TW201917191A - Manufacturing method for starting material for cerium-based abrasive agent, and manufacturing method for cerium-based abrasive agent - Google Patents
Manufacturing method for starting material for cerium-based abrasive agent, and manufacturing method for cerium-based abrasive agent Download PDFInfo
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- TW201917191A TW201917191A TW107131696A TW107131696A TW201917191A TW 201917191 A TW201917191 A TW 201917191A TW 107131696 A TW107131696 A TW 107131696A TW 107131696 A TW107131696 A TW 107131696A TW 201917191 A TW201917191 A TW 201917191A
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- Prior art keywords
- cerium
- rare earth
- based abrasive
- mass
- raw material
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- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 141
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 74
- 239000003082 abrasive agent Substances 0.000 title claims abstract description 69
- 239000007858 starting material Substances 0.000 title abstract 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 95
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 51
- 238000010298 pulverizing process Methods 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 35
- 238000009826 distribution Methods 0.000 claims abstract description 14
- 230000001186 cumulative effect Effects 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims description 80
- -1 rare earth fluoride Chemical class 0.000 claims description 60
- 238000000034 method Methods 0.000 claims description 39
- 239000002002 slurry Substances 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000010304 firing Methods 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 15
- 150000002910 rare earth metals Chemical class 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 229910052779 Neodymium Inorganic materials 0.000 claims description 10
- 125000001153 fluoro group Chemical group F* 0.000 claims description 10
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 6
- 239000002612 dispersion medium Substances 0.000 claims description 5
- 238000001238 wet grinding Methods 0.000 claims 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000009837 dry grinding Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 49
- 238000005498 polishing Methods 0.000 description 34
- 239000011521 glass Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 239000002609 medium Substances 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000000691 measurement method Methods 0.000 description 6
- 239000011268 mixed slurry Substances 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 3
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 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
- 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 208000032544 Cicatrix Diseases 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
- 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
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 231100000241 scar Toxicity 0.000 description 2
- 230000037387 scars Effects 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241000703769 Culter Species 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002156 adsorbate 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- 239000000919 ceramic Substances 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
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000000892 gravimetry Methods 0.000 description 1
- 229940005740 hexametaphosphate Drugs 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000012857 radioactive material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- 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
- C01F17/241—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion containing two or more rare earth metals, e.g. NdPrO3 or LaNdPrO3
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
-
- 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
-
- 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
- C01F17/253—Halides
- C01F17/265—Fluorides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Food Science & Technology (AREA)
- Mechanical Engineering (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Crushing And Pulverization Processes (AREA)
Abstract
Description
本發明係關於在使用於液晶面板、硬碟、特定頻率截止用過濾器等之玻璃基板、光學透鏡用玻璃基板等之玻璃材的研磨中使用的鈰系研磨材之製造中所使用的原料之製造方法，及鈰系研磨材之製造方法。The present invention relates to raw materials used in the production of cerium-based abrasive materials used for polishing glass materials such as liquid crystal panels, hard disks, filters for specific frequency cutoffs, and the like, and glass substrates for optical lenses. Manufacturing method, and manufacturing method of cerium-based abrasives.
玻璃材使用於各種用途中，且依照該用途可能有必須表面研磨的情形。特別是使用於液晶面板、硬碟、特定頻率截止用過濾器等之玻璃基板、光學透鏡用玻璃基板等之玻璃材，尋求著在不產生研磨傷痕等之缺陷下，高精度且高效率的表面研磨。
在如此之玻璃材的表面研磨中，由於研磨效率優異，故多使用鈰系研磨材。Glass materials are used in various applications, and depending on the application, surface grinding may be necessary. In particular, glass materials used in glass substrates such as liquid crystal panels, hard disks, filters for specific frequency cutoffs, etc., and glass substrates for optical lenses are sought for high-precision and high-efficiency surfaces without causing defects such as abrasive scratches. Grind.
In such surface polishing of glass materials, cerium-based polishing materials are often used because of their excellent polishing efficiency.
鈰系研磨材，以往係藉由於混合氧化稀土原料中加入水進行濕式粉碎，之後依序經過乾燥、燒成、破碎及分級之各步驟來製造(例如，參照專利文獻1)。
[先前技術文獻]
[專利文獻]Cerium-based abrasives have conventionally been produced by adding water to a mixed rare earth oxide raw material to perform wet pulverization, and then sequentially through various steps of drying, firing, crushing, and classification (for example, see Patent Document 1).
[Prior technical literature]
[Patent Literature]
[專利文獻1] 日本特開2002-224949號公報[Patent Document 1] Japanese Patent Application Publication No. 2002-224949
[發明所欲解決之課題][Problems to be Solved by the Invention]
為了以低成本製造鈰系研磨材，期望以生產效率更高的方法製造。因此，在以往之如同上述之製造方法中，期望在混合原料及水進行濕式粉碎的步驟中，盡可能地提高經混合氧化稀土原料及水而成之漿體中固體成分濃度，進而可使接下來之乾燥步驟時間縮短化。In order to produce cerium-based abrasives at a low cost, it is desirable to produce them by a method with higher production efficiency. Therefore, in the conventional manufacturing method as described above, it is desirable to increase the solid content concentration in the slurry obtained by mixing the rare earth oxide raw material and water as much as possible in the step of wet pulverizing the mixed raw material and water. The time of the next drying step is shortened.
然而，若增加混合氧化稀土原料的進料量，且提高漿體中的固體成分濃度，則漿體的黏性變高，有變得難以藉由攪拌混合等使其均勻化的傾向。
因此，有著在濕式粉碎步驟中，難以使每1批次的混合氧化稀土原料之進料量增加，進而在將水分含量多之漿體進行乾燥的步驟中，亦無法使1批次中所得之乾燥品的量增加，且乾燥效率亦差等之課題。However, if the feed amount of the mixed rare earth oxide raw material is increased and the solid content concentration in the slurry is increased, the viscosity of the slurry becomes high, and it tends to become difficult to make it uniform by stirring and mixing.
Therefore, in the wet pulverization step, it is difficult to increase the feed amount of each batch of mixed rare earth oxide raw materials, and then in the step of drying the slurry with a large moisture content, it is impossible to obtain in one batch The amount of dried products increases, and the drying efficiency is also poor.
針對如同上述之課題，本發明者們針對使濕式粉碎步驟中之混合氧化稀土原料之進料量增加的方法進行反覆研究，發現對混合氧化稀土原料施以特定之處理是有效的。In response to the above-mentioned problems, the present inventors conducted repeated studies on the method of increasing the feed amount of the mixed rare earth oxide raw material in the wet pulverization step, and found that it is effective to apply a specific treatment to the mixed rare earth oxide raw material.
即，本發明之目的在於提供一種於鈰系研磨材之製造中，藉由使粉碎步驟中之每1批次的混合氧化稀土之進料量增加，而製造可使生產效率提升之鈰系研磨材用原料的方法，及鈰系研磨材之製造方法。
[解決課題之手段]That is, an object of the present invention is to provide a cerium-based grinding process that can increase production efficiency by increasing the amount of mixed rare earth oxide feed per batch in the grinding step. The method of raw materials for materials, and the method of manufacturing cerium-based abrasives.
[Means for solving problems]
本發明係基於發現在鈰系研磨材之製造中，藉由對混合氧化稀土原料施以乾式破碎處理，而可使濕式粉碎步驟中之混合氧化稀土的進料量增加，且使生產效率提升。The present invention is based on the discovery that in the manufacture of cerium-based abrasives, by applying dry crushing treatment to the mixed rare earth oxide raw material, the feed amount of the mixed rare earth oxide in the wet pulverization step can be increased and the production efficiency can be improved .
即，本發明係提供以下[1]~[13]者。
[1]一種鈰系研磨材用原料之製造方法，其特徵為藉由將混合氧化稀土進行乾式破碎處理的步驟得到由破碎品構成之鈰系研磨材用原料，
前述混合氧化稀土中，總稀土類元素之以氧化物換算的含量為80質量%以上，且鈰之以氧化物換算量計的含量相對於前述總稀土類元素之以氧化物換算量計的含量為50質量%以上，
前述破碎品係鬆裝密度超過0.60g/cm3
且1.50g/cm3
以下，且於體積分佈50%累積值的粒徑為2μm以上且20μm以下。
[2]如上述[1]中記載之系研磨材用原料之製造方法，其中前述破碎品之鬆裝密度為0.80g/cm3
以上。
[3]如上述[1]或[2]中記載的鈰系研磨劑用原料之製造方法，其中前述混合氧化稀土包含選自鑭、釹及鐠中之1種以上。
[4]一種鈰系研磨材之製造方法，其特徵為在鈰系研磨材之製造方法中，包含粉碎藉由如上述[1]~[3]中任一項記載之製造方法而得之鈰系研磨材用原料的步驟。
[5]如上述[4]中記載的鈰系研磨材之製造方法，其中在粉碎前述鈰系研磨材用原料之前，包含於前述鈰系研磨材用原料中添加氟化稀土的步驟。
[6]如上述[4]中記載的鈰系研磨材之製造方法，其中粉碎前述鈰系研磨材用原料的步驟為濕式粉碎步驟。
[7]如上述[6]中記載的鈰系研磨材之製造方法，其中藉由前述濕式粉碎步驟，得到包含前述鈰系研磨材用原料的漿體，前述鈰系研磨材用原料的漿體係以水作為分散介質，且固體成分濃度為55質量%以上。
[8]如上述[6]中記載的鈰系研磨材之製造方法，其中在前述濕式粉碎步驟之後，包含依序進行乾燥、燒成、破碎及分級的步驟。
[9]如上述[8]中記載的鈰系研磨劑之製造方法，其中在前述濕式粉碎步驟之後，以600~1200℃進行燒成。
[10]如上述[8]中記載的鈰系研磨劑之製造方法，其中在前述濕式粉碎步驟之後，進行燒成0.1~10小時。
[11]如上述[5]中記載的鈰系研磨劑之製造方法，其中前述氟化稀土中，總稀土類元素之以氧化物換算量計的含量為80質量%以上。
[12]如上述[5]中記載的鈰系研磨劑之製造方法，其中前述氟化稀土中之氟原子含量為10~30%。
[13]如上述[5]中記載的鈰系研磨劑之製造方法，其中以前述鈰系研磨材用原料與氟化稀土之合計100質量%中之氟化稀土的量成為1~40質量%之方式，添加前述氟化稀土。
[發明效果]That is, the present invention provides the following [1] to [13].
[1] A method for manufacturing a raw material for cerium-based abrasives, characterized in that a raw material for cerium-based abrasives composed of crushed products is obtained by the step of dry crushing a mixed rare earth oxide,
In the aforementioned mixed rare earth oxide, the content of oxides in terms of total rare earth elements is 80% by mass or more, and the content of cerium in terms of oxides is relative to the content of oxides in terms of total rare earths 50% by mass or more,
The bulk density of the aforementioned crushed line exceeds 0.60 g / cm 3 and 1.50 g / cm 3 or less, and the particle size at the cumulative value of 50% of the volume distribution is 2 μm or more and 20 μm or less.
[2] The method for producing raw materials for abrasives as described in [1] above, wherein the bulk density of the crushed product is 0.80 g / cm 3 or more.
[3] The method for producing a raw material for a cerium-based abrasive as described in the above [1] or [2], wherein the mixed rare earth oxide contains one or more kinds selected from lanthanum, neodymium, and gallium.
[4] A method for producing a cerium-based abrasive, characterized in that the method for producing a cerium-based abrasive includes crushing cerium obtained by the production method described in any one of the above [1] to [3] It is a step of grinding raw materials.
[5] The method for producing a cerium-based abrasive as described in [4] above, which includes the step of adding rare earth fluoride to the raw material for cerium-based abrasive before crushing the raw material for cerium-based abrasive.
[6] The method for producing a cerium-based abrasive as described in [4] above, wherein the step of pulverizing the raw material for the cerium-based abrasive is a wet pulverization step.
[7] The method for producing a cerium-based abrasive as described in [6] above, wherein a slurry including the raw material for the cerium-based abrasive is obtained by the wet pulverization step, and the slurry for the raw material for the cerium-based abrasive is obtained The system uses water as a dispersion medium, and the solid content concentration is 55% by mass or more.
[8] The method for producing a cerium-based abrasive as described in [6] above, wherein after the wet pulverization step, steps of drying, firing, crushing, and classifying are included in sequence.
[9] The method for producing a cerium-based abrasive as described in [8] above, wherein after the wet pulverization step, firing is performed at 600 to 1200 ° C.
[10] The method for producing a cerium-based abrasive as described in [8] above, wherein after the wet pulverization step, firing is performed for 0.1 to 10 hours.
[11] The method for producing a cerium-based abrasive as described in [5] above, wherein the content of the total rare earth element in terms of oxide in the fluorinated rare earth is 80% by mass or more.
[12] The method for producing a cerium-based abrasive as described in [5] above, wherein the content of fluorine atoms in the rare earth fluoride is 10 to 30%.
[13] The method for producing a cerium-based abrasive as described in [5] above, wherein the amount of rare earth fluoride in 100% by mass of the total amount of the raw material for cerium-based abrasive and the rare earth fluoride becomes 1 to 40% by mass In this way, the aforementioned rare earth fluoride is added.
[Inventive effect]
若依據本發明之鈰系研磨材用原料之製造方法，可提供可使鈰系研磨材之生產效率提升的原料。
又，若依據使用前述鈰系研磨材用原料的本發明之鈰系研磨材之製造方法，由於可使粉碎步驟中之每1批次的混合氧化稀土之進料量增加，故可使生產效率提升，進而謀求生產成本之低減化。According to the method for manufacturing raw materials for cerium-based abrasives of the present invention, raw materials that can improve the production efficiency of cerium-based abrasives can be provided.
In addition, according to the method of manufacturing the cerium-based abrasive material of the present invention using the raw material for cerium-based abrasive material, the feed amount of the mixed rare earth oxide per batch in the pulverization step can be increased, so that the production efficiency Improve, and then seek to reduce production costs.
以下，詳細說明本發明。
[鈰系研磨材用原料之製造方法]
本發明之鈰系研磨材用原料之製造方法，其特徵為藉由將總稀土類元素之以氧化物換算量計的含量(以下，亦稱為「TREO」(Total Rare Earth Oxide之簡寫))為80質量%以上，且鈰之以氧化物換算量計的含量相對於前述TREO為50質量%以上的混合氧化稀土進行乾式破碎處理之步驟，得到由鬆裝密度為超過0.60g/cm3
且1.50g/cm3
以下，且於體積分佈50%累積值的粒徑為2μm以上20μm以下之破碎品構成之鈰系研磨材用原料。
藉由將如此之混合氧化稀土進行乾式破碎處理，獲得可使鈰系研磨材之生產效率提升的鈰系研磨材用原料。
此外，本發明中所謂之TREO，可藉由草酸鹽沉澱、燒成及重量法來測定，具體而言，可藉由後述之實施例中記載之方法來測定。
又，稀土類元素之含量，可藉由高頻感應耦合電漿(ICP)分析或螢光X射線分析等之機器分析來測定，本發明中，將由藉由ICP發光分光分析(ICP-AES)而得之測定值換算稀土類元素作為氧化物的值，定為氧化物換算量。Hereinafter, the present invention will be described in detail.
[Method for manufacturing raw materials for cerium-based abrasives]
The method for producing raw materials for cerium-based abrasives of the present invention is characterized by the content of total rare earth elements in terms of oxide conversion (hereinafter, also referred to as "TREO" (short for Total Rare Earth Oxide)) Is 80% by mass or more, and the content of cerium in terms of oxides is dry crushed with respect to the mixed rare earth oxide with TREO of 50% by mass or more, and the bulk density exceeds 0.60 g / cm 3 and 1. A raw material for cerium-based abrasives composed of a crushed product with a particle size of 1.50 g / cm 3 or less and a cumulative value of 50% in the volume distribution of 2 μm or more and 20 μm or less.
By subjecting such mixed rare earth oxides to dry crushing, raw materials for cerium-based abrasives that can increase the production efficiency of cerium-based abrasives are obtained.
In addition, the TREO in the present invention can be measured by oxalate precipitation, calcination, and gravimetry, and specifically, it can be measured by the method described in the examples described later.
In addition, the content of rare earth elements can be measured by machine analysis such as high frequency inductively coupled plasma (ICP) analysis or fluorescent X-ray analysis. In the present invention, it will be determined by ICP emission spectrometry (ICP-AES) The measured value converted rare earth element as the value of the oxide is determined as the oxide conversion amount.
(混合氧化稀土)
本發明中使用之混合氧化稀土，TREO為80質量%以上，且鈰之以氧化物換算量計的含量相對於TREO為50質量%以上。
此外，本說明書所謂之「混合氧化稀土」之「混合」，係指包含複數種稀土類元素的意思。
由鈰系研磨材之生產效率提升的觀點來看，混合氧化稀土中之TREO為83質量%以上較佳，更佳為85質量%以上。
由與上述相同的觀點來看，混合氧化稀土含有之總稀土類元素中鈰作為主成分，鈰之以氧化物換算量計的含量相對於TREO為53質量%以上較佳，更佳為55質量%以上。
前述混合氧化稀土中，亦可包含鈰以外之稀土類元素，作為前述稀土類元素，可舉例例如鑭、釹、鐠等。(Mixed rare earth oxide)
In the mixed rare earth oxide used in the present invention, TREO is 80% by mass or more, and the content of cerium in terms of oxide is 50% by mass or more relative to TREO.
In addition, the term “mixed” of “mixed rare earth oxides” in this specification means to include a plurality of rare earth elements.
From the viewpoint of improving the production efficiency of the cerium-based abrasive, TREO in the mixed rare earth oxide is preferably 83% by mass or more, and more preferably 85% by mass or more.
From the same viewpoint as above, cerium in the total rare earth elements contained in the mixed rare earth oxide is the main component, and the content of cerium in terms of oxide is preferably 53 mass% or more relative to TREO, more preferably 55 mass %the above.
The mixed rare earth oxide may also contain rare earth elements other than cerium, and examples of the rare earth elements include lanthanum, neodymium, and gallium.
前述混合氧化稀土，可藉由將混合碳酸稀土或混合單氧基碳酸稀土、混合草酸稀土、混合氫氧化稀土等之混合輕稀土化合物進行燒成而得。此外，此處所謂之「混合」，亦與上述之混合氧化稀土之「混合」同義。
作為前述混合輕稀土化合物，係以減少鹼金屬、鹼土類金屬及放射性物質等之非稀土類成分的雜質成分，以及中重稀土之含量者較佳，以鈰作為主成分者更佳。作為混合輕稀土化合物，例如，適合使用以TREO為45~55質量%，且前述鈰之以氧化物換算量計的含量相對於TREO為約65質量%的混合碳酸稀土。
此外，本說明書中所謂之「中重稀土」，係指原子編號較鉕(Pm)大的稀土類元素。中重稀土以外之稀土類元素稱為「輕稀土」。The aforementioned mixed rare earth oxide can be obtained by firing mixed light rare earth compounds such as mixed rare earth carbonate or mixed monooxy rare earth carbonate, mixed rare earth oxalate and mixed rare earth hydroxide. In addition, the so-called "mixing" here is also synonymous with the above-mentioned "mixing" of mixed rare earth oxides.
As the aforementioned mixed light rare earth compound, an impurity component that reduces non-rare earth components such as alkali metals, alkaline earth metals, and radioactive materials, and a content of medium-heavy rare earth are preferred, and cerium is the main component. As the mixed light rare earth compound, for example, a mixed rare earth carbonate having TREO of 45 to 55% by mass and the content of the cerium in terms of oxides relative to TREO of about 65% by mass is suitably used.
In addition, the "medium heavy rare earth" in this specification means a rare earth element with an atomic number larger than that of Pm. Rare earth elements other than medium and heavy rare earths are called "light rare earths."
混合輕稀土化合物之調製方法並無特別限定。混合輕稀土化合物，例如，可藉由自含稀土類元素之礦石利用化學性處理分離減少稀土類元素以外的雜質成分及中重稀土的含量而得。
作為含稀土類元素之礦石，例如，適合使用由含大量鈰之，天然的氟碳鈰鑭礦或獨居石等之原料礦石所得之稀土精礦等。The preparation method of the mixed light rare earth compound is not particularly limited. The mixed light rare earth compound can be obtained, for example, by reducing the content of impurity components other than rare earth elements and medium-heavy rare earths by chemical separation from ore containing rare earth elements.
As the ore containing rare earth elements, for example, rare earth concentrates obtained from raw material ores containing a large amount of cerium, natural bastnasite or monazite, etc. are suitably used.
混合輕稀土化合物的調製中，作為減少雜質成分之含量的化學性處理方法，硫酸焙燒法為普遍的方法。硫酸焙燒法，係將經粉碎之前述原料礦石與硫酸一起焙燒生成硫酸鹽，將此硫酸鹽溶解於水去除作為不溶物之雜質成分的方法。雜質成分之含量，在混合輕稀土化合物中，減少至1質量%以下較佳。
又，作為減少中重稀土之含量的化學性處理方法，溶劑萃取法為普遍的。具體而言，可藉由在進行了減少原料礦石之雜質成分含量的處理之後，利用氫氧化鈉等之鹼做成混合氫氧化稀土，將此以鹽酸溶解做成混合氯化稀土水溶液，使用有機溶劑進行溶劑萃取來進行。溶劑萃取中，視需要，可使用萃取程度之調整或添加劑等之使用等之公知的方法，來調整鈰及其他輕稀土之各含量。中重稀土之含量，在混合輕稀土化合物中，減少至1質量%以下較佳。
混合輕稀土化合物，亦可包含在進行了減少雜質成分之含量的處理之後，使用碳酸鈉或重碳酸銨等做成碳酸鹽之混合碳酸稀土，及/或，使用草酸等做成草酸鹽之混合草酸稀土。In the preparation of mixed light rare earth compounds, as a chemical treatment method for reducing the content of impurity components, the sulfuric acid roasting method is a common method. The sulfuric acid roasting method is a method of roasting the crushed raw material ore and sulfuric acid together to produce sulfate, and dissolving the sulfate in water to remove impurity components as insoluble materials. The content of the impurity component is preferably reduced to less than 1% by mass in the mixed light rare earth compound.
In addition, as a chemical treatment method for reducing the content of medium and heavy rare earths, the solvent extraction method is common. Specifically, after processing to reduce the impurity content of the raw material ore, a mixed rare earth hydroxide is made with an alkali such as sodium hydroxide, and this is dissolved in hydrochloric acid to make a mixed rare earth chloride aqueous solution. The solvent is extracted by solvent. In the solvent extraction, if necessary, a known method such as adjustment of the degree of extraction or use of additives may be used to adjust the contents of cerium and other light rare earths. The content of the medium and heavy rare earth is preferably reduced to less than 1% by mass in the mixed light rare earth compound.
The mixed light rare earth compound may also include a mixed rare earth carbonate made of sodium carbonate or ammonium bicarbonate, etc., after being treated to reduce the content of impurity components, and / or made of oxalate made of oxalic acid, etc. Mixed rare earth oxalate.
將混合輕稀土化合物進行燒成獲得混合氧化稀土時的燒成溫度，雖可視混合輕稀土化合物之組成來適當地調整，但以500~1100℃較佳，更佳為500~1000℃，再更佳為600~900℃。燒成時間以0.5~48小時較佳，更佳為1~40小時，再更佳為1.5~30小時。燒成氛圍為大氣中較佳。The firing temperature when firing the mixed light rare earth compound to obtain the mixed rare earth oxide can be adjusted appropriately according to the composition of the mixed light rare earth compound, but it is preferably 500 to 1100 ° C, more preferably 500 to 1000 ° C, and more Preferably it is 600 ~ 900 ℃. The firing time is preferably 0.5 to 48 hours, more preferably 1 to 40 hours, and even more preferably 1.5 to 30 hours. The firing atmosphere is preferably in the atmosphere.
此外，混合氧化稀土亦有被市售，亦可使用市售品作為用以獲得破碎品之原料。市售品之混合氧化稀土中，亦有殘存有其製造原料之混合碳酸稀土或混合單氧基碳酸稀土、混合草酸稀土等的情形。In addition, mixed rare earth oxides are also commercially available, and commercially available products can also be used as raw materials for obtaining crushed products. In the commercially available mixed rare earth oxides, mixed rare earth carbonates, mixed monooxygenated rare earth carbonates, mixed rare earth oxalates, etc., of the raw materials for their manufacture, may remain.
(乾式破碎處理步驟)
本發明中，將前述混合氧化稀土進行乾式破碎處理，獲得由破碎品構成之鈰系研磨材用原料。
乾式破碎處理步驟中，以使凝集之混合氧化稀土粒子成為特定之鬆裝密度及粒徑之方式進行。
如上述進行所得之通常的混合氧化稀土之粒徑為5~30μm左右，微晶徑通常為30~150Å。微晶徑，係藉由以X射線繞射裝置由主波峰的半高寬使用謝樂公式算出而求得。乾式破碎處理中，獲得比多結晶體之一次粒子粒徑更大之粒徑尺寸的凝集粒子。獲得由如此之粒子構成之破碎品的乾式破碎處理，係可與後述之粉碎步驟中之「粉碎」區別者。
乾式粉碎處理，可使用公知的乾式破碎(粉碎)裝置來進行。由獲得特定性狀之粒子的觀點來看，例如，適合使用錘磨機(原子化器atomizer)、針磨機等。(Dry crushing process steps)
In the present invention, the mixed rare earth oxide is subjected to dry crushing treatment to obtain a raw material for cerium-based abrasives composed of crushed products.
In the dry crushing treatment step, the aggregated mixed rare earth oxide particles are made to have a specific bulk density and particle size.
The particle diameter of the usual mixed rare earth oxide obtained as described above is about 5 to 30 μm, and the crystallite diameter is usually 30 to 150Å. The crystallite diameter is obtained by using the X-ray diffraction device to calculate the half-height width of the main peak using the Xie Le formula. In the dry crushing process, aggregated particles having a particle size larger than the primary particle size of the polycrystalline body are obtained. The dry crushing process to obtain a crushed product composed of such particles can be distinguished from the "crushing" in the crushing step described later.
The dry crushing process can be performed using a known dry crushing (crushing) device. From the viewpoint of obtaining particles with specific properties, for example, a hammer mill (atomizer), a pin mill, or the like is suitably used.
＜鬆裝密度＞
藉由乾式破碎處理步驟而得之破碎品，鬆裝密度為超過0.60g/cm3
且1.50g/cm3
以下，較佳為0.80g/cm3
以上。
此外，本發明所謂之「鬆裝密度」，係指以依循
JIS R 9301-2-3:1999(氧化鋁粉末-第2部：物性測定方法-3：鬆裝密度及壓實密度)之「3.鬆裝密度之測定方法」的方法所測定之值。
若破碎品之鬆裝密度為0.60g/cm3
以下，則為了濕式粉碎等而該破碎品與水混合做成漿體時，漿體之黏性容易變高，無法增加用以做成均勻漿體之混合氧化稀土的進料量。另一方面，超過1.50g/cm3
超時，難以操作，實用上不佳。
由使濕式粉碎步驟中之混合氧化稀土的進料量更多，謀求鈰系研磨材之生產效率的提升之觀點來看，破碎品之鬆裝密度為0.80g/cm3
以上較佳，更佳為0.85g/cm3
以上。又，破碎品之鬆裝密度的上限，由操作容易性之觀點來看，以1.30g/cm3
以下較佳，更佳為1.00g/cm3
以下。<Loose density>
The crushed product obtained by the dry crushing treatment step has a bulk density of more than 0.60 g / cm 3 and 1.50 g / cm 3 or less, preferably 0.80 g / cm 3 or more.
In addition, the so-called "loose density" of the present invention refers to
JIS R 9301-2-3: 1999 (Alumina powder-Part 2: Physical property measurement method-3: Bulk density and compacted density) The value measured by the method of "3. Bulk density measurement method".
If the bulk density of the crushed product is 0.60g / cm 3 or less, when the crushed product is mixed with water to make a slurry for wet crushing, etc., the viscosity of the slurry is likely to become high and cannot be increased to make it uniform. Feed amount of mixed rare earth oxide in slurry. On the other hand, if it exceeds 1.50 g / cm 3 over time, it is difficult to handle, and it is not good in practice.
From the viewpoint of increasing the feed amount of the mixed rare earth oxide in the wet pulverization step and improving the production efficiency of the cerium-based abrasive, the bulk density of the crushed product is preferably 0.80 g / cm 3 or more, and more Preferably, it is 0.85 g / cm 3 or more. In addition, the upper limit of the bulk density of the crushed product is preferably 1.30 g / cm 3 or less, and more preferably 1.00 g / cm 3 or less from the viewpoint of ease of handling.
＜平均粒徑(D50)＞
由前述破碎品構成之鈰系研磨材用原料，平均粒徑為2~20μm，較佳為2~18μm，更佳為3~15μm。
此外，本發明所謂之「平均粒徑」，係指於體積分佈50%累積值的粒徑，亦表示為「D50」。此平均粒徑，可藉由雷射繞射散射法來測定。具體而言，係以下述實施例中記載之Microtrac粒度分佈分析儀所測定之值。
破碎品之平均粒徑若未達2μm，則粒子過細而操作困難，實用上不佳。另一方面，超過20μm時，由於粒子過粗，為了濕式粉碎等將該破碎品與水混合做成漿體時，容易沉降，難以得到均勻的漿體，又，之後的粉碎步驟中變得需要很多時間，故不佳。<Average particle size (D50)>
The raw material for cerium-based abrasives composed of the aforementioned crushed product has an average particle size of 2-20 μm, preferably 2-18 μm, and more preferably 3-15 μm.
In addition, the "average particle diameter" in the present invention refers to the particle diameter at 50% of the cumulative value of the volume distribution, and is also expressed as "D50". This average particle size can be determined by laser diffraction scattering method. Specifically, it is the value measured by the Microtrac particle size distribution analyzer described in the following examples.
If the average particle size of the crushed product is less than 2 μm, the particles are too fine and difficult to handle, which is not practical. On the other hand, when it exceeds 20 μm, the particles are too coarse, and when the crushed product is mixed with water to make a slurry for wet crushing, it is easy to settle and it is difficult to obtain a uniform slurry. It takes a lot of time, so it is not good.
[鈰系研磨材之製造方法]
本發明之鈰系研磨材之製造方法，其特徵為包含粉碎藉由上述而得之鈰系研磨材用原料的步驟。
藉由使用如上述之由混合氧化稀土之破碎品構成之鈰系研磨材用原料，可使鈰系研磨材之製造中的生產效率提升。[Manufacturing method of cerium-based abrasive]
The method for producing a cerium-based abrasive material of the present invention is characterized by including the step of pulverizing the raw material for the cerium-based abrasive material obtained as described above.
By using the raw material for the cerium-based abrasive material composed of the crushed product of mixed rare earth oxide as described above, the production efficiency in the production of the cerium-based abrasive material can be improved.
(粉碎步驟)
本發明之鈰系研磨材之製造方法中之鈰系研磨材用原料的粉碎步驟，雖可為乾式粉碎步驟亦可為濕式粉碎步驟，但依據下述理由，以濕式粉碎步驟較佳。(Crushing step)
The pulverization step of the raw material for cerium-based abrasives in the method for producing cerium-based abrasives of the present invention may be either a dry pulverization step or a wet pulverization step, but a wet pulverization step is preferred for the following reasons.
＜濕式粉碎步驟＞
鈰系研磨材之製造方法中，特別是濕式粉碎步驟中，由於藉由使用由前述破碎品構成之鈰系研磨材用原料，與水混合時之漿體黏性的增加被抑制，故可增加每1批次之混合氧化稀土的進料量，進而亦可謀求之後的漿體之乾燥步驟中的乾燥效率的提升。即，藉由上述而得之鈰系研磨材用原料，藉由供至濕式粉碎步驟，可特別有助於鈰系研磨材之生產效率的提升效果。<Wet crushing step>
In the method of manufacturing cerium-based abrasives, especially in the wet pulverization step, by using the raw material for cerium-based abrasives composed of the aforementioned crushed product, the increase in the viscosity of the slurry when mixed with water is suppressed. Increasing the feeding amount of mixed rare earth oxide per batch can further improve the drying efficiency in the subsequent slurry drying step. That is, the raw material for cerium-based abrasives obtained as described above can be particularly useful for improving the production efficiency of cerium-based abrasives by being supplied to the wet pulverization step.
濕式粉碎步驟，由均質地粉碎之觀點，又，如後述，破碎品以外添加其他成分時，由均勻地混合之觀點來看，藉由濕式球磨機(珠磨機)等之介質碾磨機來進行較佳。作為分散介質，雖適合使用水，但由分散性提升之觀點來看，亦可使用與醇等之混合溶劑。The wet pulverization step is from the viewpoint of homogeneous pulverization, and, as will be described later, when other components other than the crushed product are added, from the viewpoint of uniform mixing, a medium mill such as a wet ball mill (bead mill) is used To do better. As the dispersion medium, although water is suitably used, from the viewpoint of improving the dispersibility, a mixed solvent with alcohol or the like can also be used.
藉由濕式粉碎步驟而得之鈰系研磨材的原料漿體，由生產性之提升及製造成本等之觀點來看，以水作為分散介質，且固體成分濃度為55質量%以上較佳，更佳為57質量%以上，再更佳為60質量%以上。此外，此處所謂之「固體成分」，濕式粉碎之對象僅為前述破碎品時，係指該破碎品，如後述，破碎品以外添加其他成分時，係指此等成分之固體成分及破碎品的合計。
原料漿體中之固體成分的粒徑，由在之後步驟中的操作性等之觀點來看，平均粒徑(D50)為0.3~10μm較佳，更佳為0.5~7μm，再更佳為0.5~5μm。The raw material slurry of the cerium-based abrasive obtained by the wet pulverization step is preferably water with a dispersing medium and a solid content concentration of 55 mass% or more from the viewpoint of productivity improvement and manufacturing cost. It is more preferably 57% by mass or more, and even more preferably 60% by mass or more. In addition, the so-called "solid content" here refers to the crushed product when the object of wet crushing is only the aforementioned crushed product. As described later, when other components are added to the crushed product, it refers to the solid content and crushing of these components The total of products.
The particle size of the solid content in the raw material slurry is preferably from 0.3 to 10 μm, more preferably from 0.5 to 7 μm, and even more preferably from the viewpoint of operability in the subsequent steps, etc. ~ 5μm.
鈰系研磨材，可為僅由前述破碎品之成分而成者，或是又，由研磨材之研磨特性的提升之觀點來看，亦可包含前述破碎品之成分以外的成分，例如，添加有氟成分較佳。
此情形中，破碎品之成分以外的成分，欲與破碎品均勻地混合，在粉碎破碎品之前添加於破碎品中較佳。於破碎品添加氟成分之情形中，於破碎品添加氟化稀土較佳。即，在粉碎由混合氧化稀土之破碎品構成之鈰系研磨材用原料之前，包含於該鈰系研磨材用原料添加氟化稀土的步驟較佳。The cerium-based abrasive material may be composed of only the components of the crushed product, or from the viewpoint of improving the polishing properties of the abrasive material, it may also contain components other than the components of the crushed product, for example, by adding Fluorine is preferred.
In this case, components other than those of the crushed product are to be uniformly mixed with the crushed product, and are preferably added to the crushed product before crushing the crushed product. In the case of adding a fluorine component to a crushed product, it is preferable to add a rare earth fluoride to the crushed product. That is, before pulverizing the raw material for cerium-based abrasives composed of a crushed product of mixed rare earth oxide, the step of adding rare earth fluoride to the raw material for cerium-based abrasives is preferable.
(氟化稀土)
氟化稀土，作為前述氟成分，係在使鈰系研磨材之氟原子含量增加的目的下進行添加。
鈰系研磨材藉由包含氟，可使研磨速度等之研磨特性提升。若使用氟化稀土，可較直接使用氟化銨或氫氟酸等之氟化物更安全且簡便地，以低成本製造含氟之鈰系研磨材。(Rare Earth Fluoride)
The rare earth fluoride is added as the fluorine component for the purpose of increasing the fluorine atom content of the cerium-based abrasive.
The inclusion of fluorine in the cerium-based abrasive can improve the polishing characteristics such as the polishing speed. If rare earth fluoride is used, it is safer and easier to directly use fluorides such as ammonium fluoride or hydrofluoric acid, and it is possible to produce fluorine-containing cerium-based abrasives at low cost.
氟化稀土，TREO較佳為80質量%以上，更佳為83質量%以上，再更佳為85質量%以上。又，氟化稀土係含有之總稀土類元素中以鈰作為主成分者較佳，鈰之以氧化物換算量計的含量相對於TREO，較佳為50質量%以上，更佳為53質量%以上，再更佳為55質量%以上。又，氟化稀土中之氟原子含量，較佳為10~30質量%，更佳為15~30質量%，再更佳為20~30質量%。For the rare earth fluoride, TREO is preferably 80% by mass or more, more preferably 83% by mass or more, and even more preferably 85% by mass or more. Moreover, it is preferable that cerium is the main component of the total rare earth elements contained in the fluorinated rare earths. The content of cerium in terms of oxide is preferably 50% by mass or more and more preferably 53% by mass relative to TREO. Above, even more preferably 55% by mass or more. In addition, the content of fluorine atoms in the fluorinated rare earth is preferably 10 to 30% by mass, more preferably 15 to 30% by mass, and even more preferably 20 to 30% by mass.
作為如此之氟化稀土，可使用上述混合輕稀土化合物中，藉由添加氫氟酸、氟化銨或酸性氟化銨等之氟化物，進行熱處理而得之混合氟化稀土。此外，此處所謂之「混合」，亦與上述之混合氧化稀土的「混合」同義。
前述熱處理，由獲得均質且研磨特性優異之鈰系研磨材的觀點來看，以400℃以下之溫度較佳。熱處理氛圍為大氣中較佳。As such a rare earth fluoride, a mixed rare earth fluoride obtained by adding a fluoride such as hydrofluoric acid, ammonium fluoride, or acidic ammonium fluoride to the above-mentioned mixed light rare earth compound, and performing heat treatment. In addition, the so-called "mixing" here is also synonymous with the above-mentioned "mixing" of mixed rare earth oxides.
From the viewpoint of obtaining a homogeneous cerium-based abrasive having excellent polishing characteristics, the heat treatment is preferably at a temperature of 400 ° C or lower. The heat treatment atmosphere is preferably in the atmosphere.
添加於由前述破碎品構成之鈰系研磨材用原料中之氟化稀土的量，視製造之鈰系研磨材所要求的氟原子含量來適當地決定。由獲得優異之研磨特性的觀點來看，前述破碎品與氟化稀土之合計100質量%中氟化稀土的量，以成為1~40質量%之方式添加較佳，更佳為3~35質量%，再更佳為5~30質量%。The amount of rare earth fluoride added to the raw material for cerium-based abrasives composed of the aforementioned crushed product is appropriately determined depending on the content of fluorine atoms required for the cerium-based abrasives produced. From the viewpoint of obtaining excellent grinding properties, the amount of rare earth fluoride in the total of 100% by mass of the crushed product and rare earth fluoride is preferably added so as to become 1 to 40% by mass, more preferably 3 to 35% by mass %, And even better is 5 to 30% by mass.
(濕式粉碎步驟的後步驟)
本發明之鈰系研磨材之製造方法，在前述濕式粉碎步驟之後，包含依序進行乾燥、燒成、破碎及分級的步驟較佳。即，將前述濕式粉碎步驟中所得之漿體乾燥後，進行燒成、破碎、分級，而製造鈰系研磨材較佳。
若依據經過如此之步驟的製造方法，由於前述漿體為固體成分濃度高，其乾燥效率亦提升，進而，亦可使鈰系研磨材之生產效率提升，謀求製造成本之低減化。
乾燥、燒成、破碎及分級，可與鈰系研磨材之公知的製造方法中使用的方法同樣地進行。
此外，燒成步驟中，由獲得均質且研磨特性優異之鈰系研磨材的觀點來看，燒成溫度較佳為600~1200℃，更佳為650~1150℃，再更佳為700~1100℃。於目標設定溫度的燒成時間，較佳為0.1~10小時，更佳為0.5~6小時，再更佳為0.5~4小時。燒成氛圍，以大氣中較佳。(After the wet crushing step)
The method for manufacturing a cerium-based abrasive material of the present invention preferably includes the steps of drying, firing, crushing, and classifying in order after the wet pulverization step. That is, it is preferable to produce the cerium-based abrasive by drying, crushing, and classifying the slurry obtained in the foregoing wet pulverization step.
According to the manufacturing method through such steps, since the slurry has a high solid content concentration, its drying efficiency is also improved, and further, the production efficiency of the cerium-based abrasive can also be improved, and the manufacturing cost can be reduced.
Drying, firing, crushing, and classification can be carried out in the same manner as the method used in the known production method of cerium-based abrasives.
In addition, in the firing step, the firing temperature is preferably 600 to 1200 ° C, more preferably 650 to 1150 ° C, and even more preferably 700 to 1100 from the viewpoint of obtaining a homogeneous cerium-based abrasive having excellent polishing characteristics ℃. The firing time at the target set temperature is preferably 0.1 to 10 hours, more preferably 0.5 to 6 hours, and even more preferably 0.5 to 4 hours. The firing atmosphere is preferably in the atmosphere.
(鈰系研磨材)
藉由本發明之製造方法而得之鈰系研磨材，由研磨特性之觀點來看，TREO較佳為85質量%以上，更佳為90質量%以上，前述鈰之以氧化物換算量計的含量相對於TREO，較佳為55~95質量%，更佳為60~95質量%。
又，鈰系研磨材以包含鑭、釹及鐠者較佳，此情形中，以鑭之以氧化物換算量計的含量相對於TREO為5~40質量%，釹之以氧化物換算量計的含量相對於TREO為0.01~5質量%，鐠之以氧化物換算量計的含量相對於TREO為0.01~5質量%較佳。
又，鈰系研磨材，由成為具有優異之研磨特性者的觀點來看，包含氟原子較佳，此情形中，氟原子之含量為0.5~10質量%較佳。(Cerium-based abrasive)
The cerium-based abrasive obtained by the production method of the present invention has a TREO of preferably 85% by mass or more, and more preferably 90% by mass or more, from the viewpoint of polishing characteristics. The content of the aforementioned cerium in terms of oxide conversion Relative to TREO, it is preferably 55 to 95% by mass, and more preferably 60 to 95% by mass.
In addition, the cerium-based abrasive is preferably composed of lanthanum, neodymium, and aluminum. In this case, the content of lanthanum in terms of oxide is 5 to 40% by mass relative to TREO, and the content of neodymium in terms of oxide The content of R is 0.01 to 5% by mass relative to TREO, and the content in terms of oxide conversion amount is preferably 0.01 to 5% by mass relative to TREO.
In addition, the cerium-based polishing material preferably contains fluorine atoms from the viewpoint of having excellent polishing properties. In this case, the content of fluorine atoms is preferably 0.5 to 10% by mass.
鈰系研磨材，雖亦依據研磨對象或研磨條件等，但平均粒徑(D50)為0.3~5.0μm較佳，更佳為0.5~ 4.0μm，再更佳為0.5~3.0μm。Although the cerium-based polishing material also depends on the polishing object or polishing conditions, the average particle diameter (D50) is preferably 0.3 to 5.0 μm, more preferably 0.5 to 4.0 μm, and even more preferably 0.5 to 3.0 μm.
前述鈰系研磨材，雖通常以粉末狀操作，但研磨時，例如，使其分散於水等之分散介質中，以漿體之狀態使用。漿體中之研磨材的分散濃度，雖依研磨對象或研磨條件等適當地調整，但通常為1~30質量%。作為分散介質，適合使用水，或醇、丙酮、四氫呋喃等之水溶性有機溶劑，通常使用水。Although the above-mentioned cerium-based abrasive is usually handled in powder form, at the time of polishing, for example, it is dispersed in a dispersion medium such as water and used as a slurry. The dispersion concentration of the polishing material in the slurry is appropriately adjusted according to the polishing object, polishing conditions, etc., but it is usually 1 to 30% by mass. As the dispersion medium, water or a water-soluble organic solvent such as alcohol, acetone, tetrahydrofuran, etc. is suitable, and water is usually used.
又，研磨材之漿體，在分散性提升、沉降防止、穩定性提升及作業性提升等之目的下，視需要，在不妨礙研磨特性的範圍內，可添加乙二醇、聚乙二醇等之二醇類；三聚磷酸、六偏磷酸鹽等之磷酸鹽；聚丙烯酸鹽等之高分子分散劑、甲基纖維素、羧基甲基纖維素等之纖維素醚類；聚乙烯醇等之水溶性高分子等之添加劑。添加有添加劑時之各添加劑的添加量，相對於漿體中之研磨材100質量份而言，通常為0.01~20質量份，較佳為0.05~15質量份，更佳為0.1~10質量份。In addition, the slurry of the grinding material can be added with ethylene glycol or polyethylene glycol within the range that does not hinder the grinding characteristics for the purpose of improving dispersibility, preventing sedimentation, improving stability, and improving workability. Glycols such as tripolyphosphoric acid and hexametaphosphate; polymer dispersants such as polyacrylates, cellulose ethers such as methyl cellulose and carboxymethyl cellulose; polyvinyl alcohol, etc. Additives such as water-soluble polymers. When the additive is added, the amount of each additive added is usually 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the abrasive in the slurry. .
若使用前述鈰系研磨材，可抑制於玻璃基板等之研磨面產生的研磨傷痕(刮痕)，同時維持高的研磨速度，有效率地進行研磨。
前述鈰系研磨材，特別適合使用於光碟或磁碟用之玻璃基板、液晶顯示器用之玻璃基板、彩色濾光器或光罩用之玻璃基板、光學透鏡用之玻璃基板等、各種玻璃材及玻璃製品的最終研磨。
[實施例]If the cerium-based polishing material is used, polishing scratches (scratches) generated on the polishing surface of a glass substrate or the like can be suppressed, while maintaining a high polishing rate, and performing efficient polishing.
The aforementioned cerium-based abrasives are particularly suitable for glass substrates for optical discs or magnetic discs, glass substrates for liquid crystal displays, glass substrates for color filters or photomasks, glass substrates for optical lenses, etc., various glass materials and Final grinding of glass products.
[Example]
以下，雖藉由實施例具體說明本發明，但本發明並不限定於下述實施例。Hereinafter, although the present invention is specifically described by way of examples, the present invention is not limited to the following examples.
[混合氧化稀土原料之調製]
(原料A)
將含有TREO 47質量%、中重稀土以氧化物換算計為2質量%、釹以氧化物換算計為8質量%的原料礦石(稀土精礦)，藉由硫酸焙燒法及溶劑萃取法進行處理，將稀土類元素以外之雜質成分減少至1質量%以下，中重稀土減少至以氧化物換算計為1質量%以下，得到稀土類元素之含量經調整的混合輕稀土化合物。此混合輕稀土化合物，相對於TREO而言，鈰之以氧化物換算量([CeO2
])計的含量為65質量%，鑭之以氧化物換算量([La2
O3
])計的含量為34質量%，釹之以氧化物換算量([Nd2
O3
])計的含量為0.6質量%、鐠之以氧化物換算量計的含量([Pr6
O11
])為0.1質量%。
將此混合輕稀土化合物以重碳酸銨進行處理，得到混合碳酸稀土。此外，混合碳酸稀土，TREO為49質量%。
將此混合碳酸稀土4000kg，以梭動窯在大氣中以800℃熱處理10小時，得到混合氧化稀土。此外，混合氧化稀土，TREO為93質量%，且該鈰之以氧化物換算量計的含量相對於TREO為65質量%。[Preparation of mixed rare earth oxide raw materials]
(Raw material A)
Raw material ore (rare earth concentrate) containing 47% by mass of TREO, 2% by mass of medium-heavy rare earth in oxide conversion and 8% by mass of neodymium in oxide conversion is processed by sulfuric acid roasting method and solvent extraction method The impurity components other than rare earth elements are reduced to less than 1% by mass, and the medium and heavy rare earths are reduced to less than 1% by mass in terms of oxide to obtain a mixed light rare earth compound with an adjusted content of rare earth elements. For this mixed light rare earth compound, the content of cerium in terms of oxide conversion ([CeO 2 ]) is 65% by mass relative to TREO, and that of lanthanum in terms of oxide conversion ([La 2 O 3 ]) The content is 34% by mass, the content of neodymium in terms of oxides ([Nd 2 O 3 ]) is 0.6% by mass, and the content of neodymium in terms of oxides ([Pr 6 O 11 ]) is 0.1 mass %.
The mixed light rare earth compound is treated with ammonium bicarbonate to obtain mixed rare earth carbonate. In addition, the mixed rare earth carbonate has a TREO of 49% by mass.
This mixed rare earth carbonate 4000kg was heat-treated in the atmosphere at 800 ° C for 10 hours in a shuttle kiln to obtain mixed rare earth oxide. In addition, mixed rare earth oxide, TREO was 93% by mass, and the content of the cerium in terms of oxide was 65% by mass relative to TREO.
(原料B~D)
使用與原料A之調製中使用的相同的混合輕稀土化合物，藉由調整其處理條件及混合碳酸稀土之熱處理條件，分別調製如下述表1所示之TREO及[CeO2
]/TREO的原料B~D。(Raw material B ~ D)
Using the same mixed light rare earth compound used in the preparation of the raw material A, by adjusting the processing conditions and heat treatment conditions of the mixed rare earth carbonate, the raw materials B of TREO and [CeO 2 ] / TREO shown in Table 1 below are prepared respectively ~ D.
(原料E)
使用相對於TREO而言，鈰之以氧化物換算量([CeO2
])計的含量為59質量%，鑭之以氧化物換算量計的含量([La2
O3
])為36質量%，釹之以氧化物換算量計的含量([Nd2
O3
])為0.1質量%，鐠之以氧化物換算量計的含量([Pr6
O11
])為4.5質量%之混合輕稀土化合物，藉由調整其處理條件及混合碳酸稀土之熱處理條件，調製如下述表1所示之TREO及[CeO2
]/TREO的原料E。(Raw material E)
Using TREO, the content of cerium in terms of oxides ([CeO 2 ]) is 59% by mass, and the content of lanthanum in terms of oxides ([La 2 O 3 ]) is 36% by mass , The content of neodymium in terms of oxides ([Nd 2 O 3 ]) is 0.1% by mass, and the content of neodymium in terms of oxides ([Pr 6 O 11 ]) is 4.5% by mass of mixed light rare earth The compound was prepared with TREO and [CeO 2 ] / TREO raw materials E shown in Table 1 below by adjusting the processing conditions and heat treatment conditions of the mixed rare earth carbonate.
[破碎品之製造]
(實施例1)
將原料A 1500kg投入原子化器(不二電機工業股份有限公司(現 不二PAUDAL股份有限公司)製，型號「EII7.5」)中，以旋轉數8000rpm進行乾式破碎處理(1)。
(實施例2~5)
實施例1中，使用原料B~E代替原料A，除此之外與實施例1同樣地進行，各別進行乾式破碎處理(1)。
(實施例6)
實施例1中，原子化器之旋轉數定為5000rpm，除此之外與實施例1同樣地進行，各別進行乾式破碎處理(2)。
(實施例7)
實施例2中，原子化器之旋轉數定為5000rpm，除此之外與實施例2同樣地進行，各別進行乾式破碎處理(2)。[Manufacture of broken products]
(Example 1)
1500 kg of raw material A was put into an atomizer (Fuji Electric Industries Co., Ltd. (now Fuji Electric Co., Ltd.), model "EII7.5"), and dry crushing was performed at a rotation number of 8000 rpm (1).
(Examples 2 to 5)
In Example 1, the raw materials B to E were used instead of the raw material A, and the same procedure as in Example 1 was performed except that the dry crushing treatment (1) was performed separately.
(Example 6)
In Example 1, except that the number of revolutions of the atomizer was set to 5000 rpm, it was carried out in the same manner as in Example 1, and each was subjected to dry crushing treatment (2).
(Example 7)
In Example 2, except that the number of revolutions of the atomizer was set to 5000 rpm, it was carried out in the same manner as in Example 2, and each was subjected to dry crushing treatment (2).
(比較例1~3)
對於原料A~C，將未進行乾式破碎處理者分別做成比較例1~3。(Comparative examples 1 to 3)
For the raw materials A to C, those without dry crushing treatment were made into Comparative Examples 1 to 3, respectively.
[破碎品及未破碎品之物性測定]
對於由上述實施例中所得之破碎品構成之鈰系研磨材用原料，及比較例之未破碎品(原料A~C)，測定鬆裝密度及平均粒徑(D50)。此等之測定結果總結表示於下述表1。
各測定方法如下述。
＜鬆裝密度＞
以依據JIS R 9301-2-3:1999(氧化鋁粉末-第2部：物性測定方法-3：鬆裝密度及壓實密度)之「3.鬆裝密度之測定方法」的方法進行測定。
＜平均粒徑(D50)＞
利用Microtrac粒度分佈分析儀「MT3300II」(日機裝股份有限公司製)，藉由雷射繞射散射法進行粒度分佈測定，將於體積分佈50%累積值的粒徑(D50)定為平均粒徑。[Determination of physical properties of broken and unbroken products]
For the raw materials for the cerium-based abrasives composed of the crushed products obtained in the above examples, and the unbroken products of the comparative examples (raw materials A to C), the bulk density and average particle diameter (D50) were measured. The results of these measurements are summarized in Table 1 below.
Each measurement method is as follows.
<Loose density>
The measurement was carried out in accordance with "3. Measurement method of bulk density" according to JIS R 9301-2-3: 1999 (Alumina powder-Part 2: Measurement method of physical properties-3: Bulk density and compacted density).
<Average particle size (D50)>
Using the Microtrac particle size distribution analyzer "MT3300II" (manufactured by Nikkiso Co., Ltd.), the particle size distribution is measured by the laser diffraction scattering method, and the particle size (D50) of the 50% cumulative value of the volume distribution is determined as the average particle path.
[漿體調製評估]
對於由上述實施例中所得之破碎品構成之鈰系研磨材用原料，及比較例之未破碎品(原料A~C)的各試料，分別與水混合，進行漿體調製評估。
首先，於100ml燒杯中，加入破碎品或未破碎品之試料40g及水，分別調整成53、57及62質量%的濃度，以玻璃棒攪拌混合，以目視觀察評估混合物(漿體)的狀態。此等之評估結果總結表示於下述表1。[Slurry Modulation Evaluation]
The raw materials for the cerium-based abrasive material composed of the crushed products obtained in the above examples, and the unbroken products of the comparative examples (raw materials A to C) were mixed with water and evaluated for slurry preparation.
First, add 40g of broken or unbroken sample and water to a 100ml beaker, adjust to concentrations of 53, 57 and 62% by mass respectively, stir and mix with a glass rod, and visually evaluate the state of the mixture (slurry) . The evaluation results are summarized in Table 1 below.
評估基準如下述。
A：可以手輕易攪拌的黏度，成為均勻的漿體。
B：雖成為漿體，但以手的攪拌有些困難。
C：幾乎不能攪拌，未成為漿體。
評估A及B之情形中，可說是可在濕式粉碎中獲得均勻的漿體。評估C之情形中，在濕式粉碎中獲得均勻的漿體為困難。The evaluation criteria are as follows.
A: The viscosity can be easily stirred by hand to become a uniform slurry.
B: Although it becomes a slurry, it is difficult to stir by hand.
C: It is almost impossible to stir, and it does not become a slurry.
In the case of evaluating A and B, it can be said that a uniform slurry can be obtained in wet pulverization. In the case of evaluation C, it was difficult to obtain a uniform slurry in wet pulverization.
由表1所示結果可明白，經乾式破碎處理之，由特定之鬆裝密度及平均粒徑的破碎品構成之鈰系研磨材用原料(實施例1~7)，即使在提高漿體中之混合氧化稀土的破碎品(固體成分)之濃度的情形中，亦可得到均勻的漿體。因此，若使用前述鈰系研磨材用原料，使增加濕式粉碎步驟中之混合氧化稀土的進料量成為可能。From the results shown in Table 1, it can be understood that the raw materials for cerium-based abrasive materials (Examples 1 to 7) composed of crushed products of specific bulk density and average particle diameter after dry crushing treatment, even in the improvement of the slurry In the case of the concentration of the crushed product (solid content) of mixed rare earth oxide, a uniform slurry can also be obtained. Therefore, if the aforementioned raw material for cerium-based abrasives is used, it becomes possible to increase the feed amount of the mixed rare earth oxide in the wet pulverization step.
[鈰系研磨材之製造]
(實施例8)
於實施例1(原料A之製造過程)中所得之混合輕稀土化合物中加入氫氟酸進行混合後，在大氣中以400℃熱處理2小時，得到混合氟化稀土。此混合氟化稀土，TREO為83質量%，鈰之以氧化物換算量([CeO2
])計的含量相對於該TREO為65質量%，又，氟原子含量為26質量%。
將水1000kg，與實施例2中調製之混合氧化稀土的破碎品(鈰系研磨劑用原料)及前述混合氟化稀土的混合物(混合質量比76:24)之合計1400kg於漿體槽攪拌混合後，以濕式球磨機(介質：直徑5mm氧化鋯製球)混合粉碎17小時，藉此得到均勻的混合漿體。
將此混合漿體投入迴轉窯，於大氣中以700℃乾燥後，以1000℃燒成。將所得之燒成體放置冷卻後，進行破碎、分級，製造鈰系研磨材。[Manufacture of Ce-based abrasives]
(Example 8)
After adding hydrofluoric acid to the mixed light rare earth compound obtained in Example 1 (manufacturing process of raw material A) and mixing, heat treatment was performed at 400 ° C for 2 hours in the atmosphere to obtain mixed rare earth fluoride. In this mixed rare earth fluoride, TREO is 83% by mass, and the content of cerium in terms of oxide conversion ([CeO 2 ]) is 65% by mass relative to the TREO, and the fluorine atom content is 26% by mass.
1000 kg of water was mixed with a total of 1400 kg of a mixture of the crushed product of mixed rare earth oxide prepared in Example 2 (raw material for cerium-based abrasives) and the aforementioned mixture of mixed rare earth fluoride (mixed mass ratio 76:24) in the slurry tank After that, it was mixed and pulverized in a wet ball mill (medium: ball made of zirconia with a diameter of 5 mm) for 17 hours, thereby obtaining a uniform mixed slurry.
This mixed slurry was put into a rotary kiln, dried at 700 ° C in the atmosphere, and fired at 1000 ° C. After the obtained fired body was left to cool, it was crushed and classified to produce a cerium-based abrasive.
(比較例4)
將水1000kg，與比較例2之混合氧化稀土的未破碎品及與實施例8相同之混合氟化稀土的混合物(混合質量比76:24)之合計1000kg於漿體槽攪拌混合後，以濕式球磨機(介質：直徑5mm氧化鋯製球)混合粉碎19小時，藉此得到均勻的混合漿體。
將此混合漿體與實施例8同樣地進行乾燥、燒成、破碎及分級，製造鈰系研磨材。(Comparative Example 4)
1000 kg of water, a total of 1000 kg of the unbroken product of the mixed rare earth oxide of Comparative Example 2 and the same mixture of mixed rare earth fluoride (mixed mass ratio 76:24) as in Example 8 were stirred and mixed in the slurry tank, wet Ball mill (medium: balls made of zirconia with a diameter of 5 mm) was mixed and pulverized for 19 hours, thereby obtaining a uniform mixed slurry.
This mixed slurry was dried, calcined, crushed and classified in the same manner as in Example 8 to produce a cerium-based abrasive.
[鈰系研磨材之組成分析]
對於上述實施例及比較例中所得之各鈰系研磨材，測定TREO、相對於TREO之各稀土類元素之以氧化物換算量([CeO2
]、[La2
O3
]、[Nd2
O3
]、[Pr6
O11
])計的含量，及氟原子(F)含量。此等之測定結果總結表示於下述表2。
各測定方法如下述。
＜TREO＞
於將鈰系研磨材酸溶解而成的溶液中，添加氨水。將生成之沉澱物過濾、洗淨，去除鹼金屬後，再度進行酸溶解。於此溶液中添加草酸，將生成之沉澱物進行燒成以重量法求得TREO。
＜相對於TREO之各稀土類元素之以氧化物換算量計的含量＞
將鈰系研磨材酸溶解，將以ICP-AES法測定之各稀土類元素量換算作為氧化物的值，定為氧化物換算量。
＜氟原子含量＞
使鈰系研磨材鹼溶融並進行溫水萃取，以氟離子計(離子電極法)測定。[Analysis of the composition of cerium-based abrasives]
For each of the cerium-based abrasives obtained in the above examples and comparative examples, the amount of TREO, the oxide-converted amount of each rare earth element relative to TREO ([CeO 2 ], [La 2 O 3 ], [Nd 2 O 3 ], [Pr 6 O 11 ]) and fluorine atom (F) content. The results of these measurements are summarized in Table 2 below.
Each measurement method is as follows.
＜ TREO ＞
Aqueous solution is added to the solution obtained by dissolving the cerium-based abrasive in acid. The resulting precipitate is filtered and washed to remove alkali metals, and then acid-dissolved again. Oxalic acid was added to this solution, and the resulting precipitate was calcined to obtain TREO gravimetrically.
<Content of each rare earth element in TREO in terms of oxide conversion amount>
The cerium-based abrasive was dissolved in acid, and the amount of each rare earth element measured by the ICP-AES method was converted to an oxide value, and the amount was converted to oxide.
<Content of fluorine atoms>
The cerium-based abrasive was melted with alkali and subjected to warm water extraction, and measured with a fluoride ion meter (ion electrode method).
[鈰系研磨材之物性測定]
對於上述實施例及比較例中所得之各鈰系研磨材，測定粒度分佈及比表面積。此等之測定結果亦總結表示於表2。
各測定方法如下述。
＜粒徑＞
以粒度分佈測定裝置(貝克曼庫爾特股份有限公司製「庫爾特粒度分佈測量裝置」，30μm直徑孔管)進行粒度分佈測定，求得於體積分佈50%累積值的粒徑(D50)。
＜比表面積＞
依據JIS R 1626:1996(藉由精細陶瓷粉體之氣體吸附BET法之比表面積的測定方法)之「6.2 流動法(3.5)一點法」來測定。吸附質氣體使用氮。[Measurement of physical properties of cerium-based abrasives]
For each of the cerium-based abrasives obtained in the above examples and comparative examples, the particle size distribution and specific surface area were measured. The results of these measurements are also summarized in Table 2.
Each measurement method is as follows.
<Particle size>
The particle size distribution was measured with a particle size distribution measuring device ("Culter particle size distribution measuring device" manufactured by Beckman Coulter Co., Ltd., 30 μm diameter orifice), and the particle size (D50) obtained from the 50% cumulative value of the volume distribution .
<Specific surface area>
Measured according to "6.2 Flow method (3.5) One-point method" of JIS R 1626: 1996 (Measurement method of specific surface area by gas adsorption BET method of fine ceramic powder). Nitrogen is used as the adsorbate gas.
[研磨評估]
使用上述實施例及比較例中所得之各鈰系研磨材，調製以濃度10質量%使其分散於水而成之研磨材漿體。使用此研磨材漿體，以下述之研磨條件，以單面研磨機研磨TFT液晶顯示器用無鹼玻璃之試料(50mm×50mm×厚度1.1mm，研磨面積25cm2
)，對於研磨速度及研磨傷痕進行評估。評估結果總結表示於表2。
＜研磨條件＞
研磨墊 ：發泡聚胺甲酸酯
下定盤旋轉數：260rpm
研磨時壓力 ：80g/cm2
研磨時間 ：20分鐘×3片[Grind evaluation]
Using each of the cerium-based abrasives obtained in the above Examples and Comparative Examples, a slurry of abrasives prepared by dispersing it in water at a concentration of 10% by mass was prepared. Using this polishing material slurry, a sample of alkali-free glass for TFT liquid crystal display (50mm × 50mm × thickness 1.1mm, polishing area 25cm 2 ) was polished with a single-side grinder under the following polishing conditions, and the polishing rate and polishing scars were carried out Evaluation. The evaluation results are summarized in Table 2.
＜ Polishing conditions ＞
Grinding pad: foamed polyurethane lower plate rotation number: 260rpm
Pressure during grinding: 80g / cm 2
Grinding time: 20 minutes × 3 pieces
各評估方法如下述。
＜研磨速度＞
每1片試料以測微器測定5處之研磨前後的厚度，求得厚度之減少量的平均值(ΔT[μm])。將試料3片之[ΔT/研磨時間(20分鐘)]的平均值定為研磨速度。
＜研磨傷痕＞
利用微分干涉顯微鏡(奧林巴斯股份有限公司製「BX51M」)以倍率50倍觀察試料之研磨面計測傷痕之條數，求得試料3片之平均值。The evaluation methods are as follows.
<Grinding speed>
For each sample, the micrometer was used to measure the thickness of 5 places before and after polishing, and the average value of the thickness reduction (ΔT [μm]) was obtained. The average value of [ΔT / grinding time (20 minutes)] of 3 samples was defined as the polishing rate.
<Abrasive scars>
Using a differential interference microscope ("BX51M" manufactured by Olympus Corporation) to observe the number of scratches on the polished surface of the sample at a magnification of 50 times, the average of 3 samples was obtained.
由表2可明白，確認到在濕式粉碎步驟中，使用混合氧化稀土之未破碎品作為原料之情形(比較例4)，漿體中之固體成分濃度50質量%幾乎為進料量之上限，相對於此，使用混合氧化稀土之破碎品作為原料之情形(實施例8)，可使進料量增加至漿體中之固體成分濃度61質量%左右，且，至得到均勻的混合漿體為止的濕式粉碎之處理時間亦可縮短。
又，確認到由使用混合氧化稀土之破碎品作為原料之固體成分濃度高的混合漿體所製造之鈰系研磨材(實施例8)，與使用混合氧化稀土之未破碎品作為原料之利用以往方法製造之鈰系研磨材(比較例4)相比，組成、物性及研磨特性(研磨評估)為相同。
由此可知，本發明之製造方法，可說是可在不使鈰系研磨材之研磨特性降低下，使生產效率提升者。As can be understood from Table 2, in the case of using the unbroken product of mixed rare earth oxide as the raw material in the wet pulverization step (Comparative Example 4), the solid content concentration of 50% by mass in the slurry is almost the upper limit of the feed amount Contrary to this, in the case of using a crushed product of mixed rare earth oxide as a raw material (Example 8), the feed amount can be increased to about 61% by mass of the solid content concentration in the slurry, and, until a uniform mixed slurry is obtained The processing time of the wet crushing up to now can also be shortened.
In addition, it has been confirmed that cerium-based abrasives (Example 8) manufactured from a mixed slurry using a crushed product of mixed rare earth oxide as a raw material and a high solid content concentration, and an unbroken product using a mixed rare earth oxide as a raw material have been used conventionally Compared with the cerium-based abrasive material (Comparative Example 4) produced by the method, the composition, physical properties, and polishing characteristics (grinding evaluation) were the same.
From this, it can be said that the manufacturing method of the present invention can improve production efficiency without reducing the polishing characteristics of the cerium-based abrasive.
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- 2018-09-06 CN CN201880058079.XA patent/CN111051463B/en active Active
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- 2018-09-10 TW TW107131696A patent/TWI695060B/en active
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| JP6839767B2 (en) | 2021-03-10 |
| TWI695060B (en) | 2020-06-01 |
| CN111051463B (en) | 2022-01-11 |
| KR20200026288A (en) | 2020-03-10 |
| WO2019049932A1 (en) | 2019-03-14 |
| JPWO2019049932A1 (en) | 2020-05-28 |
| KR102423338B1 (en) | 2022-07-21 |
| MY192996A (en) | 2022-09-20 |
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