CN115461427B - Cerium-based polishing material slurry stock solution, method for producing same, and polishing liquid - Google Patents
Cerium-based polishing material slurry stock solution, method for producing same, and polishing liquid Download PDFInfo
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- CN115461427B CN115461427B CN202180030312.5A CN202180030312A CN115461427B CN 115461427 B CN115461427 B CN 115461427B CN 202180030312 A CN202180030312 A CN 202180030312A CN 115461427 B CN115461427 B CN 115461427B
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- cerium
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- polishing
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- 239000002002 slurry Substances 0.000 title claims abstract description 147
- 238000005498 polishing Methods 0.000 title claims abstract description 123
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 85
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000011550 stock solution Substances 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 title abstract description 45
- 239000007788 liquid Substances 0.000 title abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 69
- -1 phosphoric acid compound Chemical class 0.000 claims abstract description 67
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 29
- 125000000129 anionic group Chemical group 0.000 claims abstract description 29
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 29
- 238000009826 distribution Methods 0.000 claims abstract description 9
- 238000000790 scattering method Methods 0.000 claims abstract description 6
- 230000001186 cumulative effect Effects 0.000 claims abstract description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 238000010333 wet classification Methods 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 5
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 4
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 claims description 3
- 238000007561 laser diffraction method Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 abstract description 31
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 4
- 235000011007 phosphoric acid Nutrition 0.000 description 26
- 238000000034 method Methods 0.000 description 21
- 150000002910 rare earth metals Chemical class 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 10
- 239000011324 bead Substances 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000010304 firing Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000002612 dispersion medium Substances 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000003082 abrasive agent Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 239000008234 soft water Substances 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- GIXFALHDORQSOQ-UHFFFAOYSA-N 2,4,6,8-tetrahydroxy-1,3,5,7,2$l^{5},4$l^{5},6$l^{5},8$l^{5}-tetraoxatetraphosphocane 2,4,6,8-tetraoxide Chemical compound OP1(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)O1 GIXFALHDORQSOQ-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 229940120146 EDTMP Drugs 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 239000006061 abrasive grain Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 description 1
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- 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
-
- 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
- C09K3/1409—Abrasive particles per se
Abstract
The invention provides a cerium-based polishing material slurry stock solution having excellent polishing performance on glass materials and excellent productivity, a method for producing the same, and a polishing liquid. The cerium-based abrasive slurry stock solution of the present invention contains mixed rare earth oxide particles and water, wherein the cerium-based abrasive slurry stock solution contains an anionic water-soluble polymer and a phosphoric acid compound, the content (TREO) of all rare earth elements in terms of oxide is 10.0 to 40.0% by mass, the content in terms of cerium oxide in the above is 50.0% by mass or more, the content of the anionic water-soluble polymer is 1.5 to 10.0 parts by mass relative to the 100 parts by mass, and the particle diameter (50) of the slurry particles at 50% cumulative volume in the particle size distribution obtained by a laser diffraction scattering method is 0.10 to 0.35 [ mu ] m.
Description
Technical Field
The present invention relates to a cerium-based polishing material slurry stock solution used for polishing glass materials used for glass substrates such as liquid crystal panels, hard disks, filters for specific frequency cut-off, and glass substrates for optical lenses, a method for producing the same, and a polishing liquid.
Background
Glass materials are used for various purposes, and depending on the purpose, surface polishing may be necessary. In particular, glass materials used for glass substrates such as liquid crystal panels, hard disks, filters for specific frequency cut-off, and glass substrates for optical lenses are required to have high smoothness and to perform surface polishing with high efficiency.
In the surface polishing of glass materials requiring such excellent polishing performance, for example, cerium-based polishing materials as described in patent document 1 or patent document 2 are often used.
Further, with the development of the demand for higher precision of the polished surface of the glass material, there is an increasing demand for a cerium-based polishing material slurry (polishing liquid) having finer particles in order to reduce the surface roughness of the glass material.
[ Prior Art literature ]
[ patent literature ]
[ patent document 1] International publication No. 2019/049932
[ patent document 2] Japanese patent application laid-open No. 2019-208029
Disclosure of Invention
[ problem to be solved by the invention ]
However, in the cerium-based polishing material slurry, when particles in the slurry are thinned, it is difficult to maintain the polishing rate and the polishing force for smoothing, and there is a possibility that the polishing performance for the glass material may be lowered. In addition, there is also a problem that productivity of the slurry stock solution of the cerium-based abrasive is lowered, and production cost of the slurry stock solution is increased.
Therefore, there is a need for a cerium-based abrasive slurry stock solution that can maintain the polishing rate and the polishing force of the glass material at a high level, has suppressed manufacturing costs, and has excellent productivity
The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a cerium-based polishing material slurry stock solution having excellent polishing performance for glass materials and excellent productivity, a method for producing the same, and a polishing liquid.
[ means for solving the problems ]
The present invention has been completed based on the following findings: in a cerium-based abrasive slurry using mixed rare earth oxide particles as abrasive grains, a specific amount of an anionic water-soluble polymer and a phosphoric acid compound are used in combination to obtain good polishing performance, and a stock solution of the cerium-based abrasive slurry (polishing liquid) having good polishing performance can be produced with high productivity.
Namely, the present invention provides the following schemes [1] to [8].
[1]A cerium-based abrasive slurry stock solution containing mixed rare earth oxide particles and water, wherein the cerium-based abrasive slurry stock solution contains an anionic water-soluble polymer and a phosphoric acid compound, the content (TREO) of all rare earth elements in terms of oxide is 10.0 to 40.0 mass%, the content (TREO) of the TREO in terms of oxide of cerium is 50.0 mass% or more, the content of the anionic water-soluble polymer is 1.5 to 10.0 mass parts relative to 100 mass parts of the TREO, and the particle diameter (D) of the slurry particles at 50% of the cumulative volume in a particle size distribution obtained by a laser diffraction scattering method 50 ) 0.10 to 0.35 mu m.
[2] The cerium-based abrasive slurry stock solution according to the above [1], wherein the fluorine atom content is 0.1 mass% or less.
[3] The slurry stock solution of cerium-based abrasive material according to the above [1] or [2], wherein the anionic water-soluble polymer is a polycarboxylic acid-based polymer.
[4] The slurry stock solution of cerium-based abrasive material according to the above [3], wherein the polycarboxylic acid-based polymer is at least 1 selected from the group consisting of acrylic acid, copolymers of acrylic acid and maleic acid, and alkali metal salts thereof.
[5] The cerium-based abrasive slurry stock solution according to any one of [1] to [4], wherein the phosphate compound is at least 1 selected from the group consisting of tripolyphosphate, pyrophosphoric acid, hexametaphosphate, and alkali metal salts thereof.
[6] The cerium-based abrasive slurry stock solution according to any one of [1] to [5], wherein the content of the phosphoric acid compound is 0.5 to 10.0 parts by mass based on 100 parts by mass of the TREO.
[7] A process for producing a cerium-based abrasive slurry stock solution according to any one of the above [1] to [6], which comprises a step of wet-pulverizing a mixed raw material containing the mixed rare earth oxide particles, water and the anionic water-soluble polymer to obtain a pulverized slurry, a step of wet-classifying the pulverized slurry to obtain a classified slurry, and a step of adding water and the phosphoric acid compound to the classified slurry and mixing the obtained classified slurry to obtain a cerium-based abrasive slurry stock solution.
[8] A polishing slurry obtained by diluting the cerium-based polishing slurry stock solution according to any one of [1] to [6] with water, wherein TREO is 0.1 to 10.0% by mass.
[ Effect of the invention ]
The cerium-based polishing material slurry stock solution of the present invention is excellent in productivity and can provide a polishing liquid having excellent polishing performance for glass materials.
In addition, according to the production method of the present invention, the cerium-based abrasive slurry stock solution can be produced well.
Therefore, the polishing liquid obtained by using the cerium-based polishing material slurry stock solution of the present invention can suppress the manufacturing cost while maintaining good polishing performance for glass materials.
Detailed Description
The embodiments of the cerium-based polishing slurry stock solution, the method for producing the same, and the polishing liquid obtained by using the cerium-based polishing slurry stock solution according to the present invention will be described in detail below.
[ stock solution of cerium-based abrasive slurry ]
The cerium-based abrasive slurry stock solution of the present embodiment is a slurry containing mixed rare earth oxide particles and water, and contains an anionic water-soluble polymer and a phosphoric acid compound. The content of the entire rare earth elements in the cerium-based abrasive slurry stock solution (TREO; total Rare Earth Oxides for short) is 10.0 to 40.0 mass% in terms of oxide, and the content of the cerium oxide (CeO) in the TREO is 10.0 to 40 mass% in terms of oxide 2 ) The converted content (hereinafter referred to as "Ce amount") is 50.0 mass% or more. The content of the anionic water-soluble polymer in the slurry is 1.5 to 10.0 parts by mass based on 100 parts by mass of the TREO. The cerium-based abrasive slurry stock solution is characterized in that the slurry particles have a particle size (D 50 ) 0.10 to0.35μm。
The term "cerium-based polishing material" in the present invention refers to a polishing material having a content of 50.0 mass% or more in terms of cerium oxide relative to TREO in the polishing material.
(Mixed rare earth oxide particles)
The term "mixed" of mixed rare earth oxides of the mixed rare earth oxide particles in this embodiment means that a plurality of rare earth elements are contained. The mixed rare earth oxide may contain a rare earth element other than Ce. Examples of the rare earth element include La, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb.
The TREO in the mixed rare earth oxide particles is preferably 80.0 mass% or more, more preferably 85.0 mass% or more, and still more preferably 90.0 to 100 mass% from the viewpoint of improving the productivity of the cerium-based abrasive slurry stock solution suitable for the surface polishing process of a glass material.
From the same viewpoint, among all the rare earth elements contained, ce is the main component, and the Ce amount (Ce amount/TREO) in TREO is preferably 50.0 mass% or more, more preferably 60.0 mass% or more, and still more preferably 65.0 to 100 mass%.
The TREO can be measured by oxalate precipitation, firing, and gravimetric method, and specifically, can be measured by the method described in examples below.
The content of each rare earth element such as Ce can be measured by a machine analysis such as high-frequency Inductively Coupled Plasma (ICP) analysis or fluorescent X-ray analysis, and in the present embodiment, the measurement value by ICP emission spectrometry (ICP-AES) is used as the oxide conversion amount by using the value obtained by converting each rare earth element into an oxide.
The mixed rare earth oxide can be obtained by, for example, firing a mixed light rare earth compound such as a mixed rare earth carbonate, a mixed rare earth monocarbonate, a mixed rare earth oxalate, or a mixed rare earth hydroxide. The term "mixing" as used herein is synonymous with "mixing" of the above-mentioned mixed rare earth oxides.
The mixed light rare earth compound is preferably an impurity component of a non-rare earth component such as an alkali metal, an alkaline earth metal, or a radioactive substance, and the content of a medium-heavy rare earth is reduced, and more preferably Ce is a main component. For example, a mixed rare earth carbonate having a TREO of 45 to 55 mass% and a Ce amount (Ce amount/TREO) of about 65 mass% is suitably used as the mixed light rare earth compound.
In the present specification, the medium-heavy rare earth means a rare earth element having a larger atomic number than Pm, and the rare earth elements other than the medium-heavy rare earth are referred to as light rare earth.
The method for preparing the mixed light rare earth compound is not particularly limited. The mixed light rare earth compound can be obtained, for example, by separating and reducing the impurity components other than rare earth elements and the content of medium and heavy rare earth in the rare earth element-containing ore by chemical treatment.
For example, rare earth ore concentrate obtained from a raw material ore such as natural monazite or bastnaesite containing a large amount of Ce is suitably used as the rare earth element-containing ore.
In the preparation of the mixed light rare earth compound, sulfuric acid calcination is a general method as a chemical treatment method for reducing the content of impurity components. The method of roasting sulfuric acid, in which the crushed raw ore is roasted together with sulfuric acid to produce a sulfate (rare earth sulfate), the sulfate is dissolved in water to form a rare earth sulfate solution, and impurity components of insoluble matters are removed by filtration or the like. The content of the impurity component in the mixed light rare earth compound is preferably reduced to 1.0 mass% or less.
In addition, as a chemical treatment method for reducing the content of the medium and heavy rare earth, for example, a method may be carried out in which a carbonate is added to the sulfuric acid rare earth solution obtained by roasting the sulfuric acid to obtain a crude rare earth carbonate, hydrochloric acid is added thereto to obtain a mixed rare earth chloride aqueous solution, and solvent extraction is carried out using an organic solvent. In the solvent extraction, the content of Ce and other light rare earths can be adjusted as required by a known method of adjusting the extraction degree or using additives and the like. The content of the medium-heavy rare earth in the mixed light rare earth compound is preferably reduced to 1.0 mass% or less.
The mixed light rare earth compound may contain a mixed rare earth carbonate which is a carbonate using sodium carbonate or ammonium bicarbonate or the like and/or a mixed rare earth oxalate which is an oxalate using oxalic acid or the like after the treatment for reducing the content of the impurity components.
The firing temperature at which the mixed light rare earth compound is fired to obtain the mixed rare earth oxide is appropriately adjusted depending on the composition of the mixed light rare earth compound, and is preferably 600 to 1200 ℃, more preferably 700 to 1150 ℃, and still more preferably 800 to 1100 ℃. The firing time is preferably 0.5 to 48 hours, more preferably 1 to 40 hours, and still more preferably 1.5 to 30 hours. The firing environment is preferably an atmospheric environment.
The mixed rare earth oxide obtained by firing is D measured by a laser diffraction scattering method 50 Particles having a particle diameter of 20 μm or less, more preferably 3 to 18 μm, still more preferably 5 to 15 μm are preferred. After firing, the particles may be mechanically pulverized to adjust the particle size as described above.
The mixed rare earth oxide particles are commercially available, and commercially available products can be used as the raw material. In the commercially available mixed rare earth oxide particles, there may be cases where mixed rare earth carbonate, mixed rare earth monooxide carbonate, mixed rare earth oxalate, or the like remains as a raw material for production thereof.
The cerium-based abrasive slurry stock solution of the present embodiment preferably has a fluorine atom content of 0.1 mass% or less, more preferably 0.05 mass% or less, and still more preferably 0.01 mass% or less, from the viewpoint of reducing the load on the environment. If the fluorine atom content is 0.1 mass% or less, the cerium-based abrasive slurry stock solution may be said to contain substantially no fluorine atoms.
The fluorine atoms that can be contained in the slurry stock solution of the cerium-based abrasive material of the present embodiment are considered to originate from only the mixed rare earth oxide particles, and the fluorine atoms originating from the anionic water-soluble polymer, the phosphoric acid compound and water are considered to be 0 mass%. Therefore, the fluorine atom content in the slurry stock solution of the cerium-based abrasive is estimated from the measured value of the fluorine atom content in the mixed rare earth oxide particles used for the production of the slurry.
The fluorine atom content in the mixed rare earth oxide particles can be measured by an ion electrode method by alkali-melting the mixed rare earth oxide particles to thereby solubilize the mixed rare earth oxide particles in water.
(TREO)
The TREO in the cerium-based abrasive slurry stock solution of the present embodiment is derived from mixed rare earth oxide particles, and is preferably 10.0 to 40.0 mass%, more preferably 15.0 to 35.0 mass%, and still more preferably 20.0 to 30.0 mass% in terms of productivity, polishing performance, and the like.
(Water)
The cerium-based abrasive slurry stock solution is a slurry containing water, and water is used as a dispersion medium. In view of dispersibility of slurry particles, soft water or pure water is preferably used as water.
As the dispersion medium, an aqueous dispersion medium other than water (for example, a water-soluble organic solvent such as alcohol, acetone, tetrahydrofuran, etc.) may be contained within a range that does not impair the effects of the present invention, and usually, only water is preferable.
The water content in the slurry stock solution of the cerium-based polishing material is adjusted to 40.0 mass% or less of TREO as appropriate in accordance with the desired polishing process of the glass material. The content of water in the cerium-based abrasive slurry stock solution is preferably 60% by mass or more, more preferably 65.0 to 90.0% by mass, and still more preferably 70.0 to 85.0% by mass, from the viewpoints of uniform dispersibility, viscosity, and the like of components other than water in the cerium-based abrasive slurry stock solution.
(anionic Water-soluble Polymer)
The anionic water-soluble polymer according to the present embodiment is an ionic environment in which negative charges are formed by dissociation in ion-exchanged water, and is dissolved in 100g of water at 25℃to 10g or more.
The cerium-based polishing slurry stock solution contains 1.5 to 10.0 parts by mass, more preferably 2.0 to 8.0 parts by mass, and still more preferably 2.2 to 5.0 parts by mass of the anionic water-soluble polymer per 100 parts by mass of the TREO.
The content of the anionic water-soluble polymer in the cerium-based abrasive slurry stock solution is 1.5 parts by mass or more relative to 100 parts by mass of the TREO, so that a homogeneous slurry can be easily produced, and productivity of the cerium-based abrasive slurry stock solution can be improved. When the content is 10.0 parts by mass or less, the slurry can be easily maintained in homogeneity, and a cerium-based abrasive slurry stock solution excellent in productivity can be easily obtained.
The anionic water-soluble polymer is preferably a polycarboxylic acid polymer or a polysulfonic acid polymer, and among them, a polycarboxylic acid polymer is particularly preferred from the viewpoint of easy dispersion of mixed rare earth oxide particles in water to obtain a homogeneous slurry. Of these, 1 kind may be used alone, or 2 or more kinds may be used in combination. The polycarboxylic acid polymer in the present embodiment is a polymer in which the amount of the unsaturated carboxylic acid-derived monomer is 60 mol% or more based on 100 mol% of the constituent monomer units.
Examples of the polycarboxylic acid polymer include (meth) acrylic acid copolymers such as poly (meth) acrylic acid, polyhydroxyl (meth) acrylic acid, and copolymers of (meth) acrylic acid and maleic acid; copolymers of olefins with maleic acid, copolymers of alkylene oxide adducts of maleic acid with ethylene oxide or propylene oxide of allyl alcohol, copolymers of allylsulfonic acid with maleic acid, and the like, or alkali metal salts of sodium salts, potassium salts, and the like thereof. Among them, polyacrylic acid, copolymers of acrylic acid and maleic acid, or alkali metal salts thereof are particularly preferable; more preferably a copolymer of acrylic acid and maleic acid or an alkali metal salt thereof.
(phosphoric acid compound)
The cerium-based abrasive slurry stock solution contains the anionic water-soluble polymer and a phosphoric acid compound. By using the phosphoric acid compound together with the anionic water-soluble polymer, the polishing liquid obtained by diluting the cerium-based polishing material slurry stock solution can maintain good polishing performance on a glass material.
The content of the phosphoric acid compound in the cerium-based polishing material slurry stock solution is preferably 0.5 to 10.0 parts by mass, more preferably 0.8 to 8.0 parts by mass, and still more preferably 1.0 to 5.0 parts by mass, per 100 parts by mass of the tremo, in order to maintain good polishing performance of the polishing liquid with respect to a glass material.
Examples of the phosphoric acid compound include inorganic phosphoric acids such as tripolyphosphoric acid, pyrophosphoric acid, tetrametaphosphoric acid, hexametaphosphoric acid, orthophosphoric acid, and phosphorous acid; organic phosphonic acids such as aminotrimethylene phosphonic acid, 1-hydroxyethylidene-1, 1-diphosphonic acid, ethylenediamine tetramethylene phosphonic acid, diethylenetriamine pentamethylene phosphonic acid, and the like; or alkali metal salts such as sodium salts and potassium salts thereof. They may be used singly or in combination of 1 or more than 2. Particularly preferred among them are tripolyphosphoric acid, pyrophosphoric acid, hexametaphosphoric acid or their alkali metal salts.
The cerium-based polishing slurry stock solution may be optionally added with additives such as a pH adjuster, a defoaming agent, and a rust inhibitor, as long as the polishing performance of the polishing slurry prepared by using the slurry stock solution is not impaired.
(D 50 )
The particle diameter D of slurry particles in the cerium-based abrasive slurry stock solution 50 0.10 to 0.35. Mu.m, preferably 0.15 to 0.30. Mu.m, more preferably 0.17 to 0.28. Mu.m.
The aforementioned D 50 The particle size distribution is obtained from the particle size distribution measured by the laser diffraction scattering method, and specifically, the particle size distribution is measured by a Microtrac particle size distribution meter described in the following examples.
The aforementioned D 50 If the particle diameter is 0.10 μm or more, a cerium-based polishing slurry stock solution can be produced with good productivity. Further, by making the aforementioned D 50 When the polishing surface is 0.35 μm or less, the polishing surface can be smoothed well by using the polishing liquid prepared from the cerium-based polishing material slurry stock solution, and excellent polishing performance can be easily obtained.
[ method for producing cerium-based polishing slurry stock solution ]
The cerium-based abrasive slurry stock solution of the present embodiment can be suitably produced by the production method of the present embodiment including the steps of: wet-pulverizing a mixed raw material containing mixed rare earth oxide particles, water and the anionic water-soluble polymer to obtain a pulverized slurry (1); wet classifying the crushed slurry to obtain classified slurry; and (3) adding water and the phosphoric acid compound to the classification slurry and mixing them to obtain a cerium-based abrasive slurry stock solution.
The steps are described in order below.
(step (1))
In the step (1), a mixed raw material containing mixed rare earth oxide particles, water and the anionic water-soluble polymer is wet-pulverized to obtain a pulverized slurry.
The above mixed raw materials can be wet-pulverized with water as a dispersion medium to efficiently produce a homogeneous pulverized slurry while suppressing thickening of the slurry.
The wet grinding is preferably performed by a media mill (media mill) such as a ball mill or a bead mill, from the viewpoint of obtaining a homogeneous grinding slurry. As the dispersion medium, a water-soluble organic solvent such as alcohol may be mixed in addition to water for use in view of improving dispersibility.
In wet grinding using a bead mill, for example, even if the mixed rare earth oxide particles have a high concentration of 50 mass% or more, the mixed raw materials can be ground into a ground slurry without impeding safe and stable grinding due to an increase in the internal pressure and temperature of the mill, and thus the productivity can be said to be excellent.
The wet pulverization is performed to increase D of slurry particles in the subsequent step (2) 50 In terms of the yield of the classified slurry of 0.10 to 0.35. Mu.m, for example, in the case of using a bead mill, it is preferable to use zirconia beads (bead diameter of 0.1 to 0.5 mm) and to obtain a crushed slurry by crushing at a mill peripheral speed of 5 to 10 m/s.
(step (2))
In the step (2), the crushed slurry obtained in the step (1) is wet-classified to obtain classified slurry.
From the viewpoint of obtaining a polishing liquid exhibiting good polishing performance for glass materials, as described above, the wet classification is performed by using D of slurry particles in a cerium-based polishing material slurry stock solution 50 Is 0.10 to 0.35 mu m. Further, the slurry particles in the classification slurrySon D 50 Can be regarded as D which is the same as the slurry particles in the slurry stock solution of the cerium-based abrasive material 50 Approximately equal.
In the wet classification, it is preferable to remove at least large particles having a particle diameter exceeding 5.0. Mu.m.
The wet classification method is not particularly limited, and may be performed using, for example, a liquid cyclone, a centrifugal settler, a slurry classifier, or the like.
(step (3))
In the step (3), water and the phosphoric acid compound are added to the classified slurry obtained in the step (2) and mixed to obtain the cerium-based abrasive slurry stock solution.
The cerium-based abrasive slurry stock solution of the present embodiment uses the anionic water-soluble polymer and the phosphoric acid compound in combination, but the phosphoric acid compound tends to significantly thicken when the slurry is prepared by mixing the slurry stock solution with the anionic water-soluble polymer at the same time or before the addition of the anionic water-soluble polymer. In this embodiment, therefore, the phosphoric acid compound is added to the classification slurry at a later stage to produce a cerium-based polishing material slurry stock solution.
In view of suppressing the thickening accompanying the addition of the phosphoric acid compound, water is also added to the classification slurry and mixed together with the phosphoric acid compound. The phosphoric acid compound may be added by dissolving it in water.
The method of mixing is not particularly limited as long as the phosphoric acid compound can be stirred and mixed to a degree that the phosphoric acid compound can be dissolved in water. For example, the mixing may be performed by a stirrer such as a high-speed shearing machine, or may be performed by a medium mill such as a ball mill or a bead mill.
The cerium-based polishing slurry stock solution obtained in the above manner may be prepared by adding additives such as a pH adjuster, a defoaming agent, and a rust inhibitor as needed, within a range that does not interfere with the polishing performance of the polishing slurry prepared by using the slurry stock solution.
[ polishing liquid ]
The cerium-based polishing slurry stock solution is diluted with water to prepare a polishing slurry according to the polishing apparatus used, the polishing performance required, and the like. The above-mentioned preparation liquid is preferably used in the range of 0.1 to 10.0 mass%, more preferably 0.5 to 9.0 mass%, and even more preferably 1.0 to 8.0 mass% from the viewpoint of cost, in view of exhibiting good polishing performance on glass materials.
In addition, the polishing liquid may be prepared by adding additives such as a pH adjuster, a defoaming agent, and a rust inhibitor, as necessary, in a range that does not interfere with the polishing performance of the polishing liquid, in consideration of the specifications of the polishing object or the polishing apparatus.
The polishing method using the polishing liquid is not particularly limited, and a method using a known polishing apparatus or the like can be applied. The polishing liquid can be used by a known method when finishing polishing such as mirror polishing of a glass material with a single-side polishing machine or a double-side polishing machine.
The cerium-based polishing material slurry stock solution is excellent in productivity, and the polishing liquid prepared by the polishing material slurry stock solution has excellent polishing performance on glass materials, and is particularly suitable for finishing polishing various glass materials and glass products such as glass substrates for magnetic disks, glass substrates for liquid crystal displays, glass substrates for color filters or photomasks, glass substrates for optical lenses, and the like.
Examples
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples.
In the following examples and comparative examples, the TREO, the content in terms of oxide of the medium and heavy rare earth, the content in terms of oxide of Ce (Ce amount/TREO) relative to the TREO, and the fluorine atom content were obtained as follows.
[TREO]
Ammonia is added to a solution in which a measurement sample is acid-dissolved. The precipitate thus produced is filtered, washed to remove alkali metal, and then subjected to acid dissolution again. Oxalic acid was added to the solution, and the resultant precipitate was calcined in the atmosphere to obtain TREO by a weight method.
[ content in terms of oxide of medium-heavy rare earth ]
The amount of each rare earth element was measured by the ICP-AES method by acid-dissolving the measurement sample, and the amount was obtained by summing up the values obtained by converting the medium-heavy rare earth element into an oxide.
[ Ce amount/TREO ]
The measurement sample was acid-dissolved, and the Ce amount measured by the ICP-AES method was converted to an oxide, and the value was calculated relative to the value of TREO.
[ fluorine atom content ]
The measurement sample (mixed rare earth oxide particles) was subjected to alkali fusion, extraction with warm water, and measurement was performed by a fluorimeter (horiba corporation; ion electrode method). The anionic water-soluble polymer, the phosphoric acid compound, and water were regarded as containing no fluorine atoms, and the fluorine atom content in the polishing slurry stock solution was estimated from the fluorine atom content in the mixed rare earth oxide particles used in the production of the cerium-based polishing slurry stock solution.
[ production of cerium-based polishing slurry stock solution ]
Example 1
A mixed light rare earth compound having an adjusted content of rare earth elements is obtained by treating a rare earth concentrate (ore) containing 47.0 mass% TREO and 2.0 mass% TREO in terms of oxide by a sulfuric acid roasting method and a solvent extraction method, and reducing the content of impurities other than rare earth elements to 1.0 mass% or less and the content of medium and heavy rare earth elements to 1.0 mass% or less in terms of oxide. The mixed light rare earth compound was carbonated with ammonium bicarbonate to obtain a mixed rare earth carbonate, and then the mixed rare earth carbonate was calcined in an electric furnace at 900 ℃ for 10 hours in the atmosphere to obtain mixed rare earth oxide particles (D 50 :10 μm). In the mixed rare earth oxide particles, TREO is 97.0 mass% and the fluorine atom content is 0 mass%.
To 5000g of the mixed rare earth oxide particles were added soft water 3475g and a sodium salt ("POIZ (registered trademark) 521", manufactured by Kagaku corporation, an aqueous solution having a solid content of 40% by mass (the solid content is regarded as a polymer component); "AA-MA" in Table 1), which was added in an amount of 4.1 parts by mass (in terms of solid content) based on 100 parts by mass of TREO in the mixed rare earth oxide particles (the mixed rare earth oxide particle concentration was 55.7% by mass), and the mixture was subjected to a grinding treatment for 3 hours by a bead mill (beads: zirconium oxide, diameter: 0.3mm; mill peripheral speed: 8 m/s).
The crushed slurry was wet-classified to remove large particles (particle size exceeding 5.0 μm) and obtain a classified slurry. In the above-mentioned classified slurry, a phosphoric acid compound (sodium tripolyphosphate) was dissolved in soft water, and the mixture was added in an amount of 4.1 parts by mass based on 100 parts by mass of the TREO in the mixed rare earth oxide particles, followed by stirring and mixing, to prepare a cerium-based abrasive slurry stock solution having a TREO content of 23.1% by mass.
Examples 2 to 10 and comparative examples 1 to 5
A cerium-based abrasive slurry stock solution was produced in the same manner as in example 1, with the following raw material blend compositions shown in table 1.
The "AA" of the anionic water-soluble polymer in table 1 is a sodium salt of polyacrylic acid ("POIZ (registered trademark) 530", manufactured by huawang corporation, a 40 mass% aqueous solution of solid content concentration (the solid content is regarded as a polymer component)). Further, the "-" sign indicates that no addition was made.
[ evaluation measurement ]
The cerium-based abrasive slurry stock solutions produced in the above examples and comparative examples were subjected to the following evaluation measurements. Further, polishing performance was evaluated by using a polishing liquid prepared by diluting the cerium-based polishing material slurry stock solution with pure water.
The evaluation results are summarized in table 1 below.
[D 50]
The particle size distribution of the slurry particles was measured by a Microtrac particle size distribution meter "MT3300II" (manufactured by Nikkin corporation) by a laser diffraction scattering method, and the particle diameter (D) at 50% of the cumulative volume was obtained 50 )。
[ productivity ]
In the production of a cerium-based abrasive slurry stock solution, the following evaluation in the step of obtaining a crushed slurry is regarded as an evaluation of productivity because the production performance is greatly affected by the greatest workload in preparing the crushed slurry.
The upper limit concentration of mixed rare earth oxide particles in the crushed slurry was obtained without increasing the internal pressure and temperature of the bead mill (the internal pressure was 0.3MPa or less and the temperature was 55 ℃ or less), and the evaluation was performed based on the upper limit concentration by the following evaluation criteria.
(evaluation criterion)
A: concentration of 55 mass% or more
B: the concentration is 50% by mass or more and less than 55% by mass
C: the concentration is 40% by mass or more and less than 50% by mass
D: the concentration is less than 40 mass percent
The cases of A and B were evaluated, and it could be said that productivity was excellent. On the other hand, the cases of C and D were evaluated, and it was determined that productivity was poor.
[ polishing Property ]
The cerium-based polishing slurry stock solution was diluted with pure water to prepare a polishing slurry having a TREO of 5.0% by mass. Using this polishing liquid, a polishing test was performed under the following polishing conditions with a single-sided polishing machine, and the polishing rate and surface roughness (arithmetic average roughness Ra) were measured as follows.
The polishing rate was obtained by measuring the thickness of each sample before and after polishing by a micrometer for 4 parts of each 1 sample to be polished, and obtaining an arithmetic average value.
The surface roughness (Ra) was obtained by measuring the polished surface of the sample after 120 minutes polishing with a stylus profiler (P-12; manufactured by KLA-Tencor).
< milling Condition >
Grinding an object sample: commercially available blue plate glass (50 mm. Times.50 mm. Times.1.10 mm in thickness, 25cm in polishing area) 2 )
Polishing pad: suede pad
Lower platform rotation number: 260rpm
Pressure at grinding: 80g/cm 2
As is clear from Table 1, it was found that the cerium-based abrasive slurry stock solutions (examples 1 to 10) having specific particle diameters, which were produced by using specific amounts of the anionic water-soluble polymer and the phosphoric acid compound in combination, were excellent in productivity. Further, it was observed that the polishing liquid obtained by diluting the cerium-based polishing material slurry stock solution was able to polish with good surface roughness (Ra) (working accuracy) without decreasing the polishing rate even when the polishing time elapsed for 120 minutes, while maintaining the polishing force.
From this, it can be said that the cerium-based polishing slurry stock solution of the present embodiment can provide a polishing slurry exhibiting excellent polishing performance for glass materials while improving productivity.
Claims (4)
1. A cerium-based abrasive slurry stock solution containing mixed rare earth oxide particles and water,
the stock solution of the cerium-based abrasive slurry contains an anionic water-soluble polymer and a phosphoric acid compound,
the TREO, which is the oxide-converted content of all rare earth elements, is 10.0 to 40.0 mass%, and the oxide-converted content of cerium in the TREO is 50.0 mass% or more,
the anionic water-soluble polymer is contained in an amount of 1.5 to 10.0 parts by mass per 100 parts by mass of the TREO,
particle diameter (D) of slurry particles at 50% of cumulative volume in particle size distribution obtained by laser diffraction/scattering method 50 ) 0.10-0.35 mu m,
the anionic water-soluble polymer is 1 or more selected from the group consisting of copolymers of acrylic acid and maleic acid and alkali metal salts thereof,
the phosphoric acid compound is at least 1 selected from the group consisting of tripolyphosphoric acid, pyrophosphoric acid, hexametaphosphoric acid, and alkali metal salts thereof,
the content of the phosphoric acid compound is 0.5 to 10.0 parts by mass per 100 parts by mass of the TREO.
2. The cerium-based abrasive slurry stock solution according to claim 1, wherein the fluorine atom content is 0.1 mass% or less.
3. A method for producing the cerium-based abrasive slurry stock solution according to claim 1 or 2, comprising the steps of:
a step of wet-pulverizing a mixed raw material containing the mixed rare earth oxide particles, water and the anionic water-soluble polymer to obtain a pulverized slurry,
wet classifying the crushed slurry to obtain classified slurry,
And adding water and the phosphoric acid compound to the classification slurry and mixing the mixture to obtain the cerium-based abrasive slurry stock solution.
4. A polishing slurry obtained by diluting the cerium-based polishing slurry stock solution according to claim 1 or 2 with water, wherein the TREO in the polishing slurry is 0.1 to 10.0% by mass.
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| PCT/JP2021/012102 WO2021220672A1 (en) | 2020-04-27 | 2021-03-24 | Cerium-based polishing slurry raw material solution, method for producing same and polishing solution |
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| JPWO2006025308A1 (en) * | 2004-08-31 | 2008-05-08 | 松下電器産業株式会社 | Content purchase processing terminal, method thereof, and program |
| KR100864996B1 (en) * | 2004-09-28 | 2008-10-23 | 히다치 가세고교 가부시끼가이샤 | Cmp polishing compound and method for polishing substrate |
| TWI662116B (en) | 2014-05-30 | 2019-06-11 | 日商日立化成股份有限公司 | CMP polishing liquid, CMP polishing liquid set, and polishing method |
| WO2017051029A1 (en) * | 2015-09-25 | 2017-03-30 | Addifab Aps | Additive manufacturing device and system, modular build platform and build platform unit |
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| JP2005353681A (en) * | 2004-06-08 | 2005-12-22 | Hitachi Chem Co Ltd | Cmp abrasive for semiconductor insulation film and its manufacturing method, and method of polishing substrate |
| JP2008001907A (en) * | 2007-07-26 | 2008-01-10 | Mitsui Mining & Smelting Co Ltd | Cerium-based abrasive slurry and method for producing cerium-based abrasive slurry |
| CN102473621A (en) * | 2009-12-10 | 2012-05-23 | 日立化成工业株式会社 | Cmp polishing liquid, method of polishing substrate, and electronic component |
| JP2012038361A (en) * | 2010-08-03 | 2012-02-23 | Showa Denko Kk | Cerium oxide-based polishing agent and method for manufacturing hard disk substrate made of glass |
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| JPWO2021220672A1 (en) | 2021-11-04 |
| JP7400956B2 (en) | 2023-12-19 |
| WO2021220672A1 (en) | 2021-11-04 |
| TW202142669A (en) | 2021-11-16 |
| CN115461427A (en) | 2022-12-09 |
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