JP5259933B2 - Raw material for cerium-based abrasive, method for producing cerium-based abrasive, and cerium-based abrasive - Google Patents

Description

  The present invention relates to a cerium-based abrasive material and a cerium-based abrasive material. Specifically, the present invention relates to a raw material for a cerium-based abrasive containing a rare earth monooxycarbonate or rare earth hydroxide carbonate, and a rare earth carbonate or rare earth oxide, and containing cerium as a main component, and a cerium-based abrasive obtained therefrom.

  The cerium-based abrasive is used for polishing glass such as a glass substrate for hard disk, a glass substrate for liquid crystal or plasma display, and glass for CRT, crystal, semiconductor, etc., and is particularly suitable for polishing glass or crystal.

  Conventionally, as a method for producing this cerium-based abrasive, one having a step of pulverizing by heating a cerium-based rare earth carbonate immersed in an aqueous solution is known. This prior art describes that a carbonate is converted to a monooxy carbonate by immersion heat treatment (see Patent Document 1).

  The raw material for the cerium-based abrasive contains cerium-based rare earth carbonate and cerium-based rare earth oxide as main components, and the ignition loss when heated at 1000 ° C. for 1 hour is 0.5 to 25 on a dry weight basis. % Is known (see Patent Document 2). Furthermore, a cerium-based calcination is produced by mixing ammonium hydrogen carbonate, which is more than three times the theoretical amount in the reaction of rare earth salts such as cerium salts, with rare earth salts, and then heating the mixture to heat the precipitated rare earth hydroxide carbonate. A method for producing an abrasive is known (see Patent Document 3).

JP 2002-348563 A JP 2002-309236 A JP 2003-238934 A

  By the way, the raw material which consists of the monooxy carbonate obtained by the immersion heat processing described in patent document 1, the raw material which adjusted the ignition loss containing the carbonate and oxide described in patent document 2, or patent When the raw material composed of the rare earth hydroxide carbonate described in Document 3 is used for the production of a cerium-based abrasive, it can produce an excellent abrasive with a high polishing speed and less generation of scratches. However, cerium-based abrasives manufactured from these prior art raw materials should be sufficiently satisfactory in recent polishing of glass substrates for hard disks, that is, in polishing applications that require extremely high surface accuracy. I could not polish.

  Therefore, the present invention provides a raw material for a cerium-based abrasive suitable for producing a cerium-based abrasive that provides a polished surface with excellent surface accuracy and has a high polishing speed. Another object of the present invention is to provide a method for producing a cerium-based abrasive using the raw material, and to provide a cerium-based abrasive that can realize a highly accurate polished surface and has a high polishing speed.

  In order to solve the above problems, a raw material for a cerium-based abrasive according to the present invention contains at least one of a rare earth carbonate or a rare earth oxide, and at least one of a rare earth monooxy carbonate or a rare earth hydroxide carbonate, and a rare earth element. As the main component, cerium was used as the main component. When such raw materials are used for the production of cerium-based abrasives, sintering occurs uniformly and moderately during roasting, and when used for polishing, an abrasive that produces a polished surface with high polishing speed and high accuracy is manufactured. it can.

In the cerium-based abrasive raw material according to the present invention, the rare earth element needs to contain cerium as a main component. The meaning of the main component indicates that the cerium content is the largest among the rare earth elements among the content of the raw material converted into an oxide, that is, the cerium oxide content is the highest among all the rare earth oxide equivalents. The cerium oxide content in the total rare earth oxide equivalent weight in the raw material _(CeO 2 / TREO) is preferably at least 40 mass%, more preferably at least 50 wt%. This is because such a raw material has a high polishing rate and can produce a long-life cerium-based abrasive.

  In the cerium-based abrasive of the present invention, powder X-ray diffraction measurement using a CuKα1 line was performed on 2θ under the conditions of a tube voltage of 40 kV, a tube current of 150 mA, a scan speed of 4 ° / min, and a sampling width of 0.02 °. When measured for a range including 5 to 40 °, the maximum peak (a1) that appears in the range of 2θ of 10.4 ± 1.0 ° and the maximum peak that appears in the range of 28.3 ± 0.7 ° ( Among the a2), the peak intensity (A) of the larger peak (a), the maximum peak (b1) appearing in the range of 25.9 ± 1.0 °, and 17.8 ± 0.5 ° It is preferable that the ratio (B / A) obtained from the peak intensity (B) of the larger peak (b) out of the maximum peak (b2) appearing in the range is 0.01 to 2.0. When the peak intensity ratio (B / A) is less than 0.01, polishing flaws are likely to occur when polishing is performed with a cerium-based abrasive produced from such a raw material. On the other hand, if it exceeds 2.0, the polishing rate of a cerium-based abrasive produced from such a raw material becomes low. And it is more preferable that this peak intensity ratio (B / A) is 0.02-1.7, and it is further more preferable that it is 0.05-1.5.

  For the powder X-ray diffraction measurement in the present invention, Cu-Kα1 ray is used, tube voltage 40 kV, tube current 150 mA, scan speed 4 ° / min, sampling width 0.02 °, scan range 2θ = 5-40 °. The range is, for example, 5 to 80 °.

  In addition, regarding the peak intensity obtained by powder X-ray diffraction measurement, when the background cannot be ignored, in the chart of the peak intensity of X-ray diffraction, if possible, the base line is drawn so as to be the lower tangent, and the peak position The peak intensity is obtained by subtracting the intensity of the lower tangent from the top intensity at. For example, in the case of a raw material obtained by calcining a rare earth carbonate containing a rare earth monooxy carbonate or a rare earth hydroxide carbonate, the maximum peak appearing at 28.3 ± 0.7 ° is a slightly broad peak of the oxide, In many cases, the base line can usually be drawn around 20 ° to 40 °.

Further, the maximum peak in the X-ray diffraction of each substance is specifically as follows. For example, the maximum peak that appears in the range of 2θ of 10.4 ± 1.0 ° is that of cerium carbonate hydrate (ICDD card No. 38-0377, Ce ₂ (CO ₃ ) ₃ · 8H ₂ O). Yes, even if rare earth elements such as lanthanum and neodymium are included in addition to cerium, a peak appears at almost the same position.

The maximum peaks appearing in the range of 2θ of 28.3 ± 0.7 ° are usually cerium oxide (CeO ₂ ) (ICDD card No. 34-0394 or 43-1002), Ce _0.75 Nd _0.25 O. _1.875 (ICDD card No. 28-0266), Ce _0.5 Nd _0.5 O _1.75 (ICDD card No. 28-0267). In the case of high-purity CeO ₂ , the maximum peak tends to appear at about 28.6 °, but if a rare earth element such as lanthanum or neodymium is included in addition to cerium, the peak shifts to a lower angle side. Moreover, although the peak of cerium carbonate octahydrate also exists in this range, the intensity of the peak of cerium carbonate octahydrate is 10.4 ± 1. If the maximum peak at 28.3 ± 0.7 ° is larger than the maximum peak at 0 °, there is no effect. In the present specification, these oxide peaks may be collectively referred to as Ce (IV) -containing rare earth oxide peaks.

The maximum peak appearing in the range of 2θ of 15.9 ± 1.0 ° is that of cerium monooxycarbonate (Ce ₂ (CO ₃ ) ₂ O.H ₂ O) (ICDD card No. 44-0617). In addition to cerium, even if it contains rare earth elements such as lanthanum and neodymium, a peak appears at almost the same position.

The maximum peak that appears in the range of 2θ of 17.8 ± 0.5 ° is that of cerium hydroxide carbonate (CeCO ₃ OH) (ICDD card No. 32-0189), but besides cerium, lanthanum, neodymium, etc. Even if the rare earth element is contained, a peak appears at almost the same position.

  The cerium-based abrasive raw material according to the present invention preferably has a loss on ignition on the basis of dry mass at a temperature of 1000 ° C. for 2 hours of 5 mass% to 45 mass%. This ignition loss is specified by the mass reduction rate after the cerium-based abrasive raw material that is the object is sufficiently dried at 105 ° C. in advance. When the loss on ignition is less than 5% by mass, the manufactured abrasive tends to generate abrasive flaws, and when it exceeds 45% by mass, the polishing rate of the manufactured abrasive tends to decrease. And in the raw material which does not contain an oxide, 25-40 mass% is preferable, and in the raw material containing an oxide, 5-25 mass% is preferable.

  The cerium-based abrasive raw material according to the present invention described above (hereinafter sometimes simply referred to as a raw material) is made of a rare earth monooxy carbonate, a rare earth hydroxide carbonate, a rare earth carbonate, or a rare earth oxide (hereinafter referred to as these materials). Substances may be referred to simply as materials), but these materials can be obtained as follows.

First, the rare earth monooxy carbonate or rare earth hydroxide carbonate in the present invention can be produced by using a rare earth carbonate obtained as follows or a rare earth refined liquid which is an intermediate substance thereof. In other words, after cerium-containing rare earth concentrate is decomposed by sulfuric acid decomposition method or alkali decomposition method, impurities other than rare earth elements are separated and removed mainly by fractional precipitation and fractional dissolution, and if necessary, mainly by rare earth components by solvent extraction method Is separated and purified to prepare a rare earth purified liquid. Then, the rare earth carbonate precipitate is produced by mixing the rare earth refined liquid with a carbonate-based precipitant such as ammonium hydrogen carbonate. This is filtered and washed with water to produce a rare earth carbonate. The rare earth carbonate thus obtained is almost identical to cerium carbonate hydrate (ICDD card No. 38-0377, Ce ₂ (CO ₃ ) ₃ · 8H ₂ O) by X-ray diffraction measurement. A diffraction pattern is obtained, and cerium monooxycarbonate (Ce ₂ (CO ₃ ) ₂ O.H ₂ O) (ICDD card No. 44-0617) or cerium hydroxide carbonate (CeCO ₃ OH) (ICDD card No. 32-0189) ) Is different.

  The rare earth monooxy carbonate in the present invention can be produced by mixing the rare earth carbonate and water and heating at 60 to 100 ° C. Regarding heating, the water may be heated before mixing with the rare earth carbonate or may be heated after mixing.

  Further, when the above rare earth refined solution and a carbonate-type precipitant such as ammonium hydrogen carbonate are mixed, a precipitate of rare earth carbonate is formed, and when this is filtered and washed with water, it becomes a rare earth carbonate. The salt may be produced by heat treatment at 60 to 100 ° C. without filtration or washing with water, that is, in a state where the precipitate is produced, or by adding an alkali such as a carbonate-based precipitant or ammonia water. it can. Then, the amount of the carbonate-based precipitant used for the precipitation of the rare earth carbonate is set to 1.2 times or more of the theoretical amount relative to the rare earth refined liquid, or after the precipitation is formed, an alkali such as a precipitant or ammonia water is added. When heated, the hydroxide carbonate can be produced almost certainly.

  Furthermore, the rare earth oxide in the present invention can be produced by roasting the rare earth carbonate, oxalate, hydroxide and the like, but the rare earth carbonate is heated at a temperature of 550 to 750 ° C. for 10 hours or more, preferably 24 A product produced by roasting for more than an hour is suitable as a raw material for producing a cerium-based abrasive with a small number of abrasive scratches and a high polishing rate.

The raw material for the cerium-based abrasive of the present invention can be produced by mixing so as to contain at least one of a rare earth carbonate or a rare earth oxide, and at least one of a rare earth monooxy carbonate or a rare earth hydroxide carbonate, The mixing ratio at this time is as follows. When the cerium-based abrasive raw material is used without being calcined after mixing, the mixing ratio in the TREO mass of rare earth carbonate or rare earth oxide: rare earth monooxy carbonate or rare earth hydroxide carbonate is 95: 5 to 5 : 95 is preferable. More preferably, it is 90:10 to 10:90, and further preferably 80:20 to 20:80. When mixed at such a ratio, the above-mentioned X-ray diffraction peak intensity ratio can be easily obtained in a suitable range. In addition, when the raw materials are mixed and calcined and used, the mixing ratio may be selected so that the rare earth monooxy carbonate or hydroxide carbonate is larger than 20: 1. It is. In the present invention, roasting in the case of producing a raw material means firing so that only the peak of the rare earth oxide is observed in the X-ray diffraction measurement, and calcination in the case of producing the raw material. Refers to firing to a state where peaks other than rare earth oxides (rare earth monooxy carbonate, rare earth hydroxide carbonate, rare earth carbonate, etc.) remain in the X-ray diffraction measurement.

Furthermore, when manufacturing the raw material for cerium-based abrasives of the present invention, it is necessary that cerium is a main component as the rare earth element contained in the raw material after mixing. CeO ₂ / TREO is preferably 40% by mass or more, and more preferably 50% by mass or more. In addition, each material before mixing, that is, rare earth monooxy carbonate, rare earth hydroxide carbonate, rare earth carbonate, and rare earth oxide is preferably 40% by mass or more, or 50% by mass or more of CeO ₂ / TREO. . For example, a rare earth carbonate mainly composed of cerium as a rare earth element and CeO ₂ / TREO of 40% by mass or 50% by mass, or this rare earth carbonate is roasted at 550 to 750 ° C. for 10 hours or more. If at least one of the rare earth oxides prepared in this way and at least one of the rare earth monooxy carbonate or rare earth hydroxide carbonate produced from the rare earth carbonate are mixed, the CeO ₂ / The TREO can be the same as that of the raw material after mixing.

  Moreover, the raw material for cerium-based abrasives according to the present invention can be partially obtained as a rare earth monooxycarbonate or a rare earth hydroxide carbonate by subjecting the rare earth carbonate to steam treatment. As the steam used here, steam of 100 ° C. or higher generated by a general steam generating boiler can be used, and the amount of steam used is preferably 0.05 to 0.5 kg per 1 kg of TREO. Note that cerium monooxycarbonate is likely to be produced when subjected to steam treatment.

  As another method, the rare earth carbonate is subjected to a low temperature (40 ° C. or more and less than 60 ° C.) immersion heat treatment, so that a part of the rare earth carbonate is changed to a rare earth monooxy carbonate or a rare earth hydroxide carbonate, and the cerium according to the present invention. It is also possible to produce raw materials for system abrasives. In this case, the rare earth carbonate and water may be mixed and then heated, or the rare earth carbonate may be mixed with the heated water. Further, when the temperature is lower than 40 ° C., rare earth monooxy carbonate is hardly generated, and when the temperature is 60 ° C. or higher, the ratio of the rare earth monooxy carbonate tends to be excessive. When mixed with dilute aqueous ammonia instead of water and heated at low temperature, a rare earth carbonate partially made of rare earth hydroxide carbonate or monooxy carbonate can be obtained.

  Furthermore, the raw material for a cerium-based abrasive according to the present invention can be produced by partially using rare earth monooxycarbonate or rare earth hydroxide carbonate during the production of the rare earth carbonate. When the rare earth purified liquid and the precipitating agent are mixed at a temperature of 50 ° C. or higher, a part thereof can be a rare earth monooxy carbonate or a rare earth hydroxide carbonate. Usually, in this method, a rare earth monooxycarbonate is likely to be produced, but if a carbonate-based precipitant is used 1.5 times or more of the theoretical amount, a rare earth hydroxide carbonate is likely to be produced.

  The raw material for the cerium-based abrasive of the present invention can also be produced by calcining rare earth monooxycarbonate or rare earth hydroxide carbonate. A calcination temperature of 200 to 600 ° C. and a calcination time of 1 to 72 hours are suitable. Specifically, the calcining temperature is preferably 24 to 72 hours at 200 ° C., 4 to 48 hours at 400 ° C., and 1 to 12 hours at 600 ° C. And when manufacturing a raw material by calcination, it is preferable to calcine so that the ignition loss after calcination may be 5-25 mass%. In the X-ray diffraction of the cerium-based abrasive raw material of the present invention, at least one of a rare earth monooxy carbonate or a rare earth hydroxide carbonate and a rare earth oxide peak can be confirmed.

  In addition, this calcining treatment includes a raw material produced by mixing and adjusting the above materials, a raw material produced by subjecting a rare earth carbonate to steam treatment, a raw material produced by subjecting a rare earth carbonate to low-temperature immersion heating treatment, and a rare earth carbonate. It is also possible to carry out the process for each raw material produced by converting a part of the rare earth monooxycarbonate or rare earth hydroxide carbonate during production. A cerium-based abrasive produced from a calcined raw material can increase the polishing speed while having a highly accurate surface to be polished. In the case of this calcination treatment, it is preferable that the raw material used for calcination does not contain a rare earth oxide. Suitable calcining temperature, calcining time, and ignition loss are the same as above. When at least one of rare earth monooxy carbonate or rare earth hydroxide carbonate and a raw material containing rare earth carbonate are calcined, the peak of rare earth carbonate appearing at 10.4 ± 1.0 ° at 2θ is Although it tends to disappear, the peak may be detected.

  The cerium-based abrasive raw material of the present invention can also be produced by mixing at least one of a rare earth monooxy carbonate or a rare earth hydroxide carbonate and a calcined rare earth carbonate. In this case, a rare earth carbonate partially containing a rare earth carbonate that has been partially calcined or a rare earth carbonate that has been calcined under the above calcining conditions can be used.

  Furthermore, the above-mentioned rare earth carbonate is calcined, and a part of the calcined rare earth carbonate is converted to a rare earth monooxy carbonate or a rare earth hydroxide carbonate, and the above steam treatment or low-temperature immersion heat treatment is performed. By carrying out, the raw material for cerium-based abrasives according to the present invention can also be produced.

  When producing a cerium-based abrasive using the above-described cerium-based abrasive material of the present invention, the raw material is preferably roasted at 600 to 1200 ° C. When the roasting temperature is less than 600 ° C., the polishing speed of the obtained cerium-based abrasive is reduced. When the roasting temperature is higher than 1200 ° C., polishing with the obtained cerium-based abrasive tends to generate a lot of scratches. . As for this roasting temperature, 700-1100 degreeC is more preferable. And as baking time, 0.2 to 72 hours are preferable, and 0.5 to 48 hours are more preferable. When the roasting time is less than 0.2 hours, the polishing speed of the obtained cerium-based polishing becomes small, and when it exceeds 72 hours, many abrasive scratches tend to occur.

  Further, when producing a cerium-based abrasive using the raw material for cerium-based abrasive of the present invention, the raw material has a particle size (D50) having a cumulative volume of 50% from the small particle size side by the laser diffraction / scattering method. It is preferable to grind | pulverize so that it may become 0.3-4.0 micrometers. It is preferable to use a wet medium mill for the pulverization treatment. Usually, it is preferable to use a pulverizing medium having a diameter of 0.2 to 5 mm. In the case of a medium other than a sphere, the same range as a sphere having a diameter of 0.2 to 5 mm is preferable. In addition, when performing a wet grinding process, it is preferable to filter, dry, and crush before baking.

  And when manufacturing a cerium type abrasive | polishing material using the raw material for cerium type abrasives of this invention, it is preferable to perform a dry grinding | pulverization and a dry classification after baking. After roasting, wet grinding or wet classification can be performed to obtain a cerium-based abrasive slurry. Naturally, an abrasive slurry can also be obtained by mixing cerium-based abrasive powder with a dispersion medium such as water, and the slurry obtained by wet pulverization or wet classification is dried and pulverized to obtain a cerium-based abrasive. It is also possible to obtain a powder.

  According to the present invention, it is possible to easily manufacture an excellent cerium-based abrasive with a high polishing speed and less generation of polishing scratches. In particular, it is possible to provide a cerium-based abrasive for polishing such as a glass substrate for a hard disk, that is, a polishing application that requires extremely high surface accuracy.

  Hereinafter, although the best mode in the present invention is described based on an example, the present invention is not limited to the following example.

  First, the cerium-based abrasive raw material used when the cerium-based abrasive of this example was manufactured will be described. Table 1 shows some of the raw material types used in this example.

  Each raw material of d1 to d18 shown in Table 1 is a mixture of a rare earth carbonate (c1), a rare earth oxide (c2), a rare earth monooxycarbonate (c3), or a rare earth hydroxide carbonate (c4) at a predetermined ratio. It was obtained by adjusting. Therefore, the materials c1 to c4 used as the raw materials will be described.

Rare earth carbonate (c1: CeO ₂ / TREO 60 mass%) was produced as follows. Chinese rare earth carbonate (CeO ₂ / TREO 60 mass%, this material is c0) was dissolved in hydrochloric acid, filtered and diluted with water to obtain a rare earth solution of TREO 52 g / L, pH 2.0. Then, the rare earth solution (about 20 ° C.) is added over 60 minutes at a constant addition rate to the stirring solution of the ammonium hydrogen carbonate aqueous solution (0.5 mol / L, about 20 ° C.) to form a precipitate. The precipitate was recovered by filtration and washing with water. The amount of ammonium hydrogen carbonate used was 1.2 times the theoretical amount with respect to rare earth elements. When the X-ray diffraction pattern of the rare earth carbonate (c1) was examined, it was consistent with Ce ₂ (CO ₃ ) ₃ · 8H ₂ O, and the rare earth monooxy carbonate (Ce ₂ (CO ₃ ) ₂ O · H ₂ O) and rare earth hydroxide hydroxide (CeCO ₃ OH) peaks were not observed. The same result was obtained with Chinese rare earth carbonate (c0).

The rare earth oxide (c2: CeO ₂ / TREO 60 mass%) is composed of the rare earth carbonate (c1).
Was obtained by baking at 720 ° C. for 48 hours. When the X-ray diffraction pattern of the rare earth oxide (c2) was examined, it was consistent with the Ce (IV) -containing rare earth oxide, and rare earth carbonate (Ce ₂ (CO ₃ ) ₃ · 8H ₂ O), rare earth monooxy The peaks of carbonate (Ce ₂ (CO ₃ ) ₂ O · H ₂ O) and rare earth hydroxide carbonate (CeCO ₃ OH) were not observed.

Rare earth monooxy carbonate (c3: CeO ₂ / TREO 60 mass%) is a mixture of the rare earth carbonate (c1) and pure water at a mass ratio of 1: 2, heated to 90 ° C., and maintained at 90 ° C. for 12 hours. And then cooled to 50 ° C. and then filtered. When the X-ray diffraction pattern of the rare earth monooxycarbonate (c3) was examined, it was consistent with the rare earth monooxycarbonate (Ce ₂ (CO ₃ ) ₂ O.H ₂ O), and the Ce (IV) -containing rare earth oxide , rare earth carbonate _{(Ce 2 (CO 3) 3} · 8H 2 O), peaks of the rare earth hydroxycarbonate (CeCO ₃ OH) was observed.

The rare earth hydroxide carbonate (c4: CeO ₂ / TREO 60% by mass) was mixed with an aqueous solution of ammonium hydrogen carbonate (0.5 mol / L, about 20 ° C.), and the rare earth solution in the rare earth carbonate described above was stirred. (TREO 52 g / L, pH 2.0, about 20 ° C.) was added over 60 minutes at a constant addition rate, and after forming a precipitate, the temperature was raised to 90 ° C. without filtration and maintained at 90 ° C. for 12 hours. The mixture was allowed to cool to 50 ° C. and then filtered and washed with water. The amount of ammonium hydrogen carbonate used was 1.5 times the theoretical amount with respect to rare earth elements. When the X-ray diffraction pattern of the rare earth hydroxide carbonate (c4) was examined, it was in agreement with the rare earth hydroxide carbonate (CeCO ₃ OH), and the Ce (IV) -containing rare earth oxide, rare earth carbonate (Ce ₂ ( The peaks of CO ₃ ) ₃ · 8H ₂ O) and rare earth monooxycarbonate (Ce ₂ (CO ₃ ) ₂ O · H ₂ O) were not observed.

  The materials c1 to c4 obtained as described above were mixed at the respective ratios shown in Table 1 to produce cerium-based abrasive raw materials d1 to d18. Moreover, each raw material of d1-d18 did not perform a calcination process. In addition, about the material of said c0, c1, c3 which is not mixed, it used as a raw material for cerium type abrasives of a comparative example.

Next, the cerium-based abrasive raw material obtained by a method other than the mixing preparation shown in Table 1 will be described. Here, a case where a raw material is produced by making a part of the rare earth carbonate (c1) into a rare earth monooxycarbonate or a rare earth hydroxide carbonate (hereinafter, this production method is referred to as a precipitation generation method) is shown. . In this precipitation generation method, when the rare earth carbonate (c1) is produced, a Chinese rare earth carbonate (CeO ₂ / TREO 60% by mass) is dissolved in hydrochloric acid, and then filtered and diluted with water to give TREO 52 g / L, pH 2. 0 rare earth solution was obtained, and an aqueous solution of ammonium hydrogen carbonate as a precipitating agent was added thereto under a predetermined condition to produce a precipitate to produce a raw material. Specifically, the rare earth solution heated to 70 ° C. was added to the stirred ammonium hydrogen carbonate aqueous solution (0.5 mol / L, about 20 ° C.) at a constant addition rate over 60 minutes, and precipitation was performed. The precipitate was collected by filtration and washing with water. In this precipitation generation method, the amount of ammonium hydrogen carbonate used is 1.2 times the theoretical amount of the rare earth element (e1), 1.5 times the amount of raw material (e2), 2.0 times the amount of raw material (e3) The following three types were manufactured. These e1 to e3 cerium-based abrasive materials had a CeO ₂ / TREO content of 60% by mass.

As another method other than the mixing preparation, a rare earth carbonate was steamed to produce a cerium-based abrasive material (hereinafter referred to as a steaming method). In this steam treatment method, 0.2 kg of steam (140 ° C., 118 kPa (1.2 kgf / cm ² )) per 1 kg of TREO is sprayed on the rare earth carbonate (c1) for 5 minutes, and the raw material for cerium-based abrasive ( e4) was produced.

  Further, as another method other than the mixed preparation, a rare earth carbonate (c1) was subjected to a low temperature immersion heat treatment to produce a cerium-based abrasive raw material (hereinafter referred to as a low temperature immersion heat treatment method). In this low temperature immersion heat treatment method, the rare earth carbonate (c1) and pure water are mixed at a mass ratio of 1: 2 (mixed solution temperature 20 ° C.), and the mixed solution is heated to 50 ° C. A cerium-based abrasive raw material (e5) was produced by filtering after holding at 12 ° C. for 12 hours.

Since each of the cerium-based abrasive materials (d1 to d18, e1 to e5) described above has a CeO ₂ / TREO content of 60% by mass, different CeO ₂ / TREO materials were also produced. Each rare earth carbonate produced in China with a CeO ₂ / TREO content of 34% by mass, 40% by mass, 50% by mass, and ≧ 99.9% by mass is treated under the same conditions as the rare earth carbonate (c1). After the preparation, it was produced by steam treatment. The conditions for the steam treatment were the same as in the production of e4. Here, raw material f1 (CeO ₂ / TREO 34 mass%, La ₂ O ₃ / TREO 39 mass%), raw material f2 (CeO ₂ / TREO 40 mass%, La ₂ O ₃ / TREO 35 mass%), raw material f3 (CeO ₂ / TREO 50 4% of mass%, La ₂ O ₃ / TREO 30 mass%) and raw material f4 (CeO ₂ /TREO≧99.9 mass%) were produced.

  Since each cerium-based abrasive material (d1 to d18, e1 to e5) described above was not calcined, a calcined material was further produced. The calcined raw material includes a raw material (g1) produced by calcining the rare earth carbonate (c1), a raw material (g2) produced by calcining the rare earth monooxycarbonate (c3), a rare earth A raw material (g3) produced by calcining a hydroxide carbonate (c4), a raw material produced by calcining a raw material (e2) produced with a precipitant use amount of 1.5 times in the above precipitation generation method ( 5 types of the raw material (g5) manufactured by calcining the raw material (e4) manufactured by g4) and the said steam processing method were prepared. All of the five types of calcining treatments were performed under calcining conditions of 500 ° C. for 6 hours.

  Subsequently, a cerium-based abrasive produced using the above-described cerium-based abrasive material will be described. A basic manufacturing flow of a cerium-based abrasive is shown in FIG. The raw materials used were the raw materials d1 to d18, the raw materials e1 to e5, the raw materials f1 to f4, and the raw materials g1 to g5. For comparison, rare earth carbonate (c0), rare earth carbonate (c1), rare earth Monooxycarbonate (c3) was also used as a raw material. Each cerium-based abrasive (Examples 1 to 40, Comparative Examples 1 to 9) shown in Tables 2 to 4 was produced using these raw materials according to the production flow shown in FIG. The manufacturing flow shown in FIG. 1 will be explained. First, wet pulverization is performed by adding 200 kg of pure water to 100 kg of raw material and using an attritor (made by Mitsui Mining Co., Ltd .: using 3 mmφ zirconia ball grinding media). A wet milling process for hours was performed. Then, it filtered with the filter press and pulverized what was dried and processed using the atomizer (Fuji Paudal Co., Ltd. product). And after crushing what was crushed at 900 degreeC for 48 hours, it grind | pulverized using the said atomizer. Then, each cerium-type abrasive was manufactured by classifying with a classifier (turbo classifier: manufactured by Nissin Engineering Co., Ltd.).

  Further, in the production of the cerium-based abrasive, the conditions were changed with respect to the baking conditions and the fluorination treatment, which are production conditions. Specifically, as shown in Tables 2 to 4, the raw material e4 was subjected to a test in which the roasting temperature was changed. Moreover, about the raw material f1-the raw material f4, the test which temperature-adjusted so that the abrasive particle size might become the same besides the baking temperature 900 degreeC was also implemented. As for the fluorination treatment, raw materials e4 and g4 were prepared by adding 10% HF in an amount corresponding to 6% by mass with F / TREO while stirring the slurry after wet pulverization.

For each of the obtained cerium-based abrasives, the average particle size (D ₅₀ ) and the specific surface area were measured by the BET method. Further, the polishing speed, the scratches, and the surface properties of the surface to be polished (surface roughness Ra, minute waviness) )investigated. The results are shown in Tables 2-4. Moreover, about the used raw material, each peak intensity | strength obtained by the X-ray diffraction, its intensity ratio, and ignition loss were investigated. Hereinafter, each measurement will be described.

Measurement of average particle size (D ₅₀ ): Particle size distribution of each abrasive material and each cerium-based abrasive using a laser diffraction / scattering particle size distribution analyzer (manufactured by Horiba, Ltd .: LA-920) Was measured to determine the average particle diameter (D ₅₀ : particle diameter <median diameter> at a cumulative mass of 50% by mass from the small particle diameter side).

Measurement of BET specific surface area (BET): Conforms to “6.2 Flow method (3.5) single point method” in JIS R 1626-1996 (Method of measuring specific surface area of fine ceramic powder by gas adsorption BET method) Then, the specific surface area of the cerium-based abrasive was measured. At that time, a mixed gas of helium as a carrier gas and nitrogen as an adsorbate gas was used.

Polishing speed: A polishing tester (HSP-2I type, manufactured by Taito Seiki Co., Ltd.) was prepared as a polishing machine. This polishing tester polishes the polishing target surface with a polishing pad while supplying a slurry-like polishing material to the polishing target surface. The abrasive grain concentration of the abrasive slurry was 100 g / L (dispersion medium was water only). In this polishing test, a slurry-like abrasive was supplied at a rate of 5 liters / minute, and the abrasive was recycled. The polishing object was 65 mmφ flat panel glass. A polishing pad made of polyurethane was used. The polishing pad pressure on the polishing surface was 9.8 kPa (100 g / cm ² ), the rotation speed of the polishing tester was set at 100 min ⁻¹ (rpm), and polishing was performed for a predetermined time. And after performing the polishing process for the specific time, it washed with water, dried, measured the glass weight before and behind polishing, calculated | required the reduction | decrease amount of the glass weight by polishing, and calculated | required the polishing value based on this value. In this polishing evaluation, the polishing rate was evaluated using this polishing value. In addition, as shown in Table 4, this polishing rate evaluation value was calculated based on the polishing value obtained with the cerium-based polishing material of Comparative Example 1 as a reference (100). The measurement object of the abrasive scratches, arithmetic average microwaviness, and arithmetic average surface roughness (Ra) described later is glass that has been subjected to a polishing treatment for a specific time, then washed with water and dried.

Abrasion scratches: Abrasion scratches are evaluated by observing the polished glass surface with a reflection method using a 300,000 lux halogen lamp as the light source, scoring the number of large and fine scratches, and then deducting the score from 100 points. The method was performed. In this scratch evaluation, the polishing accuracy required for finish polishing of a glass substrate for a hard disk (HD) or LCD was used as a criterion. Specifically, in Tables 4 and 5, “◎” is 98 points or more (very suitable for finishing polishing of glass substrates for HD and LCD), and “◯” is 95 points less than 98 points. That it is above (suitable for finishing polishing of HD / LCD glass substrates), and “△” is less than 95 points and 90 points or more (can be used for finishing polishing of HD / LCD glass substrates). "X" indicates that it is less than 90 points (cannot be used for finish polishing of glass substrates for HD and LCD).

Arithmetic average micro-waviness: The arithmetic average micro-waviness uses a three-dimensional surface structure analysis microscope (New View 200 manufactured by Zygo) to scan the polishing surface with white light at a measurement wavelength of 0.2 to 1.4 mm. Measured.

Arithmetic average surface roughness Ra: This arithmetic average surface roughness is determined by using DFM (dynamic force mode) with a probe microscope SPA-400 (manufactured by SSI Nanotechnology Co., Ltd.). The 10 μm × 10 μm range was measured to obtain the arithmetic average surface roughness (Ra: nm) value.

X-ray diffraction: Crystal diffraction analysis of each raw material was performed with an X-ray analyzer (manufactured by Mac Science, MXP18). The measurement conditions were Cu-Kα1 wire, tube voltage 40 kV, tube current 150 mA, scan speed 4 ° / min, sampling width 0.02 °, scan range 2θ = 5 ° -80 °. Then, from the obtained X-ray diffraction pattern, within the range including 2θ = 5 to 40 °, the maximum peak (a1) where 2θ appears in the range of 10.4 ± 1.0 ° and 28.3 ± 0. The maximum peak (a2) appearing in the range of 7 ° was identified, and the maximum peak intensity of both was compared to determine the larger peak intensity (A). Similarly, the maximum peak (b1) appearing in the range of 25.9 ± 1 ° ± 1.0 ° and the maximum peak (b2) appearing in the range of 17.8 ± 0.5 ° are specified, and both The maximum peak intensity was compared to determine the larger peak intensity (B). And the peak intensity ratio (B / A) was computed.

Ignition loss: Ignition loss was measured in accordance with 4.2 ignition loss test of JIS K 0067-1992 "Method for weight loss and residue test" of raw materials dried at 105 ° C for 24 hours. did. However, in this JIS standard, the ignition temperature is stipulated as 650 ± 50 ° C. However, since the stable result cannot be obtained at this temperature, the ignition temperature was measured as 1000 ± 50 ° C.

  As shown in Tables 2 to 4, it was found that the cerium-based abrasive of this example had good characteristics with respect to the polishing speed and the scratches. In particular, the results of polishing scratches and micro undulations have proved to be extremely suitable for polishing such as glass substrates for hard disks, that is, for polishing applications that require extremely high surface accuracy.

Manufacturing flow diagram of cerium-based abrasive.

Claims (5)

In a raw material for a cerium-based abrasive containing at least one of a rare earth carbonate or a rare earth oxide, and at least one of a rare earth monooxy carbonate or a rare earth hydroxide carbonate, the rare earth element having cerium as a main component,
At least one of the rare earth carbonate or rare earth oxide and at least one of the rare earth monooxy carbonate or rare earth hydroxide carbonate are mixed in advance, and used without being calcined after mixing,
The mixing of at least one of the rare earth carbonate or rare earth oxide and at least one of the rare earth monooxy carbonate or rare earth hydroxide carbonate is in the range of 90:10 to 10:90 in terms of the mixing ratio based on the total rare earth oxide equivalent. And
When the cerium-based abrasive raw material is subjected to powder X-ray diffraction measurement for a range including 2θ = 5 to 40 °, the maximum peak (a1) appearing in the range of 2θ of 10.4 ± 1.0 ° and 28. Among the maximum peaks (a2) appearing in the range of 3 ± 0.7 °, the peak intensity (A) of the larger peak (a),
Of the maximum peak (b1) appearing in the range of 2θ 15.9 ± 1.0 ° and the maximum peak (b2) appearing in the range of 17.8 ± 0.5 °, the larger peak (b) A raw material for a cerium-based abrasive, which has a peak intensity (B) and a ratio (B / A) obtained from 0.02 to 1.5. The powder X-ray diffraction measurement is performed using a CuKα1 line under the conditions of a tube voltage of 40 kV, a tube current of 150 mA, a scan speed of 4 ° / min, and a sampling width of 0.02 °. material. The cerium-based abrasive raw material according to claim 1 or 2, wherein the ignition loss based on dry mass at a temperature of 1000 ° C for 2 hours is 5 mass% to 45 mass%. The cerium-based abrasive raw material according to any one of claims 1 to 3, wherein the cerium oxide content (CeO ₂ / TREO) in the amount of all rare earth oxides is 40% by mass or more. The manufacturing method of the cerium type abrasive | polishing material which has the process of baking at 600-1200 degreeC using the raw material for cerium type abrasive | polishing materials of any one of Claims 1-4.

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