TW200846430A - Glass polishing compositions and methods - Google Patents

Abstract

The present invention provides glass polishing compositions and methods suitable for polishing a glass substrate at a down force of 110 g/cm2 or less. One preferred polishing composition comprises a particulate cerium oxide abrasive (e.g., 1 to 15 percent by weight) suspended in an aqueous carrier containing a polymeric stabilizer, e.g., 50 to 1500 ppm of the stabilizer, and optionally, a water soluble inorganic salt. Preferably, the particulate cerium oxide abrasive has a mean particle size in the range of 0.35 to 0.9 μm. Another preferred composition comprises 1 to 15 percent by weight of a particulate cerium oxide abrasive characterized by a mean particle size of at least 0.2 μm and a purity of at least 99.9% CeO2, on a weight basis, suspended in an aqueous carrier at a pH at least 1 unit higher or lower than the isoelectric point (IEP) of the cerium oxide abrasive.

Description

200846430 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a composition and a method for polishing a glass substrate. More particularly, the invention relates to the use of a cerium oxide polishing composition for polishing, glass surfaces. [Prior Art] Liquid crystal display (LCD) and organic light emitting diode (OLED) flat panel devices typically include a thin glass glazing panel on the display surface outside the LCD or OLED unit structure. It is desirable that the panel be thin and highly uniform to minimize the weight of the panel and provide excellent optical properties. OLED and LCD grade glasses include soda lime glass and alkaline earth metal oxide-Al203-SiO2 glass, such as EAGLE® 2000 glass, EAGLEX® L glass, and 1737 glass and the like, which are commercially available from Corning Inc., Corning, New York. . The soil metal oxide component of the glass preferably comprises one or more oxides selected from the group consisting of MgO, CaO, SrO and BaO. Conventional systems for glass panel polishing typically utilize a two-step process that involves removing the initial polishing or etching step of the body of the material (subject removal step), followed by mixing and fixing with water Abrasive pad or glue* A polishing or polishing step of a polishing composition of relatively large cerium oxide particles (e.g., having an average particle size of 2 microns or greater) used in combination. The buffing or polishing step is primarily used to remove damage caused by the body removal step (e. g., pits, scratches, and the like). Since such systems achieve relatively low glass removal rates, for example, removal rates of less than 500 nanometers per minute (nm/min; 0·5 μπι/πήη), such conventional polishing systems 125872.doc 200846430 It does not fully meet the requirements of the glass surface of polished flat panel displays. Such low

The nature of the study is downgraded. In addition, and pits. Surface scratches and pits make the panel light Large cerium oxide particles tend to settle out of the water in the conveyor line and the slurry reservoir, resulting in manufacturing difficulties. In the polishing technique, the substrate carrier or polishing head is mounted on the carrier assembly and placed in contact with the polishing pad in the polishing apparatus. The carrier assembly provides a controlled pressure (downforce) to the substrate to force the substrate against the polishing pad. The pad moves relative to the substrate due to an external driving force. The relative movement of the pad to the substrate acts to abrade the surface of the substrate to remove a portion of the material from the surface of the substrate, thereby polishing the surface. Polishing is typically further aided by the chemical activity of the polishing composition and/or the mechanical activity of the abrasive suspended in the polishing composition. In a typical glass polishing system as described above, a relatively high pressure below 丨丨〇 gram/square centimeter (g/cm, 1.56 rpm/psi) must be used to achieve a suitable removal rate. These higher pressures increase the breakage rate of relatively thin glass panels used in LCD and OLED devices. There is a need to develop polishing compositions that are capable of polishing glass, particularly OLED and LCD grade glass panels, with pressures below 11 〇 g/cm2 or less and that have improved slurry processing properties relative to conventional cerium oxide polishing slurry. The lower downforce reduces the amount of glass breakage during polishing relative to conventional polishing methods. It is also desirable to provide a polishing slurry having an improved glass removal rate (i.e., a removal rate greater than 5 Å nm/min) relative to the large particle cerium oxide polishing system typically employed. The present invention provides such compositions. These and other advantages of the present invention, as well as the inventive features, are apparent from the description of the invention. SUMMARY OF THE INVENTION The present invention is directed to a glass polishing composition and a method suitable for polishing glass, particularly OLED and LCD grade glass panels, using 110 fine 2 or less pressure. The preferred aqueous glass polishing composition of the present invention comprises suspension in a stabilizer-containing and optionally water-soluble inorganic salt (e.g., tooth recording)

A particulate cerium oxide abrasive in an aqueous carrier. In a preferred embodiment, the composition comprises a particulate cerium oxide abrasive having an average of from 350 (10) to 900 nm (〇.35 (4) to 〇9 (iv)) suspended in an aqueous carrier by means of a polymeric stabilizer. The stabilizer comprises at least one acidic polymer selected from the group consisting of polyacrylates (e.g., polyacrylic acid), polydecyl acrylate (e.g., polymethacrylic acid), and poly(ethylene). a sulfonate) (for example, poly(ethylenesulfonic acid)), which may be present in the polishing composition in acid form, in salt form (eg, an alkali metal salt) or in partially neutralized form. In another embodiment, 'combination The composition comprises at least one polar nonionic or anionic polymer selected from the group consisting of polyvinylpyrrolidone (PVP), poly(ethylene glycol), poly(2-ethylsulfonium), (4) Ethylcellulose and page gum. The cerium oxide abrasive preferably comprises at least 99.9% by weight of Ce02. In another aspect, the glass polishing composition of the present invention comprises cerium to 5% by weight suspended in waterborne loading. The purity in the agent is by weight At least 99.9% Ce〇2 granular cerium oxide abrasive. The average particle size of the cerium oxide abrasive is at least 〇·2 μπι, preferably in the range of 〇·2 0111 to 11 and the pH value is 872 125 125872.doc 200846430 The isoelectric point (IEP) of the abrasive is at least 1 unit high or low. Typically, the pH of the IEp of cerium oxide is in the range of 6 to 7. In a preferred embodiment, the value of the composition is in the range of 3 to 4. And, as the case may be, 1 to 2 parts per million; more than 5 to 10 ppm) of pyridinic acid (i.e., pyridine-2.carboxylic acid) as a stabilizer. Pyridinium is especially preferred when an abrasive is used at a concentration of 1% by weight. In another preferred embodiment, the value of the composition is in the range of 8 to 9. When used for polishing glass, especially OLED and LCD grade glass panels, such as soda lime glass and alkaline earth metal oxide-Al203-SiO2 glass panels, the present invention provides a relatively greater than nm/min ratio. High glass removal rate. The compositions and methods of the present invention are desirable and readily adaptable for large scale applications. One of the advantages of the stabilized glass polishing composition of the present invention is improved processing properties (i.e., less cerium oxide particles settle on the transfer line and in the slurry reservoir) and improved recyclability. A preferred method embodiment comprises the steps of: contacting a surface of a substrate with a polishing pad and an aqueous glass polishing composition of the present invention; and moving the polishing pad relative to the substrate while maintaining at least a portion of the composition and the substrate and substrate The surface contact therebetween lasts a period of time sufficient to grind at least a portion of the glass from the surface. [Embodiment] The present invention provides a glass polishing composition and a method for polishing a glass panel used in LCD and OLED displays, particularly under pressure of 11 〇 g/cm2 or more. In a first aspect, the glass polishing composition comprises cerium oxide particles suspended in an aqueous carrier by means of a polymeric stabilizer. In some of the more examples, the composition also comprises a water soluble inorganic salt. 125872.doc •10· 200846430 The polymerization stabilizer can be any substance that provides an oxygen (tetra) particle stabilizer. Non-limiting examples of suitable stabilizers include acidic polymers (e.g., propylene polymers, methacrylic polymers, and vinyl sulfonate polymers), polar nonionic polymers (e.g., ethylene chelating polymerization) , ethyl alcohol agglomerate, 2-ethyloxazoline polymer, hydroxyalkyl cellulose) and anionic polysaccharide (xanthan gum). In a preferred embodiment, the stabilizer comprises at least one polymer selected from the group consisting of polyacrylic acid, polymethacrylic acid, and poly(ethylene vinyl), which may be in the form of an acid, a salt or a portion. And the form. In another preferred embodiment, the stabilizer comprises at least one polymer selected from the group consisting of: polyvinylpyrrolidone (pvp), poly(vinyl alcohol), poly(2-ethyl Oxazoline), hydroxyethyl cellulose and xanthan gum. For convenience, the terms "acrylate", ",, polyacrylate", "methacrylic acid polymethacrylate", "quot; sulfonic acid vinegar" and "poly" "Ester)" refers to its acid form, salt form and partially neutralized form. Preferably, the stabilizer is present in the composition in an amount ranging from 5 Torr to 15 (10) parts per million (p_, more preferably (10) to 1000 ppm) of the active ingredient. When polyacrylic acid is used in the method of the present invention, When methyl acetoacetate and/or polyethylene acid S is intended as a stabilizer, the stabilizer preferably has a molecular weight in the range of from 3 Å to 4 M 00 g/mol (g/mol). Stable unless otherwise stated The molecular weight of the agent is a weight average molecular weight (Mw) determined by a solution property technique such as intrinsic viscosity and/or gel permeation chromatography (GPC). When PVP is used as the (four) agent, pvp preferably has from just up to 1,000. In the knives of the 〇〇〇g/m〇l range, as indicated by the so-called K value, it is preferably in the range of 25 to 90. When using poly(ethylene glycol) as a stabilizer I25872. Doc 11 - 200846430 卞 (vinyl alcohol) preferably has a knife in the range of 12 〇〇〇 to 2 〇〇〇〇〇 curry 1. When using poly(2_ethyl 嗔0 sitting lining) as a stabilizer , poly(2-ethylf ° (4)) preferably has a molecular range of 50, _ to 5 〇〇, _ g / mol. The colloidal stability of the particles in the polishing composition is increased by preventing the cerium oxide particles from accumulating and flocculation in the polishing population. Water! The raw inorganic salt (when present) preferably comprises the total composition The weight ratio of the calendering composition is from 0.05 to 〇1% by weight, more preferably 〇% by weight. Preferred inorganic salts include water-soluble salts such as mascara (for example, chlorohydrin). Particularly preferred water-soluble inorganic salts It is a chlorinating planer. VIII. Without wishing to be bound by theory, it is believed that a water-soluble inorganic salt such as chlorinated provides a relatively high ionic strength which increases the friction between the cerium oxide particles and the surface of the glass, thereby Advantageously, the glass removal rate is increased. The cerium oxide abrasive used in this first aspect of the invention preferably has from 350 (10) to _mn, more preferably 45 Å (10) as determined by laser light scattering techniques well known in the art. An average particle size in the range of up to 5 〇〇 nm. The oxygen abrasive is preferably present in the polishing composition in an amount ranging from 15% by weight, more preferably from 5 to 10% by weight, based on the total weight of the composition. Parallel The composition may have any positive value compatible with the core of the composition and suitable for use in a Bronze application. In 4 embodiments, such as when using PVP as a stabilizer, the pH is preferably moderately acidic (eg, '4' To 6). In other embodiments, the pH of the composition is in the range of neutral to alkaline, such as in the range of 7 to 11, more preferably 7 to 9. In the second aspect, the glass of the marriage is The composition comprises from 丨 to 重量% by weight suspended in an aqueous carrier at a purity of at least 99.9%. 125872.doc -12- 200846430

Granular cerium oxide abrasive of Ce〇2. In this second aspect of the invention, the cerium oxide abrasive has an average particle size in the range of at least 〇 2 μπι, preferably 〇 2 0111 to 11 μπι and a pH value equal to the isoelectric point of the cerium oxide abrasive (ΙΕρ ) High or low at least 1 unit. Usually, the pH of the cerium oxide is in the range of 6 to 7.

Typically, conventional cerium oxide abrasives are used at or near the IEp of the polished glass (pH 6-7). It has been surprisingly found that when used at a pH higher or lower than the pH of the IEP, it has a purity of at least 99·9 by weight of Ce 2 (, ultrapure, yttrium oxide) and at least 〇· The cerium oxide having an average particle size of 2, preferably 22 _ to 11 μηη provides a significantly higher glass removal rate of the polished glass. In a preferred embodiment, the composition of the second aspect has a pH value in the range of 3 to 4 and optionally comprises from 2 to 4 parts per million (four) melon; preferably from $ to 10 ppm) of picolinic acid. As a stabilizer. When an abrasive is used at a lower concentration (e.g., a work weight % concentration), it is especially preferred to have - formic acid. In a further preferred embodiment of the invention, the pH of the composition is in the range of 8 to 9. The oxidized decoration of the combination of the present month 4 is ideally suspended in the water of the polishing sputum, and the wounded towel is preferably in a colloidally stable state. The term "gelling" is a suspension of particles + in a liquid carrier. "colloidal stability" means that the material has the smallest particle size over time. In the case of the present invention, if the abrasive is placed in a 100 mL graduated cylinder and allowed to stand for 2 hours without agitation, the bottom of the cylinder is 50 mL/min ([B] In g/mL, it is concentrated with the particles in the 5 〇mL at the top of the cylinder ([T], g/mL, i i „人). The difference is divided by the initial concentration of the particles in the composition. 125872.doc -13- 200846430 ([C], expressed in g/mL) is less than or equal to 〇·5 (ie, ([β] [T])/[C]S0.5), and the particulate abrasive is considered to have colloidal stability. The value of [B]-[T])/[C] is desirably less than or equal to 〇3 and preferably less than or equal to 0, 1. The aqueous carrier of the composition of the present invention may be any suitable for glass polishing. Processed aqueous liquids. The compositions include water, aqueous alcoholic solutions, and the like. The aqueous carrier preferably comprises deionized water. The compositions of the present invention may optionally comprise one or more additives, such as surfactants, biocidal agents. Agents and Analogs The polishing compositions of the present invention can be prepared by any suitable technique, and many such techniques are known to those skilled in the art. For example, the compositions can be batchwise Prepared by a continuous process. Typically the compositions can be prepared by combining the components in any order. The term "component" as used herein includes individual ingredients (eg, abrasives, stabilizers, water soluble inorganic salts, acids, a base and its analogs) and any combination of ingredients. For example, a water-soluble inorganic salt and a stabilizer may be dissolved in water, an abrasive may be dispersed in the resulting solution, and then the components may be uniformly dispersed by any means. The method of incorporating into the composition adds and mixes any other components. If desired, the pH can be adjusted at any suitable time. If desired, the pH of the composition can be adjusted with any suitable acid, base or buffer. The pH adjusting agent includes, but is not limited to, potassium hydroxide, ammonium hydroxide, and nitric acid. The composition may also be provided in the form of a concentrate intended to be diluted with an appropriate amount of water prior to use. In this embodiment, the composition concentrate may comprise a certain amount of cerium oxide abrasive, stabilizer, water-soluble 125872.doc -14- 200846430 inorganic salt and any other components dissolved in an aqueous carrier, such The concentrate was diluted so that the amount of water of the solvent, the components will be appropriately within the scope of the polishing composition

The compositions of the present invention may be incorporated into a single pre-formulated composition comprising a dispersion comprising at least one stabilizer compound, an optional inorganic salt, and other optional ingredients (if necessary) at the desired pH. A cerium oxide abrasive in an aqueous carrier at a value. Alternatively, the composition can be provided in a two-part form (i.e., a two-part article) to avoid potential changes in the activity of the slurry over time. The two-part article comprises a first container comprising at least a stabilizer and optionally an inorganic salt; and a second container comprising a ground in dry form or preferably in an aqueous carrier (eg, deionized water) A cerium oxide particulate abrasive in the form of a slurry. Preferably, the first container and the second container together with the instructions for mixing the contents of the container to form a composition of the present invention. The solar value of each package can be selected and the concentration of the various components such that, after mixing the contents of the first container with the contents of the second container, for example, is it suitable to suspend it in an appropriate amount? Suitable for this type of cerium oxide (for example, di 5% by weight) in an aqueous carrier containing 11 (for example, 7 to U) and containing an appropriate amount of stabilizer (for example, 5 to 15 Å) and optional components A polishing composition of the inventive method. Including at least one dissolved in a first aqueous carrier, the second container is packaged together, and the particulate cerium oxide in the second container carrier is in an average particle size of from 350 nm to 900 nms. In a preferred embodiment, the two The partial product comprises a first container, a stabilizer in the aqueous carrier, and the first phase comprises a suspension preferably in the second water

Within the range of nm<, and the stabilizer is 125872.doc -15- 200846430 is selected from the group consisting of polyacrylates, polymethacrylates, poly(vinylsulfonate), and salts of any of the foregoing. After mixing the contents of the first container with the contents of the second container, the polishing composition of the present invention is formed, the composition comprising 1 to 15% by weight of the cerium oxide abrasive and 5 to 15 ppm The at least one stabilizer. In another preferred embodiment, the two-part article comprises a first container comprising at least one stabilizer dissolved in the first aqueous carrier and packaged with a second container, the second container A particulate cerium oxide abrasive preferably suspended in a second aqueous carrier is included. The cerium oxide abrasive is characterized in that the average particle size is in the range of 350 nm to 900 nm, and the at least one stabilizer is selected from the group consisting of polyvinylpyrrolidone, poly(vinyl alcohol), and poly(vinyl ether). A group consisting of oxazoline, hydroxyethyl cellulose and xanthan gum. After mixing the contents of the first container with the contents of the second container, the polishing composition of the present invention is formed, the composition comprising from 15% by weight of the cerium oxide abrasive and from 50 to 1500 ppmi of the at least one stable Agent. Optionally, the first package of the two-part article may comprise a concentration of a water-soluble inorganic salt (e.g., a cerium salt) such that the mixed polishing composition comprises from 5 to 0.1% by weight of a salt of cerium. Both the first and second aqueous carriers preferably comprise deionized water. The formulations and physicochemical properties of the two aqueous carriers may be the same or different (for example, the pH of each carrier may be the same or different as needed or desired, and each carrier may contain the same or different amounts Optional wounds such as solvents, biocides, buffers, surfactants and the like. The preferred method of the present invention comprises (1) contacting the glass substrate with a polishing pad and the polishing composition of the present invention as described in 125872.doc •16·200846430; and (π) moving the polishing pad relative to the substrate and There is at least a portion of the polishing composition therebetween, whereby at least a portion of the glass is ground from the surface of the substrate to polish the substrate. The glass substrate is preferably an OLED or LCD grade glass, such as soda lime glass or alkaline earth metal oxide-Al2〇rSiO2 glass, wherein the soil metal oxide comprises one or more selected from the group consisting of MgO, CaO, SrO and the well-known in the art. BaO oxide. The polishing method of the present invention is suitable for use in combination with a chemical mechanical (CMP) polishing apparatus. A CMP apparatus typically includes a platen that moves in use and has a velocity resulting from orbital, linear or circular motion. A polishing pad is mounted to the platen and moves with the platen. A carrier assembly holds a substrate to be polished. Polishing is achieved by contacting the substrate with the mat while maintaining a portion of the polishing composition of the present invention disposed between the mat and the substrate. The substrate is then moved relative to the surface of the wiper pad while the substrate is forced against the pad surface at a pressure (preferably 1 1 〇 g/em 2 or less) selected to be sufficient for the desired glass removal rate. The polishing of the substrate is achieved by a combination of chemical polishing and mechanical action of the polishing pad and the polishing composition on the surface of the substrate. The substrate can be planarized or polished with the polishing composition of the present invention using any suitable polishing pad (e.g., a polishing surface). Suitable evacuation pads include, for example, fixed abrasive pads, woven pads, and non-woven pads. In addition, suitable polishing pads can comprise any suitable polymer having different densities, hardnesses, thicknesses, compressibility, ability to rebound after compression, and compression modulus. Suitable polymers include, for example, polyvinyl chloride, polyvinyl fluoride, nylon, fluorocarbon, carbonate, polyester, polyacrylate, polyether, polyethylene, polyamine, 125872.doc -17- 200846430 Polyurethane, polystyrene, polypropylene, coformed products thereof, and mixtures thereof. The following examples are intended to further illustrate the invention, but should not be construed as limiting the scope of the invention in any way. - Example 1 This example illustrates the polishing of a glass substrate according to the present invention using an aqueous polishing composition comprising cerium oxide and PVP as a stabilizer. Two polishing compositions (Compositions 1A and 1B) of the present invention were prepared. Composition 1A contained an oxidized abrasive of 5 lbs/i in water of pH 5, p vp (K9 〇) in ppm, and a chlorinated planer of 1000 ppm. Composition (7) contains 5% by weight of oxidized abrasive in water at pH 5 (average particle size of 500 nm, purity greater than or equal to 99.9% Ce〇2) and 1000 ppm of polyvinylpyrrolidone (K9〇) . A comparative composition (Composition 1C) was also prepared which contained 5% of cerium oxide abrasive in water to which no salt or stabilizer was added. Using these three compositions, a 4 cm X 4 cm LCD 0 grade glass test panel (alkaline earth metal oxide (Mg〇, Ca〇, Sr〇,

Ba0)-Al203-Si02 ; Corning EAGLE 正 2000) : No g/cm2 (1.56 psi) pressure, 100 ml/min (mL/min) slurry 'flow rate, 85 rpm carrier speed And the platen speed of 1 rpm. The glass removal rate in micrometers per minute (μπι/min) obtained from each composition is shown in Fig. 1. The results in Figure i indicate that Composition i A provides a 20/〇 improvement in glass removal rate compared to the removal rate obtained using Composition (1). In addition, the composition provides improved processing properties as compared to composition 1C (i.e., less sedimentation in the transfer line and slurry reservoir than in 125872.doc -18 · 200846430). In Fig. 1, the left bar indicates the removal rate obtained from the control composition 1C, the middle bar indicates the removal rate obtained from the composition 1B, and the right bar indicates the removal obtained from the composition 1A. rate. Example 2 This example illustrates the polishing of a glass substrate with a polishing composition in accordance with the present invention. A polishing composition 2A comprising 1% by weight of cerium oxide abrasive (average particle size 5 〇〇 nm) and 1 〇〇〇 ppm of DAXAD® 32 in water at pH 8.5 (available from Hampshire Chemical Corp) was prepared. ·, Lexington

Massachusetts Polyammonium Methacrylate Stabilizer). A control composition (Composition 2B) was also prepared, which contained 1% by weight of an emulsifying abrasive in water at pH 8.5. Polishing 4 cm X 4 cm LCD-grade glass test panels (c〇rning EAGLE® 2000) using compositions 2A and 2B under the following polishing conditions: pressure under lio g/cm2, slurry flow rate at 100 mL/min, carrier at 85 rpm Speed and platen speed of 100 。. Each freshly prepared composition was used in two polishing tests. Next, the dispersion of the used composition of 2 persons was collected (recycled) and used in three additional polishing tests. The dispersion of the previously used control composition 2]8 was also recycled in the same manner. The glass removal rate obtained from each composition in each polishing test is shown in Fig. 2, in which π abrasive pulp Γ was a control group (composition 2B), and slurry 2 was a composition 2 Α. The results in Figure 2 show that Composition 2A always provides an improved removal rate compared to the results obtained using Composition 2B, even after repeated use of the polishing composition three times. This indicates that the dispersion of the cerium oxide particles in the composition of the present invention is significantly improved by the presence of the stabilizer as compared with the control group, the stability of the dispersion is 125872.doc -19-200846430, and the dispersion is stable when the recycled slurry is used. Sexuality prevents the removal rate from decreasing. EXAMPLE 3 This example illustrates the polishing of a glass substrate with the polishing composition of the present invention, and a polishing group based on cerium oxide having a purity of less than 99.9% Ce02.

, the compound is compared. The compositions evaluated in this example all had a pH of 8 to 9, and the abrasive concentration was 10% except for the compositions 3G and 3H using 1% by weight of the abrasive. The composition was polished using a composition of 4 cm x 4 _ cm LCD grade glass test panel (Corning EAGLE® 2000) under the following polishing conditions: pressure below 110 g/cm2, slurry flow rate of 100 mL/min, carrier speed of 85 rpm and 100 Platen speed of rpm. The results are shown in Table 1. Compositions 3H, 31 and 3J are examples of the invention, while compositions 3A to 3G are comparative examples. Table 1 ·· Composition (pH 8-9) Ce02 purity (% by weight 〇6〇2) Average particle size (μιη) Glass removal rate (μιη/min) 3A 79.9 1 0.5 3B 49.6 4.7 0.4 3C 50.6 3.3 0.38 3D 55.1 3.7 0.26 3E 75 0.6 , 1·5 , 3* 0.4 3F 85 1 0.5 3G > 99.9 0.08 0.1 (1% abrasive) 3H >99.9 0.22 0.37 (1% abrasive) 31 >99.95 10 0.8 3J > 99.95 0.5 0.8 125872.doc -20- 200846430 *This material exhibits three peaks in the particle size distribution. The data in Table 1 shows that compositions 31 and 3 J of the present invention using highly pure cerium oxide have significantly higher glass removal rates than the comparative compositions 3A to 3G. Similarly, the composition 3H of the present invention having a polishing agent concentration of 1% is significantly higher than the composition 3G (abrasive concentration of 1%) having an average particle size of 0.2 μm or less (for example, 80 nm). The rate of removal. In an independent evaluation, six other compositions of the present invention were prepared using the same cerium oxide materials as compositions 31 and 3 J at different abrasive concentrations and pH values (see Table 2). Compositions 3K to 3P were used as compared to the results obtained for the polished glass panels described above for compositions 3A to 3J, as compared to the same cerium oxide materials (compositions 3S and 3T) having a pH of 5. Compositions 30 and 3P of the present invention comprise 1 〇 ppm and 5 ppm bite formic acid as stabilizers, respectively. The results are shown in Table 2. Table 2: Composition (pH) Ce02 concentration Weight ❶ / 〇 Average particle size μ ΐϋ Glass removal rate μιη / min 3K (8.5) 10 0.5 0.7 3L (8.5) 5 10 0.68 3M (8.5) 5 0.5 0.62 3N (3.5) 5 0.5 0.66 30(3.5) 1 0.5 0.52(10 decanoic acid) 3P(3.5) 1 0.5 0.55(5 ppm0 ratio biting formic acid) 3R(3.5) 1 0.5 0.3 3S(5) 10 0.5 0.5 3T(5) 10 10 0.5 The results in 2 show that the composition of the present invention at pH 3.5 and 8.5 is surprisingly superior to the use of pH 5 under the concentration of 5 125872.doc -21 - 200846430 and 10 bismuth bismuth 〇 5 μιη Comparative examples of cerium oxide (3S and 3Τ). Similarly, each has a pH of 3.5. /. Compositions 30 and 3P of the present invention having a concentration of oxidized quinone and including added 0 compared to o-formic acid are surprisingly superior to comparative compositions also included in 1% cerium oxide at pH 3.5 but not added to sigma formic acid. 3 R. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows the glass removal rate (RRU pm/ obtained by polishing a glass panel using a polishing composition comprising cerium oxide and PVP with or without chlorination planing according to the method of the present invention. Min is a bar graph compared to the results obtained using a composition containing only cerium oxide. 2 shows the glass removal rate (RR in μΓη/min) obtained by polishing a glass panel using a polishing composition comprising cerium oxide and polymethyl methacrylate according to the method of the present invention, and the use only contains A graph comparing the results obtained for the composition of cerium oxide. 125872.doc -22-

Claims (1)

200846430 X. Patent application scope: 1 . A method for polishing a glass comprising: polishing a surface of a glass substrate with an aqueous glass polishing composition for a period of time sufficient to remove a portion of the glass from the surface; wherein the polishing composition The granules containing an average particle size in the range of from 〇35 to 〇9 pm in an aqueous carrier containing from 1 to 5 mils of core in a polymerization agent containing 50 to 1500 parts per million (ppm) of a polymeric stabilizer. Cerium oxide abrasive. 2. The method of claim 1, wherein the polymerization stabilizer comprises at least one polymer selected from the group consisting of polyacrylic acid, polyacrylic acid, poly(ethylenesulfonic acid), a salt thereof Partially neutralized form. 3. The method of claim 1, wherein the polymeric stabilizer comprises at least one polymer selected from the group consisting of polyvinylpyrrolidone, poly(ethylene glycol), poly(2·ethyl oxalate) Oxazoline), hydroxyethyl cellulose and xanthan gum. 4. The method of claim 1, wherein the polishing composition further comprises a water-soluble inorganic salt. 5. The method of claim 4, wherein the water-soluble inorganic salt comprises 铯.5 to 〇1 by weight of the cerium salt. 6. The method of claim 1, wherein the glass substrate comprises an alkaline earth metal oxide-Al2〇3-Si〇2 glass, wherein the alkaline earth metal oxide comprises one or more groups selected from the group consisting of MgO, CaO, SrO, and BaO. Oxide. a glass polishing method comprising the steps of: Ο) contacting a surface of a glass substrate with a polishing pad and an aqueous glass light-removing composition under a pressure of 11 〇g/cm 2 or less; and 125872 .doc 200846430 (b) causing relative movement between the polishing pad and the substrate while maintaining a portion of the composition in contact with the surface between the pad and the substrate for at least a period of time sufficient to polish the glass from the surface of the substrate. a portion of the time; wherein the light-removing composition comprises from 1 to 15% by weight of the aqueous carrier comprising 5 to 15 parts per million (ppm) of a polymeric stabilizer characterized by 〇·35 μπι to 0.9 Granular cerium oxide abrasive with average particle size in the range of μπι0 8. The method of claim 7, wherein the polymeric stabilizer comprises at least one polymer selected from the group consisting of polyacrylic acid, polymethyl propyl ketone, poly(ethylene sulfonic acid), salts thereof Partially neutralized form. 9. The method of claim 7, wherein the polymeric stabilizer comprises at least one polymer selected from the group consisting of polyvinylpyrrolidone (I) (ethylene glycol), poly(2-ethyl) Ethyl acetate, trans-ethyl cellulose and xanthan gum. 10. The method of claim 7 wherein the composition further comprises from 0.05 to 1% by weight of a water-soluble inorganic salt. 11. The method of claim 7, wherein the glass substrate comprises an alkaline earth metal oxide 2〇3 Sl〇2 glass filler, wherein the soil metal oxide comprises one or more selected from the group consisting of Mg〇, Ca〇, and Sr〇. An oxide of the group consisting of secrets. 12. Composition #' contains 1 to 15% by weight of particulate cerium oxide having an average particle size of 0.35 μηιη to 〇."m dry circumference suspended in an aqueous carrier comprising 5 to 1500 ppm of a polymeric stabilizer. 13. The composition of claim 12, which further comprises a water-soluble inorganic salt. 125872.doc 200846430 14. The composition of claim 13, wherein the water-soluble inorganic salt comprises a planing salt. 5. The composition of claim 13, wherein the water-soluble inorganic salt is present in the composition in an amount ranging from 〇 to 0.1% by weight. 16. The composition of claim 12, wherein the polymeric stabilizer A polymer comprising at least one group selected from the group consisting of polyacrylic acid, polymethyl. propyl hydrazine, poly(ethylene sulfonic acid)' salts thereof and partially neutralized forms thereof. a composition, wherein the polymeric stabilizer comprises at least one polymer of a group consisting of φ t free of: polyethylene 比 唆 唆, poly (vinyl alcohol), poly (2-ethyl oxazoline), hydroxyl Ethyl cellulose and xanthan gum. 18. - Two-part product, A first container comprising a polymeric stabilizer dissolved in a first aqueous carrier, the first container being packaged with a second container, the second container comprising particles suspended in a second aqueous carrier a cerium oxide abrasive; wherein the cerium oxide abrasive is characterized by an average particle size ranging from 0.35 to 0.9 μm; and wherein after mixing the contents of the first container with the contents of the second container, Forming a polishing composition comprising from 15% by weight of the cerium oxide abrasive and from 50 to 1500 ppm of the polymeric stabilizer. * 19. The article of claim U, wherein the polymeric stabilizer comprises at least one Selectively: a polymer of a group consisting of polyacrylic acid, polymethyl methic acid, poly(vinyl sulfonic acid) 'salt thereof and a partially neutralized form thereof. 20. The article of claim 18, wherein The polymeric tanning agent comprises at least one polymer selected from the group consisting of polyvinylpyrrolidone, poly(ethylene glycol), poly(2-ethyl(tetra)lin), phenylethylcellulose, and yellow Original 125872.doc 200846 430 Glue. A glass polishing composition comprising from 1 to 15% by weight. /c suspended in an aqueous carrier characterized by an average particle size of at least 〇2 pm and at least 99.9% by weight of Ce〇 a granular oxidized abrasive having a purity of at least 1 unit higher than an isoelectric point (IEp) of the cerium oxide abrasive, wherein the aqueous carrier has a composition of the composition of claim 21, wherein The cerium oxide abrasive has an average particle size ranging from μ2 μιη to 11 μπι. 23. The composition of claim 21, wherein the 1 > 11 value is in the range of 3 to 4. 24. The composition of claim 23, further comprising from 1 to 2 ppm of pyridinium. 25. The composition of claim 21, wherein the pH is in the range of 8 to 9. 26. A method of glass polishing comprising polishing a surface of a glass substrate with an aqueous glass polishing composition for a period of time sufficient to remove at least a portion of the glass from the surface; wherein the polishing composition comprises from 1 to 5 weights % suspended in an aqueous carrier characterized by an average particle size of at least 2 μmηη and a particulate cerium oxide abrasive having a purity of at least 99.9% Ce〇2 by weight, the pH of the aqueous carrier being greater than the oxidation The isoelectric point (IEP) of the 钸 abrasive is at least 1 unit high or low. 27. The method of claim 26, wherein the cerium oxide abrasive has an average particle size in the range of from 〇2 to 11 μπι. 28. The method of claim 26, wherein the pH is in the range of 3 to 4. 29. The method of claim 28, wherein the composition further comprises from 1 to 2 ppm of decanoic acid. 125872.doc 200846430 3 0. The method of claim 26, wherein the pH is in the range of 8 to 9. The method of claim 26, wherein the glass substrate comprises an alkaline earth metal oxide-AUCb-SiO2 glass, wherein the alkaline earth metal oxide comprises one or more oxides selected from the group consisting of Mg〇, CaO, SrO, and BaO. . 3 2. A method of polishing a glass comprising the steps of: (a) contacting a surface of a glass substrate with a polishing pad and an aqueous glass polishing composition under a pressure of 110 g/cm 2 or less; b) causing relative movement between the polishing pad and the substrate while maintaining a portion of the composition in contact with the surface between the pad and the substrate for a period of time sufficient to polish at least a portion of the glass from the surface of the substrate; Wherein the polishing composition comprises from 1 to 15% by weight of a particulate cerium oxide abrasive characterized by an average particle size of at least 0. 2 μηη suspended in an aqueous carrier and a purity of at least 99.9% Ce〇2 by weight. The pH of the aqueous carrier is at least 1 unit higher or lower than the isoelectric point (IEP) of the cerium oxide abrasive. 33. The method of claim 32, wherein the cerium oxide abrasive has an average particle size in the range of from 20 to 11 μm. 34. The method of claim 32, wherein the threshold is in the range of 3 to 4. 35. The method of claim 34, wherein the composition further comprises a ratio of n to 1 to 2 ppm of n. 36. The method of claim 32, wherein the threshold is in the range of 8 to 9. The method of claim 32, wherein the glass substrate comprises an alkaline earth metal oxide-Al2〇3_Si〇2 glass, wherein the soil metal oxide comprises one or more selected from the group consisting of MgO, CaO, SrO, and BaO. Oxide. 125872.doc