MXPA98010646A - Compositions of coating and ink containing black of carbon treated with sili - Google Patents

Abstract

The present invention relates to: Coating and ink compositions comprising a carbon black treated with silicone are exposed. The carbon black treated with silicone may have at least one organic group attached and the ink and coating compositions may comprise a combination of carbon black products treated with silicone, with and / or without at least one bound organic group, and an untreated carbon black. Methods to improve the ability to form a jet, improve the tone of blue, decrease plaque wear, reduce the premix residue, modify the rheological properties or improve the water resistance of the ink and coating compositions, incorporating black carbon treated with silicone

Description

CQ FQSTTIONS OF RECUBLE FILLING AND T? NTA CONTAINING BLACK CARBÓ TREATED WITH SILICON Field of the invention This invention relates to compositions of ink, and coating containing silicon-treated carbon black.

DISCUSSION OF THE RELATED TECHNIQUE The inks are liquid or colored pastes formulated to transfer an image. Pigments such as carbon black are used to impart the desired properties to an ink system. The desired properties of the inks include visual characteristics such as the ability to form a jet, opacity and blue tone. Other performance characteristics include appropriate biological properties, water resistance and permanence.

For "reason" it is economical, it is "desirable to have a pigment that is easily dispersed in the ink formulation. The measure of the dispersion rate is the premix residue. Properties such as premix residue thus have a significant influence on the economy of ink production. The coatings are used for treatments P1799 / 9BMX decorative, protective and functional of many kinds of surfaces. Pigments are also commonly used in coatings to impart desired properties. Similar desired properties may include ability to form jet, opacity, and blue tone, as well as appropriate rheological properties. As in the inks, for economic reasons, it is desirable to have a pigment that is easily dispersed in the coating formulation. Some coatings, such as those for subsea pipelines, are for protective purposes. Others, such as exterior automotive coatings, satisfy both decorative and protective functions. Still others provide friction control on boat decks or car seats. There is a need for improved ink and coating compositions available for use in a variety of applications.

SUMMARY OF THE INVENTION The present invention relates to ink and coating compositions comprising a carbon black treated with silicon. The carbon black treated with silicon can have at least one organic group attached. The present invention also relates to ink and coating compositions comprising a combination of P1799 / 98MX carbon black products treated with silicon, with and / or at least one organic group bound, and an untreated carbon black. The present invention also relates to methods for: improving the ability to form a jet, improve blue tone, improve plaque wear, reduce the premix residue, modify the rheological properties or improve the water resistance of ink compositions and coating when incorporating carbon black treated with silicon in them. Both the foregoing general description and the following detailed description are exemplary, and are intended to provide additional explanation of the invention as claimed.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to ink and coating compositions comprising carbon black treated with silicon. The ink and coating compositions of the present invention may comprise a carbon black treated with silicon. The carbon black treated with silicon may not have a bonded organic group or may have at least one organic group attached, or may comprise either a carbon black treated with silicon having at least one organic group attached or a carbon black P1799 / 98MX treated with silicon that does not have a bound organic group. Untreated carbon black can be combined with any type of carbon black treated with silicon, or with a mixture of both types of carbon black treated with silicon. The "untreated carbon black" is a carbon black that has not been treated with silicon. The "treated carbon black" may be completely untreated or may have one or more organic groups attached, or may have been treated differently. The ink and coating compositions of the present invention advantageously provide an improvement in one or more of the ability to form a jet, blue tone, plaque wear, premix residue, rheological properties, and water resistance. The silicon-treated carbon black of the ink or coating of the present invention typically contains from about 0.1 to about 25% by weight of silicon, based on the weight of the silicon-treated carbon black. Preferably, the carbon black treated with silicon contains from about 0.2 wt% to about 10 wt% silicon, and more preferably from about 0.2 to about 5.4 wt%, based on the weight of the black of carbon treated with silicon. P1799 / 98MX Typically, silicon-treated carbon black may be present in the ink or coating in amounts of about 60% by weight, based on the weight of the ink or coating. Preferably, the carbon black treated with silicon is present between about 10 and about 25% by weight for finished inks and between about 2 and about 25% by weight for coatings. In both inks and coatings, it is not unusual to disperse the carbon black at a higher charge and then reduce it to the desired, final charge after the dispersion step. The ink and coating compositions of the present invention may be aqueous or non-aqueous, and the ink compositions may be used in inkjet printing applications. Aqueous compositions include mixtures of water and other miscible or water dispersible substances, such as alcohol. The ink and coating compositions of the present invention may exhibit unique rheological properties, depending on whether the compositions are aqueous or non-aqueous and the particular base used in the composition. The ink compositions of the invention may optionally further include resins / polymers, additives, fillers and / or diluents. When they are used, the ingredients of the P1799 / 98MX composition and ink as those listed above are weighed, and mixed and ground together separately, according to the desired formulas. The ink compositions of the invention are useful in, for example, printing inks, ultraviolet cure inks, rubber stamp inks, and inks for other applications. The McGra-Hill 's Encyclopedia of Science and Technology, 6th edition, volume 9, pages 171-klO 176, provides additional details of the types of inks available and their uses, all of which are incorporated herein by reference. For a general discussion of the properties, preparation and uses of aqueous inks, see The Printing Manual, 5th edition, Leach et al., Eds. Chapman and Hill, 1993, incorporated herein by reference. The various aqueous ink compositions are also described, for example, in U.S. Patent Nos. 2,833,736; 3,607,813; 4,104,833; 4,308,061 and 5,026,755, the descriptions of which are incorporated herein by reference. Non-aqueous inks are used for many applications where aqueous vehicles are not suitable. For example, the inks to be printed on substrates non-porous, hydrophobic, such as glass, metal or plastic P1799 / 98MX must be quick drying. Therefore, solvents such as ketones, esters, alcohols or hydrocarbons are frequently used in place of water. These solvent-based inks are widely used for the industrial marking of cardboard boxes and various containers and metal or plastic components. A common type of non-aqueous ink is newspaper ink. A typical newspaper ink can be made in two stages. First, a pigment, for example, the silicon-treated carbon black of the present invention, and a carrier are mixed to form a "premix", and the premix is then milled to achieve optimum pigment dispersion. In general, lower premix residues result in faster or better dispersion, resulting in improved economy for the producer. The flow properties of the ink at low constant stress speeds are affected by the dispersion characteristics of the ink pigments. Depending on the application, different flow levels are desirable. In screen printing inks, it is desirable to have inks with short flows so that the inks do not flow through the screen in a premature manner. In rotogravure printing, longer flows may be desirable as the ink travels P1799 / 98H2C on the ink rollers. Frequently, biological additives are added to adjust these flows. Jet printing or inkjet printing is a non-impact process, where ink droplets are produced and deposited on a substrate, such as paper, transparent film, or textile material in response to an electrical signal. Conventional inks for jet or inkjet printers comprise a colorant such as a dye which is soluble in the klO vehicle of the ink. However, the dyes have several disadvantages when used in the ink jets. The dyes can be redissolved in the water, the images of the dyes are stained or removed by rubbing in contact with markers, and the dyes exhibit poor stability to the light. Pigments used as colorants in ink jet inks offer superior properties in areas such as water resistance, light resistance, image density and thermal clarity. The carbon black pigment treated with silicon must be expressed and stabilize in the ink jet ink so that properties such as ejection ability, print quality, and optical density are not adversely affected. The coating compositions of the invention include pigments of carbon black treated with P1799 / 98MX silicon, a solvent, and optionally, one or more ingredients selected from binders, for example, resins or polymers, and various other additives. Coatings can be manufactured and applied as liquids and converted to "solid" films after application to the substrate. Coatings are used for decorative, protective and functional treatments of many kinds of surfaces. These surfaces include spirals, metals, appliances, furniture, veneers, wood, plywood, marine, maintenance, automobiles, boats and cardboard. As mentioned above, the ink and coating compositions of the present invention can comprise any number of additives. For example, in an ink composition for use as a jet or ink jet ink, a humectant may be added to reduce the rate of evaporation of the water in an ink composition to minimize plugging of the nozzle of the head of the ink. printing in jet or inkjet applications, as an example! If the ink begins to dry, the concentration of the humectant increases and evaporation further decreases. Wetting agents can also affect other properties of inks or coatings, such as P1799 / 98MX viscosity, pH, surface tension, optical density and print quality. Preferred humectants include ethylene glycol, propylene glycol, diethylene glycols, glycerin, dipropylene glycols, polyethylene glycols, polypropylene glycols, amides, ethers, carboxylic acids, esters, alcohols, organosulfides, organosulphoxides, sulfones, alcohol derivatives, carbitol, butyl carbitol, cellosolve, ether derivatives. , aminoalcohols, and ketones. Biocides such as benzoate or sorbate salts , 10 may be important in aqueous inks and coatings to prevent bacterial growth. The binders that bind to the substrate to retain the colorant in the substrate can be added in a variety of ink and coating compositions.

Examples include polyester, polyester-melamine, styrene-acrylic acid copolymers, copolymers of styrene-acrylic acid-alkyl acrylate, styrene-maleic acid copolymers, styrene-maleic acid-methyl acrylate copolymers, styrene-copolymers acid methacrylic, copolymers of styrene-methacrylic acid-alkyl acrylate, copolymers of styrene-maleic ester medium, copolymers of vinyl-naphthalene-acrylic acid, copolymers of vinyl-naphthalene-maleic acid, and salts thereof. The drying acceleration agents promote evaporation once the ink or P1799 / 98MX coating is placed on the substrate. These include sodium lauryl sulfate, N, N-diethyl-m-toluamide, cyclohexylpyrrolidone, and butyl carbitol. Penetrating agents such as alcohols, sodium lauryl sulfate, esters and ketones allow the ink to penetrate the surface of the paper. The alcohols can also be used to increase the drying rate of the ink or liquid coating. And the surfactant agents similar to detergents and soap reduce the surface tension to allow the ink or coating to spread on the substrate. The ink or coating compositions of the present invention can be prepared using conventional techniques. Specifically, milling, such as milling with steel pellets or mixing with three rollers, can be employed to obtain good dispersion of the silicon-treated carbon black in the composition. The silicon-treated carbon black pigment of the present invention can be obtained by manufacturing the carbon black in the presence of volatilizable silicon-containing compounds. A full description of this manufacturing process is found in U.S. Patent Application Serial No. 08 / 446,142 for "Elastomeric Compounds Incorporating Silicon-treated Carbon Blacks and Coupling Agents," and P1799 / 98MX U.S. Patent Application Serial No. 08 / 446,141 for "Elastomeric Compounds Incorporating Silicon-treated Carbon Blacks," the descriptions of which are hereby fully incorporated by reference. carbon blacks treated with silicon are preferably produced in a carbon black, modular oven or "in stages" reactor. Hot combustion gases are generated by contacting a gaseous liquid fuel with a suitable oxidizing stream such as oxygen, air, or mixtures of air and oxygen. Among the fuels suitable for contacting the oxidizing stream are any readily combustible gas, vapor or liquid streams such as natural gas, hydrogen, methane, acetylene, alcohols or kerosene. However, it is generally preferred to use fuels having a high content of carbon-containing components and in particular hydrocarbons. The air to fuel ratio varies with the type of fuel used. When natural gas is used to produce the carbon blacks of the present invention, the air to fuel ratio can be from about 10: 1 to about 1000: 1 by volume. To facilitate the generation of hot combustion gases, the oxidant stream can be pre-heated. The carbon black feed is injected into P1799 / 98MX the gas stream to a point downstream of the flow. Preferred carbon black feeds include petroleum refinery sources such as oils decanted from catalytic disintegration operations, as well as by-products of cooking operations and olefin manufacturing operations. In the reaction zone portion of the reactor, the feed is pyrolyzed to carbon black. The reaction is stopped in an extinction zone of the reactor, quenching or quenching which serves to cool the carbon black particles, reduces the temperature of the gas stream, and decreases the reaction rate. Optionally, the extension can be in stages, or it can take at several points in the reactor. After the carbon black is quenched, the cooled gases and the carbon black pass downstream to some conventional cooling and separation means, whereby the carbon black is recovered. Separation of the carbon black from the gas stream is easily accomplished by a conventional means such as for example: a precipitator, cyclone separator, 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 an agglomeration step. P1799 / 98HX The silicon-treated carbon blacks of the present invention can be produced by introducing a volatilizable silicon-containing compound into the carbon black reactor at a point upstream of the extension zone. Useful volatilizable compounds can include any compound that is volatilizable at the temperatures of the carbon black reactor. Examples include, but are not limited to: silicates such as tetraethoxy orthosilicate (TEOS) ilO tetramethoxy orthosilicate and the like; the silanes such as tetrachlorosilane, trichloro-methylsilane and the like; and volatile silicone polymers such as octamethylcyclotetrasiloxane (OMTS) and the like. The flow rate of the volatilizable compound will determine the weight percentage of silicon in the treated carbon black. The volatilizable compound can be premixed with the feed that forms the carbon black and fed into the reaction zone.

Alternatively, the volatilizable compound can be introduced into the reaction zone separately from the feed introduction point. This introduction can be upstream or downstream of the injection point of the feed, with the condition that the volatile compound is introduced current P1799 / 98MX above the extension area. In the volatilization and exposure to high temperatures in the reactor, the compound decomposes and reacts with other species in the reaction zone, producing carbon black treated with silicon, such that silicon or silicon-containing species become a intrinsic part of carbon black. If the volatilizable compound is introduced substantially simultaneously with the feed, the silicon-treated regions are distributed throughout the length of at least a portion of the carbon black aggregate. The volatilizable compound can be introduced alternatively into the reaction zone at a point after the carbon black formation has begun, but before it has been subjected to extinction. In this case, aggregates of silicon-treated carbon black are obtained, in which silicon or a silicon-containing species is present mainly on or near the surface of the carbon black aggregate. In addition to volatilizable compounds, decomposable compounds that are not necessarily volatilizable can be used to produce carbon blacks treated with silicon. In addition, carbon black coated with silica as described in U.S. Patent Application Serial No. 08 / 446,140 for "Elastomeric Compounds Incorporating Partially Coated P1799 / 98MX Carbon Blacks, "the disclosure of which is incorporated herein by reference, may also be used in the dyeing and coating compositions of the present invention.In the silicon-treated carbon black of the present invention, the silicon or a silicon-containing species that includes, but is not limited to, silicon oxides, for example, Si02 and silicon carbides, may be distributed through at least a portion of the carbon black aggregate as an intrinsic part of the black The aggregates of silicon-treated carbon blacks of the present invention are not a mixture of discrete aggregates of carbon black and discrete silica aggregates, but include at least one silicon-containing region either on the surface of the aggregate or carbon black or inside it When the silicon-treated carbon black is examined under the STEM-EDX (transmission electron microscope by X-ray energy dispersion), the silicon signal that corresponds to the silicon-containing species is found to be present in individual aggregates of carbon black. By comparison, in a physical mixture of silicon and carbon black, the STEM-EDX examination reveals distinctly separate aggregates of silica and carbon black.

P1799 / 98HX An alternative way to describe that the aggregate of silicon-treated carbon black is an aggregate comprising a carbon phase and a phase of the silicon-containing species. The aggregate, contains in this way at least two phases, one of which is carbon and the other of which is a species that contains silicon. The silicon-containing species, which is part of the aggregate, does not bind to an aggregate of carbon black similar to a silica coupling agent, but is actually part of the same aggregate as the carbon phase. The details of the preparation of the silicon-treated carbon black are further explained in U.S. patent applications serial numbers 08 / 446,141, filed May 22, 1995; 08 / 446,142 filed May 22, 1995; 08 / 528,895 filed September 15, 1995; and 08 / 750,017 filed November 22, 1996, which is a PCT national phase application number WO 96/37547 filed May 21, 1996. All of these patents and applications are hereby incorporated by reference in their entirety. Optionally, the carbon blacks treated with silicon of the present invention can have at least one organic group attached. These carbon black can be prepared, for example, based on the descriptions in the North American patent application serial number.

P1799 / 98MX 18 / 356,660, filed December 15, 1994, and its application for continuation in part, serial number 08 / 572,525, filed on December 14, 1995, the description from which they are fully incorporated by reference in the I presented . The organic group or groups are preferably bonded to the carbon black treated with silicon according to the methods described in the above applications. The organic group can be an aliphatic group or a cyclic organic group or an organic compound having an aliphatic portion and a cyclic portion. The organic group can be substituted or unsubstituted, branched or unbranched. Aliphatic groups include, for example, groups derived from alkanes, alkenes, alcohols, ethers, aldehydes, ketones, carboxylic acids and carbohydrates. Cyclic organic groups include, but are not limited to: alicyclic hydrocarbon groups (e.g., cycloalkyls, cycloalkenyls) heterocyclic hydrocarbon groups (e.g., pyrrolidinyl, pyrrolinyl and piperidinyl, morpholino, like), aryl groups (e.g., phenyl, naphthyl, anthracenyl, and the like), and heteroaryl groups (imidazolyl, pyrazolyl , pyridinyl, thienyl, thiazolyl, furyl, triazinyl, indolyl, and the like). When the organic group is replaced, it can P1799 / 98MX contain any functional group compatible with the formation of a diazonium salt. The functional groups include, but are not limited to: R, OR, COR, COOR, OCOR, halogen, CN, NR2, S02NR (COR), S02NR2, NR (COR), CONR2, N02, S03M (where M is H, Li , Na, Cs, or K), S03NR4 and N = NR '. R is independently hydrogen, alkyl of 1 to 20 carbon atoms substituted or unsubstituted (branched or unbranched), alkenyl of 2 to 20 carbon atoms substituted or unsubstituted, (C2-C4 alkyleneoxy) XR "or a substituted aryl or not replaced. R 'is independently hydrogen, alkyl of 1 to 20 carbon atoms substituted or unsubstituted (branched or unbranched) or a substituted or unsubstituted aryl. R "is hydrogen, an alkyl of 1 to 20 carbon atoms substituted or unsubstituted, an alkenyl of 3 to 20 carbon atoms substituted or unsubstituted, an alkanoyl of 1 to 20 carbon atoms substituted or unsubstituted or an aroyl replaced or not replaced. The integer x varies from 1-40 and preferably from 2-25. An organic group is an aromatic group of the formula AyAr-, which corresponds to a primary amine of the formula AyARNH2. In this formula, the variables have the following meanings: Ar is an aromatic radical selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl and biphenyl, pyridinyl, P1799 / 98MX and triazil; A is a substituent on the aromatic radical independently selected from a functional group described above or A is a linear, branched or cyclic hydrocarbon radical (preferably containing 1 to 20 carbon atoms), unsubstituted or substituted with one or more of these functional groups; and is an integer from 1 to 5, when Ar is phenyl, from 1 to 7 when Ar is naphthyl, from 1 to 9 when Ar is anthracenyl, phenanthrenyl or biphenyl, or from 1 to 4 when Ar is pyridinyl, or from 1 a 2 when Ar is triazinyl. When A is a group (C2-C4 alkyleneoxy) XR ", it may be a polyethoxylate group, a polypropoxylate group, or a random mixture of blocks of the two. The carbon black can have a bonded organic group having a) an aromatic group or an alkyl group of 1 to 12 carbon atoms, and b) at least one group of the formula S02NR2 or S02NR (COR). R may independently be hydrogen, an alkyl of 1 to 20 carbon atoms substituted or unsubstituted, an alkenyl of 3 to 20 carbon atoms substituted or unsubstituted, (C2-C4 alkyleneoxy) XR 'or a substituted or unsubstituted aryl; R 'is hydrogen, an alkyl of 1 to 20 carbon atoms, substituted or unsubstituted, an alkenyl of 3 to 20 carbon atoms substituted or unsubstituted, an alkanoyl of 1 to 20 carbon atoms substituted or unsubstituted, or aroyl P1799 / 98MX substituted or unsubstituted; x is from 1 to 40. The aromatic groups include: p-CeH4S02NH2, p-C6H4S02NHCsH13, p-C6H4SO, NHCOCH, p-C6H4S02NHC0CsH11, and p-C6H4S02NHCOCßHs. The organic groups which can be attached to the carbon black treated with silicon are organic groups substituted with an ionic or ionizable group as a functional group. An ionizable group is one capable of forming an ionic group in the medium of use. The ionic group can be an anionic group or a cationic group or the ionizable group can form an anion or a cation. Ionizable functional groups that form anions include, for example, acid groups or salts of acid groups. Therefore, acidic groups include groups derived from organic acids. When an organic group contains an ionizable group that forms an anion, such that an organic group may have a) an aromatic group or an alkyl group of 1 to 12 carbon atoms or b) at least one acid group having a pKa of at least 11, or at least one salt of an acid group having a pKa of less than 11, or a mixture of at least one acid group having a pKa of less than 11 and at least one salt of an acid group having a pKa.de 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. Preferably, the pKa is less than 10 and preferably P1799 / 98MX less than 9. The aromatic group or the alkyl group of 1 to 12 carbon atoms of the organic group can be directly attached to the carbon black. The aromatic group may be additionally substituted or unsubstituted, for example, with alkyl groups. The organic group can be a phenyl or naphthyl group and the acid group is a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, or a carboxylic acid group. The organic group may also be a substituted or unsubstituted sulfophenyl group, or a salt thereof; a substituted or unsubstituted (polysulfo) phenyl group or a salt thereof; a substituted or unsubstituted sulfonaphthyl group or a salt thereof, - or a substituted or unsubstituted (polysulfo) naphthyl group or a salt thereof. A substituted sulfonyl group is a hydroxysulfonyl group or a salt thereof. Specific organic groups having an ionizable functional group that forms an anion are p-sulfonyl, 4-hydroxy-3-sulfophenyl, and 2-sulfoethyl. The amines represent examples of ionizable functional groups that form cationic groups. For example, amines can be protonated to form ammonium groups in the acid medium. Preferably, an organic group having an amine substituent has a pKb of less than 5. The quaternary ammonium groups and the P1799 / 98MX quaternary phosphonium groups also represent examples of cationic groups. Preferably, the organic group contains an aromatic group such as a phenyl or naphthyl group and a quaternary ammonium or quaternary phosphonium group. The aromatic group is preferably directly attached to the carbon black treated with silicon. Quaternized cyclic amines, and even quaternized aromatic amines, can also be used as the aromatic group. In this manner, N-substituted pyridinium compounds, such as N-methyl-pyridyl, can be used in this regard. Other examples include, in a non-exclusive manner :, 3-C3H4N (C-, Hs) + X-, C6H4NCSHS + X 'CSH4C0CH2N (CH3) 3 + X- CßH4C0CH2 (NCsHs) * X "CsH4N (C2Hsr? -, CsH4N (CH3) 3 +? -, and CSH4CH2N (CH3) 3 + X_, where X" is a halide or an anion derived from a mineral or organic acid Alternatively, or in combination with the joining methods described above, the chemical groups can be attached by reacting with the functional groups on the surface in the carbon black treated with silicon For example, the carbon black treated with silicon can be reacted with a trialkoxyalkylsilane, such as octadecyltriethoxysilane, to improve the compatibility of certain compositions.

P1799 / 98MX for: improving the ability to form a jet, improve the blue tone, improve the wear resistance of the plate, reduce the premix residue, modify the rheological properties or improve the water resistance of the ink and coating compositions. incorporate in them the carbon black treated with silicon. In method for improving the jetting ability of an ink composition or coating, the silicon-treated carbon black contains flO preferably from 0.2 to 5.4 weight percent silicon, based on the weight of silicon-treated carbon black. In a method for improving the blue tone of an ink composition or coating, the silicon-treated carbon black preferably contains from 0.2 to 5.4 percent by weight. weight of silicon, based on the weight of carbon black treated with silicon. A method for improving the plate wear of an ink composition or coating, the silicon-treated carbon black preferably contains from 0.2 to 25 weight percent of silicon, in more Preferably from 0.2 to 10 weight percent, based on the weight of the carbon black treated with silicon. In a method for reducing the premix residue of an ink composition or coating, the silicon-treated carbon black preferably contains from 0.2 to 25 weight percent of silicon, more preferably from 0.2 to 10 percent in P1799 98MX based on the weight of carbon black treated with silicon. In a method for modifying the rheological properties of an ink composition or coating, the silicon-treated carbon black preferably contains from 1 to 25 weight percent silicon, based on the weight of the silicon-treated carbon black. And in a method for improving the water resistance of an ink composition or coating, the silicon-treated carbon black preferably contains from 0.2 to 25 weight percent silicon, based on the weight of the silicon-treated carbon black. The invention will be further clarified by the following examples, which are proposed to be exclusively exemplary of the invention. In the examples below, the DBP absorption is measured by the ASTM D2414 method. Similarly, CDBP and coloring power are measured by methods ASTM D3493 and ASTM D3265. The area of the external surface and nitrogen (t-area) is measured after the example preparation and measurement procedure described in ASTM D3037. For this measurement, the nitrogen absorption isotherm extends up to 0.5 relative pressure. The relative pressure is the pressure (P) divided by the saturation pressure (P0) (the pressure at which it condenses at P1799 / 98MX nitrogen). The thickness of the absorption layer (tx) was then calculated using the relationship: ti 13.99 ^ 0.034-log (/ Po) The volume (V) of nitrogen absorbed is then plotted against tx. So, was a straight line adjusted through the data points for t? , values between 3.9 and 6.2 Angstroms. The t-area was then obtained from the slope of this line as follows: / - area, m 2 / g = 15.41 xpendiente Hunter color was measured using the instrument Hunter Lab Sean 6000, at 10 degrees, D 65 CIELAB Color Space manufactured by Hunter Associates in Fairfax, Va. The c '^ "' instrument is calibrated using black and white normal tiles." L "is the clarity / darkness scale with higher numbers that are lighter," a "is the scale of red (+) / greenery ( -), and "b" is the scale of yellow (+) / blue (-) .The color values are obtained from a point or trace down of the ink on a paper substrate.The fade is measured using the A-9 method of P1799 / 98MX Ne spaper Association of America. Plate wear is measured by placing a portion of the ink on a felt substrate and mechanically rubbing it repeatedly for 6 hours with a brass plate under normal pressure. The weight loss of the bronze plate after 6 hours is given as the plate wear in grams. The classification of the dispersion is made by viewing a wet film of 0.1 thousandths of an inch with a transmission microscope at a magnification of 100x. The level of dispersion (ie, the quantity and size of undispersed black) is compared to a normal graph. The scale goes from A to F for the amount of undispersed agglomerates and from 1 to 6 for the size. The higher the number and the smaller the letter, the poorer the dispersion quality. The brightness is measured using the ASTM method D523. The viscosity of Laray steel bar is measured using the D4040 ASTM method. Vertical glass plate flow is measured by the distance a sample of 0.5 cc of ink travels down a vertical glass plate after the samples are allowed to stand for 0, 30, and 60 minutes before the plate rises . The properties of the extension measuring device are measured using a Toyoseiki extension measuring device, manufactured by Testing Machines Inc, as described in the Japanese P1799 / 98MX Industrial Standard, Testing, Methods for Lithography and Letterpress Inks (JIS K5701-4.1.2). The residue is measured by pouring the ink formulations onto a pair of stacked stencils with the stencils on the top of the bottom that are + 325M and +625M, respectively. The stencils are then washed with industrial alcohols until it is observed that the alcohols are visually clear. The stencils are then dried in a dewatered oven at approximately 220 ° F. The residue in the screen + 325M is then weighed to determine the + 325M residue as a percent by weight of the initial ink formulation.

Example 1 Three carbon blacks were evaluated in a normal, low-fading, newspaper ink formulation. Blacks are described in Table I below. Sample A is a conventional carbon black and samples B and C are carbon blacks treated with silicon. Carbon blacks treated with silicon are produced by premixing OMTS with the feed that forms the carbon black as written above. The three carbon blacks are described in Table I below.

P1799 / 98HX Table I Each carbon black was premixed in a newspaper ink composition, based on naphthenic oil, at 20% by weight carbon black filler for 35 minutes using a Dispermat® high speed disk disperser (Getzman GmBH, Germany) at a tip speed of 2300 feet per minute. The mixture was then dispersed in a vertical ball mill containing 1.5 mm steel balls (# 550 from Schold Machine Corp, Chicago, IL) until the dispersion quality, as measured with a NPIRI milling measuring device using Method D1316 ASTM, did not have "stretch marks" and where the "spots" disappeared at 20 microns or less. The final dispersion was reduced to 16% by weight of carbon black with the reduction vehicle. The ink composition for the three carbon blacks is presented in Table II below.

P1799 / 98MX Table II Hyprene "* products were obtained from Ergor Refining, Vicksburg, MS Exxprint" was obtained from Exxon, Houston TX. The PiccoMR resin was obtained from Hercules INC, Wilmington, DE. The MagieMR oil was obtained from Magie Bross, Franklin Park, IL. Claytone ™ was obtained from Southern Clay Products, Gonzales, TX. The results of the test are shown in Table III below. All prints were prepared for evaluation when printing at an optical density of 1.0 in a newspaper print using a P1799 / 98MX RNA print capacity tester 52 manufactured by Research North America, Cherry Hill, NJ. Table III The premix residue was lower for blacks P1799 / 98MX carbon treated with silicon. Carbon blacks treated with silicon showed an improved jetting ability and an enhanced blue tone as measured by the lower L and b values for the Hunter color of samples 5 B and C relative to sample A. Carbon blacks treated with silicon also showed improved plate wear on plate A.

Example 2 | 10 Three carbon blacks were evaluated in a flexographic, acrylic, aqueous formulation. Sample D was a conventional carbon black and samples E and F were carbon blacks treated with silicon. Carbon blacks are described in Table IV below. The carbon blacks treated with silicon were produced as described above when premixing OMTS with the feed that produces the carbon black.

Table IV 20 P1799 / 98MX Each carbon black was premixed in a flexographic, acrylic, aqueous ink composition at 24.4% by weight carbon black for 30 minutes using a Dispermat * 5 high speed disc disperser, at a tip speed of 2300 feet per minute. The premix was then expressed in a horizontal ball mill (Model M-50 Eliger Machinery, Bensonville, IL) with 2 mm stainless steel balls. 150 grams of the ink composition was recycled through the mill for 45 minutes at a flow rate of about 200 grams per minute. 10 grams of the material were removed at 15 minute intervals and reduced to 9.76% by weight of the carbon black with additional water and resin before the color and dispersion evaluation. The reduction was made by agitation of the dispersion, water and resin for 15 minutes in a paint shaker (Model 5400, Red Devil Equipment, Union, N.J). The ink composition for the three blacks is presented in Table V below.

Table V P1799 / 98MX JoncrylMR acrylic resin was obtained from S.C. Johnson, Racine, Wl. The DymsolMR acrylic resin was obtained from Henkel Corp. Kankakel, IL, Byk 020 was obtained from Byk chemie, Wallinford, The results of the test are shown in Table VI below.

Table VI P1799 / 98MX Carbon blacks treated with silicon showed better dispersion, ie, faster compared to sample D. Carbon blacks treated with silicon were also darker and bluer as indicated by the smaller "L" Hunter values and "b" Hunter more negative.

EXAMPLE 3 Samples, D, E and F of carbon black were evaluated in a normal heat hardening, bright ink formulation prepared in a mill of P1799 / 98MX three rollers. The carbon black samples were prepared by grinding in a three roll mill (Kent Machine Works, Brooklin, NY). A premix consisting of 105 grams of carbon black and 245 grams of the main grinding batch (consisting of 9 parts of the heat hardened grinding vehicle LV - 3427XL obtained from La ter International, Northnbrook, IL, to a part of Magie ™ naphthenic oil) was prepared in the Dispermant running at 5000 rpm for 30 minutes. This mixture, 50 g, is milled in the Kent three-roll mill running at 70 ° F. The samples were allowed to dilute when mixed with an equal amount of the main grinding batch and then applied to a production grinding measuring apparatus G-2 NIPRI for the evaluation of grinding. Additional passes were made without reading the grinding meter was not above 20. The finished ink was produced by mixing the ground material with an equal weight of the main reduction lot (3 parts of LV-3427XL, 12 parts of LV 6025 , a reduction vehicle obtained from Lawter International, Northbrook, IL; 5 parts of MAGIESOL 47) and passing once through the three-roll mill. The fineness of the grind data for samples D, E and F, and the viscosity measurements for the resulting inks are shown in Table VII below.

P1799 / 98MX The numbers in the grinding data table are in microns as measured in a G-2 grinding meter and indicate the level where 5 grams defective in the grinding meter are detected. Designations greater than 50 indicate delayed separation of the carbon black from the grinding vehicle. The optical properties for the inks elaborated from samples D, E and F were determined for impressions made using the klO print capacity tester RNA-52. The values are shown in Table VIII.A and Table VIII.B. The values for the film thickness of 1 and 2 microns were calculated from the regression of the data of the prints having a range of film thicknesses. The sample with the highest content of If it was dispersed somewhat easier than the non-silicon sample added in the three-roll mill. . The viscosity measurements in Table VII show the effect of increasing the Si content in this ink formulation. Under low conditions constant effort (flow in vertical glass plate), sample F, which has the highest Si content, showed a significantly lower flow than either sample D or E. once the constant effort is applied to these inks, the rheological differences become smaller. The inclination of the extension measuring device (indicator P1799 / 98MX of the flow capacity at higher constant stress) is greater for sample F, just the opposite of that observed for flow in vertical glass plate.

Table VII P1799 / 98MX Properties of the ink Viscosity of Laray steel bar Viscosity (equilibrium at 2500 61.9 67.0 63.2 Elasticity limit (dynes / cm 695 590 621 to 2.5 s "2) Flow in vertical glass plate (mm) Without adjustment 20 minutes 70 75 45 40 minutes 85 89 51 60 minutes 99 100 55 minutes of adjustment 20 minutes 50 46 21 40 minutes 65 60 31 60 minutes 75 71 36 60 minutes of adjustment 20 minutes 45 40 19 40 minutes 57 52 27 60 minutes 69 61 34 Properties of the extension measuring device Slope (mm) 8.3 8.1 9.7 P1799 / 98MX Table VIII.A Optical properties of an elaborated film made from samples D-F Table VIII.B optical properties of a 2 micron film made from D-F samples It is seen that at a relatively high level of silicon treatment, 5.5% Si by weight, there is a significant decrease in the flow capacity at low shear (lower values in flow plate P1799 / 98MX vertical) and a significant increase in the flow capacity at higher shear (high values of the slope of the properties of the extension measuring device). In this way, carbon black treated with silicon can be used as a rheological modifier.

Example 4 Ink jet or inkjet inks were prepared from the carbon blacks treated with silicon G and H (described below) having CH4 (NC5H5) + groups attached. Plaque nitrite (2.85 g) was added to a solution of 3.1 g of N- (4-aminophenyl) iridinium chloride in 100 g of water and the mixture was stirred at 70-80 ° C for 1 hour. The mixture was filtered after stirring overnight at room temperature. Each of the two carbon blacks treated with silicon (approximately 10 g) were added separately to grams of the filtrate, and approximately 55 grams of water were added. The resulting mixtures were heated to 70 ° C 0.5 grams of 37% aqueous HCl were added. The dispersions were stirred at 70 ° C for 1.5 hours and room temperature overnight. In this way, mixtures of silicon-treated carbon black having C6H4 (NCSHS) * and water were formed. Sample G is a carbon black treated with P1799 / 98MX silicon containing 1.6% silicon having a t-area of 119 m2 / g and a DBP absorption value of 115 cc / 100 g. Sample H is a silicon-treated carbon black containing 5.2% silicon and has a t-area of 125.5 m2 / g j and a DBP absorption of 105 cc / 100 g. The samples were produced by premixing OMTS with the feed that produces the carbon black, as discussed above. Inks were prepared by diluting the dispersions with water so that the contents of the solids were 10 3-7% by weight as shown below. The inks were drawn like a film using a 3-mil inch Bird applicator and allowed to dry for 10 minutes. A portion of the image was rinsed with a stream of water until no additional ink was washed. After the After drying at room temperature, the optical densities of the washed and unwashed portions were measured to determine the percent water resistance. These J - r results are summarized in Table IX. The average particle diameters and maximum particle diameters are measured using a MICROTRAC ultrafine particle analyzer from Leeds & Northrup Co, St. Petersburg, FL. The surface tensions of the inks were measured using a CSC DU NUOY tensiometer, number 70535 of CSC Scientific Co Inc, Fairfax, Va, using the P1799 / 98MX Procedures D-1331 and D-1590 of ASTM. The viscosities were measured using a cover cup number 1 and number 2 of Norcross Corporation, Newton, MA using ASTM procedure D4212.

Table IX These results show that carbon blacks treated with silicon are useful in inkjet inks, that the prints made from this ink have excellent water resistance. - Other embodiments of the present invention will be apparent to those skilled in the art.

P1799 / 98MX of the consideration of the specification and practice of the invention described herein. It is proposed that the specification of the examples be considered as examples only, with a scope and true spirit of the invention indicated by the following claims.

P1799 / 98MX

Claims (50)

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. An ink composition comprising a carbon black treated with silicon. The ink composition according to claim 1, wherein at least a portion of silicon-treated carbon black is silicon-treated carbon black having at least one bound organic group. 3. The ink composition according to claim 1, further comprising carbon black having at least one bound organic group, or blends of carbon black having at least one bonded organic group and silicon-treated carbon black having the less a united organic group. 4. The ink composition according to claim 1, further comprising untreated carbon black. The ink composition according to claim 1, wherein the silicon-treated carbon black is present in an amount of up to about 60% by weight of the composition. 6. The ink composition according to P1799 / 98KX claim 1, wherein the silicon-treated carbon black aggregates have silicon-containing regions mainly on the surface. The ink composition according to claim 1, wherein the aggregates of the silicon-treated carbon black have silicon-containing regions dispersed throughout. The ink composition according to claim 1, wherein the silicon-treated carbon black contains from about 0.1 to about 25% by weight of silicon, based on the weight of silicon-treated carbon black. The ink composition according to claim 8, wherein the silicon-treated carbon black contains from about 0.2 to about 10% by weight in silicon, based on the weight of the silicon-treated carbon black. The ink composition according to claim 9, wherein the silicon-treated carbon black contains from about 0.2 to about 5.4% by weight based on the weight of silicon-treated carbon black. 11. The ink composition according to claim 1, wherein the composition is aqueous. 12. The ink composition according to P1799 / 98MX claim 1, where the composition is not aqueous. 13. A coating composition comprising a carbon black treated with silicon. The coating composition according to claim 13, wherein at least a portion of the silicon-treated carbon black is silicon-treated carbon black having at least one bound organic group. 15. The coating composition of claim 13, further comprising carbon black having at least one bound organic group, or blends of carbon black having at least one bonded organic group and silicon-treated carbon black having the less a united organic group. 16. The coating composition of claim 13, further comprising untreated carbon black. 17. The coating composition of claim 13, wherein the silicon-treated carbon black is present in an amount of up to 60% by weight of the composition. 18. The coating composition according to claim 13, wherein the silicon-treated carbon black aggregates have silicon-containing regions mainly on the surface. 19. The coating composition according to P1799 / 98MX claim 13, wherein the aggregates of the silicon-treated carbon black have silicon-containing regions dispersed throughout. The coating composition according to claim 13, wherein the silicon-treated carbon black contains from about 0.1 to about 20% by weight of silicon, based on the weight of silicon-treated carbon black. 21. The coating composition according to claim 20, wherein the carbon black treated with silicon contains from about 0.5 to about 10% by weight of silicon, based on the weight of carbon black treated with silicon. 22. The coating composition according to claim 20, wherein the silicon-treated carbon black contains from about 0.2 to about 5.4% by weight based on the weight of the silicon-treated carbon black. 23. The coating composition according to claim 13, wherein the composition is aqueous. 24. The coating composition according to claim 13, wherein the composition is non-aqueous. 25. An aqueous inkjet ink composition comprising an aqueous vehicle and carbon black treated with silicon. P1799 / 98MX 26. A non-aqueous inkjet ink composition comprising a nonaqueous and carbon black vehicle treated with silicon. 27. A method for improving the jetting ability of an ink or coating, comprising the step of incorporating a silicon-treated carbon black into the ink or coating. The method according to claim 27, wherein the silicon-treated carbon black contains from 0.2 to 5.4% by weight of silicon, based on the weight of the silicon-treated carbon black. 29. A method for improving the blue tone of an ink or coating, comprising the step of incorporating a silicon-treated carbon black into the ink or coating. 30. The method according to claim 29, wherein the silicon-treated carbon black contains from 0.2 to 5.4% by weight of silicon, based on the weight of silicon-treated carbon black. 31. A method for improving plaque wear of an ink or coating, comprising the step of incorporating a silicon-treated carbon black into the ink or coating. 32. The method according to claim 31, wherein the carbon black treated with silicon contains P1799 / 98MX 0.2 to 25% by weight of silicon, based on the weight of carbon black treated with silicon. 33. A method for reducing the premix residue of an ink or coating, comprising the step of incorporating a silicon-treated carbon black into the ink or coating. 34. The method according to claim 33, wherein the silicon-treated carbon black contains from 0.2 to 25% by weight of silicon, based on the weight of carbon black treated with silicon. 35. A method for modifying the rheological properties of an ink or coating, comprising the step of incorporating a silicon-treated carbon black into the ink or coating. 36. The method according to claim 35, wherein the carbon black treated with silicon contains from 1 to 25% by weight of silicon, based on the weight of the carbon black treated with silicon. 37. A method for improving water resistance in an ink or coating, comprising the step of incorporating a silicon-treated carbon black into the ink or coating. 38. The method according to claim 37, wherein the carbon black treated with silicon contains from 0.2 to 25% by weight of silicon, based on the weight of P1799 / 98MX carbon black treated with silicon. 39. The ink composition according to claim 2, wherein the bound organic group is selected from an ionic group, ionizable group or mixtures thereof. 40. The ink composition according to claim 39, wherein the bound organic group is selected from sulfonic acid, or salts thereof, carboxylic acid or salts thereof, a quaternary ammonium group, SONR2, or SO-NR ( COR), wherein R is independently hydrogen, an alkyl of 1 to 20 carbon atoms substituted or unsubstituted, an alkenyl of 3 to 20 carbon atoms substituted or unsubstituted, (C2-C4 alkyleneoxy) R 'or a substituted aryl or unsubstituted, and R1 is hydrogen, an alkyl of 1 to 20 carbon atoms substituted or unsubstituted, an alkenyl of 3 to 20 carbon atoms substituted or unsubstituted, an alkanoyl of 1 to 20 carbon atoms substituted or unsubstituted or substituted or unsubstituted aroyl; and x is from. 1 to 40. 41. The ink composition according to claim 39, wherein the bound organic group is 42. The ink composition according to claim 39, wherein the bound organic group is P1799 / 98MX 43. The ink composition according to claim 39, wherein the bound organic group is selected from C6H4NC5H5 + X "or CßH4N (CH3) 3 + X", where X1 is a halide or anion derived from a mineral or organic acid. 44. The ink composition according to claim 39, wherein the bound organic group is selected from C6HSO2NH2 or CsHSOaNH (COCH3). 45. The coating composition according to claim 2, wherein the bound organic group is selected from an ionic group, an ionizable group, or mixtures thereof. 46. The coating composition according to claim 45, wherein the bound organic group is selected from sulfonic acid, or salts thereof, carboxylic acid or salts thereof, a quaternary ammonium group, S0NR2, or S02NR (COR) , wherein R is independently hydrogen, a substituted or unsubstituted alkyl of 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl of 3 to 20 carbon atoms, (C2-C4 alkyleneoxy) xR 'or a substituted or unsubstituted aryl , and R 'is hydrogen, an alkyl of 1 to 20 carbon atoms substituted or unsubstituted, an alkenyl of 3 to 20 carbon atoms substituted or unsubstituted, an alkanoyl of 1 to 20 carbon atoms P1799 / 98MX substituted or unsubstituted or substituted or unsubstituted aroyl; and x is from 1 to 40. 47. The coating composition according to claim 45, wherein the bound organic group is p- 48. The coating composition according to claim 45, wherein the bound organic group is 49. The ink coating composition according to claim 45, wherein the bound organic group is selected from CsH4NCsH5 + X "or C <sHN (CH3 ) 3 + X ", where X1 is a halide or an anion derived from a mineral or organic acid. 50. The coating composition according to claim 45, wherein the bound organic group is selected from C6H4S02NH2 or CsH4S02NH (COCH3). 52. A dye comprising a carbon black treated with silicon. P1799 / 98MX