WO2022024714A1 - Semiconductor substrate cleaning solution - Google Patents

Semiconductor substrate cleaning solution Download PDF

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Publication number
WO2022024714A1
WO2022024714A1 PCT/JP2021/025893 JP2021025893W WO2022024714A1 WO 2022024714 A1 WO2022024714 A1 WO 2022024714A1 JP 2021025893 W JP2021025893 W JP 2021025893W WO 2022024714 A1 WO2022024714 A1 WO 2022024714A1
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WIPO (PCT)
Prior art keywords
group
acid
semiconductor substrate
cleaning liquid
mass
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PCT/JP2021/025893
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French (fr)
Japanese (ja)
Inventor
直子 大内
哲也 上村
祐継 室
Original Assignee
富士フイルムエレクトロニクスマテリアルズ株式会社
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Priority to JP2022540127A priority Critical patent/JP7469474B2/en
Publication of WO2022024714A1 publication Critical patent/WO2022024714A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/34—Derivatives of acids of phosphorus
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/08—Liquid soap, e.g. for dispensers; capsuled
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting

Definitions

  • the present invention relates to a cleaning liquid for a semiconductor substrate.
  • Semiconductor elements such as CCD (Charge-Coupled Device) and memory are manufactured by forming fine electronic circuit patterns on a substrate using photolithography technology. Specifically, a resist film is formed on a laminate having a metal film as a wiring material, an etching stop layer, and an interlayer insulating layer on a substrate, and a photolithography step and a dry etching step (for example, plasma etching treatment). ) Is performed to manufacture a semiconductor element.
  • CCD Charge-Coupled Device
  • memory are manufactured by forming fine electronic circuit patterns on a substrate using photolithography technology. Specifically, a resist film is formed on a laminate having a metal film as a wiring material, an etching stop layer, and an interlayer insulating layer on a substrate, and a photolithography step and a dry etching step (for example, plasma etching treatment). ) Is performed to manufacture a semiconductor element.
  • a dry etching step for example, plasma etching treatment
  • CMP chemical mechanical polishing
  • a polishing slurry containing polishing fine particles for example, silica, alumina, etc.
  • Chemical Mechanical Polishing processing may be performed.
  • the polishing fine particles used in the CMP treatment, the polished wiring metal film, and / or the metal component derived from the barrier metal and the like tend to remain on the surface of the semiconductor substrate after the CMP treatment. Since these residues can short-circuit the wiring and affect the electrical characteristics of the semiconductor, a cleaning step of removing these residues from the surface of the semiconductor substrate is generally performed.
  • Patent Document 1 states that "a compound having a carboxyl group and / or a carboxylate group and having a structure in which a hydroxyl group is bonded to carbons at the ⁇ and ⁇ positions of the carboxyl group and / or the carboxylate group. (A) and a cleaning agent for electronic materials containing water. "
  • the present inventors have studied the cleaning liquid for semiconductor substrates described in Patent Document 1 and the like, and found that they show excellent cleaning performance for a semiconductor substrate having a metal film containing tungsten after CMP treatment, and that tungsten is used. It was found that it is difficult to achieve both excellent corrosion suppression performance against tungsten when cleaning the metal film containing it.
  • the present invention is for a semiconductor substrate which exhibits excellent cleaning performance for a semiconductor substrate having a metal film containing tungsten after CMP treatment and also has excellent corrosion suppressing performance against tungsten when cleaning a metal film containing tungsten.
  • the subject is to provide a cleaning solution.
  • the present inventor has found that the above problem can be solved by the following configuration.
  • a cleaning liquid for a semiconductor substrate used for cleaning a semiconductor substrate Contains polymers, alkanolamines, complexing agents with acid groups, and water.
  • the weight average molecular weight of the polymer is 2000-900000, and the polymer has a weight average molecular weight of 2000-90000.
  • the content of the complexing agent is 2.5% by mass or more and less than 20.0% by mass with respect to the total mass of the cleaning liquid for semiconductor substrates.
  • a cleaning liquid for a semiconductor substrate, wherein the pH of the cleaning liquid for a semiconductor substrate is less than 7.0.
  • a cleaning liquid for a substrate can be provided.
  • the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
  • the “content” of the component means the total content of the two or more kinds of components.
  • “ppm” means “parts-per-million ( 10-6 )” and “ppb” means “parts-per-billion ( 10-9 )”.
  • the described compounds may contain isomers (compounds having the same number of atoms but different structures), optical isomers, and isotopes, unless otherwise specified. Further, the isomers and isotopes may contain only one species, or may contain a plurality of species.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (both are trade names manufactured by Toso Co., Ltd.) as columns. Value converted using polystyrene, which is a standard material measured by a gel permeation chromatography (GPC) analyzer, using THF (tetrahydrogen) as an eluent, a differential refractometer as a detector, and polystyrene as a standard material.
  • GPC gel permeation chromatography
  • the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight.
  • the cleaning liquid for a semiconductor substrate (hereinafter, also referred to as "cleaning liquid") of the present invention is a cleaning liquid used for cleaning a semiconductor substrate, and has a predetermined polymer, an alkanolamine, and a predetermined amount of acid groups, which will be described later. It contains an agent and water, and the pH of the cleaning solution is less than 7.0.
  • the pH of the cleaning solution is less than 7.0.
  • the pH of the cleaning liquid is preferably 0.1 to 6.9, more preferably 1.0 to 6.9, and even more preferably 2.0 to 6.9 in that the effect of the present invention is more excellent.
  • 2.5 to 6.0 are particularly preferable, and 5.0 to 6.5 are most preferable.
  • the pH of the washing liquid can be measured by a method according to JIS Z8802-1984 using a known pH meter.
  • the pH is a value at a measurement temperature of 25 ° C.
  • the cleaning liquid contains a polymer.
  • the weight average molecular weight (Mw) of the polymer is 2000 to 900,000, and 2000 to 800,000 is preferable, 2000 to 500,000 is more preferable, 2000 to 50000 is further preferable, and 2000 to 30000 is more preferable in that the effect of the present invention is more excellent. Is particularly preferable.
  • the value of the weight average molecular weight is the value of the weight average molecular weight in terms of polyethylene glycol measured by GPC (gel permeation chromatography).
  • a water-soluble polymer is preferable.
  • the "water-soluble polymer” is a compound in which two or more structural units are connected in a linear or network shape via covalent bonds, and the mass of the polymer dissolved in 100 g of water at 20 ° C. is 0.1 g. The above compounds are intended.
  • the cleaning performance of the cleaning liquid is improved by interacting with the substrate having a metal film or the polishing fine particles (for example, silica and alumina) contained in the polishing slurry.
  • water-soluble polymer examples include polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polystyrene sulfonic acid, and salts thereof; styrene, ⁇ -methylstyrene, and / or.
  • Polymers of monomers such as 4-methylstyrene and monomers of (meth) acrylic acid and / or acids such as maleic acid and salts thereof; (meth) acrylic acid and malein.
  • Polymers with acids and salts thereof benzenesulfonic acid and / or polymers having structural units having aromatic hydrocarbon groups condensed with naphthalenesulfonic acid and the like with formalin, and salts thereof.
  • Vinyl-based synthetic polymers such as polyvinyl alcohol, polyoxyethylene, polyvinylpyrrolidone, polyvinylpyridine, polyacrylamide, polyvinylformamide, polyethyleneimine, polyvinyloxazoline, polyvinylimidazole, and polyallylamine; hydroxyethylcellulose, carboxymethylcellulose, and processing. Examples thereof include modified products of natural polysaccharides such as starch.
  • the water-soluble polymer a polymer having an acid group (for example, a carboxy group, a phosphoric acid group, and a sulfonic acid group) is preferable, and polyacrylic acid, polymaleic acid, styrene and (meth) acrylic acid, And / or a polymer with an acid monomer such as maleic acid, a copolymer of (meth) acrylic acid with maleic acid, or salts thereof are more preferred.
  • an acid group for example, a carboxy group, a phosphoric acid group, and a sulfonic acid group
  • polyacrylic acid, polymaleic acid, styrene and (meth) acrylic acid, And / or a polymer with an acid monomer such as maleic acid, a copolymer of (meth) acrylic acid with maleic acid, or salts thereof are more preferred.
  • the water-soluble polymer may be a homopolymer or a copolymer obtained by copolymerizing two or more kinds of monomers.
  • the monomer include a monomer having a carboxy group, a monomer having a sulfonic acid group, a monomer having a hydroxyl group, a monomer having a polyethylene oxide chain, and a monomer having an amino group.
  • a monomer selected from the group consisting of monomers having a heterocycle As the water-soluble polymer, a polymer consisting substantially only of structural units derived from the monomers selected from the above group is preferable.
  • the water-soluble polymer is substantially only the structural unit derived from the monomer selected from the above group means that, for example, the content of the structural unit derived from the monomer selected from the above group is It means that it is 95 to 100% by mass (preferably 99 to 100% by mass) with respect to the total mass of the polymer.
  • the polymer preferably has a structural unit having a carboxy group (a structural unit derived from (meth) acrylic acid, etc.).
  • the content of the structural unit having a carboxy group is preferably 30 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 85 to 100% by mass, based on the total mass of the polymer.
  • polymer examples include water-soluble polymers described in paragraphs [0043] to [0047] of JP-A-2016-171294, and the contents thereof are incorporated in the present specification.
  • the polymer may be used alone or in combination of two or more.
  • the content of the polymer is preferably 0.01 to 10% by mass, more preferably 0.05 to 3% by mass, still more preferably 0.5 to 2% by mass, based on the total mass of the washing liquid.
  • the content of the polymer is within the above range, the polymer is appropriately adsorbed on the surface of the substrate and can contribute to the improvement of the corrosion suppressing performance of the cleaning liquid, and the viscosity and / or the cleaning performance of the cleaning liquid is well balanced. Can be done.
  • the content of the polymer is preferably 1.0 to 45.0% by mass, more preferably 10.0 to 45.0% by mass, and 10.0 to 40% by mass with respect to the total mass of the washing liquid excluding the solvent. 0% by mass is more preferable.
  • the cleaning solution contains an alkanolamine.
  • the alkanolamine is a compound having at least one of a primary amino group to a tertiary amino group and further having at least one hydroxyl group (preferably a hydroxyalkyl group) in the molecule.
  • Alkanolamines do not contain the quaternary ammonium compounds described below.
  • the number of hydroxyl groups contained in the alkanolamine is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2.
  • the total number of primary amino groups to tertiary amino groups contained in the alkanolamine is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.
  • the alkanolamine preferably has any of a primary amino group to a tertiary amino group, and more preferably has any of a primary amino group and a secondary amino group. It is more preferable to have a primary amino group.
  • the compound represented by the formula (A) is preferable.
  • Ra1 and Ra2 each independently represent an alkyl group which may have a hydrogen atom or a hydroxyl group.
  • the alkyl group may be linear or branched.
  • the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
  • the number of hydroxyl groups contained in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.
  • La1 represents an alkylene group which may have a hydroxyl group.
  • the alkylene group may be linear or branched.
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
  • the number of hydroxyl groups contained in the alkylene group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 0.
  • alkanolamine examples include monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), tris (hydroxymethyl) aminomethane, N-methylethanolamine, N-methyl-N, N-diethanolamine, and the like.
  • alkanolamines are isopropanolamine, monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), tris (hydroxymethyl) aminomethane, N-ethylethanolamine, monopropanolamine and triisopropanolamine.
  • MEA monoethanolamine
  • DEA diethanolamine
  • TEA triethanolamine
  • N-Methylethanolamine, 2-amino-2-methyl-1-propanol, and 2- (dimethylamino) -2-methyl-1-propanol preferably at least one selected from the group.
  • the pKa (acid dissociation constant) of the alkanolamine is preferably 5.00 to 20.00, more preferably 7.50 to 15.00, and 9.00 to 14.50 from the viewpoint of excellent stability of the washing solution over time. More preferred.
  • at least one alkanolamine satisfies the above pKa range, more preferably the alkanolamine having the highest content satisfies the above pKa range, and the total mass of the alkanolamine.
  • pKa is a value obtained by using SC-Database (http://acadsoft.co.uk/scdbase/SCDB_software/scdb_download.htm).
  • the ClogP value of the alkanolamine is preferably -5.00 to 1.00, more preferably -2.00 to 1.00, and even more preferably -1.00 to 1.00.
  • the LogP value is a value obtained by calculating the common logarithm logP of 1-octanol and the partition coefficient P to water.
  • known ones can be used.
  • the Clog value is a value using the ClogP program incorporated in ChemBioDrowUltra12.0 of Cambridgest.
  • the alkanolamine may be used alone or in combination of two or more.
  • the content of alkanolamine is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 7.0% by mass, based on the total mass of the cleaning liquid, because the performance of the cleaning liquid is well-balanced. 0.01 to 5.0% by mass is more preferable, 0.01 to 3.0% by mass is particularly preferable, and 0.01 to 2.0% by mass is most preferable.
  • the content of alkanolamine is preferably 0.01 to 30.0% by mass, more preferably 0.1 to 30.0% by mass, and 1.0 to 30% with respect to the total mass of the cleaning liquid excluding the solvent. 0% by mass is more preferable, and 1.0 to 25.0% by mass is particularly preferable.
  • the cleaning liquid contains a complexing agent having an acid group (hereinafter, also referred to as "specific complexing agent").
  • the specific complexing agent is a compound having an acid group and binding to a metal ion to form a complex ion.
  • the specific complexing agent is a compound different from the components contained in the cleaning liquid described above, the surfactant, the anticorrosive agent, the preservative, and the pH adjuster described later.
  • the content of the specific complexing agent is 2.5% by mass or more and less than 20.0% by mass with respect to the total mass of the cleaning liquid, and 2.5 to 18.5% by mass is used from the viewpoint of improving the cleaning performance.
  • the content of the specific complexing agent is preferably 45.0 to 98.0% by mass, more preferably 50.0 to 95.0% by mass, and 50.0 to 50.0 to 98.0% by mass with respect to the total mass of the cleaning liquid excluding the solvent. 90.0% by mass is more preferable, 50.0 to 85.0% by mass is particularly preferable, and 50.0 to 70.0% by mass is most preferable.
  • the acid group contained in the specific complexing agent examples include a carboxy group, a phosphoric acid group, a sulfonic acid group, a phosphonic acid group, a sulfinic acid group, and a sulfenic acid group.
  • the specific complexing agent preferably has at least one selected from the group consisting of a carboxy group, a phosphoric acid group, a phosphonic acid group, and a sulfonic acid group, and preferably has a carboxy group, a phosphonic acid group, and a sulfonic acid group.
  • the specific complexing agent preferably has any one of a carboxy group, a phosphoric acid group, a phosphonic acid group, and a sulfonic acid group.
  • the number of acid groups contained in the specific complexing agent is preferably 1 to 10, more preferably 1 to 7, further preferably 1 to 6, and particularly preferably 1 to 4.
  • a complexing agent having a carboxy group is a complexing agent having at least one carboxy group in the molecule.
  • the specific complexing agent having a carboxy group include aminopolycarboxylic acid, amino acid, aliphatic carboxylic acid, and aromatic carboxylic acid. Among them, as the specific complexing agent having a carboxy group, an aminopolycarboxylic acid or an amino acid is preferable, and an aminopolycarboxylic acid is more preferable.
  • the amino acid When the specific complexing agent contains an amino acid, the amino acid has a coordination portion and a hydrophilic portion in the molecule, so that the amino acid is applied to the abrasive fine particles (for example, silica, alumina, etc.) contained in the substrate having a metal film or the polishing slurry.
  • the abrasive fine particles for example, silica, alumina, etc.
  • the number of carboxy groups contained in the specific complexing agent is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 4.
  • aminopolycarboxylic acid a compound represented by the formula (B1) is preferable.
  • n 1 represents an integer from 1 to 10. Among them, as n 1 , an integer of 1 to 5 is preferable, an integer of 1 to 3 is more preferable, and an integer of 2 to 3 is further preferable.
  • aminopolycarboxylic acid examples include nitrilotriacetic acid, butylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraminehexacacetic acid, 1,3-diamino-2-hydroxypropane-N, N.
  • N', N'-tetraacetic acid propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid, ethylenediaminediaminetetraacetic acid, ethylenediaminediaminepropionic acid, 1,6-hexamethylene-diamine -N, N, N', N'-tetraacetic acid, N, N-bis (2-hydroxybenzyl) ethylenediamine-N, N-diacetate, diaminopropanetetraacetic acid, 1,4,7,10-tetraazacyclo Included are dodecane-tetraacetic acid, diaminopropanol tetraacetic acid, (hydroxyethyl) ethylenediaminetriacetic acid, and iminodiacetic acid (IDA).
  • DTPA or EDTA is preferable as the aminopolycarboxylic acid
  • the compound represented by the formula (B2) is preferable, and the compound represented by the formula (B3) is more preferable.
  • R b1 represents a hydrocarbon group which may have a hydrogen atom or a hetero atom.
  • the hydrocarbon group may be linear, branched, or cyclic (may be monocyclic or polycyclic).
  • the hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms.
  • Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
  • an alkyl group, an alkenyl group, an alkylene group, or an aryl group which may have a heteroatom is preferable, and an alkyl group which may have a heteroatom is more preferable.
  • R b2 and R b3 independently represent a hydrogen atom or a hydroxyalkyl group, respectively.
  • the hydroxyl alkyl group (alkyl group having a hydroxy group) has preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms.
  • Examples of the hydroxylalkyl group include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, and a hydroxyhexyl group. Of these, a hydroxyethyl group is preferable.
  • R b4 represents a hydrogen atom, a hydroxyl group, a carboxy group, or -SR b7 .
  • R b7 represents a hydrogen atom or an alkyl group.
  • the alkyl group may be linear, branched or cyclic.
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably a methyl group.
  • L b1 represents a single bond or an alkylene group.
  • the alkylene group may be linear, branched, or cyclic.
  • the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • R b5 and R b6 are synonymous with R b2 and R b3 in the above-mentioned formula (B2), and the preferable range is also the same.
  • amino acids examples include alanine (2-aminopropionic acid or 3-aminopropionic acid), arginine, asparagine, aspartic acid, cystine, cysteine, glutamine, glutamic acid, glycine or its derivatives, isoleucine, leucine, lysine, methionine, phenylalanine. , Serin, etionin, threonine, tyrosine, valine, tryptophan, histidine or derivatives thereof, 2-amino-3-aminopropaneic acid, and proline.
  • the amino acid include the compounds described in paragraphs [0021] to [0023] of JP-A-2016-086094.
  • the glycine derivative examples include N, N-di (2-hydroxyethyl) glycine.
  • the histidine derivative the compounds described in JP-A-2015-165561 and JP-A-2015-165562 can be incorporated, and the contents thereof are incorporated in the present specification.
  • the amino acid may contain at least one selected from the group consisting of serine, alanine, glycine or a derivative thereof, methionine, histidine or a derivative thereof, arginine, glutamic acid, asparagine, aspartic acid, glutamic acid, and cysteine.
  • the aliphatic carboxylic acid is a compound having a carboxy group and an aliphatic group in the molecule. Moreover, it is preferable that the aliphatic carboxylic acid further has a hydroxyl group.
  • a compound represented by the formula (B4) is preferable.
  • L b2 represents a single bond or a divalent linking group.
  • the divalent linking group represented by L b2 include an ether group, a carbonyl group, an ester group, a thioether group, -SO 2- , and -NT- (T is a substitution of, for example, a hydrogen atom or an alkyl group).
  • Group a divalent hydrocarbon group (for example, an alkylene group, an alkenylene group, an alkynylene group, and an arylene group), and a group combining these groups can be mentioned.
  • the divalent linking group may be linear, branched or cyclic.
  • the divalent linking group represented by L b2 may further have a substituent.
  • substituents examples include an alkyl group, an aryl group, a hydroxyl group, a carboxy group, an amino group, and a halogen atom.
  • divalent linking group a single bond or a divalent hydrocarbon group is preferable, and an alkylene group is more preferable.
  • the number of carbon atoms of the divalent linking group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5.
  • the aliphatic carboxylic acid examples include gluconic acid, glycolic acid, glyceric acid, citric acid, maleic acid, malic acid, tartaric acid, oxalic acid, malonic acid, and succinic acid.
  • the aliphatic carboxylic acid is preferably contained at least one selected from the group consisting of citric acid, tartaric acid, and succinic acid.
  • Aromatic carboxylic acid is a compound having a carboxy group and an aromatic group in the molecule.
  • Examples of the aromatic carboxylic acid include phenyllactic acid, hydroxyphenyllactic acid, and phenylsuccinic acid.
  • a complexing agent having a phosphoric acid group is a complexing agent having at least one phosphoric acid group in the molecule.
  • the complexing agent having a phosphoric acid group is a compound different from the above-mentioned complexing agent.
  • the number of phosphoric acid groups contained in the specific complexing agent is preferably 1 to 10, more preferably 2 to 8, and even more preferably 4 to 7.
  • the complexing agent having a phosphoric acid group examples include polyphosphoric acid such as diphosphoric acid, metaphosphoric acid, and hexametaphosphoric acid, and phytic acid.
  • polyphosphoric acid such as diphosphoric acid, metaphosphoric acid, and hexametaphosphoric acid
  • phytic acid examples include diphosphate, hexametaphosphoric acid, or phytic acid.
  • diphosphate, hexametaphosphoric acid, or phytic acid is preferable, and phytic acid is more preferable.
  • a complexing agent having a sulfonic acid group is a complexing agent having at least one sulfonic acid group in the molecule.
  • the complexing agent having a sulfonic acid group is a compound different from the above-mentioned complexing agent.
  • the number of sulfonic acid groups contained in the specific complexing agent is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
  • a compound represented by the formula (C) is preferable.
  • RC represents an alkyl or aryl group which may have a substituent.
  • the alkyl group which may have a substituent represented by RC may be linear, branched or cyclic (may be monocyclic or polycyclic).
  • the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms.
  • the aryl group which may have a substituent represented by RC may be a monocyclic ring, a polycyclic ring, or a fused ring.
  • the aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 8 carbon atoms.
  • substituent having the alkyl group and the aryl group include an alkyl group, an aryl group, a hydroxyl group, a carboxy group, an amino group and a halogen atom, and an alkyl group is preferable.
  • the complexing agent having a sulfonic acid group examples include naphthalene sulfonic acid, p-toluene sulfonic acid, camphor sulfonic acid, benzene sulfonic acid, methane sulfonic acid, and ethane sulfonic acid. Among them, p-toluenesulfonic acid, methanesulfonic acid, or ethanesulfonic acid is preferable as the complexing agent having a sulfonic acid group.
  • a complexing agent having a phosphonic acid group is a complexing agent having at least one phosphonic acid group in the molecule.
  • the complexing agent having a phosphonic acid group is a compound different from the complexing agent described above.
  • the number of phosphonic acid groups contained in the specific complexing agent is preferably 1 or more, more preferably 2 or more, further preferably 2 to 10, particularly preferably 2 to 4, and most preferably 2 to 3.
  • Examples of the complexing agent having a phosphonic acid group include a compound represented by the formula (P1), a compound represented by the formula (P2), and a compound represented by the formula (P3).
  • X represents a hydrogen atom or a hydroxyl group.
  • a hydroxyl group is preferable.
  • R 11 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • the alkyl group having 1 to 10 carbon atoms represented by R 11 may be linear, branched or cyclic.
  • R11 an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is more preferable.
  • n- represents a normal-form.
  • Examples of the compound represented by the formula (P1) include ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO), 1-hydroxypropyriden-1,1'-diphosphonic acid, or 1 -Hydroxybutylidene-1,1'-diphosphonic acid is preferred.
  • HEDPO 1-hydroxyethylidene-1,1'-diphosphonic acid
  • 1-hydroxypropyriden-1,1'-diphosphonic acid or 1 -Hydroxybutylidene-1,1'-diphosphonic acid is preferred.
  • Q represents a hydrogen atom or R 13 -PO 3 H 2 .
  • R 12 and R 13 each independently represent an alkylene group.
  • Examples of the alkylene group represented by R 12 include an alkylene group having 1 to 12 carbon atoms.
  • the alkylene group may be linear, branched or cyclic, and is preferably linear or branched.
  • an alkylene group having 1 to 6 carbon atoms is preferable, an alkylene group having 1 to 4 carbon atoms is more preferable, and an ethylene group is further preferable.
  • Examples of the alkylene group represented by R 13 include an alkylene group having 1 to 10 carbon atoms.
  • the alkylene group may be linear, branched or cyclic, and is preferably linear or branched.
  • an alkylene group having 1 to 4 carbon atoms is preferable, a methylene group or an ethylene group is more preferable, and a methylene group is further preferable.
  • Y represents a hydrogen atom, -R 13 -PO 3 H 2 , or a group represented by the formula (P4).
  • a group represented by -R 13 -PO 3 H 2 or the formula (P4) is preferable, and a group represented by the formula (P4) is more preferable.
  • Q and R 13 are synonymous with Q and R 13 in formula (P2).
  • Examples of the compound represented by the formula (P2) include ethylaminobis (methylenephosphonic acid), dodecylaminobis (methylenephosphonic acid), nitrilotris (methylenephosphonic acid) (NTPO), and ethylenediaminebis (methylenephosphonic acid) (EDDPO).
  • 1,3-propylene diaminebis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) (EDTPO), ethylenediaminetetra (ethylenephosphonic acid), 1,3-propylenediaminetetra (methylenephosphonic acid) (PDTMP), 1,2-Diaminopropanetetra (methylenephosphonic acid) or 1,6-hexamethylenediaminetetra (methylenephosphonic acid) is preferable.
  • R 14 and R 15 each independently represent an alkylene group having 1 to 4 carbon atoms.
  • the alkylene group having 1 to 4 carbon atoms represented by R 14 and R 15 may be linear or branched.
  • Examples of the alkylene group having 1 to 4 carbon atoms represented by R 14 and R 15 include a methylene group, an ethylene group, a propylene group, a trimethylene group, an ethylmethylene group, a tetramethylene group, a 2-methylpropylene group and 2-. Examples thereof include a methyltrimethylene group and an ethylethylene group, and an ethylene group is preferable.
  • n represents an integer of 1 to 4. Among them, n is preferably an integer of 1 to 2.
  • At least four of Z 1 to Z 4 and n Z 5s represent an alkyl group having a phosphonic acid group, and the rest represent an alkyl group.
  • Examples of the alkyl group in the alkyl group having an alkyl group and a phosphonic acid group represented by Z 1 to Z 5 include a linear alkyl group having 1 to 4 carbon atoms and a branched chain having 1 to 4 carbon atoms. Alkyl groups are mentioned, and methyl groups are preferable.
  • the number of phosphonic acid groups in the alkyl group having a phosphonic acid group represented by Z 1 to Z 5 is preferably 1 to 2, more preferably 1.
  • Examples of the alkyl group having a phosphonic acid group represented by Z 1 to Z 5 include a linear or branched alkyl group having 1 to 4 carbon atoms and having 1 or 2 phosphonic acid groups.
  • the (mono) phosphonomethyl group or the (mono) phosphonoethyl group is preferable, and the (mono) phosphonomethyl group is more preferable.
  • Z 1 to Z 5 it is preferable that all of Z 1 to Z 4 and n Z 5 are the above-mentioned alkyl groups having a phosphonic acid group.
  • Examples of the compound represented by the formula (P3) include diethylenetriaminepenta (methylenephosphonic acid) (DEPPO), diethylenetriaminepenta (ethylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), or triethylenetetraminehexa (ethylenephosphon). Acid) is preferred.
  • Examples of the complexing agent having a phosphonic acid group include the compounds described in paragraphs [0026] to [0036] of International Publication No. 2018/020878, and paragraphs [0031] of International Publication No. 2018/030006.
  • the compounds ((co) polymers) described in [0046] can be incorporated, and the contents thereof are incorporated in the present specification.
  • the carbon number of the complexing agent having a phosphonic acid group is preferably 12 or less, more preferably 10 or less, still more preferably 8 or less.
  • the lower limit is not particularly limited, and 1 or more is preferable, and 2 or more is more preferable.
  • the complexing agent having a phosphonic acid group the compound represented by the above formula (P1), the compound represented by the formula (P2), or the compound represented by the formula (P3) is preferable, and HEDPO is more preferable. preferable.
  • the specific complexing agent includes a compound represented by the formula (B1), a compound represented by the formula (B2), a compound represented by the formula (B4), a compound represented by the formula (C), and a phosphoric acid group. It is preferable to contain at least one selected from the group consisting of the complexing agent having and the compound represented by the formula (P1), and the compound represented by the formula (B1) and the compound represented by the formula (B3). It is selected from the group consisting of a compound, a compound represented by the formula (B4), a compound represented by the formula (C), diphosphate, hexametaphosphate, phytic acid, and a compound represented by the formula (P1).
  • the specific complexing agent may form a salt.
  • the salt include alkali metal salts such as sodium salt and potassium salt, ammonium salt, hydrochloride, carbonate, and acetate.
  • the molecular weight of the specific complexing agent is preferably 600 or less, more preferably 450 or less, still more preferably 300 or less.
  • the lower limit of the molecular weight is not particularly limited, and is preferably 50 or more.
  • the carbon number of the specific complexing agent is preferably 15 or less, more preferably 10 or less.
  • the lower limit of the number of carbon atoms is not particularly limited, and is preferably 2 or more.
  • the specific complexing agent may be used alone or in combination of two or more.
  • the mass ratio of the content of the specific complexing agent to the content of the alkanolamine [content of the specific complexing agent / content of alkanolamine] is preferably 0.1 to 2000.0, preferably 0.1 to 1850. 0 is more preferable, 0.1 to 1500.0 is even more preferable, 0.1 to 1000.0 is further preferable, 0.1 to 400.0 is particularly preferable, and 20.0 to 400.0 is most preferable.
  • the mass ratio of the content of the specific complexing agent to the content of the polymer [content of the specific complexing agent / content of the polymer] is preferably 0.03 to 200.0, preferably 1.0 to 100. 0 is more preferable, and 1.5 to 50.0 is even more preferable.
  • the cleaning liquid contains water as a solvent.
  • the water is not particularly limited as long as it does not adversely affect the semiconductor substrate, and distilled water, deionized water, and pure water (preferably ultrapure water) can be used.
  • pure water or ultrapure water is preferable because it contains almost no impurities and has less influence on the semiconductor substrate in the manufacturing process of the semiconductor substrate.
  • the water content may be the balance of the components contained in the cleaning liquid.
  • the water content is preferably 1.0% by mass or more, more preferably 30.0% by mass or more, further preferably 60.0% by mass or more, and 85.0% by mass or more with respect to the total mass of the cleaning liquid.
  • the upper limit is not particularly limited, and is preferably 99.0% by mass or less, more preferably 97.0% by mass or less, based on the total mass of the cleaning liquid.
  • the cleaning liquid may contain a surfactant.
  • the surfactant is a compound different from the components contained in the above-mentioned cleaning liquid.
  • the surfactant is a compound having a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule.
  • examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.
  • the surfactant preferably contains an anionic surfactant, more preferably contains a phosphate ester-based surfactant, and is at least selected from the group consisting of an alkyl phosphate ester and a polyoxyethylene alkyl phosphate ester.
  • the cleaning liquid contains one, and it is particularly preferable to contain an alkyl phosphate ester.
  • the cleaning liquid contains a surfactant, it is possible to improve the corrosion suppressing performance of the metal film and the cleaning performance of the abrasive fine particles and the like.
  • Surfactants often have hydrophobic groups selected from the group consisting of aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups in combination thereof.
  • the hydrophobic group of the surfactant is not particularly limited, but when the hydrophobic group contains an aromatic hydrocarbon group, the number of carbon atoms is preferably 6 or more, and more preferably 10 or more. When the hydrophobic group does not contain an aromatic hydrocarbon group and is composed only of an aliphatic hydrocarbon group, the number of carbon atoms is preferably 9 or more, and more preferably 12 or more.
  • the upper limit of the number of carbon atoms of the hydrophobic group is not particularly limited, but is preferably 20 or less, and more preferably 18 or less.
  • the total carbon number of the surfactant is preferably 16 to 100.
  • anionic surfactant examples include a phosphate ester-based surfactant having a phosphate ester group, a phosphonic acid-based surfactant having a phosphonic acid group, a sulfonic acid-based surfactant having a sulfonic acid group, and a carboxy group.
  • examples thereof include a carboxylic acid-based surfactant having a sulfate ester group and a sulfate ester-based surfactant having a sulfate ester group.
  • phosphoric acid ester-based surfactant examples include an alkyl phosphate ester, a polyoxyalkylene alkyl ether phosphoric acid ester, and salts thereof. Of these, alkyl phosphate esters are preferred.
  • the phosphoric acid ester and the polyoxyalkylene alkyl ether phosphoric acid ester may be a monoester or a diester alone, or may be a mixture of the monoester and the diester.
  • the salt of the phosphoric acid ester-based surfactant include a sodium salt, a potassium salt, an ammonium salt, and an organic amine salt.
  • an alkyl group contained in the alkyl phosphate ester and the polyoxyalkylene alkyl ether phosphoric acid ester an alkyl group having 2 to 24 carbon atoms is preferable, an alkyl group having 6 to 18 carbon atoms is more preferable, and an alkyl having 12 to 18 carbon atoms is more preferable. The group is more preferred.
  • alkylene group contained in the polyoxyalkylene alkyl ether phosphoric acid ester an alkylene group having 2 to 6 carbon atoms is preferable, and an ethylene group or a 1,2-propanediyl group is more preferable.
  • the number of repetitions of the oxyalkylene group in the polyoxyalkylene ether phosphoric acid ester is preferably 1 to 12, more preferably 1 to 10.
  • Examples of the phosphoric acid ester-based surfactant include octyl phosphate, lauryl phosphate, tridecyl phosphate, myristyl phosphate, cetyl phosphate, stearyl phosphate, polyoxyethylene octyl ether phosphate, and polyoxyethylene.
  • Lauryl ether phosphate ester, polyoxyethylene tridecyl ether phosphate ester, or polyoxyethylene myristyl ether phosphate ester is preferable, and lauryl phosphate ester, tridecyl phosphate ester, myristyl phosphate ester, cetyl phosphate ester, stearyl phosphate are preferable.
  • Esters or polyoxyethylene myristyl ether phosphate esters are more preferred, and lauryl phosphate esters, cetyl phosphate esters, stearyl phosphate esters, or polyoxyethylene myristyl ether phosphate esters are even more preferred.
  • phosphonic acid-based surfactant examples include alkylphosphonic acid, polyvinylphosphonic acid, and aminomethylphosphonic acid described in JP-A-2012-057108.
  • sulfonic acid-based surfactant examples include alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid, alkyl methyl taurine, sulfosuccinic acid diester, polyoxyalkylene alkyl ether sulfonic acid, and salts thereof. Can be mentioned.
  • alkyl group contained in the sulfonic acid-based surfactant an alkyl group having 2 to 24 carbon atoms is preferable, and an alkyl group having 6 to 18 carbon atoms is more preferable.
  • alkylene group contained in the polyoxyalkylene alkyl ether sulfonic acid an ethylene group or a 1,2-propanediyl group is preferable.
  • the number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether sulfonic acid is preferably 1 to 12, more preferably 1 to 6.
  • sulfonic acid-based surfactant examples include hexanesulfonic acid, octanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid (DBSA), and dinitrobenzene.
  • DBSA dodecylbenzenesulfonic acid
  • LDPEDSA laurildodecylphenyl ether disulfonic acid
  • dodecane sulfonic acid, DBSA, DNBSA, or LDPEDSA is preferable, and DBSA, DNBSA, or LDPEDSA is more preferable.
  • Carboxylic acid-based surfactant examples include an alkylcarboxylic acid, an alkylbenzenecarboxylic acid, a polyoxyalkylene alkyl ether carboxylic acid, and salts thereof.
  • alkyl group contained in the carboxylic acid-based surfactant an alkyl group having 7 to 25 carbon atoms is preferable, and an alkyl group having 11 to 17 carbon atoms is more preferable.
  • alkylene group of the polyoxyalkylene alkyl ether carboxylic acid an ethylene group or a 1,2-propanediyl group is preferable.
  • the number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether carboxylic acid is preferably 1 to 12, more preferably 1 to 6.
  • carboxylic acid-based surfactant examples include lauric acid, myristic acid, palmitic acid, stearic acid, polyoxyethylene lauryl ether acetic acid, and polyoxyethylene tridecyl ether acetic acid.
  • sulfuric acid ester-based surfactant examples include an alkyl sulfate ester, a polyoxyalkylene alkyl ether sulfuric acid ester, and salts thereof.
  • alkyl group contained in the alkyl sulfate ester and the polyoxyalkylene alkyl ether sulfuric acid ester an alkyl group having 2 to 24 carbon atoms is preferable, and an alkyl group having 6 to 18 carbon atoms is more preferable.
  • alkylene group contained in the polyoxyalkylene alkyl ether sulfuric acid ester an ethylene group or a 1,2-propanediyl group is preferable.
  • the number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether sulfuric acid ester is preferably 1 to 12, more preferably 1 to 6.
  • sulfate ester-based surfactant examples include lauryl sulfate ester, myristyl sulfate ester, and polyoxyethylene lauryl ether sulfate ester.
  • surfactant examples include paragraphs [0092] to [0090] of JP-A-2015-158662, paragraphs [0045]-[0046] of JP-A-2012-151273, and JP-A-2009-147389.
  • the compounds described in paragraphs [0014] to [0020] of the publication may also be incorporated, and the contents thereof are incorporated in the present specification.
  • the surfactant may be used alone or in combination of two or more.
  • the content of the surfactant is preferably 0.001 to 8.0% by mass, more preferably 0.005 to 5.0% by mass, based on the total mass of the cleaning liquid, because the performance of the cleaning liquid is well-balanced. , 0.01-3.0% by mass is more preferable.
  • the content of the surfactant is preferably 1.0 to 30.0% by mass, more preferably 5.0 to 20.0% by mass, and 10.0 to 20% by mass with respect to the total mass of the cleaning liquid excluding the solvent. .0% by mass is more preferable.
  • the cleaning liquid may contain an anticorrosive agent.
  • the anticorrosion agent include a carboxylic acid, a heterocyclic compound having a heterocyclic structure in the molecule, a catechol compound, a hydroxylamine compound, a biguanide compound, a hydrazide compound, an ascorbic acid compound, a reducing sulfur compound, and a molecular weight of 500 or more. Polyhydroxy compounds of.
  • Carboxylic acid is a compound having a carboxy group in the molecule.
  • Carboxylic acid is a compound different from the components contained in the above-mentioned cleaning liquid.
  • Examples of the carboxylic acid include propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexaneic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid and 2-.
  • Examples thereof include methylhexanoic acid, n-octanoic acid, and 2-ethylhexanoic acid.
  • a heterocyclic compound is a compound having a heterocyclic structure in the molecule.
  • the heterocyclic compound is a compound different from the components contained in the above-mentioned cleaning solution.
  • Examples of the heterocyclic structure of a heterocyclic compound include a heterocycle (nitrogen-containing heterocycle) in which at least one of the atoms constituting the ring is a nitrogen atom.
  • Examples of the heterocyclic compound having a nitrogen-containing heterocycle include an azole compound, a pyridine compound, a pyrazine compound, a pyrimidine compound, a piperazine compound, and a cyclic amidin compound.
  • the heterocyclic compound at least one selected from the group consisting of an azole compound, a pyridine compound, a pyrazine compound, and a pyrimidine compound is preferable.
  • the azole compound is a compound having at least one nitrogen atom and having an aromatic 5-membered ring.
  • the number of nitrogen atoms contained in the hetero 5-membered ring of the azole compound is preferably 1 to 4, more preferably 1 to 3.
  • the azole compound may have a substituent on the hetero 5-membered ring. Examples of the substituent include a hydroxyl group, a carboxy group, a mercapto group, an amino group, an alkyl group having 1 to 4 carbon atoms which may have an amino group, and a 2-imidazolyl group.
  • Examples of the azole compound include an imidazole compound in which one of the atoms constituting the azole ring is a nitrogen atom, a pyrazole compound in which two of the atoms constituting the azole ring are nitrogen atoms, and one of the atoms constituting the azole ring.
  • One is a nitrogen atom
  • the other is a thiazole compound which is a sulfur atom
  • three of the atoms constituting the azole ring are triazole compounds which are nitrogen atoms
  • four of the atoms constituting the azole ring are nitrogen atoms.
  • Examples include tetrazole compounds.
  • imidazole compound examples include imidazole, 1-methylimidazole, 2-methylimidazole, 5-methylimidazole, 1,2-dimethylimidazole, 2-mercaptoimidazole, 4,5-dimethyl-2-mercaptoimidazole and 4-hydroxy.
  • Examples of the pyrazole compound include pyrazole, 4-pyrazolecarboxylic acid, 1-methylpyrazole, 3-methylpyrazole, 3-amino-5-methylpyrazole, 3-amino-5-hydroxypyrazole, 3-aminopyrazole, and Examples include 4-aminopyrazole.
  • thiazole compound examples include 2,4-dimethylthiazole, benzothiazole, and 2-mercaptobenzothiazole.
  • triazole compound examples include 1,2,4-triazol, 3-methyl-1,2,4-triazole, 3-amino-1,2,4-triazole and 1,2,3-triazol.
  • -L 1-methyl-1,2,3-triazole, benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4
  • examples thereof include -carboxybenzotriazole, 5-methylbenzotriazole, and 2,2'- ⁇ [(5-methyl-1H-benzotriazole-1-yl) methyl] imino ⁇ diethanol.
  • tetrazole compound examples include 1H-tetrazole (1,2,3,4-tetrazole), 5-methyl-1,2,3,4-tetrazole and 5-amino-1,2,3.
  • examples thereof include 4-tetrazole, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, and 1- (2-dimethylaminoethyl) -5-mercaptotetrazole.
  • the azole compound at least one selected from the group consisting of an imidazole compound, a pyrazole compound, a thiazole compound, a triazole compound and a tetrazole compound is preferable, and imidazole, pyrazole, 2,4-dimethylthiazole, 1,2,4-triazole and the like. 1H-tetrazole (1,2,3,4-tetrazole) or adenin is more preferable.
  • the pyridine compound is a compound having a hetero 6-membered ring (pyridine ring) containing one nitrogen atom and having aromaticity.
  • the pyridine compound may have a substituent on the pyridine ring. Examples of the substituent include a hydroxyl group, an amino group, a cyano group, an alkyl group having 1 to 4 carbon atoms, and an alkylamide group having 1 to 4 carbon atoms.
  • pyridine compound examples include pyridine, 3-aminopyridine, 4-aminopyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2-acetamidopyridine, 2-cyanopyridine, 2-carboxypyridine, and 4-carboxypyridine.
  • pyridine is preferable.
  • the pyrazine compound is a compound having aromaticity and having a hetero 6-membered ring (pyrazine ring) containing two nitrogen atoms located at the para position.
  • the pyrimidine compound is a compound having aromaticity and having a hetero 6-membered ring (pyrimidine ring) containing two nitrogen atoms located at the meta position.
  • the pyrazine compound and the pyrimidine compound may have a substituent on the ring. Examples of the substituent include a hydroxyl group, an amino group, a carboxy group, and an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group.
  • pyrazine compound examples include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, 2,3,5-trimethylpyrazine, 2,3,5,6-tetramethylpyrazine and 2-ethyl-3-methylpyrazine. , And 2-amino-5-methylpyrazine, with pyrazine being preferred.
  • Examples of the pyrimidine compound include pyrimidine, 2-methylpyrimidine, 2-aminopyrimidine, and 4,6-dimethylpyrimidine, and pyrimidine is preferable.
  • the piperazine compound is a compound having a hetero 6-membered ring (piperazine ring) in which the opposite -CH- group of the cyclohexane ring is replaced with a nitrogen atom.
  • the piperazine compound may have a substituent on the piperazine ring. Examples of such a substituent include a hydroxyl group, an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, and an aryl group having 6 to 10 carbon atoms.
  • piperazine compound examples include piperazine, 1-methylpiperazine, 1-ethylpiperazine, 1-propylpiperazine, 1-butylpiperazine, 2-methylpiperazine, 1,4-dimethylpiperazine, 2,5-dimethylpiperazine, 2, 6-Dimethylpiperazine, 1-phenylpiperazine, 2-hydroxypiperazine, 2-hydroxymethylpiperazine, 1- (2-hydroxyethyl) piperazine (HEP), and 1,4-bis (3-aminopropyl) piperazine (BAP). ), And piperazine, 1-methylpiperazine, 2-methylpiperazine, HEP, or BAP is preferable, and HEP or BAP is more preferable.
  • the number of ring members of the above heterocycle contained in the cyclic amidine compound is preferably 5 to 6, more preferably 6.
  • the cyclic amidine compound may have a substituent on the above heterocycle. Examples of the substituent include an amino group, an oxo group, and an alkyl group having 1 to 4 carbon atoms. Further, the two substituents on the above heterocycle may be bonded to each other to form a divalent linking group (preferably an alkylene group having 3 to 6 carbon atoms).
  • Examples of the cyclic amidine compound include diazabicycloundecene (1,8-diazabicyclo [5.4.0] undec-7-en: DBU) and diazabicyclononene (1,5-diazabicyclo [4.3.
  • Nona-5-en DBN
  • 3,4,6,7,8,9,10,11-octahydro-2H-pyrimid [1.2-a] azocin
  • 3,4,6,7,8 9-Hexahydro-2H-pyrido [1.2-a] pyrimidine
  • 2,5,6,7-tetrahydro-3H-pyrrolo [1.2-a] imidazole 3-ethyl-2,3,4,6 , 7,8,9,10-octahydropyrimid [1.2-a] azepine
  • creatinine with DBU or DBN being preferred.
  • heterocyclic compound examples include 1,3-dimethyl-2-imidazolidinone, a compound having a hetero5-membered ring having no aromaticity such as imidazolidinethione, and a 7-membered ring containing a nitrogen atom. Also mentioned are compounds having.
  • Examples of the compound having a 7-membered ring containing a nitrogen atom include hexahydro-1H-1,4-diazepine, 1-methylhexahydro-1H-1,4-diazepine, and 2-methylhexahydro-1H-1,4.
  • -Diazepine, 6-methylhexahydro-1H-1,4-diazepine, 2,7-diazabicyclo [3.2.1] octane, and 1,3-diazabicyclo [3.2.2] nonane can be mentioned.
  • the catechol compound means at least one selected from the group consisting of pyrocatechol (benzene-1,2-diol) and catechol derivatives.
  • the catechol derivative means a compound in which at least one substituent is substituted with pyrocatechol.
  • the catechol compound is a compound different from the components contained in the above-mentioned cleaning solution. Examples of the substituent contained in the catechol derivative include a hydroxyl group, a carboxy group, a carboxylic acid ester group, a sulfo group, a sulfonic acid ester group, and an alkyl group (preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms).
  • the carboxy group and the sulfo group that the catechol derivative has as a substituent may be a salt with a cation. Further, the alkyl group and the aryl group that the catechol derivative has as a substituent may further have a substituent.
  • catechol compound examples include pyrocatechol, 4-tert-butylcatechol, pyrogallol, gallate, methyl gallate, 1,2,4-benzenetriol, and Tyrone. Of these, pyrocatechol, pyrogallol, or gallic acid is preferable.
  • Hydroxylamine compound means at least one selected from the group consisting of hydroxylamine (NH 2 OH), hydroxylamine derivatives, and salts thereof.
  • the hydroxylamine compound is a compound different from the components contained in the above-mentioned cleaning liquid.
  • the hydroxylamine derivative means a compound in which at least one organic group is substituted with hydroxylamine (NH 2 OH). Examples of the hydroxylamine or the salt of the hydroxylamine derivative include inorganic acid salts and organic acid salts.
  • a salt with an inorganic acid in which at least one non-metal selected from the group consisting of Cl, S, N, and P is bonded to hydrogen is preferable.
  • Hydrochloride, sulfate, or nitrate is more preferred.
  • Examples of the hydroxylamine compound include a compound represented by the general formula (5).
  • R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group having 1 to 6 carbon atoms represented by R 6 and R 7 may be linear, branched or cyclic.
  • Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group and an isopentyl group.
  • Se-pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert -Hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, and cyclohexyl group can be mentioned.
  • R 6 and R 7 an alkyl group having 1 to 6 carbon atoms is preferable, an ethyl group or an n-propyl group is more preferable, and an ethyl group is further preferable.
  • hydroxylamine compound examples include hydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N-ethylhydroxylamine, N, N-diethylhydroxylamine (DEHA), Nn-propylhydroxylamine, and the like.
  • Roxylamine N, N-bis (2-methylpentyl) hydroxylamine, N-1,2-dimethylbutylhydroxylamine, N, N-bis (1,2-dimethylbutyl) hydroxylamine, N-2,3-dimethyl Butyl hydroxylamine, N, N-bis (2,3-dimethylbutyl) hydroxylamine, N-1-ethylbutylhydroxylamine, N, N-bis (1-ethylbutyl) hydroxylamine, N-cyclohexylhydroxylamine, and Examples include N, N-dicyclohexylhydroxylamine.
  • hydroxylamine compound hydroxylamine, N-ethylhydroxylamine, DEHA, or Nn-propylhydroxylamine is preferable, and hydroxylamine is more preferable.
  • hydroxylamine compound a commercially available compound may be used, or a compound appropriately synthesized by a known method may be used.
  • the biguanide compound is a compound having a biguanide group and a biguanide compound which is a salt thereof.
  • the number of biguanide groups contained in the biguanide compound may be singular or plural.
  • Examples of the biguanide compound include the compounds described in paragraphs [0034] to [0055] of JP-A-2017-504190, the contents of which are incorporated in the present specification.
  • Examples of the compound having a biguanide group include ethylene diviguanide, propylene diviguanide, tetramethylene diviguanide, pentamethylene diviguanide, hexamethylene diviguanide, heptamethylene diviguanide, octamethylene diviguanide, and 1,1'-hexamethylenebis ( 5- (p-chlorophenyl) biguanide) (chlorhexidine), 2- (benzyloxymethyl) pentane-1,5-bis (5-hexylbiguanide), 2- (phenylthiomethyl) pentane-1,5-bis (5) -Phenetyl biguanide), 3- (phenylthio) hexane-1,6-bis (5-hexylbiguanide), 3- (phenylthio) hexane-1,6-bis (5-cyclohexylbiguanide), 3- (benzylthio) hexane-
  • a hydrochloride salt, an acetate salt, or a gluconate salt is preferable, and a gluconate salt salt is more preferable.
  • a gluconate salt salt is more preferable.
  • chlorhexidine gluconate (CHG) is preferable.
  • the hydrazide compound means a compound in which the hydroxyl group of an acid is substituted with a hydrazino group (-NH-NH 2 ), and a derivative thereof (a compound in which at least one substituent is substituted with a hydrazino group).
  • the hydrazide compound may have one or more hydrazino groups. Examples of the hydrazide compound include carboxylic acid hydrazide and sulfonic acid hydrazide, and carbohydrazide (CHZ) is preferable.
  • the ascorbic acid compound means at least one selected from the group consisting of ascorbic acid, ascorbic acid derivatives, and salts thereof.
  • the ascorbic acid derivative include ascorbic acid phosphate ester and ascorbic acid sulfate ester. Among them, ascorbic acid is preferable as ascorbic acid.
  • the reducing sulfur compound is a compound having reducing property and containing a sulfur atom.
  • the reducing sulfur compound include thioglycolic acid, dithiodiglycolic acid, bis (2,3-dihydroxypropylthio) ethylene, and 3- (2,3-dihydroxypropylthio) -2-methyl-propylsulfonate sodium. , 1-thioglycerol, 2-mercaptoethanol, and 3-mercapto-1-propanol.
  • a compound having an SH group mercapto compound
  • thioglycolic acid or dithiodiglycolic acid is more preferable.
  • the polyhydroxy compound is an organic compound having two or more (for example, 2 to 200) alcoholic hydroxyl groups in one molecule.
  • the polyhydroxy compound is a compound different from the components contained in the cleaning liquid described above.
  • the molecular weight of the polyhydroxy compound (meaning a weight average molecular weight when it has a molecular weight distribution) is 500 or more, preferably 500 to 3000.
  • polyhydroxy compound examples include polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol; Oligosaccharides such as; polysaccharides such as starch, glycogen, cellulose, chitin, and chitosan, and hydrolyzates thereof, and polyethylene glycol is preferable.
  • polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol
  • Oligosaccharides such as; polysaccharides such as starch, glycogen, cellulose, chitin, and chitosan, and hydrolyzates thereof, and polyethylene glycol is preferable.
  • Cyclodextrin is also preferable as the polyhydroxy compound.
  • Cyclodextrin is a kind of cyclic oligosaccharide having a cyclic structure in which a plurality of D-glucoses are bound by a glucosidic bond.
  • a compound in which 5 or more glucoses (for example, 6 to 8 glucoses) are bound can be mentioned.
  • Examples of the cyclodextrin include ⁇ -cyclodextrin, ⁇ -cyclodextrin, and ⁇ -cyclodextrin, and ⁇ -cyclodextrin is preferable.
  • the anticorrosion agent may include at least one selected from the group consisting of catechol compounds, heterocyclic compounds, hydroxyamine compounds, biguanide compounds, ascorbic acid, reducing sulfur compounds, and polyhydroxy compounds having a molecular weight of 500 or more. It is preferable to include a heterocyclic compound.
  • the anticorrosive agent may be used alone or in combination of two or more.
  • the content of the anticorrosive agent is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5.0% by mass, and 0.05 to 3.0% by mass with respect to the total mass of the cleaning liquid. More preferred.
  • the content of the anticorrosive agent is preferably 0.2 to 20.0% by mass, more preferably 1.0 to 10.0% by mass, and 1.5 to 5. 0% by mass is more preferable.
  • the cleaning solution may contain a preservative.
  • the preservative is a compound different from the components contained in the above-mentioned cleaning liquid.
  • Examples of preservatives include benzoic acid, sodium benzoate, salicylic acid, propionic acid, isopropyl paraoxybenzoate, isobutyl paraoxybenzoate, ethyl paraoxybenzoate, methyl paraoxybenzoate, butyl paraoxybenzoate, propyl paraoxybenzoate, and sulfite.
  • examples include substances, tea catechins, apple polyphenols, pectin degradation products, chitosan, lysoteam, and ⁇ -polylysine.
  • benzoic acid, sorbic acid, salicylic acid, or propionic acid is preferable as the preservative.
  • Benzoic acid, sorbic acid, salicylic acid, and propionic acid may also be used as a pH adjuster and a metal dissolving agent described later.
  • the preservative may be used alone or in combination of two or more.
  • the content of the preservative is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5.0% by mass, and 0.05 to 3.0% by mass with respect to the total mass of the cleaning liquid. More preferred.
  • the content of the anticorrosive agent is preferably 0.2 to 20.0% by mass, more preferably 1.0 to 10.0% by mass, and 1.5 to 5. 0% by mass is more preferable.
  • the cleaning liquid preferably contains at least one selected from the group consisting of a surfactant, an anticorrosive agent, and an antiseptic, and contains at least one selected from the group consisting of a surfactant and an anticorrosive agent. It is more preferable, it is more preferable to contain an anticorrosive agent, and it is particularly preferable to contain a heterocyclic compound.
  • the cleaning liquid may contain an oxidizing agent.
  • the oxidizing agent is a compound different from the components contained in the cleaning liquid described above.
  • the oxidizing agent include peroxides, persulfides (for example, monopersulfides and dipersulfides, etc.), percarbonates, their acids, and salts thereof.
  • the oxidizing agent include oxidized halide (periodic acid such as iodic acid, metaperiodic acid and orthoperiodic acid, and salts thereof), periodic acid, periodic acid salt, cerium compound, and the like.
  • ferricyanides potassium ferricyanide, etc.
  • the oxidizing agent may be used alone or in combination of two or more.
  • the content of the oxidizing agent is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, still more preferably 0.1 to 3% by mass, based on the total mass of the cleaning liquid.
  • the cleaning solution may contain a pH regulator to adjust and maintain the pH of the cleaning solution.
  • the pH adjuster is a compound different from the components contained in the cleaning solution described above.
  • Examples of the pH adjuster include a quaternary ammonium compound, a basic compound, and an acidic compound. Of these, a quaternary ammonium compound, sulfuric acid, or potassium hydroxide is preferable. However, it is permissible to adjust the pH of the cleaning solution by adjusting the amount of each component added as described above.
  • the quaternary ammonium compound is a compound different from the components contained in the above-mentioned cleaning liquid.
  • the quaternary ammonium compound is preferably a compound having a quaternary ammonium cation in which a nitrogen atom is substituted with four hydrocarbon groups (preferably an alkyl group).
  • the quaternary ammonium compound is a compound having a quaternary ammonium cation in which a nitrogen atom in the pyridine ring is bonded to a substituent (hydrocarbon group such as an alkyl group and an aryl group), such as an alkylpyridinium. May be good.
  • Examples of the quaternary ammonium compound include a quaternary ammonium hydroxide, a quaternary ammonium fluoride, a quaternary ammonium bromide, a quaternary ammonium iodide, a quaternary ammonium acetate, and a quaternary ammonium compound.
  • Examples include carbonates of quaternary ammonium.
  • a quaternary ammonium hydroxide represented by the formula (4) is preferable.
  • R 8 represents an alkyl group which may have a hydroxyl group or a phenyl group as a substituent.
  • the four R8s may be the same or different from each other.
  • alkyl group represented by R 8 an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
  • alkyl group represented by R8 which may have a hydroxyl group or a phenyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-hydroxyethyl group, or a benzyl group is preferable, and a methyl group is used.
  • Ethyl group, propyl group, butyl group, or 2-hydroxyethyl group is more preferable, and methyl group, ethyl group, or 2-hydroxyethyl group is further preferable.
  • quaternary ammonium compound examples include tetramethylammonium hydroxide (TMAH), trimethylethylammonium hydroxide (TMEAH), dimethyldiethylammonium hydroxide (DMDEAH), methyltriethylammonium hydroxide (MTEAH), and tetraethylammonium hydroxide.
  • TMAH tetramethylammonium hydroxide
  • TAEAH trimethylethylammonium hydroxide
  • DMDEAH dimethyldiethylammonium hydroxide
  • MTEAH methyltriethylammonium hydroxide
  • TMAH tetramethylammonium hydroxide
  • TAEAH trimethylethylammonium hydroxide
  • DMDEAH dimethyldiethylammonium hydroxide
  • MTEAH methyltriethylammonium hydroxide
  • tetraethylammonium hydroxide examples include tetramethyl
  • TEAH Tetrapropyl Ammonium Hydroxide
  • TBAH Tetrabutyl Ammonium Hydroxide
  • 2-Hydroxyethyl Trimmonium Ammonium Hydroxide Cold
  • Bis (2-Hydroxyethyl) Dimethyl Ammonium Hydroxide Tri (2-) Examples thereof include hydroxyethyl) methylammonium hydroxide, tetra (2-hydroxyethyl) ammonium hydroxide, benzyltrimethylammonium hydroxide (BTMAH), and cetyltrimethylammonium hydroxide.
  • TMAH, TEAH, choline, TBAH, MTEAH, DMDEAH, or TPAH is preferable, and TMAH, TEAH, or choline is more preferable.
  • the quaternary ammonium compound preferably has an asymmetric structure from the viewpoint of excellent damage resistance.
  • having an asymmetric structure in a quaternary ammonium compound is meant that none of the four hydrocarbon groups substituting for nitrogen atoms are the same.
  • Examples of the quaternary ammonium compound having an asymmetric structure include TMEAH, DEDHH, TEMAH, choline, and bis (2-hydroxyethyl) dimethylammonium hydroxide.
  • Examples of the basic compound include a basic organic compound and a basic inorganic compound.
  • Examples of the basic organic compound include amine oxides, nitros, nitroso, oximes, ketooximes, aldoximes, lactams, isocyanides, and ureas.
  • Examples of the basic inorganic compound include alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia.
  • Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide.
  • Examples of the alkaline earth metal hydroxide include calcium hydroxide, strontium hydroxide, and barium hydroxide.
  • the acidic compound examples include inorganic acids.
  • a salt of the acidic compound may be used as long as it becomes an acid or an acid ion (anion) in an aqueous solution.
  • inorganic acid examples include hydrochloric acid, sulfuric acid, sulfite, nitric acid, nitrite, phosphoric acid, boric acid, and hexafluorophosphate.
  • the inorganic acid may form a salt.
  • the salt of the inorganic acid include an ammonium salt of an inorganic acid, and specifically, ammonium chloride, ammonium sulfate, ammonium sulfite, ammonium nitrate, ammonium nitrite, ammonium phosphate, ammonium borate, and phosphorus hexafluoride. Ammonium sulphate can be mentioned.
  • the pH adjuster may be used alone or in combination of two or more.
  • the content of the pH adjuster is not particularly limited, and is appropriately adjusted according to the type and amount of other components and the pH of the target cleaning solution.
  • the content of the pH adjuster is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5.0% by mass, and 0.05 to 3.0% by mass with respect to the total mass of the cleaning liquid. Is more preferable.
  • the content of the pH adjuster is preferably 0.2 to 20.0% by mass, more preferably 1.0 to 10.0% by mass, and 1.5 to 5 to the total mass of the cleaning liquid excluding the solvent. .0% by mass is more preferable.
  • the cleaning liquid may contain an organic solvent.
  • the organic solvent is a compound different from the components contained in the cleaning liquid described above.
  • a known organic solvent can be used, and a hydrophilic organic solvent is preferable.
  • the hydrophilic organic solvent include alcohol-based solvents, ketone-based solvents, ester-based solvents, sulfone-based solvents, sulfoxide-based solvents, nitrile-based solvents, and amide-based solvents.
  • the hydrophilic organic solvent is preferably an alcohol solvent or a nitrile solvent.
  • alcohol-based solvent examples include alkanediol such as alkylene glycol, alkoxy alcohol such as glycol monoether, saturated aliphatic monohydric alcohol, unsaturated non-aromatic monohydric alcohol, and low molecular weight alcohol containing a cyclic structure. Can be mentioned.
  • alkanediol examples include glycol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-diol, 1,4-butanediol, and 1,3-.
  • alkanediol examples include butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, and alkylene glycol.
  • alkylene glycol examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol.
  • alkoxy alcohol examples include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and glycol monoether.
  • glycol monoether examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol.
  • Monobutyl ether triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy- 1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene Examples thereof include glycol monobenzyl ether and diethylene glycol monobenzyl ether.
  • saturated aliphatic monohydric alcohol examples include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, and t-pentyl alcohol. And 1-hexanol.
  • unsaturated non-aromatic monohydric alcohols examples include allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol.
  • low molecular weight alcohols containing a cyclic structure examples include tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol.
  • ketone solvent examples include acetone, propanone, cyclobutanone, cyclopentanone, cyclohexanone, diacetone alcohol, 2-butanone, 5-hexanedione, 1,4-cyclohexanedione, 3-hydroxyacetophenone, and 1,3-cyclohexane.
  • examples include dione and cyclohexanone.
  • ester solvent examples include glycol monoesters such as ethyl acetate, ethylene glycol monoacetate, and diethylene glycol monoacetate; propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. , And glycol monoether monoesters such as ethylene glycol monoethyl ether acetate.
  • sulfone solvent examples include sulfolane, 3-methylsulfolane, and 2,4-dimethylsulfolane.
  • sulfoxide-based solvent examples include dimethyl sulfoxide.
  • a sulfoxide solvent it is preferable to use a grade in which inorganic ions such as sulfate ion, chloride ion, or nitrate ion and metal ion are reduced, or further purify the solvent.
  • nitrile solvent examples include acetonitrile.
  • amide solvent examples include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ⁇ -caprolactam, formamide, and N.
  • -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, and hexamethylphosphoric triamide can be mentioned.
  • the organic solvent may be used alone or in combination of two or more.
  • the content of the organic solvent is preferably 0.01 to 80% by mass, more preferably 0.01 to 50% by mass, further preferably 0.01 to 10% by mass, and 0.01 to the total mass of the cleaning liquid. ⁇ 1% by mass is particularly preferable.
  • the cleaning liquid may contain a fluorine compound.
  • the fluorine compound include the compounds described in paragraphs [0013] to [0015] of JP-A-2005-150236, and the contents thereof are incorporated in the present specification.
  • the amount of the fluorine compound used is not particularly limited and can be appropriately adjusted as long as the effect of the present invention is not impaired.
  • the content of each of the above components is determined by gas chromatography-mass spectrometry (GC-MS: Gas Chromatography-Mass Spectrometry) method, liquid chromatography-mass spectrometry (LC-MS: Liquid Chromatography-Mass Spectrometry) method, and ion exchange. It can be measured by a known method such as a chromatography (IC: Ion-exchange Chromatography) method.
  • GC-MS Gas Chromatography-Mass Spectrometry
  • LC-MS Liquid Chromatography-Mass Spectrometry
  • ion exchange ion exchange
  • the cleaning liquid may contain a metal as an impurity.
  • Content of the above metals eg, metal elements such as Fe, Co, Na, K, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag
  • it is preferably 5 mass ppm or less, and more preferably 1 mass ppm or less, based on the total mass of the cleaning liquid. Since it is assumed that a higher-purity cleaning liquid is required in the manufacture of the most advanced semiconductor element, the metal content is lower than 1 mass ppm (that is, the total mass of the cleaning liquid).
  • the lower limit of the metal content is not particularly limited, but 0 is preferable with respect to the total mass of the cleaning liquid.
  • the content of potassium (K) is preferably 1000 mass ppb or less, and more preferably 100 mass ppb or less, based on the total mass of the washing liquid.
  • the lower limit is not particularly limited, but 0 is preferable.
  • the mass ratio of the content of potassium (K) to the content of sodium (Na) [(potassium content) / sodium content] is preferably 0.1 to 10.
  • a method for reducing the metal content for example, a method of performing purification treatment such as filtration using an ion exchange resin or a filter at the stage of raw materials used in producing the cleaning liquid or at the stage after the production of the cleaning liquid.
  • the cleaning liquid may contain particles.
  • the particle means a particle having a diameter (particle size) of 0.01 ⁇ m or more when the shape of the particle is regarded as a sphere.
  • the content of particles having a particle size of 0.01 ⁇ m or more is preferably 1000 or less, and more preferably 500 or less, per 1 mL of the cleaning liquid.
  • the lower limit is not particularly limited, and 0 is preferable. It is also preferable that the content of particles having a particle size of 0.01 ⁇ m or more measured by the measuring method described later is not more than the detection limit.
  • the particle content can be measured in the liquid phase by using a commercially available measuring device in a light scattering type submerged particle measuring method using a laser as a light source.
  • the particles include, for example, particles such as dust, dust, organic solids, and inorganic solids contained as impurities in the raw material of the cleaning liquid, and dust, dust, and organic solids brought in as contaminants during the preparation of the cleaning liquid. , And particles such as inorganic solids, and those that finally exist as particles without being dissolved in the cleaning liquid fall under this category.
  • Examples of the method for removing particles include purification treatment such as filtering described later.
  • the cleaning liquid may be a kit in which the raw material is divided into a plurality of parts.
  • the cleaning liquid can be produced by a known method. Hereinafter, the method for producing the cleaning liquid will be described in detail.
  • the method for preparing the cleaning liquid is not particularly limited, and for example, the cleaning liquid can be produced by mixing the above-mentioned components.
  • the order and / or timing of mixing each of the above-mentioned components is not particularly limited, and for example, the polymer, alkanolamine, specific complexing agent, and water are sequentially added to a container containing purified pure water. After that, a mixed solution is prepared by stirring, and a pH adjusting agent is further added to the obtained mixed solution to adjust the pH. Further, when water and each component are added to the container, they may be added all at once or divided into a plurality of times.
  • the stirring device and stirring method used for preparing the cleaning liquid are not particularly limited, and a known device as a stirrer or a disperser can be used.
  • a known device as a stirrer or a disperser can be used.
  • the stirrer include an industrial mixer, a portable stirrer, a mechanical stirrer, and a magnetic stirrer.
  • the disperser include an industrial disperser, a homogenizer, an ultrasonic disperser, and a bead mill.
  • the mixing of each component in the preparation step of the cleaning liquid, the purification treatment described later, and the storage temperature of the produced cleaning liquid are preferably 40 ° C. or lower, more preferably 30 ° C. or lower.
  • the lower limit of the storage temperature is not particularly limited, and is preferably 5 ° C. or higher, more preferably 10 ° C. or higher.
  • Refining process It is preferable to perform a purification treatment in advance on any one or more of the raw materials for preparing the cleaning liquid.
  • the purification treatment include known methods such as distillation, ion exchange, and filtration.
  • the degree of purification for example, it is preferable to purify until the purity of the raw material is 99% by mass or more, and it is more preferable to purify until the purity of the stock solution is 99.9% by mass or more.
  • the purification treatment method examples include a method of passing a raw material through an ion exchange resin or an RO membrane (Reverse Osmosis Membrane), distillation of the raw material, and filtering described later.
  • a purification treatment a plurality of the above-mentioned purification methods may be combined and carried out.
  • the raw material is subjected to primary purification by passing it through an RO membrane, and then passed through a purification device made of a cation exchange resin, an anion exchange resin, or a mixed bed type ion exchange resin. You may.
  • the purification treatment may be carried out a plurality of times.
  • the filter used for filtering is not particularly limited as long as it is used for filtration purposes and the like.
  • the filter include fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, polyethylene and polypropylene (PP), and the like.
  • fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, polyethylene and polypropylene (PP), and the like.
  • the filter is made of a material selected from the group consisting of polyethylene, polypropylene (including high-density polypropylene), fluororesin (including PTFE and PFA), and polyamide-based resin (including nylon).
  • the critical surface tension of the filter is preferably 70 to 95 mN / m, more preferably 75 to 85 mN / m.
  • the value of the critical surface tension of the filter is the manufacturer's nominal value.
  • the pore diameter of the filter is preferably 2 to 20 nm, more preferably 2 to 15 nm. Within the above range, it is possible to reliably remove fine foreign substances such as impurities and agglomerates contained in the raw material while suppressing clogging of filtration.
  • the nominal value of the filter manufacturer can be referred to.
  • Filtering may be performed only once or twice or more. When filtering is performed twice or more, the filters used may be the same or different.
  • Filtering is preferably performed at 25 ° C. or lower, more preferably room temperature (23 ° C.) or lower, and even more preferably 20 ° C. or lower.
  • the upper limit is not particularly limited, and is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, and even more preferably 10 ° C. or higher.
  • the cleaning liquid (including the aspect of the kit) can be filled in any container, stored, transported, and used as long as corrosiveness is not a problem.
  • a container having a high degree of cleanliness inside the container and suppressing elution of impurities from the inner wall of the container's accommodating portion into each liquid is preferable for semiconductor applications.
  • the container include various containers commercially available as a container for a semiconductor cleaning liquid. Specific examples thereof include the "clean bottle” series manufactured by Aicello Chemical Corporation and the "pure bottle” manufactured by Kodama Resin Industry.
  • the inner wall of the container accommodating portion and the wetted portion between each liquid are formed of a fluororesin (perfluororesin) or a metal that has been subjected to rust prevention and metal elution prevention treatment.
  • a container is preferable.
  • the inner wall of the container is made of one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a resin different from this, stainless steel, hasteroi, inconel, monel, and the like. It is preferably formed from a metal that has been subjected to rust-preventive and metal elution-preventing treatments.
  • a fluororesin (perfluororesin) is preferable.
  • a container whose inner wall is a fluororesin When a container whose inner wall is a fluororesin is used, the occurrence of a problem of elution of ethylene or propylene oligomer can be suppressed as compared with a container whose inner wall is a polyethylene resin, a polypropylene resin, or a polyethylene-polypropylene resin.
  • Examples of the container whose inner wall is a fluororesin include, for example, a FluoroPure PFA composite drum manufactured by Entegris, page 4 of JP-A-3-502677, page 3 of International Publication No. 2004/016526, and Examples include the containers described on pages 9 and 16 of International Publication No. 99/46309.
  • quartz and an electropolished metal material are also preferably used for the inner wall of the container.
  • the metal material used in the production of the electropolished metal material contains at least one selected from the group consisting of chromium and nickel, and the total content of chromium and nickel is the total mass of the metal material. , 25% by mass or more of the metal material is preferable, and 30% by mass or more of the metal material is more preferable.
  • the upper limit of the total content of chromium and nickel in the metal material is not particularly limited, and is preferably 90% by mass or less. Examples of the metal material include stainless steel and nickel-chromium alloy.
  • the inside of the container is cleaned before filling with the cleaning liquid.
  • the liquid used for the cleaning preferably has a reduced amount of metal impurities in the liquid.
  • the cleaning liquid may be bottling, transported and stored in a container such as a gallon bottle or a coated bottle after production.
  • the inside of the container may be replaced with an inert gas (nitrogen, argon, etc.) having a purity of 99.99995% by volume or more.
  • the inert gas preferably has a low water content.
  • the temperature for transportation and storage may be room temperature, or may be ⁇ 20 ° C. to 20 ° C. from the viewpoint of preventing deterioration. Further, the temperature may be controlled in order to obtain the above temperature.
  • the clean room preferably meets the 14644-1 clean room standard. It is preferable to satisfy any one of ISO (International Organization for Standardization) class 1, ISO class 2, ISO class 3, and ISO class 4, more preferably to satisfy ISO class 1 or ISO class 2, and satisfy ISO class 1. Is even more preferable.
  • ISO International Organization for Standardization
  • the cleaning liquid is preferably used in a cleaning step for cleaning a semiconductor substrate that has been subjected to chemical mechanical polishing (CMP) treatment.
  • CMP chemical mechanical polishing
  • the cleaning liquid can also be used for cleaning the semiconductor substrate in the semiconductor substrate manufacturing process. Further, it can also be used for buffing treatment as described later.
  • Examples of the object to be cleaned by the cleaning liquid include a semiconductor substrate having a metal film containing tungsten.
  • “on the semiconductor substrate” includes, for example, any of the front and back surfaces, the side surfaces, the inside of the groove, and the like of the semiconductor substrate.
  • the metal film on the semiconductor substrate includes not only the case where the metal film is directly on the surface of the semiconductor substrate but also the case where the metal film is present on the semiconductor substrate via another layer.
  • Examples of the metal contained in the metal film include W (tungsten).
  • the metal film may contain a metal other than W.
  • Other metals include, for example, Cu (copper), Co (cobalt), Ti (tantalum), Ta (tantalum), Ru (ruthenium), Cr (chromium), Hf (hafnium), Os (osmium), Pt ( At least one metal selected from the group consisting of platinum), Ni (nickel), Mn (manganese), Cu (copper), Zr (zirconium), Mo (molybdenum), La (lanthanum), and Ir (iridium). M is mentioned.
  • Examples of the semiconductor substrate to be cleaned by the cleaning liquid include a substrate having a metal wiring film, a barrier metal, and an insulating film on the surface of the wafer constituting the semiconductor substrate.
  • Examples of the wafer constituting the semiconductor substrate include a silicon (Si) wafer, a silicon carbide (SiC) wafer, a wafer made of a silicon-based material such as a resin-based wafer containing silicon (glass epoxy wafer), and gallium phosphorus (GaP). ) Wafers, gallium arsenic (GaAs) wafers, and indium phosphorus (InP) wafers.
  • the silicon wafer include an n-type silicon wafer in which a silicon wafer is doped with a pentavalent atom (for example, phosphorus (P), arsenic (As), antimony (Sb), etc.), and a silicon wafer is trivalent.
  • Examples thereof include a p-type silicon wafer doped with an atom of (for example, boron (B), gallium (Ga), etc.).
  • Examples of silicon for silicon wafers include amorphous silicon, single crystal silicon, polycrystalline silicon, and polysilicon.
  • the wafer a wafer made of a silicon-based material such as a silicon wafer, a silicon carbide wafer, and a resin-based wafer (glass epoxy wafer) containing silicon is preferable.
  • the semiconductor substrate may further have an insulating film on the above-mentioned wafer.
  • the insulating film include a silicon oxide film (for example, a silicon dioxide (SiO 2 ) film, a tetraethyl orthosilicate (Si (OC 2 H 5 ) 4 ) film (TEOS film), etc.), and a silicon nitride film (for example, a silicon nitride film).
  • Silicon nitride (Si 3N 4 ), silicon nitride carbide ( SiNC ), etc.), and low dielectric constant (Low-k) films eg, carbon-doped silicon oxide (SiOC) films, and silicon carbide (SiC). Membrane, etc.).
  • Examples of the metal film containing tungsten include a metal film made of only metallic tungsten (tungsten metal film) and a metal film made of an alloy of tungsten and a metal other than tungsten (tungsten alloy metal film). ).
  • Examples of the tungsten alloy metal film include a tungsten-titanium alloy metal film (WTi alloy metal film) and a tungsten-cobalt alloy metal film (WCo alloy metal film).
  • the tungsten-containing film can be used, for example, at the connection portion between the barrier metal or via and the wiring.
  • the method for forming the above-mentioned insulating film and the tungsten-containing film on the wafer constituting the semiconductor substrate is not particularly limited as long as it is a known method.
  • a method for forming the insulating film for example, a silicon oxide film is formed by heat-treating a wafer constituting a semiconductor substrate in the presence of oxygen gas, and then silane and ammonia gas are introduced to form a chemical vapor deposition. Examples thereof include a method of forming a silicon nitride film by a vapor deposition (CVD) method.
  • CVD vapor deposition
  • a method for forming the tungsten-containing film for example, a circuit is formed on a wafer having the above-mentioned insulating film by a known method such as a resist, and then a tungsten-containing film and a cobalt-containing film are contained by a method such as plating and a CVD method. Examples include a method of forming a film.
  • a substrate having a metal wiring film, a barrier metal, and an insulating film is formed by a combined action of a chemical action using a polishing slurry containing polishing fine particles (abrasive grains) and a mechanical action by mechanical polishing. It is a process of flattening the surface of.
  • abrasive grains for example, silica and alumina
  • a polished metal wiring film for example, metal impurities (metal residue) derived from the barrier metal, etc. Impurities may remain.
  • organic residues derived from the CMP treatment liquid used in the CMP treatment may remain.
  • the semiconductor substrate subjected to the CMP treatment is used for cleaning treatment for removing these impurities from the surface.
  • Examples of the semiconductor substrate subjected to the CMP treatment include Vol. 84, No. 3.
  • the substrate subjected to the CMP treatment according to 2018 can be mentioned.
  • the surface of the semiconductor substrate which is the object to be cleaned by the cleaning liquid, may be further subjected to buffing treatment after being subjected to CMP treatment.
  • the buffing process is a process of reducing impurities on the surface of a semiconductor substrate by using a polishing pad. Specifically, the surface of the semiconductor substrate subjected to the CMP treatment is brought into contact with the polishing pad, and the semiconductor substrate and the polishing pad are relatively slid while supplying the buffing composition to the contact portion. .. As a result, impurities on the surface of the semiconductor substrate are removed by the frictional force of the polishing pad and the chemical action of the buffing composition.
  • a known buffing composition can be appropriately used depending on the type of the semiconductor substrate and the type and amount of impurities to be removed.
  • the components contained in the buffing composition include water-soluble polymers such as polyvinyl alcohol, water as a dispersion medium, and acids such as nitric acid.
  • the buffing treatment it is preferable to buff the semiconductor substrate using the above-mentioned cleaning liquid as the buffing composition.
  • the polishing device and polishing conditions used in the buffing process can be appropriately selected from known devices and conditions according to the type of semiconductor substrate, the object to be removed, and the like. Examples of the buffing process include the processes described in paragraphs [805] to [0088] of International Publication No. 2017/169539, and these contents are incorporated in the present specification.
  • the method for cleaning the semiconductor substrate is not particularly limited as long as it includes a cleaning step of cleaning the semiconductor substrate subjected to the CMP treatment using the above-mentioned cleaning liquid.
  • the cleaning step of cleaning the semiconductor substrate using the cleaning liquid is not particularly limited as long as it is a known method performed on the semiconductor substrate treated with CMP, and a cleaning member such as a brush is used while supplying the cleaning liquid to the semiconductor substrate.
  • Scrub cleaning that physically contacts the surface of the semiconductor substrate to remove residues
  • immersion type that immerses the semiconductor substrate in the cleaning liquid
  • spin (drop) type that drops the cleaning liquid while rotating the semiconductor substrate
  • cleaning liquid A spray type for spraying can be mentioned.
  • the immersion type cleaning it is preferable to perform ultrasonic treatment on the cleaning liquid in which the semiconductor substrate is immersed from the viewpoint of further reducing impurities remaining on the surface of the semiconductor substrate.
  • the cleaning step may be performed only once or twice or more. When washing twice or more, the same method may be repeated, or different methods may be combined.
  • the semiconductor substrate cleaning method may be either a single-wafer method or a batch method.
  • the single-wafer method is a method of processing semiconductor substrates one by one
  • the batch method is a method of processing a plurality of semiconductor substrates at the same time.
  • the temperature of the cleaning liquid used for cleaning the semiconductor substrate is not particularly limited as long as it is a temperature usually used in this field.
  • the temperature of the cleaning liquid may be room temperature (23 ° C.), and the temperature may be arbitrarily selected in order to improve the cleaning property and suppress the damage resistance to the member.
  • the temperature of the cleaning liquid is preferably 10 to 60 ° C, more preferably 15 to 50 ° C.
  • the cleaning time in cleaning the semiconductor substrate can be appropriately adjusted depending on the type and content of the components contained in the cleaning liquid, and from the viewpoint of practicality, the cleaning time is preferably 10 seconds to 2 minutes, preferably 20 seconds to 1 minute 30 seconds. Is more preferable, and 30 seconds to 1 minute is further preferable.
  • the supply amount (supply rate) of the cleaning liquid in the cleaning step of the semiconductor substrate is not particularly limited, and is preferably 50 to 5000 mL / min, more preferably 500 to 2000 mL / min.
  • a mechanical stirring method may be used in order to further enhance the cleaning ability of the cleaning liquid.
  • the mechanical stirring method include a method of circulating the cleaning liquid on the semiconductor substrate, a method of flowing or spraying the cleaning liquid on the semiconductor substrate, and a method of stirring the cleaning liquid by ultrasonic waves or megasonics.
  • a step of rinsing and cleaning the semiconductor substrate with a solvent may be performed.
  • the rinsing step is preferably performed continuously after the cleaning step of the semiconductor substrate, and is preferably a rinsing step using a rinsing solvent (rinsing solution) for 5 seconds to 5 minutes.
  • the rinsing step may be performed using the above-mentioned mechanical stirring method.
  • the rinsing solution examples include water (preferably De Ionize water), methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone, ⁇ -butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether. Acetate can be mentioned. Further, the rinsing solution may be an aqueous rinsing solution having a pH of more than 8.0 (diluted aqueous ammonium hydroxide or the like). As a method of contacting the rinsing liquid with the semiconductor substrate, the above-mentioned method of contacting the cleaning liquid with the semiconductor substrate can be similarly applied.
  • a drying step of drying the semiconductor substrate may be performed.
  • the drying method include a spin drying method, a method of flowing a dry gas over a semiconductor substrate, a method of heating a substrate by a heating means such as a hot plate or an infrared lamp, a marangoni drying method, a rotagoni drying method, and IPA (isopropyl). Alcohol) drying method and combinations thereof can be mentioned.
  • the pH of the cleaning solution was measured at 25 ° C. using a pH meter (manufactured by HORIBA, Ltd., model “F-74”) in accordance with JIS Z8802-1984. Further, in the production of the cleaning liquids of Examples and Comparative Examples, the handling of the container, the preparation, filling, storage, and analysis measurement of the cleaning liquid were all performed in a clean room at a level satisfying ISO class 2 or less.
  • Asparagin L-asparagin, Fuji Film Wako Pure Chemical Industries, Ltd.
  • Asparaginic acid L-asparaginic acid, Fuji Film Wako Pure Chemical Industries, Ltd.
  • Glutamic acid L-glutamic acid, Fuji Film Wako Pure Chemical Industries, Ltd.
  • Cysteine L-cysteine, Fujifilm Wako Pure Chemical Industries, Ltd.
  • Citrate Fujifilm Wako Pure Chemical Industries, Ltd.
  • Tartrate acid L-Tartrate acid
  • DTPA Diethylenetriamine pentaacetic acid, Wako Pure Chemical Industries, Ltd.
  • ⁇ HEDPO 1-hydroxyethylidene-1,1-diphosphonic acid
  • Thermophos "Dequest 2000" ⁇ EDTA: ethylenediamine tetraacetic acid, manufactured by Kirest Co., Ltd.
  • ⁇ DHEG N, N-bis (2-hydroxyethyl) glycine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • Sodium acid Fujifilm Wako Pure Chemical Industries, Ltd.
  • Diphosphate Fujifilm Wako Pure Chemical Industries, Ltd.
  • ⁇ p-Toluenesulfonic acid Fujifilm Wako Pure Chemical Industries, Ltd.
  • Methanesulfonic acid Fujifilmwa Made by Kojunyaku Co., Ltd.
  • ⁇ Etansulfonic acid Made by Fujifilm Wako Pure Chemical Industries, Ltd.
  • ⁇ Salicylic acid manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Made ⁇ Anti-corrosion agent>
  • ⁇ Pyrocatecol Made by Fujifilm Wako Pure Chemical Industries, Ltd.
  • ⁇ Pyrogalol Made by Fujifilm Wako Pure Chemical Industries, Ltd.
  • ⁇ Gluttonous acid Made by Fujifilm Wako Pure Chemical Industries, Ltd. ⁇ Pyrazole: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ⁇ 2,4-dimethylthiazole: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ⁇ 1,2,4-triazol: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • the cleaning performance (residue removal performance) when the metal film after the CMP treatment was cleaned was evaluated using the cleaning liquids of each Example or Comparative Example.
  • FREX-300SII polishing equipment, manufactured by Ebara Corporation
  • W2000 polishing liquid
  • the supply speed of the polishing liquid is 0.28 ml / (min ⁇ cm 2 )
  • the polishing pressure is 2.
  • a wafer (12 inches in diameter) having a metal film made of tungsten on the surface was subjected to CMP treatment under the conditions of 0.0 psi and a polishing time of 60 seconds.
  • each cleaning solution was adjusted to room temperature (23 ° C.), scrubbed with each cleaning solution for 60 seconds, and dried.
  • a defect detection device the number of defects on the polished surface of the obtained wafer was detected, and each defect was observed with an SEM (scanning electron microscope) to classify the defects. If necessary, the constituent elements were analyzed by EDAX (energy dispersive X-ray analyzer) to identify the components. As a result, the number of defects based on the residue was determined, and the cleaning performance was evaluated according to the following evaluation criteria (evaluation 6 is the most excellent in cleaning performance).
  • the number of target defects is less than 20 5: The number of target defects is 20 or more and less than 50 4: The number of target defects is 50 or more and less than 100 3: The number of target defects is 100 or more and less than 200 2: The number of target defects is 200 or more and less than 300 1: The number of target defects is 300 or more
  • Corrosion suppression performance The corrosion suppression performance when the metal film was washed was evaluated using the cleaning liquids of each Example or Comparative Example. Wafers (12 inches in diameter) having a metal film made of tungsten on the surface were cut, and 2 cm ⁇ wafer coupons were prepared respectively. The thickness of each metal film was 200 nm. The wafer was immersed in each cleaning liquid at room temperature (23 ° C.) at a stirring rotation speed of 250 rpm, and 30 minutes after being immersed in each cleaning liquid of a metal film made of tungsten, the thickness of the disappeared metal film was determined. .. From the disappeared film thickness, the corrosion rate of the metal film per unit time was calculated. Corrosion suppression performance was evaluated according to the following evaluation criteria.
  • Corrosion rate is 0.2 ⁇ / min or less 5: Corrosion rate is more than 0.2 ⁇ / min, 0.5 ⁇ / min or less 4: Corrosion rate is more than 0.5 ⁇ / min or less, 1 ⁇ / min or less 3: Corrosion rate is More than 1 ⁇ / min, less than 3 ⁇ / min 2: Corrosion rate is more than 3 ⁇ / min, less than 5 ⁇ / min 1: Corrosion rate is more than 5 ⁇ / min
  • the table below shows the composition and evaluation results of the cleaning liquids of each Example and Comparative Example.
  • the "Mw” column indicates the weight average molecular weight.
  • the “content (% by mass)” column indicates the content (unit: mass%) of each component with respect to the total mass of the cleaning liquid.
  • the “active ingredient amount (% by mass)” column shows the content of each component with respect to the total mass of the cleaning liquid excluding the solvent.
  • the column “(C) / (B)” represents the mass ratio of the content of the specific complexing agent to the content of the alkanolamine [content of the specific complexing agent / content of alkanolamine].
  • the column “(C) / (A)” represents the mass ratio of the content of the specific complexing agent to the content of the polymer [content of the specific complexing agent / content of the polymer].
  • the numerical value in the “pH” column indicates the pH of the cleaning solution measured by the above pH meter at 25 ° C.
  • “* 1” in the “pH” column means that, if necessary, H 2 SO 4 (sulfuric acid) was added in an amount so that the pH of the prepared cleaning solution would be the value in the “pH” column.
  • the “remaining portion” in the "water” column means that water constitutes the rest of the cleaning liquid other than each component.
  • the cleaning solution of the present invention obtained the desired effect. From the comparison between Examples 1 and 60 to 63 and Examples 64 to 66, it was confirmed that the effect was more excellent when the weight average molecular weight of the polymer was 2000 to 500,000. From the comparison between Examples 1 and 17 to 21 and Examples 22 to 23, the mass ratio of the content of the specific complexing agent to the content of the alkanolamine [(C) / (B)] is 0. When it was 1 to 1000.0, it was confirmed that the effect was more excellent. Further, when [(C) / (B)] was 0.1 to 400.0, it was confirmed that the effect was further excellent.
  • the specific complexing agent is a compound represented by the formula (B1), a compound represented by the formula (B3), and a compound represented by the formula (B4).
  • the effect is more excellent when it contains at least one selected from the group consisting of the compound represented by the formula (C), diphosphate, hexamethaphosphate, phytic acid, and the compound represented by the formula (P1). It was confirmed that. From the comparison between Examples 29 to 30 and Example 1 and the like, it was confirmed that the effect was more excellent when the cleaning liquid further contained a surfactant. From the comparison with Examples 83 to 102 and 106 to 107, it was confirmed that the cleaning liquid was more effective when it further contained an anticorrosive agent.
  • the buffed wafer was washed over 30 seconds using a sample of each diluted washing solution adjusted to room temperature (23 ° C.), and then dried.
  • the cleaning performance of the cleaning liquid was evaluated on the polished surface of the obtained wafer according to the evaluation test method of [Evaluation of cleaning performance] described above, it was confirmed that the same evaluation results as the cleaning liquid of each of the above-mentioned Examples were shown. Was done.

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Abstract

The present invention provides a semiconductor substrate cleaning solution that exhibits excellent cleaning performance for CMP processed semiconductor substrates which have a tungsten-containing metal film, and that also exhibits excellent corrosion-inhibiting performance with respect to tungsten during the cleaning of a tungsten-containing metal film. A semiconductor substrate cleaning solution according to the present invention is used to clean semiconductor substrates and contains a polymer, an alkanolamine, an acid group-containing complexing agent, and water. The weight-average molecular weight of the polymer is 2,000-900,000, the content of the complexing agent relative to the total mass of the semiconductor substrate cleaning solution is at least 2.5 mass% and less than 20.0 mass%, and the pH of the semiconductor substrate cleaning solution is less than 7.0.

Description

半導体基板用洗浄液Cleaning liquid for semiconductor substrates
　本発明は、半導体基板用洗浄液に関する。 The present invention relates to a cleaning liquid for a semiconductor substrate.
　ＣＣＤ（Charge-Coupled Device）及びメモリ等の半導体素子は、フォトリソグラフィー技術を用いて、基板上に微細な電子回路パターンを形成して製造される。具体的には、基板上に、配線材料となる金属膜、エッチング停止層、及び、層間絶縁層を有する積層体上にレジスト膜を形成し、フォトリソグラフィー工程及びドライエッチング工程（例えば、プラズマエッチング処理）を実施することにより、半導体素子が製造される。 Semiconductor elements such as CCD (Charge-Coupled Device) and memory are manufactured by forming fine electronic circuit patterns on a substrate using photolithography technology. Specifically, a resist film is formed on a laminate having a metal film as a wiring material, an etching stop layer, and an interlayer insulating layer on a substrate, and a photolithography step and a dry etching step (for example, plasma etching treatment). ) Is performed to manufacture a semiconductor element.
　半導体素子の製造において、金属配線膜、バリアメタル、及び、絶縁膜等を有する半導体基板表面を、研磨微粒子（例えば、シリカ、アルミナ等）を含む研磨スラリーを用いて平坦化する化学機械研磨（ＣＭＰ：Chemical Mechanical Polishing）処理を行うことがある。ＣＭＰ処理では、ＣＭＰ処理で使用する研磨微粒子、研磨された配線金属膜、及び／又は、バリアメタル等に由来する金属成分が、ＣＭＰ処理後の半導体基板表面に残存しやすい。
　これらの残渣物は、配線間を短絡し、半導体の電気的な特性に影響を及ぼし得ることから、半導体基板の表面から、これらの残渣物を除去する洗浄工程が一般的に行われている。 In the manufacture of semiconductor devices, chemical mechanical polishing (CMP) is used to flatten the surface of a semiconductor substrate having a metal wiring film, barrier metal, insulating film, etc., using a polishing slurry containing polishing fine particles (for example, silica, alumina, etc.). : Chemical Mechanical Polishing) processing may be performed. In the CMP treatment, the polishing fine particles used in the CMP treatment, the polished wiring metal film, and / or the metal component derived from the barrier metal and the like tend to remain on the surface of the semiconductor substrate after the CMP treatment.
Since these residues can short-circuit the wiring and affect the electrical characteristics of the semiconductor, a cleaning step of removing these residues from the surface of the semiconductor substrate is generally performed.
　例えば、特許文献１には、「カルボキシル基及び／又はカルボキシレート基を有し、かつ、カルボキシル基及び／又はカルボキシレート基のα位及びβ位にある炭素にヒドロキシル基が結合した構造を有する化合物（Ａ）および水を含有する電子材料用洗浄剤。」が記載されている。 For example, Patent Document 1 states that "a compound having a carboxyl group and / or a carboxylate group and having a structure in which a hydroxyl group is bonded to carbons at the α and β positions of the carboxyl group and / or the carboxylate group. (A) and a cleaning agent for electronic materials containing water. "
特開２０１４－１４１６６９号公報Japanese Unexamined Patent Publication No. 2014-141669
　本発明者らは、特許文献１等に記載の半導体基板用洗浄液について検討したところ、ＣＭＰ処理後のタングステンを含む金属膜を有する半導体基板に対して優れた洗浄性能を示すこと、及び、タングステンを含む金属膜を洗浄した際のタングステンに対する腐食抑制性能に優れることの両立が困難であることを知見した。 The present inventors have studied the cleaning liquid for semiconductor substrates described in Patent Document 1 and the like, and found that they show excellent cleaning performance for a semiconductor substrate having a metal film containing tungsten after CMP treatment, and that tungsten is used. It was found that it is difficult to achieve both excellent corrosion suppression performance against tungsten when cleaning the metal film containing it.
　本発明は、ＣＭＰ処理後のタングステンを含む金属膜を有する半導体基板に対して優れた洗浄性能を示し、かつ、タングステンを含む金属膜を洗浄した際のタングステンに対する腐食抑制性能にも優れる半導体基板用洗浄液を提供することを課題とする。 The present invention is for a semiconductor substrate which exhibits excellent cleaning performance for a semiconductor substrate having a metal film containing tungsten after CMP treatment and also has excellent corrosion suppressing performance against tungsten when cleaning a metal film containing tungsten. The subject is to provide a cleaning solution.
　本発明者は、以下の構成により上記課題を解決できることを見出した。 The present inventor has found that the above problem can be solved by the following configuration.
　〔１〕　半導体基板を洗浄するために用いられる、半導体基板用洗浄液であって、
　重合体、アルカノールアミン、酸基を有する錯化剤、及び、水を含み、
　重合体の重量平均分子量が、２０００～９０００００であり、
　錯化剤の含有量が、半導体基板用洗浄液の全質量に対して、２．５質量％以上２０．０質量％未満であり、
　半導体基板用洗浄液のｐＨが、７．０未満である、半導体基板用洗浄液。
　〔２〕　錯化剤が、カルボキシ基、リン酸基、ホスホン酸、及び、スルホン酸基からなる群から選択される少なくとも１つを有する、〔１〕に記載の半導体基板用洗浄液。
　〔３〕　重合体の重量平均分子量が、２０００～５０００００である、〔１〕又は〔２〕に記載の半導体基板用洗浄液。
　〔４〕　アルカノールアミンのｐＫａが、７．５０～１５．００である、〔１〕～〔３〕のいずれか１つに記載の半導体基板用洗浄液。
　〔５〕　アルカノールアミンが、モノエタノールアミン、イソプロパノールアミン、及び、トリスヒドロキシメチルアミノメタンからなる群から選択される少なくとも１つを含む、〔１〕～〔４〕のいずれか１つに記載の半導体基板用洗浄液。
　〔６〕　アルカノールアミンの含有量が、半導体基板用洗浄液の全質量に対して、０．０１～７．０質量％である、〔１〕～〔５〕のいずれか１つに記載の半導体基板用洗浄液。
　〔７〕　アルカノールアミンの含有量に対する、錯化剤の含有量の質量比が、０．１～１０００．０である、〔１〕～〔６〕のいずれか１つに記載の半導体基板用洗浄液。
　〔８〕　重合体の含有量に対する、錯化剤の含有量の質量比が、１．０～１００．０である、〔１〕～〔７〕のいずれか１つに記載の半導体基板用洗浄液。
　〔９〕　錯化剤の含有量が、半導体基板用洗浄液の全質量に対して、３．０～１０．０質量％である、〔１〕～〔８〕のいずれか１つに記載の半導体基板用洗浄液。
　〔１０〕　錯化剤の含有量が、半導体基板用洗浄液の全質量に対して、３．０～４．０質量％である、〔１〕～〔９〕のいずれか１つに記載の半導体基板用洗浄液。
　〔１１〕　更に、防食剤を含む、〔１〕～〔１０〕のいずれか１つに記載の半導体基板用洗浄液。
　〔１２〕　更に、界面活性剤を含む、〔１〕～〔１１〕のいずれか１つに記載の半導体基板用洗浄液。
　〔１３〕　界面活性剤が、アニオン性界面活性剤を含む、〔１２〕に記載の半導体基板用洗浄液。
　〔１４〕　界面活性剤が、アルキルリン酸エステル及びポリオキシエチレンアルキルリン酸エステルからなる群から選択される少なくとも１つを含む、〔１２〕又は〔１３〕に記載の半導体基板用洗浄液。
　〔１５〕　更に、親水性有機溶媒を含む、〔１〕～〔１４〕のいずれか１つに記載の半導体基板用洗浄液。
　〔１６〕　半導体基板が、タングステンを含む金属膜を有する、〔１〕～〔１５〕のいずれか１つに記載の半導体基板用洗浄液。
〔１７〕　化学機械研磨処理が施された半導体基板に適用される洗浄液として用いられる、〔１〕～〔１６〕のいずれか１つに記載の半導体基板用洗浄液。 [1] A cleaning liquid for a semiconductor substrate used for cleaning a semiconductor substrate.
Contains polymers, alkanolamines, complexing agents with acid groups, and water.
The weight average molecular weight of the polymer is 2000-900000, and the polymer has a weight average molecular weight of 2000-90000.
The content of the complexing agent is 2.5% by mass or more and less than 20.0% by mass with respect to the total mass of the cleaning liquid for semiconductor substrates.
A cleaning liquid for a semiconductor substrate, wherein the pH of the cleaning liquid for a semiconductor substrate is less than 7.0.
[2] The cleaning solution for a semiconductor substrate according to [1], wherein the complexing agent has at least one selected from the group consisting of a carboxy group, a phosphoric acid group, a phosphonic acid, and a sulfonic acid group.
[3] The cleaning liquid for a semiconductor substrate according to [1] or [2], wherein the polymer has a weight average molecular weight of 2000 to 500,000.
[4] The cleaning solution for a semiconductor substrate according to any one of [1] to [3], wherein the pKa of the alkanolamine is 7.50-15.00.
[5] The semiconductor according to any one of [1] to [4], wherein the alkanolamine contains at least one selected from the group consisting of monoethanolamine, isopropanolamine, and trishydroxymethylaminomethane. Cleaning liquid for substrates.
[6] The semiconductor substrate according to any one of [1] to [5], wherein the content of alkanolamine is 0.01 to 7.0% by mass with respect to the total mass of the cleaning liquid for semiconductor substrates. Cleaning solution for.
[7] The cleaning liquid for a semiconductor substrate according to any one of [1] to [6], wherein the mass ratio of the content of the complexing agent to the content of the alkanolamine is 0.1 to 1000.0. ..
[8] The cleaning liquid for a semiconductor substrate according to any one of [1] to [7], wherein the mass ratio of the content of the complexing agent to the content of the polymer is 1.0 to 100.0. ..
[9] The semiconductor according to any one of [1] to [8], wherein the content of the complexing agent is 3.0 to 10.0% by mass with respect to the total mass of the cleaning liquid for a semiconductor substrate. Cleaning liquid for substrates.
[10] The semiconductor according to any one of [1] to [9], wherein the content of the complexing agent is 3.0 to 4.0% by mass with respect to the total mass of the cleaning liquid for a semiconductor substrate. Cleaning liquid for substrates.
[11] The cleaning liquid for a semiconductor substrate according to any one of [1] to [10], which further contains an anticorrosive agent.
[12] The cleaning liquid for a semiconductor substrate according to any one of [1] to [11], which further contains a surfactant.
[13] The cleaning liquid for a semiconductor substrate according to [12], wherein the surfactant contains an anionic surfactant.
[14] The cleaning solution for a semiconductor substrate according to [12] or [13], wherein the surfactant comprises at least one selected from the group consisting of an alkyl phosphate ester and a polyoxyethylene alkyl phosphate ester.
[15] The cleaning liquid for a semiconductor substrate according to any one of [1] to [14], which further contains a hydrophilic organic solvent.
[16] The cleaning liquid for a semiconductor substrate according to any one of [1] to [15], wherein the semiconductor substrate has a metal film containing tungsten.
[17] The cleaning liquid for a semiconductor substrate according to any one of [1] to [16], which is used as a cleaning liquid applied to a semiconductor substrate subjected to a chemical mechanical polishing treatment.
　本発明によれば、ＣＭＰ処理後のタングステンを含む金属膜を有する半導体基板に対して優れた洗浄性能に優れ、かつ、タングステンを含む金属膜を洗浄した際のタングステンに対する腐食抑制性能にも優れる半導体基板用洗浄液を提供できる。 According to the present invention, a semiconductor having excellent cleaning performance for a semiconductor substrate having a metal film containing tungsten after CMP treatment and also having excellent corrosion suppressing performance for tungsten when the metal film containing tungsten is cleaned. A cleaning liquid for a substrate can be provided.
　以下に、本発明を実施するための形態の一例を説明する。
　本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。 Hereinafter, an example of a mode for carrying out the present invention will be described.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
　本明細書において、ある成分が２種以上存在する場合、その成分の「含有量」は、それら２種以上の成分の合計含有量を意味する。
　本明細書において、「ｐｐｍ」は「parts-per-million（１０－６）」を意味し、「ｐｐｂ」は「parts-per-billion（１０－９）」を意味する。
　本明細書において、記載の化合物は、特に制限がない場合、異性体（原子数が同じであるが構造が異なる化合物）、光学異性体、及び、同位体を含んでいてもよい。また、異性体及び同位体は、１種のみを含んでいてもよいし、複数種を含んでいてもよい。 In the present specification, when a certain component is present in two or more kinds, the "content" of the component means the total content of the two or more kinds of components.
As used herein, "ppm" means "parts-per-million ( 10-6 )" and "ppb" means "parts-per-billion ( 10-9 )".
In the present specification, the described compounds may contain isomers (compounds having the same number of atoms but different structures), optical isomers, and isotopes, unless otherwise specified. Further, the isomers and isotopes may contain only one species, or may contain a plurality of species.
　本明細書において、ｐｓｉとは、ｐｏｕｎｄ－ｆｏｒｃｅ　ｐｅｒ　ｓｑｕａｒｅ　ｉｎｃｈ；重量ポンド毎平方インチを意図し、１ｐｓｉ＝６８９４．７６Ｐａを意図する。 In the present specification, psi is intended for pound-force per squaree inch; 1 psi = 6894.76 Pa for every pound-force per square inch.
　本明細書において、特に制限がない場合、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、ＴＳＫｇｅｌ　ＧＭＨｘＬ、ＴＳＫｇｅｌ　Ｇ４０００ＨｘＬ、又は、ＴＳＫｇｅｌ　Ｇ２０００ＨｘＬ（いずれも東ソー株式会社製の商品名）をカラムとして用い、ＴＨＦ（テトラヒドロフラン）を溶離液として用い、示差屈折計を検出器として用い、ポリスチレンを標準物質として用い、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）分析装置により測定した標準物質のポリスチレンを用いて換算した値である。
　本明細書において、特に制限がない場合、分子量分布が有する化合物の分子量は、重量平均分子量である。 In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are TSKgel GMHxL, TSKgel G4000HxL, or TSKgel G2000HxL (both are trade names manufactured by Toso Co., Ltd.) as columns. Value converted using polystyrene, which is a standard material measured by a gel permeation chromatography (GPC) analyzer, using THF (tetrahydrogen) as an eluent, a differential refractometer as a detector, and polystyrene as a standard material. Is.
In the present specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight.
［半導体基板用洗浄液］
　本発明の半導体基板用洗浄液（以下「洗浄液」ともいう。）は、半導体基板を洗浄するために用いられる洗浄液であって、後述する所定の重合体、アルカノールアミン、所定量の酸基を有する錯化剤、及び、水を含み、洗浄液のｐＨが７．０未満である。 [Cleaning liquid for semiconductor substrates]
The cleaning liquid for a semiconductor substrate (hereinafter, also referred to as "cleaning liquid") of the present invention is a cleaning liquid used for cleaning a semiconductor substrate, and has a predetermined polymer, an alkanolamine, and a predetermined amount of acid groups, which will be described later. It contains an agent and water, and the pH of the cleaning solution is less than 7.0.
　上記構成によって本発明の課題が解決されるメカニズムは明らかではないが、上記各成分が協調的に作用し、所望の効果が得られたと推測される。
　重合体、アルカノールアミン、及び、酸基を有する錯化剤が、ＣＭＰ処理後の半導体基板表面の残存物と相互作用することで、洗浄性能の向上、及び、腐食抑制性能の向上に寄与したと推測される。
　以下、洗浄液の、ＣＭＰ処理後のタングステンを含む金属膜を有する半導体基板に対する洗浄性能、及び、タングステンを含む金属膜を洗浄した際のタングステンに対する腐食抑制性能の少なくとも一方の性能がより優れることを、本発明の効果がより優れるともいう。 The mechanism by which the above-mentioned configuration solves the problem of the present invention is not clear, but it is presumed that the above-mentioned components act cooperatively to obtain a desired effect.
It is said that the polymer, alkanolamine, and complexing agent having an acid group interact with the residue on the surface of the semiconductor substrate after the CMP treatment, thereby contributing to the improvement of cleaning performance and corrosion suppression performance. Guessed.
Hereinafter, the cleaning performance of the cleaning liquid for a semiconductor substrate having a metal film containing tungsten after CMP treatment and the corrosion suppressing performance for tungsten when cleaning the metal film containing tungsten are more excellent. It is also said that the effect of the present invention is superior.
〔ｐＨ〕
　洗浄液のｐＨは、７．０未満である。
　なかでも、本発明の効果がより優れる点で、洗浄液のｐＨとしては、０．１～６．９が好ましく、１．０～６．９がより好ましく、２．０～６．９が更に好ましく、２．５～６．０が特に好ましく、５．０～６．５が最も好ましい。
　洗浄液のｐＨは、公知のｐＨメーターを用いてＪＩＳ　Ｚ８８０２－１９８４に準拠した方法により測定できる。上記ｐＨは、測定温度２５℃における値である。 [PH]
The pH of the cleaning solution is less than 7.0.
Among them, the pH of the cleaning liquid is preferably 0.1 to 6.9, more preferably 1.0 to 6.9, and even more preferably 2.0 to 6.9 in that the effect of the present invention is more excellent. , 2.5 to 6.0 are particularly preferable, and 5.0 to 6.5 are most preferable.
The pH of the washing liquid can be measured by a method according to JIS Z8802-1984 using a known pH meter. The pH is a value at a measurement temperature of 25 ° C.
　以下、洗浄液に含まれる各成分について説明する。 Hereinafter, each component contained in the cleaning liquid will be described.
〔重合体〕
　洗浄液は、重合体を含む。
　重合体の重量平均分子量（Ｍｗ）は、２０００～９０００００であり、本発明の効果がより優れる点で、２０００～８０００００が好ましく、２０００～５０００００がより好ましく、２０００～５００００が更に好ましく、２０００～３００００が特に好ましい。
　重量平均分子量の値は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によって測定されたポリエチレングリコール換算の重量平均分子量の値である。 [Polymer]
The cleaning liquid contains a polymer.
The weight average molecular weight (Mw) of the polymer is 2000 to 900,000, and 2000 to 800,000 is preferable, 2000 to 500,000 is more preferable, 2000 to 50000 is further preferable, and 2000 to 30000 is more preferable in that the effect of the present invention is more excellent. Is particularly preferable.
The value of the weight average molecular weight is the value of the weight average molecular weight in terms of polyethylene glycol measured by GPC (gel permeation chromatography).
　重合体としては、水溶性重合体が好ましい。
　「水溶性重合体」とは、２以上の構造単位が、線状又は網目状に共有結合を介して連なった化合物であって、２０℃の水１００ｇに溶解する重合体の質量が０．１ｇ以上である化合物を意図する。
　水溶性重合体を含む場合、金属膜を有する基板、又は、研磨スラリーに含まれる研磨微粒子（例えば、シリカ及びアルミナ等）と相互作用することで、洗浄液の洗浄性能が向上する。 As the polymer, a water-soluble polymer is preferable.
The "water-soluble polymer" is a compound in which two or more structural units are connected in a linear or network shape via covalent bonds, and the mass of the polymer dissolved in 100 g of water at 20 ° C. is 0.1 g. The above compounds are intended.
When the water-soluble polymer is contained, the cleaning performance of the cleaning liquid is improved by interacting with the substrate having a metal film or the polishing fine particles (for example, silica and alumina) contained in the polishing slurry.
　水溶性重合体としては、例えば、ポリアクリル酸、ポリメタクリル酸、ポリマレイン酸、ポリビニルスルホン酸、ポリアリルスルホン酸、ポリスチレンスルホン酸、及び、これらの塩；スチレン、α－メチルスチレン、及び／又は、４－メチルスチレン等の単量体と、（メタ）アクリル酸、及び／又は、マレイン酸等の酸の単量体との共重合体、及び、これらの塩；（メタ）アクリル酸と、マレイン酸との共重合体、及び、これらの塩：ベンゼンスルホン酸、及び／又は、ナフタレンスルホン酸等をホルマリンで縮合させた芳香族炭化水素基を有する構造単位を有する重合体、及び、これらの塩；ポリビニルアルコール、ポリオキシエチレン、ポリビニルピロリドン、ポリビニルピリジン、ポリアクリルアミド、ポリビニルホルムアミド、ポリエチレンイミン、ポリビニルオキサゾリン、ポリビニルイミダゾール、及び、ポリアリルアミン等のビニル系合成重合体；ヒドロキシエチルセルロース、カルボキシメチルセルロース、及び、加工澱粉等の天然多糖類の変性物が挙げられる。
　なかでも、水溶性重合体としては、酸基（例えば、カルボキシ基、リン酸基、及び、スルホン酸基）を有する重合体が好ましく、ポリアクリル酸、ポリマレイン酸、スチレンと（メタ）アクリル酸、及び／又は、マレイン酸等の酸の単量体との共重合体、（メタ）アクリル酸とマレイン酸との共重合体、又は、これらの塩がより好ましい。 Examples of the water-soluble polymer include polyacrylic acid, polymethacrylic acid, polymaleic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polystyrene sulfonic acid, and salts thereof; styrene, α-methylstyrene, and / or. Polymers of monomers such as 4-methylstyrene and monomers of (meth) acrylic acid and / or acids such as maleic acid and salts thereof; (meth) acrylic acid and malein. Polymers with acids and salts thereof: benzenesulfonic acid and / or polymers having structural units having aromatic hydrocarbon groups condensed with naphthalenesulfonic acid and the like with formalin, and salts thereof. Vinyl-based synthetic polymers such as polyvinyl alcohol, polyoxyethylene, polyvinylpyrrolidone, polyvinylpyridine, polyacrylamide, polyvinylformamide, polyethyleneimine, polyvinyloxazoline, polyvinylimidazole, and polyallylamine; hydroxyethylcellulose, carboxymethylcellulose, and processing. Examples thereof include modified products of natural polysaccharides such as starch.
Among them, as the water-soluble polymer, a polymer having an acid group (for example, a carboxy group, a phosphoric acid group, and a sulfonic acid group) is preferable, and polyacrylic acid, polymaleic acid, styrene and (meth) acrylic acid, And / or a polymer with an acid monomer such as maleic acid, a copolymer of (meth) acrylic acid with maleic acid, or salts thereof are more preferred.
　水溶性重合体は、ホモ重合体であっても、２種以上の単量体を共重合させた共重合体であってもよい。
　上記単量体としては、例えば、カルボキシ基を有する単量体、スルホン酸基を有する単量体、ヒドロキシル基を有する単量体、ポリエチレンオキシド鎖を有する単量体、アミノ基を有する単量体、及び、複素環を有する単量体からなる群から選択される単量体が挙げられる。
　水溶性重合体としては、実質的に、上記群から選択される単量体に由来する構造単位のみからなる重合体が好ましい。水溶性重合体が、実質的に、上記群から選択される単量体に由来する構造単位のみであるとは、例えば、上記群から選択される単量体に由来する構造単位の含有量が、重合体の全質量に対して、９５～１００質量％（９９～１００質量％が好ましい）であることを意味する。 The water-soluble polymer may be a homopolymer or a copolymer obtained by copolymerizing two or more kinds of monomers.
Examples of the monomer include a monomer having a carboxy group, a monomer having a sulfonic acid group, a monomer having a hydroxyl group, a monomer having a polyethylene oxide chain, and a monomer having an amino group. , And a monomer selected from the group consisting of monomers having a heterocycle.
As the water-soluble polymer, a polymer consisting substantially only of structural units derived from the monomers selected from the above group is preferable. The fact that the water-soluble polymer is substantially only the structural unit derived from the monomer selected from the above group means that, for example, the content of the structural unit derived from the monomer selected from the above group is It means that it is 95 to 100% by mass (preferably 99 to 100% by mass) with respect to the total mass of the polymer.
　重合体は、カルボキシ基を有する構造単位（（メタ）アクリル酸に由来する構造単位等）を有することが好ましい。
　カルボキシ基を有する構造単位の含有量は、重合体の全質量に対して、３０～１００質量％が好ましく、７０～１００質量％がより好ましく、８５～１００質量％が更に好ましい。 The polymer preferably has a structural unit having a carboxy group (a structural unit derived from (meth) acrylic acid, etc.).
The content of the structural unit having a carboxy group is preferably 30 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 85 to 100% by mass, based on the total mass of the polymer.
　重合体としては、例えば、特開２０１６－１７１２９４号公報の段落［００４３］～［００４７］に記載の水溶性重合体も挙げられ、これらの内容は本明細書に組み込まれる。 Examples of the polymer include water-soluble polymers described in paragraphs [0043] to [0047] of JP-A-2016-171294, and the contents thereof are incorporated in the present specification.
　重合体は、１種単独で使用してもよく、２種以上を使用してもよい。
　重合体の含有量は、洗浄液の全質量に対して、０．０１～１０質量％が好ましく、０．０５～３質量％がより好ましく、０．５～２質量％が更に好ましい。
　重合体の含有量が上記範囲内である場合、重合体が基板の表面に適度に吸着して洗浄液の腐食抑制性能の向上に寄与でき、かつ、洗浄液の粘度及び／又は洗浄性能のバランスも良好にできる。
　重合体の含有量は、溶媒を除いた洗浄液の全質量に対して、１．０～４５．０質量％が好ましく、１０．０～４５．０質量％がより好ましく、１０．０～４０．０質量％が更に好ましい。 The polymer may be used alone or in combination of two or more.
The content of the polymer is preferably 0.01 to 10% by mass, more preferably 0.05 to 3% by mass, still more preferably 0.5 to 2% by mass, based on the total mass of the washing liquid.
When the content of the polymer is within the above range, the polymer is appropriately adsorbed on the surface of the substrate and can contribute to the improvement of the corrosion suppressing performance of the cleaning liquid, and the viscosity and / or the cleaning performance of the cleaning liquid is well balanced. Can be done.
The content of the polymer is preferably 1.0 to 45.0% by mass, more preferably 10.0 to 45.0% by mass, and 10.0 to 40% by mass with respect to the total mass of the washing liquid excluding the solvent. 0% by mass is more preferable.
〔アルカノールアミン〕
　洗浄液は、アルカノールアミンを含む。
　アルカノールアミンは、第１級アミノ基～第３級アミノ基のうち少なくとも１つを有し、分子内にヒドロキシル基を少なくとも１つ（ヒドロキシアルキル基が好ましい）を更に有する化合物である。
　アルカノールアミンは、後述する第４級アンモニウム化合物を含まない。 [Alkanolamine]
The cleaning solution contains an alkanolamine.
The alkanolamine is a compound having at least one of a primary amino group to a tertiary amino group and further having at least one hydroxyl group (preferably a hydroxyalkyl group) in the molecule.
Alkanolamines do not contain the quaternary ammonium compounds described below.
　アルカノールアミンが有するヒドロキシル基の数は、１～５が好ましく、１～３がより好ましく、１～２が更に好ましい。
　アルカノールアミンが有する第１級アミノ基～第３級アミノ基の合計の数は、１～５が好ましく、１～３がより好ましく、１が更に好ましい。
　また、アルカノールアミンは、第１級アミノ基～第３級アミノ基のいずれかを有することが好ましく、第１級アミノ基、及び、第２級アミノ基のいずれかを有することがより好ましく、第１級アミノ基を有することが更に好ましい。 The number of hydroxyl groups contained in the alkanolamine is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1 to 2.
The total number of primary amino groups to tertiary amino groups contained in the alkanolamine is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.
Further, the alkanolamine preferably has any of a primary amino group to a tertiary amino group, and more preferably has any of a primary amino group and a secondary amino group. It is more preferable to have a primary amino group.
　アルカノールアミンとしては、式（Ａ）で表される化合物が好ましい。 As the alkanolamine, the compound represented by the formula (A) is preferable.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　式（Ａ）中、Ｒａ１及びＲａ２は、それぞれ独立に、水素原子又はヒドロキシル基を有していてもよいアルキル基を表す。
　上記アルキル基は、直鎖状又は分岐鎖状であってもよい。
　上記アルキル基の炭素数は、１～１０が好ましく、１～５がより好ましく、１～３が更に好ましい。
　上記アルキル基が有するヒドロキシル基の数は、１～５が好ましく、１～３がより好ましく、１が更に好ましい。 In the formula (A), Ra1 and Ra2 each independently represent an alkyl group which may have a hydrogen atom or a hydroxyl group.
The alkyl group may be linear or branched.
The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
The number of hydroxyl groups contained in the alkyl group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1.
　Ｌａ１は、ヒドロキシル基を有していてもよいアルキレン基を表す。
　上記アルキレン基は、直鎖状又は分岐鎖状であってもよい。
　上記アルキレン基の炭素数は、１～１０が好ましく、１～５がより好ましく、１～４が更に好ましく、１～３が特に好ましい。
　上記アルキレン基が有するヒドロキシル基の数は、１～５が好ましく、１～３がより好ましく、０が更に好ましい。 La1 represents an alkylene group which may have a hydroxyl group.
The alkylene group may be linear or branched.
The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
The number of hydroxyl groups contained in the alkylene group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 0.
　アルカノールアミンとしては、例えば、モノエタノールアミン（ＭＥＡ）、ジエタノールアミン（ＤＥＡ）、トリエタノールアミン（ＴＥＡ）、トリス（ヒドロキシメチル)アミノメタン、Ｎ－メチルエタノールアミン、Ｎ－メチル－Ｎ，Ｎ－ジエタノールアミン、Ｎ，Ｎ－ジメチルエタノールアミン、Ｎ，Ｎ－ジエチルエタノールアミン、Ｎ，Ｎ－ジブチルエタノールアミン、Ｎ－（β－アミノエチル）エタノールアミン、Ｎ－エチルエタノールアミン、モノプロパノールアミン、ジプロパノールアミン、トリプロパノールアミン、イソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、２－アミノ－２－メチル－１－プロパノール、２－（ジメチルアミノ）－２－メチル－１－プロパノール、及び、ジメチルモノエタノールアミンが挙げられる。
　なかでも、アルカノールアミンは、イソプロパノールアミン、モノエタノールアミン（ＭＥＡ）、ジエタノールアミン（ＤＥＡ）、トリエタノールアミン（ＴＥＡ）、トリス（ヒドロキシメチル)アミノメタン、Ｎ－エチルエタノールアミン、モノプロパノールアミン、トリイソプロパノールアミン、Ｎ－メチルエタノールアミン、２－アミノ－２－メチル－１－プロパノール、及び、２－（ジメチルアミノ）－２－メチル－１－プロパノールからなる群から選択される少なくとも１つを含むことが好ましく、モノエタノールアミン、イソプロパノールアミン、及び、トリスヒドロキシメチルアミノメタンからなる群から選択される少なくとも１つを含むことがより好ましく、イソプロパノールアミンを含むことが更に好ましい。 Examples of the alkanolamine include monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), tris (hydroxymethyl) aminomethane, N-methylethanolamine, N-methyl-N, N-diethanolamine, and the like. N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, N- (β-aminoethyl) ethanolamine, N-ethylethanolamine, monopropanolamine, dipropanolamine, tri Examples thereof include propanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-2-methyl-1-propanol, 2- (dimethylamino) -2-methyl-1-propanol, and dimethylmonoethanolamine. ..
Among them, alkanolamines are isopropanolamine, monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), tris (hydroxymethyl) aminomethane, N-ethylethanolamine, monopropanolamine and triisopropanolamine. , N-Methylethanolamine, 2-amino-2-methyl-1-propanol, and 2- (dimethylamino) -2-methyl-1-propanol, preferably at least one selected from the group. , Monoethanolamine, isopropanolamine, and at least one selected from the group consisting of trishydroxymethylaminomethane, more preferably, and even more preferably isopropanolamine.
　アルカノールアミンのｐＫａ（酸解離定数）は、洗浄液の経時安定性が優れる点から、５．００～２０．００が好ましく、７．５０～１５．００がより好ましく、９．００～１４．５０が更に好ましい。
　２つ以上のアルカノールアミンを含む場合、少なくとも１つのアルカノールアミンが上記ｐＫａの範囲を満たすことが好ましく、含有量が最も大きいアルカノールアミンが上記ｐＫａの範囲を満たすことがより好ましく、アルカノールアミンの全質量に対して、５０質量％以上含まれるアルカノールアミンがｐＫａの範囲を満たすことが更に好ましい。
　ｐＫａとは、ＳＣ－Ｄａｔａｂａｓｅ（http://acadsoft.co.uk/scdbase/SCDB_software/scdb_download.htm）を用いて求められる値である。 The pKa (acid dissociation constant) of the alkanolamine is preferably 5.00 to 20.00, more preferably 7.50 to 15.00, and 9.00 to 14.50 from the viewpoint of excellent stability of the washing solution over time. More preferred.
When two or more alkanolamines are contained, it is preferable that at least one alkanolamine satisfies the above pKa range, more preferably the alkanolamine having the highest content satisfies the above pKa range, and the total mass of the alkanolamine. On the other hand, it is more preferable that the alkanolamine contained in an amount of 50% by mass or more satisfies the range of pKa.
pKa is a value obtained by using SC-Database (http://acadsoft.co.uk/scdbase/SCDB_software/scdb_download.htm).
　アルカノールアミンのＣｌｏｇＰ値は、－５．００～１．００が好ましく、－２．００～１．００がより好ましく、－１．００～１．００が更に好ましい。
　本明細書において、ＣｌｏｇＰ値とは、１－オクタノールと水への分配係数Ｐの常用対数ｌｏｇＰを計算によって求められる値である。ＣｌｏｇＰ値の計算に用いる方法及びソフトウェアは、公知の物を使用できる。本明細書において、特に制限がない場合、Ｃｌｏｇ値は、Ｃａｍｂｒｉｄｇｅｓｏｆｔ社のＣｈｅｍＢｉｏＤｒａｗＵｌｔｒａ１２．０に組み込まれたＣｌｏｇＰプログラムを用いた値である。 The ClogP value of the alkanolamine is preferably -5.00 to 1.00, more preferably -2.00 to 1.00, and even more preferably -1.00 to 1.00.
As used herein, the LogP value is a value obtained by calculating the common logarithm logP of 1-octanol and the partition coefficient P to water. As the method and software used for calculating the ClogP value, known ones can be used. In the present specification, unless otherwise specified, the Clog value is a value using the ClogP program incorporated in ChemBioDrowUltra12.0 of Cambridgest.
　アルカノールアミンは、１種単独で使用してもよく、２種以上を使用してもよい。
　アルカノールアミンの含有量は、洗浄液の性能がバランスよく優れる点から、洗浄液の全質量に対して、０．０１～１０．０質量％が好ましく、０．０１～７．０質量％がより好ましく、０．０１～５．０質量％が更に好ましく、０．０１～３．０質量％が特に好ましく、０．０１～２．０質量％が最も好ましい。
　アルカノールアミンの含有量は、溶媒を除いた洗浄液の全質量に対して、０．０１～３０．０質量％が好ましく、０．１～３０．０質量％がより好ましく、１．０～３０．０質量％が更に好ましく、１．０～２５．０質量％が特に好ましい。 The alkanolamine may be used alone or in combination of two or more.
The content of alkanolamine is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 7.0% by mass, based on the total mass of the cleaning liquid, because the performance of the cleaning liquid is well-balanced. 0.01 to 5.0% by mass is more preferable, 0.01 to 3.0% by mass is particularly preferable, and 0.01 to 2.0% by mass is most preferable.
The content of alkanolamine is preferably 0.01 to 30.0% by mass, more preferably 0.1 to 30.0% by mass, and 1.0 to 30% with respect to the total mass of the cleaning liquid excluding the solvent. 0% by mass is more preferable, and 1.0 to 25.0% by mass is particularly preferable.
〔酸基を有する錯化剤〕
　洗浄液は、酸基を有する錯化剤（以下「特定錯化剤」ともいう。）を含む。
　特定錯化剤とは、酸基を有し、金属イオンと結合して錯イオンを形成する化合物である。特定錯化剤は、上述した洗浄液に含まれる成分、後述する界面活性剤、防食剤、防腐剤、及び、ｐＨ調整剤とは異なる化合物である。
　特定錯化剤の含有量は、洗浄液の全質量に対して、２．５質量％以上２０．０質量％未満であり、洗浄性能が向上する点から、２．５～１８．５質量％が好ましく、２．５～１５．０質量％がより好ましく、２．５～１０．０質量％が更に好ましく、３．０～１０．０質量％が特に好ましく、３．０～４．０質量％が最も好ましい。
　特定錯化剤の含有量は、溶媒を除いた洗浄液の全質量に対して、４５．０～９８．０質量％が好ましく、５０．０～９５．０質量％がより好ましく、５０．０～９０．０質量％が更に好ましく、５０．０～８５．０質量％が特に好ましく、５０．０～７０．０質量％が最も好ましい。 [Complex agent with acid group]
The cleaning liquid contains a complexing agent having an acid group (hereinafter, also referred to as "specific complexing agent").
The specific complexing agent is a compound having an acid group and binding to a metal ion to form a complex ion. The specific complexing agent is a compound different from the components contained in the cleaning liquid described above, the surfactant, the anticorrosive agent, the preservative, and the pH adjuster described later.
The content of the specific complexing agent is 2.5% by mass or more and less than 20.0% by mass with respect to the total mass of the cleaning liquid, and 2.5 to 18.5% by mass is used from the viewpoint of improving the cleaning performance. Preferably, 2.5 to 15.0% by mass is more preferable, 2.5 to 10.0% by mass is further preferable, 3.0 to 10.0% by mass is particularly preferable, and 3.0 to 4.0% by mass is particularly preferable. Is the most preferable.
The content of the specific complexing agent is preferably 45.0 to 98.0% by mass, more preferably 50.0 to 95.0% by mass, and 50.0 to 50.0 to 98.0% by mass with respect to the total mass of the cleaning liquid excluding the solvent. 90.0% by mass is more preferable, 50.0 to 85.0% by mass is particularly preferable, and 50.0 to 70.0% by mass is most preferable.
　特定錯化剤が有する酸基としては、例えば、カルボキシ基、リン酸基、スルホン酸基、ホスホン酸基、スルフィン酸基、及び、スルフェン酸基が挙げられる。
　なかでも、上記特定錯化剤は、カルボキシ基、リン酸基、ホスホン酸基、及び、スルホン酸基からなる群から選択される少なくとも１つを有することが好ましく、カルボキシ基、ホスホン酸基、及び、スルホン酸からなる群から選択される少なくとも１つを有することがより好ましく、カルボキシ基を有することが更に好ましい。
　また、特定錯化剤は、カルボキシ基、リン酸基、ホスホン酸基、及び、スルホン酸基のいずれかを有することも好ましい。
　特定錯化剤が有する酸基の数は、１～１０が好ましく、１～７がより好ましく、１～６が更に好ましく、１～４が特に好ましい。 Examples of the acid group contained in the specific complexing agent include a carboxy group, a phosphoric acid group, a sulfonic acid group, a phosphonic acid group, a sulfinic acid group, and a sulfenic acid group.
Among them, the specific complexing agent preferably has at least one selected from the group consisting of a carboxy group, a phosphoric acid group, a phosphonic acid group, and a sulfonic acid group, and preferably has a carboxy group, a phosphonic acid group, and a sulfonic acid group. , It is more preferable to have at least one selected from the group consisting of sulfonic acid, and it is further preferable to have a carboxy group.
Further, the specific complexing agent preferably has any one of a carboxy group, a phosphoric acid group, a phosphonic acid group, and a sulfonic acid group.
The number of acid groups contained in the specific complexing agent is preferably 1 to 10, more preferably 1 to 7, further preferably 1 to 6, and particularly preferably 1 to 4.
＜カルボキシ基を有する錯化剤＞
　カルボキシ基を有する錯化剤は、分子内に少なくとも１つのカルボキシ基を有する錯化剤である。
　カルボキシ基を有する特定錯化剤としては、例えば、アミノポリカルボン酸、アミノ酸、脂肪族カルボン酸、及び、芳香族カルボン酸が挙げられる。
　なかでも、カルボキシ基を有する特定錯化剤としては、アミノポリカルボン酸、又は、アミノ酸が好ましく、アミノポリカルボン酸がより好ましい。
　特定錯化剤がアミノ酸を含む場合、アミノ酸は、分子内に配位部と親水部とが存在するため、金属膜を有する基板若しくは研磨スラリーに含まれる研磨微粒子（例えば、シリカ、アルミナ等）に配位しやすく、又は、アミノ酸が研磨微粒子に配位することで、研磨微粒子の表面が親水化して効率的に研磨微粒子を除去できる。
　上記特定錯化剤が有するカルボキシ基の数は、１～１０が好ましく、１～５がより好ましく、１～４が更に好ましい。 <Coordinating agent with carboxy group>
A complexing agent having a carboxy group is a complexing agent having at least one carboxy group in the molecule.
Examples of the specific complexing agent having a carboxy group include aminopolycarboxylic acid, amino acid, aliphatic carboxylic acid, and aromatic carboxylic acid.
Among them, as the specific complexing agent having a carboxy group, an aminopolycarboxylic acid or an amino acid is preferable, and an aminopolycarboxylic acid is more preferable.
When the specific complexing agent contains an amino acid, the amino acid has a coordination portion and a hydrophilic portion in the molecule, so that the amino acid is applied to the abrasive fine particles (for example, silica, alumina, etc.) contained in the substrate having a metal film or the polishing slurry. By easily coordinating or by coordinating amino acids to the abrasive fine particles, the surface of the abrasive fine particles becomes hydrophilic and the abrasive fine particles can be efficiently removed.
The number of carboxy groups contained in the specific complexing agent is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 4.
　アミノポリカルボン酸としては、式（Ｂ１）で表される化合物が好ましい。 As the aminopolycarboxylic acid, a compound represented by the formula (B1) is preferable.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　ｎ１は、１～１０の整数を表す。
　なかでも、ｎ１としては、１～５の整数が好ましく、１～３の整数がより好ましく、２～３の整数が更に好ましい。 n 1 represents an integer from 1 to 10.
Among them, as n 1 , an integer of 1 to 5 is preferable, an integer of 1 to 3 is more preferable, and an integer of 2 to 3 is further preferable.
　アミノポリカルボン酸としては、例えば、ニトリロ三酢酸、ブチレンジアミン四酢酸、ジエチレントリアミン五酢酸（ＤＴＰＡ）、エチレンジアミンテトラプロピオン酸、トリエチレンテトラミン六酢酸、１，３－ジアミノ－２－ヒドロキシプロパン－Ｎ，Ｎ，Ｎ’，Ｎ’－四酢酸、プロピレンジアミン四酢酸、エチレンジアミン四酢酸（ＥＤＴＡ）、トランス－１，２－ジアミノシクロヘキサン四酢酸、エチレンジアミン二酢酸、エチレンジアミンジプロピオン酸、１，６－ヘキサメチレン－ジアミン－Ｎ，Ｎ，Ｎ’，Ｎ’－四酢酸、Ｎ，Ｎ－ビス（２－ヒドロキシベンジル）エチレンジアミン－Ｎ，Ｎ－二酢酸、ジアミノプロパン四酢酸、１，４，７，１０－テトラアザシクロドデカン－四酢酸、ジアミノプロパノール四酢酸、（ヒドロキシエチル）エチレンジアミン三酢酸、及び、イミノジ酢酸（ＩＤＡ）が挙げられる。
　なかでも、アミノポリカルボン酸としては、ＤＴＰＡ又はＥＤＴＡが好ましい。 Examples of the aminopolycarboxylic acid include nitrilotriacetic acid, butylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraminehexacacetic acid, 1,3-diamino-2-hydroxypropane-N, N. , N', N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid, ethylenediaminediaminetetraacetic acid, ethylenediaminediaminepropionic acid, 1,6-hexamethylene-diamine -N, N, N', N'-tetraacetic acid, N, N-bis (2-hydroxybenzyl) ethylenediamine-N, N-diacetate, diaminopropanetetraacetic acid, 1,4,7,10-tetraazacyclo Included are dodecane-tetraacetic acid, diaminopropanol tetraacetic acid, (hydroxyethyl) ethylenediaminetriacetic acid, and iminodiacetic acid (IDA).
Among them, DTPA or EDTA is preferable as the aminopolycarboxylic acid.
　アミノ酸としては、式（Ｂ２）で表される化合物が好ましく、式（Ｂ３）で表される化合物がより好ましい。 As the amino acid, the compound represented by the formula (B2) is preferable, and the compound represented by the formula (B3) is more preferable.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　式（Ｂ２）中、Ｒｂ１は、水素原子、又は、ヘテロ原子を有していてもよい炭化水素基を表す。
　上記炭化水素基は、直鎖状、分岐鎖状、又は、環状（単環又は多環であってもよい）であってもよい。
　上記炭化水素基の炭素数は、１～２０が好ましく、１～１０がより好ましく、１～５が更に好ましい。
　上記炭化水素基としては、例えば、脂肪族炭化水素基及び芳香族炭化水素基が挙げられる。
　上記炭化水素基としては、ヘテロ原子を有していてもよい、アルキル基、アルケニル基、アルキレン基、又は、アリール基が好ましく、ヘテロ原子を有していてもよいアルキル基がより好ましい。 In formula (B2), R b1 represents a hydrocarbon group which may have a hydrogen atom or a hetero atom.
The hydrocarbon group may be linear, branched, or cyclic (may be monocyclic or polycyclic).
The hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms.
Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
As the hydrocarbon group, an alkyl group, an alkenyl group, an alkylene group, or an aryl group which may have a heteroatom is preferable, and an alkyl group which may have a heteroatom is more preferable.
　Ｒｂ２及びＲｂ３は、それぞれ独立に、水素原子又はヒドロキシアルキル基を表す。
　上記ヒドロキシルアルキル基（ヒドロキシ基を有するアルキル基）の炭素数は、１～１０が好ましく、１～５がより好ましく、１～３が更に好ましい。
　上記ヒドロキシルアルキル基としては、例えば、ヒドロキシエチル基、ヒドロキシプロピル基、ヒドロキシブチル基、ヒドロキシペンチル基、及び、ヒドロキシヘキシル基が挙げられる。なかでも、ヒドロキシエチル基が好ましい。 R b2 and R b3 independently represent a hydrogen atom or a hydroxyalkyl group, respectively.
The hydroxyl alkyl group (alkyl group having a hydroxy group) has preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms.
Examples of the hydroxylalkyl group include a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group, a hydroxypentyl group, and a hydroxyhexyl group. Of these, a hydroxyethyl group is preferable.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　Ｒｂ４は、水素原子、ヒドロキシル基、カルボキシ基、又は、－ＳＲｂ７を表す。
　Ｒｂ７は、水素原子又はアルキル基を表す。
　上記アルキル基は、直鎖状、分岐鎖状、又は、環状であってもよい。
　上記アルキル基の炭素数は、１～１０が好ましく、１～５がより好ましく、１～３が更に好ましく、メチル基が特に好ましい。 R b4 represents a hydrogen atom, a hydroxyl group, a carboxy group, or -SR b7 .
R b7 represents a hydrogen atom or an alkyl group.
The alkyl group may be linear, branched or cyclic.
The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably a methyl group.
　Ｌｂ１は、単結合又はアルキレン基を表す。
　上記アルキレン基は、直鎖状、分岐鎖状、又は、環状であってもよい。
　上記アルキレン基の炭素数は、１～１０が好ましく、１～５がより好ましく、１～３が更に好ましい。 L b1 represents a single bond or an alkylene group.
The alkylene group may be linear, branched, or cyclic.
The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms.
　Ｒｂ５及びＲｂ６は、上述した式（Ｂ２）中、Ｒｂ２及びＲｂ３と同義であり、好適範囲も同じである。 R b5 and R b6 are synonymous with R b2 and R b3 in the above-mentioned formula (B2), and the preferable range is also the same.
　アミノ酸としては、例えば、アラニン（２－アミノプロピオン酸又は３－アミノプロピオン酸）、アルギニン、アスパラギン、アスパラギン酸、シスチン、システイン、グルタミン、グルタミン酸、グリシン又はその誘導体、イソロイシン、ロイシン、リシン、メチオニン、フェニルアラニン、セリン、エチオニン、トレオニン、チロシン、バリン、トリプトファン、ヒスチジン又はその誘導体、２－アミノ－３－アミノプロパン酸、及び、プロリンが挙げられる。
　アミノ酸としては、特開２０１６－０８６０９４号公報の段落［００２１］～［００２３］に記載の化合物も挙げられる。
　グリシン誘導体としては、Ｎ，Ｎ－ジ（２－ヒドロキシエチル）グリシンが挙げられる。
　ヒスチジン誘導体としては、特開２０１５－１６５５６１号公報、及び、特開２０１５－１６５５６２号公報等に記載の化合物が援用でき、これらの内容は、本明細書に組み込まれる。
　なかでも、アミノ酸は、セリン、アラニン、グリシン又はその誘導体、メチオニン、ヒスチジン又はその誘導体、アルギニン、グルタミン、アスパラギン、アスパラギン酸、グルタミン酸、及び、システインからなる群から選択される少なくとも１つを含むことが好ましく、セリン、アラニン、グリシン又はその誘導体、メチオニン、アスパラギン酸、グルタミン酸、及び、システインからなる群から選択される少なくとも１つを含むことがより好ましく、グリシン誘導体が更に好ましく、Ｎ，Ｎ－ビス（２－ヒドロキシエチル）グリシン（ＤＨＥＧ）が特に好ましい。 Examples of amino acids include alanine (2-aminopropionic acid or 3-aminopropionic acid), arginine, asparagine, aspartic acid, cystine, cysteine, glutamine, glutamic acid, glycine or its derivatives, isoleucine, leucine, lysine, methionine, phenylalanine. , Serin, etionin, threonine, tyrosine, valine, tryptophan, histidine or derivatives thereof, 2-amino-3-aminopropaneic acid, and proline.
Examples of the amino acid include the compounds described in paragraphs [0021] to [0023] of JP-A-2016-086094.
Examples of the glycine derivative include N, N-di (2-hydroxyethyl) glycine.
As the histidine derivative, the compounds described in JP-A-2015-165561 and JP-A-2015-165562 can be incorporated, and the contents thereof are incorporated in the present specification.
Among them, the amino acid may contain at least one selected from the group consisting of serine, alanine, glycine or a derivative thereof, methionine, histidine or a derivative thereof, arginine, glutamic acid, asparagine, aspartic acid, glutamic acid, and cysteine. It is more preferable to contain at least one selected from the group consisting of serine, alanine, glycine or a derivative thereof, methionine, aspartic acid, glutamic acid, and cysteine, and a glycine derivative is further preferable, and N, N-bis ( 2-Hydroxyethyl) glycine (DHEG) is particularly preferred.
　脂肪族カルボン酸は、分子内に、カルボキシ基と、脂肪族基とを有する化合物である。
　また、脂肪族カルボン酸は、ヒドロキシル基を更に有することが好ましい。 The aliphatic carboxylic acid is a compound having a carboxy group and an aliphatic group in the molecule.
Moreover, it is preferable that the aliphatic carboxylic acid further has a hydroxyl group.
　脂肪族カルボン酸としては、式（Ｂ４）で表される化合物が好ましい。 As the aliphatic carboxylic acid, a compound represented by the formula (B4) is preferable.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　式（Ｂ４）中、Ｌｂ２は、単結合又は２価の連結基を表す。
　Ｌｂ２で表される２価の連結基としては、例えば、エーテル基、カルボニル基、エステル基、チオエーテル基、－ＳＯ２－、－ＮＴ－（Ｔは、例えば、水素原子又はアルキル基等の置換基）、２価の炭化水素基（例えば、アルキレン基、アルケニレン基、アルキニレン基、及びアリーレン基）、及び、これらを組み合わせた基が挙げられる。
　上記２価の連結基は、直鎖状、分岐鎖状、又は、環状であってもよい。
　Ｌｂ２で表される２価の連結基は、更に置換基を有していてもよい。上記置換基としては、例えば、アルキル基、アリール基、ヒドロキシル基、カルボキシ基、アミノ基、及び、ハロゲン原子が挙げられる。
　なかでも、上記２価の連結基としては、単結合又は２価の炭化水素基が好ましく、アルキレン基がより好ましい。
　上記２価の連結基の炭素数は、１～１５が好ましく、１～１０がより好ましく、１～５が更に好ましい。 In formula (B4), L b2 represents a single bond or a divalent linking group.
Examples of the divalent linking group represented by L b2 include an ether group, a carbonyl group, an ester group, a thioether group, -SO 2- , and -NT- (T is a substitution of, for example, a hydrogen atom or an alkyl group). Group), a divalent hydrocarbon group (for example, an alkylene group, an alkenylene group, an alkynylene group, and an arylene group), and a group combining these groups can be mentioned.
The divalent linking group may be linear, branched or cyclic.
The divalent linking group represented by L b2 may further have a substituent. Examples of the substituent include an alkyl group, an aryl group, a hydroxyl group, a carboxy group, an amino group, and a halogen atom.
Among them, as the divalent linking group, a single bond or a divalent hydrocarbon group is preferable, and an alkylene group is more preferable.
The number of carbon atoms of the divalent linking group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5.
　脂肪族カルボン酸としては、例えば、グルコン酸、グリコール酸、グリセリン酸、クエン酸、マレイン酸、リンゴ酸、酒石酸、シュウ酸、マロン酸、及び、コハク酸が挙げられる。
　なかでも、脂肪族カルボン酸は、クエン酸、酒石酸、及び、コハク酸からなる群から選択される少なくとも１つ含むことが好ましい。 Examples of the aliphatic carboxylic acid include gluconic acid, glycolic acid, glyceric acid, citric acid, maleic acid, malic acid, tartaric acid, oxalic acid, malonic acid, and succinic acid.
Among them, the aliphatic carboxylic acid is preferably contained at least one selected from the group consisting of citric acid, tartaric acid, and succinic acid.
　芳香族カルボン酸は、分子内に、カルボキシ基と、芳香族基とを有する化合物である。
　芳香族カルボン酸としては、例えば、フェニル乳酸、ヒドロキシフェニル乳酸、及び、フェニルコハク酸が挙げられる。 Aromatic carboxylic acid is a compound having a carboxy group and an aromatic group in the molecule.
Examples of the aromatic carboxylic acid include phenyllactic acid, hydroxyphenyllactic acid, and phenylsuccinic acid.
＜リン酸基を有する錯化剤＞
　リン酸基を有する錯化剤は、分子内に、少なくとも１つのリン酸基を有する錯化剤である。
　リン酸基を有する錯化剤は、上述した錯化剤とは異なる化合物である。
　特定錯化剤が有するリン酸基の数は、１～１０が好ましく、２～８がより好ましく、４～７が更に好ましい。 <Complex agent with phosphoric acid group>
A complexing agent having a phosphoric acid group is a complexing agent having at least one phosphoric acid group in the molecule.
The complexing agent having a phosphoric acid group is a compound different from the above-mentioned complexing agent.
The number of phosphoric acid groups contained in the specific complexing agent is preferably 1 to 10, more preferably 2 to 8, and even more preferably 4 to 7.
　リン酸基を有する錯化剤としては、例えば、二リン酸、メタリン酸、及び、ヘキサメタリン酸等のポリリン酸、並びに、フィチン酸が挙げられる。
　なかでも、リン酸基を有する錯化剤としては、二リン酸、ヘキサメタリン酸、又は、フィチン酸が好ましく、フィチン酸がより好ましい。 Examples of the complexing agent having a phosphoric acid group include polyphosphoric acid such as diphosphoric acid, metaphosphoric acid, and hexametaphosphoric acid, and phytic acid.
Among them, as the complexing agent having a phosphoric acid group, diphosphate, hexametaphosphoric acid, or phytic acid is preferable, and phytic acid is more preferable.
＜スルホン酸基を有する錯化剤＞
　スルホン酸基を有する錯化剤は、分子内に少なくとも１つのスルホン酸基を有する錯化剤である。
　スルホン酸基を有する錯化剤は、上述した錯化剤とは異なる化合物である。
　上記特定錯化剤が有するスルホン酸基の数は、１～１０が好ましく、１～５がより好ましく、１～３が更に好ましい。 <Complex agent with sulfonic acid group>
A complexing agent having a sulfonic acid group is a complexing agent having at least one sulfonic acid group in the molecule.
The complexing agent having a sulfonic acid group is a compound different from the above-mentioned complexing agent.
The number of sulfonic acid groups contained in the specific complexing agent is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
　スルホン酸基を有する錯化剤としては、式（Ｃ）で表される化合物が好ましい。 As the complexing agent having a sulfonic acid group, a compound represented by the formula (C) is preferable.
　ＲＣ－ＳＯ３Ｈ　　式（Ｃ）
　式（Ｃ）中、ＲＣは、置換基を有していてもよい、アルキル基又はアリール基を表す。
　ＲＣで表される置換基を有していてもよいアルキル基としては、直鎖状、分岐鎖状、又は、環状（単環又は多環であってもよい）であってもよい。
　上記アルキル基の炭素数としては、１～１０が好ましく、１～５がより好ましく、１～３が更に好ましい。
　ＲＣで表される置換基を有していてもよいアリール基としては、単環、多環、又は、縮合環であってもよい。
　上記アリール基の炭素数としては、６～３０が好ましく、６～２０がより好ましく、６～１５が更に好ましく、６～８が特に好ましい。
　上記アルキル基及びアリール基が有する置換基としては、例えば、アルキル基、アリール基、ヒドロキシル基、カルボキシ基、アミノ基、及び、ハロゲン原子が挙げられ、アルキル基が好ましい。 RC -SO 3H formula (C)
In formula ( C ), RC represents an alkyl or aryl group which may have a substituent.
The alkyl group which may have a substituent represented by RC may be linear, branched or cyclic (may be monocyclic or polycyclic).
The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms.
The aryl group which may have a substituent represented by RC may be a monocyclic ring, a polycyclic ring, or a fused ring.
The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 8 carbon atoms.
Examples of the substituent having the alkyl group and the aryl group include an alkyl group, an aryl group, a hydroxyl group, a carboxy group, an amino group and a halogen atom, and an alkyl group is preferable.
　スルホン酸基を有する錯化剤として、例えば、ナフタレンスルホン酸、ｐ－トルエンスルホン酸、カンファースルホン酸、ベンゼンスルホン酸、メタンスルホン酸、及び、エタンスルホン酸が挙げられる。
　なかでも、スルホン酸基を有する錯化剤としては、ｐ－トルエンスルホン酸、メタンスルホン酸、又は、エタンスルホン酸が好ましい。 Examples of the complexing agent having a sulfonic acid group include naphthalene sulfonic acid, p-toluene sulfonic acid, camphor sulfonic acid, benzene sulfonic acid, methane sulfonic acid, and ethane sulfonic acid.
Among them, p-toluenesulfonic acid, methanesulfonic acid, or ethanesulfonic acid is preferable as the complexing agent having a sulfonic acid group.
＜ホスホン酸基を有する錯化剤＞
　ホスホン酸基を有する錯化剤は、分子内に少なくとも１つのホスホン酸基を有する錯化剤である。
　ホスホン酸基を有する錯化剤は、上述した錯化剤とは異なる化合物である。
　特定錯化剤が有するホスホン酸基の数は、１以上が好ましく、２以上がより好ましく、２～１０が更に好ましく、２～４が特に好ましく、２～３が最も好ましい。 <Complex agent with phosphonic acid group>
A complexing agent having a phosphonic acid group is a complexing agent having at least one phosphonic acid group in the molecule.
The complexing agent having a phosphonic acid group is a compound different from the complexing agent described above.
The number of phosphonic acid groups contained in the specific complexing agent is preferably 1 or more, more preferably 2 or more, further preferably 2 to 10, particularly preferably 2 to 4, and most preferably 2 to 3.
　ホスホン酸基を有する錯化剤としては、例えば、式（Ｐ１）で表される化合物、式（Ｐ２）で表される化合物、及び、式（Ｐ３）で表される化合物が挙げられる。 Examples of the complexing agent having a phosphonic acid group include a compound represented by the formula (P1), a compound represented by the formula (P2), and a compound represented by the formula (P3).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　式（Ｐ１）中、Ｘは、水素原子又はヒドロキシル基を表す。
　Ｘとしては、ヒドロキシル基が好ましい。 In formula (P1), X represents a hydrogen atom or a hydroxyl group.
As X, a hydroxyl group is preferable.
　Ｒ１１は、水素原子又は炭素数１～１０のアルキル基を表す。
　Ｒ１１で表される炭素数１～１０のアルキル基は、直鎖状、分岐鎖状、又は、環状であってもよい。
　Ｒ１１としては、炭素数１～６のアルキル基が好ましく、メチル基、エチル基、ｎ－プロピル基、又は、イソプロピル基がより好ましい。
　なお、本明細書に記載するアルキル基の具体例において、ｎ－はｎｏｒｍａｌ－体を表す。 R 11 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
The alkyl group having 1 to 10 carbon atoms represented by R 11 may be linear, branched or cyclic.
As R11, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is more preferable.
In the specific examples of the alkyl group described in the present specification, n- represents a normal-form.
　式（Ｐ１）で表される化合物としては、エチリデンジホスホン酸、１－ヒドロキシエチリデン－１，１’－ジホスホン酸（ＨＥＤＰＯ）、１－ヒドロキシプロピリデン－１，１’－ジホスホン酸、又は、１－ヒドロキシブチリデン－１，１’－ジホスホン酸が好ましい。 Examples of the compound represented by the formula (P1) include ethylidene diphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO), 1-hydroxypropyriden-1,1'-diphosphonic acid, or 1 -Hydroxybutylidene-1,1'-diphosphonic acid is preferred.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式（Ｐ２）中、Ｑは、水素原子又はＲ１３－ＰＯ３Ｈ２を表す。
　Ｑとしては、－Ｒ１３－ＰＯ３Ｈ２が好ましい。
　Ｒ１２及びＲ１３は、それぞれ独立に、アルキレン基を表す。
　Ｒ１２で表されるアルキレン基としては、例えば、炭素数１～１２のアルキレン基が挙げられる。
　上記アルキレン基は、直鎖状、分岐鎖状、又は、環状であってもよく、直鎖状又は分岐鎖状が好ましい。
　Ｒ１２で表されるアルキレン基としては、炭素数１～６のアルキレン基が好ましく、炭素数１～４のアルキレン基がより好ましく、エチレン基が更に好ましい。 In formula (P2), Q represents a hydrogen atom or R 13 -PO 3 H 2 .
As Q, -R 13 -PO 3 H 2 is preferable.
R 12 and R 13 each independently represent an alkylene group.
Examples of the alkylene group represented by R 12 include an alkylene group having 1 to 12 carbon atoms.
The alkylene group may be linear, branched or cyclic, and is preferably linear or branched.
As the alkylene group represented by R 12 , an alkylene group having 1 to 6 carbon atoms is preferable, an alkylene group having 1 to 4 carbon atoms is more preferable, and an ethylene group is further preferable.
　Ｒ１３で表されるアルキレン基としては、炭素数１～１０のアルキレン基が挙げられる。
　上記アルキレン基は、直鎖状、分岐鎖状、又は、環状であってもよく、直鎖状又は分岐鎖状が好ましい。
　上記アルキレン基としては、炭素数１～４のアルキレン基が好ましく、メチレン基又はエチレン基がより好ましく、メチレン基が更に好ましい。 Examples of the alkylene group represented by R 13 include an alkylene group having 1 to 10 carbon atoms.
The alkylene group may be linear, branched or cyclic, and is preferably linear or branched.
As the alkylene group, an alkylene group having 1 to 4 carbon atoms is preferable, a methylene group or an ethylene group is more preferable, and a methylene group is further preferable.
　Ｙは、水素原子、－Ｒ１３－ＰＯ３Ｈ２、又は、式（Ｐ４）で表される基を表す。
　Ｙとしては、－Ｒ１３－ＰＯ３Ｈ２又は式（Ｐ４）で表される基が好ましく、式（Ｐ４）で表される基がより好ましい。 Y represents a hydrogen atom, -R 13 -PO 3 H 2 , or a group represented by the formula (P4).
As Y, a group represented by -R 13 -PO 3 H 2 or the formula (P4) is preferable, and a group represented by the formula (P4) is more preferable.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　式（Ｐ４）中、Ｑ及びＲ１３は、式（Ｐ２）中、Ｑ及びＲ１３と同義である。 In formula (P4), Q and R 13 are synonymous with Q and R 13 in formula (P2).
　式（Ｐ２）で表される化合物としては、エチルアミノビス（メチレンホスホン酸）、ドデシルアミノビス（メチレンホスホン酸）、ニトリロトリス（メチレンホスホン酸）（ＮＴＰＯ）、エチレンジアミンビス（メチレンホスホン酸）（ＥＤＤＰＯ）、１，３－プロピレンジアミンビス（メチレンホスホン酸）、エチレンジアミンテトラ（メチレンホスホン酸）（ＥＤＴＰＯ）、エチレンジアミンテトラ（エチレンホスホン酸）、１，３－プロピレンジアミンテトラ（メチレンホスホン酸）（ＰＤＴＭＰ）、１，２－ジアミノプロパンテトラ（メチレンホスホン酸）、又は、１，６－ヘキサメチレンジアミンテトラ（メチレンホスホン酸）が好ましい。 Examples of the compound represented by the formula (P2) include ethylaminobis (methylenephosphonic acid), dodecylaminobis (methylenephosphonic acid), nitrilotris (methylenephosphonic acid) (NTPO), and ethylenediaminebis (methylenephosphonic acid) (EDDPO). ), 1,3-propylene diaminebis (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid) (EDTPO), ethylenediaminetetra (ethylenephosphonic acid), 1,3-propylenediaminetetra (methylenephosphonic acid) (PDTMP), 1,2-Diaminopropanetetra (methylenephosphonic acid) or 1,6-hexamethylenediaminetetra (methylenephosphonic acid) is preferable.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式（Ｐ３）中、Ｒ１４及びＲ１５は、それぞれ独立に、炭素数１～４のアルキレン基を表す。
　Ｒ１４及びＲ１５で表される炭素数１～４のアルキレン基は、直鎖状又は分岐鎖状であってもよい。
　Ｒ１４及びＲ１５で表される炭素数１～４のアルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基、トリメチレン基、エチルメチレン基、テトラメチレン基、２－メチルプロピレン基、２－メチルトリメチレン基、及び、エチルエチレン基が挙げられ、エチレン基が好ましい。 In the formula (P3), R 14 and R 15 each independently represent an alkylene group having 1 to 4 carbon atoms.
The alkylene group having 1 to 4 carbon atoms represented by R 14 and R 15 may be linear or branched.
Examples of the alkylene group having 1 to 4 carbon atoms represented by R 14 and R 15 include a methylene group, an ethylene group, a propylene group, a trimethylene group, an ethylmethylene group, a tetramethylene group, a 2-methylpropylene group and 2-. Examples thereof include a methyltrimethylene group and an ethylethylene group, and an ethylene group is preferable.
　ｎは１～４の整数を表す。
　なかでも、ｎとしては、１～２の整数が好ましい。 n represents an integer of 1 to 4.
Among them, n is preferably an integer of 1 to 2.
　Ｚ１～Ｚ４及びｎ個のＺ５のうち少なくとも４つは、ホスホン酸基を有するアルキル基を表し、残りはアルキル基を表す。
　Ｚ１～Ｚ５で表される、アルキル基及びホスホン酸基を有するアルキル基におけるアルキル基としては、例えば、炭素数１～４の直鎖状アルキル基、及び、炭素数１～４の分岐鎖状アルキル基が挙げられ、メチル基が好ましい。
　Ｚ１～Ｚ５で表されるホスホン酸基を有するアルキル基におけるホスホン酸基の数は、１～２が好ましく、１がより好ましい。
　Ｚ１～Ｚ５で表されるホスホン酸基を有するアルキル基としては、例えば、炭素数１～４の直鎖状又は分岐鎖状であって、ホスホン酸基を１又は２つ有するアルキル基が挙げられ、（モノ）ホスホノメチル基、又は、（モノ）ホスホノエチル基が好ましく、（モノ）ホスホノメチル基がより好ましい。
　Ｚ１～Ｚ５としては、Ｚ１～Ｚ４及びｎ個のＺ５の全てが、上記のホスホン酸基を有するアルキル基であることが好ましい。 At least four of Z 1 to Z 4 and n Z 5s represent an alkyl group having a phosphonic acid group, and the rest represent an alkyl group.
Examples of the alkyl group in the alkyl group having an alkyl group and a phosphonic acid group represented by Z 1 to Z 5 include a linear alkyl group having 1 to 4 carbon atoms and a branched chain having 1 to 4 carbon atoms. Alkyl groups are mentioned, and methyl groups are preferable.
The number of phosphonic acid groups in the alkyl group having a phosphonic acid group represented by Z 1 to Z 5 is preferably 1 to 2, more preferably 1.
Examples of the alkyl group having a phosphonic acid group represented by Z 1 to Z 5 include a linear or branched alkyl group having 1 to 4 carbon atoms and having 1 or 2 phosphonic acid groups. The (mono) phosphonomethyl group or the (mono) phosphonoethyl group is preferable, and the (mono) phosphonomethyl group is more preferable.
As Z 1 to Z 5 , it is preferable that all of Z 1 to Z 4 and n Z 5 are the above-mentioned alkyl groups having a phosphonic acid group.
　式（Ｐ３）で表される化合物としては、ジエチレントリアミンペンタ（メチレンホスホン酸）（ＤＥＰＰＯ）、ジエチレントリアミンペンタ（エチレンホスホン酸）、トリエチレンテトラミンヘキサ（メチレンホスホン酸）、又は、トリエチレンテトラミンヘキサ（エチレンホスホン酸）が好ましい。 Examples of the compound represented by the formula (P3) include diethylenetriaminepenta (methylenephosphonic acid) (DEPPO), diethylenetriaminepenta (ethylenephosphonic acid), triethylenetetraminehexa (methylenephosphonic acid), or triethylenetetraminehexa (ethylenephosphon). Acid) is preferred.
　ホスホン酸基を有する錯化剤としては、国際公開第２０１８／０２０８７８号明細書の段落［００２６］～［００３６］に記載の化合物、及び、国際公開第２０１８／０３０００６号明細書の段落［００３１］～［００４６］に記載の化合物（（共）重合体）が援用でき、これらの内容は本明細書に組み込まれる。 Examples of the complexing agent having a phosphonic acid group include the compounds described in paragraphs [0026] to [0036] of International Publication No. 2018/020878, and paragraphs [0031] of International Publication No. 2018/030006. The compounds ((co) polymers) described in [0046] can be incorporated, and the contents thereof are incorporated in the present specification.
　ホスホン酸基を有する錯化剤の炭素数は、１２以下が好ましく、１０以下がより好ましく、８以下が更に好ましい。下限は特に制限されず、１以上が好ましく、２以上がより好ましい。
　ホスホン酸基を有する錯化剤としては、上記の式（Ｐ１）で表される化合物、式（Ｐ２）で表される化合物、又は、式（Ｐ３）で表される化合物が好ましく、ＨＥＤＰＯがより好ましい。 The carbon number of the complexing agent having a phosphonic acid group is preferably 12 or less, more preferably 10 or less, still more preferably 8 or less. The lower limit is not particularly limited, and 1 or more is preferable, and 2 or more is more preferable.
As the complexing agent having a phosphonic acid group, the compound represented by the above formula (P1), the compound represented by the formula (P2), or the compound represented by the formula (P3) is preferable, and HEDPO is more preferable. preferable.
　特定錯化剤は、式（Ｂ１）で表される化合物、式（Ｂ２）で表される化合物、式（Ｂ４）で表される化合物、式（Ｃ）で表される化合物、リン酸基を有する錯化剤、及び、式（Ｐ１）で表される化合物からなる群から選択される少なくとも１つを含むことが好ましく、式（Ｂ１）で表される化合物、式（Ｂ３）で表される化合物、式（Ｂ４）で表される化合物、式（Ｃ）で表される化合物、二リン酸、ヘキサメタリン酸、フィチン酸、及び、式（Ｐ１）で表される化合物からなる群から選択される少なくとも１つを含むことがより好ましく、式（Ｂ１）で表される化合物、式（Ｃ）で表される化合物、フィチン酸、及び、式（Ｐ１）で表される化合物からなる群から選択される少なくとも１つを含むことが更に好ましい。 The specific complexing agent includes a compound represented by the formula (B1), a compound represented by the formula (B2), a compound represented by the formula (B4), a compound represented by the formula (C), and a phosphoric acid group. It is preferable to contain at least one selected from the group consisting of the complexing agent having and the compound represented by the formula (P1), and the compound represented by the formula (B1) and the compound represented by the formula (B3). It is selected from the group consisting of a compound, a compound represented by the formula (B4), a compound represented by the formula (C), diphosphate, hexametaphosphate, phytic acid, and a compound represented by the formula (P1). It is more preferable to contain at least one, and it is selected from the group consisting of the compound represented by the formula (B1), the compound represented by the formula (C), the phytic acid, and the compound represented by the formula (P1). It is more preferable to include at least one compound.
　特定錯化剤は、塩を形成していてもよい。
　上記塩としては、例えば、ナトリウム塩及びカリウム塩等のアルカリ金属塩、アンモニウム塩、塩酸塩、炭酸塩、並びに、酢酸塩が挙げられる。 The specific complexing agent may form a salt.
Examples of the salt include alkali metal salts such as sodium salt and potassium salt, ammonium salt, hydrochloride, carbonate, and acetate.
　特定錯化剤の分子量は、６００以下が好ましく、４５０以下がより好ましく、３００以下が更に好ましい。上記分子量の下限は特に制限されず、５０以上が好ましい。
　特定錯化剤の炭素数は、１５以下が好ましく、１０以下がより好ましい。上記炭素数の下限は特に制限されず、２以上が好ましい。 The molecular weight of the specific complexing agent is preferably 600 or less, more preferably 450 or less, still more preferably 300 or less. The lower limit of the molecular weight is not particularly limited, and is preferably 50 or more.
The carbon number of the specific complexing agent is preferably 15 or less, more preferably 10 or less. The lower limit of the number of carbon atoms is not particularly limited, and is preferably 2 or more.
　特定錯化剤は、１種単独で使用してもよく、２種以上を使用してもよい。
　アルカノールアミンの含有量に対する、特定錯化剤の含有量の質量比〔特定錯化剤の含有量／アルカノールアミンの含有量〕は、０．１～２０００．０が好ましく、０．１～１８５０．０がより好ましく、０．１～１５００．０がより一層好ましく、０．１～１０００．０が更に好ましく、０．１～４００．０が特に好ましく、２０．０～４００．０が最も好ましい。
　重合体の含有量に対する、特定錯化剤の含有量の質量比〔特定錯化剤の含有量／重合体の含有量〕が、０．０３～２００．０が好ましく、１．０～１００．０がより好ましく、１．５～５０．０が更に好ましい。 The specific complexing agent may be used alone or in combination of two or more.
The mass ratio of the content of the specific complexing agent to the content of the alkanolamine [content of the specific complexing agent / content of alkanolamine] is preferably 0.1 to 2000.0, preferably 0.1 to 1850. 0 is more preferable, 0.1 to 1500.0 is even more preferable, 0.1 to 1000.0 is further preferable, 0.1 to 400.0 is particularly preferable, and 20.0 to 400.0 is most preferable.
The mass ratio of the content of the specific complexing agent to the content of the polymer [content of the specific complexing agent / content of the polymer] is preferably 0.03 to 200.0, preferably 1.0 to 100. 0 is more preferable, and 1.5 to 50.0 is even more preferable.
〔水〕
　洗浄液は、溶媒として、水を含む。
　上記水としては、半導体基板に悪影響を及ぼさないものであれば特に制限されず、蒸留水、脱イオン水、及び、純水（超純水が好ましい）が使用できる。
　上記水としては、不純物をほとんど含まない点、及び、半導体基板の製造工程における半導体基板への影響がより少ない点から、純水又は超純水が好ましい。 〔water〕
The cleaning liquid contains water as a solvent.
The water is not particularly limited as long as it does not adversely affect the semiconductor substrate, and distilled water, deionized water, and pure water (preferably ultrapure water) can be used.
As the water, pure water or ultrapure water is preferable because it contains almost no impurities and has less influence on the semiconductor substrate in the manufacturing process of the semiconductor substrate.
　水の含有量は、洗浄液に含まれる成分の残部であればよい。
　水の含有量は、洗浄液の全質量に対して、１．０質量％以上が好ましく、３０．０質量％以上がより好ましく、６０．０質量％以上が更に好ましく、８５．０質量％以上が特に好ましい。上限は特に制限されず、洗浄液の全質量に対して、９９．０質量％以下が好ましく、９７．０質量％以下がより好ましい。 The water content may be the balance of the components contained in the cleaning liquid.
The water content is preferably 1.0% by mass or more, more preferably 30.0% by mass or more, further preferably 60.0% by mass or more, and 85.0% by mass or more with respect to the total mass of the cleaning liquid. Especially preferable. The upper limit is not particularly limited, and is preferably 99.0% by mass or less, more preferably 97.0% by mass or less, based on the total mass of the cleaning liquid.
〔界面活性剤〕
　洗浄液は、界面活性剤を含んでいてもよい。
　界面活性剤は、上述した洗浄液に含まれる成分とは異なる化合物である。
　界面活性剤としては、１分子中に親水基と、疎水基（親油基）とを有する化合物である。界面活性剤としては、例えば、アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤、及び、両性界面活性剤が挙げられる。
　界面活性剤は、アニオン性界面活性剤を含むことが好ましく、リン酸エステル系界面活性剤を含むことがより好ましく、アルキルリン酸エステル及びポリオキシエチレンアルキルリン酸エステルからなる群から選択される少なくとも１つを含むことが更に好ましく、アルキルリン酸エステルを含むことが特に好ましい。
　洗浄液が界面活性剤を含む場合、金属膜の腐食抑制性能の向上、及び、研磨微粒子等の洗浄性能を向上できる。 [Surfactant]
The cleaning liquid may contain a surfactant.
The surfactant is a compound different from the components contained in the above-mentioned cleaning liquid.
The surfactant is a compound having a hydrophilic group and a hydrophobic group (lipophilic group) in one molecule. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants.
The surfactant preferably contains an anionic surfactant, more preferably contains a phosphate ester-based surfactant, and is at least selected from the group consisting of an alkyl phosphate ester and a polyoxyethylene alkyl phosphate ester. It is more preferable to contain one, and it is particularly preferable to contain an alkyl phosphate ester.
When the cleaning liquid contains a surfactant, it is possible to improve the corrosion suppressing performance of the metal film and the cleaning performance of the abrasive fine particles and the like.
　界面活性剤は、脂肪族炭化水素基、芳香族炭化水素基、及び、これらの組み合わせた基からなる群から選択される疎水基を有する場合が多い。
　界面活性剤が有する疎水基としては、特に制限されないが、疎水基が芳香族炭化水素基を含む場合、炭素数が６以上であることが好ましく、炭素数１０以上であることがより好ましい。疎水基が芳香族炭化水素基を含まず、脂肪族炭化水素基のみから構成される場合、炭素数が９以上であることが好ましく、炭素数が１２以上であることがより好ましい。疎水基の炭素数の上限は特に制限されないが、２０以下が好ましく、１８以下がより好ましい。界面活性剤全体の炭素数は、１６～１００が好ましい。 Surfactants often have hydrophobic groups selected from the group consisting of aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups in combination thereof.
The hydrophobic group of the surfactant is not particularly limited, but when the hydrophobic group contains an aromatic hydrocarbon group, the number of carbon atoms is preferably 6 or more, and more preferably 10 or more. When the hydrophobic group does not contain an aromatic hydrocarbon group and is composed only of an aliphatic hydrocarbon group, the number of carbon atoms is preferably 9 or more, and more preferably 12 or more. The upper limit of the number of carbon atoms of the hydrophobic group is not particularly limited, but is preferably 20 or less, and more preferably 18 or less. The total carbon number of the surfactant is preferably 16 to 100.
＜アニオン性界面活性剤＞
　アニオン性界面活性剤としては、例えば、リン酸エステル基を有するリン酸エステル系界面活性剤、ホスホン酸基を有するホスホン酸系界面活性剤、スルホン酸基を有するスルホン酸系界面活性剤、カルボキシ基を有するカルボン酸系界面活性剤、及び、硫酸エステル基を有する硫酸エステル系界面活性剤が挙げられる。 <Anionic surfactant>
Examples of the anionic surfactant include a phosphate ester-based surfactant having a phosphate ester group, a phosphonic acid-based surfactant having a phosphonic acid group, a sulfonic acid-based surfactant having a sulfonic acid group, and a carboxy group. Examples thereof include a carboxylic acid-based surfactant having a sulfate ester group and a sulfate ester-based surfactant having a sulfate ester group.
（リン酸エステル系界面活性剤）
　リン酸エステル系界面活性剤としては、例えば、アルキルリン酸エステル、ポリオキシアルキレンアルキルエーテルリン酸エステル、及び、これらの塩が挙げられる。
　なかでも、アルキルリン酸エステルが好ましい。 (Phosphoric acid ester-based surfactant)
Examples of the phosphoric acid ester-based surfactant include an alkyl phosphate ester, a polyoxyalkylene alkyl ether phosphoric acid ester, and salts thereof.
Of these, alkyl phosphate esters are preferred.
　リン酸エステル及びポリオキシアルキレンアルキルエーテルリン酸エステルは、モノエステル又はジエステルの単体であってもよいし、モノエステル及びジエステルの混合物であってもよい。
　リン酸エステル系界面活性剤の塩としては、例えば、ナトリウム塩、カリウム塩、アンモニウム塩、及び、有機アミン塩が挙げられる。
　アルキルリン酸エステル及びポリオキシアルキレンアルキルエーテルリン酸エステルが有するアルキル基としては、炭素数２～２４のアルキル基が好ましく、炭素数６～１８のアルキル基がより好ましく、炭素数１２～１８のアルキル基が更に好ましい。
　ポリオキシアルキレンアルキルエーテルリン酸エステルが有するアルキレン基としては、炭素数２～６のアルキレン基が好ましく、エチレン基、又は、１，２－プロパンジイル基がより好ましい。
　また、ポリオキシアルキレンエーテルリン酸エステルにおけるオキシアルキレン基の繰返し数は、１～１２が好ましく、１～１０がより好ましい。 The phosphoric acid ester and the polyoxyalkylene alkyl ether phosphoric acid ester may be a monoester or a diester alone, or may be a mixture of the monoester and the diester.
Examples of the salt of the phosphoric acid ester-based surfactant include a sodium salt, a potassium salt, an ammonium salt, and an organic amine salt.
As the alkyl group contained in the alkyl phosphate ester and the polyoxyalkylene alkyl ether phosphoric acid ester, an alkyl group having 2 to 24 carbon atoms is preferable, an alkyl group having 6 to 18 carbon atoms is more preferable, and an alkyl having 12 to 18 carbon atoms is more preferable. The group is more preferred.
As the alkylene group contained in the polyoxyalkylene alkyl ether phosphoric acid ester, an alkylene group having 2 to 6 carbon atoms is preferable, and an ethylene group or a 1,2-propanediyl group is more preferable.
The number of repetitions of the oxyalkylene group in the polyoxyalkylene ether phosphoric acid ester is preferably 1 to 12, more preferably 1 to 10.
　リン酸エステル系界面活性剤としては、オクチルリン酸エステル、ラウリルリン酸エステル、トリデシルリン酸エステル、ミリスチルリン酸エステル、セチルリン酸エステル、ステアリルリン酸エステル、ポリオキシエチレンオクチルエーテルリン酸エステル、ポリオキシエチレンラウリルエーテルリン酸エステル、ポリオキシエチレントリデシルエーテルリン酸エステル、又は、ポリオキシエチレンミリスチルエーテルリン酸エステルが好ましく、ラウリルリン酸エステル、トリデシルリン酸エステル、ミリスチルリン酸エステル、セチルリン酸エステル、ステアリルリン酸エステル、又は、ポリオキシエチレンミリスチルエーテルリン酸エステルがより好ましく、ラウリルリン酸エステル、セチルリン酸エステル、ステアリルリン酸エステル、又は、ポリオキシエチレンミリスチルエーテルリン酸エステルが更に好ましい。 Examples of the phosphoric acid ester-based surfactant include octyl phosphate, lauryl phosphate, tridecyl phosphate, myristyl phosphate, cetyl phosphate, stearyl phosphate, polyoxyethylene octyl ether phosphate, and polyoxyethylene. Lauryl ether phosphate ester, polyoxyethylene tridecyl ether phosphate ester, or polyoxyethylene myristyl ether phosphate ester is preferable, and lauryl phosphate ester, tridecyl phosphate ester, myristyl phosphate ester, cetyl phosphate ester, stearyl phosphate are preferable. Esters or polyoxyethylene myristyl ether phosphate esters are more preferred, and lauryl phosphate esters, cetyl phosphate esters, stearyl phosphate esters, or polyoxyethylene myristyl ether phosphate esters are even more preferred.
　リン酸エステル系界面活性剤としては、特開２０１１－０４０５０２号公報の段落［００１２］～［００１９］に記載の化合物も援用でき、これらの内容は本明細書に組み込まれる。 As the phosphoric acid ester-based surfactant, the compounds described in paragraphs [0012] to [0019] of JP2011-040502A can also be incorporated, and these contents are incorporated in the present specification.
（ホスホン酸系界面活性剤）
　ホスホン酸系界面活性剤としては、例えば、アルキルホスホン酸、ポリビニルホスホン酸、及び、特開２０１２－０５７１０８号公報に記載のアミノメチルホスホン酸が挙げられる。 (Phosphonate-based surfactant)
Examples of the phosphonic acid-based surfactant include alkylphosphonic acid, polyvinylphosphonic acid, and aminomethylphosphonic acid described in JP-A-2012-057108.
（スルホン酸系界面活性剤）
　スルホン酸系界面活性剤としては、例えば、アルキルスルホン酸、アルキルベンゼンスルホン酸、アルキルナフタレンスルホン酸、アルキルジフェニルエーテルジスルホン酸、アルキルメチルタウリン、スルホコハク酸ジエステル、ポリオキシアルキレンアルキルエーテルスルホン酸、及び、これらの塩が挙げられる。 (Sulfonic acid-based surfactant)
Examples of the sulfonic acid-based surfactant include alkyl sulfonic acid, alkyl benzene sulfonic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid, alkyl methyl taurine, sulfosuccinic acid diester, polyoxyalkylene alkyl ether sulfonic acid, and salts thereof. Can be mentioned.
　上記スルホン酸系界面活性剤が有するアルキル基としては、炭素数２～２４のアルキル基が好ましく、炭素数６～１８のアルキル基がより好ましい。
　ポリオキシアルキレンアルキルエーテルスルホン酸が有するアルキレン基としては、エチレン基、又は、１，２－プロパンジイル基が好ましい。
　ポリオキシアルキレンアルキルエーテルスルホン酸におけるオキシアルキレン基の繰返し数は、１～１２が好ましく、１～６がより好ましい。 As the alkyl group contained in the sulfonic acid-based surfactant, an alkyl group having 2 to 24 carbon atoms is preferable, and an alkyl group having 6 to 18 carbon atoms is more preferable.
As the alkylene group contained in the polyoxyalkylene alkyl ether sulfonic acid, an ethylene group or a 1,2-propanediyl group is preferable.
The number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether sulfonic acid is preferably 1 to 12, more preferably 1 to 6.
　スルホン酸系界面活性剤としては、例えば、ヘキサンスルホン酸、オクタンスルホン酸、デカンスルホン酸、ドデカンスルホン酸、トルエンスルホン酸、クメンスルホン酸、オクチルベンゼンスルホン酸、ドデシルベンゼンスルホン酸（ＤＢＳＡ）、ジニトロベンゼンスルホン酸（ＤＮＢＳＡ）、及び、ラウリルドデシルフェニルエーテルジスルホン酸（ＬＤＰＥＤＳＡ）が挙げられる。
　なかでも、ドデカンスルホン酸、ＤＢＳＡ、ＤＮＢＳＡ、又は、ＬＤＰＥＤＳＡが好ましく、ＤＢＳＡ、ＤＮＢＳＡ、又は、ＬＤＰＥＤＳＡがより好ましい。 Examples of the sulfonic acid-based surfactant include hexanesulfonic acid, octanesulfonic acid, decanesulfonic acid, dodecanesulfonic acid, toluenesulfonic acid, cumenesulfonic acid, octylbenzenesulfonic acid, dodecylbenzenesulfonic acid (DBSA), and dinitrobenzene. Examples thereof include sulfonic acid (DNBSA) and laurildodecylphenyl ether disulfonic acid (LDPEDSA).
Of these, dodecane sulfonic acid, DBSA, DNBSA, or LDPEDSA is preferable, and DBSA, DNBSA, or LDPEDSA is more preferable.
（カルボン酸系界面活性剤）
　カルボン酸系界面活性剤としては、例えば、アルキルカルボン酸、アルキルベンゼンカルボン酸、及び、ポリオキシアルキレンアルキルエーテルカルボン酸、並びに、これらの塩が挙げられる。 (Carboxylic acid-based surfactant)
Examples of the carboxylic acid-based surfactant include an alkylcarboxylic acid, an alkylbenzenecarboxylic acid, a polyoxyalkylene alkyl ether carboxylic acid, and salts thereof.
　上記カルボン酸系界面活性剤が有するアルキル基としては、炭素数７～２５のアルキル基が好ましく、炭素数１１～１７のアルキル基がより好ましい。
　ポリオキシアルキレンアルキルエーテルカルボン酸が有するアルキレン基としては、エチレン基、又は、１，２－プロパンジイル基が好ましい。
　ポリオキシアルキレンアルキルエーテルカルボン酸におけるオキシアルキレン基の繰返し数は、１～１２が好ましく、１～６がより好ましい。 As the alkyl group contained in the carboxylic acid-based surfactant, an alkyl group having 7 to 25 carbon atoms is preferable, and an alkyl group having 11 to 17 carbon atoms is more preferable.
As the alkylene group of the polyoxyalkylene alkyl ether carboxylic acid, an ethylene group or a 1,2-propanediyl group is preferable.
The number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether carboxylic acid is preferably 1 to 12, more preferably 1 to 6.
　カルボン酸系界面活性剤としては、例えば、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ポリオキシエチレンラウリルエーテル酢酸、及び、ポリオキシエチレントリデシルエーテル酢酸が挙げられる。 Examples of the carboxylic acid-based surfactant include lauric acid, myristic acid, palmitic acid, stearic acid, polyoxyethylene lauryl ether acetic acid, and polyoxyethylene tridecyl ether acetic acid.
（硫酸エステル系界面活性剤）
　硫酸エステル系界面活性剤としては、例えば、アルキル硫酸エステル、及び、ポリオキシアルキレンアルキルエーテル硫酸エステル、並びに、これらの塩が挙げられる。 (Sulfuric acid ester-based surfactant)
Examples of the sulfuric acid ester-based surfactant include an alkyl sulfate ester, a polyoxyalkylene alkyl ether sulfuric acid ester, and salts thereof.
　アルキル硫酸エステル及びポリオキシアルキレンアルキルエーテル硫酸エステルが有するアルキル基としては、炭素数２～２４のアルキル基が好ましく、炭素数６～１８のアルキル基がより好ましい。
　ポリオキシアルキレンアルキルエーテル硫酸エステルが有するアルキレン基としては、エチレン基、又は、１，２－プロパンジイル基が好ましい。
　ポリオキシアルキレンアルキルエーテル硫酸エステルにおけるオキシアルキレン基の繰返し数は、１～１２が好ましく、１～６がより好ましい。 As the alkyl group contained in the alkyl sulfate ester and the polyoxyalkylene alkyl ether sulfuric acid ester, an alkyl group having 2 to 24 carbon atoms is preferable, and an alkyl group having 6 to 18 carbon atoms is more preferable.
As the alkylene group contained in the polyoxyalkylene alkyl ether sulfuric acid ester, an ethylene group or a 1,2-propanediyl group is preferable.
The number of repetitions of the oxyalkylene group in the polyoxyalkylene alkyl ether sulfuric acid ester is preferably 1 to 12, more preferably 1 to 6.
　硫酸エステル系界面活性剤としては、例えば、ラウリル硫酸エステル、ミリスチル硫酸エステル、及び、ポリオキシエチレンラウリルエーテル硫酸エステルが挙げられる。 Examples of the sulfate ester-based surfactant include lauryl sulfate ester, myristyl sulfate ester, and polyoxyethylene lauryl ether sulfate ester.
　界面活性剤としては、例えば、特開２０１５－１５８６６２号公報の段落［００９２］～［００９６］、特開２０１２－１５１２７３号公報の段落［００４５］～［００４６］、及び、特開２００９－１４７３８９号公報の段落［００１４］～［００２０］に記載の化合物も援用でき、これらの内容は本明細書に組み込まれる。 Examples of the surfactant include paragraphs [0092] to [0090] of JP-A-2015-158662, paragraphs [0045]-[0046] of JP-A-2012-151273, and JP-A-2009-147389. The compounds described in paragraphs [0014] to [0020] of the publication may also be incorporated, and the contents thereof are incorporated in the present specification.
　界面活性剤は、１種単独で使用してもよく、２種以上を使用してもよい。
　界面活性剤の含有量は、洗浄液の性能がバランスよく優れる点から、洗浄液の全質量に対して、０．００１～８．０質量％が好ましく、０．００５～５．０質量％がより好ましく、０．０１～３．０質量％が更に好ましい。
　界面活性剤の含有量は、溶媒を除いた洗浄液の全質量に対して、１．０～３０．０質量％が好ましく、５．０～２０．０質量％がより好ましく、１０．０～２０．０質量％が更に好ましい。 The surfactant may be used alone or in combination of two or more.
The content of the surfactant is preferably 0.001 to 8.0% by mass, more preferably 0.005 to 5.0% by mass, based on the total mass of the cleaning liquid, because the performance of the cleaning liquid is well-balanced. , 0.01-3.0% by mass is more preferable.
The content of the surfactant is preferably 1.0 to 30.0% by mass, more preferably 5.0 to 20.0% by mass, and 10.0 to 20% by mass with respect to the total mass of the cleaning liquid excluding the solvent. .0% by mass is more preferable.
〔防食剤〕
　洗浄液は、防食剤を含んでいてもよい。
　防食剤としては、例えば、カルボン酸、分子内にヘテロ環構造を有するヘテロ環式化合物、カテコール化合物、ヒドロキシルアミン化合物、ビグアニド化合物、ヒドラジド化合物、アスコルビン酸化合物、還元性硫黄化合物、及び、分子量５００以上のポリヒドロキシ化合物が挙げられる。 [Corrosion inhibitor]
The cleaning liquid may contain an anticorrosive agent.
Examples of the anticorrosion agent include a carboxylic acid, a heterocyclic compound having a heterocyclic structure in the molecule, a catechol compound, a hydroxylamine compound, a biguanide compound, a hydrazide compound, an ascorbic acid compound, a reducing sulfur compound, and a molecular weight of 500 or more. Polyhydroxy compounds of.
＜カルボン酸＞
　カルボン酸は、分子内に、カルボキシ基を有する化合物である。
　カルボン酸は、上述した洗浄液に含まれる成分とは異なる化合物である。
　カルボン酸としては、例えば、プロピオン酸、酪酸、吉草酸、２－メチル酪酸、ｎ－ヘキサン酸、３，３－ジメチル酪酸、２－エチル酪酸、４－メチルペンタン酸、ｎ－ヘプタン酸、２－メチルヘキサン酸、ｎ－オクタン酸、及び、２－エチルヘキサン酸が挙げられる。 <Carboxylic acid>
Carboxylic acid is a compound having a carboxy group in the molecule.
Carboxylic acid is a compound different from the components contained in the above-mentioned cleaning liquid.
Examples of the carboxylic acid include propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexaneic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid and 2-. Examples thereof include methylhexanoic acid, n-octanoic acid, and 2-ethylhexanoic acid.
＜ヘテロ環式化合物＞
　ヘテロ環式化合物は、分子内にヘテロ環構造を有する化合物である。
　ヘテロ環式化合物は、上述した洗浄液に含まれる成分とは異なる化合物である。
　ヘテロ環式化合物が有するヘテロ環構造は、例えば、環を構成する原子の少なくとも１つが窒素原子であるヘテロ環（含窒素ヘテロ環）が挙げられる。
　上記の含窒素ヘテロ環を有するヘテロ環式化合物としては、例えば、アゾール化合物、ピリジン化合物、ピラジン化合物、ピリミジン化合物、ピペラジン化合物、及び、環状アミジン化合物が挙げられる。
　なかでも、ヘテロ環式化合物としては、アゾール化合物、ピリジン化合物、ピラジン化合物、及び、ピリミジン化合物からなる群から選択される少なくとも１つが好ましい。 <Heterocyclic compound>
A heterocyclic compound is a compound having a heterocyclic structure in the molecule.
The heterocyclic compound is a compound different from the components contained in the above-mentioned cleaning solution.
Examples of the heterocyclic structure of a heterocyclic compound include a heterocycle (nitrogen-containing heterocycle) in which at least one of the atoms constituting the ring is a nitrogen atom.
Examples of the heterocyclic compound having a nitrogen-containing heterocycle include an azole compound, a pyridine compound, a pyrazine compound, a pyrimidine compound, a piperazine compound, and a cyclic amidin compound.
Among them, as the heterocyclic compound, at least one selected from the group consisting of an azole compound, a pyridine compound, a pyrazine compound, and a pyrimidine compound is preferable.
　アゾール化合物は、窒素原子を少なくとも１つ含み、芳香族性を有するヘテロ５員環を有する化合物である。
　アゾール化合物が有するヘテロ５員環に含まれる窒素原子の数は、１～４が好ましく、１～３がより好ましい。
　アゾール化合物は、ヘテロ５員環上に置換基を有してもよい。上記置換基としては、例えば、ヒドロキシル基、カルボキシ基、メルカプト基、アミノ基、アミノ基を有していてもよい炭素数１～４のアルキル基、及び、２－イミダゾリル基が挙げられる。 The azole compound is a compound having at least one nitrogen atom and having an aromatic 5-membered ring.
The number of nitrogen atoms contained in the hetero 5-membered ring of the azole compound is preferably 1 to 4, more preferably 1 to 3.
The azole compound may have a substituent on the hetero 5-membered ring. Examples of the substituent include a hydroxyl group, a carboxy group, a mercapto group, an amino group, an alkyl group having 1 to 4 carbon atoms which may have an amino group, and a 2-imidazolyl group.
　アゾール化合物としては、例えば、アゾール環を構成する原子のうち１つが窒素原子であるイミダゾール化合物、アゾール環を構成する原子のうち２つが窒素原子であるピラゾール化合物、アゾール環を構成する原子のうち１つが窒素原子であり、他の１つが硫黄原子であるチアゾール化合物、アゾール環を構成する原子のうち３つが窒素原子であるトリアゾール化合物、及び、アゾール環を構成する原子のうち４つが窒素原子であるテトラゾール化合物が挙げられる。 Examples of the azole compound include an imidazole compound in which one of the atoms constituting the azole ring is a nitrogen atom, a pyrazole compound in which two of the atoms constituting the azole ring are nitrogen atoms, and one of the atoms constituting the azole ring. One is a nitrogen atom, the other is a thiazole compound which is a sulfur atom, three of the atoms constituting the azole ring are triazole compounds which are nitrogen atoms, and four of the atoms constituting the azole ring are nitrogen atoms. Examples include tetrazole compounds.
　イミダゾール化合物としては、例えば、イミダゾール、１－メチルイミダゾール、２－メチルイミダゾール、５－メチルイミダゾール、１，２－ジメチルイミダゾール、２－メルカプトイミダゾール、４，５－ジメチル－２－メルカプトイミダゾール、４－ヒドロキシイミダゾール、２，２’－ビイミダゾール、４－イミダゾールカルボン酸、ヒスタミン、ベンゾイミダゾール、及び、プリン塩基（アデニン等）が挙げられる。 Examples of the imidazole compound include imidazole, 1-methylimidazole, 2-methylimidazole, 5-methylimidazole, 1,2-dimethylimidazole, 2-mercaptoimidazole, 4,5-dimethyl-2-mercaptoimidazole and 4-hydroxy. Examples thereof include imidazole, 2,2'-biimidazole, 4-imidazole carboxylic acid, histamine, benzoimidazole, and purine base (adenine and the like).
　ピラゾール化合物としては、例えば、ピラゾール、４－ピラゾールカルボン酸、１－メチルピラゾール、３－メチルピラゾール、３－アミノ－５－メチルピラゾール、３－アミノ－５－ヒドロキシピラゾール、３－アミノピラゾール、及び、４－アミノピラゾールが挙げられる。 Examples of the pyrazole compound include pyrazole, 4-pyrazolecarboxylic acid, 1-methylpyrazole, 3-methylpyrazole, 3-amino-5-methylpyrazole, 3-amino-5-hydroxypyrazole, 3-aminopyrazole, and Examples include 4-aminopyrazole.
　チアゾール化合物としては、例えば、２，４－ジメチルチアゾール、ベンゾチアゾール、及び、２－メルカプトベンゾチアゾールが挙げられる。 Examples of the thiazole compound include 2,4-dimethylthiazole, benzothiazole, and 2-mercaptobenzothiazole.
　トリアゾール化合物としては、例えば、１，２，４－トリアゾ－ル、３－メチル－１，２，４－トリアゾ－ル、３－アミノ－１，２，４－トリアゾール、１，２，３－トリアゾ－ル、１－メチル－１，２，３－トリアゾ－ル、ベンゾトリアゾール、１－ヒドロキシベンゾトリアゾール、１－ジヒドロキシプロピルベンゾトリアゾール、２，３－ジカルボキシプロピルベンゾトリアゾール、４－ヒドロキシベンゾトリアゾール、４－カルボキシベンゾトリアゾール、５－メチルベンゾトリアゾール、及び、２，２’－｛［（５－メチル－１Ｈ－ベンゾトリアゾール－１－イル）メチル］イミノ｝ジエタノールが挙げられる。 Examples of the triazole compound include 1,2,4-triazol, 3-methyl-1,2,4-triazole, 3-amino-1,2,4-triazole and 1,2,3-triazol. -L, 1-methyl-1,2,3-triazole, benzotriazole, 1-hydroxybenzotriazole, 1-dihydroxypropylbenzotriazole, 2,3-dicarboxypropylbenzotriazole, 4-hydroxybenzotriazole, 4 Examples thereof include -carboxybenzotriazole, 5-methylbenzotriazole, and 2,2'-{[(5-methyl-1H-benzotriazole-1-yl) methyl] imino} diethanol.
　テトラゾール化合物としては、例えば、１Ｈ－テトラゾール（１，２，３，４－テトラゾ－ル）、５－メチル－１，２，３，４－テトラゾ－ル、５－アミノ－１，２，３，４－テトラゾ－ル、１，５－ペンタメチレンテトラゾール、１－フェニル－５－メルカプトテトラゾール、及び、１－（２－ジメチルアミノエチル）－５－メルカプトテトラゾールが挙げられる。 Examples of the tetrazole compound include 1H-tetrazole (1,2,3,4-tetrazole), 5-methyl-1,2,3,4-tetrazole and 5-amino-1,2,3. Examples thereof include 4-tetrazole, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, and 1- (2-dimethylaminoethyl) -5-mercaptotetrazole.
　アゾール化合物としては、イミダゾール化合物、ピラゾール化合物、チアゾール化合物、トリアゾール化合物、テトラゾール化合物からなる群から選択される少なくとも１つが好ましく、イミダゾール、ピラゾール、２,４－ジメチルチアゾール、１，２，４－トリアゾール、１Ｈ－テトラゾール（１，２，３，４－テトラゾ－ル）、又は、アデニンがより好ましい。 As the azole compound, at least one selected from the group consisting of an imidazole compound, a pyrazole compound, a thiazole compound, a triazole compound and a tetrazole compound is preferable, and imidazole, pyrazole, 2,4-dimethylthiazole, 1,2,4-triazole and the like. 1H-tetrazole (1,2,3,4-tetrazole) or adenin is more preferable.
　ピリジン化合物は、窒素原子を１つ含み、芳香族性を有するヘテロ６員環（ピリジン環）を有する化合物である。
　ピリジン化合物は、ピリジン環上に置換基を有してもよい。上記置換基としては、例えば、ヒドロキシル基、アミノ基、シアノ基、炭素数１～４のアルキル基、及び、炭素数１～４のアルキルアミド基が挙げられる。 The pyridine compound is a compound having a hetero 6-membered ring (pyridine ring) containing one nitrogen atom and having aromaticity.
The pyridine compound may have a substituent on the pyridine ring. Examples of the substituent include a hydroxyl group, an amino group, a cyano group, an alkyl group having 1 to 4 carbon atoms, and an alkylamide group having 1 to 4 carbon atoms.
　ピリジン化合物としては、例えば、ピリジン、３－アミノピリジン、４－アミノピリジン、３－ヒドロキシピリジン、４－ヒドロキシピリジン、２－アセトアミドピリジン、２－シアノピリジン、２－カルボキシピリジン、及び、４－カルボキシピリジンが挙げられ、ピリジンが好ましい。 Examples of the pyridine compound include pyridine, 3-aminopyridine, 4-aminopyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2-acetamidopyridine, 2-cyanopyridine, 2-carboxypyridine, and 4-carboxypyridine. However, pyridine is preferable.
　ピラジン化合物は、芳香族性を有し、パラ位に位置する窒素原子を２つ含むヘテロ６員環（ピラジン環）を有する化合物である。
　ピリミジン化合物は、芳香族性を有し、メタ位に位置する窒素原子を２つ含むヘテロ６員環（ピリミジン環）を有する化合物である。
　ピラジン化合物及びピリミジン化合物は、環上に置換基を有してもよい。上記置換基としては、例えば、ヒドロキシル基、アミノ基、カルボキシ基、及び、ヒドロキシル基を有してもよい炭素数１～４のアルキル基が挙げられる。 The pyrazine compound is a compound having aromaticity and having a hetero 6-membered ring (pyrazine ring) containing two nitrogen atoms located at the para position.
The pyrimidine compound is a compound having aromaticity and having a hetero 6-membered ring (pyrimidine ring) containing two nitrogen atoms located at the meta position.
The pyrazine compound and the pyrimidine compound may have a substituent on the ring. Examples of the substituent include a hydroxyl group, an amino group, a carboxy group, and an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group.
　ピラジン化合物としては、例えば、ピラジン、２－メチルピラジン、２，５－ジメチルピラジン、２，３，５－トリメチルピラジン、２，３，５，６－テトラメチルピラジン、２－エチル－３－メチルピラジン、及び、２－アミノ－５－メチルピラジンが挙げられ、ピラジンが好ましい。 Examples of the pyrazine compound include pyrazine, 2-methylpyrazine, 2,5-dimethylpyrazine, 2,3,5-trimethylpyrazine, 2,3,5,6-tetramethylpyrazine and 2-ethyl-3-methylpyrazine. , And 2-amino-5-methylpyrazine, with pyrazine being preferred.
　ピリミジン化合物としては、例えば、ピリミジン、２－メチルピリミジン、２－アミノピリミジン、及び、４，６－ジメチルピリミジンが挙げられ、ピリミジンが好ましい。 Examples of the pyrimidine compound include pyrimidine, 2-methylpyrimidine, 2-aminopyrimidine, and 4,6-dimethylpyrimidine, and pyrimidine is preferable.
　ピペラジン化合物は、シクロヘキサン環の対向する－ＣＨ－基が窒素原子に置き換わったヘテロ６員環（ピペラジン環）を有する化合物である。
　ピペラジン化合物は、ピペラジン環上に置換基を有してもよい。そのような置換基としては、例えば、ヒドロキシル基、ヒドロキシル基を有していてもよい炭素数１～４のアルキル基、及び、炭素数６～１０のアリール基が挙げられる。 The piperazine compound is a compound having a hetero 6-membered ring (piperazine ring) in which the opposite -CH- group of the cyclohexane ring is replaced with a nitrogen atom.
The piperazine compound may have a substituent on the piperazine ring. Examples of such a substituent include a hydroxyl group, an alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group, and an aryl group having 6 to 10 carbon atoms.
　ピペラジン化合物としては、例えば、ピペラジン、１－メチルピペラジン、１－エチルピペラジン、１－プロピルピペラジン、１－ブチルピペラジン、２－メチルピペラジン、１，４－ジメチルピペラジン、２，５－ジメチルピペラジン、２，６－ジメチルピペラジン、１－フェニルピペラジン、２－ヒドロキシピペラジン、２－ヒドロキシメチルピペラジン、１－（２－ヒドロキシエチル）ピペラジン（ＨＥＰ）、及び、１，４－ビス（３－アミノプロピル）ピペラジン（ＢＡＰ）が挙げられ、ピペラジン、１－メチルピペラジン、２－メチルピペラジン、ＨＥＰ、又は、ＢＡＰが好ましく、ＨＥＰ又はＢＡＰがより好ましい。 Examples of the piperazine compound include piperazine, 1-methylpiperazine, 1-ethylpiperazine, 1-propylpiperazine, 1-butylpiperazine, 2-methylpiperazine, 1,4-dimethylpiperazine, 2,5-dimethylpiperazine, 2, 6-Dimethylpiperazine, 1-phenylpiperazine, 2-hydroxypiperazine, 2-hydroxymethylpiperazine, 1- (2-hydroxyethyl) piperazine (HEP), and 1,4-bis (3-aminopropyl) piperazine (BAP). ), And piperazine, 1-methylpiperazine, 2-methylpiperazine, HEP, or BAP is preferable, and HEP or BAP is more preferable.
　環状アミジン化合物は、環内にアミジン構造（＞Ｎ－Ｃ＝Ｎ－）を含むヘテロ環を有する化合物である。
　環状アミジン化合物が有する上記のヘテロ環の環員数は、５～６個が好ましく、６個がより好ましい。
　環状アミジン化合物は、上記のヘテロ環上に置換基を有していてもよい。上記置換基としては、アミノ基、オキソ基、及び、炭素数１～４のアルキル基が挙げられる。また、上記のヘテロ環上の２つの置換基が互いに結合して、２価の連結基（好ましくは炭素数３～６のアルキレン基）を形成していてもよい。 The cyclic amidine compound is a compound having a heterocycle containing an amidine structure (> NC = N—) in the ring.
The number of ring members of the above heterocycle contained in the cyclic amidine compound is preferably 5 to 6, more preferably 6.
The cyclic amidine compound may have a substituent on the above heterocycle. Examples of the substituent include an amino group, an oxo group, and an alkyl group having 1 to 4 carbon atoms. Further, the two substituents on the above heterocycle may be bonded to each other to form a divalent linking group (preferably an alkylene group having 3 to 6 carbon atoms).
　環状アミジン化合物としては、例えば、ジアザビシクロウンデセン（１，８－ジアザビシクロ［５．４．０］ウンデカ－７－エン：ＤＢＵ）、ジアザビシクロノネン（１，５－ジアザビシクロ［４．３．０］ノナ－５－エン：ＤＢＮ）、３，４，６，７，８，９，１０，１１－オクタヒドロ－２Ｈ－ピリミド［１．２－ａ］アゾシン、３，４，６，７，８，９－ヘキサヒドロ－２Ｈ－ピリド［１．２－ａ］ピリミジン、２，５，６，７－テトラヒドロ－３Ｈ－ピロロ［１．２－ａ］イミダゾール、３－エチル－２，３，４，６，７，８，９，１０－オクタヒドロピリミド［１．２－ａ］アゼピン、及び、クレアチニンが挙げられ、ＤＢＵ又はＤＢＮが好ましい。 Examples of the cyclic amidine compound include diazabicycloundecene (1,8-diazabicyclo [5.4.0] undec-7-en: DBU) and diazabicyclononene (1,5-diazabicyclo [4.3. 0] Nona-5-en: DBN), 3,4,6,7,8,9,10,11-octahydro-2H-pyrimid [1.2-a] azocin, 3,4,6,7,8 , 9-Hexahydro-2H-pyrido [1.2-a] pyrimidine, 2,5,6,7-tetrahydro-3H-pyrrolo [1.2-a] imidazole, 3-ethyl-2,3,4,6 , 7,8,9,10-octahydropyrimid [1.2-a] azepine, and creatinine, with DBU or DBN being preferred.
　ヘテロ環式化合物としては、例えば、１，３－ジメチル－２－イミダゾリジノン、及び、イミダゾリジンチオン等の芳香族性を有さないヘテロ５員環を有する化合物、並びに、窒素原子を含む７員環を有する化合物も挙げられる。 Examples of the heterocyclic compound include 1,3-dimethyl-2-imidazolidinone, a compound having a hetero5-membered ring having no aromaticity such as imidazolidinethione, and a 7-membered ring containing a nitrogen atom. Also mentioned are compounds having.
　窒素原子を含む７員環を有する化合物としては、例えば、ヘキサヒドロ－１Ｈ－１，４－ジアゼピン、１－メチルヘキサヒドロ－１Ｈ－１，４－ジアゼピン、２－メチルヘキサヒドロ－１Ｈ－１，４－ジアゼピン、６－メチルヘキサヒドロ－１Ｈ－１，４－ジアゼピン、２，７－ジアザビシクロ［３．２．１］オクタン、及び、１，３－ジアザビシクロ［３．２．２］ノナンが挙げられる。 Examples of the compound having a 7-membered ring containing a nitrogen atom include hexahydro-1H-1,4-diazepine, 1-methylhexahydro-1H-1,4-diazepine, and 2-methylhexahydro-1H-1,4. -Diazepine, 6-methylhexahydro-1H-1,4-diazepine, 2,7-diazabicyclo [3.2.1] octane, and 1,3-diazabicyclo [3.2.2] nonane can be mentioned.
＜カテコール化合物＞
　カテコール化合物は、ピロカテコール（ベンゼン－１，２－ジオール）、及び、カテコール誘導体からなる群より選択される少なくとも１種を意味する。
　カテコール誘導体とは、ピロカテコールに少なくとも１つの置換基が置換されてなる化合物を意味する。
　カテコール化合物は、上述した洗浄液に含まれる成分とは異なる化合物である。
　カテコール誘導体が有する置換基としては、例えば、ヒドロキシル基、カルボキシ基、カルボン酸エステル基、スルホ基、スルホン酸エステル基、アルキル基（炭素数１～６が好ましく、炭素数１～４がより好ましい）、及び、アリール基（フェニル基が好ましい）が挙げられる。
　カテコール誘導体が置換基として有するカルボキシ基、及び、スルホ基は、カチオンとの塩であってもよい。また、カテコール誘導体が置換基として有するアルキル基、及び、アリール基は、更に置換基を有していてもよい。 <Catechol compound>
The catechol compound means at least one selected from the group consisting of pyrocatechol (benzene-1,2-diol) and catechol derivatives.
The catechol derivative means a compound in which at least one substituent is substituted with pyrocatechol.
The catechol compound is a compound different from the components contained in the above-mentioned cleaning solution.
Examples of the substituent contained in the catechol derivative include a hydroxyl group, a carboxy group, a carboxylic acid ester group, a sulfo group, a sulfonic acid ester group, and an alkyl group (preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms). , And an aryl group (preferably a phenyl group).
The carboxy group and the sulfo group that the catechol derivative has as a substituent may be a salt with a cation. Further, the alkyl group and the aryl group that the catechol derivative has as a substituent may further have a substituent.
　カテコール化合物としては、例えば、ピロカテコール、４－ｔｅｒｔ－ブチルカテコール、ピロガロール、没食子酸、没食子酸メチル、１，２，４－ベンゼントリオール、及び、タイロンが挙げられる。なかでも、ピロカテコール、ピロガロール、又は、没食子酸が好ましい。 Examples of the catechol compound include pyrocatechol, 4-tert-butylcatechol, pyrogallol, gallate, methyl gallate, 1,2,4-benzenetriol, and Tyrone. Of these, pyrocatechol, pyrogallol, or gallic acid is preferable.
＜ヒドロキシルアミン化合物＞
　ヒドロキシルアミン化合物は、ヒドロキシルアミン（ＮＨ２ＯＨ）、ヒドロキシルアミン誘導体、及び、それらの塩からなる群から選択される少なくとも１種を意味する。
　ヒドロキシルアミン化合物は、上述した洗浄液に含まれる成分とは異なる化合物である。
　ヒドロキシルアミン誘導体とは、ヒドロキシルアミン（ＮＨ２ＯＨ）に少なくとも１つの有機基が置換されてなる化合物を意味する。
　ヒドロキシルアミン又はヒドロキシルアミン誘導体の塩としては、無機酸塩及び有機機酸塩が挙げられる。
　なかでも、ヒドロキシルアミン又はヒドロキシルアミン誘導体の塩としては、Ｃｌ、Ｓ、Ｎ、及び、Ｐからなる群から選択される少なくとも１種の非金属が水素と結合してなる無機酸との塩が好ましく、塩酸塩、硫酸塩、又は、硝酸塩がより好ましい。 <Hydroxylamine compound>
Hydroxylamine compound means at least one selected from the group consisting of hydroxylamine (NH 2 OH), hydroxylamine derivatives, and salts thereof.
The hydroxylamine compound is a compound different from the components contained in the above-mentioned cleaning liquid.
The hydroxylamine derivative means a compound in which at least one organic group is substituted with hydroxylamine (NH 2 OH).
Examples of the hydroxylamine or the salt of the hydroxylamine derivative include inorganic acid salts and organic acid salts.
Among them, as the salt of the hydroxylamine or the hydroxylamine derivative, a salt with an inorganic acid in which at least one non-metal selected from the group consisting of Cl, S, N, and P is bonded to hydrogen is preferable. , Hydrochloride, sulfate, or nitrate is more preferred.
　ヒドロキシルアミン化合物としては、例えば、一般式（５）で表される化合物が挙げられる。 Examples of the hydroxylamine compound include a compound represented by the general formula (5).
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　式（５）中、Ｒ６及びＲ７は、それぞれ独立に、水素原子又は炭素数１～６のアルキル基を表す。 In formula (5), R 6 and R 7 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
　Ｒ６及びＲ７で表される炭素数１～６のアルキル基は、直鎖状、分岐鎖状、又は、環状であってもよい。
　上記アルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、シクロブチル基、ｎ－ペンチル基、イソペンチル基、ｓｅｃ－ペンチル基、ｔｅｒｔ－ペンチル基、ネオペンチル基、２－メチルブチル基、１，２－ジメチルプロピル基、１－エチルプロピル基、シクロペンチル基、ｎ－ヘキシル基、イソヘキシル基、ｓｅｃ－ヘキシル基、ｔｅｒｔ－ヘキシル基、ネオヘキシル基、２－メチルペンチル基、１，２－ジメチルブチル基、２，３－ジメチルブチル基、１－エチルブチル基、及び、シクロヘキシル基が挙げられる。
　なかでも、Ｒ６及びＲ７としては、炭素数１～６のアルキル基が好ましく、エチル基又はｎ－プロピル基がより好ましく、エチル基が更に好ましい。 The alkyl group having 1 to 6 carbon atoms represented by R 6 and R 7 may be linear, branched or cyclic.
Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, an n-pentyl group and an isopentyl group. , Se-pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert -Hexyl group, neohexyl group, 2-methylpentyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1-ethylbutyl group, and cyclohexyl group can be mentioned.
Among them, as R 6 and R 7 , an alkyl group having 1 to 6 carbon atoms is preferable, an ethyl group or an n-propyl group is more preferable, and an ethyl group is further preferable.
　ヒドロキシルアミン化合物としては、例えば、ヒドロキシルアミン、Ｎ－メチルヒドロキシルアミン、Ｎ，Ｎ－ジメチルヒドロキシルアミン、Ｎ－エチルヒドロキシルアミン、Ｎ，Ｎ－ジエチルヒドロキシルアミン（ＤＥＨＡ）、Ｎ－ｎ－プロピルヒドロキシルアミン、Ｎ，Ｎ－ジ－ｎ－プロピルヒドロキシルアミン、Ｎ－イソプロピルヒドロキシルアミン、Ｎ，Ｎ－ジイソプロピルヒドロキシルアミン、Ｎ－ｎ－ブチルヒドロキシルアミン、Ｎ，Ｎ－ジ－ｎ－ブチルヒドロキシルアミン、Ｎ－イソブチルヒドロキシルアミン、Ｎ，Ｎ－ジイソブチルヒドロキシルアミン、Ｎ－ｓｅｃ－ブチルヒドロキシルアミン、Ｎ，Ｎ－ジ－ｓｅｃ－ブチルヒドロキシルアミン、Ｎ－ｔｅｒｔ－ブチルヒドロキシルアミン、Ｎ，Ｎ－ジ－ｔｅｒｔ－ブチルヒドロキシルアミン、Ｎ－シクロブチルヒドロキシルアミン、Ｎ，Ｎ－ジシクロブチルヒドロキシルアミン、Ｎ－ｎ－ペンチルヒドロキシルアミン、Ｎ，Ｎ－ジ－ｎ－ペンチルヒドロキシルアミン、Ｎ－イソペンチルヒドロキシルアミン、Ｎ，Ｎ－ジイソペンチルヒドロキシルアミン、Ｎ－ｓｅｃ－ペンチルヒドロキシルアミン、Ｎ，Ｎ－ジ－ｓｅｃ－ペンチルヒドロキシルアミン、Ｎ－ｔｅｒｔ－ペンチルヒドロキシルアミン、Ｎ，Ｎ－ジ－ｔｅｒｔ－ペンチルヒドロキシルアミン、Ｎ－ネオペンチルヒドロキシルアミン、Ｎ，Ｎ－ジネオペンチルヒドロキシルアミン、Ｎ－２－メチルブチルヒドロキシルアミン、Ｎ，Ｎ－ビス（２－メチルブチル）ヒドロキシルアミン、Ｎ－１，２－ジメチルプロピルヒドロキシルアミン、Ｎ，Ｎ－ビス（１，２－ジメチルプロピル）ヒドロキシルアミン、Ｎ－１－エチルプロピルヒドロキシルアミン、Ｎ，Ｎ－ビス（１－エチルプロピル）ヒドロキシルアミン、Ｎ－シクロペンチルヒドロキシルアミン、Ｎ，Ｎ－ジシクロペンチルヒドロキシルアミン、Ｎ－ｎ－ヘキシルヒドロキシルアミン、Ｎ，Ｎ－ジ－ｎ－ヘキシルヒドロキシルアミン、Ｎ－イソヘキシルヒドロキシルアミン、Ｎ，Ｎ－ジイソヘキシルヒドロキシルアミン、Ｎ－ｓｅｃ－ヘキシルヒドロキシルアミン、Ｎ，Ｎ－ジ－ｓｅｃ－ヘキシルヒドロキシルアミン、Ｎ－ｔｅｒｔ－ヘキシルヒドロキシルアミン、Ｎ，Ｎ－ジ－ｔｅｒｔ－ヘキシルヒドロキシルアミン、Ｎ－ネオヘキシルヒドロキシルアミン、Ｎ，Ｎ－ジネオヘキシルヒドロキシルアミン、Ｎ－２－メチルペンチルヒドロキシルアミン、Ｎ，Ｎ－ビス（２－メチルペンチル）ヒドロキシルアミン、Ｎ－１，２－ジメチルブチルヒドロキシルアミン、Ｎ，Ｎ－ビス（１，２－ジメチルブチル）ヒドロキシルアミン、Ｎ－２，３－ジメチルブチルヒドロキシルアミン、Ｎ，Ｎ－ビス（２，３－ジメチルブチル）ヒドロキシルアミン、Ｎ－１－エチルブチルヒドロキシルアミン、Ｎ，Ｎ－ビス（１－エチルブチル）ヒドロキシルアミン、Ｎ－シクロヘキシルヒドロキシルアミン、及び、Ｎ，Ｎ－ジシクロヘキシルヒドロキシルアミンが挙げられる。
　なかでも、ヒドロキシルアミン化合物としては、ヒドロキシルアミン、Ｎ－エチルヒドロキシルアミン、ＤＥＨＡ、又は、Ｎ－ｎ－プロピルヒドロキシルアミンが好ましく、ヒドロキシルアミンがより好ましい。
　ヒドロキシルアミン化合物は、市販のものを用いてもよいし、公知の方法によって適宜合成したものを用いてもよい。 Examples of the hydroxylamine compound include hydroxylamine, N-methylhydroxylamine, N, N-dimethylhydroxylamine, N-ethylhydroxylamine, N, N-diethylhydroxylamine (DEHA), Nn-propylhydroxylamine, and the like. N, N-di-n-propyl hydroxylamine, N-isopropylhydroxylamine, N, N-diisopropylhydroxylamine, Nn-butylhydroxylamine, N, N-di-n-butylhydroxylamine, N-isobutylhydroxylamine Amine, N, N-diisobutyl hydroxylamine, N-sec-butyl hydroxylamine, N, N-di-sec-butyl hydroxylamine, N-tert-butyl hydroxylamine, N, N-di-tert-butyl hydroxylamine, N-Cyclobutyl hydroxylamine, N, N-dicyclobutyl hydroxylamine, Nn-pentyl hydroxylamine, N, N-di-n-pentyl hydroxylamine, N-isopentyl hydroxylamine, N, N-diiso Pentyl hydroxylamine, N-sec-pentyl hydroxylamine, N, N-di-sec-pentyl hydroxylamine, N-tert-pentyl hydroxylamine, N, N-di-tert-pentyl hydroxylamine, N-neopentyl hydroxylamine , N, N-dineopentyl hydroxylamine, N-2-methylbutyl hydroxylamine, N, N-bis (2-methylbutyl) hydroxylamine, N-1,2-dimethylpropyl hydroxylamine, N, N-bis ( 1,2-dimethylpropyl) hydroxylamine, N-1-ethylpropyl hydroxylamine, N, N-bis (1-ethylpropyl) hydroxylamine, N-cyclopentyl hydroxylamine, N, N-dicyclopentyl hydroxylamine, N- n-hexyl hydroxylamine, N, N-di-n-hexyl hydroxylamine, N-isohexyl hydroxylamine, N, N-diisohexyl hydroxylamine, N-sec-hexyl hydroxylamine, N, N-di-sec -Hexyl hydroxylamine, N-tert-hexyl hydroxylamine, N, N-di-tert-hexyl hydroxylamine, N-neohexyl hydroxylamine, N, N-dineohexyl hydroxylamine, N-2-methylpentylhydr. Roxylamine, N, N-bis (2-methylpentyl) hydroxylamine, N-1,2-dimethylbutylhydroxylamine, N, N-bis (1,2-dimethylbutyl) hydroxylamine, N-2,3-dimethyl Butyl hydroxylamine, N, N-bis (2,3-dimethylbutyl) hydroxylamine, N-1-ethylbutylhydroxylamine, N, N-bis (1-ethylbutyl) hydroxylamine, N-cyclohexylhydroxylamine, and Examples include N, N-dicyclohexylhydroxylamine.
Among them, as the hydroxylamine compound, hydroxylamine, N-ethylhydroxylamine, DEHA, or Nn-propylhydroxylamine is preferable, and hydroxylamine is more preferable.
As the hydroxylamine compound, a commercially available compound may be used, or a compound appropriately synthesized by a known method may be used.
＜ビグアニド化合物＞
　ビグアニド化合物は、ビグアニド基を有する化合物、及び、その塩であるビグアニド化合物である。
　ビグアニド化合物が有するビグアニド基の数は、単数又は複数であってもよい。
　ビグアニド化合物としては、特表２０１７－５０４１９０号公報の段落［００３４］～［００５５］に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。 <Biguanide compound>
The biguanide compound is a compound having a biguanide group and a biguanide compound which is a salt thereof.
The number of biguanide groups contained in the biguanide compound may be singular or plural.
Examples of the biguanide compound include the compounds described in paragraphs [0034] to [0055] of JP-A-2017-504190, the contents of which are incorporated in the present specification.
　ビグアニド基を有する化合物としては、エチレンジビグアニド、プロピレンジビグアニド、テトラメチレンジビグアニド、ペンタメチレンジビグアニド、ヘキサメチレンジビグアニド、ヘプタメチレンジビグアニド、オクタメチレンジビグアニド、１，１’－ヘキサメチレンビス（５－（ｐ－クロロフェニル）ビグアニド）（クロルヘキシジン）、２－（ベンジルオキシメチル）ペンタン－１，５－ビス（５－ヘキシルビグアニド）、２－（フェニルチオメチル）ペンタン－１，５－ビス（５－フェネチルビグアニド）、３－（フェニルチオ）ヘキサン－１，６－ビス（５－ヘキシルビグアニド）、３－（フェニルチオ）ヘキサン－１，６－ビス（５－シクロヘキシルビグアニド）、３－（ベンジルチオ）ヘキサン－１，６－ビス（５－ヘキシルビグアニド）、又は、３－（ベンジルチオ）ヘキサン－１，６－ビス（５－シクロヘキシルビグアニド）が好ましく、クロルヘキシジンがより好ましい。
　ビグアニド基を有する化合物の塩としては、塩酸塩、酢酸塩、又は、グルコン酸塩が好ましく、グルコン酸塩がより好ましい。
　ビグアニド化合物としては、クロルヘキシジングルコン酸塩（ＣＨＧ）が好ましい。 Examples of the compound having a biguanide group include ethylene diviguanide, propylene diviguanide, tetramethylene diviguanide, pentamethylene diviguanide, hexamethylene diviguanide, heptamethylene diviguanide, octamethylene diviguanide, and 1,1'-hexamethylenebis ( 5- (p-chlorophenyl) biguanide) (chlorhexidine), 2- (benzyloxymethyl) pentane-1,5-bis (5-hexylbiguanide), 2- (phenylthiomethyl) pentane-1,5-bis (5) -Phenetyl biguanide), 3- (phenylthio) hexane-1,6-bis (5-hexylbiguanide), 3- (phenylthio) hexane-1,6-bis (5-cyclohexylbiguanide), 3- (benzylthio) hexane- 1,6-bis (5-hexylbiguanide) or 3- (benzylthio) hexane-1,6-bis (5-cyclohexylbiguanide) is preferred, and chlorhexidine is more preferred.
As the salt of the compound having a biguanide group, a hydrochloride salt, an acetate salt, or a gluconate salt is preferable, and a gluconate salt salt is more preferable.
As the biguanide compound, chlorhexidine gluconate (CHG) is preferable.
＜ヒドラジド化合物＞
　ヒドラジド化合物は、酸のヒドロキシル基をヒドラジノ基（－ＮＨ－ＮＨ２）で置換してなる化合物、及び、その誘導体（ヒドラジノ基に少なくとも１つの置換基が置換されてなる化合物）を意味する。
　ヒドラジド化合物は、１つ又は２つ以上のヒドラジノ基を有していてもよい。
　ヒドラジド化合物としては、例えば、カルボン酸ヒドラジド及びスルホン酸ヒドラジドが挙げられ、カルボヒドラジド（ＣＨＺ）が好ましい。 <Hydrazide compound>
The hydrazide compound means a compound in which the hydroxyl group of an acid is substituted with a hydrazino group (-NH-NH 2 ), and a derivative thereof (a compound in which at least one substituent is substituted with a hydrazino group).
The hydrazide compound may have one or more hydrazino groups.
Examples of the hydrazide compound include carboxylic acid hydrazide and sulfonic acid hydrazide, and carbohydrazide (CHZ) is preferable.
＜アスコルビン酸化合物＞
　アスコルビン酸化合物は、アスコルビン酸、アスコルビン酸誘導体、及び、それらの塩からなる群から選択される少なくとも１種を意味する。
　アスコルビン酸誘導体としては、例えば、アスコルビン酸リン酸エステル、及び、アスコルビン酸硫酸エステルが挙げられる。
　なかでも、アスコルビン酸としては、アスコルビン酸が好ましい。 <Ascorbic acid compound>
The ascorbic acid compound means at least one selected from the group consisting of ascorbic acid, ascorbic acid derivatives, and salts thereof.
Examples of the ascorbic acid derivative include ascorbic acid phosphate ester and ascorbic acid sulfate ester.
Among them, ascorbic acid is preferable as ascorbic acid.
＜還元性硫黄化合物＞
　還元性硫黄化合物は、還元性を有し、硫黄原子を含む化合物である。
　還元性硫黄化合物としては、例えば、チオグリコール酸、ジチオジグリコール酸、ビス（２，３－ジヒドロキシプロピルチオ）エチレン、３－（２，３－ジヒドロキシプロピルチオ）－２－メチル－プロピルスルホン酸ナトリウム、１－チオグリセロール、２－メルカプトエタノール、及び、３－メルカプト－１－プロパノールが挙げられる。
　なかでも、ＳＨ基を有する化合物（メルカプト化合物）が好ましく、チオグリコール酸又はジチオジグリコール酸がより好ましい。 <Reducing sulfur compound>
The reducing sulfur compound is a compound having reducing property and containing a sulfur atom.
Examples of the reducing sulfur compound include thioglycolic acid, dithiodiglycolic acid, bis (2,3-dihydroxypropylthio) ethylene, and 3- (2,3-dihydroxypropylthio) -2-methyl-propylsulfonate sodium. , 1-thioglycerol, 2-mercaptoethanol, and 3-mercapto-1-propanol.
Among them, a compound having an SH group (mercapto compound) is preferable, and thioglycolic acid or dithiodiglycolic acid is more preferable.
＜分子量５００以上のポリヒドロキシ化合物＞
　上記ポリヒドロキシ化合物は、１分子中に２つ以上（例えば、２～２００）のアルコール性ヒドロキシル基を有する有機化合物である。
　上記ポリヒドロキシ化合物は、上述した洗浄液に含まれる成分とは異なる化合物である。
　上記ポリヒドロキシ化合物の分子量（分子量分布を有する場合は、重量平均分子量を意味する）は、５００以上であり、５００～３０００が好ましい。 <Polyhydroxy compound with a molecular weight of 500 or more>
The polyhydroxy compound is an organic compound having two or more (for example, 2 to 200) alcoholic hydroxyl groups in one molecule.
The polyhydroxy compound is a compound different from the components contained in the cleaning liquid described above.
The molecular weight of the polyhydroxy compound (meaning a weight average molecular weight when it has a molecular weight distribution) is 500 or more, preferably 500 to 3000.
　上記ポリヒドロキシ化合物としては、例えば、ポリエチレングリコール、ポリプロピレングルコール、及び、ポリオキシエチレンポリオキシプロピレングリコール等のポリオキシアルキレングリコール；マンニノトリオース、セロトリオース、ゲンチアノース、ラフィノース、メレチトース、セロテトロース、及び、スタキオース等のオリゴ糖；デンプン、グリコーゲン、セルロース、キチン、及び、キトサン等の多糖類、並びに、それらの加水分解物が挙げられ、ポリエチレングリコールが好ましい。 Examples of the polyhydroxy compound include polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol; Oligosaccharides such as; polysaccharides such as starch, glycogen, cellulose, chitin, and chitosan, and hydrolyzates thereof, and polyethylene glycol is preferable.
　上記ポリヒドロキシ化合物としては、シクロデキストリンも好ましい。
　シクロデキストリンは、複数のＤ－グルコースがグルコシド結合によって結合し、環状構造をとった環状オリゴ糖の１種である。例えば、グルコースが５個以上（例えば、６～８個）結合した化合物が挙げられる。
　シクロデキストリンとしては、例えば、α－シクロデキストリン、β－シクロデキストリン、及び、γ－シクロデキストリンが挙げられ、γ－シクロデキストリンが好ましい。 Cyclodextrin is also preferable as the polyhydroxy compound.
Cyclodextrin is a kind of cyclic oligosaccharide having a cyclic structure in which a plurality of D-glucoses are bound by a glucosidic bond. For example, a compound in which 5 or more glucoses (for example, 6 to 8 glucoses) are bound can be mentioned.
Examples of the cyclodextrin include α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, and γ-cyclodextrin is preferable.
　防食剤は、カテコール化合物、ヘテロ環式化合物、ヒドロキシアミン化合物、ビグアニド化合物、アスコルビン酸、還元性硫黄化合物、及び、分子量５００以上のポリヒドロキシ化合物からなる群から選択される少なくとも１つを含むことが好ましく、ヘテロ環式化合物を含むことがより好ましい。 The anticorrosion agent may include at least one selected from the group consisting of catechol compounds, heterocyclic compounds, hydroxyamine compounds, biguanide compounds, ascorbic acid, reducing sulfur compounds, and polyhydroxy compounds having a molecular weight of 500 or more. It is preferable to include a heterocyclic compound.
　防食剤は、１種単独で使用してもよく、２種以上を使用してもよい。
　防食剤の含有量は、洗浄液の全質量に対して、０．０１～１０．０質量％が好ましく、０．０５～５．０質量％がより好ましく、０．０５～３．０質量％が更に好ましい。
　防食剤の含有量は、溶媒を除いた洗浄液の全質量に対して、０．２～２０．０質量％が好ましく、１．０～１０．０質量％がより好ましく、１．５～５．０質量％が更に好ましい。 The anticorrosive agent may be used alone or in combination of two or more.
The content of the anticorrosive agent is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5.0% by mass, and 0.05 to 3.0% by mass with respect to the total mass of the cleaning liquid. More preferred.
The content of the anticorrosive agent is preferably 0.2 to 20.0% by mass, more preferably 1.0 to 10.0% by mass, and 1.5 to 5. 0% by mass is more preferable.
〔防腐剤〕
　洗浄液は、防腐剤を含んでいてもよい。
　防腐剤は、上述した洗浄液に含まれる成分とは異なる化合物である。
　防腐剤としては、例えば、安息香酸、安息香酸ナトリウム、サリチル酸、プロピオン酸、パラオキシ安息香酸イソプロピル、パラオキシ安息香酸イソブチル、パラオキシ安息香酸エチル、パラオキシ安息香酸メチル、パラオキシ安息香酸ブチル、パラオキシ安息香酸プロピル、亜硫酸ナトリウム、次亜硫酸ナトリウム、ピロ亜硫酸カリウム、ソルビン酸、ソルビン酸カリウム、デヒドロ酢酸ナトリウム、ツヤプリシン、ウド抽出物、エゴノキ抽出物、カワラヨモギ抽出物、ウーロン茶抽出物、しらこたん白抽出物、酵素分解ハトムギ抽出物、茶カテキン類、リンゴポリフェノール、ペクチン分解物、キトサン、リゾチーム、及び、ε－ポリリジンが挙げられる。
　なかでも、防腐剤としては、安息香酸、ソルビン酸、サリチル酸、又は、プロピオン酸が好ましい。 〔Preservative〕
The cleaning solution may contain a preservative.
The preservative is a compound different from the components contained in the above-mentioned cleaning liquid.
Examples of preservatives include benzoic acid, sodium benzoate, salicylic acid, propionic acid, isopropyl paraoxybenzoate, isobutyl paraoxybenzoate, ethyl paraoxybenzoate, methyl paraoxybenzoate, butyl paraoxybenzoate, propyl paraoxybenzoate, and sulfite. Sodium, sodium hyposulfate, potassium pyrosulfate, sorbic acid, potassium sorbate, sodium dehydroacetate, luster, udo extract, egonoki extract, kawarayomogi extract, oolong tea extract, shirako protein extract, enzymatically decomposed honeybee extract Examples include substances, tea catechins, apple polyphenols, pectin degradation products, chitosan, lysoteam, and ε-polylysine.
Among them, benzoic acid, sorbic acid, salicylic acid, or propionic acid is preferable as the preservative.
　安息香酸、ソルビン酸、サリチル酸、及び、プロピオン酸は、後述するｐＨ調整剤及び金属溶解剤としても使用してもよい。 Benzoic acid, sorbic acid, salicylic acid, and propionic acid may also be used as a pH adjuster and a metal dissolving agent described later.
　防腐剤は、１種単独で使用してもよく、２種以上を使用してもよい。
　防腐剤の含有量は、洗浄液の全質量に対して、０．０１～１０．０質量％が好ましく、０．０５～５．０質量％がより好ましく、０．０５～３．０質量％が更に好ましい。
　防食剤の含有量は、溶媒を除いた洗浄液の全質量に対して、０．２～２０．０質量％が好ましく、１．０～１０．０質量％がより好ましく、１．５～５．０質量％が更に好ましい。 The preservative may be used alone or in combination of two or more.
The content of the preservative is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5.0% by mass, and 0.05 to 3.0% by mass with respect to the total mass of the cleaning liquid. More preferred.
The content of the anticorrosive agent is preferably 0.2 to 20.0% by mass, more preferably 1.0 to 10.0% by mass, and 1.5 to 5. 0% by mass is more preferable.
　洗浄液は、界面活性剤、防食剤、及び、防腐剤からなる群から選択される少なくとも１つを含むことが好ましく、界面活性剤、及び、防食剤からなる群から選択される少なくとも１つを含むことがより好ましく、防食剤を含むことが更に好ましく、ヘテロ環式化合物を含むことが特に好ましい。 The cleaning liquid preferably contains at least one selected from the group consisting of a surfactant, an anticorrosive agent, and an antiseptic, and contains at least one selected from the group consisting of a surfactant and an anticorrosive agent. It is more preferable, it is more preferable to contain an anticorrosive agent, and it is particularly preferable to contain a heterocyclic compound.
〔酸化剤〕
　洗浄液は、酸化剤を含んでいてもよい。
　酸化剤は、上述した洗浄液に含まれる成分とは異なる化合物である。
　酸化剤としては、例えば、過酸化物、過硫化物（例えば、モノ過硫化物及びジ過硫化物等）、過炭酸塩、それらの酸、及び、それらの塩が挙げられる。
　酸化剤としては、例えば、酸化ハライド（ヨウ素酸、メタ過ヨウ素酸及びオルト過ヨウ素酸等の過ヨウ素酸、及び、それらの塩等）、過ホウ酸、過ホウ酸塩、セリウム化合物、及び、フェリシアン化物（フェリシアン化カリウム等）が挙げられる。 〔Oxidant〕
The cleaning liquid may contain an oxidizing agent.
The oxidizing agent is a compound different from the components contained in the cleaning liquid described above.
Examples of the oxidizing agent include peroxides, persulfides (for example, monopersulfides and dipersulfides, etc.), percarbonates, their acids, and salts thereof.
Examples of the oxidizing agent include oxidized halide (periodic acid such as iodic acid, metaperiodic acid and orthoperiodic acid, and salts thereof), periodic acid, periodic acid salt, cerium compound, and the like. Examples include ferricyanides (potassium ferricyanide, etc.).
　酸化剤は、１種単独で使用してもよく、２種以上を使用してもよい。
　酸化剤の含有量は、洗浄液の全質量に対して、０．０１～１０質量％が好ましく、０．０５～５質量％がより好ましく、０．１～３質量％が更に好ましい。 The oxidizing agent may be used alone or in combination of two or more.
The content of the oxidizing agent is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, still more preferably 0.1 to 3% by mass, based on the total mass of the cleaning liquid.
〔ｐＨ調整剤〕
　洗浄液は、洗浄液のｐＨを調整及び維持するためにｐＨ調整剤を含んでいてもよい。
　ｐＨ調整剤は、上述した洗浄液に含まれる成分とは異なる化合物である。
　ｐＨ調整剤としては、例えば、第４級アンモニウム化合物、塩基性化合物、及び、酸性化合物が挙げられる。
　なかでも、第４級アンモニウム化合物、硫酸、又は、水酸化カリウムが好ましい。
　ただし、上述した各成分の添加量を調整することで、洗浄液のｐＨを調整させることは許容される。 [PH regulator]
The cleaning solution may contain a pH regulator to adjust and maintain the pH of the cleaning solution.
The pH adjuster is a compound different from the components contained in the cleaning solution described above.
Examples of the pH adjuster include a quaternary ammonium compound, a basic compound, and an acidic compound.
Of these, a quaternary ammonium compound, sulfuric acid, or potassium hydroxide is preferable.
However, it is permissible to adjust the pH of the cleaning solution by adjusting the amount of each component added as described above.
　第４級アンモニウム化合物は、上述した洗浄液に含まれる成分とは異なる化合物である。
　第４級アンモニウム化合物は、窒素原子に４つの炭化水素基（アルキル基が好ましい）が置換してなる第４級アンモニウムカチオンを有する化合物が好ましい。また、第４級アンモニウム化合物は、アルキルピリジニウムのように、ピリジン環における窒素原子が置換基（アルキル基及びアリール基等の炭化水素基等）と結合した第４級アンモニウムカチオンを有する化合物であってもよい。
　第４級アンモニウム化合物としては、例えば、第４級アンモニウム水酸化物、第４級アンモニウムフッ化物、第４級アンモニウム臭化物、第４級アンモニウムヨウ化物、第４級アンモニウムの酢酸塩、及び、第４級アンモニウムの炭酸塩が挙げられる。 The quaternary ammonium compound is a compound different from the components contained in the above-mentioned cleaning liquid.
The quaternary ammonium compound is preferably a compound having a quaternary ammonium cation in which a nitrogen atom is substituted with four hydrocarbon groups (preferably an alkyl group). Further, the quaternary ammonium compound is a compound having a quaternary ammonium cation in which a nitrogen atom in the pyridine ring is bonded to a substituent (hydrocarbon group such as an alkyl group and an aryl group), such as an alkylpyridinium. May be good.
Examples of the quaternary ammonium compound include a quaternary ammonium hydroxide, a quaternary ammonium fluoride, a quaternary ammonium bromide, a quaternary ammonium iodide, a quaternary ammonium acetate, and a quaternary ammonium compound. Examples include carbonates of quaternary ammonium.
　第４級アンモニウム化合物としては、式（４）で表される第４級アンモニウム水酸化物が好ましい。
　　（Ｒ８）４Ｎ＋ＯＨ－　　　（４）
　式（４）中、Ｒ８は、置換基としてヒドロキシル基又はフェニル基を有していてもよいアルキル基を表す。４つのＲ８は、互いに同一であっても異なっていてもよい。 As the quaternary ammonium compound, a quaternary ammonium hydroxide represented by the formula (4) is preferable.
(R 8 ) 4 N + OH- ( 4)
In formula (4), R 8 represents an alkyl group which may have a hydroxyl group or a phenyl group as a substituent. The four R8s may be the same or different from each other.
　Ｒ８で表されるアルキル基としては、炭素数１～４のアルキル基が好ましく、メチル基又はエチル基がより好ましい。
　Ｒ８で表されるヒドロキシル基又はフェニル基を有していてもよいアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、２－ヒドロキシエチル基、又は、ベンジル基が好ましく、メチル基、エチル基、プロピル基、ブチル基、又は、２－ヒドロキシエチル基がより好ましく、メチル基、エチル基、又は、２－ヒドロキシエチル基が更に好ましい。 As the alkyl group represented by R 8 , an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
As the alkyl group represented by R8 which may have a hydroxyl group or a phenyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-hydroxyethyl group, or a benzyl group is preferable, and a methyl group is used. , Ethyl group, propyl group, butyl group, or 2-hydroxyethyl group is more preferable, and methyl group, ethyl group, or 2-hydroxyethyl group is further preferable.
　第４級アンモニウム化合物としては、例えば、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、トリメチルエチルアンモニウムヒドロキシド（ＴＭＥＡＨ）、ジメチルジエチルアンモニウムヒドロキシド（ＤＭＤＥＡＨ）、メチルトリエチルアンモニウムヒドロキシド（ＭＴＥＡＨ）、テトラエチルアンモニウムヒドロキシド（ＴＥＡＨ）、テトラプロピルアンモニウムヒドロキシド（ＴＰＡＨ）、テトラブチルアンモニウムヒドロキシド（ＴＢＡＨ）、２－ヒドロキシエチルトリメチルアンモニウムヒドロキシド（コリン）、ビス（２－ヒドロキシエチル）ジメチルアンモニウムヒドロキシド、トリ（２－ヒドロキシエチル）メチルアンモニウムヒドロキシド、テトラ（２－ヒドロキシエチル）アンモニウムヒドロキシド、ベンジルトリメチルアンモニウムヒドロキシド（ＢＴＭＡＨ）、及び、セチルトリメチルアンモニウムヒドロキシドが挙げられる。
　第４級アンモニウム化合物としては、例えば、特開２０１８－１０７３５３号公報の段落［００２１］に記載の化合物も援用でき、これらの内容は本明細書に組み込まれる。
　なかでも、第４級アンモニウム化合物としては、ＴＭＡＨ、ＴＥＡＨ、コリン、ＴＢＡＨ、ＭＴＥＡＨ、ＤＭＤＥＡＨ、又は、ＴＰＡＨが好ましく、ＴＭＡＨ、ＴＥＡＨ、又は、コリンがより好ましい。 Examples of the quaternary ammonium compound include tetramethylammonium hydroxide (TMAH), trimethylethylammonium hydroxide (TMEAH), dimethyldiethylammonium hydroxide (DMDEAH), methyltriethylammonium hydroxide (MTEAH), and tetraethylammonium hydroxide. (TEAH), Tetrapropyl Ammonium Hydroxide (TPAH), Tetrabutyl Ammonium Hydroxide (TBAH), 2-Hydroxyethyl Trimmonium Ammonium Hydroxide (Colin), Bis (2-Hydroxyethyl) Dimethyl Ammonium Hydroxide, Tri (2-) Examples thereof include hydroxyethyl) methylammonium hydroxide, tetra (2-hydroxyethyl) ammonium hydroxide, benzyltrimethylammonium hydroxide (BTMAH), and cetyltrimethylammonium hydroxide.
As the quaternary ammonium compound, for example, the compound described in paragraph [0021] of JP-A-2018-107353 can also be incorporated, and the contents thereof are incorporated in the present specification.
Among them, as the quaternary ammonium compound, TMAH, TEAH, choline, TBAH, MTEAH, DMDEAH, or TPAH is preferable, and TMAH, TEAH, or choline is more preferable.
　第４級アンモニウム化合物は、耐ダメージ性に優れる点から、非対称構造を有することも好ましい。第４級アンモニウム化合物が「非対称構造を有する」とは、窒素原子に置換する４つの炭化水素基がいずれも同一ではないことを意味する。
　非対称構造を有する第４級アンモニウム化合物としては、例えば、ＴＭＥＡＨ、ＤＥＤＭＡＨ、ＴＥＭＡＨ、コリン、及び、ビス（２－ヒドロキシエチル）ジメチルアンモニウムヒドロキシドが挙げられる。 The quaternary ammonium compound preferably has an asymmetric structure from the viewpoint of excellent damage resistance. By "having an asymmetric structure" in a quaternary ammonium compound is meant that none of the four hydrocarbon groups substituting for nitrogen atoms are the same.
Examples of the quaternary ammonium compound having an asymmetric structure include TMEAH, DEDHH, TEMAH, choline, and bis (2-hydroxyethyl) dimethylammonium hydroxide.
　塩基性化合物としては、塩基性有機化合物及び塩基性無機化合物が挙げられる。
　塩基性有機化合物としては、例えば、アミンオキシド、ニトロ、ニトロソ、オキシム、ケトオキシム、アルドオキシム、ラクタム、イソシアニド類、及び、尿素が挙げられる。
　塩基性無機化合物としては、例えば、アルカリ金属水酸化物、アルカリ土類金属水酸化物、及び、アンモニアが挙げられる。
　アルカリ金属水酸化物としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、及び、水酸化セシウムが挙げられる。
　アルカリ土類金属水酸化物としては、例えば、水酸化カルシウム、水酸化ストロンチウム、及び、水酸化バリウムが挙げられる。 Examples of the basic compound include a basic organic compound and a basic inorganic compound.
Examples of the basic organic compound include amine oxides, nitros, nitroso, oximes, ketooximes, aldoximes, lactams, isocyanides, and ureas.
Examples of the basic inorganic compound include alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia.
Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide.
Examples of the alkaline earth metal hydroxide include calcium hydroxide, strontium hydroxide, and barium hydroxide.
　酸性化合物としては、例えば、無機酸が挙げられる。
　酸性化合物としては、水溶液中で酸又は酸イオン（アニオン）となるものであれば、酸性化合物の塩を用いてもよい。 Examples of the acidic compound include inorganic acids.
As the acidic compound, a salt of the acidic compound may be used as long as it becomes an acid or an acid ion (anion) in an aqueous solution.
　無機酸としては、例えば、塩酸、硫酸、亜硫酸、硝酸、亜硝酸、リン酸、ホウ酸、及び、六フッ化リン酸が挙げられる。 Examples of the inorganic acid include hydrochloric acid, sulfuric acid, sulfite, nitric acid, nitrite, phosphoric acid, boric acid, and hexafluorophosphate.
　無機酸は、塩を形成していてもよい。
　無機酸の塩としては、例えば、無機酸のアンモニウム塩が挙げられ、具体的には、塩化アンモニウム、硫酸アンモニウム、亜硫酸アンモニウム、硝酸アンモニウム、亜硝酸アンモニウム、リン酸アンモニウム、ホウ酸アンモニウム、及び、六フッ化リン酸アンモニウムが挙げられる。 The inorganic acid may form a salt.
Examples of the salt of the inorganic acid include an ammonium salt of an inorganic acid, and specifically, ammonium chloride, ammonium sulfate, ammonium sulfite, ammonium nitrate, ammonium nitrite, ammonium phosphate, ammonium borate, and phosphorus hexafluoride. Ammonium sulphate can be mentioned.
　ｐＨ調整剤は、１種単独で使用してもよく、２種以上を使用してもよい。
　ｐＨ調整剤の含有量は、特に制限されず、他の成分の種類及び量、並びに、目的とする洗浄液のｐＨに応じて適宜調整される。
　ｐＨ調整剤の含有量は、洗浄液の全質量に対して、０．０１～１０．０質量％が好ましく、０．０５～５．０質量％がより好ましく、０．０５～３．０質量％が更に好ましい。
　ｐＨ調整剤の含有量は、溶媒を除いた洗浄液の全質量に対して、０．２～２０．０質量％が好ましく、１．０～１０．０質量％がより好ましく、１．５～５．０質量％が更に好ましい。 The pH adjuster may be used alone or in combination of two or more.
The content of the pH adjuster is not particularly limited, and is appropriately adjusted according to the type and amount of other components and the pH of the target cleaning solution.
The content of the pH adjuster is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 5.0% by mass, and 0.05 to 3.0% by mass with respect to the total mass of the cleaning liquid. Is more preferable.
The content of the pH adjuster is preferably 0.2 to 20.0% by mass, more preferably 1.0 to 10.0% by mass, and 1.5 to 5 to the total mass of the cleaning liquid excluding the solvent. .0% by mass is more preferable.
〔有機溶媒〕
　洗浄液は、有機溶媒を含んでいてもよい。
　有機溶媒は、上述した洗浄液に含まれる成分とは異なる化合物である。
　有機溶媒としては、公知の有機溶媒を用いることができ、親水性有機溶媒が好ましい。
　親水性有機溶媒としては、アルコール系溶媒、ケトン系溶媒、エステル系溶媒、スルホン系溶媒、スルホキシド系溶媒、ニトリル系溶媒、及び、アミド系溶媒が挙げられる。
　なかでも、親水性有機溶媒としては、アルコール系溶媒、又は、ニトリル系溶媒が好ましい。 [Organic solvent]
The cleaning liquid may contain an organic solvent.
The organic solvent is a compound different from the components contained in the cleaning liquid described above.
As the organic solvent, a known organic solvent can be used, and a hydrophilic organic solvent is preferable.
Examples of the hydrophilic organic solvent include alcohol-based solvents, ketone-based solvents, ester-based solvents, sulfone-based solvents, sulfoxide-based solvents, nitrile-based solvents, and amide-based solvents.
Among them, the hydrophilic organic solvent is preferably an alcohol solvent or a nitrile solvent.
　アルコール系溶媒としては、例えば、アルキレングリコール等のアルカンジオール、グリコールモノエーテル等のアルコキシアルコール、飽和脂肪族１価のアルコール、不飽和非芳香族１価アルコール、及び、環状構造を含む低分子量のアルコールが挙げられる。 Examples of the alcohol-based solvent include alkanediol such as alkylene glycol, alkoxy alcohol such as glycol monoether, saturated aliphatic monohydric alcohol, unsaturated non-aromatic monohydric alcohol, and low molecular weight alcohol containing a cyclic structure. Can be mentioned.
　アルカンジオールとしては、例えば、グリコール、２－メチル－１，３－プロパンジオール、１，３－プロパンジオール、２，２－ジメチル－１，３－ジオール、１，４－ブタンジオール、１，３－ブタンジオール、１，２－ブタンジオール、２，３－ブタンジオール、ピナコール、及び、アルキレングリコールが挙げられる。 Examples of the alkanediol include glycol, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-diol, 1,4-butanediol, and 1,3-. Examples thereof include butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, and alkylene glycol.
　アルキレングリコールとしては、例えば、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、及び、テトラエチレングリコールが挙げられる。 Examples of the alkylene glycol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol.
　アルコキシアルコールとしては、例えば、３－メトキシ－３－メチル－１－ブタノール、３－メトキシ－１－ブタノール、１－メトキシ－２－ブタノール、及び、グリコールモノエーテルが挙げられる。 Examples of the alkoxy alcohol include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and glycol monoether.
　グリコールモノエーテルとしては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノｎ－プロピルエーテル、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノｎ－ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリエチレングリコールモノブチルエーテル、１－メトキシ－２－プロパノール、２－メトキシ－１－プロパノール、１－エトキシ－２－プロパノール、２－エトキシ－１－プロパノール、プロピレングリコールモノ－ｎ－プロピルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノ－ｎ－プロピルエーテル、トリプロピレングリコールモノエチルエーテル、トリプロピレングリコールモノメチルエーテル、エチレングリコールモノベンジルエーテル、及び、ジエチレングリコールモノベンジルエーテルが挙げられる。 Examples of the glycol monoether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol. Monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy- 1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene Examples thereof include glycol monobenzyl ether and diethylene glycol monobenzyl ether.
　飽和脂肪族１価のアルコールとしては、例えば、メタノール、エタノール、ｎ－プロピルアルコール、イソプロピルアルコール、１－ブタノール、２－ブタノール、イソブチルアルコール、ｔｅｒｔ－ブチルアルコール、２－ペンタノール、ｔ－ペンチルアルコール、及び、１－ヘキサノールが挙げられる。 Examples of the saturated aliphatic monohydric alcohol include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 2-pentanol, and t-pentyl alcohol. And 1-hexanol.
　不飽和非芳香族１価のアルコールとしては、例えば、アリルアルコール、プロパルギルアルコール、２－ブテニルアルコール、３－ブテニルアルコール、及び、４－ペンテン－２－オールが挙げられる。 Examples of unsaturated non-aromatic monohydric alcohols include allyl alcohol, propargyl alcohol, 2-butenyl alcohol, 3-butenyl alcohol, and 4-penten-2-ol.
　環状構造を含む低分子量のアルコールとしては、例えば、テトラヒドロフルフリルアルコール、フルフリルアルコール、及び、１，３－シクロペンタンジオールが挙げられる。 Examples of low molecular weight alcohols containing a cyclic structure include tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol.
　ケトン系溶媒としては、例えば、アセトン、プロパノン、シクロブタノン、シクロペンタノン、シクロヘキサノン、ジアセトンアルコール、２－ブタノン、５－ヘキサンジオン、１，４－シクロヘキサンジオン、３－ヒドロキシアセトフェノン、１，３－シクロヘキサンジオン、及び、シクロヘキサノンが挙げられる。 Examples of the ketone solvent include acetone, propanone, cyclobutanone, cyclopentanone, cyclohexanone, diacetone alcohol, 2-butanone, 5-hexanedione, 1,4-cyclohexanedione, 3-hydroxyacetophenone, and 1,3-cyclohexane. Examples include dione and cyclohexanone.
　エステル系溶媒としては、例えば、酢酸エチル、エチレングリコールモノアセタート、及び、ジエチレングリコールモノアセタート等のグリコールモノエステル；プロピレングリコールモノメチルエーテルアセタート、エチレングリコールモノメチルエーテルアセタート、プロピレングリコールモノエチルエーテルアセタート、及び、エチレングリコールモノエチルエーテルアセタート等のグリコールモノエーテルモノエステルが挙げられる。 Examples of the ester solvent include glycol monoesters such as ethyl acetate, ethylene glycol monoacetate, and diethylene glycol monoacetate; propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. , And glycol monoether monoesters such as ethylene glycol monoethyl ether acetate.
　スルホン系溶媒としては、例えば、スルホラン、３－メチルスルホラン、及び、２，４－ジメチルスルホランが挙げられる。 Examples of the sulfone solvent include sulfolane, 3-methylsulfolane, and 2,4-dimethylsulfolane.
　スルホキシド系溶媒としては、例えば、ジメチルスルホキシドが挙げられる。
　スルホキシド系溶媒を用いる場合、硫酸イオン、塩化物イオン、又は、硝酸イオン等の無機イオン、及び、金属イオンが低減されたグレードのものを用いるか、又は、更に精製して用いることが好ましい。 Examples of the sulfoxide-based solvent include dimethyl sulfoxide.
When a sulfoxide solvent is used, it is preferable to use a grade in which inorganic ions such as sulfate ion, chloride ion, or nitrate ion and metal ion are reduced, or further purify the solvent.
　ニトリル系溶媒としては、例えば、アセトニトリルが挙げられる。 Examples of the nitrile solvent include acetonitrile.
　アミド系溶媒としては、例えば、Ｎ，Ｎ－ジメチルホルムアミド、１－メチル－２－ピロリドン、２－ピロリジノン、１，３－ジメチル－２－イミダゾリジノン、２－ピロリジノン、ε－カプロラクタム、ホルムアミド、Ｎ－メチルホルムアミド、アセトアミド、Ｎ－メチルアセトアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルプロパンアミド、及び、ヘキサメチルホスホリックトリアミドが挙げられる。 Examples of the amide solvent include N, N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, and N. -Methylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, and hexamethylphosphoric triamide can be mentioned.
　有機溶媒は、１種単独で使用してもよく、２種以上を使用してもよい。
　有機溶媒の含有量は、洗浄液の全質量に対して、０．０１～８０質量％が好ましく、０．０１～５０質量％がより好ましく、０．０１～１０質量％が更に好ましく、０．０１～１質量％が特に好ましい。 The organic solvent may be used alone or in combination of two or more.
The content of the organic solvent is preferably 0.01 to 80% by mass, more preferably 0.01 to 50% by mass, further preferably 0.01 to 10% by mass, and 0.01 to the total mass of the cleaning liquid. ~ 1% by mass is particularly preferable.
〔他の成分〕
　洗浄液は、フッ素化合物を含んでいてもよい。
　フッ素化合物としては、例えば、特開２００５－１５０２３６号公報の段落［００１３］～［００１５］に記載の化合物が挙げられ、これらの内容は本明細書に組み込まれる。
　フッ素化合物の使用量は特に制限されず、本発明の効果を妨げない範囲で適宜調整できる。 [Other ingredients]
The cleaning liquid may contain a fluorine compound.
Examples of the fluorine compound include the compounds described in paragraphs [0013] to [0015] of JP-A-2005-150236, and the contents thereof are incorporated in the present specification.
The amount of the fluorine compound used is not particularly limited and can be appropriately adjusted as long as the effect of the present invention is not impaired.
　上記各成分の含有量は、ガスクロマトグラフィー－質量分析（ＧＣ－ＭＳ：Gas Chromatography-Mass Spectrometry）法、液体クロマトグラフィー－質量分析（ＬＣ－ＭＳ：Liquid Chromatography-Mass Spectrometry）法、及び、イオン交換クロマトグラフィー（ＩＣ：Ion-exchange Chromatography）法等の公知の方法によって測定できる。 The content of each of the above components is determined by gas chromatography-mass spectrometry (GC-MS: Gas Chromatography-Mass Spectrometry) method, liquid chromatography-mass spectrometry (LC-MS: Liquid Chromatography-Mass Spectrometry) method, and ion exchange. It can be measured by a known method such as a chromatography (IC: Ion-exchange Chromatography) method.
〔洗浄液の物性〕
＜金属含有量＞
　洗浄液は、不純物として金属を含んでいてもよい。
　上記金属（例えば、Ｆｅ、Ｃｏ、Ｎａ、Ｋ、Ｃｕ、Ｍｇ、Ｍｎ、Ｌｉ、Ａｌ、Ｃｒ、Ｎｉ、Ｚｎ、Ｓｎ、及び、Ａｇ等の金属元素）の含有量（イオン濃度として測定される）が、洗浄液の全質量に対して、いずれも５質量ｐｐｍ以下であることが好ましく、１質量ｐｐｍ以下であることがより好ましい。
　最先端の半導体素子の製造においては、更に高純度の洗浄液が求められることが想定されることから、金属の含有量が、洗浄液の全質量に対して、１質量ｐｐｍよりも低い値（すなわち、質量ｐｐｂオーダー以下）であることが更に好ましく、１００質量ｐｐｂ以下であることが特に好ましく、１０質量ｐｐｂ未満であることが最も好ましい。上記金属の含有量の下限は特に制限されないが、洗浄液の全質量に対して、０が好ましい。 [Physical characteristics of cleaning liquid]
<Metal content>
The cleaning liquid may contain a metal as an impurity.
Content of the above metals (eg, metal elements such as Fe, Co, Na, K, Cu, Mg, Mn, Li, Al, Cr, Ni, Zn, Sn, and Ag) (measured as an ion concentration). However, it is preferably 5 mass ppm or less, and more preferably 1 mass ppm or less, based on the total mass of the cleaning liquid.
Since it is assumed that a higher-purity cleaning liquid is required in the manufacture of the most advanced semiconductor element, the metal content is lower than 1 mass ppm (that is, the total mass of the cleaning liquid). It is more preferably on the order of mass ppb or less), particularly preferably 100 mass ppb or less, and most preferably less than 10 mass ppb. The lower limit of the metal content is not particularly limited, but 0 is preferable with respect to the total mass of the cleaning liquid.
　カリウム（Ｋ）の含有量は、洗浄液の全質量に対して、１０００質量ｐｐｂ以下が好ましく、１００質量ｐｐｂ以下がより好ましい。下限は特に制限されないが、０が好ましい。
　ナトリウム（Ｎａ）の含有量に対する、カリウム（Ｋ）の含有量の質量比〔（カリウムの含有量）／ナトリウムの含有量〕は、０．１～１０が好ましい。 The content of potassium (K) is preferably 1000 mass ppb or less, and more preferably 100 mass ppb or less, based on the total mass of the washing liquid. The lower limit is not particularly limited, but 0 is preferable.
The mass ratio of the content of potassium (K) to the content of sodium (Na) [(potassium content) / sodium content] is preferably 0.1 to 10.
　金属の含有量を低減する方法としては、例えば、洗浄液を製造する際に使用する原材料の段階、又は、洗浄液の製造後の段階において、イオン交換樹脂又はフィルタを用いてろ過等の精製処理する方法；原材料又は製造された洗浄液を収容する容器として、後述する不純物の溶出が少ない容器を用いる方法；洗浄液の製造時に配管等から金属成分が溶出しないように、配管内壁にフッ素系樹脂のライニングを施す方法；蒸留する方法が挙げられる。 As a method for reducing the metal content, for example, a method of performing purification treatment such as filtration using an ion exchange resin or a filter at the stage of raw materials used in producing the cleaning liquid or at the stage after the production of the cleaning liquid. A method of using a container with a small amount of impurities, which will be described later, as a container for accommodating raw materials or manufactured cleaning liquid; Method; Examples include a method of distillation.
＜粒子＞
　洗浄液は、粒子を含んでいてもよい。
　粒子とは、粒子の形状を球体とみなした場合における直径（粒径）が０．０１μｍ以上である粒子を意味する。 <Particles>
The cleaning liquid may contain particles.
The particle means a particle having a diameter (particle size) of 0.01 μm or more when the shape of the particle is regarded as a sphere.
　粒径０．０１μｍ以上の粒子の含有量は、洗浄液１ｍＬ当たり１０００個以下が好ましく、５００個以下がより好ましい。下限は特に制限されず、０が好ましい。
　また、後述する測定方法で測定された粒径０．０１μｍ以上の粒子の含有量が、検出限界以下であることも好ましい。
　粒子の含有量は、レーザを光源とした光散乱式液中粒子測定方式における市販の測定装置を利用して、液相で測定できる。 The content of particles having a particle size of 0.01 μm or more is preferably 1000 or less, and more preferably 500 or less, per 1 mL of the cleaning liquid. The lower limit is not particularly limited, and 0 is preferable.
It is also preferable that the content of particles having a particle size of 0.01 μm or more measured by the measuring method described later is not more than the detection limit.
The particle content can be measured in the liquid phase by using a commercially available measuring device in a light scattering type submerged particle measuring method using a laser as a light source.
　粒子としては、例えば、洗浄液の原料に不純物として含まれる塵、埃、有機固形物、及び、無機固形物等の粒子、並びに、洗浄液の調製中に汚染物として持ち込まれる塵、埃、有機固形物、及び、無機固形物等の粒子が挙げられ、最終的に洗浄液中で溶解せずに粒子として存在するものが該当する。
　粒子の除去方法としては、例えば、後述するフィルタリング等の精製処理が挙げられる。 The particles include, for example, particles such as dust, dust, organic solids, and inorganic solids contained as impurities in the raw material of the cleaning liquid, and dust, dust, and organic solids brought in as contaminants during the preparation of the cleaning liquid. , And particles such as inorganic solids, and those that finally exist as particles without being dissolved in the cleaning liquid fall under this category.
Examples of the method for removing particles include purification treatment such as filtering described later.
　洗浄液は、その原料を複数に分割したキットとしてもよい。 The cleaning liquid may be a kit in which the raw material is divided into a plurality of parts.
〔洗浄液の製造〕
　洗浄液は、公知の方法により製造できる。
　以下、洗浄液の製造方法について詳述する。 [Manufacturing of cleaning liquid]
The cleaning liquid can be produced by a known method.
Hereinafter, the method for producing the cleaning liquid will be described in detail.
＜調液工程＞
　洗浄液の調液方法は特に制限されず、例えば、上述した各成分を混合することにより洗浄液を製造できる。
　上述した各成分を混合する順序、及び／又は、タイミングは、特に制限されず、例えば、精製した純水を入れた容器に、重合体、アルカノールアミン、特定錯化剤、及び、水を順次添加した後、撹拌して混合液を調製し、得られた混合液に、更にｐＨ調整剤を添加してｐＨを調整することにより、調製する方法が挙げられる。また、水及び各成分を容器に添加する場合、一括して添加してもよいし、複数回にわたって分割して添加してもよい。 <Liquid preparation process>
The method for preparing the cleaning liquid is not particularly limited, and for example, the cleaning liquid can be produced by mixing the above-mentioned components.
The order and / or timing of mixing each of the above-mentioned components is not particularly limited, and for example, the polymer, alkanolamine, specific complexing agent, and water are sequentially added to a container containing purified pure water. After that, a mixed solution is prepared by stirring, and a pH adjusting agent is further added to the obtained mixed solution to adjust the pH. Further, when water and each component are added to the container, they may be added all at once or divided into a plurality of times.
　洗浄液の調液に使用する攪拌装置及び攪拌方法は、特に制限されず、攪拌機又は分散機として公知の装置を使用できる。
　攪拌機としては、例えば、工業用ミキサー、可搬型攪拌器、メカニカルスターラー、及び、マグネチックスターラーが挙げられる。
　分散機としては、例えば、工業用分散器、ホモジナイザー、超音波分散器、及び、ビーズミルが挙げられる。 The stirring device and stirring method used for preparing the cleaning liquid are not particularly limited, and a known device as a stirrer or a disperser can be used.
Examples of the stirrer include an industrial mixer, a portable stirrer, a mechanical stirrer, and a magnetic stirrer.
Examples of the disperser include an industrial disperser, a homogenizer, an ultrasonic disperser, and a bead mill.
　洗浄液の調液工程における各成分の混合、及び、後述する精製処理、並びに、製造された洗浄液の保管温度は、４０℃以下が好ましく、３０℃以下がより好ましい。上記保管温度の下限は特に制限させず、５℃以上が好ましく、１０℃以上がより好ましい。上記の温度範囲で洗浄液の調液、処理及び／又は保管を行うことにより、長期間にわたって洗浄液の性能を安定に維持できる。 The mixing of each component in the preparation step of the cleaning liquid, the purification treatment described later, and the storage temperature of the produced cleaning liquid are preferably 40 ° C. or lower, more preferably 30 ° C. or lower. The lower limit of the storage temperature is not particularly limited, and is preferably 5 ° C. or higher, more preferably 10 ° C. or higher. By preparing, treating and / or storing the cleaning liquid in the above temperature range, the performance of the cleaning liquid can be stably maintained for a long period of time.
（精製処理）
　洗浄液を調製するための原料のいずれか１種以上に対して、事前に精製処理を行うことが好ましい。
　精製処理としては、例えば、蒸留、イオン交換、及び、ろ過等の公知の方法が挙げられる。
　精製の程度としては、例えば、原料の純度が９９質量％以上となるまで精製することが好ましく、原液の純度が９９．９質量％以上となるまで精製することがより好ましい。 (Refining process)
It is preferable to perform a purification treatment in advance on any one or more of the raw materials for preparing the cleaning liquid.
Examples of the purification treatment include known methods such as distillation, ion exchange, and filtration.
As for the degree of purification, for example, it is preferable to purify until the purity of the raw material is 99% by mass or more, and it is more preferable to purify until the purity of the stock solution is 99.9% by mass or more.
　精製処理の方法としては、例えば、原料を、イオン交換樹脂又はＲＯ膜（Reverse Osmosis Membrane）等に通液する方法、原料の蒸留、及び、後述するフィルタリングが挙げられる。
　精製処理として、上述した精製方法を複数組み合わせて実施してもよい。例えば、原料に対して、ＲＯ膜に通液する１次精製を行った後、カチオン交換樹脂、アニオン交換樹脂、又は、混床型イオン交換樹脂からなる精製装置に通液する２次精製を実施してもよい。
　また、精製処理は、複数回実施してもよい。 Examples of the purification treatment method include a method of passing a raw material through an ion exchange resin or an RO membrane (Reverse Osmosis Membrane), distillation of the raw material, and filtering described later.
As the purification treatment, a plurality of the above-mentioned purification methods may be combined and carried out. For example, the raw material is subjected to primary purification by passing it through an RO membrane, and then passed through a purification device made of a cation exchange resin, an anion exchange resin, or a mixed bed type ion exchange resin. You may.
Moreover, the purification treatment may be carried out a plurality of times.
（フィルタリング）
　フィルタリングに用いるフィルタとしては、ろ過用途等に用いられているものであれば特に制限されない。
　上記フィルタとしては、例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）及びテトラフルオロエチレンパーフルオロアルキルビニルエーテル共重合体（ＰＦＡ）等のフッ素系樹脂、ナイロン等のポリアミド系樹脂、並びに、ポリエチレン及びポリプロピレン（ＰＰ）等のポリオレフィン樹脂（高密度又は超高分子量を含む）からなる群から選択される材料からなるフィルタが挙げられる。
　なかでも、上記フィルタとしては、ポリエチレン、ポリプロピレン（高密度ポリプロピレンを含む）、フッ素系樹脂（ＰＴＦＥ及びＰＦＡを含む）、及び、ポリアミド系樹脂（ナイロンを含む）からなる群から選択される材料からなるフィルタが好ましく、フッ素系樹脂からなるフィルタがより好ましい。
　上記材料により形成されたフィルタを使用して原料のろ過を行うことで、欠陥の原因に成り得る極性の高い異物を効果的に除去できる。 (filtering)
The filter used for filtering is not particularly limited as long as it is used for filtration purposes and the like.
Examples of the filter include fluororesins such as polytetrafluoroethylene (PTFE) and tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), polyamide resins such as nylon, polyethylene and polypropylene (PP), and the like. Examples thereof include filters made of materials selected from the group consisting of polyethylene resins (including high density or ultra high molecular weight).
Among them, the filter is made of a material selected from the group consisting of polyethylene, polypropylene (including high-density polypropylene), fluororesin (including PTFE and PFA), and polyamide-based resin (including nylon). A filter is preferable, and a filter made of a fluororesin is more preferable.
By filtering the raw material using a filter formed of the above material, it is possible to effectively remove highly polar foreign matter that may cause defects.
　フィルタの臨界表面張力としては、７０～９５ｍＮ／ｍが好ましく、７５～８５ｍＮ／ｍがより好ましい。フィルタの臨界表面張力の値は、製造メーカーの公称値である。
　上記臨界表面張力の範囲のフィルタを使用することで、欠陥の原因に成り得る極性の高い異物を効果的に除去できる。 The critical surface tension of the filter is preferably 70 to 95 mN / m, more preferably 75 to 85 mN / m. The value of the critical surface tension of the filter is the manufacturer's nominal value.
By using a filter in the range of the critical surface tension, it is possible to effectively remove highly polar foreign substances that may cause defects.
　フィルタの孔径としては、２～２０ｎｍが好ましく、２～１５ｎｍがより好ましい。上記範囲である場合、ろ過の詰まりを抑制しつつ、原料中に含まれる不純物及び凝集物等の微細な異物を確実に除去することが可能となる。上記孔径は、フィルタメーカーの公称値を参照できる。 The pore diameter of the filter is preferably 2 to 20 nm, more preferably 2 to 15 nm. Within the above range, it is possible to reliably remove fine foreign substances such as impurities and agglomerates contained in the raw material while suppressing clogging of filtration. For the hole diameter, the nominal value of the filter manufacturer can be referred to.
　フィルタリングは、１回のみであってもよいし、２回以上行ってもよい。
　フィルタリングを２回以上行う場合、用いるフィルタは同じであってもよいし、異なっていてもよい。 Filtering may be performed only once or twice or more.
When filtering is performed twice or more, the filters used may be the same or different.
　フィルタリングは、２５℃以下で行うことが好ましく、室温（２３℃）以下がより好ましく、２０℃以下が更に好ましい。上限は特に制限されず、０℃以上が好ましく、５℃以上がより好ましく、１０℃以上が更に好ましい。上記の温度範囲でフィルタリングを行う場合、原料中に溶解する粒子性の異物及び不純物の量を低減し、異物及び不純物を効率的に除去できる。 Filtering is preferably performed at 25 ° C. or lower, more preferably room temperature (23 ° C.) or lower, and even more preferably 20 ° C. or lower. The upper limit is not particularly limited, and is preferably 0 ° C. or higher, more preferably 5 ° C. or higher, and even more preferably 10 ° C. or higher. When filtering is performed in the above temperature range, the amount of particulate foreign matter and impurities dissolved in the raw material can be reduced, and the foreign matter and impurities can be efficiently removed.
（容器）
　洗浄液（キットの態様を含む）は、腐食性等が問題とならない限り、任意の容器に充填して保管、運搬、及び、使用できる。 (container)
The cleaning liquid (including the aspect of the kit) can be filled in any container, stored, transported, and used as long as corrosiveness is not a problem.
　容器としては、半導体用途向けに、容器内のクリーン度が高く、容器の収容部の内壁から各液への不純物の溶出が抑制された容器が好ましい。
　上記容器としては、半導体洗浄液用容器として市販されている各種容器が挙げられる。具体的には、アイセロ化学（株）製の「クリーンボトル」シリーズ、及び、コダマ樹脂工業製の「ピュアボトル」が挙げられる。
　洗浄液を収容する容器としては、容器収容部の内壁等と各液との接液部が、フッ素系樹脂（パーフルオロ樹脂）、又は、防錆及び金属溶出防止処理が施された金属で形成された容器が好ましい。
　容器の内壁は、ポリエチレン樹脂、ポリプロピレン樹脂、及び、ポリエチレン－ポリプロピレン樹脂からなる群から選択される１種以上の樹脂、若しくは、これとは異なる樹脂、又は、ステンレス、ハステロイ、インコネル、及び、モネル等の防錆及び金属溶出防止処理が施された金属から形成されることが好ましい。 As the container, a container having a high degree of cleanliness inside the container and suppressing elution of impurities from the inner wall of the container's accommodating portion into each liquid is preferable for semiconductor applications.
Examples of the container include various containers commercially available as a container for a semiconductor cleaning liquid. Specific examples thereof include the "clean bottle" series manufactured by Aicello Chemical Corporation and the "pure bottle" manufactured by Kodama Resin Industry.
As a container for accommodating a cleaning liquid, the inner wall of the container accommodating portion and the wetted portion between each liquid are formed of a fluororesin (perfluororesin) or a metal that has been subjected to rust prevention and metal elution prevention treatment. A container is preferable.
The inner wall of the container is made of one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, or a resin different from this, stainless steel, hasteroi, inconel, monel, and the like. It is preferably formed from a metal that has been subjected to rust-preventive and metal elution-preventing treatments.
　上記の異なる樹脂としては、フッ素系樹脂（パーフルオロ樹脂）が好ましい。
　内壁がフッ素系樹脂である容器を用いる場合、内壁が、ポリエチレン樹脂、ポリプロピレン樹脂、又は、ポリエチレン－ポリプロピレン樹脂である容器と比較して、エチレン又はプロピレンのオリゴマーの溶出という不具合の発生を抑制できる。
　上記内壁がフッ素系樹脂である容器としては、例えば、Ｅｎｔｅｇｒｉｓ社製　ＦｌｕｏｒｏＰｕｒｅＰＦＡ複合ドラム、特表平３－５０２６７７号公報の第４頁、国際公開第２００４／０１６５２６号明細書の第３頁、並びに、国際公開第９９／４６３０９号明細書の第９頁及び１６頁に記載の容器が挙げられる。 As the above-mentioned different resins, a fluororesin (perfluororesin) is preferable.
When a container whose inner wall is a fluororesin is used, the occurrence of a problem of elution of ethylene or propylene oligomer can be suppressed as compared with a container whose inner wall is a polyethylene resin, a polypropylene resin, or a polyethylene-polypropylene resin.
Examples of the container whose inner wall is a fluororesin include, for example, a FluoroPure PFA composite drum manufactured by Entegris, page 4 of JP-A-3-502677, page 3 of International Publication No. 2004/016526, and Examples include the containers described on pages 9 and 16 of International Publication No. 99/46309.
　容器の内壁には、上述したフッ素系樹脂の他に、石英及び電解研磨された金属材料（すなわち、電解研磨済みの金属材料）も好ましく用いられる。
　上記電解研磨された金属材料の製造に用いられる金属材料は、クロム及びニッケルからなる群から選択される少なくとも１種を含み、クロム及びニッケルの含有量の合計は、金属材料の全質量に対して、２５質量％超である金属材料が好ましく、３０質量％以上である金属材料がより好ましい。
　金属材料におけるクロム及びニッケルの含有量の合計の上限は、特に制限されず、９０質量％以下が好ましい。
　上記金属材料としては、例えば、ステンレス鋼、及び、ニッケル－クロム合金が挙げられる。 In addition to the above-mentioned fluororesin, quartz and an electropolished metal material (that is, an electropolished metal material) are also preferably used for the inner wall of the container.
The metal material used in the production of the electropolished metal material contains at least one selected from the group consisting of chromium and nickel, and the total content of chromium and nickel is the total mass of the metal material. , 25% by mass or more of the metal material is preferable, and 30% by mass or more of the metal material is more preferable.
The upper limit of the total content of chromium and nickel in the metal material is not particularly limited, and is preferably 90% by mass or less.
Examples of the metal material include stainless steel and nickel-chromium alloy.
　金属材料を電解研磨する方法としては、公知の方法を用いることができる。
　上記電解研磨する方法としては、例えば、特開２０１５－２２７５０１号公報の段落［００１１］～［００１４］、及び、特開２００８－２６４９２９号公報の段落［００３６］～［００４２］に記載された方法が挙げられる。 As a method for electrolytically polishing a metal material, a known method can be used.
Examples of the method for electrolytic polishing are described in paragraphs [0011] to [0014] of JP-A-2015-227501 and paragraphs [0036] to [0042] of JP-A-2008-264929. Can be mentioned.
　上記容器は、洗浄液を充填する前にその内部が洗浄されることが好ましい。
　上記洗浄に使用される液体は、その液中における金属不純物量が低減されていることが好ましい。洗浄液は、製造後にガロン瓶又はコート瓶等の容器にボトリングし、輸送及び保管されてもよい。 It is preferable that the inside of the container is cleaned before filling with the cleaning liquid.
The liquid used for the cleaning preferably has a reduced amount of metal impurities in the liquid. The cleaning liquid may be bottling, transported and stored in a container such as a gallon bottle or a coated bottle after production.
　保管における洗浄液中の成分の変化を防ぐ観点から、容器内を純度９９．９９９９５体積％以上の不活性ガス（窒素又はアルゴン等）で置換していてもよい。
　上記不活性ガスは、含水率が少ないことが好ましい。また、輸送及び保管における温度としては、常温であってもよく、変質を防ぐ観点から、－２０℃～２０℃であってもよい。
　また、上記温度にするために、温度制御を行ってもよい。 From the viewpoint of preventing changes in the components in the cleaning liquid during storage, the inside of the container may be replaced with an inert gas (nitrogen, argon, etc.) having a purity of 99.99995% by volume or more.
The inert gas preferably has a low water content. The temperature for transportation and storage may be room temperature, or may be −20 ° C. to 20 ° C. from the viewpoint of preventing deterioration.
Further, the temperature may be controlled in order to obtain the above temperature.
（クリーンルーム）
　洗浄液の製造、容器の開封及び洗浄、洗浄液の充填等を含めた取り扱い、処理分析、並びに、測定は、全てクリーンルームで行うことが好ましい。
　上記クリーンルームは、１４６４４－１クリーンルーム基準を満たすことが好ましい。ＩＳＯ（国際標準化機構）クラス１、ＩＳＯクラス２、ＩＳＯクラス３、及び、ＩＳＯクラス４のいずれかを満たすことが好ましく、ＩＳＯクラス１又はＩＳＯクラス２を満たすことがより好ましく、ＩＳＯクラス１を満たすことが更に好ましい。 (Clean room)
It is preferable that the manufacturing of the cleaning liquid, the opening and cleaning of the container, the handling including the filling of the cleaning liquid, the processing analysis, and the measurement are all performed in a clean room.
The clean room preferably meets the 14644-1 clean room standard. It is preferable to satisfy any one of ISO (International Organization for Standardization) class 1, ISO class 2, ISO class 3, and ISO class 4, more preferably to satisfy ISO class 1 or ISO class 2, and satisfy ISO class 1. Is even more preferable.
［洗浄液の用途］
　洗浄液は、化学機械研磨（ＣＭＰ）処理が施された半導体基板を洗浄する洗浄工程に使用することが好ましい。洗浄液は、半導体基板の製造プロセスにおける半導体基板の洗浄に使用することもできる。更には、後述するようにバフ研磨処理にも使用できる。 [Use of cleaning liquid]
The cleaning liquid is preferably used in a cleaning step for cleaning a semiconductor substrate that has been subjected to chemical mechanical polishing (CMP) treatment. The cleaning liquid can also be used for cleaning the semiconductor substrate in the semiconductor substrate manufacturing process. Further, it can also be used for buffing treatment as described later.
〔洗浄対象物〕
　洗浄液の洗浄対象物としては、例えば、タングステンを含む金属膜を有する半導体基板が挙げられる。
　本明細書において、「半導体基板上」とは、例えば、半導体基板の表裏、側面、及び、溝内等のいずれも含む。また、半導体基板上の金属膜とは、半導体基板の表面上に直接金属膜がある場合のみならず、半導体基板上に他の層を介して金属膜がある場合も含む。 [Items to be cleaned]
Examples of the object to be cleaned by the cleaning liquid include a semiconductor substrate having a metal film containing tungsten.
In the present specification, "on the semiconductor substrate" includes, for example, any of the front and back surfaces, the side surfaces, the inside of the groove, and the like of the semiconductor substrate. Further, the metal film on the semiconductor substrate includes not only the case where the metal film is directly on the surface of the semiconductor substrate but also the case where the metal film is present on the semiconductor substrate via another layer.
　金属膜に含まれる金属としては、Ｗ（タングステン）が挙げられる。
　金属膜は、Ｗ以外の他の金属を含んでいてもよい。他の金属としては、例えば、Ｃｕ（銅）、Ｃｏ（コバルト）、Ｔｉ（チタン）、Ｔａ（タンタル）、Ｒｕ（ルテニウム）、Ｃｒ（クロム）、Ｈｆ（ハフニウム）、Ｏｓ（オスミウム）、Ｐｔ（白金）、Ｎｉ（ニッケル）、Ｍｎ（マンガン）、Ｃｕ（銅）、Ｚｒ（ジルコニウム）、Ｍｏ（モリブデン）、Ｌａ（ランタン）、及び、Ｉｒ（イリジウム）からなる群から選択される少なくとも１つの金属Ｍが挙げられる。 Examples of the metal contained in the metal film include W (tungsten).
The metal film may contain a metal other than W. Other metals include, for example, Cu (copper), Co (cobalt), Ti (tantalum), Ta (tantalum), Ru (ruthenium), Cr (chromium), Hf (hafnium), Os (osmium), Pt ( At least one metal selected from the group consisting of platinum), Ni (nickel), Mn (manganese), Cu (copper), Zr (zirconium), Mo (molybdenum), La (lanthanum), and Ir (iridium). M is mentioned.
　洗浄液の洗浄対象物である半導体基板としては、例えば、半導体基板を構成するウエハの表面に、金属配線膜、バリアメタル、及び、絶縁膜を有する基板が挙げられる。 Examples of the semiconductor substrate to be cleaned by the cleaning liquid include a substrate having a metal wiring film, a barrier metal, and an insulating film on the surface of the wafer constituting the semiconductor substrate.
　半導体基板を構成するウエハとしては、例えば、シリコン（Ｓｉ）ウエハ、シリコンカーバイド（ＳｉＣ）ウエハ、及び、シリコンを含む樹脂系ウエハ（ガラスエポキシウエハ）等のシリコン系材料からなるウエハ、ガリウムリン（ＧａＰ）ウエハ、ガリウムヒ素（ＧａＡｓ）ウエハ、並びに、インジウムリン（ＩｎＰ）ウエハが挙げられる。
　シリコンウエハとしては、例えば、シリコンウエハに５価の原子（例えば、リン（Ｐ）、ヒ素（Ａｓ）、及び、アンチモン（Ｓｂ）等）をドープしたｎ型シリコンウエハ、並びに、シリコンウエハに３価の原子（例えば、ホウ素（Ｂ）、及び、ガリウム（Ｇａ）等）をドープしたｐ型シリコンウエハが挙げられる。
　シリコンウエハのシリコンとしては、例えば、アモルファスシリコン、単結晶シリコン、多結晶シリコン、及び、ポリシリコンが挙げられる。
　なかでも、上記ウエハとしては、シリコンウエハ、シリコンカーバイドウエハ、及び、シリコンを含む樹脂系ウエハ（ガラスエポキシウエハ）等のシリコン系材料からなるウエハが好ましい。 Examples of the wafer constituting the semiconductor substrate include a silicon (Si) wafer, a silicon carbide (SiC) wafer, a wafer made of a silicon-based material such as a resin-based wafer containing silicon (glass epoxy wafer), and gallium phosphorus (GaP). ) Wafers, gallium arsenic (GaAs) wafers, and indium phosphorus (InP) wafers.
Examples of the silicon wafer include an n-type silicon wafer in which a silicon wafer is doped with a pentavalent atom (for example, phosphorus (P), arsenic (As), antimony (Sb), etc.), and a silicon wafer is trivalent. Examples thereof include a p-type silicon wafer doped with an atom of (for example, boron (B), gallium (Ga), etc.).
Examples of silicon for silicon wafers include amorphous silicon, single crystal silicon, polycrystalline silicon, and polysilicon.
Among them, as the wafer, a wafer made of a silicon-based material such as a silicon wafer, a silicon carbide wafer, and a resin-based wafer (glass epoxy wafer) containing silicon is preferable.
　半導体基板は、上記したウエハに絶縁膜を更に有していてもよい。
　絶縁膜としては、例えば、シリコン酸化膜（例えば、二酸化ケイ素（ＳｉＯ２）膜、及び、オルトケイ酸テトラエチル（Ｓｉ（ＯＣ２Ｈ５）４）膜（ＴＥＯＳ膜）等）、シリコン窒化膜（例えば、窒化シリコン（Ｓｉ３Ｎ４）、及び、窒化炭化シリコン（ＳｉＮＣ）等）、並びに、低誘電率（Ｌｏｗ－ｋ）膜（例えば、炭素ドープ酸化ケイ素（ＳｉＯＣ）膜、及び、シリコンカーバイド（ＳｉＣ）膜等）が挙げられる。 The semiconductor substrate may further have an insulating film on the above-mentioned wafer.
Examples of the insulating film include a silicon oxide film (for example, a silicon dioxide (SiO 2 ) film, a tetraethyl orthosilicate (Si (OC 2 H 5 ) 4 ) film (TEOS film), etc.), and a silicon nitride film (for example, a silicon nitride film). Silicon nitride (Si 3N 4 ), silicon nitride carbide ( SiNC ), etc.), and low dielectric constant (Low-k) films (eg, carbon-doped silicon oxide (SiOC) films, and silicon carbide (SiC). Membrane, etc.).
　タングステンを含む金属膜（タングステン含有膜）としては、例えば、金属タングステンのみからなる金属膜（タングステン金属膜）、及び、タングステンと、タングステン以外の金属とからなる合金製の金属膜（タングステン合金金属膜）が挙げられる。
　タングステン合金金属膜としては、例えば、タングステン－チタン合金金属膜（ＷＴｉ合金金属膜）、及び、タングステン－コバルト合金金属膜（ＷＣｏ合金金属膜）が挙げられる。
　タングステン含有膜は、例えば、バリアメタル又はビアと、配線との接続部に使用できる。 Examples of the metal film containing tungsten (tungsten-containing film) include a metal film made of only metallic tungsten (tungsten metal film) and a metal film made of an alloy of tungsten and a metal other than tungsten (tungsten alloy metal film). ).
Examples of the tungsten alloy metal film include a tungsten-titanium alloy metal film (WTi alloy metal film) and a tungsten-cobalt alloy metal film (WCo alloy metal film).
The tungsten-containing film can be used, for example, at the connection portion between the barrier metal or via and the wiring.
　半導体基板を構成するウエハ上に、上記の絶縁膜、及び、タングステン含有膜を形成する方法としては、公知の方法であれば特に制限されない。
　絶縁膜の形成方法としては、例えば、半導体基板を構成するウエハに対して、酸素ガス存在下で熱処理を行うことによりシリコン酸化膜を形成し、次いで、シラン及びアンモニアのガスを流入して、化学気相蒸着（ＣＶＤ：Chemical Vapor Deposition）法によりシリコン窒化膜を形成する方法が挙げられる。
　タングステン含有膜の形成方法としては、例えば、上記の絶縁膜を有するウエハ上に、レジスト等の公知の方法で回路を形成し、次いで、鍍金及びＣＶＤ法等の方法により、タングステン含有膜及びコバルト含有膜を形成する方法が挙げられる。 The method for forming the above-mentioned insulating film and the tungsten-containing film on the wafer constituting the semiconductor substrate is not particularly limited as long as it is a known method.
As a method for forming the insulating film, for example, a silicon oxide film is formed by heat-treating a wafer constituting a semiconductor substrate in the presence of oxygen gas, and then silane and ammonia gas are introduced to form a chemical vapor deposition. Examples thereof include a method of forming a silicon nitride film by a vapor deposition (CVD) method.
As a method for forming the tungsten-containing film, for example, a circuit is formed on a wafer having the above-mentioned insulating film by a known method such as a resist, and then a tungsten-containing film and a cobalt-containing film are contained by a method such as plating and a CVD method. Examples include a method of forming a film.
＜ＣＭＰ処理＞
　ＣＭＰ処理は、例えば、研磨微粒子（砥粒）を含む研磨スラリーを用いる化学的作用と、機械的研磨による機械的作用との複合作用によって、金属配線膜、バリアメタル、及び、絶縁膜を有する基板の表面を平坦化する処理である。
　ＣＭＰ処理が施された半導体基板の表面には、ＣＭＰ処理で使用した砥粒（例えば、シリカ及びアルミナ等）、研磨された金属配線膜、及び、バリアメタルに由来する金属不純物（金属残渣）等の不純物が残存することがある。また、ＣＭＰ処理の際に用いたＣＭＰ処理液に由来する有機残渣物が残存する場合もある。これらの不純物は、例えば、配線間を短絡させ、半導体基板の電気的特性を劣化させるおそれがあるため、ＣＭＰ処理が施された半導体基板は、これらの不純物を表面から除去するための洗浄処理に供される。
　ＣＭＰ処理が施された半導体基板としては、例えば、精密工学会誌　Ｖｏｌ．８４、Ｎｏ．３、２０１８に記載のＣＭＰ処理が施された基板が挙げられる。 <CMP processing>
In the CMP treatment, for example, a substrate having a metal wiring film, a barrier metal, and an insulating film is formed by a combined action of a chemical action using a polishing slurry containing polishing fine particles (abrasive grains) and a mechanical action by mechanical polishing. It is a process of flattening the surface of.
On the surface of the semiconductor substrate subjected to the CMP treatment, abrasive grains (for example, silica and alumina) used in the CMP treatment, a polished metal wiring film, metal impurities (metal residue) derived from the barrier metal, etc. Impurities may remain. In addition, organic residues derived from the CMP treatment liquid used in the CMP treatment may remain. Since these impurities may cause a short circuit between wirings and deteriorate the electrical characteristics of the semiconductor substrate, for example, the semiconductor substrate subjected to the CMP treatment is used for cleaning treatment for removing these impurities from the surface. Served.
Examples of the semiconductor substrate subjected to the CMP treatment include Vol. 84, No. 3. The substrate subjected to the CMP treatment according to 2018 can be mentioned.
＜バフ研磨処理＞
　洗浄液の洗浄対象物である半導体基板の表面は、ＣＭＰ処理が施された後、更にバフ研磨処理が施されていてもよい。
　バフ研磨処理は、研磨パッドを用いて半導体基板の表面における不純物を低減する処理である。具体的には、ＣＭＰ処理が施された半導体基板の表面と、研磨パッドとを接触させて、その接触部分にバフ研磨用組成物を供給しながら半導体基板と、研磨パッドとを相対摺動させる。その結果、半導体基板の表面の不純物が、研磨パッドによる摩擦力及びバフ研磨用組成物による化学的作用によって除去される。 <Buffing treatment>
The surface of the semiconductor substrate, which is the object to be cleaned by the cleaning liquid, may be further subjected to buffing treatment after being subjected to CMP treatment.
The buffing process is a process of reducing impurities on the surface of a semiconductor substrate by using a polishing pad. Specifically, the surface of the semiconductor substrate subjected to the CMP treatment is brought into contact with the polishing pad, and the semiconductor substrate and the polishing pad are relatively slid while supplying the buffing composition to the contact portion. .. As a result, impurities on the surface of the semiconductor substrate are removed by the frictional force of the polishing pad and the chemical action of the buffing composition.
　バフ研磨用組成物としては、半導体基板の種類、並びに、除去対象とする不純物の種類及び量に応じて、公知のバフ研磨用組成物を適宜使用できる。バフ研磨用組成物に含まれる成分としては、例えば、ポリビニルアルコール等の水溶性ポリマー、分散媒としての水、及び、硝酸等の酸が挙げられる。
　また、バフ研磨処理の一実施形態としては、バフ研磨用組成物として、上記の洗浄液を用いて半導体基板にバフ研磨処理を施すことが好ましい。
　バフ研磨処理において使用する研磨装置及び研磨条件等については、半導体基板の種類及び除去対象物等に応じて、公知の装置及び条件から適宜選択できる。
　バフ研磨処理としては、例えば、国際公開２０１７／１６９５３９号の段落［００８５］～［００８８］に記載の処理が挙げられ、これらの内容は本明細書に組み込まれる。 As the buffing composition, a known buffing composition can be appropriately used depending on the type of the semiconductor substrate and the type and amount of impurities to be removed. Examples of the components contained in the buffing composition include water-soluble polymers such as polyvinyl alcohol, water as a dispersion medium, and acids such as nitric acid.
Further, as one embodiment of the buffing treatment, it is preferable to buff the semiconductor substrate using the above-mentioned cleaning liquid as the buffing composition.
The polishing device and polishing conditions used in the buffing process can be appropriately selected from known devices and conditions according to the type of semiconductor substrate, the object to be removed, and the like.
Examples of the buffing process include the processes described in paragraphs [805] to [0088] of International Publication No. 2017/169539, and these contents are incorporated in the present specification.
〔半導体基板の洗浄方法〕
　半導体基板の洗浄方法は、上記洗浄液を用いて、ＣＭＰ処理が施された半導体基板を洗浄する洗浄工程を含むものであれば特に制限されない。 [How to clean the semiconductor substrate]
The method for cleaning the semiconductor substrate is not particularly limited as long as it includes a cleaning step of cleaning the semiconductor substrate subjected to the CMP treatment using the above-mentioned cleaning liquid.
　洗浄液を用いて半導体基板を洗浄する洗浄工程としては、ＣＭＰ処理された半導体基板に対して行われる公知の方法であれば特に制限されず、半導体基板に洗浄液を供給しながらブラシ等の洗浄部材を半導体基板の表面に物理的に接触させて残渣物等を除去するスクラブ洗浄、洗浄液に半導体基板を浸漬する浸漬式、半導体基板を回転させながら洗浄液を滴下するスピン（滴下）式、及び、洗浄液を噴霧する噴霧（スプレー）式が挙げられる。　浸漬式の洗浄では、半導体基板の表面に残存する不純物をより低減できる観点から、半導体基板が浸漬している洗浄液に対して超音波処理を施すことが好ましい。
　上記洗浄工程は、１回のみ実施してもよく、２回以上実施してもよい。２回以上洗浄する場合には同じ方法を繰り返してもよいし、異なる方法を組み合わせてもよい。 The cleaning step of cleaning the semiconductor substrate using the cleaning liquid is not particularly limited as long as it is a known method performed on the semiconductor substrate treated with CMP, and a cleaning member such as a brush is used while supplying the cleaning liquid to the semiconductor substrate. Scrub cleaning that physically contacts the surface of the semiconductor substrate to remove residues, immersion type that immerses the semiconductor substrate in the cleaning liquid, spin (drop) type that drops the cleaning liquid while rotating the semiconductor substrate, and cleaning liquid. A spray type for spraying can be mentioned. In the immersion type cleaning, it is preferable to perform ultrasonic treatment on the cleaning liquid in which the semiconductor substrate is immersed from the viewpoint of further reducing impurities remaining on the surface of the semiconductor substrate.
The cleaning step may be performed only once or twice or more. When washing twice or more, the same method may be repeated, or different methods may be combined.
　半導体基板の洗浄方法としては、枚葉方式、及び、バッチ方式のいずれであってもよい。枚葉方式とは、半導体基板を１枚ずつ処理する方式であり、バッチ方式とは、複数枚の半導体基板を同時に処理する方式である。 The semiconductor substrate cleaning method may be either a single-wafer method or a batch method. The single-wafer method is a method of processing semiconductor substrates one by one, and the batch method is a method of processing a plurality of semiconductor substrates at the same time.
　半導体基板の洗浄に用いる洗浄液の温度は、通常この分野で行われる温度であれば特に制限はない。
　洗浄液の温度は、室温（２３℃）であってもよく、洗浄性の向上や部材への対ダメージ性を抑えるために、温度を任意に選択してもよい。
　なかでも、洗浄液の温度は、１０～６０℃が好ましく、１５～５０℃がより好ましい。 The temperature of the cleaning liquid used for cleaning the semiconductor substrate is not particularly limited as long as it is a temperature usually used in this field.
The temperature of the cleaning liquid may be room temperature (23 ° C.), and the temperature may be arbitrarily selected in order to improve the cleaning property and suppress the damage resistance to the member.
Among them, the temperature of the cleaning liquid is preferably 10 to 60 ° C, more preferably 15 to 50 ° C.
　半導体基板の洗浄における洗浄時間は、洗浄液に含まれる成分の種類及び含有量等により適宜調整でき、実用性の観点から、洗浄時間は、１０秒間～２分間が好ましく、２０秒間～１分３０秒間がより好ましく、３０秒間～１分間が更に好ましい。 The cleaning time in cleaning the semiconductor substrate can be appropriately adjusted depending on the type and content of the components contained in the cleaning liquid, and from the viewpoint of practicality, the cleaning time is preferably 10 seconds to 2 minutes, preferably 20 seconds to 1 minute 30 seconds. Is more preferable, and 30 seconds to 1 minute is further preferable.
　半導体基板の洗浄工程における洗浄液の供給量（供給速度）は特に制限されず、５０～５０００ｍＬ／分が好ましく、５００～２０００ｍＬ／分がより好ましい。 The supply amount (supply rate) of the cleaning liquid in the cleaning step of the semiconductor substrate is not particularly limited, and is preferably 50 to 5000 mL / min, more preferably 500 to 2000 mL / min.
　半導体基板の洗浄において、洗浄液の洗浄能力をより増進するために、機械的撹拌方法を用いてもよい。
　機械的撹拌方法としては、例えば、半導体基板上で洗浄液を循環させる方法、半導体基板上で洗浄液を流過又は噴霧させる方法、及び、超音波又はメガソニックにより洗浄液を撹拌する方法が挙げられる。 In cleaning the semiconductor substrate, a mechanical stirring method may be used in order to further enhance the cleaning ability of the cleaning liquid.
Examples of the mechanical stirring method include a method of circulating the cleaning liquid on the semiconductor substrate, a method of flowing or spraying the cleaning liquid on the semiconductor substrate, and a method of stirring the cleaning liquid by ultrasonic waves or megasonics.
　上記の半導体基板の洗浄の後に、半導体基板を溶媒によってすすいで清浄する工程（以下「リンス工程」ともいう。）を行ってもよい。
　リンス工程は、半導体基板の洗浄工程の後に連続して行われ、リンス溶媒（リンス液）を用いて５秒間～５分間にわたってすすぐ工程であることが好ましい。リンス工程は、上述の機械的撹拌方法を用いて行ってもよい。 After cleaning the semiconductor substrate, a step of rinsing and cleaning the semiconductor substrate with a solvent (hereinafter, also referred to as “rinse step”) may be performed.
The rinsing step is preferably performed continuously after the cleaning step of the semiconductor substrate, and is preferably a rinsing step using a rinsing solvent (rinsing solution) for 5 seconds to 5 minutes. The rinsing step may be performed using the above-mentioned mechanical stirring method.
　リンス液としては、例えば、水（脱イオン（ＤＩ：De Ionize）水が好ましい）、メタノール、エタノール、イソプロピルアルコール、Ｎ－メチルピロリジノン、γ－ブチロラクトン、ジメチルスルホキシド、乳酸エチル、及び、プロピレングリコールモノメチルエーテルアセテートが挙げられる。
　また、リンス液としては、ｐＨ８．０超の水性リンス液（希釈した水性の水酸化アンモニウム等）であってもよい。
　リンス液を半導体基板に接触させる方法としては、上述した洗浄液を半導体基板に接触させる方法を同様に適用できる。 Examples of the rinsing solution include water (preferably De Ionize water), methanol, ethanol, isopropyl alcohol, N-methylpyrrolidinone, γ-butyrolactone, dimethyl sulfoxide, ethyl lactate, and propylene glycol monomethyl ether. Acetate can be mentioned.
Further, the rinsing solution may be an aqueous rinsing solution having a pH of more than 8.0 (diluted aqueous ammonium hydroxide or the like).
As a method of contacting the rinsing liquid with the semiconductor substrate, the above-mentioned method of contacting the cleaning liquid with the semiconductor substrate can be similarly applied.
　また、上記リンス工程の後に、半導体基板を乾燥させる乾燥工程を行ってもよい。
　乾燥方法としては、例えば、スピン乾燥法、半導体基板上に乾性ガスを流過させる方法、ホットプレート若しくは赤外線ランプ等の加熱手段によって基板を加熱する方法、マランゴニ乾燥法、ロタゴニ乾燥法、ＩＰＡ（イソプロピルアルコール）乾燥法、及び、それらの組み合わせが挙げられる。 Further, after the rinsing step, a drying step of drying the semiconductor substrate may be performed.
Examples of the drying method include a spin drying method, a method of flowing a dry gas over a semiconductor substrate, a method of heating a substrate by a heating means such as a hot plate or an infrared lamp, a marangoni drying method, a rotagoni drying method, and IPA (isopropyl). Alcohol) drying method and combinations thereof can be mentioned.
　以下に、実施例に基づいて本発明を更に詳細に説明する。以下の実施例に示す材料、使用量、及び、割合等は、本発明の趣旨を逸脱しない限り適宜変更できる。つまり、本発明の範囲は以下に示す実施例により限定的に解釈されない。 Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, proportions, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. That is, the scope of the present invention is not limitedly construed by the examples shown below.
　以下の実施例において、洗浄液のｐＨは、ｐＨメーター（株式会社堀場製作所製、型式「Ｆ－７４」）を用いて、ＪＩＳ　Ｚ８８０２－１９８４に準拠して２５℃において測定した。
　また、実施例及び比較例の洗浄液の製造において、容器の取り扱い、洗浄液の調液、充填、保管、及び、分析測定は、全てＩＳＯクラス２以下を満たすレベルのクリーンルームで行った。 In the following examples, the pH of the cleaning solution was measured at 25 ° C. using a pH meter (manufactured by HORIBA, Ltd., model “F-74”) in accordance with JIS Z8802-1984.
Further, in the production of the cleaning liquids of Examples and Comparative Examples, the handling of the container, the preparation, filling, storage, and analysis measurement of the cleaning liquid were all performed in a clean room at a level satisfying ISO class 2 or less.
［洗浄液の原料］
　洗浄液を製造するために、以下の化合物を使用した。
　実施例で使用した各種成分はいずれも、半導体グレードに分類されるもの、又は、それに準ずる高純度グレードに分類されるものを使用した。 [Raw material for cleaning liquid]
The following compounds were used to produce the cleaning solution.
As the various components used in the examples, those classified into semiconductor grade or those classified into high-purity grade equivalent thereto were used.
〔重合体〕
・ポリマレイン酸（Ｍｗ＝２，０００）：日油（株）製、商品名「ノンポールＰＷＡ－５０Ｗ」
・ポリアクリル酸（Ｍｗ＝５，０００）：富士フイルム和光純薬（株）製、商品名「ポリアクリル酸５，０００」
・ポリアクリル酸（Ｍｗ＝１０，０００）：日本触媒（株）製、商品名「アクアリックＨＬ４１５」
・アクリル酸－マレイン酸共重合体（Ｍｗ＝１０，０００）：日本触媒（株）製、商品名「アクアリックＴＬ３７」
・スチレン－マレイン酸共重合体（Ｍｗ＝１０，０００）：第一工業製薬（株）製、商品名「ＤＫＳディスコートＮ－１０」
・ポリアクリル酸（Ｍｗ＝２５，０００）：富士フイルム和光純薬（株）製、商品名「ポリアクリル酸２５，０００」
・ポリアクリル酸（Ｍｗ＝５０，０００）：東亞合成（株）製、商品名「ジュリマーＡＣ－１０Ｌ」
・ポリアクリル酸アンモニウム（Ｍｗ＝１００，０００）：東亞合成（株）製、商品名「アロンＡ－３０」
・ポリアクリル酸（Ｍｗ＝２５０，０００）：富士フイルム和光純薬（株）製、商品名「ポリアクリル酸２５０，０００」
・ポリアクリル酸（Ｍｗ＝８００，０００）：東亞合成（株）製、商品名「ジュリマーＡＣ－１０Ｈ」
・ポリアクリル酸（Ｍｗ＝１,０００，０００）：富士フイルム和光純薬（株）製、商品名「ポリアクリル酸１,０００，０００」 [Polymer]
-Polymaleic acid (Mw = 2,000): Made by NOF CORPORATION, trade name "Non-Pole PWA-50W"
-Polyacrylic acid (Mw = 5,000): Wako Pure Chemical Industries, Ltd., trade name "Polyacrylic acid 5,000"
-Polyacrylic acid (Mw = 10,000): manufactured by Nippon Shokubai Co., Ltd., trade name "Aqualic HL415"
-Acrylic acid-maleic acid copolymer (Mw = 10,000): manufactured by Nippon Shokubai Co., Ltd., trade name "Aqualic TL37"
-Styrene-maleic acid copolymer (Mw = 10,000): manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name "DKS Disccoat N-10"
-Polyacrylic acid (Mw = 25,000): Wako Pure Chemical Industries, Ltd., trade name "Polyacrylic acid 25,000"
-Polyacrylic acid (Mw = 50,000): manufactured by Toagosei Co., Ltd., trade name "Julimer AC-10L"
-Ammonium polyacrylate (Mw = 100,000): Made by Toagosei Co., Ltd., trade name "Aron A-30"
-Polyacrylic acid (Mw = 250,000): Wako Pure Chemical Industries, Ltd., trade name "Polyacrylic acid 250,000"
-Polyacrylic acid (Mw = 800,000): manufactured by Toagosei Co., Ltd., trade name "Julimer AC-10H"
-Polyacrylic acid (Mw = 1,000,000): Made by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "Polyacrylic acid 1,000,000"
〔アルカノールアミン〕
・イソプロパノールアミン：富士フイルム和光純薬（株）製、ＣｌｏｇＰ値－０．８２、ｐＫａ１２．９２
・モノエタノールアミン：富士フイルム和光純薬（株）製、ＣｌｏｇＰ値－１．３１、ｐＫａ９．５０
・ジエタノールアミン：富士フイルム和光純薬（株）製、ＣｌｏｇＰ値－１．５０、ｐＫａ８．８８
・トリエタノールアミン：富士フイルム和光純薬（株）製、ＣｌｏｇＰ値‐１．１１、ｐＫａ７．８８
・トリスヒドロキシメチルアミノメタン：富士フイルム和光純薬（株）製、ＣｌｏｇＰ値－１．３８、ｐＫａ８．３０
・Ｎ－エチルエタノールアミン：富士フイルム和光純薬（株）製、ＣｌｏｇＰ値－１．６９、ｐＫａ１０．１２
・モノプロパノールアミン：富士フイルム和光純薬（株）製、ＣｌｏｇＰ値－１．１２、ｐＫａ９．９６
・トリイソプロパノールアミン：富士フイルム和光純薬（株）製、ＣｌｏｇＰ値－０．０７、ｐＫａ１４．３７
・Ｎ－メチルエタノールアミン：富士フイルム和光純薬（株）製、ＣｌｏｇＰ値－０．９７、ｐＫａ９．８８
・２－アミノ－２－メチル－１－プロパノール：富士フイルム和光純薬（株）製、ＣｌｏｇＰ値－０．６１、ｐＫａ９．７０
・２－（ジメチルアミノ）－２－メチル－１－プロパノール：富士フイルム和光純薬（株）製、ＣｌｏｇＰ値０．３７、ｐＫａ１０．２０ [Alkanolamine]
-Isopropanolamine: manufactured by Wako Pure Chemical Industries, Ltd., ClogP value -0.82, pKa12.92
-Monoethanolamine: manufactured by Wako Pure Chemical Industries, Ltd., ClogP value -1.31, pKa9.50
-Diethanolamine: manufactured by Wako Pure Chemical Industries, Ltd., ClogP value -1.50, pKa8.88
-Triethanolamine: manufactured by Wako Pure Chemical Industries, Ltd., ClogP value-1.11, pKa7.88
-Tris hydroxymethylaminomethane: manufactured by Wako Pure Chemical Industries, Ltd., ClogP value -1.38, pKa 8.30
-N-Ethylethanolamine: manufactured by Wako Pure Chemical Industries, Ltd., ClogP value -1.69, pKa10.12
-Monopropanolamine: manufactured by Wako Pure Chemical Industries, Ltd., ClogP value-1.12, pKa9.96
-Triisopropanolamine: manufactured by Wako Pure Chemical Industries, Ltd., ClogP value -0.07, pKa14.37
-N-Methylethanolamine: manufactured by Wako Pure Chemical Industries, Ltd., ClogP value -0.97, pKa9.88
-2-Amino-2-methyl-1-propanol: manufactured by Wako Pure Chemical Industries, Ltd., ClogP value -0.61, pKa9.70
-2- (Dimethylamino) -2-methyl-1-propanol: manufactured by Wako Pure Chemical Industries, Ltd., ClogP value 0.37, pKa10.20
〔酸基を有する錯化剤〕
・セリン：Ｌ－セリン、富士フイルム和光純薬（株）製
・グリシン：富士フイルム和光純薬（株）製
・アラニン：Ｌ－アラニン、富士フイルム和光純薬（株）製
・メチオニン：Ｌ－メチオニン、富士フイルム和光純薬（株）製
・ヒスチジン：Ｌ－ヒスチジン、富士フイルム和光純薬（株）製
・アルギニン：Ｌ－アルギニン、富士フイルム和光純薬（株）製
・グルタミン：Ｌ－グルタミン、富士フイルム和光純薬（株）製
・アスパラギン：Ｌ－アスパラギン、富士フイルム和光純薬（株）製
・アスパラギン酸：Ｌ－アスパラギン酸、富士フイルム和光純薬（株）製
・グルタミン酸：Ｌ－グルタミン酸、富士フイルム和光純薬（株）製
・システイン：Ｌ－システイン、富士フイルム和光純薬（株）製
・クエン酸：富士フイルム和光純薬（株）製
・酒石酸：Ｌ－酒石酸、富士フイルム和光純薬（株）製
・コハク酸：富士フイルム和光純薬（株）製
・ＤＴＰＡ：ジエチレントリアミン五酢酸、富士フイルム和光純薬（株）製
・ＨＥＤＰＯ：１－ヒドロキシエチリデン－１，１－ジホスホン酸、サーモフォス社製「Ｄｅｑｕｅｓｔ　２０００」
・ＥＤＴＡ：エチレンジアミン四酢酸、キレスト社製
・ＤＨＥＧ：Ｎ，Ｎ－ビス（２－ヒドロキシエチル）グリシン、富士フイルム和光純薬（株）製
・フィチン酸：富士フイルム和光純薬（株）製
・ヘキサメタリン酸ナトリウム：富士フイルム和光純薬（株）製
・二リン酸：富士フイルム和光純薬（株）製
・ｐ－トルエンスルホン酸：富士フイルム和光純薬（株）製
・メタンスルホン酸：富士フイルム和光純薬（株）製
・エタンスルホン酸：富士フイルム和光純薬（株）製 [Complex agent with acid group]
・ Serin: L-serine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ Glycin: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ Alanin: L-alanine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ Methionin: L-methionine , Fujifilm Wako Pure Chemical Industries, Ltd. ・ Histidine: L-histidine, Fujifilm Wako Pure Chemical Industries, Ltd. ・ Arginine: L-Arginine, Fujifilm Wako Pure Chemical Industries, Ltd. ・ Glutamine: L-Glutamine, Fuji Film Wako Pure Chemical Industries, Ltd. ・ Asparagin: L-asparagin, Fuji Film Wako Pure Chemical Industries, Ltd. ・ Asparaginic acid: L-asparaginic acid, Fuji Film Wako Pure Chemical Industries, Ltd. ・ Glutamic acid: L-glutamic acid, Fuji Film Wako Pure Chemical Industries, Ltd. ・ Cysteine: L-cysteine, Fujifilm Wako Pure Chemical Industries, Ltd. ・ Citrate: Fujifilm Wako Pure Chemical Industries, Ltd. ・ Tartrate acid: L-Tartrate acid, Fujifilm Wako Pure Chemical Industries, Ltd. Wako Pure Chemical Industries, Ltd. ・ DTPA: Diethylenetriamine pentaacetic acid, Wako Pure Chemical Industries, Ltd. ・ HEDPO: 1-hydroxyethylidene-1,1-diphosphonic acid, Thermophos "Dequest 2000"
・ EDTA: ethylenediamine tetraacetic acid, manufactured by Kirest Co., Ltd. ・ DHEG: N, N-bis (2-hydroxyethyl) glycine, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Sodium acid: Fujifilm Wako Pure Chemical Industries, Ltd. ・ Diphosphate: Fujifilm Wako Pure Chemical Industries, Ltd. ・ p-Toluenesulfonic acid: Fujifilm Wako Pure Chemical Industries, Ltd. ・ Methanesulfonic acid: Fujifilmwa Made by Kojunyaku Co., Ltd. ・ Etansulfonic acid: Made by Fujifilm Wako Pure Chemical Industries, Ltd.
〔その他〕
＜界面活性剤＞
・ＣＲＯＤＡＦＯＳ　ＫＤ－６６：アルキルリン酸エステル、クローダ製
・ポリオキシエチレンアルキルリン酸エステル：日光ケミカルズ製、商品名「ＮＩＫＫＯＬ　ＤＤＰ－８」
＜有機溶媒＞
・メタノール：富士フイルム和光純薬（株）製
・エチレングリコール：富士フイルム和光純薬（株）製
・アセトニトリル：富士フイルム和光純薬（株）製
＜防腐剤＞
・プロピオン酸：富士フイルム和光純薬（株）製
・安息香酸：富士フイルム和光純薬（株）製
・ソルビン酸：富士フイルム和光純薬（株）製
・サリチル酸：富士フイルム和光純薬（株）製
＜防食剤＞
・ピロカテコール：富士フイルム和光純薬（株）製
・ピロガロール：富士フイルム和光純薬（株）製
・没食子酸：富士フイルム和光純薬（株）製
・イミダゾール：富士フイルム和光純薬（株）製
・ピラゾール：富士フイルム和光純薬（株）製
・２，４－ジメチルチアゾール：富士フイルム和光純薬（株）製
・１，２，４－トリアゾ－ル：富士フイルム和光純薬（株）製
・１Ｈ－テトラゾール（１，２，３，４－テトラゾ－ル）：富士フイルム和光純薬（株）製
・３－アミノ－５－メチルピラゾール：富士フイルム和光純薬（株）製
・アデニン：富士フイルム和光純薬（株）製
・ピリジン：富士フイルム和光純薬（株）製
・ピラジン：富士フイルム和光純薬（株）製
・ピリミジン：富士フイルム和光純薬（株）製
・ヒドロキシルアミン：富士フイルム和光純薬（株）製
・クロルヘキシジングルコン酸塩：富士フイルム和光純薬（株）製
・アスコルビン酸：富士フイルム和光純薬（株）製
・チオグリコール酸：富士フイルム和光純薬（株）製
・ジチオジグリコール酸：富士フイルム和光純薬（株）製
・ポリエチレングリコール：富士フイルム和光純薬（株）製
・シクロデキストリン：富士フイルム和光純薬（株）製
＜ｐＨ調剤剤＞
・ＴＭＡＨ：テトラメチルアンモニウムヒドロキシド、富士フイルム和光純薬（株）製
・ＴＥＡＨ：テトラエチルアンモニウムヒドロキシド、富士フイルム和光純薬（株）製
・コリン：富士フイルム和光純薬（株）製
・硫酸：富士フイルム和光純薬（株）製 〔others〕
<Surfactant>
-CRODAFOS KD-66: Alkyl phosphate ester, manufactured by Crowder-Polyoxyethylene alkyl phosphate ester: manufactured by Nikko Chemicals, trade name "NIKKOL DDP-8"
<Organic solvent>
・ Methanol: Wako Pure Chemical Industries, Ltd. ・ Ethylene glycol: Wako Pure Chemical Industries, Ltd. ・ Acetonitrile: Wako Pure Chemical Industries, Ltd. <Preservatives>
・ Propionic acid: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ Benzoic acid: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ Sorbic acid: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ Salicylic acid: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Made <Anti-corrosion agent>
・ Pyrocatecol: Made by Fujifilm Wako Pure Chemical Industries, Ltd. ・ Pyrogalol: Made by Fujifilm Wako Pure Chemical Industries, Ltd. ・ Gluttonous acid: Made by Fujifilm Wako Pure Chemical Industries, Ltd.・ Pyrazole: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ 2,4-dimethylthiazole: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ 1,2,4-triazol: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・1H-Tetrazole (1,2,3,4-tetrazole): Fujifilm Wako Pure Chemical Industries, Ltd., 3-Amino-5-Methylpyrazole: Fujifilm Wako Pure Chemical Industries, Ltd. Adenin: Fujifilm Wako Pure Chemical Industries, Ltd. ・ pyridine: Fujifilm Wako Pure Chemical Industries, Ltd. ・ Pyrazine: Fujifilm Wako Pure Chemical Industries, Ltd. ・ Pirimidine: Fujifilm Wako Pure Chemical Industries, Ltd. ・ hydroxylamine: Fujifilm Japanese Kojunyaku Co., Ltd. ・ Chlorhexyzing luconate: Fujifilm Wako Pure Chemical Industries, Ltd. ・ Ascorbic acid: Fujifilm Wako Pure Chemical Industries, Ltd. ・ Thioglycolic acid: Fujifilm Wako Pure Chemical Industries, Ltd. ・ Dithio Diglycolic acid: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., polyethylene glycol: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., cyclodextrin: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. <pH preparation>
・ TMAH: Tetramethylammonium Hydroxide, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ TEAH: Tetraethylammonium Hydroxide, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ Colin: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ・ Sulfate: Made by Fujifilm Wako Pure Chemical Industries, Ltd.
〔ｐＨ調整剤及び水〕
　本実施例における洗浄液の製造工程では、ｐＨ調整剤として硫酸（Ｈ２ＳＯ４）及び超純水を用いた。　ｐＨ調整剤（硫酸）の含有量は、実施例及び比較例のいずれの洗浄液においても、洗浄液の全質量に対して、２質量％以下であった。 [PH regulator and water]
In the process of producing the cleaning liquid in this example, sulfuric acid (H 2 SO 4 ) and ultrapure water were used as pH adjusters. The content of the pH adjuster (sulfuric acid) was 2% by mass or less with respect to the total mass of the cleaning liquid in both the cleaning liquids of Examples and Comparative Examples.
［洗浄液の製造］
　実施例１の洗浄液の製造方法について、説明する。
　超純水に、イソプロパノールアミン、セリン、及び、ポリアクリル酸（Ｍｗ＝１０,０００）を、後述する表に従って添加した後、調製される洗浄液のｐＨが３．０となるようにｐＨ調整剤として硫酸を添加した。得られた混合液を十分に攪拌することにより、実施例１の洗浄液を得た。 [Manufacturing of cleaning liquid]
The method for producing the cleaning liquid of Example 1 will be described.
Isopropanolamine, serine, and polyacrylic acid (Mw = 10,000) are added to ultrapure water according to the table below, and then the pH of the prepared cleaning solution is adjusted to 3.0 as a pH adjuster. Sulfuric acid was added. The cleaning liquid of Example 1 was obtained by sufficiently stirring the obtained mixed liquid.
　後述する表に従って、各成分を調整した以外は、実施例１と同様の製造方法によって、各実施例及び比較例の洗浄液を、それぞれ製造した。 The cleaning solutions of each Example and Comparative Example were produced by the same production method as in Example 1 except that each component was adjusted according to the table described later.
〔洗浄性能〕
　各実施例又は比較例の洗浄液を用いて、ＣＭＰ処理後の金属膜を洗浄した際の洗浄性能（残渣物除去性能）を評価した。
　ＦＲＥＸ－３００ＳII（研磨装置、荏原製作所社製）を用いて、研磨液（Ｗ２０００、Ｃａｂｏｔ社製）を使用し、研磨液の供給速度を０．２８ｍｌ／（ｍｉｎ・ｃｍ２）、研磨圧力を２．０ｐｓｉ、及び、研磨時間を６０秒間の条件により、表面にタングステンからなる金属膜を有するウエハ（直径１２インチ）をＣＭＰ処理した。
　その後、各洗浄液の温度を室温（２３℃）に調整し、各洗浄液を用いて６０秒間スクラブ洗浄し、乾燥処理した。欠陥検出装置を用いて、得られたウエハの研磨面における欠陥数を検出し、各欠陥をＳＥＭ（走査電子顕微鏡）にて観測して欠陥分類を行った。必要に応じ、構成元素をＥＤＡＸ（エネルギー分散型Ｘ線分析装置）により分析し成分の特定を行った。これにより、残渣物に基づく欠陥の数を求め、下記の評価基準に従って洗浄性能を評価した（評価６が、最も洗浄性能に優れる）。
（評価基準）
　６：対象欠陥数が２０個未満
　５：対象欠陥数が２０個以上、５０個未満
　４：対象欠陥数が５０個以上、１００個未満
　３：対象欠陥数が１００個以上、２００個未満
　２：対象欠陥数が２００個以上、３００個未満
　１：対象欠陥数が３００個以上 [Cleaning performance]
The cleaning performance (residue removal performance) when the metal film after the CMP treatment was cleaned was evaluated using the cleaning liquids of each Example or Comparative Example.
Using FREX-300SII (polishing equipment, manufactured by Ebara Corporation), using a polishing liquid (W2000, manufactured by Cabot), the supply speed of the polishing liquid is 0.28 ml / (min · cm 2 ), and the polishing pressure is 2. A wafer (12 inches in diameter) having a metal film made of tungsten on the surface was subjected to CMP treatment under the conditions of 0.0 psi and a polishing time of 60 seconds.
Then, the temperature of each cleaning solution was adjusted to room temperature (23 ° C.), scrubbed with each cleaning solution for 60 seconds, and dried. Using a defect detection device, the number of defects on the polished surface of the obtained wafer was detected, and each defect was observed with an SEM (scanning electron microscope) to classify the defects. If necessary, the constituent elements were analyzed by EDAX (energy dispersive X-ray analyzer) to identify the components. As a result, the number of defects based on the residue was determined, and the cleaning performance was evaluated according to the following evaluation criteria (evaluation 6 is the most excellent in cleaning performance).
(Evaluation criteria)
6: The number of target defects is less than 20 5: The number of target defects is 20 or more and less than 50 4: The number of target defects is 50 or more and less than 100 3: The number of target defects is 100 or more and less than 200 2: The number of target defects is 200 or more and less than 300 1: The number of target defects is 300 or more
〔腐食抑制性能〕
　各実施例又は比較例の洗浄液を用いて、金属膜を洗浄した際の腐食抑制性能を評価した。
　表面にタングステンからなる金属膜を有するウエハ（直径１２インチ）をカットし、２ｃｍ□のウエハクーポンをそれぞれ準備した。各金属膜の厚さは２００ｎｍとした。各洗浄液にウエハを浸漬し、室温（２３℃）下、攪拌回転数２５０ｒｐｍにて、タングステンからなる金属膜の各洗浄液に浸漬してから３０分後に、消失した上記金属膜の膜厚を求めた。上記消失した膜厚から、上記金属膜の単位時間当たりの腐食速度を算出した。
　下記の評価基準によって腐食抑制性能を評価した。腐食速度が低いほど、洗浄液の腐食抑制性能が優れることを示す（評価６が最も腐食抑制性能が優れる）。
（評価基準）
　６：腐食速度が０．２Å／ｍｉｎ以下
　５：腐食速度が０．２Å／ｍｉｎ超、０．５Å／ｍｉｎ以下
　４：腐食速度が０．５Å／ｍｉｎ超、１Å／ｍｉｎ以下
　３：腐食速度が１Å／ｍｉｎ超、３Å／ｍｉｎ以下
　２：腐食速度が３Å／ｍｉｎ超、５Å／ｍｉｎ以下
　１：腐食速度が５Å／ｍｉｎ超 [Corrosion suppression performance]
The corrosion suppression performance when the metal film was washed was evaluated using the cleaning liquids of each Example or Comparative Example.
Wafers (12 inches in diameter) having a metal film made of tungsten on the surface were cut, and 2 cm □ wafer coupons were prepared respectively. The thickness of each metal film was 200 nm. The wafer was immersed in each cleaning liquid at room temperature (23 ° C.) at a stirring rotation speed of 250 rpm, and 30 minutes after being immersed in each cleaning liquid of a metal film made of tungsten, the thickness of the disappeared metal film was determined. .. From the disappeared film thickness, the corrosion rate of the metal film per unit time was calculated.
Corrosion suppression performance was evaluated according to the following evaluation criteria. The lower the corrosion rate, the better the corrosion suppression performance of the cleaning liquid (evaluation 6 shows the best corrosion suppression performance).
(Evaluation criteria)
6: Corrosion rate is 0.2 Å / min or less 5: Corrosion rate is more than 0.2 Å / min, 0.5 Å / min or less 4: Corrosion rate is more than 0.5 Å / min or less, 1 Å / min or less 3: Corrosion rate is More than 1 Å / min, less than 3 Å / min 2: Corrosion rate is more than 3 Å / min, less than 5 Å / min 1: Corrosion rate is more than 5 Å / min
［結果］
　以下の表に、各実施例及び比較例の、洗浄液の組成及び評価結果を示す。
　表中、「Ｍｗ」欄は、重量平均分子量を示す。
　「含有量（質量％）」欄は、洗浄液の全質量に対する、各成分の含有量（単位：質量％）を示す。
　「有効成分量（質量％）」欄は、溶媒を除いた洗浄液の全質量に対する、各成分の含有量を示す。
　「（Ｃ）／（Ｂ）」欄は、アルカノールアミンの含有量に対する、特定錯化剤の含有量の質量比〔特定錯化剤の含有量／アルカノールアミンの含有量〕を表す。
　「（Ｃ）／（Ａ）」欄は、重合体の含有量に対する、特定錯化剤の含有量の質量比〔特定錯化剤の含有量／重合体の含有量〕を表す。
　「ｐＨ」欄の数値は、上記のｐＨメーターにより測定した洗浄液の２５℃におけるｐＨを示す。
　「ｐＨ」欄の「＊１」は、必要な場合、Ｈ２ＳＯ４（硫酸）を、調製される洗浄液のｐＨが「ｐＨ」欄の数値になる量で添加したことを意味する。
　「水」欄の「残部」は、洗浄液中において各成分の以外の残りを水が構成していることを意味する。 [result]
The table below shows the composition and evaluation results of the cleaning liquids of each Example and Comparative Example.
In the table, the "Mw" column indicates the weight average molecular weight.
The "content (% by mass)" column indicates the content (unit: mass%) of each component with respect to the total mass of the cleaning liquid.
The "active ingredient amount (% by mass)" column shows the content of each component with respect to the total mass of the cleaning liquid excluding the solvent.
The column "(C) / (B)" represents the mass ratio of the content of the specific complexing agent to the content of the alkanolamine [content of the specific complexing agent / content of alkanolamine].
The column "(C) / (A)" represents the mass ratio of the content of the specific complexing agent to the content of the polymer [content of the specific complexing agent / content of the polymer].
The numerical value in the "pH" column indicates the pH of the cleaning solution measured by the above pH meter at 25 ° C.
“* 1” in the “pH” column means that, if necessary, H 2 SO 4 (sulfuric acid) was added in an amount so that the pH of the prepared cleaning solution would be the value in the “pH” column.
The "remaining portion" in the "water" column means that water constitutes the rest of the cleaning liquid other than each component.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
　表に示す通り、本発明の洗浄液は、所望の効果が得られることが確認された。
　実施例１及び６０～６３と、実施例６４～６６との比較から、重合体の重量平均分子量が、２０００～５０００００である場合、より効果が優れることが確認された。
　実施例１、及び、１７～２１と、実施例２２～２３との比較から、アルカノールアミンの含有量に対する、特定錯化剤の含有量の質量比〔（Ｃ）／（Ｂ）〕が、０．１～１０００．０である場合、より効果が優れることが確認された。また、〔（Ｃ）／（Ｂ）〕が０．１～４００．０である場合、更に効果が優れることが確認された。
　同様の実施例の比較から、錯化剤の含有量が、洗浄液の全質量に対して、３．０～１０．０質量である場合、より効果が優れることが確認された。また、錯化剤の含有量が、洗浄液の全質量に対して、３．０～４．０質量％である場合、更に効果が優れることが確認された。
　実施例１、５３～５５、６７、及び、６９と、実施例５６及び６８との比較から、重合体の含有量に対する、特定錯化剤の含有量の質量比〔（Ｃ）／（Ａ）〕が、１．５～５０．０である場合、より効果が優れることが確認された。
　実施例１等と、実施例４１～４４との比較から、特定錯化剤が式（Ｂ１）で表される化合物、式（Ｂ３）で表される化合物、式（Ｂ４）で表される化合物、式（Ｃ）で表される化合物、二リン酸、ヘキサメタリン酸、フィチン酸、及び、式（Ｐ１）で表される化合物からなる群から選択される少なくとも１つを含む場合、より効果が優れることが確認された。
　実施例２９～３０と、実施例１等との比較から、洗浄液が、更に界面活性剤を含む場合、より効果が優れることが確認された。
　実施例８３～１０２、及び、１０６～１０７との比較から、洗浄液が、更に防食剤を含む場合、より効果が優れることが確認された。 As shown in the table, it was confirmed that the cleaning solution of the present invention obtained the desired effect.
From the comparison between Examples 1 and 60 to 63 and Examples 64 to 66, it was confirmed that the effect was more excellent when the weight average molecular weight of the polymer was 2000 to 500,000.
From the comparison between Examples 1 and 17 to 21 and Examples 22 to 23, the mass ratio of the content of the specific complexing agent to the content of the alkanolamine [(C) / (B)] is 0. When it was 1 to 1000.0, it was confirmed that the effect was more excellent. Further, when [(C) / (B)] was 0.1 to 400.0, it was confirmed that the effect was further excellent.
From the comparison of similar examples, it was confirmed that the effect was more excellent when the content of the complexing agent was 3.0 to 10.0 mass with respect to the total mass of the cleaning liquid. Further, it was confirmed that the effect was further excellent when the content of the complexing agent was 3.0 to 4.0% by mass with respect to the total mass of the cleaning liquid.
From the comparison between Examples 1, 53 to 55, 67, and 69 and Examples 56 and 68, the mass ratio of the content of the specific complexing agent to the content of the polymer [(C) / (A). ] Is 1.5 to 50.0, it was confirmed that the effect is more excellent.
From the comparison between Examples 1 and the like and Examples 41 to 44, the specific complexing agent is a compound represented by the formula (B1), a compound represented by the formula (B3), and a compound represented by the formula (B4). , The effect is more excellent when it contains at least one selected from the group consisting of the compound represented by the formula (C), diphosphate, hexamethaphosphate, phytic acid, and the compound represented by the formula (P1). It was confirmed that.
From the comparison between Examples 29 to 30 and Example 1 and the like, it was confirmed that the effect was more excellent when the cleaning liquid further contained a surfactant.
From the comparison with Examples 83 to 102 and 106 to 107, it was confirmed that the cleaning liquid was more effective when it further contained an anticorrosive agent.
　上記洗浄性能の評価試験において、タングステンからなる金属配線を表面に有するウエハに対してＣＭＰ処理をそれぞれ行った後、研磨されたウエハの表面に対してバフ研磨処理を施した。
バフ研磨処理では、バフ研磨用組成物として室温（２３℃）に調整した各洗浄液を使用した。また、上記ＣＭＰ処理で使用した研磨装置を使用し、研磨圧力：２．０ｐｓｉ、バフ研磨用組成物の供給速度：０．２８ｍＬ／（分・ｃｍ２）、及び、研磨時間：６０秒間の条件で、バフ研磨処理を行った。
　その後、室温（２３℃）に調整した各希釈洗浄液のサンプルを用いて、バフ研磨処理が施されたウエハを３０秒間かけて洗浄し、次いで、乾燥処理した。
　得られたウエハの研磨面に対して、上述した〔洗浄性能の評価〕の評価試験方法に従って洗浄液の洗浄性能を評価したところ、上記の各実施例の洗浄液と同様の評価結果を示すことが確認された。 In the above-mentioned cleaning performance evaluation test, a wafer having a metal wiring made of tungsten on the surface was subjected to CMP treatment, and then the surface of the polished wafer was buffed.
In the buffing treatment, each cleaning liquid adjusted to room temperature (23 ° C.) was used as the buffing composition. Further, using the polishing device used in the above CMP treatment, the conditions are that the polishing pressure is 2.0 psi, the supply speed of the buffing composition is 0.28 mL / (minute · cm 2 ), and the polishing time is 60 seconds. Then, buffing treatment was performed.
Then, the buffed wafer was washed over 30 seconds using a sample of each diluted washing solution adjusted to room temperature (23 ° C.), and then dried.
When the cleaning performance of the cleaning liquid was evaluated on the polished surface of the obtained wafer according to the evaluation test method of [Evaluation of cleaning performance] described above, it was confirmed that the same evaluation results as the cleaning liquid of each of the above-mentioned Examples were shown. Was done.

Claims (17)

  1. 　半導体基板を洗浄するために用いられる、半導体基板用洗浄液であって、
    　重合体、アルカノールアミン、酸基を有する錯化剤、及び、水を含み、
    　前記重合体の重量平均分子量が、２０００～９０００００であり、
    　前記錯化剤の含有量が、前記半導体基板用洗浄液の全質量に対して、２．５質量％以上２０．０質量％未満であり、
    　前記半導体基板用洗浄液のｐＨが、７．０未満である、半導体基板用洗浄液。     A cleaning liquid for semiconductor substrates used for cleaning semiconductor substrates.
    Contains polymers, alkanolamines, complexing agents with acid groups, and water.
    The weight average molecular weight of the polymer is 2000 to 900,000, and the polymer has a weight average molecular weight of 2000 to 900,000.
    The content of the complexing agent is 2.5% by mass or more and less than 20.0% by mass with respect to the total mass of the cleaning liquid for the semiconductor substrate.
    A cleaning liquid for a semiconductor substrate, wherein the pH of the cleaning liquid for a semiconductor substrate is less than 7.0.
  2. 　前記錯化剤が、カルボキシ基、リン酸基、ホスホン酸、及び、スルホン酸基からなる群から選択される少なくとも１つを有する、請求項１に記載の半導体基板用洗浄液。 The cleaning solution for a semiconductor substrate according to claim 1, wherein the complexing agent has at least one selected from the group consisting of a carboxy group, a phosphoric acid group, a phosphonic acid, and a sulfonic acid group.
  3. 　前記重合体の重量平均分子量が、２０００～５０００００である、請求項１又は２に記載の半導体基板用洗浄液。 The cleaning liquid for a semiconductor substrate according to claim 1 or 2, wherein the polymer has a weight average molecular weight of 2000 to 500,000.
  4. 　前記アルカノールアミンのｐＫａが、７．５０～１５．００である、請求項１～３のいずれか１項に記載の半導体基板用洗浄液。 The cleaning liquid for a semiconductor substrate according to any one of claims 1 to 3, wherein the pKa of the alkanolamine is 7.50-15.00.
  5. 　前記アルカノールアミンが、モノエタノールアミン、イソプロパノールアミン、及び、トリスヒドロキシメチルアミノメタンからなる群から選択される少なくとも１つを含む、請求項１～４のいずれか１項に記載の半導体基板用洗浄液。 The cleaning solution for a semiconductor substrate according to any one of claims 1 to 4, wherein the alkanolamine contains at least one selected from the group consisting of monoethanolamine, isopropanolamine, and trishydroxymethylaminomethane.
  6. 　前記アルカノールアミンの含有量が、前記半導体基板用洗浄液の全質量に対して、０．０１～７．０質量％である、請求項１～５のいずれか１項に記載の半導体基板用洗浄液。 The cleaning liquid for a semiconductor substrate according to any one of claims 1 to 5, wherein the content of the alkanolamine is 0.01 to 7.0% by mass with respect to the total mass of the cleaning liquid for a semiconductor substrate.
  7. 　前記アルカノールアミンの含有量に対する、前記錯化剤の含有量の質量比が、０．１～１０００．０である、請求項１～６のいずれか１項に記載の半導体基板用洗浄液。 The cleaning liquid for a semiconductor substrate according to any one of claims 1 to 6, wherein the mass ratio of the content of the complexing agent to the content of the alkanolamine is 0.1 to 1000.0.
  8. 　前記重合体の含有量に対する、前記錯化剤の含有量の質量比が、１．０～１００．０である、請求項１～７のいずれか１項に記載の半導体基板用洗浄液。 The cleaning liquid for a semiconductor substrate according to any one of claims 1 to 7, wherein the mass ratio of the content of the complexing agent to the content of the polymer is 1.0 to 100.0.
  9. 　前記錯化剤の含有量が、前記半導体基板用洗浄液の全質量に対して、３．０～１０．０質量％である、請求項１～８のいずれか１項に記載の半導体基板用洗浄液。 The cleaning liquid for a semiconductor substrate according to any one of claims 1 to 8, wherein the content of the complexing agent is 3.0 to 10.0% by mass with respect to the total mass of the cleaning liquid for a semiconductor substrate. ..
  10. 　前記錯化剤の含有量が、前記半導体基板用洗浄液の全質量に対して、３．０～４．０質量％である、請求項１～９のいずれか１項に記載の半導体基板用洗浄液。 The cleaning liquid for a semiconductor substrate according to any one of claims 1 to 9, wherein the content of the complexing agent is 3.0 to 4.0% by mass with respect to the total mass of the cleaning liquid for a semiconductor substrate. ..
  11. 　更に、防食剤を含む、請求項１～１０のいずれか１項に記載の半導体基板用洗浄液。 The cleaning liquid for a semiconductor substrate according to any one of claims 1 to 10, further comprising an anticorrosive agent.
  12. 　更に、界面活性剤を含む、請求項１～１１のいずれか１項に記載の半導体基板用洗浄液。 The cleaning liquid for a semiconductor substrate according to any one of claims 1 to 11, further comprising a surfactant.
  13. 　前記界面活性剤が、アニオン性界面活性剤を含む、請求項１２に記載の半導体基板用洗浄液。 The cleaning liquid for a semiconductor substrate according to claim 12, wherein the surfactant contains an anionic surfactant.
  14. 　前記界面活性剤が、アルキルリン酸エステル及びポリオキシエチレンアルキルリン酸エステルからなる群から選択される少なくとも１つを含む、請求項１２又は１３に記載の半導体基板用洗浄液。 The cleaning solution for a semiconductor substrate according to claim 12 or 13, wherein the surfactant comprises at least one selected from the group consisting of an alkyl phosphate ester and a polyoxyethylene alkyl phosphate ester.
  15. 　更に、親水性有機溶媒を含む、請求項１～１４のいずれか１項に記載の半導体基板用洗浄液。 The cleaning liquid for a semiconductor substrate according to any one of claims 1 to 14, further comprising a hydrophilic organic solvent.
  16. 　前記半導体基板が、タングステンを含む金属膜を有する、請求項１～１５のいずれか１項に記載の半導体基板用洗浄液。 The cleaning liquid for a semiconductor substrate according to any one of claims 1 to 15, wherein the semiconductor substrate has a metal film containing tungsten.
  17. 　化学機械研磨処理が施された半導体基板に適用される洗浄液として用いられる、請求項１～１６のいずれか１項に記載の半導体基板用洗浄液。 The cleaning liquid for a semiconductor substrate according to any one of claims 1 to 16, which is used as a cleaning liquid applied to a semiconductor substrate that has been subjected to a chemical mechanical polishing treatment.
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