was 8-12 ⁇ m.
  • Pre-baking was performed to prepare a pre-baked film. All prebakings were performed at 120 ° C. for 3 minutes.
  • the obtained prebake film is subjected to an inert oven (CLH-21CD-S, manufactured by Koyo Thermo System Co., Ltd.) under a nitrogen stream at an oxygen concentration of 20 ppm or less at 50 ° C.
  • the temperature was raised to 250 ° C. at 3.5 ° C./min, and then heat treatment was performed at 250 ° C. for 1 hour to obtain a cured film.
  • the obtained cured film was formed into a circular opening pattern of 50 ⁇ m on a cylindrical copper wiring with an irradiation amount of 600 mJ / cm 2 using a carbon dioxide laser (wavelength 10600 nm) to obtain a pattern-forming film.
  • the obtained prebake film can form a circular opening pattern of 50 ⁇ m on a cylindrical copper wiring using an exposure machine i-line stepper (NSR-2005i9C, manufactured by Nikon Corporation). Using such a mask, exposure was performed at an exposure amount of 800 mJ / cm 2 .
  • TMAH tetramethylammonium
  • aqueous solution manufactured by Tama Chemical Industry Co., Ltd.
  • cyclopentanone under the condition that the film thickness change of the unexposed part before and after development is 1.5 ⁇ m. It was developed, then rinsed with pure water or propylene glycol monomethyl ether acetate, and shaken off to dry. Then, the pattern film was raised to 250 ° C. from 50 ° C. to 3.5 ° C./min at an oxygen concentration of 20 ppm or less under a nitrogen stream using an inert oven (CLH-21CD-S manufactured by Koyo Thermo System Co., Ltd.).
  • CLH-21CD-S manufactured by Koyo Thermo System Co., Ltd.
  • the mixture was heated and subsequently heat-treated at 250 ° C. for 1 hour to cure the pattern-forming film to obtain a cured film.
  • the thickness of the pattern film after pre-baking and development was measured using the optical interferometry film thickness measuring device Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. with a refractive index of 1.629 and cured.
  • the film thickness was measured with a refractive index of 1.773.
  • the sample in which the pattern was formed (hereinafter referred to as the sample) was put into a thermal cycle tester (conditions: ⁇ 65 ° C./30 min to 150 ° C./30 min) and subjected to 200 cycle treatment. Then, the sample was taken out and the presence or absence of cracks in the cured film was observed using an optical microscope. Observe a total of 10 locations, 2 each at the center of the substrate and 4 ends of the substrate. Those with a slightly defective rating were evaluated as 2 and those with a crack occurrence number of 5 to 10 were evaluated as defective with 1. The smaller the number of cracks, the better the crack resistance.
  • a varnish was spin-coated on a silicon wafer using a spin coater, and then prebaked at 120 ° C. for 3 minutes using a hot plate to prepare a prebaked film having a film thickness of 11 ⁇ m.
  • a gray scale mask (1 to 50 ⁇ m, 1 of 1 to 50 ⁇ m) for sensitivity measurement using a parallel light mask aligner (hereinafter referred to as PLA) (PLA-501F manufactured by Canon Inc.) as a light source on the obtained prebake film. 1) exposed with contacts via a line & space pattern). Then, after exposure at 120 ° C.
  • the film thickness was measured after development, and in the case of the negative type, the minimum exposure amount in which the residual film ratio of the exposed portion exceeded 90% was defined as the sensitivity (mJ / cm 2 ). In the case of the positive type, the minimum exposure amount and sensitivity were set so that the film thickness of the exposed portion was 5 nm or less (detection limit or less). The exposure amount was measured with an I-line illuminance meter.
  • the monomer having the following structure used in the present invention is prepared by reacting 4-iodoaniline, 2-amino-4-iodophenol, and 4-iodobenzoic acid with reference to Journal of Fluidine Chemistry 130 (2009) 573-580, respectively. , Monomer (X), Monomer (Y), and Monomer (Z), respectively.
  • the obtained reaction solution was added to 800 ml of ethyl alcohol to form a precipitate composed of a crude polymer.
  • the produced crude polymer was filtered off and dissolved in 300 mL of tetrahydrofuran to obtain a crude polymer solution.
  • the obtained crude polymer solution was added dropwise to 6 L of water to precipitate a polymer, and the precipitate was collected by filtration, washed with water three times, and then vacuum dried to form a powdery polyimide precursor (A-35). Powder was obtained.
  • the obtained reaction solution was added to 800 ml of ethyl alcohol to form a precipitate composed of a crude polymer.
  • the produced crude polymer was filtered off and dissolved in 300 mL of tetrahydrofuran to obtain a crude polymer solution.
  • the obtained crude polymer solution was added dropwise to 6 L of water to precipitate a polymer, and the precipitate was collected by filtration, washed with water three times, and then vacuum dried to form a powdery polyimide precursor (A-45). Powder was obtained.
  • Examples 1 to 46, Comparative Examples 1 to 16 A varnish was prepared by adding ⁇ -butyrolactone as a component (B), a component (C), a component (D), and a component (E) to 10 g of the component (A).
  • (B-1) component (manufactured by Daito Chemix Co., Ltd.), (B-2) component (manufactured by BASF Co., Ltd.) and (C-1) component (manufactured by Gun Ei Chemical Industry Co., Ltd.) used in the examples. ), (C-2) component and (D) component (manufactured by DIC Corporation) are as follows.
  • Tables 1 and 2 show the characteristic results of the resin compositions obtained in each Example and Comparative Example.
  • the resin composition of the present invention includes a surface protective film such as a semiconductor element, an interlayer insulating film, an insulating layer of a display device such as an organic light emitting element, a flattening film of a thin film transistor (hereinafter referred to as TFT) substrate, and a wiring protective insulating film of a circuit substrate.
  • a surface protective film such as a semiconductor element, an interlayer insulating film, an insulating layer of a display device such as an organic light emitting element, a flattening film of a thin film transistor (hereinafter referred to as TFT) substrate, and a wiring protective insulating film of a circuit substrate.
  • TFT thin film transistor

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PCT/JP2021/038380 2020-11-10 2021-10-18 樹脂組成物、硬化膜、絶縁膜または保護膜、アンテナ素子、並びに電子部品、表示装置または半導体装置及びその製造方法 Ceased WO2022102345A1 (ja)

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JPWO2023022123A1 (https=) * 2021-08-17 2023-02-23
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