MXPA97008944A - Colored mineral agglutinants with black smoke containing sili - Google Patents

Abstract

Binder compositions are provided which include a mineral binder and a carbon black containing silicon. The carbon black containing silicon can have an ionic or ionizable organic group or can be oxidized. Carbon blacks containing silicon can be prepared by an oven method. The binder compositions of the present invention have improved color and weathering properties, in comparison, with binder compositions prepared with carbon blacks containing silicon and having ionic or ionizable organic groups attached, exhibit excellent dispersibility, even in pelletized or agglomerated form. From the binder compositions, articles such as for example roofing tiles can be prepared. A method for improving the color stability of a mineral binder composition is also contemplated. The carbon blacks containing silicon as described above are added to the binder composition miner

Description

COLORED MINERAL AGGLUTINANTS WITH BLACK SMOKE CONTAINING SILICON CJVMPO OF THE INVENTION This invention relates to mineral binder systems which as dyes include carbon black or smoke products containing silicon.

BACKGROUND OF THE INVENTION Mineral binders such as, for example, concrete, cement, mortar and mortar for exteriors, are often colored to improve their aesthetic appearance. Coloring can be effected by applying either a colored coating to the exposed surfaces of a cured or set mineral binder or premixing small amounts of one or more pigments in a mineral binder system before setting to uniformly color the system. The pigments in the premix method can be added either to a dry mineral mixture, for example, in the case of concrete, to the cement-sand mixture or, it can be added to the water used to set the mineral mixture. It is preferred to the method of coloring by premix because the colored surface coatings are not permanent, but rather P15B6 / 97MX peel, discolor and, hence, weather better faster than premixed colorants. The pigments for mineral binding systems that will be exposed to outdoor conditions must be resistant to alkali, firm in color, resistant to industrial atmospheres and should be weatherized at a rate or speed comparable to the rate or speed at which the binder is weathering same, so that the surface appearance does not change unevenly or unevenly with time. Additionally, for ease of use, the pigment should be relatively free of dust to facilitate mixing to achieve maximum coloring power and should be easily dispersible. Black pigments are particularly desirable dyes for mineral binder systems because with their use a wide variety of colors and color tones can be obtained either alone or in combination with other pigments. Black oxides of iron and blacks of smoke or coal are common black pigments. Carbon blacks or carbon blacks exhibit excellent coloring properties, alkali resistance, color fastness and chemical stability. However, carbon blacks or carbon blacks are not the preferred pigments in mineral binding systems exposed to weathering P1S86 / 97MX outdoors because the surface appearance of bodies containing carbon black exhibit undesirable changes such as, for example, fading with weathering. The fading is attributed to a preferential leaching and the washing or dragging of the carbon black pigment of the mineral binder system. Additionally, when carbon black is used in combination with other colorants, the appearance of the other colorant becomes more pronounced with weathering during the passage of time due to selective leaching and entrainment or washing of the carbon black pigment. Consequently, black carbon or smoke has had limited use in systems that are exposed to outdoor weathering. Another drawback for the use of carbon black as a colorant in indoor or outdoor applications is that, depending on the physical form in which it is supplied, carbon blacks are excessively dusty or difficult to disperse. The process used to incorporate carbon blacks or smoke in binder systems depends on the way in which the pigment is supplied and the processing equipment available to the user. Carbon blacks or powdered smoke have apparent densities ranging from about 0.02 to 0.1 g / cc and are called "spongy" blacks.

P1586 / 97MX Due to its low densities and its large surface areas, spongy products are cohesive, have very poor transport properties, are difficult to handle in bulk and, they are normally supplied in a sealed way. However, spongy carbon blacks are dispersible and can develop their full coloring potential by relatively simple grinding procedures. The handling properties for a given grade of carbon black improve with an increase in densification such as, for example, by pelletizing. For example, spongy blacks usually become denser by pelleting them to improve their bulk handling properties. These procedures provide apparent densities ranging from about 0.2 to 0.7 g / cc. However, the dispersibility is degraded progressively as the density of the pellet increases. Thus, there is an exchange or concession between the improvement in bulk handling properties and the degradation in dispersibility. Due to the advantages of increased cleaning, pelletized carbon blacks are generally preferred for introducing carbon blacks or smoke in the mineral binder systems despite the need for an increase in grinding or milling to form an intimate blend. and uniform. P15T6 / 97MX The carbon black agglomerates, either in pelletized or spongy form, must be decomposed mainly in aggregates (smaller dispersible units of carbon black) for a complete development of color. This is achieved either by grinding to the dry mix or predispersing the carbon black in the aqueous medium. For example, in the preparation of colored concrete, carbon black can be ground into a dry sand-cement mixture and, subsequently, the amount of water required and necessary to set the mixture can be added. Alternatively, an aqueous dispersion of the carbon black in all or in part of the required volume of water necessary to set the mixture, can be uniformly mixed in the sand-cement mixture. Since carbon blacks tend to be active surface hydrophobic agents, they are frequently used to promote wetting, to improve dispersion processes and to help stabilize dispersion. For example, U.S. Patent No. 4,006,031, discloses the use of fluorine-containing wetting agents used with carbon blacks in an attempt to improve the weathering properties of mineral binder systems. European Patent Publication No. 50354, describes the use of surface-active polymers, which P15B6 / 97MX disperse the carbon black in an aqueous medium used to set the mineral binder system. The polymer is deactivated after drying. However, in dry grinding or predispersion, the carbon black, either spongy or pelletized, must still be milled to achieve or obtain a satisfactory pigment dispersion. Thus, the need for carbon black or smoke colorants continues for mineral binder systems that exhibit both improved weathering properties and / or are easily dispersible in pelletized form.

BRIEF DESCRIPTION OF THE DRAWING Figure 1 is a schematic view of a portion of a type of furnace reactor for carbon black, which can be used to produce carbon blacks containing silicon.

SUMMARY OF THE INVENTION Binder compositions comprising a mineral binder and carbon black containing silicon are provided. Carbon black or silicon-containing carbon black may be bonded to an ionic or ionizable organic group or that may be oxidized. The carbon blacks containing silicon can be prepared by a P1S86 / 97MX oven method. The binder compositions of the present invention have improved coloring and weathering properties compared to binder compositions prepared with conventional carbon blacks. In addition, the binder compositions incorporating carbon blacks or silicon-containing carbon blacks have ionic or ionizable organic groups that exhibit excellent dispersibility, even in pelletized form. Articles such as for example roofing shingles can be prepared from the binder compositions of the present invention. A method for improving the color stability of a mineral binder composition is also contemplated. The carbon blacks containing silicon as described above are added to the mineral binder composition.

DETAILED DESCRIPTION OF THE INVENTION The present inventors have discovered that the weathering properties of mineral binder compositions and articles pigmented with carbon black or smoke can be improved by incorporating carbon blacks or carbon therein. that contain silicon. Mineral binders, include but not P1586 / 97MX are limited to, concrete, cement, mortar, exterior plaster formulations and the like. Conventionally known additives for mineral binder systems can also be incorporated in the mineral binder or in the binder composition. The blacks of smoke exist generally in the form of aggregates. The silicon-containing carbon blacks of the present invention are usually in aggregate form and are not physical mixtures of aggregates or particles containing silicon and carbon black aggregates. The aggregates of the present invention generally include a major portion of carbon and a minor portion of silicon. The silicon-containing carbon black or carbon aggregates of the present invention include at least one silicon-containing region in at least a portion of the surface of the carbon black aggregate. The morphology of carbon blacks containing "silicon" can be observed, for example, by scanning electron microscopy (STEM). When the STE is coupled with an energy dispersive x-ray analysis (EDX), it can be identified components or elemental compositions of the individual carbon black or carbon aggregates containing silicon A physical mixture of carbon black and silica will result in the identification of aggregates that P1586 / 97MX for the most part show Si content and little carbon content. In this way, when multiple aggregates are examined in a mixture, some of the aggregates will show a high Si / C signal, corresponding to silica particles or aggregates. In a typical analysisFor example, five mg of carbon black can be dispersed in 20 ml of chloroform and subjected to ultrasonic energy using a probe sonicator (-385 Heat Systems Ultra Sonicator). A 2 ml aliquot would then be dispersed in 15 ml of chloroform using a sonicator probe for three minutes. The resulting dispersion is placed on a 200 mesh nickel grid with aluminum substrate. The grid is then placed in a Fisons HB501 Electronic Scanning Electron Microscope (Fisons, West Sussex, England) equipped with an Oxford Link AN10000 Dispersive Energy X-ray Analyzer (Oxford Line, Concord Massachusetts). Initially, the grid is scanned or swept for potential silica aggregates at a low magnification (less than 200,000X). This is done by looking for aggregates that have the highest Si / C account ratio. After this initial scan or sweep, thirty aggregates are usually selected for a more detailed analysis with a higher increase (of between 200,000X and P1586 / 97MX 2,000,000X). The selected aggregates should include all the aggregates that contain the highest Si / C account allocations as identified by the initial sweep. In this way, the highest Si / C account properties are determined. For example, a mixture of N-234 carbon black or 3.7% by weight silica (L90) (1.7% Si) has a higher Si / C count ratio, by aggregate, of 49. A Carbon black containing silicon prepared, as described further below, injecting octamethylcyclotetrasyl-xan into the feedstock (3.28% Si) has a maximum Si / C count ratio of 0.27. Thus, a low count ratio of Si / C is indicative of a carbon black or silicon-containing carbon black. The presence of silicon-containing regions on the surface can be determined, for example, by treating carbon blacks containing silicon with a hydrofluoric acid solution, for example, 10% by volume which will dissolve at least a portion of silicon in regions containing silicon in at least a portion of the surface of the carbon black aggregate. For example, extraction with hydrofluoric acid (HF) can be carried out by taking 5 grams of the carbon black and then extracting them with 100 ml of the acid at 10 percent v / v for 1 hour. P1S86 / 97MX The silicon-containing carbon blacks of the present invention include, but are not limited to, carbon black aggregates in which the silicon is distributed throughout the carbon black or a portion thereof, but at least A portion of the silicon-containing regions are accessible to the surface of the carbon black aggregate. For example, carbon black can form a matrix through which at least a portion of the silicon is distributed. These silicon-containing carbon blacks are carbon blacks which are normally obtained by introducing a volatilizable silicon-containing compound into a carbon black reactor during the manufacture of the carbon black and can be produced, for example, in a reactor method. of oven for modular smoke or "in stages", as shown in Figure 1. The furnace reactor for carbon black of Figure 1"has a combustion zone 1 with a zone of convergent diameter 2, a zone of injection of feedstock with a restricted diameter 3 and a reaction zone 4. To produce blacks of smoke with the reactor described above, in the combustion zone 1 hot combustion gases are generated by contacting a liquid or gaseous fuel with a suitable oxidant stream, P1586 / 97MX such as for example air, oxygen or mixtures of air and oxygen. Among the fuels suitable for use in contacting the oxidant stream in the combustion zone 1 for generating the hot combustion gases, any easily combustible streams of gas, vapor or liquid, such as for example natural gas, hydrogen, are included, methane, acetylene, alcohols or kerosene. However, it is generally preferred to use fuels having a high content of carbon-containing components and, in particular, to use the hydrocarbons. The ratio of air to fuel varies with the type of fuel used. When natural gas is used to produce carbon blacks containing silicon, the air to fuel ratio can be between about 10: 1 to about 1000: 1.

To facilitate the generation of hot combustion gases, it can be preheated to the oxidant stream. "The hot combustion gas stream flows downstream of zones 1 and 2 to zones 3 and 4. The flow direction of the hot combustion gases is shown in Figure 1 by an arrow. The carbon black is introduced into the injection zone 3 of the feed material at point 7. The feed material is injected into the gas stream through nozzles designed for P1S86 / 97MX optimal distribution of oil in the gas stream. These nozzles can be either single-fluid or two-fluid, bi-fluid. The bi-fluid nozzles can use steam or air to atomize the fuel. The nozzles of a single fluid can be atomized by pressure or the raw material can be injected directly into the gas stream. In the latter case, atomization occurs by the force of the gas stream. The carbon blacks can be produced by the pyrolysis or partial combustion of any liquid or gaseous hydrocarbon. Preferred carbon black feedstocks include petroleum refinery sources, such as decanted oils from catalytic thermoforming operations, as well as by-products of coking operations and olefin manufacturing operations. The mixture of feed material that produces carbon black and the hot combustion gases flows downstream through zones 3 and 4. In the reaction zone portion of the reactor, the feed material is pyrolyzed in carbon black . The reaction stops in the extinguished or extinguished zone of the reactor. The quencher or extinguisher 8 is located downstream of the reaction zone and sprinkles a quench fluid, usually water, in the stream of freshly black carbon particles.

P1586 / 97MX formed. The extinguisher or extinguisher serves to cool the carbon black particles, to reduce the temperature of the gas stream and to decrease the reaction speed. Q is the distance from the beginning of the reaction zone 4 to the point of extinction or extinction 8 and, it will vary according to the position of the damper or extinguisher. Optionally, the shutdown may be in stages or may occur at several points within the reactor. After the carbon black is quenched, the cooled gases and the carbon black pass downstream to any conventional cooling and separation medium, thereby recovering carbon black or carbon black. Separation of the carbon black from the gas stream is easily accomplished by a conventional means such as, for example, a precipitator, a cyclone separator, a bag filter or other means known to those skilled in the art. After the carbon black has been separated from the gas stream, it is optionally subjected to a pelletizing step. Silicon-containing carbon blacks are manufactured by introducing a volatilizable silicon compound into the carbon black reactor at a point upstream of the quenched or quenched zone. Useful volatilizable silicon compounds are those that are volatilizable at reactor temperatures to P1586 / 97MX carbon black. Volatile silicon compounds suitable, but not limited to, silicates such as for example, tetramethoxy- and tetraethoxyorthosilicates (TEOS); silanes such as, for example, tetrachlorosilane and trichloromethylsilane, volatile silicone polymers such as, for example, octamethylcyclotetrasiloxane (OMTS), and mixtures of any of the foregoing. The volatilizable silicon compound can be premixed with the carbon black-forming feed material and introduced with the feed material into the reaction zone. Alternatively, the silicon compound can be introduced into the reaction zone separately from the point of injection of the feed material. This introduction can be upstream or downstream of the injection point of the feed material, provided that the silicon compound is introduced upstream of the zone of off or * extinction. For example, referring to Figure 1, the silicon compound can be introduced at point 12 or at any other point in the reaction zone. With volatilization and exposure to elevated temperatures in the reactor, the silicon compound decomposes and reacts with other species in the reaction zone, producing carbon black containing silicon. An example of a species that contains silicon is the P1586 / 97MX silica. In addition to volatilizable compounds, decomposable compounds, which are not necessarily volatilizable, can also be used to produce carbon black treated with silicon. If the silicon precursor is introduced substantially simultaneously with the feedstock, a silicon-containing carbon black compound is obtained, wherein the silicon-containing regions are distributed through the aggregate. In a second embodiment of the furnace reactor method, the silicon compound is introduced into the reaction zone at a point where the carbon black formation process has begun, but the reaction current has not yet been subjected to the shutdown or extinction. In this embodiment, silicon-containing carbon blacks are obtained in which the silicon or the silicon-containing species are present mainly on the surface of the carbon black or close to it. The present inventors also believe that the silicon-containing carbon blacks of the present invention can include, but are not limited to, carbon black aggregates that are coated such that at least a portion of the carbon black remains uncoated and the carbon black is not totally P1586 / 97MX encapsulated The coating may form a shell or partial wrap around the carbon black but, in this form, it usually does not leave the carbon black matrix in any other degree or extent necessary for the adhesion or absorption of the shell or shell to the core. of carbon black or smoke. While the present inventors have not been able to duplicate these carbon or carbon blacks, it is believed that these silicon-containing carbon or carbon blacks can be prepared, for example, by precipitation methods known in the art, such as for example , the method described in the Japanese Patent Application (Kokai) No. HEI 5 (1993) -178604. A reactant containing silicon, for example, an organosilicate such as a tetraethylorthosilicate or a silane such as for example tetraethoxysilane, is diluted with a solvent such as methanol, to produce a solution of the silicon compound with a concentration of about 1 to about 20% by weight of the silicon compound. Another solution is prepared by adding from about 5 to about 20% aqueous solution of 28% ammonia to ethanol. Carbon black or carbon is added to the ammonia solution, while stirring the mixture continuously. Simultaneously, the solution of the compound of P1586 / 97MX silicon is added dropwise. After up to several hours of this operation, the material is filtered and dried. The product obtained is carbon black or carbon, at least partially coated with silica. Preferably, the added silicon comprises from about 0.1 to about 20 parts by weight and, more preferably from about 1 to about 10 parts by weight based on 100 parts by weight of the carbon black or silicon-containing carbon. The silicon-containing carbon blacks useful in the present invention can be oxidized by oxidizing agents such as for example nitric acid and the like. Additionally, these carbon blacks containing silicon can be modified by linking an organic group that includes an ionic or ionizable group. These modified silicon-containing carbon blacks can be prepared by reacting a silicon-containing carbon black with a diazonium salt in a liquid reaction medium to attach at least one organic group to the surface of the carbon black or of coal. The diazonium salt may contain the organic group that will be attached to carbon black or carbon black. A diazonium salt is an organic compound that has one or more diazonium groups. He P1586 / 97MX preferred reaction medium includes water, any medium containing water and any medium containing alcohol. Water is the most preferred medium. Various methods of preparation are described in the United States Patent Application. 08 / 356,660, filed December 15, 1994. A diazonium salt used in the preparation of the modified silicon-containing carbon blacks needs only to be sufficiently stable to allow reaction with carbon black. In this way, the reaction can be carried out with some diazonium salts which are otherwise considered unstable and subject to decomposition. Some decomposition processes can compete with the reaction between the carbon black containing silicon and the diazonium salt and can reduce the total number of organic groups bound to its surface. In addition, the reaction may be carried out at elevated temperatures, where many diazonium salts may be susceptible to decomposition. The elevated temperatures can also advantageously increase the solubility of the diazonium salt in the reaction medium and improve its handling during the process. However, elevated temperatures can result in some loss of the diazonium salt due to other decomposition processes. P1586 / 97MX The carbon black containing silicon can be reacted with a diazonium salt either as a dilute and easily stirred aqueous pulp or, preferably in the presence of the appropriate amount of water for pelletization of the silicon-containing carbon black. The diazonium salt can be generated either in the presence of carbon black or silicon-containing carbon or can be generated separately from the carbon black or silicon-containing carbon. The organic groups which can be attached, preferably chemically, to the silicon-containing carbon black, are preferably organic groups substituted with an ionic group or an ionizable group as a functional group. An ionizable group is one that is capable of forming an ionic group in the medium of use, that is, the binder composition. The ionic group can be anionic or cationic and the ionizable group can form an anion or urt cation. Ionizable functional groups that form anions include, but are not limited to, acid groups or salts of acid groups, including those derived from organic acids. Preferably, the organic group has (a) an aromatic group or an alkyl group C] _-Ci2 Y >; (b) At least one acid group having a pKa less than. 11 or, a mixture of at least one acid group having a pKa P15B6 / 97MX less than 11. The pKa of the acid group refers to the pKa of the organic group as a whole, not only of the acid substituent. More preferably, the pKa is less than 10 and, most preferably, the pKa is less than 9. The aromatic group may be unsubstituted or substituted with, for example, one or more alkyl groups. Preferably, the aromatic group or the alkyl group of the organic group is directly attached to the carbon black containing silicon. The C ^ -C ^ alkyl group can be branched or unbranched and is preferably ethyl. More preferably, the organic group is a phenyl or naphthyl group and, the acid group is a sulfonic acid group, a sulfinic acid group, a phosphonic acid group or a carboxylic acid group. Preferred acidic groups include, but are not limited to, COOH, -SO3H and -PO3H2 and their salts, such as, for example, -COONa, -COOK, -COO ~ NR + 4, -S03Na, -HP? 3Na, - S03"NR + 4 and -P? 3Na, wherein R is an alkyl or phenyl group The particularly preferred ionizable substituents are -COOH and -SO3H and their sodium and potassium salts.More preferably, the organic group is a substituted sulfophenyl group or unsubstituted or a salt thereof or a substituted or unsubstituted (polysulfo) phenyl group or a salt thereof, a substituted or unsubstituted sulphonaphthyl group or a salt thereof.

P1586 S7MX preferred sulfophenyl substituted is a hydroxysulfophenyl group or a salt thereof. Specific organic groups having an ionizable functional group that form an anion are p-sulfophenyl, 4-hydroxy-3-sulphophenyl and 2-sulfoethyl. The quaternary ammonium groups (-NR3 +) and the quaternary phosphonium groups (-PR3"1") are non-limiting examples of cationic groups which can be attached to the organic groups as mentioned above. Preferably, the organic group includes an aromatic group such as for example a phenyl group or a naphthyl group and a quaternary ammonium group or a quaternary phosphonium group. The aromatic group is preferably directly attached to the carbon black or silicon-containing carbon. Quaternary cyclic amines and quaternary aromatic amines can also be used as the organic group. Thus, "N-substituted pyridinium compounds, such as for example N-methyl-pyridyl, can be used in this regard." An advantage of silicon-containing carbon black products and having a substituted attached organic group. with an ionic or ionisable group, is that these modified carbon black or silicon carbon products can have an increase in their dispersibility in water with respect to the corresponding ones P15T6 / 97MX carbon blacks containing unmodified silicon. In general, the water dispersibility of a silicon-containing carbon black product increases with the number of organic groups bonded to the carbon black containing silicon and having an ionizable group or several ionizable groups bound to a given organic group . In this way, the increase in the number of ionizable groups associated with carbon black or silicon-containing products must increase their dispersibility in water. In accordance with the above, water dispersibility can be controlled and optimized. When modified, dispersible water-containing carbon blacks are prepared in water, it is preferred to ionize the ionic or ionizable groups in the reaction medium. The resulting product can be used as is or be diluted before use. The carbon black containing modified silicon can be pelletized, preferably by a conventional wet process, a fine or small pelletizing operation. Modified silicon-containing carbon black products can be dried by techniques used for conventional carbon blacks that include, but are not limited to, drying in stoves and in rotary kilns. However, excessive drying can cause a loss in the degree of dispersibility P1586 / 97MX in water. If a carbon or carbon black containing modified silicon is not dispersed in an aqueous vehicle as easily as desired, carbon black or carbon containing modified silicon can be dispersed using conventionally known techniques, such as, for example, grinding or milling. Modified and unmodified silicon carbon blacks can be incorporated into the binder compositions of the present invention, either in solid form or as a preformed liquid dispersion. Preferably, the carbon black containing modified or unmodified silicon is present in an amount less than or equal to 5 parts by weight and, most preferably, from about 0.1 to about 1 part by weight, based on 100 parts by weight. weight of the total binder composition. The binder compositions are prepared by combining the silicon-containing carbon black or carbon and the mineral binder by methods conventional in the art, such as, for example, mixing, preferably by a low shear or shear method. The silicon-modified carbon black can be mixed with a mineral-dry binder or can be premixed with a setting liquid such as, for example, water and then added to the mineral binder.

P1586 / 97MX As stated at the beginning, the carbon black containing silicon can also be modified to have at least one organic group bonded to the carbon black containing silicon. Alternatively, a mixture of carbon black or carbon-containing silicon and a carbon black or modified carbon having at least one bound organic group can be used. In addition, within the limits of this application is also the use of a mixture of silica and a carbon black containing silicon. Also, any combination of additional components with the carbon black containing silicon can be used such as for example one or more of the following: a) a carbon black containing silicon with a bound organic group; b) a modified carbon black that has an organic group attached; "c) silica, d) modified silica, having, for example, a bonded organic group, and / or e) carbon black or smoke, Examples of silica include, but are not limited to, silica, precipitated silica, amorphous silica, vitreous silica, fumed silica, fused silica, silicates and other Si-containing fillers, such as, for example, P1586 / 97MX clay, talc, wollastonite, etc. The silicas are available commercially from sources such as, for example, Cabot Corporation, under the registered name Cabosil; PPG Industries under the registered names Hi-Sil and Ceptane, - Rhone-Poulenc under the registered name Zeosil; and, Degussa AG under the registered names Ultrasil and Coupsil. The articles can be prepared from the binder compositions of the present invention by methods known to those skilled in the art. Examples of these items include, but are not limited to, shingles for roofing and facades for construction.

DESCRIPTION OF THE PREFERRED MODALITIES The following examples illustrate the invention without limitation. All parts are provided by weight unless otherwise indicated.

ANALYTICAL METHODS The structural level of carbon blacks and carbon blacks containing silicon was determined using the absorption of n-dibutyl phthalate (DBP) (test procedure of ASTM D 2414-93) and crushed DBP (test procedure ASTM D 3493-86). He P15T6 / 97MX surface area was determined by nitrogen uptake (test procedure of ASTM D 3037-Method A). The silicon content of the samples was determined by calcination (test procedure of ASTM D 1506-94). The ash values were used to calculate the percent Si in the samples. The dye intensity was determined by the test procedure of ASTM D 3265-93. The fine pelleting was carried out using a continuous fine pelletizing device on a pilot scale. The unit included a cylindrical body 25.5 cm (10 inches) in diameter by 91 cm (36 inches) long with a rotor running along its axis. The rotor, which has approximately 70 rolls of 1.27 cm (0.5 in.) in diameter that extend through the walls of the unit, was rotated at 1000 R.P.M. to form the pellets. As the cohesion fluid, water was used in the process of pellet formation. The dispersibility of the product was measured by dispersing the various products in an aqueous medium having a pH of about 10 under conditions of low shear or shearing with a magnetic stirrer for 30 minutes. The surfactant cetyltrimethylammonium bromide was added to the carbon blacks which do not contain silicon and which are not modified. The density P1586 / 97MX pulp optics, (DO) reduced shear stress »was determined at a wavelength of 550 nm. The pulp was then sonicated (to reflect intense grinding) and the optical density (SO) of the pulp was determined. The percentage change in optical density before and after sonification was calculated. ? (DO) = 100 [(DO) sonifiCada "(DO) eSf F cort. Network .1 / (D °) sonicated A large percentage of change in this value indicates poor dispersibility at low shear stress for the dispersion conditions used The reflectance values from the reflectance spectrum of non-weathering and weathered concrete forms were used to calculate the L *, a * and b * values of the International Commission on Illumination CIÉ 1976. L * represents the luminosity coordinate that runs from 0 for a pure black to 100 for a pure white, a * -represents the red-green coordinate and its value becomes larger as the degree of red coloration increases, b * represents the yellow-blue coordinate and its value becomes larger as the degree of yellowing increases.The concrete forms were weathered by contacting the concrete forms for 30 seconds with the undiluted SURCE CLEAN® 600 detergent (a mixture of P1586 / 97MX of organic and inorganic acids combined with wetting agents which is normally diluted with water and used to clean new masonry works - ProSoco - Inc., Kansas City, Kansas). The concrete forms were washed with abundant quantities of distilled water and dried. Again the reflectances of the surface were determined. The pure detergent, undiluted, vigorously attacked the alkaline concrete so that some surface layers were washed or entrained. Changes in L *, a * and b *, ie,? L *? A * and? B *, before and after treatment, were used to measure preferential leaching. In this way, the change of color with the wash, provided by the difference of the values L *, a * and b * before washing subtracted from the same values found after washing provided the values? L *,? A * and? B *. ? L * = L * (after washing) - L * (before washing),? A * = a * (after washing) - a * (before washing), and? B * = b * (after washing) washing) - b * (before washing).

Preparation of Carbon Black or Carbon ASTM N-234 Carbon black or carbon ASTM N-234 P1586 / 97MX prepared using a pilot scale reactor generally shown in Figure 1 and having the following dimensions.

The reaction conditions set out in Table B below were used. An additive for structure control (potassium acetate solution) was injected into the feed material to maintain the specification structure of the carbon black or carbon N-234. A commercially available example of N-234 is Vulcam® 7H carbon black from Cabot Corporation, Boston, MA.

P1586 / 97MX Example 1: Preparation of Carbon Blacks Containing Silicon. A pilot scale reactor as described above and illustrated in Figure 1, was used to produce carbon black or silicon-containing carbon by injecting a silicon compound into the hydrocarbon feedstock under the process conditions listed in FIG. Table 1. Because it is known that changes in the reaction temperature alter the black surface area and that the reaction temperature is very sensitive to the total flow rate of the feed material in the injection zone (Zone 3, Figure 1). ), the flow rate of the feed material was adjusted in a descending manner to roughly compensate for the introduction of the silicon compound, so that a constant temperature was maintained. In the material of feeding it. injected an additive for control of P1586 / 97MX structure (potassium acetate solution) at a consistent flow rate for the carbon black preparation ASTM N-234. The flow rate of this additive remained constant throughout the preparation of the carbon black containing silicon.

The silicon content and the surface area were analyzed in carbon black or carbon black containing silicon. The results are listed in Table 2 below.

P1S86 / 97MX Example 2; Preparation of a carbon black or carbon containing silicon. Carbon black or carbon-containing silicon was prepared by injecting a silicon compound after the oil injection plane at point 12, as indicated in Figure 1. The process conditions are listed below in FIG. Table 3 In the carbon black containing the resulting silicon, the silicon content and the surface area were analyzed. The results are illustrated below in Table 4.

P1586 / 97MX Examples 3-7: Smoke Blacks Containing Silicon Produced by Addition of a Silicon Compound to the Feed Material. A series of carbon blacks containing silicon were produced by the addition of either tetraethoxythosilicate (TEOS) or octamethylcyclotetrasiloxane (OMTS) to the feed material used to form the carbon black or carbon black. The resulting products were then pelletized continuously. The furnace conditions were adjusted to form products having similar surface areas as illustrated in Example 1. The silicon compound used, the weight percent of silicon in the carbon black, the DBP, the surface areas and the intensities of dye of the carbon blacks containing silicon formed, are listed below in Table 5.

P1586 / 97MX Examples 8-11: Smoke Blacks Containing Silicon Produced by Addition of a Baked Silicon Compound After the Start of Carbon Black or Carbon Formation. Carbon blacks containing silicon were produced by the addition of tetraethoxyorthosilicate (TEOS) or octamethylcyclotetrasiloxane (OMTS) to a furnace after carbon black or carbon black formation began as indicated in Table 6. The furnaces were adjusted in such a way as to form products having similar surface areas and structural levels and, hence, pigmentation characteristics such as N-234 carbon blacks. The amount of silicon in the carbon or carbon black, the DBP, the surface areas, and the dye strengths of the silicon-containing carbon blacks that were formed are listed below in Table 6.

P1586 / 97MX Example 12: Union of Groups CfiH ^ SO ^ -a Carbon Blacks Containing Silicon. A solution of diazonium salt was prepared by adding sulfanilic acid (1.14 parts), nitric acid 70L; (0.784 parts) and, sodium nitrite (0.47 parts) to 100 parts of deionized water at room temperature.

Immediately thereafter, 15 parts of a carbon black containing silicon prepared according to the method of Example 7, with stirring, was added to the diazonium salt solution. After stirring for one hour, the pulp was dried overnight at 85 ° C to produce the carbon black containing modified silicon.

Example 13: Union of Groups p-C ^ H ^ SO ^ ^ - Carbon Blacks Containing Silicon. A diazonium salt solution was prepared by adding sulfanilic acid (0.554 parts), 70"nitric acid (0.403 parts) and sodium nitrite (0.221 parts), to 50 parts of chilled deionized water in an ice bath. this, the diazonium salt solution was added to a pulp containing 75 parts of deionized water and 6 parts of a carbon black containing silicon prepared in accordance with the method of P1586 / 97 X Example 5. The resulting pulp was stirred for 30 minutes and then dried overnight at 70 ° C to produce carbon black or carbon containing modified silicon.

Example 14: Union of p-CfiH¿ SOyal Carbon Black Groups Containing Silicon. A solution of diazonium salt was prepared by adding sulfanilic acid (0.924 parts), 70"nitric acid (0.672 parts) and sodium nitrite (0.368 parts) to 50 parts of chilled deionized water in an oil bath Immediately after this, the diazonium salt solution was added to a pulp containing 75 parts of deionized water and 10 parts of a carbon black containing silicon prepared according to the method of Example 10. The resulting pulp was stirred for 30 minutes and then dried overnight at 70 ° C to produce the black of modified silicon-containing carbon While the products of Examples 12-14 were not pelleted, the dried cakes had densities that were comparable to those of the pelletized silicon-containing carbon blacks and had better handling properties than their fluffy counterparts. The pelleted products could have been produced by adding the diazonium salt solution to the required volume of water P1586 / 97MX required to convert the fluffy forms of silicon-containing carbon blacks into pellets in a roller pelletizer.

Example 15: Union of Groups p-CfiHaCO? -a Carbon Black or Smoke Surfaces Containing Silicon. The mother solution A (19 parts of concentrated hydrochloric acid (approximately 36'- HCl, and 20 parts of water) and a stock solution B (8.0 parts of NaN 2 and 39.2 parts of water) were prepared. The stock solutions were cooled to 5 ° C. To 10.3 grams of the stock solution A were added 1.58 g of anthranilic acid (o-aminobenzoic acid). Then 10.5 g of stock B were added slowly while ensuring that the temperature did not exceed 10 ° C. The resulting solution was kept in an ice bath, stirred for 15 minutes and then added to a pulp of 20 parts of carbon black or silicon-containing carbon prepared according to the method of Example 5, dispersed in 300 parts. of water. The resulting pulp was stirred for 15 minutes and then dried in an oven at 70 ° C to produce the carbon black containing modified silicon.

P1586 / 97MX Example 16: Union of Groups p-CfiH4C0? -a Carbon Black Surface or Carbon Containing Silicon. The method of Example 15 was followed, substituting a carbon black containing silicon prepared according to the method of Example 10 for carbon black containing silicon. The dried cakes of the modified silicon-containing carbon blacks of Examples 15 and 16 had densities that were comparable to those of pelleted products and had better handling properties than their sponge precursors.

Examples 17-23: Dispersability. The dispersabilities of the modified and pelletized silicon-containing carbon blacks (Examples 5 and 7) and of pelletized and modified silicon-containing carbon blacks having P-C6H4SO3 groups of Examples 12-14) and "P-C6H4CO2 groups of Examples 15 and 16) attached to their surfaces were determined using the optical density method described above.The optical densities of sonicated pulps and the percentages of change in optical density are summarized in Table 7 below.

P1586 / 97MX Comparative Example 17A: Dispersability. The dispersibility of carbon black or carbon prepared in accordance with ASTM N-234 was determined in accordance with the optical density method described above. The results are summarized in Table 7 below.

The? (OD) values of the pelletized carbon black or ASTM N-234 used in Comparative Example 17A, and the silicon-containing blacks (Examples 17 and 18 and Comparative Example 17A) were closed at 100. This indicates that little dispersion occurred under low shear agitation. The values? (DO) of the samples containing an ionizable group attached to their surfaces were P1586 / 97MX much smaller, varying from 0 to 62o. This shows that the union of the ionizable groups to the surfaces of the silicon-containing carbon blacks improves their dispersabilities.

Example 24: Formulation of Concrete Colored with Iron Red Oxide and_ with Carbon Black or Carbon containing Silicon. A pigment mixture was prepared by thoroughly mixing 90 parts of red iron oxide and 6.2 parts of silicon-containing carbon black with a mortar and pestle until additional mixing did not provide additional color change. 1.4 parts of the pigment mixture were then mixed with a spatula with 60 parts of sand and 14 parts of cement. Approximately parts of water were added and the mixture was worked with spatula to form a paste. The paste was placed in channels (8.5 cm long x 1 cm wide x 1.5 cm deep) to prepare concrete forms to which they were allowed to dry slowly at ambient conditions. The reflectance spectrum of the colored and dried concrete forms was determined and, the reflection values were used to calculate the L *, a * and bd values P15T6 / 97MX Comparative Example 24A: Concrete Formulation Colored with Iron Red Oxide and_ Carbon Black. Concrete forms were prepared in accordance with the method of Example 24, substituting carbon black prepared in accordance with ASTM N-234 for carbon black containing silicon. The reflectance spectrum of the colored and dried concrete forms was determined and the reflectance values were used to calculate the L *, a * and b * values according to the International Commission on Illumination CIÉ 1976.

Comparative Examples 24B-24D: Formulation of Concrete Colored with Red Iron Oxide and; Black Oxide of Synthetic Iron. Three sets of concrete shapes were prepared in accordance with the method of Example 24, substituting 18.6 parts, 31 parts and 43.4 parts of the synthetic iron black oxide for the silicon-containing carbon black, respectively. The reflectance spectrum of the colored and dried concrete forms was determined and the reflectance values were used to calculate the L +, a * and b * values according to International Commission on Illumination CIÉ 1976.

P1586 / 97MX Example 25: Concrete Formulation Colored with Iron Red Oxide and_ Carbon Black containing Modified Silicon. 1.4 parts of red iron oxide were mixed with spatula with 60 parts of sand and 14 parts of cement. 0.0875 parts of a carbon black containing modified silicon were dispersed in 10 parts of water under low shear dispersion conditions for 30 minutes using a magnetic stirrer. The carbon black containing aqueous modified silicon was added to the sand / cement mixture to form a paste. The paste was placed in channels (8.5 cm long x 1 cm wide x 1.5 cm deep), to prepare concrete forms to which they were allowed to dry slowly under ambient conditions. The reflectance spectrum of the colored and dried concrete shapes was determined and the reflectance values were used to calculate the L *, a * and bd values Examples 26-30: Concrete Formulation Colored with Carbon Black containing Silicon. Concrete forms were prepared in accordance with the method of Example 24, substituting the silicon-containing carbon blacks of Examples 3-7, respectively. The reflectance spectrum of the colored and dry concrete was determined and the values of P15B6 / 97MX reflectance were used to calculate the Ld * and b * values according to International Commission On Illumination CIÉ 1976, as described above. The concrete forms were weathering then. The color values before the acid wash and the color change values after the acid wash are listed below in Table 8.

Comparative Examples 26A-26C: Formulation of Concrete Colored with Synthetic Iron Black Oxide. Concrete forms were prepared in accordance with the methods of Example 24, substituting synthetic black iron oxide in the amounts noted below in Table 9. The reflectance spectrum of the colored and dried concrete shapes was determined and P1586 / 97MX the reflectance values were used to calculate the values L *, a * and b * according to the International Commission on Illu ination CIÉ 1976. Concrete forms were then weathered. The color values before the acid wash and the color change values after the acid wash are listed below in Table 9. aThe amount of pigment represents the factor in which the content of black oxide of synthetic iron in concrete is higher than in products based on carbon black. The results in Table 9 show that as the amount of synthetic black iron oxide in the concrete increases, the L * value is reduced which corresponds to an increase in jet coloration (ie, to the dark degree of color). The value a * also P1586 / 97MX decreases, which means that the degree of redness is reduced, probably because the red oxide content of natural iron in the concrete is reduced. Similarly, the degree of yellow coloration is reduced. With the acid wash, the jet coloration increases as shown by the relatively large negative change in the value of? L *. On the other hand, the changes in the values of *? B * and, especially from? A *, are very small, demonstrating that the color tone of the concrete has not changed substantially with the acid wash.

Comparative Examples 26D-26E: Concrete Formulations Colored with Carbon Black. Concrete forms were prepared in accordance with the method of Example 24, substituting sponge carbon black and pelletized prepared in accordance with ASTM N-234, as indicated in Table 10 below by the pigment. "The carbon black had a surface area of 123 m2 / g, a pelleted DBP value of 122 cc / 100 g of carbon and a dye intensity of 122?,. The reflectance spectrum of the colored and dried concrete forms was determined and the reflectance values were used to calculate the L *, a * and b * values according to International Commission on Illumination CIÉ 1976. The forms of concrete were weatherized P1586 / 97MX then. The color values before the acid wash and the values of the color change after the acid wash are listed in Table 10 below.

Examples 26-30 compared to Comparative Examples 26D-26F, illustrate that the color values obtained using the carbon blacks containing silicon are similar to those obtained with conventional carbon black. The L * values of the products tend to increase (ie, to become clearer) er. the largest silicon contents in the products. This observation is in agreement with the dye intensity values presented in Table 5. With the acid wash, the values? L * are comparable with those of carbon black (Table 10). The magnitudes of the values? A * and? B * on the other hand, are smaller. That shows P1586 / 97MX that the change in color tone of pigmented concrete with carbon black or silicon-containing carbon is less than that obtained or achieved with carbon black or conventional carbon.

Examples 31-34: Colored Concrete Formulations with Carbon Black or Carbon Containing Silicon. The concrete forms prepared in accordance with the method of Example 24, substituting the silicon-containing carbon black of Examples 8-11, respectively. The reflectance spectrum of the colored and dried concrete forms was determined and the reflectance values were used to calculate the L *, a * and b * values according to the International Commission on Illumination CIÉ 1976 as described above. The concrete forms were weathering then. The color values before the acid wash and the values of the color change after the acid wash are summarized in Table 11.

P1586 / 97MX Examples 31-34 demonstrate that silicon-containing carbon blacks formed by the addition of ur. Composite of volatile silicon after the start of the formation of carbon black or carbon gives concrete with colors a little more jet (reduced Lr values) even at higher levels of silicon with lower dye intensities than those formed with the blacks of the Examples Comparatives 26D-26F. This suggests that the carbon blacks containing silicon used in the present invention are more compatible with concrete than conventional carbon blacks. The color tone, as provided by the values a * and b X is reasonably similar to those obtained with the carbon blacks of Comparative Examples 26D-26F. The color changes with the acid wash are relatively small * / P15T6 / 97MX significantly smaller than those obtained with the carbon blacks of Comparative Examples 26D-26F. This demonstrates that the binder compositions pigmented with carbon black containing silicon are more resistant to weathering than are the binder compositions pigmented with conventional carbon black.

Examples 35-37: Concrete Formulations Colored with Carbon Blacks Containing Modified Silicon. Concrete forms were prepared in accordance with the method of Example 24, substituting the modified silicon-containing carbon blacks of Examples 12-14, respectively. The reflectance spectrum of the colored and dry concrete was determined and, the reflectance values were used to calculate the L * -, a * and b * values according to the International Commission on Illumination CIÉ 1976, as described above. The color values before the acid wash and the color change values after the acid wash are summarized in Table 12 below.

P1586 / 97MX Comparison of Examples 35-37 with Comparative Examples 26A-26C (Synthetic Iron Black Oxide) having similar jet coloration values indicate that the color change with the acid wash, as shown by the magnitudes of? A * Y ? b **, of the two sets of pigments are small and reasonably comparable. This shows that the weathering properties of modified silicon-containing carbon blacks having p-CgH4S03 ~ groups attached to their surfaces are better than those of conventional blacks and are somewhat better than those of carbon blacks containing silicon not modified.

Examples 38 and 39: Concrete Formulations Colored with Carbon Blacks Containing Modified Silicon. Concrete forms were prepared in accordance with the method of Example 24, substituting blacks from P1586 / 97MX modified silicon-containing carbon of Examples 15 and .16, respectively. The reflectance spectrum of the colored and dry concrete was determined and the reflectance values were used to calculate the L *, a * and b * values according to the International Commission on Illumination CIÉ 1976, as described above. Concrete forms were integrated. The color values before the acid wash and the color change values after the acid wash are summarized in Table 13 below.

Comparison of Examples 38 and 39 with Comparative Examples 26A-26C (synthetic iron black oxide) having similar jet coloration values indicate that the color changes with the acid wash of the two sets of pigments are small and reasonably comparable. This shows that the P1586 / 97MX weathering properties of modified silicon-containing blacks having p-C6H4C0 groups - bonded to their surfaces are better than those of conventional blacks and somewhat better than those of unmodified silicon-containing carbon blacks.

Examples 40-44: Concrete Formulations Colored with Carbon Blacks Containing Modified Silicon. Concrete forms were prepared in accordance with the method of Example 24, substituting the modified silicon-containing carbon blacks of Examples 12-16, respectively, for the carbon black containing silicon. However, the product of carbon black or carbon containing modified silicon (0.0875 parts) was added to the water used to set the concrete. Nothing was added to the red oxide of natural iron. The treated silicon-containing blacks were dispersed in the water under low shear dispersion conditions by stirring for 30 minutes using a magnetic stirrer. The reflectance spectrum of the colored and dry concrete was determined and the reflectance values were used to calculate the L *, a * and b * values according to the International Commission on Illumination CIÉ 1976, as described above. The forms of concrete were weatherized. The P1586 / 97MX color values before acid wash and color change values after acid wash are summarized in Table 14.

The values L *, a * and b * of each of Examples 40-44 are similar to those of Examples 35-39. This demonstrates that modified silicon-containing carbon blacks having organic groups containing "an ionic or ionizable group are easily dispersed using low shear dispersion conditions." In addition, the color changes resulting from the acid wash are also similar and small for the values? a * and? b *, which demonstrates their improved weathering properties.All patents, applications, methods of P1S86 / 97HX prμeba and publications mentioned herein are incorporated by reference. Many variations of the present invention will be suggested by themselves to those skilled in the art in light of the above detailed disclosure. All these modifications are within the intended total scope of the appended claims.

P1586 / 97MX

Claims (40)

1. NOVELTY OF THE INVENTION Having described the present invention, it is considered as a novelty and, therefore, the content of the following CLAIMS is claimed as property: 1. A binder composition comprising: (a) a mineral binder and (b) a carbon black or smoke that contains silicon.
2. 2. A binder composition according to claim 1, wherein the mineral binder is selected from the group consisting of cement, concrete, mortar and mortar for exteriors.
3. 3. A binder composition according to claim 1, wherein the carbon black or carbon-containing silicon is oxidized.
4. 4. A binder composition according to claim 3, wherein the carbon black or carbon-containing silicon is oxidized by nitric acid.
5. 5- A binder composition according to claim 1, wherein the carbon black or carbon-containing silicon has an organic group that contains an ionic or ionizable group.
6. 6. A binder composition according to claim 5, wherein the ionic or ionizable group is P1586 / 97MX selects from the group consisting of a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a sulfophenyl group or a salt thereof, a carboxyphenyl group or a salt thereof or any combination of any of the previous ones.
7. 7. A binder composition according to claim 1, wherein the carbon black containing silicon is pelletized.
8. 8. A binder composition according to claim 5, wherein the carbon black containing silicon is dispersible in water.
9. 9. A binder composition according to claim 5, wherein the carbon black containing silicon is dispersed in the mineral binder.
10. 10. A binder composition according to claim 9, wherein the carbon black containing silicon is dispersed by a low shear method.
11. 11. A binder composition according to claim 1, wherein the silicon-containing carbon black comprises from about 0.1 to about 20 parts by weight of silicon, based on 100 parts by weight of carbon black or silicon-containing carbon.
12. 12. A binder composition according to P1586 / 97MX claim 11, wherein the carbon or fumed black containing silicon comprises from about 1 to about 10 parts by weight of silicon, based on 100 parts by weight of the carbon black containing silicon.
13. 13. A binder composition according to claim 1, comprising about 5 or less parts by weight of carbon black or silicon-containing carbon black, based on 100 parts by weight of the total composition.
14. 14. A binder composition according to claim 13, comprising from about 0.1 to about 1 part by weight of the carbon black or silicon-containing carbon black, based on 100 parts by weight of the total composition.
15. 15. A binder composition according to claim 1, wherein the carbon or fume black containing silicon has silicon-containing regions on the carbon black or smoke surface
16. 16. A binder composition according to claim 1, wherein the carbon black containing silicon comprises an aggregate of carbon black or of smoke, wherein the silicon-containing regions are completely distributed in at least a portion of the aggregate and wherein at least a portion of the P1586 / 97MX regions containing silicon are accessible to the surface of the aggregate.
17. 17. A binder composition according to claim 1, wherein the carbon black or silicon-containing carbon black is prepared by the interaction between the products of the incomplete combustion of a hydrocarbon and the decomposition products of a volatilizable silicon-containing compound. in a furnace reactor.
18. 18. A binder composition according to claim 17, wherein the volatilizable compound is selected from the group consisting of octamethyl cyclotetrasiloxane., tetraethoxysilane, tetramethoxy ortho-silicate, tetrachlorosilane, trichloromethylsilane, and mixtures of any of the foregoing.
19. 19. A binder composition according to claim 16, wherein the carbon or fumed carbon containing silicon is oxidized.
20. 20. A binder composition according to claim 19, wherein the silicon-containing carbon black or smoke is oxidized by nitric acid.
21. 21. A binder composition according to claim 16, wherein the carbon black or smoke P1586 / 97MX
22. 22. A binder composition according to claim 21, wherein the ionic or ionizable group is selected from the group consisting of a carboxylic acid or a salt thereof, a sulfonic acid or a salt thereof, a sulfophenyl group or a salt thereof, a carboxyphenyl group or a salt thereof or any combination of any of the foregoing.
23. 23. A binder composition according to claim 16, wherein the carbon black containing silicon is pelletized.
24. 24. A binder composition according to claim 21, wherein the carbon black containing silicon is dispersible in water.
25. 25. A binder composition according to claim 21, wherein the carbon black containing silicon is dispersed in the mineral binder. -
26. 26. A binder composition according to claim 25, wherein the silicon-containing carbon black is dispersed by a low shear method.
27. 27. A binder composition according to claim 16, wherein the mineral binder is selected from the group consisting of cement, concrete, mortar and mortar for exteriors.
28. 28. A binder composition according to P1586 / 97MX claim 16, wherein the carbon black containing silicon, comprises from about 0.1 to about 20 parts by weight of silicon, based on 100 parts by weight of the carbon black or silicon-containing smoke.
29. 29. A binder composition according to claim 28, wherein the carbon black containing silicon comprises from about 1 to about 10 parts by weight of silicon based on 100 parts by weight of the carbon black or silicon-containing smoke.
30. 30. A binder composition according to claim 16, comprising about 5 or less parts by weight of carbon black or silicon-containing carbon black, based on 100 parts by weight of the total composition. .
31. 31. A binder composition according to claim 30, comprising from about 0.1 to about 1 part by weight of carbon black or silicon-containing carbon black based on 100 parts by weight of the total composition.
32. 32. A method for improving the color stability of a mineral binder composition, the method comprises adding a carbon black or silicon-containing carbon black to the mineral binder. P1586 / 97MX
33. 33. A method according to claim 32, wherein the carbon black containing silicon has an organic group containing an ionic group or a dispersible group.
34. 34. An article comprising: (a) a mineral binder and (b) a carbon or fume black containing silicon.
35. 35. An article according to claim 34, comprising a roof tile.
36. 36. The binder composition according to claim 1, further comprising silica.
37. 37. The binder composition according to claim 1, further comprising carbon black or smoke, silica, carbon black or smoke having an organic group attached thereto, iron oxide or combinations thereof.
38. 38. A binder composition according to claim 1, further comprising a carbon or a smoke carbon having an organic group attached thereto.
39. 39. A binder composition according to claim 1, further comprising carbon black or smoke.
40. 40. A binder composition according to claim 1, wherein a portion of the carbon black or P1586 / 97MX of silicon-containing carbon has an organic group bonded thereto and the binder composition further comprises a carbon black or carbon having an organic group attached thereto, silica, carbon black or carbon, iron oxide or mixtures thereof. P1586 / 97MX