WO2020100985A1 - Polishing liquid composition - Google Patents

Polishing liquid composition Download PDF

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Publication number
WO2020100985A1
WO2020100985A1 PCT/JP2019/044719 JP2019044719W WO2020100985A1 WO 2020100985 A1 WO2020100985 A1 WO 2020100985A1 JP 2019044719 W JP2019044719 W JP 2019044719W WO 2020100985 A1 WO2020100985 A1 WO 2020100985A1
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WIPO (PCT)
Prior art keywords
polishing
component
substrate
mass
less
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PCT/JP2019/044719
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French (fr)
Japanese (ja)
Inventor
多久島大樹
Original Assignee
花王株式会社
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Publication of WO2020100985A1 publication Critical patent/WO2020100985A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/84—Processes or apparatus specially adapted for manufacturing record carriers

Definitions

  • the present disclosure relates to a polishing composition, a substrate manufacturing method using the same, and a polishing method.
  • the magnetic disk substrate has improved smoothness and flatness represented by reduction of surface roughness, waviness, and edge sag (roll-off), and scratches.
  • the demand for defect reduction represented by the reduction of protrusions and pits is becoming stricter.
  • Patent Document 1 discloses an abrasive, a water-soluble polymer having a phenol skeleton in a main chain or a side chain, and a polishing liquid containing water. Compositions are disclosed (Examples in that document, Table 3).
  • Patent Document 2 (a) an inorganic abrasive, (b) an arylamine, an amino alcohol, an aliphatic amine, a heterocyclic amine, a hydroxamic acid, an aminocarboxylic acid, a cyclic monocarboxylic acid.
  • a polishing additive selected from the group consisting of acids, unsaturated monocarboxylic acids, substituted phenols, sulfonamides, thiols, salts thereof and combinations thereof, and having a functional group of pKa of about 3-9, and (c) a liquid.
  • a polishing composition containing a carrier is disclosed.
  • Patent Document 3 discloses a metal polishing liquid containing an oxidizing agent, a metal oxide dissolving agent, a first protective film forming agent, a second protective film forming agent, and water. Polyacrylic acid, polyacrylamide and the like are described as preferable examples of the second protective film forming agent (paragraph [0036] of the same document, Examples).
  • Patent Document 4 contains a liquid medium, abrasive grains containing a hydroxide of a tetravalent metal element, a polyoxyalkylene compound, and a cationic polymer.
  • a polishing liquid in which the average HI.B value of the alkylene compound is 17.0 or less is disclosed.
  • the present disclosure contains an abrasive (component A), a water-soluble polymer (component B), an acid (component C) and an aqueous medium, wherein the component B has a phenyl ether skeleton in a main chain or a side chain.
  • the present invention relates to a polishing liquid composition which is a cationic polymer having
  • the present disclosure relates to a method for manufacturing a magnetic disk substrate, including a step of polishing a substrate to be polished with the polishing composition of the present disclosure.
  • the present disclosure includes, in another aspect, polishing a substrate to be polished with the polishing composition of the present disclosure, wherein the substrate to be polished is a substrate used for manufacturing a magnetic disk substrate. Regarding the method.
  • the present disclosure provides a polishing composition capable of reducing scratches on the surface of a substrate after polishing while ensuring a polishing rate, and a method of manufacturing a magnetic disk substrate and a method of polishing a substrate using the same.
  • the present disclosure is based on the finding that by using a polishing composition containing a predetermined cationic polymer, scratches on the substrate surface after polishing can be reduced while ensuring a polishing rate.
  • the present disclosure is, in one aspect, a polishing liquid composition containing an abrasive (component A), a water-soluble polymer (component B), an acid (component C) and an aqueous medium, wherein the component B comprises:
  • the present invention relates to a polishing liquid composition (hereinafter, also referred to as “polishing liquid composition of the present disclosure”) which is a cationic polymer having a phenyl ether skeleton in the main chain or side chain.
  • polishing composition of the present disclosure in one or a plurality of embodiments, it is possible to obtain an effect that scratches on a substrate surface after polishing can be reduced while securing a polishing rate.
  • a cationic polymer and an abrasive such as silica abrasive are not used in combination. This is because normally, the electrostatic adsorption between the positive charge of the cationic polymer and the negative charge of the abrasive such as silica abrasive grains causes the cationic polymer and the abrasive to easily crosslink and aggregate.
  • the specific cationic polymer (component B) of the present disclosure has low molecular mobility, and that it has a special three-dimensional structure and can suppress aggregation due to crosslinking with the abrasive.
  • the hydrophobic portion (phenyl ether skeleton) of the component B is adsorbed to the polishing pad and the polishing pad is positively charged, attracts the negatively charged abrasive, and contributes to the improvement of the polishing rate.
  • the component B has a mechanism that suppresses the aggregation of the abrasive in the polishing composition before it is used for polishing and promotes the adsorption of the polishing agent to the polishing pad while the polishing composition is used for polishing.
  • the aromatic ring of the component B softens the polishing pad and contributes to the reduction of scratches.
  • the present disclosure need not be limited to these mechanisms.
  • scratches on the substrate surface can be detected by, for example, an optical defect inspection device, and can be quantitatively evaluated as the number of scratches.
  • the number of scratches can be evaluated specifically by the method described in the examples.
  • abrasive As the abrasive contained in the polishing composition of the present disclosure (hereinafter, also referred to as “component A”), an abrasive generally used for polishing can be used. Metal, metal or semimetal Carbides, nitrides, oxides, borides, diamonds, etc.
  • the metal or metalloid element is derived from Group 2A, 2B, 3A, 3B, 4A, 4B, 5A, 6A, 7A or 8 of the periodic table (long period type).
  • the component A examples include silicon oxide (hereinafter referred to as silica), aluminum oxide (hereinafter referred to as alumina), silicon carbide, diamond, manganese oxide, magnesium oxide, zinc oxide, titanium oxide, cerium oxide (hereinafter referred to as ceria). ), Zirconium oxide, etc., and it is preferable to use at least one of these from the viewpoint of improving the polishing rate.
  • silica particles are preferable as the component A from the viewpoint of ensuring a polishing rate and reducing scratches.
  • the silica particles include colloidal silica, fumed silica, pulverized silica, and silica obtained by surface-modifying them, and colloidal silica is preferable.
  • the component A one type may be used alone, or two or more types may be used in combination.
  • the average particle size of the component A is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, from the viewpoint of ensuring a polishing rate and reducing scratches, and from the same viewpoint, 100 nm or less is preferable and 70 nm or less. Is more preferable, and 40 nm or less is further preferable. More specifically, the average particle size of the component A is preferably 1 nm or more and 100 nm or less, more preferably 5 nm or more and 70 nm or less, and further preferably 10 nm or more and 40 nm or less.
  • the “average particle size of the abrasive” refers to the average particle size based on the scattering intensity distribution measured at a detection angle of 90 ° in the dynamic light scattering method.
  • the average particle diameter of the abrasive can be specifically obtained by the method described in the examples.
  • the content of the component A in the polishing liquid composition of the present disclosure is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, from the viewpoint of improving the polishing rate. From the viewpoint of reducing scratches, 20% by mass or less is preferable, 15% by mass or less is more preferable, and 10% by mass or less is further preferable. Furthermore, the content of the component A is preferably 0.1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and more preferably 3% by mass or more 10 from the viewpoint of securing a polishing rate and reducing scratches. It is more preferably not more than mass%. When the component A is a combination of two or more kinds of abrasives, the content of the component A means the total content thereof. When the component A is silica, the content of the component A is a value converted into SiO 2 .
  • the water-soluble polymer (hereinafter, also referred to as “component B”) used in the polishing liquid composition of the present disclosure is a cation having a phenyl ether skeleton in its main chain or side chain from the viewpoint of ensuring a polishing rate and reducing scratches. Polymer.
  • the component B may be used alone or in combination of two or more.
  • water-soluble means that the solubility in 100 g of a pH 3 aqueous solution at 20 ° C. is 0.01 g or more.
  • the cationic polymer means a polymer having a cationic group in the repeating constitutional unit.
  • the cationic group means a functional group which becomes a cation in the presence of an acid, and includes a salt form.
  • Examples of the cationic group include organic groups containing a nitrogen atom in one or a plurality of embodiments, and examples thereof include organic groups having an amino group, a nitro group, an imino group, an ammonium group and the like.
  • the phenyl ether skeleton refers to a structure in which at least one hydrogen atom on the benzene ring is replaced with —O—X.
  • X in one or more embodiments, is a cationic group.
  • the “main chain” refers to the longest part of the linear structure formed by combining the monomer units in the water-soluble polymer of component B, and the “side chain” refers to the above linear chain. The part that is branched from.
  • a hydrophobic constituent unit and a phenyl ether skeleton in which a cationic group is ether-bonded are contained in the main chain or side chain.
  • a structural unit and a copolymer containing is preferable, a structural unit having a phenol or phenyl skeleton in the main chain or side chain, and a structural unit having a phenyl ether skeleton in which a cationic group is ether-bonded in the main chain or side chain.
  • a copolymer containing a structural unit having a phenol skeleton in a side chain and a structural unit having a phenyl ether skeleton in which a cationic group is ether-bonded in a side chain is further preferable.
  • the phenol skeleton refers to a structure in which at least one hydrogen atom of the benzene ring is substituted with a hydroxy group.
  • component B for example, a compound having a structure represented by the following formula (I) can be mentioned.
  • X represents a cationic group. From the viewpoint of ensuring a polishing rate and reducing scratches, X is preferably a cationic group containing a nitrogen atom, more preferably a cationic group containing a nitrogen atom and having 1 to 20 carbon atoms, and an amino group or a nitro group. Further, a cationic group containing at least one selected from an imino group and an ammonium group and having 1 to 20 carbon atoms is more preferable. The carbon number of the cationic group is preferably 1 or more and 20 or less, more preferably 2 or more and 15 or less, and further preferably 3 or more and 12 or less, from the viewpoint of ensuring a polishing rate and reducing scratches.
  • Examples of X in the formula (I) include —R 6 N (R 7 ) (R 8 ), —R 6 N + (R 7 ) (R 8 ) (R 9 ) ⁇ Y ⁇ .
  • R 6 is preferably a linear or branched alkylene group having 1 to 5 carbon atoms, and more preferably a linear alkylene group having 1 to 5 carbon atoms.
  • R 7 to R 9 are each independently preferably a hydrogen atom or a linear or branched hydrocarbon group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms, from the viewpoint of ensuring the polishing rate and reducing scratches.
  • Y ⁇ represents an anion.
  • the anion include halide ions such as chloride ion, bromide ion, and fluoride ion; sulfate ion; phosphate ion; nitrate ion; and the like.
  • m / n is preferably 20/80 to 80/20, more preferably 25/75 to 70/30, and still more preferably 35/65 to 70/30, from the viewpoint of securing a polishing rate and reducing scratches. Is more preferable, 35/65 to 55/45 is further preferable, and 40/60 to 50/50 is further preferable.
  • the content of the constituent represented by the formula (I) in all constituent units constituting the component B is preferably 50 mol% or more from the viewpoint of ensuring a polishing rate and reducing scratches. , 80 mol% or more is more preferable, 90 mol% or more is further preferable, and 100 mol% is the most preferable.
  • the content (mol%) of a certain structural unit in all the structural units constituting the component B depending on the synthesis conditions, all the structural units charged in the reaction tank in all the steps of the synthesis of the component B may be included. You may use the compound amount (mol%) for introducing the said structural unit prepared in the said reaction tank which occupies in the compound for introducing.
  • the constituent ratio (molar ratio) of the two constituent units may be charged into the reaction tank at all steps of the synthesis of the constituent B depending on the synthesis conditions. A compound amount ratio (molar ratio) for introducing the two constituent units may be used.
  • Component B may have other structural units not included in the formula (I). From the viewpoint of ensuring the polishing rate and reducing scratches, the content of the other structural units in all the structural units constituting the component B is preferably 10 mol% or less, more preferably 5 mol% or less, and 3 mol% or less. Is more preferable, 1 mol% or less is further preferable, and substantially 0 mol% is further preferable.
  • Ingredient B can be produced, in one embodiment, by a Mannich reaction using a dialkylamine and formaldehyde. Ingredient B can be produced, in another embodiment, by polymerizing a polymer containing a phenol skeleton with an alkylamine halogen compound.
  • each structural unit that constitutes the component B may be random, block, or graft.
  • the weight average molecular weight of the component B is preferably 500 or more, more preferably 1,000 or more, still more preferably 1,500 or more, from the viewpoint of ensuring a polishing rate and reducing scratches, and from the same viewpoint, 1,000. It is preferably 5,000 or less, more preferably 750,000 or less, still more preferably 500,000 or less. More specifically, the weight average molecular weight of the component B is preferably 500 or more and 1,000,000 or less, more preferably 1,000 or more and 750,000 or less, and further preferably 1,500 or more and 500,000 or less. In the present disclosure, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) under the conditions described in the examples.
  • GPC gel permeation chromatography
  • the content of the component B in the polishing composition of the present disclosure is preferably 0.000001 mass% or more, more preferably 0.00001 mass% or more, and 0.0001 mass from the viewpoint of ensuring a polishing rate and reducing scratches. % Or more, more preferably 0.0005% by mass or more, further preferably 0.0015% by mass or more, and from the same viewpoint, 0.01% by mass or less is preferable, and less than 0.01% by mass is more preferable.
  • the content is preferably 0.009 mass% or less, more preferably 0.006 mass% or less, further preferably 0.004 mass% or less, and further preferably 0.0025 mass% or less.
  • the content of the component B is preferably 0.000001% by mass or more and 0.01% by mass or less, more preferably 0.00001% by mass or more and 0.01% by mass or less, and 0.0001% by mass or more. 0.009 mass% or less is more preferable, 0.0005 mass% or more and 0.006 mass% or less is more preferable, and 0.0015 mass% or more and 0.004 mass% or less is further preferable.
  • the mass ratio of the component B to the component A (content of the component B / content of the component A) in the polishing composition of the present disclosure is preferably 0.0000002 or more from the viewpoint of ensuring the polishing rate and reducing scratches.
  • the above is more preferable, 0.000002 or more is more preferable, 0.0001 or more is further preferable, 0.0003 or more is further preferable, and from the same viewpoint, 0.02 or less is preferable, and 0.01 or less is more preferable.
  • 0.005 or less is more preferable, 0.003 or less is further preferable, and 0.0008 or less is further preferable.
  • the mass ratio of the component B to the component A is preferably 0.0000002 or more and 0.02 or less, more preferably 0.000002 or more and 0.01 or less, and further preferably 0.000002 or more and 0.005 or less. , 0.0001 or more and 0.003 or less are more preferable, and 0.0003 or more and 0.0008 or less are further preferable.
  • the polishing composition of the present disclosure contains an acid (component C).
  • the use of acids includes the use of acids and / or their salts.
  • the component C one type may be used alone, or two or more types may be used in combination.
  • the component C examples include inorganic acids such as nitric acid, sulfuric acid, sulfurous acid, persulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, phosphonic acid, phosphinic acid, pyrophosphoric acid, tripolyphosphoric acid, and amido sulfuric acid; organic phosphoric acid, organic phosphonic acid.
  • inorganic acids such as nitric acid, sulfuric acid, sulfurous acid, persulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, phosphonic acid, phosphinic acid, pyrophosphoric acid, tripolyphosphoric acid, and amido sulfuric acid
  • organic phosphoric acid organic phosphonic acid.
  • Organic acids such as acids and carboxylic acids; and the like. Among them, at least one selected from inorganic acids and organic phosphonic acids is preferable from the viewpoint of ensuring the polishing rate and reducing scratches.
  • the inorganic acid at least one selected from nitric acid, sulfuric acid, hydrochloric acid, perchloric acid and phosphoric acid is preferable, and at least one of phosphoric acid and sulfuric acid is more preferable.
  • the organic phosphonic acid is at least one selected from 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), and diethylenetriaminepenta (methylenephosphonic acid).
  • HEDP is preferable and HEDP is more preferable.
  • salts of these acids include salts of the above-mentioned acids with at least one selected from metals, ammonia and alkylamines.
  • the above metals include metals belonging to Groups 1 to 11 of the periodic table. Among these, from the viewpoint of ensuring the polishing rate and reducing scratches, a salt of the above-mentioned acid and a metal belonging to Group 1A or ammonia is preferable.
  • the content of the component C in the polishing composition of the present disclosure is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and 0.4% by mass from the viewpoint of ensuring a polishing rate and reducing scratches. % Or more is more preferable, and from the same viewpoint, 5% by mass or less is preferable, 3% by mass or less is more preferable, and 2% by mass or less is further preferable. More specifically, the content of the component C is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, and 0.4% by mass or more and 2% by mass or less. Is more preferable. When the component C is composed of two or more kinds of acids, the content of the component C means the total content thereof.
  • the mass ratio C / A of the component C to the component A in the polishing liquid composition of the present disclosure is 0.002 or more from the viewpoint of ensuring the polishing rate and reducing scratches. Is preferable, 0.02 or more is more preferable, 0.08 or more is further preferable, and from the same viewpoint, 1 or less is preferable, 0.6 or less is more preferable, and 0.5 or less is further preferable. More specifically, the mass ratio C / A is preferably 0.002 or more and 1 or less, more preferably 0.02 or more and 0.6 or less, and further preferably 0.08 or more and 0.5 or less.
  • aqueous medium examples of the aqueous medium contained in the polishing composition of the present disclosure include distilled water, ion-exchanged water, water such as pure water and ultrapure water, or a mixed solvent of water and a solvent.
  • the solvent include solvents that can be mixed with water (for example, alcohols such as ethanol).
  • the aqueous medium is a mixed solvent of water and a solvent, the ratio of water to the entire mixed medium may be not particularly limited as long as the effect of the present disclosure is not hindered, and from the viewpoint of economy, for example, 95 mass% or more is preferable, 98 mass% or more is more preferable, and substantially 100 mass% is further preferable.
  • ion-exchanged water and ultrapure water are preferable as the aqueous medium.
  • the content of the aqueous medium in the polishing liquid composition of the present disclosure can be the balance excluding the components A, B, C, and optional components described below that are blended as necessary.
  • the polishing composition of the present disclosure may further contain an oxidizing agent (hereinafter, also referred to as “component D”) from the viewpoint of ensuring a polishing rate and reducing scratches.
  • component D in one or more embodiments, is a halogen atom-free oxidant.
  • the component D may be used alone or in combination of two or more.
  • the component D from the viewpoint of ensuring a polishing rate and reducing scratches, for example, peroxide, permanganic acid or a salt thereof, chromic acid or a salt thereof, peroxo acid or a salt thereof, oxygen acid or a salt thereof, a metal salt, Examples include nitric acid and sulfuric acid.
  • At least one selected from hydrogen peroxide, iron nitrate (III), peracetic acid, ammonium peroxodisulfate, iron sulfate (III) and ammonium iron sulfate (III) is preferable, and from the viewpoint of improving the polishing rate, the substrate to be polished Hydrogen peroxide is more preferable from the viewpoint that metal ions do not adhere to the surface of and the viewpoint of availability.
  • the content of the component D in the polishing liquid composition of the present disclosure is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass from the viewpoint of securing a polishing rate and reducing scratches.
  • the above is more preferable, 4% by mass or less is preferable, 2% by mass or less is more preferable, and 1.5% by mass or less is further preferable.
  • the content of the component D is preferably 0.01% by mass or more and 4% by mass or less, more preferably 0.05% by mass or more and 2% by mass or less, and 0.1% by mass or more and 1.5% by mass. % Or less is more preferable.
  • the content of the component D means the total content thereof.
  • the polishing composition of the present disclosure may further contain a heterocyclic aromatic compound (including a salt thereof) (component E).
  • the component E may be one type or two or more types.
  • the component E is preferably a heterocyclic aromatic compound containing 2 or more nitrogen atoms in the heterocycle, more preferably 3 or more nitrogen atoms in the heterocycle.
  • the number is preferably 9 or more and 9 or less, more preferably 3 or more and 5 or less, still more preferably 3 or 4.
  • component E examples include 1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino-1,2,4-triazole, 3-mercapto-1,2,4- Triazole, 1H-tetrazole, 5-aminotetrazole, 1H-benzotriazole (BTA), 1H-tolyltriazole, 2-aminobenzotriazole, 3-aminobenzotriazole, and alkyl-substituted or amine-substituted compounds thereof are preferable.
  • the alkyl group in the alkyl-substituted product include a lower alkyl group having 1 to 4 carbon atoms, and more specifically, a methyl group and an ethyl group.
  • examples of the amine-substituted product include 1- [N, N-bis (hydroxyethylene) aminomethyl] benzotriazole and 1- [N, N-bis (hydroxyethylene) aminomethyl] tolyltriazole.
  • the content of the component E in the polishing liquid composition of the present disclosure is preferably 0.005 mass% or more, more preferably 0.01 mass% or more, and further preferably 0.02 mass% or more, from the viewpoint of scratch reduction. , And 10% by mass or less is preferable, 5% by mass or less is more preferable, and 1% by mass or less is further preferable. More specifically, the content of the component E is preferably 0.005 mass% or more and 10 mass% or less, more preferably 0.01 mass% or more and 5 mass% or less, and 0.02 mass% or more and 1 mass% or less. Is more preferable. When the component E is composed of two or more kinds of heterocyclic aromatic compounds, the content of the component E means the total content thereof.
  • the polishing composition of the present disclosure may further contain an aliphatic amine compound or an alicyclic amine compound (component F) from the viewpoint of scratch reduction. From the viewpoint of reducing scratches, the number of nitrogen atoms in the molecule of component F or the total number of amino groups or imino groups is preferably 2 or more and 4 or less. As the component F, one type may be used alone, or two or more types may be used in combination.
  • Examples of the aliphatic amine compound include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane and 1,4-diaminobutane from the viewpoint of scratch reduction.
  • N-aminoethylethanolamine N-amino
  • N-amino At least one selected from ethylisopropanolamine and N-aminoethyl-N-methylethanolamine is preferable, and from N-aminoethylethanolamine, N-aminoethylisopropanolamine, and N-aminoethyl-N-methylethanolamine At least one selected is more preferable, and N-aminoethylethanolamine (AEA) is further preferable.
  • AEA N-aminoethylethanolamine
  • Examples of the alicyclic amine compound include piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 1-amino-4-methylpiperazine, N-methylpiperazine, and hydroxyethylpiperazine (HEP) from the viewpoint of reducing scratches. At least one selected from the group is preferable, and hydroxyethylpiperazine (HEP) is more preferable.
  • the content of the component F in the polishing liquid composition of the present disclosure is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and preferably 10% by mass or less, It is more preferably 5% by mass or less, still more preferably 1% by mass or less. More specifically, the content of the component F is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 5% by mass or less, and 0.02% by mass or more and 1% by mass or less. Is more preferable.
  • the content of the component F means the total content thereof.
  • the polishing composition of the present disclosure may further contain other components, if necessary.
  • other components include water-soluble polymers other than the component B, thickeners, dispersants, rust preventives, basic substances, surfactants, solubilizers, and the like.
  • the content of the other component in the polishing composition of the present disclosure is preferably 0% by mass or more, more preferably more than 0% by mass, further preferably 0.1% by mass or more, and 10% by mass or less. It is preferably 5% by mass or less. More specifically, the content of the other components is preferably 0% by mass or more and 10% by mass or less, more preferably more than 0% by mass and 10% by mass or less, still more preferably 0.1% by mass or more and 5% by mass or less. ..
  • the pH of the polishing composition of the present disclosure is preferably 6 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, and from the same viewpoint, from the viewpoint of securing a polishing rate and reducing scratches. Therefore, 0.5 or more is preferable, 0.8 or more is more preferable, and 1 or more is further preferable. More specifically, the pH of the polishing composition of the present disclosure is preferably 0.5 or more and 6 or less, more preferably 0.8 or more and 5 or less, still more preferably 1 or more and 4 or less.
  • the pH can be adjusted using the above-mentioned acid (component C), a known pH adjuster, or the like.
  • the above pH is the pH of the polishing composition at 25 ° C. and can be measured using a pH meter. For example, the value after 2 minutes from immersing the electrode of the pH meter in the polishing composition is used. be able to.
  • the polishing composition of the present disclosure can be produced, for example, by blending Component A, Component B, Component C, and an aqueous medium, and if desired, Components DF and other components by a known method. That is, the present disclosure relates to, in another aspect, a method for producing a polishing composition, which includes a step of blending at least Component A, Component B, Component C, and an aqueous medium.
  • “compounding” includes mixing Component A, Component B, Component C and an aqueous medium, and optionally Components DG and other components simultaneously or in any order.
  • the abrasive of the component A may be mixed in the form of a concentrated slurry, or may be diluted with water or the like and then mixed.
  • the component A is composed of plural kinds of abrasives, the plural kinds of abrasives can be blended simultaneously or separately.
  • the component B comprises a plurality of types of cationic polymers, a plurality of types of cationic polymers can be blended simultaneously or separately.
  • the component C is composed of a plurality of types of acids, the plurality of types of acids can be blended simultaneously or separately.
  • the blending can be performed using a mixer such as a homomixer, a homogenizer, an ultrasonic disperser, and a wet ball mill.
  • the preferable blending amount of each component in the method for producing a polishing liquid composition can be the same as the preferable content of each component in the above-described polishing liquid composition of the present disclosure.
  • the “content of each component in the polishing composition” means the content of each component at the time of use, that is, when the use of the polishing composition for polishing is started.
  • the polishing composition of the present disclosure may be stored and supplied in a concentrated state as long as the storage stability is not impaired. In this case, manufacturing and transportation costs can be further reduced, which is preferable.
  • the concentrate of the polishing liquid composition of the present disclosure may be appropriately diluted with the above-mentioned aqueous medium before use.
  • the dilution ratio is not particularly limited as long as the content (when used) of each component described above can be secured after dilution, and can be set to, for example, 10 to 100 times.
  • the present disclosure relates to a kit for producing the polishing liquid composition of the present disclosure (hereinafter, also referred to as “polishing liquid kit of the present disclosure”).
  • polishing liquid kit of the present disclosure for example, polishing containing a polishing agent dispersion liquid containing the component A and an aqueous medium and an additive aqueous solution containing the component B and the component C without being mixed with each other
  • a liquid kit two-component polishing liquid composition
  • the abrasive dispersion and the additive aqueous solution are mixed at the time of use and, if necessary, diluted with an aqueous medium.
  • the aqueous medium contained in the abrasive dispersion may be the whole amount of water used for preparing the polishing composition or a part thereof.
  • the additive aqueous solution may contain a part of the aqueous medium used for preparing the polishing composition.
  • the above-mentioned optional components may be contained in the abrasive dispersion and the additive aqueous solution, respectively, if necessary. According to the polishing liquid kit of the present disclosure, it is possible to obtain a polishing liquid composition capable of reducing scratches on the surface of a substrate after polishing while ensuring a polishing rate.
  • the substrate to be polished is a substrate used for manufacturing a magnetic disk substrate in one or more embodiments.
  • the step of forming a magnetic layer on the surface of the substrate by sputtering or the like is performed to form a magnetic disk substrate. Can be manufactured.
  • Examples of the material of the substrate to be preferably used in the present disclosure include silicon, aluminum, nickel, tungsten, copper, tantalum, metals such as titanium and semimetals, or alloys thereof, glass, glassy carbon, amorphous. Examples thereof include glassy substances such as carbon, ceramic materials such as alumina, silicon dioxide, silicon nitride, tantalum nitride, and titanium carbide, and resins such as polyimide resin. Among them, it is suitable for a substrate to be polished containing a metal such as aluminum, nickel, tungsten, or copper and an alloy containing these metals as a main component.
  • Ni—P plated aluminum alloy substrate or a glass substrate such as crystallized glass, tempered glass, aluminosilicate glass or aluminoborosilicate glass is more suitable, and the Ni—P plated substrate is more suitable.
  • Aluminum alloy substrates are even more suitable.
  • the “Ni—P-plated aluminum alloy substrate” refers to an aluminum alloy substrate that has been subjected to electroless Ni—P plating after grinding the surface thereof.
  • the shape of the substrate to be polished includes, for example, a shape having a flat portion such as a disk shape, a plate shape, a slab shape, a prism shape, or a shape having a curved surface portion such as a lens.
  • a disk-shaped substrate to be polished is suitable.
  • its outer diameter is, for example, about 2 to 95 mm
  • its thickness is, for example, about 0.4 to 2 mm.
  • a magnetic disk is manufactured by polishing a substrate to be polished after a grinding step through a rough polishing step and a finish polishing step, and turning it into a magnetic disk in a recording section forming step.
  • the polishing composition of the present disclosure can be used in a polishing step of polishing a substrate to be polished, preferably a final polishing step in a method for producing a magnetic disk substrate. That is, the present disclosure includes, in another aspect, a step of polishing a substrate to be polished using the polishing liquid composition of the present disclosure (hereinafter, also referred to as “polishing step using the polishing liquid composition of the present disclosure”).
  • a method of manufacturing a magnetic disk substrate (hereinafter, also referred to as a “substrate manufacturing method of the present disclosure”).
  • the substrate manufacturing method of the present disclosure is particularly suitable for manufacturing a magnetic disk substrate for a perpendicular magnetic recording system.
  • the polishing step using the polishing composition of the present disclosure is, in one or more embodiments, supplying the polishing composition of the present disclosure to a surface to be polished of a substrate to be polished, and bringing a polishing pad into contact with the surface to be polished. And moving at least one of the polishing pad and the substrate to be polished for polishing.
  • the substrate to be polished is fixed on a surface plate to which a polishing pad such as a non-woven organic polymer polishing cloth is attached. It is a step of sandwiching and polishing the substrate to be polished by moving the platen or the substrate to be polished while supplying the polishing composition of the present disclosure to the polishing machine.
  • the polishing process using the polishing composition of the present disclosure is preferably performed after the second stage, and is performed in the final polishing process or the final polishing process. Is more preferable. At that time, in order to avoid mixing of the polishing material and the polishing liquid composition in the previous step, different polishing machines may be used, respectively. It is preferable to wash the substrate. Further, the polishing liquid composition of the present disclosure can be used in circulation polishing in which the used polishing liquid is reused.
  • the polishing machine is not particularly limited, and a known polishing machine for polishing a substrate can be used.
  • the polishing pad used in the present disclosure is not particularly limited, and for example, a suede type, a non-woven fabric type, a polyurethane independent foam type, or a two-layer type polishing pad in which these are laminated can be used. From the viewpoint of, a suede type polishing pad is preferable.
  • the polishing load in the polishing step using the polishing composition of the present disclosure is preferably 5.9 kPa or more, more preferably 6.9 kPa or more, still more preferably 7.5 kPa or more, from the viewpoint of ensuring the polishing rate. From the viewpoint of reducing scratches, it is preferably 20 kPa or less, more preferably 18 kPa or less, still more preferably 16 kPa or less. More specifically, the polishing load is preferably 5.9 to 20 kPa, more preferably 6.9 to 18 kPa, and further preferably 7.5 to 16 kPa.
  • the polishing load refers to the pressure of the surface plate applied to the polishing surface of the substrate to be polished during polishing. The polishing load can be adjusted by applying air pressure or weight to at least one of the surface plate and the substrate to be polished.
  • the supply rate of the polishing liquid composition of the present disclosure in the polishing step using the polishing liquid composition of the present disclosure is preferably 0.05 mL / min or more and 15 mL / min or less per 1 cm 2 of the substrate to be polished from the viewpoint of scratch reduction. It is more preferably 0.06 mL / min or more and 10 mL / min or less, still more preferably 0.07 mL / min or more and 1 mL / min or less, still more preferably 0.07 mL / min or more and 0.5 mL / min or less.
  • a method of supplying the polishing composition of the present disclosure to a polishing machine for example, a method of continuously supplying using a pump or the like can be mentioned.
  • supplying the polishing liquid composition to the polishing machine in addition to a method of supplying it as a single liquid containing all components, in consideration of the stability of the polishing liquid composition, etc., it is divided into a plurality of component liquids for blending, It is also possible to supply two or more liquids. In the latter case, for example, in the supply pipe or on the substrate to be polished, the plurality of component liquids for compounding are mixed to obtain the polishing liquid composition of the present disclosure.
  • the substrate manufacturing method of the present disclosure by using the polishing composition of the present disclosure, scratches on the substrate surface after polishing are reduced, and a high-quality magnetic disk substrate is manufactured with high yield and high productivity. The effect that it is possible can be exhibited.
  • the present disclosure relates to a method for polishing a substrate (hereinafter, also referred to as “polishing method of the present disclosure”) including polishing a substrate to be polished using the polishing composition of the present disclosure.
  • polishing method of the present disclosure it is possible to produce an effect that a high-quality magnetic disk substrate in which scratches on the substrate surface after polishing are reduced can be manufactured with high yield and high productivity.
  • the substrate to be polished in the polishing method of the present disclosure include those used for manufacturing a magnetic disk substrate as described above, and among them, a substrate used for manufacturing a magnetic disk substrate for a perpendicular magnetic recording system is preferable.
  • the specific polishing method and conditions may be the same as the substrate manufacturing method of the present disclosure described above.
  • Polishing a substrate to be polished using the polishing liquid composition of the present disclosure includes, in one or more embodiments, supplying the polishing liquid composition of the present disclosure to a polishing target surface of a substrate to be polished, The polishing pad is brought into contact with the substrate, and at least one of the polishing pad and the substrate to be polished is moved to perform polishing, or a surface plate to which a polishing pad such as a non-woven organic polymer polishing cloth is attached is used. That is, the polishing substrate is sandwiched, and while the polishing liquid composition of the present disclosure is supplied to the polishing machine, the platen or the substrate to be polished is moved to polish the substrate to be polished.
  • Water-soluble polymer The following were used as the water-soluble polymers B1 to B10 shown in Table 1.
  • B1 poly-p-vinylphenol / poly [N, N-dimethyl-1- (4-vinylphenoxy) methanamine] (molar ratio 45/55) [trade name: MAM3ME, manufactured by Maruzen Petrochemical Co., Ltd., weight average molecular weight 5] , 000] (X in formula I: dimethylaminomethyl group)
  • B2 poly-p-vinylphenol / poly [N, N-dimethyl-1- (4-vinylphenoxy) methanamine] (molar ratio 30/70) (synthetic product) [Maruzen Petrochemical Co., Ltd., weight average molecular weight 5, 000] (X in formula I: dimethylaminomethyl group)
  • B3 Polyallylamine [trade name: PAA-05, manufactured by Nitto Bo Medical, weight average molecular weight 5,000]
  • B4 Poly N-methyldiallylamine hydrochloride
  • polishing liquid compositions Polishing liquid compositions of Examples 1 to 10 and Comparative Examples 1 to 7)
  • Component A colloidal silica
  • component B or non-component B water-soluble polymers B1 to B10 shown in Table 1
  • component C phosphoric acid
  • component D hydrogen peroxide
  • ion-exchanged water ion-exchanged water
  • the content (effective amount) of each component in each polishing composition is shown in Table 2.
  • the content of ion-exchanged water is the balance excluding the component A, the component B or the non-component B, the component C, and the component D.
  • polishing liquid compositions of Examples 11 to 12 Component A (colloidal silica), component B (water-soluble polymer B1 shown in Table 1), component C (phosphoric acid), component D (hydrogen peroxide), and other additives (component E: BTA or component F) : HEP) and ion-exchanged water were mixed and stirred to prepare polishing liquid compositions of Examples 11 to 12 shown in Table 2.
  • the content (effective amount) of each component in each polishing composition is as shown in Table 2 for components A to D, and 0.02 mass% for component E or component F.
  • the content of ion-exchanged water is the balance excluding component A, component B, component C, component D, and other additives (component E or component F).
  • each polishing composition the following components were used as Component C to Component F.
  • Phosphoric acid manufactured by Wako Pure Chemical Industries, special grade
  • Component C Hydrogen peroxide water [concentration 35% by mass, manufactured by ADEKA]
  • Component D BTA [1,2,3-benzotriazole, manufactured by Tokyo Chemical Industry Co., Ltd.]
  • Component E HEP [N-hydroxyethylpiperazine, manufactured by Wako Pure Chemical Industries, Ltd.]
  • Component F Phosphoric acid [manufactured by Wako Pure Chemical Industries, special grade]
  • Component C Hydrogen peroxide water [concentration 35% by mass, manufactured by ADEKA]
  • Component D BTA [1,2,3-benzotriazole, manufactured by Tokyo Chemical Industry Co., Ltd.]
  • Component E HEP [N-hydroxyethylpiperazine, manufactured by Wako Pure Chemical Industries, Ltd.]
  • polishing Method Using the polishing liquid compositions of Examples 1 to 12 and Comparative Examples 1 to 7 prepared as described above, the following substrates to be polished were polished under the polishing conditions shown below. Then, the polishing rate and the number of scratches were measured. The results are shown in Table 2.
  • substrate to be polished As the substrate to be polished, a substrate obtained by roughly polishing an Ni—P plated aluminum alloy substrate with a polishing composition containing an alumina polishing material in advance was used.
  • the substrate to be polished had a thickness of 1.27 mm, an outer diameter of 95 mm and an inner diameter of 25 mm, and had a center line average roughness Ra of 1 nm measured by an AFM (Digital Instrument NanoScope IIIa Multi Mode AFM).
  • Polishing tester "Double-sided 9B polisher” manufactured by Speedfam Polishing pad: Suede type manufactured by Fuji Bow (foam layer: polyurethane elastomer, thickness 0.9 mm, average opening diameter 10 ⁇ m)
  • Polishing liquid composition supply rate 100 mL / min (supply rate per 1 cm 2 of the substrate to be polished: 0.076 mL / min)
  • Lower surface plate rotation speed 32.5 rpm
  • Polishing load 13.0kPa Polishing time: 6 minutes Number of substrates: 10
  • the polishing liquid compositions of Examples 1 to 12 effectively reduced scratches while securing a polishing rate, as compared with the polishing liquid compositions of Comparative Examples 1 to 7.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Manufacturing Of Magnetic Record Carriers (AREA)

Abstract

In one embodiment, there is provided a polishing liquid composition capable of reducing scratching of a substrate surface after polishing while ensuring polishing speed.　The present disclosure, in one embodiment, pertains to a polishing liquid composition containing an abrasive (component A), a water-soluble polymer (component B), an acid (component C), and an aqueous medium, component B being a cationic polymer that has a phenyl ether skeleton in the main chain or a side chain.

Description

研磨液組成物Polishing liquid composition
　本開示は、研磨液組成物、並びにこれを用いた基板の製造方法及び研磨方法に関する。 The present disclosure relates to a polishing composition, a substrate manufacturing method using the same, and a polishing method.
　近年、磁気ディスクドライブは小型化・大容量化が進み、高記録密度化が求められている。高記録密度化するために、単位記録面積を縮小し、弱くなった磁気信号の検出感度を向上するため、磁気ヘッドの浮上高さをより低くするための技術開発が進められている。磁気ディスク基板には、磁気ヘッドの低浮上化と記録面積の確保に対応するため、表面粗さ、うねり、端面ダレ（ロールオフ）の低減に代表される平滑性・平坦性の向上とスクラッチ、突起、ピット等の低減に代表される欠陥低減に対する要求が厳しくなっている。 In recent years, magnetic disk drives have become smaller and larger in capacity, and higher recording density is required. In order to increase the recording density, a unit recording area is reduced, and in order to improve the detection sensitivity of a weakened magnetic signal, technological development is underway to further reduce the flying height of the magnetic head. In order to reduce the flying height of the magnetic head and to secure a recording area, the magnetic disk substrate has improved smoothness and flatness represented by reduction of surface roughness, waviness, and edge sag (roll-off), and scratches. The demand for defect reduction represented by the reduction of protrusions and pits is becoming stricter.
　このような要求に対して、例えば、特公平１０－１０２０４１号公報（特許文献１）には、研磨材、主鎖又は側鎖にフェノール骨格を有する水溶性高分子、及び水を含有する研磨液組成物が開示されている（同文献の実施例、表３）。
　特表２００６－５２０５３０号公報（特許文献２）には、（ａ）無機研磨材、（ｂ）アリールアミン、アミノアルコール、脂肪族アミン、複素環式アミン、ヒドロキサム酸、アミノカルボン酸、環状モノカルボン酸、不飽和モノカルボン酸、置換フェノール、スルホンアミド、チオール、これらの塩及びそれらの組み合わせからなる群より選択され、かつｐＫａ約３～９の官能基を有する研磨添加剤、及び（ｃ）液体キャリアを含む研磨液組成物が開示されている。
　特開２００７－１４２４６４号公報（特許文献３）には、酸化剤、酸化金属溶解剤、第１保護膜形成剤、第２保護膜形成剤及び水を含む金属用研磨液が開示されており、第２保護膜形成剤の好ましい例として、ポリアクリル酸、ポリアクリルアミド等が記載されている（同文献の段落［００３６］、実施例）。
　特開２０１４－２０７２８１号公報（特許文献４）には、液状媒体と、４価金属元素の水酸化物を含む砥粒と、ポリオキシアルキレン化合物と、陽イオン性ポリマーとを含有し、ポリオキシアルキレン化合物の平均ＨＩ.Ｂ値が１７．０以下である研磨液が開示されている。 In order to meet such demands, for example, Japanese Patent Publication No. 10-102041 (Patent Document 1) discloses an abrasive, a water-soluble polymer having a phenol skeleton in a main chain or a side chain, and a polishing liquid containing water. Compositions are disclosed (Examples in that document, Table 3).
In JP-A 2006-520530 (Patent Document 2), (a) an inorganic abrasive, (b) an arylamine, an amino alcohol, an aliphatic amine, a heterocyclic amine, a hydroxamic acid, an aminocarboxylic acid, a cyclic monocarboxylic acid. A polishing additive selected from the group consisting of acids, unsaturated monocarboxylic acids, substituted phenols, sulfonamides, thiols, salts thereof and combinations thereof, and having a functional group of pKa of about 3-9, and (c) a liquid. A polishing composition containing a carrier is disclosed.
Japanese Patent Laid-Open No. 2007-142464 (Patent Document 3) discloses a metal polishing liquid containing an oxidizing agent, a metal oxide dissolving agent, a first protective film forming agent, a second protective film forming agent, and water. Polyacrylic acid, polyacrylamide and the like are described as preferable examples of the second protective film forming agent (paragraph [0036] of the same document, Examples).
Japanese Unexamined Patent Publication No. 2014-207281 (Patent Document 4) contains a liquid medium, abrasive grains containing a hydroxide of a tetravalent metal element, a polyoxyalkylene compound, and a cationic polymer. A polishing liquid in which the average HI.B value of the alkylene compound is 17.0 or less is disclosed.
　本開示は、一態様において、研磨材（成分Ａ）、水溶性高分子（成分Ｂ）、酸（成分Ｃ）及び水系媒体を含有し、前記成分Ｂが、主鎖又は側鎖にフェニルエーテル骨格を有する陽イオン性高分子である、研磨液組成物に関する。 In one aspect, the present disclosure contains an abrasive (component A), a water-soluble polymer (component B), an acid (component C) and an aqueous medium, wherein the component B has a phenyl ether skeleton in a main chain or a side chain. The present invention relates to a polishing liquid composition which is a cationic polymer having
　本開示は、その他の態様において、本開示の研磨液組成物を用いて被研磨基板を研磨する工程を含む、磁気ディスク基板の製造方法に関する。 In another aspect, the present disclosure relates to a method for manufacturing a magnetic disk substrate, including a step of polishing a substrate to be polished with the polishing composition of the present disclosure.
　本開示は、その他の態様において、本開示の研磨液組成物を用いて被研磨基板を研磨することを含み、前記被研磨基板は、磁気ディスク基板の製造に用いられる基板である、基板の研磨方法に関する。 The present disclosure includes, in another aspect, polishing a substrate to be polished with the polishing composition of the present disclosure, wherein the substrate to be polished is a substrate used for manufacturing a magnetic disk substrate. Regarding the method.
　磁気ディスクドライブの大容量化に伴い、基板の表面品質に対する要求特性はさらに厳しくなっており、基板表面のスクラッチをいっそう低減できる研磨液組成物の開発が求められている。また、一般的に、研磨速度とスクラッチとはトレードオフの関係にあり、一方が改善すれば一方が悪化するという問題がある。
　そこで、本開示は、研磨速度を確保しつつ、研磨後の基板表面のスクラッチを低減できる研磨液組成物、並びにこれを用いた磁気ディスク基板の製造方法及び基板の研磨方法を提供する。 With the increase in capacity of magnetic disk drives, the required characteristics for the surface quality of the substrate have become more severe, and development of a polishing composition capable of further reducing scratches on the substrate surface has been required. Further, generally, there is a trade-off relationship between the polishing rate and scratch, and there is a problem that if one is improved, the other is deteriorated.
Therefore, the present disclosure provides a polishing composition capable of reducing scratches on the surface of a substrate after polishing while ensuring a polishing rate, and a method of manufacturing a magnetic disk substrate and a method of polishing a substrate using the same.
　本開示は、所定の陽イオン性高分子を含有する研磨液組成物を使用すれば、研磨速度を確保しつつ、研磨後の基板表面のスクラッチを低減できるという知見に基づく。 The present disclosure is based on the finding that by using a polishing composition containing a predetermined cationic polymer, scratches on the substrate surface after polishing can be reduced while ensuring a polishing rate.
　すなわち、本開示は、一態様において、研磨材（成分Ａ）、水溶性高分子（成分Ｂ）、酸（成分Ｃ）及び水系媒体を含有する研磨液組成物であって、前記成分Ｂが、主鎖又は側鎖にフェニルエーテル骨格を有する陽イオン性高分子である、研磨液組成物（以下、「本開示の研磨液組成物」ともいう）に関する。 That is, the present disclosure is, in one aspect, a polishing liquid composition containing an abrasive (component A), a water-soluble polymer (component B), an acid (component C) and an aqueous medium, wherein the component B comprises: The present invention relates to a polishing liquid composition (hereinafter, also referred to as “polishing liquid composition of the present disclosure”) which is a cationic polymer having a phenyl ether skeleton in the main chain or side chain.
　本開示の研磨組成物によれば、一又は複数の実施形態において、研磨速度を確保しつつ、研磨後の基板表面のスクラッチを低減できるという効果が奏されうる。 According to the polishing composition of the present disclosure, in one or a plurality of embodiments, it is possible to obtain an effect that scratches on a substrate surface after polishing can be reduced while securing a polishing rate.
　本開示の効果発現のメカニズムの詳細は明らかではないが、以下のように推察される。
　一般的に、陽イオン性高分子とシリカ砥粒等の研磨材との併用は行われていない。なぜなら、通常、陽イオン性高分子の正電荷とシリカ砥粒等の研磨材の負電荷との静電吸着により、陽イオン性高分子と研磨材とが架橋して凝集しやすいからである。
　ところが、本開示の特定の陽イオン性高分子（成分Ｂ）は、分子運動性が低く、特殊な立体構造を取ることで研磨材との架橋による凝集を抑制できると考えられる。
　そして、研磨時には、成分Ｂの疎水性の部分（フェニルエーテル骨格）が研磨パッドに吸着して研磨パッドが正に帯電化し、負に帯電している研磨材を引きつけ、研磨速度の向上に寄与すると考えられる。
　すなわち、成分Ｂは、研磨に使用する前の研磨液組成物中の研磨材の凝集を抑制し、研磨液組成物を研磨に使用中は、研磨材の研磨パッドへの吸着を促進させる機構を有すると考えられる。
　さらに、成分Ｂの芳香環が研磨パッドを軟質化させ、スクラッチ低減にも寄与すると考えられる。
　但し、本開示はこれらのメカニズムに限定して解釈されなくてもよい。 Although the details of the mechanism of the effect expression of the present disclosure are not clear, it is presumed as follows.
Generally, a cationic polymer and an abrasive such as silica abrasive are not used in combination. This is because normally, the electrostatic adsorption between the positive charge of the cationic polymer and the negative charge of the abrasive such as silica abrasive grains causes the cationic polymer and the abrasive to easily crosslink and aggregate.
However, it is considered that the specific cationic polymer (component B) of the present disclosure has low molecular mobility, and that it has a special three-dimensional structure and can suppress aggregation due to crosslinking with the abrasive.
At the time of polishing, the hydrophobic portion (phenyl ether skeleton) of the component B is adsorbed to the polishing pad and the polishing pad is positively charged, attracts the negatively charged abrasive, and contributes to the improvement of the polishing rate. Conceivable.
That is, the component B has a mechanism that suppresses the aggregation of the abrasive in the polishing composition before it is used for polishing and promotes the adsorption of the polishing agent to the polishing pad while the polishing composition is used for polishing. Considered to have.
Furthermore, it is considered that the aromatic ring of the component B softens the polishing pad and contributes to the reduction of scratches.
However, the present disclosure need not be limited to these mechanisms.
　本開示において、基板表面のスクラッチは、例えば、光学式欠陥検査装置により検出可能であり、スクラッチ数として定量評価できる。スクラッチ数は、具体的には実施例に記載した方法で評価できる。 In the present disclosure, scratches on the substrate surface can be detected by, for example, an optical defect inspection device, and can be quantitatively evaluated as the number of scratches. The number of scratches can be evaluated specifically by the method described in the examples.
［研磨材（成分Ａ）］
　本開示の研磨液組成物に含まれる研磨材（以下、「成分Ａ」ともいう）としては、研磨用に一般的に使用されている研磨材を使用することができ、金属、金属若しくは半金属の炭化物、窒化物、酸化物、又はホウ化物、ダイヤモンド等が挙げられる。金属又は半金属元素は、周期律表（長周期型）の２Ａ、２Ｂ、３Ａ、３Ｂ、４Ａ、４Ｂ、５Ａ、６Ａ、７Ａ又は８族由来のものである。成分Ａの具体例としては、酸化珪素（以下、シリカという）、酸化アルミニウム（以下、アルミナという）、炭化珪素、ダイヤモンド、酸化マンガン、酸化マグネシウム、酸化亜鉛、酸化チタン、酸化セリウム（以下、セリアという）、酸化ジルコニウム等が挙げられ、これらの１種以上を使用することは研磨速度を向上させる観点から好ましい。中でも、研磨速度の確保及びスクラッチ低減の観点から、成分Ａとしては、シリカ粒子が好ましい。シリカ粒子としては、コロイダルシリカ、ヒュームドシリカ、粉砕シリカ、それらを表面修飾したシリカ等が挙げられ、コロイダルシリカが好ましい。成分Ａは、１種単独で用いてもよいし、２種以上を併用してもよい。 [Abrasive (Component A)]
As the abrasive contained in the polishing composition of the present disclosure (hereinafter, also referred to as “component A”), an abrasive generally used for polishing can be used. Metal, metal or semimetal Carbides, nitrides, oxides, borides, diamonds, etc. The metal or metalloid element is derived from Group 2A, 2B, 3A, 3B, 4A, 4B, 5A, 6A, 7A or 8 of the periodic table (long period type). Specific examples of the component A include silicon oxide (hereinafter referred to as silica), aluminum oxide (hereinafter referred to as alumina), silicon carbide, diamond, manganese oxide, magnesium oxide, zinc oxide, titanium oxide, cerium oxide (hereinafter referred to as ceria). ), Zirconium oxide, etc., and it is preferable to use at least one of these from the viewpoint of improving the polishing rate. Above all, silica particles are preferable as the component A from the viewpoint of ensuring a polishing rate and reducing scratches. Examples of the silica particles include colloidal silica, fumed silica, pulverized silica, and silica obtained by surface-modifying them, and colloidal silica is preferable. As the component A, one type may be used alone, or two or more types may be used in combination.
　成分Ａの平均粒径は、研磨速度の確保及びスクラッチ低減の観点から、１ｎｍ以上が好ましく、５ｎｍ以上がより好ましく、１０ｎｍ以上が更に好ましく、そして、同様の観点から、１００ｎｍ以下が好ましく、７０ｎｍ以下がより好ましく、４０ｎｍ以下が更に好ましい。より具体的には、成分Ａの平均粒径は、１ｎｍ以上１００ｎｍ以下が好ましく、５ｎｍ以上７０ｎｍ以下がより好ましく、１０ｎｍ以上４０ｎｍ以下が更に好ましい。本開示において、「研磨材の平均粒径」とは、動的光散乱法において検出角９０°で測定される散乱強度分布に基づく平均粒径をいう。研磨材の平均粒径は、具体的には実施例に記載の方法により求めることができる。 The average particle size of the component A is preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, from the viewpoint of ensuring a polishing rate and reducing scratches, and from the same viewpoint, 100 nm or less is preferable and 70 nm or less. Is more preferable, and 40 nm or less is further preferable. More specifically, the average particle size of the component A is preferably 1 nm or more and 100 nm or less, more preferably 5 nm or more and 70 nm or less, and further preferably 10 nm or more and 40 nm or less. In the present disclosure, the “average particle size of the abrasive” refers to the average particle size based on the scattering intensity distribution measured at a detection angle of 90 ° in the dynamic light scattering method. The average particle diameter of the abrasive can be specifically obtained by the method described in the examples.
　本開示の研磨液組成物中における成分Ａの含有量は、研磨速度を向上させる観点から、０．１質量％以上が好ましく、１質量％以上がより好ましく、３質量％以上が更に好ましく、そして、スクラッチ低減の観点から、２０質量％以下が好ましく、１５質量％以下がより好ましく、１０質量％以下が更に好ましい。さらに、成分Ａの含有量は、研磨速度の確保及びスクラッチ低減の観点から、０．１質量％以上２０質量％以下が好ましく、１質量％以上１５質量％以下がより好ましく、３質量％以上１０質量％以下が更に好ましい。成分Ａが２種以上の研磨材の組合せである場合、成分Ａの含有量は、それらの合計含有量をいう。なお、成分Ａがシリカの場合、成分Ａの含有量はＳｉＯ2換算した値である。 The content of the component A in the polishing liquid composition of the present disclosure is preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 3% by mass or more, from the viewpoint of improving the polishing rate. From the viewpoint of reducing scratches, 20% by mass or less is preferable, 15% by mass or less is more preferable, and 10% by mass or less is further preferable. Furthermore, the content of the component A is preferably 0.1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and more preferably 3% by mass or more 10 from the viewpoint of securing a polishing rate and reducing scratches. It is more preferably not more than mass%. When the component A is a combination of two or more kinds of abrasives, the content of the component A means the total content thereof. When the component A is silica, the content of the component A is a value converted into SiO 2 .
［水溶性高分子（成分Ｂ）］
　本開示の研磨液組成物に用いられる水溶性高分子（以下、「成分Ｂ」ともいう）は、研磨速度の確保及びスクラッチ低減の観点から、主鎖又は側鎖にフェニルエーテル骨格を有する陽イオン性高分子である。成分Ｂは単独で又は２種以上を混合して用いてもよい。 [Water-soluble polymer (Component B)]
The water-soluble polymer (hereinafter, also referred to as “component B”) used in the polishing liquid composition of the present disclosure is a cation having a phenyl ether skeleton in its main chain or side chain from the viewpoint of ensuring a polishing rate and reducing scratches. Polymer. The component B may be used alone or in combination of two or more.
　本開示において、「水溶性」とは、２０℃のｐＨ３の水溶液１００ｇに対する溶解度が０．０１ｇ以上であることをいう。 In the present disclosure, “water-soluble” means that the solubility in 100 g of a pH 3 aqueous solution at 20 ° C. is 0.01 g or more.
　本開示において、陽イオン性高分子とは、繰り返し構成単位内に陽イオン性基を有するポリマーをいう。陽イオン性基とは、酸の存在下で陽イオンとなる官能基をいい、塩の形態も含むものとする。陽イオン性基としては、一又は複数の実施形態において、窒素原子を含む有機基が挙げられ、例えば、アミノ基、ニトロ基、イミノ基、アンモニウム基等を有する有機基が挙げられる。 In the present disclosure, the cationic polymer means a polymer having a cationic group in the repeating constitutional unit. The cationic group means a functional group which becomes a cation in the presence of an acid, and includes a salt form. Examples of the cationic group include organic groups containing a nitrogen atom in one or a plurality of embodiments, and examples thereof include organic groups having an amino group, a nitro group, an imino group, an ammonium group and the like.
　本開示において、フェニルエーテル骨格とは、ベンゼン環の少なくとも１つの水素原子が－Ｏ－Ｘに置換された構造を示す。Ｘは、一又は複数の実施形態において、陽イオン性基である。 In the present disclosure, the phenyl ether skeleton refers to a structure in which at least one hydrogen atom on the benzene ring is replaced with —O—X. X, in one or more embodiments, is a cationic group.
　本開示において、「主鎖」とは、成分Ｂの水溶性高分子において、モノマー単位が結合して形成される直鎖構造のうち最も長い部分をいい、「側鎖」とは、前記直鎖から枝分かれしている部分をいう。 In the present disclosure, the “main chain” refers to the longest part of the linear structure formed by combining the monomer units in the water-soluble polymer of component B, and the “side chain” refers to the above linear chain. The part that is branched from.
　成分Ｂとしては、一又は複数の実施形態において、研磨速度の確保及びスクラッチ低減の観点から、疎水性の構成単位と、陽イオン性基がエーテル結合したフェニルエーテル骨格を主鎖又は側鎖に有する構成単位と、を含む共重合体が好ましく、フェノールまたはフェニル骨格を主鎖又は側鎖に有する構成単位と、陽イオン性基がエーテル結合したフェニルエーテル骨格を主鎖又は側鎖に有する構成単位と、を含む共重合体がより好ましく、フェノール骨格を側鎖に有する構成単位と、陽イオン性基がエーテル結合したフェニルエーテル骨格を側鎖に有する構成単位と、を含む共重合体が更に好ましい。ここで、フェノール骨格とは、ベンゼン環の少なくとも１つの水素原子がヒドロキシ基で置換された構造を示す。 As the component B, in one or a plurality of embodiments, from the viewpoint of ensuring a polishing rate and reducing scratches, a hydrophobic constituent unit and a phenyl ether skeleton in which a cationic group is ether-bonded are contained in the main chain or side chain. A structural unit and a copolymer containing is preferable, a structural unit having a phenol or phenyl skeleton in the main chain or side chain, and a structural unit having a phenyl ether skeleton in which a cationic group is ether-bonded in the main chain or side chain. Is more preferable, and a copolymer containing a structural unit having a phenol skeleton in a side chain and a structural unit having a phenyl ether skeleton in which a cationic group is ether-bonded in a side chain is further preferable. Here, the phenol skeleton refers to a structure in which at least one hydrogen atom of the benzene ring is substituted with a hydroxy group.
　成分Ｂの一実施形態としては、例えば、下記式（Ｉ）で表される構成を有する化合物が挙げられる。 As one embodiment of the component B, for example, a compound having a structure represented by the following formula (I) can be mentioned.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　式（Ｉ）中、Ｘは、陽イオン性基を示す。Ｘは、研磨速度の確保及びスクラッチ低減の観点から、窒素原子を含む陽イオン性基が好ましく、窒素原子を含み、炭素数１以上２０以下の陽イオン性基がより好ましく、アミノ基、ニトロ基、イミノ基及びアンモニウム基から選ばれる少なくとも１種を含み、炭素数１以上２０以下の陽イオン性基が更に好ましい。陽イオン性基の炭素数は、研磨速度の確保及びスクラッチ低減の観点から、１以上２０以下が好ましく、２以上１５以下がより好ましく、３以上１２以下が更に好ましい。 In the formula (I), X represents a cationic group. From the viewpoint of ensuring a polishing rate and reducing scratches, X is preferably a cationic group containing a nitrogen atom, more preferably a cationic group containing a nitrogen atom and having 1 to 20 carbon atoms, and an amino group or a nitro group. Further, a cationic group containing at least one selected from an imino group and an ammonium group and having 1 to 20 carbon atoms is more preferable. The carbon number of the cationic group is preferably 1 or more and 20 or less, more preferably 2 or more and 15 or less, and further preferably 3 or more and 12 or less, from the viewpoint of ensuring a polishing rate and reducing scratches.
　式（Ｉ）中のＸとしては、例えば、－Ｒ6Ｎ（Ｒ7)（Ｒ8）、－Ｒ6Ｎ+（Ｒ7）（Ｒ8）（Ｒ9）・Ｙ-が挙げられる。Ｒ6は、研磨速度の確保及びスクラッチ低減の観点から、炭素数１以上５以下の直鎖又は分岐鎖のアルキレン基が好ましく、炭素数１以上５以下の直鎖アルキレン基がより好ましい。Ｒ7～Ｒ9はそれぞれ独立に、研磨速度の確保及びスクラッチ低減の観点から、水素原子または炭素数１以上５以下の直鎖又は分岐鎖の炭化水素基が好ましく、炭素数１以上５以下のアルキル基がより好ましく、メチル基及びエチル基の少なくとも一方が更に好ましく、メチル基がより更に好ましい。Ｙ-は、アニオンを示す。アニオンとしては、塩化物イオン、臭化物イオン、フッ化物イオン等のハロゲン化物イオン；硫酸イオン；リン酸イオン；硝酸イオン；等が挙げられる。 Examples of X in the formula (I) include —R 6 N (R 7 ) (R 8 ), —R 6 N + (R 7 ) (R 8 ) (R 9 ) · Y − . From the viewpoint of ensuring a polishing rate and reducing scratches, R 6 is preferably a linear or branched alkylene group having 1 to 5 carbon atoms, and more preferably a linear alkylene group having 1 to 5 carbon atoms. R 7 to R 9 are each independently preferably a hydrogen atom or a linear or branched hydrocarbon group having 1 to 5 carbon atoms, and 1 to 5 carbon atoms, from the viewpoint of ensuring the polishing rate and reducing scratches. An alkyl group is more preferable, at least one of a methyl group and an ethyl group is further preferable, and a methyl group is still more preferable. Y − represents an anion. Examples of the anion include halide ions such as chloride ion, bromide ion, and fluoride ion; sulfate ion; phosphate ion; nitrate ion; and the like.
　式（Ｉ）中、ｍ／ｎは、研磨速度の確保及びスクラッチ低減の観点から、２０/８０～８０/２０が好ましく、２５/７５～７０/３０がより好ましく、３５/６５～７０/３０が更に好ましく、３５/６５～５５/４５が更に好ましく、４０/６０～５０/５０が更に好ましい。 In the formula (I), m / n is preferably 20/80 to 80/20, more preferably 25/75 to 70/30, and still more preferably 35/65 to 70/30, from the viewpoint of securing a polishing rate and reducing scratches. Is more preferable, 35/65 to 55/45 is further preferable, and 40/60 to 50/50 is further preferable.
　成分Ｂを構成する全構成単位中に占める式（Ｉ）で表される構成の含有量は、一又は複数の実施形態において、研磨速度の確保及びスクラッチ低減の観点から、５０モル％以上が好ましく、８０モル％以上がより好ましく、９０モル％以上が更に好ましく、１００モル％が最も好ましい。 In one or a plurality of embodiments, the content of the constituent represented by the formula (I) in all constituent units constituting the component B is preferably 50 mol% or more from the viewpoint of ensuring a polishing rate and reducing scratches. , 80 mol% or more is more preferable, 90 mol% or more is further preferable, and 100 mol% is the most preferable.
　本開示において、成分Ｂを構成する全構成単位中に占めるある構成単位の含有量（モル％）として、合成条件によっては、成分Ｂの合成の全工程で反応槽に仕込まれた全構成単位を導入するための化合物中に占める前記反応槽に仕込まれた該構成単位を導入するための化合物量（モル％）を使用してもよい。また、本開示において、成分Ｂが２種以上の構成単位を含む場合、２つの構成単位の構成比（モル比）として、合成条件によっては、前記成分Ｂの合成の全工程で反応槽に仕込まれた該２つの構成単位を導入するための化合物量比（モル比）を使用してもよい。 In the present disclosure, as the content (mol%) of a certain structural unit in all the structural units constituting the component B, depending on the synthesis conditions, all the structural units charged in the reaction tank in all the steps of the synthesis of the component B may be included. You may use the compound amount (mol%) for introducing the said structural unit prepared in the said reaction tank which occupies in the compound for introducing. Further, in the present disclosure, when the component B contains two or more kinds of constituent units, the constituent ratio (molar ratio) of the two constituent units may be charged into the reaction tank at all steps of the synthesis of the constituent B depending on the synthesis conditions. A compound amount ratio (molar ratio) for introducing the two constituent units may be used.
　成分Ｂは、式（Ｉ）に含まれないその他の構成単位を有していてもよい。成分Ｂを構成する全構成単位中に占めるその他の構成単位の含有率は、研磨速度の確保及びスクラッチ低減の観点から、１０モル％以下が好ましく、５モル％以下がより好ましく、３モル％以下が更に好ましく、１モル％以下が更に好ましく、実質的に０モル％が更に好ましい。 Component B may have other structural units not included in the formula (I). From the viewpoint of ensuring the polishing rate and reducing scratches, the content of the other structural units in all the structural units constituting the component B is preferably 10 mol% or less, more preferably 5 mol% or less, and 3 mol% or less. Is more preferable, 1 mol% or less is further preferable, and substantially 0 mol% is further preferable.
　成分Ｂは、一実施形態において、ジアルキルアミンとホルムアルデヒドを用いるマンニッヒ反応により製造できる。成分Ｂは、その他の実施形態において、フェノール骨格を含むポリマーをアルキルアミンハロゲン化合物と高分子反応させることで製造できる。 Ingredient B can be produced, in one embodiment, by a Mannich reaction using a dialkylamine and formaldehyde. Ingredient B can be produced, in another embodiment, by polymerizing a polymer containing a phenol skeleton with an alkylamine halogen compound.
　成分Ｂを構成する各構成単位の配列は、ランダム、ブロック、又はグラフトのいずれでもよい。 The arrangement of each structural unit that constitutes the component B may be random, block, or graft.
　成分Ｂの重量平均分子量は、研磨速度の確保及びスクラッチ低減の観点から、５００以上が好ましく、１，０００以上がより好ましく、１，５００以上が更に好ましく、そして、同様の観点から、１，０００，０００以下が好ましく、７５０，０００以下がより好ましく、５００，０００以下が更に好ましい。より具体的には、成分Ｂの重量平均分子量は、５００以上１，０００，０００以下が好ましく、１，０００以上７５０，０００以下がより好ましく、１，５００以上５００，０００以下が更に好ましい。本開示において、重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いて実施例に記載の条件で測定した値とする。 The weight average molecular weight of the component B is preferably 500 or more, more preferably 1,000 or more, still more preferably 1,500 or more, from the viewpoint of ensuring a polishing rate and reducing scratches, and from the same viewpoint, 1,000. It is preferably 5,000 or less, more preferably 750,000 or less, still more preferably 500,000 or less. More specifically, the weight average molecular weight of the component B is preferably 500 or more and 1,000,000 or less, more preferably 1,000 or more and 750,000 or less, and further preferably 1,500 or more and 500,000 or less. In the present disclosure, the weight average molecular weight is a value measured by gel permeation chromatography (GPC) under the conditions described in the examples.
　本開示の研磨液組成物中の成分Ｂの含有量は、研磨速度の確保及びスクラッチ低減の観点から、０．０００００１質量％以上が好ましく、０．００００１質量％以上がより好ましく、０．０００１質量％以上が更に好ましく、０．０００５質量％以上が更に好ましく、０．００１５質量％以上が更に好ましく、そして、同様の観点から、０．０１質量％以下が好ましく、０．０１質量％未満がより好ましく、０．００９質量％以下が更に好ましく、０．００６質量％以下が更に好ましく、０．００４質量％以下が更に好ましく、０．００２５質量％以下が更に好ましい。より具体的には、成分Ｂの含有量は、０．０００００１質量％以上０．０１質量％以下が好ましく、０．００００１質量％以上０．０１質量％以下がより好ましく、０．０００１質量％以上０．００９質量％以下が更に好ましく、０．０００５質量％以上０．００６質量％以下が更に好ましく、０．００１５質量％以上０．００４質量％以下が更に好ましい。 The content of the component B in the polishing composition of the present disclosure is preferably 0.000001 mass% or more, more preferably 0.00001 mass% or more, and 0.0001 mass from the viewpoint of ensuring a polishing rate and reducing scratches. % Or more, more preferably 0.0005% by mass or more, further preferably 0.0015% by mass or more, and from the same viewpoint, 0.01% by mass or less is preferable, and less than 0.01% by mass is more preferable. The content is preferably 0.009 mass% or less, more preferably 0.006 mass% or less, further preferably 0.004 mass% or less, and further preferably 0.0025 mass% or less. More specifically, the content of the component B is preferably 0.000001% by mass or more and 0.01% by mass or less, more preferably 0.00001% by mass or more and 0.01% by mass or less, and 0.0001% by mass or more. 0.009 mass% or less is more preferable, 0.0005 mass% or more and 0.006 mass% or less is more preferable, and 0.0015 mass% or more and 0.004 mass% or less is further preferable.
　本開示の研磨液組成物中の成分Ａに対する成分Ｂの質量比（成分Ｂの含有量／成分Ａの含有量）は、研磨速度の確保及びスクラッチ低減の観点から、以上が好ましく、０．００００００２以上がより好ましく、０．０００００２以上が更に好ましく、０．０００１以上が更に好ましく、０．０００３以上が更に好ましく、そして、同様の観点から、０．０２以下が好ましく、０．０１以下がより好ましく、０．００５以下が更に好ましく、０．００３以下が更に好ましく、０．０００８以下が更に好ましい。より具体的には、成分Ａに対する成分Ｂの質量比は、０．００００００２以上０．０２以下が好ましく、０．０００００２以上０．０１以下がより好ましく、０．０００００２以上０．００５以下が更に好ましく、０．０００１以上０．００３以下が更に好ましく、０．０００３以上０．０００８以下が更に好ましい。 The mass ratio of the component B to the component A (content of the component B / content of the component A) in the polishing composition of the present disclosure is preferably 0.0000002 or more from the viewpoint of ensuring the polishing rate and reducing scratches. The above is more preferable, 0.000002 or more is more preferable, 0.0001 or more is further preferable, 0.0003 or more is further preferable, and from the same viewpoint, 0.02 or less is preferable, and 0.01 or less is more preferable. , 0.005 or less is more preferable, 0.003 or less is further preferable, and 0.0008 or less is further preferable. More specifically, the mass ratio of the component B to the component A is preferably 0.0000002 or more and 0.02 or less, more preferably 0.000002 or more and 0.01 or less, and further preferably 0.000002 or more and 0.005 or less. , 0.0001 or more and 0.003 or less are more preferable, and 0.0003 or more and 0.0008 or less are further preferable.
［酸（成分Ｃ）］
　本開示の研磨液組成物は、酸（成分Ｃ）を含有する。本開示において、酸の使用は、酸及び／又はその塩の使用を含む。成分Ｃは１種単独で用いてもよいし、２種以上を併用してもよい。 [Acid (Component C)]
The polishing composition of the present disclosure contains an acid (component C). In this disclosure, the use of acids includes the use of acids and / or their salts. As the component C, one type may be used alone, or two or more types may be used in combination.
　成分Ｃとしては、例えば、硝酸、硫酸、亜硫酸、過硫酸、塩酸、過塩素酸、リン酸、ホスホン酸、ホスフィン酸、ピロリン酸、トリポリリン酸、アミド硫酸等の無機酸；有機リン酸、有機ホスホン酸、カルボン酸等の有機酸；等が挙げられる。中でも、研磨速度の確保及びスクラッチ低減の観点から、無機酸及び有機ホスホン酸から選ばれる少なくとも１種が好ましい。無機酸としては、硝酸、硫酸、塩酸、過塩素酸及びリン酸から選ばれる少なくとも１種が好ましく、リン酸及び硫酸の少なくとも一方がより好ましい。有機ホスホン酸としては、１－ヒドロキシエチリデン－１，１－ジホスホン酸（ＨＥＤＰ）、アミノトリ（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）、ジエチレントリアミンペンタ（メチレンホスホン酸）から選ばれる少なくとも１種が好ましく、ＨＥＤＰがより好ましい。これらの酸の塩としては、例えば、上記の酸と、金属、アンモニア及びアルキルアミンから選ばれる少なくとも１種との塩が挙げられる。上記金属の具体例としては、周期表の１～１１族に属する金属が挙げられる。これらの中でも、研磨速度の確保及びスクラッチ低減の観点から、上記の酸と、１Ａ族に属する金属又はアンモニアとの塩が好ましい。 Examples of the component C include inorganic acids such as nitric acid, sulfuric acid, sulfurous acid, persulfuric acid, hydrochloric acid, perchloric acid, phosphoric acid, phosphonic acid, phosphinic acid, pyrophosphoric acid, tripolyphosphoric acid, and amido sulfuric acid; organic phosphoric acid, organic phosphonic acid. Organic acids such as acids and carboxylic acids; and the like. Among them, at least one selected from inorganic acids and organic phosphonic acids is preferable from the viewpoint of ensuring the polishing rate and reducing scratches. As the inorganic acid, at least one selected from nitric acid, sulfuric acid, hydrochloric acid, perchloric acid and phosphoric acid is preferable, and at least one of phosphoric acid and sulfuric acid is more preferable. The organic phosphonic acid is at least one selected from 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid), ethylenediaminetetra (methylenephosphonic acid), and diethylenetriaminepenta (methylenephosphonic acid). HEDP is preferable and HEDP is more preferable. Examples of salts of these acids include salts of the above-mentioned acids with at least one selected from metals, ammonia and alkylamines. Specific examples of the above metals include metals belonging to Groups 1 to 11 of the periodic table. Among these, from the viewpoint of ensuring the polishing rate and reducing scratches, a salt of the above-mentioned acid and a metal belonging to Group 1A or ammonia is preferable.
　本開示の研磨液組成物中の成分Ｃの含有量は、研磨速度の確保及びスクラッチ低減の観点から、０．０１質量％以上が好ましく、０．１質量％以上がより好ましく、０．４質量％以上が更に好ましく、そして、同様の観点から、５質量％以下が好ましく、３質量％以下がより好ましく、２質量％以下が更に好ましい。より具体的には、成分Ｃの含有量は、０．０１質量％以上５質量％以下が好ましく、０．１質量％以上３質量％以下がより好ましく、０．４質量％以上２質量％以下が更に好ましい。成分Ｃが２種以上の酸からなる場合、成分Ｃの含有量はそれらの合計含有量をいう。 The content of the component C in the polishing composition of the present disclosure is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and 0.4% by mass from the viewpoint of ensuring a polishing rate and reducing scratches. % Or more is more preferable, and from the same viewpoint, 5% by mass or less is preferable, 3% by mass or less is more preferable, and 2% by mass or less is further preferable. More specifically, the content of the component C is preferably 0.01% by mass or more and 5% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less, and 0.4% by mass or more and 2% by mass or less. Is more preferable. When the component C is composed of two or more kinds of acids, the content of the component C means the total content thereof.
　本開示の研磨液組成物中の成分Ａに対する成分Ｃの質量比Ｃ／Ａ（成分Ｃの含有量／成分Ａの含有量）は、研磨速度の確保及びスクラッチ低減の観点から、０．００２以上が好ましく、０．０２以上がより好ましく、０．０８以上が更に好ましく、そして、同様の観点から、１以下が好ましく、０．６以下がより好ましく、０．５以下が更に好ましい。より具体的には、質量比Ｃ／Ａは、０．００２以上１以下が好ましく、０．０２以上０．６以下がより好ましく、０．０８以上０．５以下が更に好ましい。 The mass ratio C / A of the component C to the component A in the polishing liquid composition of the present disclosure (content of the component C / content of the component A) is 0.002 or more from the viewpoint of ensuring the polishing rate and reducing scratches. Is preferable, 0.02 or more is more preferable, 0.08 or more is further preferable, and from the same viewpoint, 1 or less is preferable, 0.6 or less is more preferable, and 0.5 or less is further preferable. More specifically, the mass ratio C / A is preferably 0.002 or more and 1 or less, more preferably 0.02 or more and 0.6 or less, and further preferably 0.08 or more and 0.5 or less.
［水系媒体］
　本開示の研磨液組成物に含まれる水系媒体としては、蒸留水、イオン交換水、純水及び超純水等の水、又は、水と溶媒との混合溶媒等が挙げられる。上記溶媒としては、水と混合可能な溶媒（例えば、エタノール等のアルコール）が挙げられる。水系媒体が、水と溶媒との混合溶媒の場合、混合媒体全体に対する水の割合は、本開示の効果が妨げられない範囲であれば特に限定されなくてもよく、経済性の観点から、例えば、９５質量％以上が好ましく、９８質量％以上がより好ましく、実質的に１００質量％が更に好ましい。被研磨基板の表面清浄性の観点から、水系媒体としては、イオン交換水及び超純水が好ましい。本開示の研磨液組成物中の水系媒体の含有量は、成分Ａ、成分Ｂ、成分Ｃ、及び必要に応じて配合される後述する任意成分を除いた残余とすることができる。 [Aqueous medium]
Examples of the aqueous medium contained in the polishing composition of the present disclosure include distilled water, ion-exchanged water, water such as pure water and ultrapure water, or a mixed solvent of water and a solvent. Examples of the solvent include solvents that can be mixed with water (for example, alcohols such as ethanol). When the aqueous medium is a mixed solvent of water and a solvent, the ratio of water to the entire mixed medium may be not particularly limited as long as the effect of the present disclosure is not hindered, and from the viewpoint of economy, for example, 95 mass% or more is preferable, 98 mass% or more is more preferable, and substantially 100 mass% is further preferable. From the viewpoint of surface cleanliness of the substrate to be polished, ion-exchanged water and ultrapure water are preferable as the aqueous medium. The content of the aqueous medium in the polishing liquid composition of the present disclosure can be the balance excluding the components A, B, C, and optional components described below that are blended as necessary.
［酸化剤（成分Ｄ）］
　本開示の研磨液組成物は、研磨速度の確保及びスクラッチ低減の観点から、酸化剤（以下、「成分Ｄ」ともいう）をさらに含有してもよい。成分Ｄは、一又は複数の実施形態において、ハロゲン原子を含まない酸化剤である。成分Ｄは、単独で又は２種以上を混合して使用してもよい。 [Oxidizing agent (component D)]
The polishing composition of the present disclosure may further contain an oxidizing agent (hereinafter, also referred to as “component D”) from the viewpoint of ensuring a polishing rate and reducing scratches. Component D, in one or more embodiments, is a halogen atom-free oxidant. The component D may be used alone or in combination of two or more.
　成分Ｄとしては、研磨速度の確保及びスクラッチ低減の観点から、例えば、過酸化物、過マンガン酸又はその塩、クロム酸又はその塩、ペルオキソ酸又はその塩、酸素酸又はその塩、金属塩類、硝酸類、硫酸類等が挙げられる。これらの中でも、過酸化水素、硝酸鉄（ＩＩＩ）、過酢酸、ペルオキソ二硫酸アンモニウム、硫酸鉄（ＩＩＩ）及び硫酸アンモニウム鉄（ＩＩＩ）から選ばれる少なくとも１種が好ましく、研磨速度向上の観点、被研磨基板の表面に金属イオンが付着しない観点及び入手容易性の観点から、過酸化水素がより好ましい。 As the component D, from the viewpoint of ensuring a polishing rate and reducing scratches, for example, peroxide, permanganic acid or a salt thereof, chromic acid or a salt thereof, peroxo acid or a salt thereof, oxygen acid or a salt thereof, a metal salt, Examples include nitric acid and sulfuric acid. Among these, at least one selected from hydrogen peroxide, iron nitrate (III), peracetic acid, ammonium peroxodisulfate, iron sulfate (III) and ammonium iron sulfate (III) is preferable, and from the viewpoint of improving the polishing rate, the substrate to be polished Hydrogen peroxide is more preferable from the viewpoint that metal ions do not adhere to the surface of and the viewpoint of availability.
　本開示の研磨液組成物中の成分Ｄの含有量は、研磨速度確保及びスクラッチ低減の観点から、０．０１質量％以上が好ましく、０．０５質量％以上がより好ましく、０．１質量％以上が更に好ましく、そして、４質量％以下が好ましく、２質量％以下がより好ましく、１．５質量％以下が更に好ましい。より具体的には、成分Ｄの含有量は、０．０１質量％以上４質量％以下が好ましく、０．０５質量％以上２質量％以下がより好ましく、０．１質量％以上１．５質量％以下が更に好ましい。成分Ｄが２種以上の酸化剤からなる場合、成分Ｄの含有量はそれらの合計含有量をいう。 The content of the component D in the polishing liquid composition of the present disclosure is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and 0.1% by mass from the viewpoint of securing a polishing rate and reducing scratches. The above is more preferable, 4% by mass or less is preferable, 2% by mass or less is more preferable, and 1.5% by mass or less is further preferable. More specifically, the content of the component D is preferably 0.01% by mass or more and 4% by mass or less, more preferably 0.05% by mass or more and 2% by mass or less, and 0.1% by mass or more and 1.5% by mass. % Or less is more preferable. When the component D is composed of two or more kinds of oxidizing agents, the content of the component D means the total content thereof.
［複素環芳香族化合物（成分Ｅ）］
　本開示の研磨液組成物は、複素環芳香族化合物（その塩も含む）（成分Ｅ）をさらに含有してもよい。成分Ｅは１種類であってもよく、２種類以上であってもよい。 [Heterocyclic aromatic compound (component E)]
The polishing composition of the present disclosure may further contain a heterocyclic aromatic compound (including a salt thereof) (component E). The component E may be one type or two or more types.
　成分Ｅとしては、スクラッチ低減の観点から、複素環内に窒素原子を２個以上含む複素環芳香族化合物であることが好ましく、複素環内に窒素原子を３個以上有することがより好ましく、３個以上９個以下が更に好ましく、３個以上５個以下が更に好ましく、３又は４個が更に好ましい。 From the viewpoint of reducing scratches, the component E is preferably a heterocyclic aromatic compound containing 2 or more nitrogen atoms in the heterocycle, more preferably 3 or more nitrogen atoms in the heterocycle. The number is preferably 9 or more and 9 or less, more preferably 3 or more and 5 or less, still more preferably 3 or 4.
　成分Ｅの具体例としては、１，２，４－トリアゾール、３－アミノ－１，２，４－トリアゾール、５－アミノ－１，２，４－トリアゾール、３－メルカプト－１，２，４－トリアゾール、１Ｈ－テトラゾール、５－アミノテトラゾール、１Ｈ－ベンゾトリアゾール（ＢＴＡ）、１Ｈ－トリルトリアゾール、２－アミノベンゾトリアゾール、３－アミノベンゾトリアゾール、及びこれらのアルキル置換体若しくはアミン置換体が好ましい。前記アルキル置換体のアルキル基としては例えば、炭素数１～４の低級アルキル基が挙げられ、より具体的にはメチル基、エチル基が挙げられる。前記アミン置換体としては１－［Ｎ，Ｎ－ビス（ヒドロキシエチレン）アミノメチル］ベンゾトリアゾール、１－［Ｎ，Ｎ－ビス（ヒドロキシエチレン）アミノメチル］トリルトリアゾールが挙げられる。 Specific examples of the component E include 1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino-1,2,4-triazole, 3-mercapto-1,2,4- Triazole, 1H-tetrazole, 5-aminotetrazole, 1H-benzotriazole (BTA), 1H-tolyltriazole, 2-aminobenzotriazole, 3-aminobenzotriazole, and alkyl-substituted or amine-substituted compounds thereof are preferable. Examples of the alkyl group in the alkyl-substituted product include a lower alkyl group having 1 to 4 carbon atoms, and more specifically, a methyl group and an ethyl group. Examples of the amine-substituted product include 1- [N, N-bis (hydroxyethylene) aminomethyl] benzotriazole and 1- [N, N-bis (hydroxyethylene) aminomethyl] tolyltriazole.
　本開示の研磨液組成物中の成分Ｅの含有量は、スクラッチ低減の観点から、０．００５質量％以上が好ましく、０．０１質量％以上がより好ましく、０．０２質量％以上が更に好ましく、そして、１０質量％以下が好ましく、５質量％以下がより好ましく、１質量％以下が更に好ましい。より具体的には、成分Ｅの含有量は、０．００５質量％以上１０質量％以下が好ましく、０．０１質量％以上５質量％以下がより好ましく、０．０２質量％以上１質量％以下が更に好ましい。成分Ｅが２種以上の複素環芳香族化合物からなる場合、成分Ｅの含有量はそれらの合計含有量をいう。 The content of the component E in the polishing liquid composition of the present disclosure is preferably 0.005 mass% or more, more preferably 0.01 mass% or more, and further preferably 0.02 mass% or more, from the viewpoint of scratch reduction. , And 10% by mass or less is preferable, 5% by mass or less is more preferable, and 1% by mass or less is further preferable. More specifically, the content of the component E is preferably 0.005 mass% or more and 10 mass% or less, more preferably 0.01 mass% or more and 5 mass% or less, and 0.02 mass% or more and 1 mass% or less. Is more preferable. When the component E is composed of two or more kinds of heterocyclic aromatic compounds, the content of the component E means the total content thereof.
［脂肪族アミン化合物又は脂環式アミン化合物（成分Ｆ）］
　本開示の研磨液組成物は、スクラッチ低減の観点から、脂肪族アミン化合物又は脂環式アミン化合物（成分Ｆ）をさらに含有してもよい。スクラッチ低減の観点から、成分Ｆの分子内の窒素原子数又はアミノ基若しくはイミノ基の併せた数は、２個以上４個以下が好ましい。成分Ｆは１種単独で用いてもよいし、２種以上の組み合わせであってもよい。 [Aliphatic amine compound or alicyclic amine compound (component F)]
The polishing composition of the present disclosure may further contain an aliphatic amine compound or an alicyclic amine compound (component F) from the viewpoint of scratch reduction. From the viewpoint of reducing scratches, the number of nitrogen atoms in the molecule of component F or the total number of amino groups or imino groups is preferably 2 or more and 4 or less. As the component F, one type may be used alone, or two or more types may be used in combination.
　前記脂肪族アミン化合物としては、スクラッチ低減の観点から、エチレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラメチルエチレンジアミン、１，２－ジアミノプロパン、１，３－ジアミノプロパン、１，４－ジアミノブタン、ヘキサメチレンジアミン、３－（ジエチルアミノ）プロピルアミン、３－（ジブチルアミノ）プロピルアミン、３－（メチルアミノ）プロピルアミン、３－（ジメチルアミノ）プロピルアミン、Ｎ－アミノエチルエタノールアミン、Ｎ－アミノエチルイソプロパノールアミン、及びＮ－アミノエチル－Ｎ－メチルエタノールアミンから選ばれる少なくとも１種が好ましく、Ｎ－アミノエチルエタノールアミン、Ｎ－アミノエチルイソプロパノールアミン、及びＮ－アミノエチル－Ｎ－メチルエタノールアミンから選ばれる少なくとも１種がより好ましく、Ｎ－アミノエチルエタノールアミン（ＡＥＡ）が更に好ましい。 Examples of the aliphatic amine compound include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane and 1,4-diaminobutane from the viewpoint of scratch reduction. , Hexamethylenediamine, 3- (diethylamino) propylamine, 3- (dibutylamino) propylamine, 3- (methylamino) propylamine, 3- (dimethylamino) propylamine, N-aminoethylethanolamine, N-amino At least one selected from ethylisopropanolamine and N-aminoethyl-N-methylethanolamine is preferable, and from N-aminoethylethanolamine, N-aminoethylisopropanolamine, and N-aminoethyl-N-methylethanolamine At least one selected is more preferable, and N-aminoethylethanolamine (AEA) is further preferable.
　前記脂環式アミン化合物としては、スクラッチ低減の観点から、ピペラジン、２－メチルピペラジン、２，５－ジメチルピペラジン、１－アミノ－４－メチルピペラジン、Ｎ－メチルピペラジン、及びヒドロキシエチルピペラジン（ＨＥＰ）から選ばれる少なくとも１種が好ましく、ヒドロキシエチルピペラジン（ＨＥＰ）がより好ましい。 Examples of the alicyclic amine compound include piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 1-amino-4-methylpiperazine, N-methylpiperazine, and hydroxyethylpiperazine (HEP) from the viewpoint of reducing scratches. At least one selected from the group is preferable, and hydroxyethylpiperazine (HEP) is more preferable.
　本開示の研磨液組成物中の成分Ｆの含有量は、スクラッチ低減の観点から、０．０１質量％以上が好ましく、０．０２質量％以上がより好ましく、そして、１０質量％以下が好ましく、５質量％以下がより好ましく、１質量％以下が更に好ましい。より具体的には、成分Ｆの含有量は、０．０１質量％以上１０質量％以下が好ましく、０．０２質量％以上５質量％以下がより好ましく、０．０２質量％以上１質量％以下が更に好ましい。成分Ｆが２種以上の脂肪族アミン化合物及び／又は脂環式アミン化合物からなる場合、成分Ｆの含有量はそれらの合計含有量をいう。 From the viewpoint of scratch reduction, the content of the component F in the polishing liquid composition of the present disclosure is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and preferably 10% by mass or less, It is more preferably 5% by mass or less, still more preferably 1% by mass or less. More specifically, the content of the component F is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 5% by mass or less, and 0.02% by mass or more and 1% by mass or less. Is more preferable. When the component F is composed of two or more kinds of aliphatic amine compounds and / or alicyclic amine compounds, the content of the component F means the total content thereof.
［その他の成分］
　本開示の研磨液組成物は、一又は複数の実施形態において、必要に応じてさらにその他の成分を含有していてもよい。その他の成分としては、例えば、成分Ｂ以外の水溶性高分子、増粘剤、分散剤、防錆剤、塩基性物質、界面活性剤、可溶化剤等が挙げられる。本開示の研磨液組成物中の前記その他の成分の含有量は、０質量％以上が好ましく、０質量％超がより好ましく、０．１質量％以上が更に好ましく、そして、１０質量％以下が好ましく、５質量％以下がより好ましい。より具体的には、その他の成分の含有量は、０質量％以上１０質量％以下が好ましく、０質量％超１０質量％以下がより好ましく、０．１質量％以上５質量％以下が更に好ましい。 [Other ingredients]
In one or a plurality of embodiments, the polishing composition of the present disclosure may further contain other components, if necessary. Examples of other components include water-soluble polymers other than the component B, thickeners, dispersants, rust preventives, basic substances, surfactants, solubilizers, and the like. The content of the other component in the polishing composition of the present disclosure is preferably 0% by mass or more, more preferably more than 0% by mass, further preferably 0.1% by mass or more, and 10% by mass or less. It is preferably 5% by mass or less. More specifically, the content of the other components is preferably 0% by mass or more and 10% by mass or less, more preferably more than 0% by mass and 10% by mass or less, still more preferably 0.1% by mass or more and 5% by mass or less. ..
［研磨液組成物のｐＨ］
　本開示の研磨液組成物のｐＨは、研磨速度の確保及びスクラッチ低減の観点から、６以下が好ましく、５以下がより好ましく、４以下が更に好ましく、３以下が更に好ましく、そして、同様の観点から、０．５以上が好ましく、０．８以上がより好ましく、１以上が更に好ましい。より具体的には、本開示の研磨液組成物のｐＨは、０．５以上６以下が好ましく、０．８以上５以下がより好ましく、１以上４以下が更に好ましい。ｐＨは、上述した酸（成分Ｃ）や公知のｐＨ調整剤等を用いて調整することができる。本開示において、上記ｐＨは、２５℃における研磨液組成物のｐＨであり、ｐＨメータを用いて測定でき、例えば、ｐＨメータの電極を研磨液組成物へ浸漬して２分後の数値とすることができる。 [PH of polishing liquid composition]
The pH of the polishing composition of the present disclosure is preferably 6 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, and from the same viewpoint, from the viewpoint of securing a polishing rate and reducing scratches. Therefore, 0.5 or more is preferable, 0.8 or more is more preferable, and 1 or more is further preferable. More specifically, the pH of the polishing composition of the present disclosure is preferably 0.5 or more and 6 or less, more preferably 0.8 or more and 5 or less, still more preferably 1 or more and 4 or less. The pH can be adjusted using the above-mentioned acid (component C), a known pH adjuster, or the like. In the present disclosure, the above pH is the pH of the polishing composition at 25 ° C. and can be measured using a pH meter. For example, the value after 2 minutes from immersing the electrode of the pH meter in the polishing composition is used. be able to.
［研磨液組成物の製造方法］
　本開示の研磨液組成物は、例えば、成分Ａ、成分Ｂ、成分Ｃ及び水系媒体と、さらに所望により、成分Ｄ～Ｆ及びその他の成分とを公知の方法で配合することにより製造できる。すなわち、本開示は、その他の態様において、少なくとも成分Ａ、成分Ｂ、成分Ｃ及び水系媒体を配合する工程を含む、研磨液組成物の製造方法に関する。本開示において「配合する」とは、成分Ａ、成分Ｂ、成分Ｃ及び水系媒体、並びに必要に応じて成分Ｄ～Ｇ及びその他の成分を同時に又は任意の順に混合することを含む。成分Ａの研磨材は、濃縮されたスラリーの状態で混合されてもよいし、水等で希釈してから混合されてもよい。成分Ａが複数種類の研磨材からなる場合、複数種類の研磨材は、同時に又はそれぞれ別々に配合できる。成分Ｂが複数種類の陽イオン性高分子からなる場合、複数種類の陽イオン性高分子は同時に又はそれぞれ別々に配合できる。成分Ｃが複数種類の酸からなる場合、複数種類の酸は、同時に又はそれぞれ別々に配合できる。前記配合は、例えば、ホモミキサー、ホモジナイザー、超音波分散機及び湿式ボールミル等の混合器を用いて行うことができる。研磨液組成物の製造方法における各成分の好ましい配合量は、上述した本開示の研磨液組成物中の各成分の好ましい含有量と同じとすることができる。 [Method for producing polishing liquid composition]
The polishing composition of the present disclosure can be produced, for example, by blending Component A, Component B, Component C, and an aqueous medium, and if desired, Components DF and other components by a known method. That is, the present disclosure relates to, in another aspect, a method for producing a polishing composition, which includes a step of blending at least Component A, Component B, Component C, and an aqueous medium. In the present disclosure, “compounding” includes mixing Component A, Component B, Component C and an aqueous medium, and optionally Components DG and other components simultaneously or in any order. The abrasive of the component A may be mixed in the form of a concentrated slurry, or may be diluted with water or the like and then mixed. When the component A is composed of plural kinds of abrasives, the plural kinds of abrasives can be blended simultaneously or separately. When the component B comprises a plurality of types of cationic polymers, a plurality of types of cationic polymers can be blended simultaneously or separately. When the component C is composed of a plurality of types of acids, the plurality of types of acids can be blended simultaneously or separately. The blending can be performed using a mixer such as a homomixer, a homogenizer, an ultrasonic disperser, and a wet ball mill. The preferable blending amount of each component in the method for producing a polishing liquid composition can be the same as the preferable content of each component in the above-described polishing liquid composition of the present disclosure.
　本開示において「研磨液組成物中の各成分の含有量」とは、使用時、すなわち、研磨液組成物の研磨への使用を開始する時点における前記各成分の含有量をいう。本開示の研磨液組成物は、その保存安定性が損なわれない範囲で濃縮された状態で保存及び供給されてもよい。この場合、製造及び輸送コストを更に低くできる点で好ましい。本開示の研磨液組成物の濃縮物は、使用時に、必要に応じて前述の水系媒体で適宜希釈して使用すればよい。希釈倍率は、希釈した後に上述した各成分の含有量（使用時）を確保できれば特に限定されるものではなく、例えば、１０～１００倍とすることができる。 In the present disclosure, the “content of each component in the polishing composition” means the content of each component at the time of use, that is, when the use of the polishing composition for polishing is started. The polishing composition of the present disclosure may be stored and supplied in a concentrated state as long as the storage stability is not impaired. In this case, manufacturing and transportation costs can be further reduced, which is preferable. At the time of use, the concentrate of the polishing liquid composition of the present disclosure may be appropriately diluted with the above-mentioned aqueous medium before use. The dilution ratio is not particularly limited as long as the content (when used) of each component described above can be secured after dilution, and can be set to, for example, 10 to 100 times.
［研磨液キット］
　本開示は、その他の態様において、本開示の研磨液組成物を製造するためのキット（以下、「本開示の研磨液キット」ともいう）に関する。本開示の研磨液キットの一実施形態としては、例えば、成分Ａ及び水系媒体を含む研磨材分散液と、成分Ｂ及び成分Ｃを含む添加剤水溶液と、を相互に混合されない状態で含む、研磨液キット（２液型研磨液組成物）が挙げられる。前記研磨材分散液と前記添加剤水溶液とは、使用時に混合され、必要に応じて水系媒体を用いて希釈される。前記研磨材分散液に含まれる水系媒体は、研磨液組成物の調製に使用する水の全量でもよいし、一部でもよい。前記添加剤水溶液には、研磨液組成物の調製に使用する水系媒体の一部が含まれていてもよい。前記研磨材分散液及び前記添加剤水溶液にはそれぞれ必要に応じて、上述した任意成分（成分Ｄ～Ｆ及びその他の成分）が含まれていてもよい。本開示の研磨液キットによれば、研磨速度を確保しつつ、研磨後の基板表面のスクラッチを低減できる研磨液組成物が得られうる。 [Polishing liquid kit]
In another aspect, the present disclosure relates to a kit for producing the polishing liquid composition of the present disclosure (hereinafter, also referred to as “polishing liquid kit of the present disclosure”). As one embodiment of the polishing liquid kit of the present disclosure, for example, polishing containing a polishing agent dispersion liquid containing the component A and an aqueous medium and an additive aqueous solution containing the component B and the component C without being mixed with each other A liquid kit (two-component polishing liquid composition) can be mentioned. The abrasive dispersion and the additive aqueous solution are mixed at the time of use and, if necessary, diluted with an aqueous medium. The aqueous medium contained in the abrasive dispersion may be the whole amount of water used for preparing the polishing composition or a part thereof. The additive aqueous solution may contain a part of the aqueous medium used for preparing the polishing composition. The above-mentioned optional components (components D to F and other components) may be contained in the abrasive dispersion and the additive aqueous solution, respectively, if necessary. According to the polishing liquid kit of the present disclosure, it is possible to obtain a polishing liquid composition capable of reducing scratches on the surface of a substrate after polishing while ensuring a polishing rate.
［被研磨基板］
　被研磨基板は、一又は複数の実施形態において、磁気ディスク基板の製造に用いられる基板である。一又は複数の実施形態において、被研磨基板の表面を本開示の研磨液組成物を用いて研磨する工程の後、スパッタ等でその基板表面に磁性層を形成する工程を行うことにより磁気ディスク基板を製造できる。 [Substrate to be polished]
The substrate to be polished is a substrate used for manufacturing a magnetic disk substrate in one or more embodiments. In one or a plurality of embodiments, after the step of polishing the surface of the substrate to be polished using the polishing composition of the present disclosure, the step of forming a magnetic layer on the surface of the substrate by sputtering or the like is performed to form a magnetic disk substrate. Can be manufactured.
　本開示において好適に使用される被研磨基板の材質としては、例えばシリコン、アルミニウム、ニッケル、タングステン、銅、タンタル、チタン等の金属若しくは半金属、又はこれらの合金や、ガラス、ガラス状カーボン、アモルファスカーボン等のガラス状物質や、アルミナ、二酸化珪素、窒化珪素、窒化タンタル、炭化チタン等のセラミック材料や、ポリイミド樹脂等の樹脂等が挙げられる。中でも、アルミニウム、ニッケル、タングステン、銅等の金属及びこれらの金属を主成分とする合金を含有する被研磨基板に好適である。被研磨基板としては、例えば、Ｎｉ－Ｐメッキされたアルミニウム合金基板や、結晶化ガラス、強化ガラス、アルミノシリケートガラス、アルミノボロシリケートガラス等のガラス基板がより適しており、Ｎｉ－Ｐメッキされたアルミニウム合金基板が更に適している。本開示において「Ｎｉ－Ｐメッキされたアルミニウム合金基板」とは、アルミニウム合金基材の表面を研削後、無電解Ｎｉ－Ｐメッキ処理したものをいう。 Examples of the material of the substrate to be preferably used in the present disclosure include silicon, aluminum, nickel, tungsten, copper, tantalum, metals such as titanium and semimetals, or alloys thereof, glass, glassy carbon, amorphous. Examples thereof include glassy substances such as carbon, ceramic materials such as alumina, silicon dioxide, silicon nitride, tantalum nitride, and titanium carbide, and resins such as polyimide resin. Among them, it is suitable for a substrate to be polished containing a metal such as aluminum, nickel, tungsten, or copper and an alloy containing these metals as a main component. As the substrate to be polished, for example, a Ni—P plated aluminum alloy substrate or a glass substrate such as crystallized glass, tempered glass, aluminosilicate glass or aluminoborosilicate glass is more suitable, and the Ni—P plated substrate is more suitable. Aluminum alloy substrates are even more suitable. In the present disclosure, the “Ni—P-plated aluminum alloy substrate” refers to an aluminum alloy substrate that has been subjected to electroless Ni—P plating after grinding the surface thereof.
　被研磨基板の形状としては、例えば、ディスク状、プレート状、スラブ状、プリズム状等の平面部を有する形状や、レンズ等の曲面部を有する形状が挙げられる。中でも、ディスク状の被研磨基板が適している。ディスク状の被研磨基板の場合、その外径は例えば２～９５ｍｍ程度であり、その厚みは例えば０．４～２ｍｍ程度である。 The shape of the substrate to be polished includes, for example, a shape having a flat portion such as a disk shape, a plate shape, a slab shape, a prism shape, or a shape having a curved surface portion such as a lens. Above all, a disk-shaped substrate to be polished is suitable. In the case of a disk-shaped substrate to be polished, its outer diameter is, for example, about 2 to 95 mm, and its thickness is, for example, about 0.4 to 2 mm.
［磁気ディスク基板の製造方法］
　一般に、磁気ディスクは、研削工程を経た被研磨基板が、粗研磨工程、仕上げ研磨工程を経て研磨され、記録部形成工程にて磁気ディスク化されて製造される。本開示における研磨液組成物は、磁気ディスク基板の製造方法における、被研磨基板を研磨する研磨工程、好ましくは仕上げ研磨工程に使用されうる。すなわち、本開示は、その他の態様において、本開示の研磨液組成物を用いて被研磨基板を研磨する工程（以下、「本開示の研磨液組成物を用いた研磨工程」ともいう）を含む、磁気ディスク基板の製造方法（以下、「本開示の基板製造方法」ともいう）に関する。本開示の基板製造方法は、とりわけ、垂直磁気記録方式用磁気ディスク基板の製造方法に適している。 [Magnetic Disk Substrate Manufacturing Method]
In general, a magnetic disk is manufactured by polishing a substrate to be polished after a grinding step through a rough polishing step and a finish polishing step, and turning it into a magnetic disk in a recording section forming step. The polishing composition of the present disclosure can be used in a polishing step of polishing a substrate to be polished, preferably a final polishing step in a method for producing a magnetic disk substrate. That is, the present disclosure includes, in another aspect, a step of polishing a substrate to be polished using the polishing liquid composition of the present disclosure (hereinafter, also referred to as “polishing step using the polishing liquid composition of the present disclosure”). , A method of manufacturing a magnetic disk substrate (hereinafter, also referred to as a “substrate manufacturing method of the present disclosure”). The substrate manufacturing method of the present disclosure is particularly suitable for manufacturing a magnetic disk substrate for a perpendicular magnetic recording system.
　本開示の研磨液組成物を用いた研磨工程は、一又は複数の実施形態において、本開示の研磨液組成物を被研磨基板の研磨対象面に供給し、前記研磨対象面に研磨パッドを接触させ、前記研磨パッド及び前記被研磨基板の少なくとも一方を動かして研磨する工程である。また、本開示の研磨液組成物を用いた研磨工程は、その他の一又は複数の実施形態において、不織布状の有機高分子系研磨布等の研磨パッドを貼り付けた定盤で被研磨基板を挟み込み、本開示の研磨液組成物を研磨機に供給しながら、定盤や被研磨基板を動かして被研磨基板を研磨する工程である。 The polishing step using the polishing composition of the present disclosure is, in one or more embodiments, supplying the polishing composition of the present disclosure to a surface to be polished of a substrate to be polished, and bringing a polishing pad into contact with the surface to be polished. And moving at least one of the polishing pad and the substrate to be polished for polishing. Further, in the polishing step using the polishing composition of the present disclosure, in another or a plurality of embodiments, the substrate to be polished is fixed on a surface plate to which a polishing pad such as a non-woven organic polymer polishing cloth is attached. It is a step of sandwiching and polishing the substrate to be polished by moving the platen or the substrate to be polished while supplying the polishing composition of the present disclosure to the polishing machine.
　被研磨基板の研磨工程が多段階で行われる場合は、本開示の研磨液組成物を用いた研磨工程は２段階目以降に行われるのが好ましく、最終研磨工程又は仕上げ研磨工程で行われるのがより好ましい。その際、前工程の研磨材や研磨液組成物の混入を避けるために、それぞれ別の研磨機を使用してもよく、またそれぞれ別の研磨機を使用した場合では、研磨工程毎に被研磨基板を洗浄することが好ましい。さらに、使用した研磨液を再利用する循環研磨においても、本開示の研磨液組成物は使用できる。研磨機としては、特に限定されず、基板研磨用の公知の研磨機が使用できる。 When the polishing process for the substrate to be polished is performed in multiple stages, the polishing process using the polishing composition of the present disclosure is preferably performed after the second stage, and is performed in the final polishing process or the final polishing process. Is more preferable. At that time, in order to avoid mixing of the polishing material and the polishing liquid composition in the previous step, different polishing machines may be used, respectively. It is preferable to wash the substrate. Further, the polishing liquid composition of the present disclosure can be used in circulation polishing in which the used polishing liquid is reused. The polishing machine is not particularly limited, and a known polishing machine for polishing a substrate can be used.
　本開示で使用される研磨パッドとしては、特に制限はなく、例えば、スエードタイプ、不織布タイプ、ポリウレタン独立発泡タイプ、又はこれらを積層した二層タイプ等の研磨パッドを使用することができ、研磨速度の観点から、スエードタイプの研磨パッドが好ましい。 The polishing pad used in the present disclosure is not particularly limited, and for example, a suede type, a non-woven fabric type, a polyurethane independent foam type, or a two-layer type polishing pad in which these are laminated can be used. From the viewpoint of, a suede type polishing pad is preferable.
　本開示の研磨液組成物を用いた研磨工程における研磨荷重は、研磨速度の確保の観点から、好ましくは５．９ｋＰａ以上、より好ましくは６．９ｋＰａ以上、更に好ましくは７．５ｋＰａ以上であり、そして、スクラッチ低減の観点から、２０ｋＰａ以下が好ましく、より好ましくは１８ｋＰａ以下、更に好ましくは１６ｋＰａ以下である。より具体的には、研磨荷重は、５．９～２０ｋＰａが好ましく、６．９～１８ｋＰａがより好ましく、７．５～１６ｋＰａが更に好ましい。本開示の製造方法において研磨荷重とは、研磨時に被研磨基板の研磨面に加えられる定盤の圧力をいう。また、研磨荷重の調整は、定盤及び被研磨基板のうち少なくとも一方に空気圧や重りを負荷することにより行うことができる。 The polishing load in the polishing step using the polishing composition of the present disclosure is preferably 5.9 kPa or more, more preferably 6.9 kPa or more, still more preferably 7.5 kPa or more, from the viewpoint of ensuring the polishing rate. From the viewpoint of reducing scratches, it is preferably 20 kPa or less, more preferably 18 kPa or less, still more preferably 16 kPa or less. More specifically, the polishing load is preferably 5.9 to 20 kPa, more preferably 6.9 to 18 kPa, and further preferably 7.5 to 16 kPa. In the manufacturing method of the present disclosure, the polishing load refers to the pressure of the surface plate applied to the polishing surface of the substrate to be polished during polishing. The polishing load can be adjusted by applying air pressure or weight to at least one of the surface plate and the substrate to be polished.
　本開示の研磨液組成物を用いた研磨工程における本開示の研磨液組成物の供給速度は、スクラッチ低減の観点から、被研磨基板１ｃｍ2当たり、好ましくは０．０５ｍＬ／分以上１５ｍＬ／分以下であり、より好ましくは０．０６ｍＬ／分以上１０ｍＬ／分以下、更に好ましくは０．０７ｍＬ／分以上１ｍＬ／分以下、更に好ましくは０．０７ｍＬ／分以上０．５ｍＬ／分以下である。 The supply rate of the polishing liquid composition of the present disclosure in the polishing step using the polishing liquid composition of the present disclosure is preferably 0.05 mL / min or more and 15 mL / min or less per 1 cm 2 of the substrate to be polished from the viewpoint of scratch reduction. It is more preferably 0.06 mL / min or more and 10 mL / min or less, still more preferably 0.07 mL / min or more and 1 mL / min or less, still more preferably 0.07 mL / min or more and 0.5 mL / min or less.
　本開示の研磨液組成物を研磨機へ供給する方法としては、例えばポンプ等を用いて連続的に供給を行う方法が挙げられる。研磨液組成物を研磨機へ供給する際は、全ての成分を含んだ１液で供給する方法の他、研磨液組成物の安定性等を考慮して、複数の配合用成分液に分け、２液以上で供給することもできる。後者の場合、例えば供給配管中又は被研磨基板上で、上記複数の配合用成分液が混合され、本開示の研磨液組成物となる。 As a method of supplying the polishing composition of the present disclosure to a polishing machine, for example, a method of continuously supplying using a pump or the like can be mentioned. When supplying the polishing liquid composition to the polishing machine, in addition to a method of supplying it as a single liquid containing all components, in consideration of the stability of the polishing liquid composition, etc., it is divided into a plurality of component liquids for blending, It is also possible to supply two or more liquids. In the latter case, for example, in the supply pipe or on the substrate to be polished, the plurality of component liquids for compounding are mixed to obtain the polishing liquid composition of the present disclosure.
　本開示の基板製造方法によれば、本開示における研磨液組成物を用いることで、研磨後の基板表面のスクラッチが低減された、高品質の磁気ディスク基板を高収率で、生産性よく製造できるという効果が奏されうる。 According to the substrate manufacturing method of the present disclosure, by using the polishing composition of the present disclosure, scratches on the substrate surface after polishing are reduced, and a high-quality magnetic disk substrate is manufactured with high yield and high productivity. The effect that it is possible can be exhibited.
［研磨方法］
　本開示は、その他の態様として、本開示の研磨液組成物を用いて被研磨基板を研磨することを含む、基板の研磨方法（以下、「本開示の研磨方法」ともいう）に関する。本開示の研磨方法を使用することにより、研磨後の基板表面のスクラッチが低減された、高品質の磁気ディスク基板を高収率で、生産性よく製造できるという効果が奏されうる。本開示の研磨方法における前記被研磨基板としては、上述のとおり、磁気ディスク基板の製造に使用されるものが挙げられ、なかでも、垂直磁気記録方式用磁気ディスク基板の製造に用いる基板が好ましい。具体的な研磨の方法及び条件は、上述した本開示の基板製造方法と同じ方法及び条件とすることができる。 [Polishing method]
As another aspect, the present disclosure relates to a method for polishing a substrate (hereinafter, also referred to as “polishing method of the present disclosure”) including polishing a substrate to be polished using the polishing composition of the present disclosure. By using the polishing method of the present disclosure, it is possible to produce an effect that a high-quality magnetic disk substrate in which scratches on the substrate surface after polishing are reduced can be manufactured with high yield and high productivity. Examples of the substrate to be polished in the polishing method of the present disclosure include those used for manufacturing a magnetic disk substrate as described above, and among them, a substrate used for manufacturing a magnetic disk substrate for a perpendicular magnetic recording system is preferable. The specific polishing method and conditions may be the same as the substrate manufacturing method of the present disclosure described above.
　本開示の研磨液組成物を用いて被研磨基板を研磨することは、一又は複数の実施形態において、本開示の研磨液組成物を被研磨基板の研磨対象面に供給し、前記研磨対象面に研磨パッドを接触させ、前記研磨パッド及び前記被研磨基板の少なくとも一方を動かして研磨することであり、或いは、不織布状の有機高分子系研磨布等の研磨パッドを貼り付けた定盤で被研磨基板を挟み込み、本開示の研磨液組成物を研磨機に供給しながら、定盤や被研磨基板を動かして被研磨基板を研磨することである。 Polishing a substrate to be polished using the polishing liquid composition of the present disclosure includes, in one or more embodiments, supplying the polishing liquid composition of the present disclosure to a polishing target surface of a substrate to be polished, The polishing pad is brought into contact with the substrate, and at least one of the polishing pad and the substrate to be polished is moved to perform polishing, or a surface plate to which a polishing pad such as a non-woven organic polymer polishing cloth is attached is used. That is, the polishing substrate is sandwiched, and while the polishing liquid composition of the present disclosure is supplied to the polishing machine, the platen or the substrate to be polished is moved to polish the substrate to be polished.
　以下、実施例により本開示をさらに詳細に説明するが、これらは例示的なものであって、本開示はこれら実施例に制限されるものではない。 Hereinafter, the present disclosure will be described in more detail with reference to examples, but these are merely examples, and the present disclosure is not limited to these examples.
１．水溶性高分子
　表１に示す水溶性高分子Ｂ１～Ｂ１０には、以下のものを用いた。
Ｂ１：ポリ－ｐ－ビニルフェノール／ポリ［Ｎ,Ｎ－ジメチル－１－（４－ビニルフェノキシ）メタンアミン］（モル比４５／５５）［商品名：ＭＡＭ３ＭＥ、丸善石油化学社製、重量平均分子量　５，０００］（式Ｉ中のＸ：ジメチルアミノメチル基）
Ｂ２：ポリ－ｐ－ビニルフェノール／ポリ［Ｎ,Ｎ－ジメチル－１－（４－ビニルフェノキシ）メタンアミン］（モル比３０／７０）（合成品）［丸善石油化学社製、重量平均分子量　５，０００］（式Ｉ中のＸ：ジメチルアミノメチル基）
Ｂ３：ポリアリルアミン［商品名：ＰＡＡ－０５、ニットーボーメディカル社製、重量平均分子量　５，０００］
Ｂ４：ポリＮ－メチルジアリルアミン塩酸塩［商品名：ＰＡＳ－Ｍ－１Ｌ、ニット―ボーメディカル社製、重量平均分子量　５，０００］
Ｂ５：ポリ－ｐ－ビニルフェノール［日本曹達社製、重量平均分子量　４，４００］
Ｂ６：ポリアクリル酸［東亜合成社製、重量平均分子量３，０００］
Ｂ７：芳香族アミノスルホン酸［商品名：フローリックＳＦ２００Ｓ、フローリック社製］
Ｂ８：ｐ－アミノフェノール（モノマー）［東京化成工業社製、分子量　１０９．１３］
Ｂ９：ポリ－ｐ－ビニルフェノール／ポリ［Ｎ,Ｎ－ジメチル－１－（４－ビニルフェノキシ）メタンアミン］（モル比４５／５５）［重量平均分子量　２，５００］（式Ｉ中のＸ：ジメチルアミノメチル基）
Ｂ１０：ポリ－ｐ－ビニルフェノール／ポリ［Ｎ,Ｎ－ジメチル－１－（４－ビニルフェノキシ）メタンアミン］（モル比４５／５５）［重量平均分子量　１２，０００］（式Ｉ中のＸ：ジメチルアミノメチル基）
　なお、２０℃のｐＨ３の水溶液１００ｇに対する溶解度は、Ｂ１～Ｂ４及びＢ６～Ｂ１０が０．０１ｇ以上であり、Ｂ５が０．０１ｇ未満である。 1. Water-soluble polymer The following were used as the water-soluble polymers B1 to B10 shown in Table 1.
B1: poly-p-vinylphenol / poly [N, N-dimethyl-1- (4-vinylphenoxy) methanamine] (molar ratio 45/55) [trade name: MAM3ME, manufactured by Maruzen Petrochemical Co., Ltd., weight average molecular weight 5] , 000] (X in formula I: dimethylaminomethyl group)
B2: poly-p-vinylphenol / poly [N, N-dimethyl-1- (4-vinylphenoxy) methanamine] (molar ratio 30/70) (synthetic product) [Maruzen Petrochemical Co., Ltd., weight average molecular weight 5, 000] (X in formula I: dimethylaminomethyl group)
B3: Polyallylamine [trade name: PAA-05, manufactured by Nitto Bo Medical, weight average molecular weight 5,000]
B4: Poly N-methyldiallylamine hydrochloride [trade name: PAS-M-1L, manufactured by Knit-Beaumedical, weight average molecular weight 5,000]
B5: Poly-p-vinylphenol [Nippon Soda Co., Ltd., weight average molecular weight 4,400]
B6: Polyacrylic acid [Toagosei Co., Ltd., weight average molecular weight 3,000]
B7: Aromatic aminosulfonic acid [Product name: Floric SF200S, manufactured by Floric]
B8: p-aminophenol (monomer) [Tokyo Kasei Kogyo KK, molecular weight 109.13]
B9: poly-p-vinylphenol / poly [N, N-dimethyl-1- (4-vinylphenoxy) methanamine] (molar ratio 45/55) [weight average molecular weight 2,500] (X in formula I: dimethyl Aminomethyl group)
B10: poly-p-vinylphenol / poly [N, N-dimethyl-1- (4-vinylphenoxy) methanamine] (molar ratio 45/55) [weight average molecular weight 12,000] (X in formula I: dimethyl Aminomethyl group)
The solubilities of 100 g of a pH 3 aqueous solution at 20 ° C. are 0.01 g or more for B1 to B4 and B6 to B10, and less than 0.01 g for B5.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
２．研磨液組成物の調製
（実施例１～１０、比較例１～７の研磨液組成物）
　成分Ａ（コロイダルシリカ）、成分Ｂ又は非成分Ｂ（表１に示す水溶性高分子Ｂ１～Ｂ１０）、成分Ｃ（リン酸）、成分Ｄ（過酸化水素）、及びイオン交換水を配合して撹拌することにより、表２に示す実施例１～１０及び比較例１～７の研磨液組成物を調製した。各研磨液組成物中の各成分の含有量（有効量）は、表２に示すとおりである。イオン交換水の含有量は、成分Ａ、成分Ｂ又は非成分Ｂ、成分Ｃ、及び成分Ｄを除いた残余である。
（実施例１１～１２の研磨液組成物）
　成分Ａ（コロイダルシリカ）、成分Ｂ（表１に示す水溶性高分子Ｂ１）、成分Ｃ（リン酸）、成分Ｄ（過酸化水素）、その他の添加剤（成分Ｅ：ＢＴＡ、又は、成分Ｆ：ＨＥＰ）、及びイオン交換水を配合して撹拌することにより、表２に示す実施例１１～１２の研磨液組成物を調製した。各研磨液組成物中の各成分の含有量（有効量）は、成分Ａ～Ｄが表２に示すとおりであり、成分Ｅ又は成分Ｆが０．０２質量％である。イオン交換水の含有量は、成分Ａ、成分Ｂ、成分Ｃ、成分Ｄ、及びその他の添加剤（成分Ｅ又は成分Ｆ）を除いた残余である。 2. Preparation of polishing liquid compositions (polishing liquid compositions of Examples 1 to 10 and Comparative Examples 1 to 7)
Component A (colloidal silica), component B or non-component B (water-soluble polymers B1 to B10 shown in Table 1), component C (phosphoric acid), component D (hydrogen peroxide), and ion-exchanged water are blended. By stirring, the polishing liquid compositions of Examples 1-10 and Comparative Examples 1-7 shown in Table 2 were prepared. The content (effective amount) of each component in each polishing composition is shown in Table 2. The content of ion-exchanged water is the balance excluding the component A, the component B or the non-component B, the component C, and the component D.
(Polishing liquid compositions of Examples 11 to 12)
Component A (colloidal silica), component B (water-soluble polymer B1 shown in Table 1), component C (phosphoric acid), component D (hydrogen peroxide), and other additives (component E: BTA or component F) : HEP) and ion-exchanged water were mixed and stirred to prepare polishing liquid compositions of Examples 11 to 12 shown in Table 2. The content (effective amount) of each component in each polishing composition is as shown in Table 2 for components A to D, and 0.02 mass% for component E or component F. The content of ion-exchanged water is the balance excluding component A, component B, component C, component D, and other additives (component E or component F).
　各研磨液組成物の調製において、成分Ｃ～成分Ｆには以下のものを使用した。
リン酸［和光純薬工業社製、特級］（成分Ｃ）
過酸化水素水［濃度３５質量％、ADEKA社製］（成分Ｄ）
ＢＴＡ［１，２，３－ベンゾトリアゾール、東京化成工業社製］（成分Ｅ）
ＨＥＰ［Ｎ－ヒドロキシエチルピペラジン、和光純薬工業社製］（成分Ｆ） In the preparation of each polishing composition, the following components were used as Component C to Component F.
Phosphoric acid [manufactured by Wako Pure Chemical Industries, special grade] (Component C)
Hydrogen peroxide water [concentration 35% by mass, manufactured by ADEKA] (Component D)
BTA [1,2,3-benzotriazole, manufactured by Tokyo Chemical Industry Co., Ltd.] (Component E)
HEP [N-hydroxyethylpiperazine, manufactured by Wako Pure Chemical Industries, Ltd.] (Component F)
２．各パラメータの測定
（１）コロイダルシリカ（成分Ａ）の平均粒径
　研磨液組成物の調製に用いた成分Ａ（コロイダルシリカ）と、成分Ｃ（リン酸）とをイオン交換水に添加し、撹拌することにより、標準試料を作製した。標準試料中における成分Ａ及び成分Ｃの含有量はそれぞれ、１質量％、０．４５質量％とした。この標準試料を動的光散乱装置（大塚電子社製DLS-6500）により、同メーカーが添付した説明書に従って、２００回積算した際の検出角９０°におけるCumulant法によって得られる散乱強度分布の面積が全体の５０％となる粒径を求め、コロイダルシリカの平均粒径とした。結果を表２に示す。 2. Measurement of Parameters (1) Average Particle Size of Colloidal Silica (Component A) Component A (colloidal silica) used for preparing the polishing composition and component C (phosphoric acid) were added to ion-exchanged water and stirred. Then, a standard sample was prepared. The contents of Component A and Component C in the standard sample were 1% by mass and 0.45% by mass, respectively. Using a dynamic light scattering device (DLS-6500 manufactured by Otsuka Electronics Co., Ltd.) for this standard sample, the area of the scattering intensity distribution obtained by the Cumulant method at a detection angle of 90 ° when integrated 200 times according to the instructions attached by the manufacturer. Was calculated to be 50% of the total, and the average particle size of the colloidal silica was determined. The results are shown in Table 2.
（２）水溶性高分子（成分Ｂ及び非成分Ｂ）の重量平均分子量
　成分Ｂ及び非成分Ｂの重量平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法により下記条件で測定した。結果を表１及び表２に示す。
＜測定条件＞
カラム：TSKgel GMPWXL+TSKgel GMPWXL（東ソー社製）
溶離液：０．２Ｍリン酸バッファー／ＣＨ3ＣＮ＝７／３（体積比）
温度：４０℃
流速：１．０ｍＬ／分
試料サイズ：２ｍｇ／ｍＬ
検出器：ＲＩ
標準物質：ポリスチレンスルホン酸ナトリウム（重量平均分子量：1,100、3,610、14,900、152,000、POLMER STANDARDS SERVICE社製） (2) Weight average molecular weight of water-soluble polymer (component B and non-component B) The weight average molecular weight of component B and non-component B was measured by the gel permeation chromatography (GPC) method under the following conditions. The results are shown in Tables 1 and 2.
<Measurement conditions>
Column: TSKgel GMPWXL + TSKgel GMPWXL (manufactured by Tosoh Corporation)
Eluent: 0.2 M phosphate buffer / CH 3 CN = 7/3 (volume ratio)
Temperature: 40 ° C
Flow rate: 1.0 mL / min Sample size: 2 mg / mL
Detector: RI
Standard substance: Sodium polystyrene sulfonate (weight average molecular weight: 1,100, 3,610, 14,900, 152,000, manufactured by POLMER STANDARDS SERVICE)
（３）ｐＨの測定
　研磨液組成物のｐＨは、ｐＨメータ（東亜ディーケーケー社製）を用いて２５℃にて測定し、電極を研磨液組成物へ浸漬して２分後の数値を採用した。結果を表２に示す。 (3) Measurement of pH The pH of the polishing composition was measured at 25 ° C using a pH meter (manufactured by Toa DKK Co., Ltd.), and the value after 2 minutes from immersing the electrode in the polishing composition was adopted. .. The results are shown in Table 2.
３．研磨方法
　前記のように調製した実施例１～１２及び比較例１～７の研磨液組成物を用いて、以下に示す研磨条件にて下記被研磨基板を研磨した。次いで、研磨速度及びスクラッチ数を測定した。その結果を表２に示す。 3. Polishing Method Using the polishing liquid compositions of Examples 1 to 12 and Comparative Examples 1 to 7 prepared as described above, the following substrates to be polished were polished under the polishing conditions shown below. Then, the polishing rate and the number of scratches were measured. The results are shown in Table 2.
［被研磨基板］
　被研磨基板として、Ｎｉ－Ｐメッキされたアルミニウム合金基板を予めアルミナ研磨材を含有する研磨液組成物で粗研磨した基板を用いた。この被研磨基板は、厚さが１．２７ｍｍ、外径が９５ｍｍ、内径が２５ｍｍであり、ＡＦＭ（Digital Instrument NanoScope IIIa Multi Mode AFM）により測定した中心線平均粗さＲａが１ｎｍであった。 [Substrate to be polished]
As the substrate to be polished, a substrate obtained by roughly polishing an Ni—P plated aluminum alloy substrate with a polishing composition containing an alumina polishing material in advance was used. The substrate to be polished had a thickness of 1.27 mm, an outer diameter of 95 mm and an inner diameter of 25 mm, and had a center line average roughness Ra of 1 nm measured by an AFM (Digital Instrument NanoScope IIIa Multi Mode AFM).
［研磨条件］
研磨試験機：スピードファム社製「両面９Ｂ研磨機」
研磨パッド：フジボウ社製スエードタイプ（発泡層：ポリウレタンエラストマー、厚さ０．９ｍｍ、平均開孔径１０μｍ）
研磨液組成物供給量：１００ｍＬ／分（被研磨基板１ｃｍ2あたりの供給速度：０．０７６ｍＬ／分）
下定盤回転数：３２．５ｒｐｍ
研磨荷重：１３．０ｋＰａ
研磨時間：６分間
基板の枚数：１０枚 [Polishing conditions]
Polishing tester: "Double-sided 9B polisher" manufactured by Speedfam
Polishing pad: Suede type manufactured by Fuji Bow (foam layer: polyurethane elastomer, thickness 0.9 mm, average opening diameter 10 μm)
Polishing liquid composition supply rate: 100 mL / min (supply rate per 1 cm 2 of the substrate to be polished: 0.076 mL / min)
Lower surface plate rotation speed: 32.5 rpm
Polishing load: 13.0kPa
Polishing time: 6 minutes Number of substrates: 10
４．評価
［研磨速度の評価］
　研磨前後の各基板１枚当たりの重さを計り（Ｓａｒｔｏｒｉｕｓ社製、「ＢＰ－２１０Ｓ」）を用いて測定し、各基板の質量変化から質量減少量を求めた。全１０枚の平均の質量減少量を研磨時間で割った値を研磨速度とし、下記式により算出した。研磨速度の測定結果を、比較例１を１００とした相対値として表２に示す。
質量減少量（ｇ）＝｛研磨前の質量（ｇ）－ 研磨後の質量（ｇ）｝
研磨速度（ｍｇ／ｍｉｎ）＝質量減少量（ｍｇ）／ 研磨時間（ｍｉｎ） 4. Evaluation [Evaluation of polishing rate]
The weight of each substrate before and after polishing was measured and measured using a “BP-210S” manufactured by Sartorius, and the amount of mass reduction was calculated from the change in mass of each substrate. The value obtained by dividing the average mass reduction amount of all 10 sheets by the polishing time was defined as the polishing rate, and was calculated by the following formula. The polishing rate measurement results are shown in Table 2 as a relative value with Comparative Example 1 set to 100.
Mass reduction amount (g) = {mass before polishing (g) -mass after polishing (g)}
Polishing rate (mg / min) = mass reduction amount (mg) / polishing time (min)
［スクラッチの評価］
測定機器：KLA ・テンコール社製、「Ｃａｎｄｅｌａ　ＯＳＡ７１００」
評価：研磨試験機に投入した基板のうち、無作為に４枚を選択し、各々の基板を１０,０００ｒｐｍにてレーザーを照射してスクラッチ数を測定した。その４枚の基板の各々両面にあるスクラッチ数（本）の合計を８で除して、基板面当たりのスクラッチ数を算出した。スクラッチ数の評価結果を、比較例１を１００とした相対値として表２に示す。 [Scratch evaluation]
Measuring instrument: KLA-Tencor, "Candela OSA7100"
Evaluation: Four substrates were randomly selected from the substrates put in the polishing tester, and each substrate was irradiated with a laser at 10,000 rpm to measure the number of scratches. The total number of scratches (on each side) of each of the four substrates was divided by 8 to calculate the number of scratches per substrate surface. The evaluation result of the number of scratches is shown in Table 2 as a relative value with Comparative Example 1 set to 100.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　上記表２に示すとおり、実施例１～１２の研磨液組成物は、比較例１～７の研磨液組成物に比べて、研磨速度を確保しつつ、スクラッチが効果的に低減されていた。 As shown in Table 2 above, the polishing liquid compositions of Examples 1 to 12 effectively reduced scratches while securing a polishing rate, as compared with the polishing liquid compositions of Comparative Examples 1 to 7.
　本開示によれば、例えば、高記録密度化に適した磁気ディスク基板を提供できる。 According to the present disclosure, it is possible to provide a magnetic disk substrate suitable for high recording density, for example.

Claims (12)

  1. 　研磨材（成分Ａ）、水溶性高分子（成分Ｂ）、酸（成分Ｃ）及び水系媒体を含有し、
    　前記成分Ｂが、主鎖又は側鎖にフェニルエーテル骨格を有する陽イオン性高分子である、研磨液組成物。     Contains an abrasive (component A), a water-soluble polymer (component B), an acid (component C) and an aqueous medium,
    A polishing composition, wherein the component B is a cationic polymer having a phenyl ether skeleton in the main chain or side chain.
  2. 　前記成分Ｂが、疎水性の構成単位と、陽イオン性基がエーテル結合したフェニルエーテル骨格を主鎖又は側鎖に有する構成単位と、を含む共重合体である、請求項１に記載の研磨液組成物。 The polishing according to claim 1, wherein the component B is a copolymer containing a hydrophobic structural unit and a structural unit having a phenyl ether skeleton in which a cationic group is ether-bonded in a main chain or a side chain. Liquid composition.
  3. 　前記成分Ｂが、フェノール骨格を主鎖又は側鎖に有する構成単位と、陽イオン性基がエーテル結合したフェニルエーテル骨格を主鎖又は側鎖に有する構成単位と、を含む共重合体である、請求項１又は２に記載の研磨液組成物。 The component B is a copolymer containing a structural unit having a phenol skeleton in the main chain or side chain, and a structural unit having a phenyl ether skeleton in which a cationic group is ether-bonded in the main chain or side chain, The polishing liquid composition according to claim 1.
  4. 　前記成分Ｂが、下記式（Ｉ）で表される構成を有する化合物である、請求項１から３のいずれかに記載の研磨液組成物。
    Figure JPOXMLDOC01-appb-C000001
     式（Ｉ）中、Ｘは、陽イオン性基を示し、ｍ／ｎは、２０/８０～８０/２０である。     The polishing composition according to claim 1, wherein the component B is a compound having a structure represented by the following formula (I).
    Figure JPOXMLDOC01-appb-C000001
     In formula (I), X represents a cationic group, and m / n is 20/80 to 80/20.
  5. 　成分Ｂの含有量が、０．０１質量％以下である、請求項１から４のいずれかに記載の研磨液組成物。 The polishing composition according to any one of claims 1 to 4, wherein the content of the component B is 0.01% by mass or less.
  6. 　成分Ａがシリカである、請求項１から５のいずれかに記載の研磨液組成物。 The polishing composition according to any one of claims 1 to 5, wherein the component A is silica.
  7. 　酸化剤をさらに含む、請求項１から６のいずれかに記載の研磨液組成物。 The polishing composition according to any one of claims 1 to 6, further comprising an oxidizing agent.
  8. 　複素環芳香族化合物、脂肪族アミン化合物及び脂環式アミン化合物から選ばれる少なくとも１種をさらに含む、請求項１から７のいずれかに記載の研磨液組成物。 The polishing composition according to any one of claims 1 to 7, further comprising at least one selected from a heterocyclic aromatic compound, an aliphatic amine compound and an alicyclic amine compound.
  9. 　前記研磨液組成物が磁気ディスク基板用研磨液組成物である、請求項１から８のいずれかに記載の研磨液組成物。 The polishing liquid composition according to any one of claims 1 to 8, wherein the polishing liquid composition is a magnetic disk substrate polishing liquid composition.
  10. 　ｐＨは６以下である、請求項１から９のいずれかに記載の研磨液組成物。 The polishing composition according to any one of claims 1 to 9, which has a pH of 6 or less.
  11. 　請求項１から１０のいずれかに記載の研磨液組成物を用いて被研磨基板を研磨する研磨工程を含む、磁気ディスク基板の製造方法。 A method for producing a magnetic disk substrate, comprising a polishing step of polishing a substrate to be polished using the polishing composition according to any one of claims 1 to 10.
  12. 　請求項１から１０のいずれかに記載の研磨液組成物を用いて被研磨基板を研磨することを含み、前記被研磨基板は、磁気ディスク基板の製造に用いられる基板である、基板の研磨方法。 A method of polishing a substrate, comprising polishing the substrate to be polished using the polishing composition according to any one of claims 1 to 10, wherein the substrate to be polished is a substrate used for manufacturing a magnetic disk substrate. ..
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005311011A (en) * 2004-04-21 2005-11-04 Sumitomo Bakelite Co Ltd Polishing composition
JP2012129406A (en) * 2010-12-16 2012-07-05 Kuraray Co Ltd Chemical mechanical polishing method and slurry used therein
WO2014034358A1 (en) * 2012-08-30 2014-03-06 日立化成株式会社 Polishing agent, polishing agent set and method for polishing base
JP2017224643A (en) * 2016-06-13 2017-12-21 Jsr株式会社 Composition for semiconductor surface treatment, surface treatment method, and method for manufacturing semiconductor device
JP2019189814A (en) * 2018-04-27 2019-10-31 三菱ケミカル株式会社 Polishing composition

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EP1218464B1 (en) * 1999-08-13 2008-08-20 Cabot Microelectronics Corporation Chemical mechanical polishing systems and methods for their use

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005311011A (en) * 2004-04-21 2005-11-04 Sumitomo Bakelite Co Ltd Polishing composition
JP2012129406A (en) * 2010-12-16 2012-07-05 Kuraray Co Ltd Chemical mechanical polishing method and slurry used therein
WO2014034358A1 (en) * 2012-08-30 2014-03-06 日立化成株式会社 Polishing agent, polishing agent set and method for polishing base
JP2017224643A (en) * 2016-06-13 2017-12-21 Jsr株式会社 Composition for semiconductor surface treatment, surface treatment method, and method for manufacturing semiconductor device
JP2019189814A (en) * 2018-04-27 2019-10-31 三菱ケミカル株式会社 Polishing composition

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