KR100463353B1 - Modified Carbon Products for Inks and Coatings - Google Patents

Abstract

The present invention relates to a modified carbon product comprising carbon to which at least one organic group is bonded. Organic groups include (a) at least one aromatic group or a C ₁ -C ₁₂ alkyl group and (b) at least one ionic group, at least one ionizable group, or a mixture of ionic groups and ionizable groups. The aromatic group or C ₁ -C ₁₂ alkyl group of the organic group is directly bonded to carbon, and the organic group has a concentration of about 0.10 to about 2.7 micromoles / m ² or modified carbon product based on the CT- or t-region of carbon. It is present in an amount having a residue value over 5% by weight. In addition, the present invention discloses an aqueous or non-aqueous coating or ink composition comprising a modified carbon product. Also disclosed is a method of increasing the flow of ink, as measured by glass plate flow, by mixing the modified carbon product as part of the ink. Finally, non-aqueous inks and coating formulations consisting of carbon in which a suitable solvent and at least one organic group are bound are described, wherein the organic groups are (a) at least one aromatic group or a C ₁ -C ₁₂ alkyl group and (b) One or more ionic groups, one or more ionizable groups, or a mixture of ionic groups and ionizable groups, and organic groups may be present in any amount).

Description

Modified Carbon Products for Inks and Coatings

The present invention relates to modified carbon products and to inks and coatings containing them.

Currently, excellent black pigments are carbon blacks, for example furnace blacks, which can be used as colorants in the form of flushed pastes or liquid concentrates in the form of dry powders. In general, the form of the colorant affects color tone, durability, bulk, transparency, gloss, rheology, end use, and print quality.

Various types of inks are currently used. Such fields include printing inks, ultraviolet curing inks, ballpoint pen inks and stamp pads or marking inks. In general, the ink can be applied by typography, lithography, flexo printing, gravure printing, silk screens, stencils, copiers, and static electricity. These inks can be used in newspapers, publications, commercial folding cardboard, books, cardboard boxes, paper bags, book covers, labels, metal containers, plastic containers, plastic films, foil stacks, food inserts, antibacterial paper, textiles, etc. It can be found in the application. McGraw-Hill's Encyclopedia of Science and Technology, Vol. 7, pgs, 159-164 further describes the types of inks available and their uses, which are incorporated herein by reference.

Coatings may contain pigments, which are used for decorative, protective, and functional treatment of various kinds of surfaces. These surfaces include the surfaces of coils, metals, appliances, furniture, hardboards, boards and plywood, ships, repair materials, automobiles, cans, and paperboards. Some coatings, such as coatings on subsea pipelines, are used for protection purposes. Others such as automotive exterior coatings fulfill decorative and protective actions. Others provide friction control on boat decks or car seats. Some coatings control contamination of vessel bottoms, while others protect cans of food and beverages. Silicon chips, printed board panels, coatings on waveguide fibers for signal transmission, magnetic coatings on video tapes, and computer disks are many high-tech applications of coatings.

Types of aqueous vehicles for aqueous inks and coatings include those in which the binder is water soluble, those dispersed like colloids, and those that are emulsified to form latex. The combination of binder and volatile liquid is called a vehicle, which may be a solution or dispersion of fine binder particles in the nonsolvent. Pigments are finely divided insoluble solid particles dispersed in a coating vehicle and completely distributed in a binder in the final film. Surfactants can be used as pigment dispersions. Components and preparation methods of aqueous coatings are described in Concised Encyclopedia of Polymers, Science and Engineering, pgs. 160-171 (1990), which is incorporated herein by reference.

Non-aqueous inks and coatings are used in a variety of applications where aqueous vehicles are not suitable. For example, the ink printed on a hydrophobic, nonporous substrate (eg metal, glass or plastic) should be quick-drying. Thus, solvents such as ketones, esters, alcohols, or hydrocarbons are often used in place of water. Such solvent-based inks are widely used for industrial labeling of cardboard boxes and various metal or plastic reservoirs and components. Specific examples thereof include newspaper ink compositions and web offset glossy thermoset ink compositions.

In addition, the inks and coatings need to be water resistant in certain cases. In this example, the water resistant resin may be dissolved in the nonaqueous solvent of the ink and coating formulation to provide the desired water resistance upon drying. The main use of such non-aqueous coatings is the coating of metal and plastic automotive parts.

Summary of the Invention

The present invention relates to a modified carbon product comprising carbon to which at least one organic group is bonded. Organic groups include (a) one or more aromatic groups or C ₁ -C ₁₂ alkyl groups and (b) one or more ionic groups, one or more ionizable groups, or a mixture of ionic and ionizable groups. As defined herein, an aromatic group or C ₁ -C ₁₂ alkyl group is bonded directly to carbon, and the organic group is at a concentration of about 0.10 to about 2.7 micromoles / m ² or an amount such that the modified carbon product is not readily dispersed in water. Which is defined herein.

The invention also relates to an aqueous or non-aqueous coating or ink composition comprising the modified carbon product described above.

The present invention further relates to a non-aqueous coating or ink composition comprising a modified carbon product and a non-aqueous solvent. The modified carbon product comprises carbon to which one or more organic groups are bonded, wherein the organic groups comprise (a) one or more aromatic groups or C ₁ -C ₁₂ alkyl groups and (b) one or more ionic groups, one or more ionizable groups, Or mixtures of ionic groups and groups that can be ionized. The aromatic group or C ₁ -C ₁₂ alkyl group is bonded directly to carbon and there is no limit to the amount of organic groups that may be present.

Carbon as used herein may be in crystalline or amorphous form. Examples include, but are not limited to, graphite, carbon black, carbon fiber, glassy carbon, and activated carbon or activated carbon. Finely divided forms of these are preferred, and it is also possible to use mixtures of different carbons.

Description of the Preferred Embodiments

Modified carbon products of the present invention include carbons having one or more organic groups bonded thereto. This organic group comprises a) one or more aromatic groups or C ₁ -C ₁₂ alkyl groups and b) one or more ionic groups, one or more ionizable groups, or a mixture of ionic groups and ionizable groups. The aromatic group or C ₁ -C ₁₂ alkyl group of the organic group is directly bonded to carbon. Organic groups are also present in concentrations of about 0.10 to about 2.7 micromoles / m ² or in amounts in which the modified carbon product is not readily dispersed in water as defined herein.

Carbon may be in crystalline or amorphous form. Examples include, but are not limited to, graphite, carbon black, glassy carbon, activated carbon, carbon fiber, activated carbon, and mixtures thereof. Finely divided forms of these are preferred, and it is also possible to use mixtures of different carbons.

The modified carbon product may preferably be prepared by reacting carbon with a diazonium salt in a liquid reaction medium to bond one or more organic groups to the carbon surface. Diazonium salts may contain organic groups bonded to carbon. Diazonium salts are organic compounds having one or more diazonium groups. Preferred reaction media include water, any medium containing water, and any medium containing alcohol. Water is the most preferred medium. Examples of modified carbon products where the carbon is carbon black and various preferred methods of making them are described in US patent application Ser. No. 08 / 356,660 (title “Reaction of Carbon Black with Diazonium Salts, Resultant Carbon Black Products and Their Uses”, December 1994 15). One application) and its continuing application, US patent application Ser. No. 08 / 572,525, filed December 14, 1995, both of which are incorporated herein by reference. Examples of modified carbon products where the carbon is not carbon black and various preferred methods for their preparation are described in US Pat. No. 5,554,739 (title "Reaction of Carbon Materials With Diazonium Salts and Resultant Carbon Products"), WO 96/18696 and WO 96/18688. And all of which are incorporated herein by reference.

In the preferred preparation of the above modified carbon product, the diazonium salt only needs to be stable enough to allow reaction with carbon. Therefore, it is believed that this reaction can be carried out with some diazonium salts, otherwise it will be unstable and degrade. Some decomposition processes can compete with the reaction between carbon and diazonium salts and reduce the total number of organic groups bound to carbon. In addition, this reaction can be carried out at elevated temperatures, where many diazonium salts can be affected by decomposition. In addition, elevated temperatures can advantageously increase the solubility of the diazonium salt in the reaction medium and improve handleability during the reaction. However, elevated temperatures may cause some loss of diazonium salts due to other decomposition reactions. This diazonium salt can be prepared during the reaction. The modified carbon product of the present invention preferably does not include by-products or unbound salts.

In a preferred method of preparation, the carbon black can be reacted with the diazonium salt as a dilute, easily stirred aqueous slurry, or with the diazonium salt in the presence of an appropriate amount of water for carbon black pellet formation. If desired, carbon black pellets can be formed using conventional pelletization techniques. Other carbons can be reacted with diazonium salts in a similar manner. In addition, when the modified carbon product is used, for example, in non-aqueous inks and coatings, using carbon other than carbon black, preferably, the carbon is ground to a fine particle size before reacting with the diazonium salt in the preferred method so that the ink And undesired precipitation of the modified carbon product in the coating. In addition, when a modified carbon product is used in an ink jet ink using carbon other than carbon black, preferably, the carbon is ground to a fine particle size before reacting with the diazonium salt in a preferred method to cause undesirable precipitation in the ink. Should be prevented. Additional means for stabilizing particles may be needed in ink jet inks when using small amounts of organic groups on carbon. One such method includes the use of polymer dispersants.

In one embodiment of the invention the amount of organic groups bonded to carbon is important for future use of the modified carbon product in applications such as in coating formulations and ink systems. In particular, the amount should be small. In other words, the amount of organic groups can be from about 0.10 to about 2.7 micromoles, preferably from about 0.4 to about 2.5 micromoles per m ² of carbon used based on the CTAB or the t-region of carbon. Another method of characterizing a small amount of organic groups bonded to carbon to form a modified carbon product is to measure the residue of the modified carbon product. In particular, this residue value is obtained by first adding modified carbon to an aqueous solution, such as water, and then passing the aqueous solution containing the modified carbon through a screen having 325 mesh, followed by washing with water until the filtrate becomes colorless. Measure The pH of the water can be adjusted to increase the ionization of the groups on the carbon. Weigh the modified carbon that does not pass through the screen. The weight percentage of the amount not passed through the screen is the residue value. For the purposes of the present invention, modified carbon having a residue value of about 5% by weight or more may not be considered "dispersible in water".

It is generally believed that the greater the amount of organic groups bonded to carbon, the better the properties. However, in certain cases, even a small amount of organic groups bonded to carbon exhibits better properties. Such superior properties have been found by using the modified carbon products of the present invention in nonaqueous applications such as, for example, nonaqueous ink systems including nonaqueous glossy ink systems and nonaqueous coating formulations. When the modified carbon product of the present invention is used in such systems and formulations, improved spraying, pale blue shade and gloss have been obtained, and in certain cases the rheology of the ink as measured by Laray viscosity , Flowmeter values and vertical glass flow characteristics were modified. In some ink formulations, the fluidity is significantly increased over that of the untreated carbon compound.

As mentioned above, the organic group includes an aromatic group or a C ₁ -C ₁₂ alkyl group. Aromatic groups include, but are not limited to, unsaturated cyclic hydrocarbons containing one or more rings. The aromatic group may be substituted or unsubstituted. Aromatic groups include aryl groups (eg, phenyl, naphthyl, anthracenyl, etc.) and heteroaryl groups (imidazolyl, pyrazolyl, pyridinyl, thienyl, thiazolyl, furyl, triazinyl, indolyl, etc.) do. C ₁ -C ₁₂ alkyl groups may be branched or unbranched, preferably ethyl.

Groups that can be ionized are those capable of forming ionic groups in the use medium. The ionic group may be an anionic group or a cationic group, and the group that may be ionized may form an anion or a cation.

Ionic functional groups that form anions include, for example, acidic groups or salts of acidic groups. Thus, the organic group may comprise a group derived from an organic acid. Preferably, when the organic group contains an ionizable group which forms an anion, the organic group is at least one acidic group having (a) an aromatic group or a C ₁ -C ₁₂ alkyl group and (b) a pKa of less than 11 or less than 11 Salts of at least one acidic group having a pKa, or a mixture of at least one acidic group having a pKa of less than 11 and at least one acidic group having a pKa of less than 11. The pKa of an acidic group means pKa of the whole organic group not only an acidic substituent. More preferably, pKa is less than 10, most preferably less than 9. Aromatic groups can be further substituted or unsubstituted, for example, with alkyl groups. More preferably, the organic group is a phenyl or naphthyl group, and the acidic group is a sulfonic acid group, a sulfinic acid group, a phosphonic acid group or a carboxylic acid group. Examples are -COOH, -SO ₃ H and -PO ₃ H ₂ , -SO ₂ NHCOR and their salts, for example -COONa, -COOK, -COO ^- NR ₄ ⁺ , -SO ₃ Na, -HPO ₃ Na, -SO ₃ ^- NR ₄ ^+, and PO ₃ Na ₂ includes an (where, R is being saturated or unsaturated alkyl or phenyl group). Particularly preferred ionic substituents are -COOH and -SO ₃ H and their sodium and potassium salts.

Therefore, it is preferred to treat carbon with aryl diazonium salts containing at least one acidic functional group. Examples of aryl diazonium salts include, but are not limited to, sulfanic acid, 4-aminobenzoic acid, 4-amino salicylic acid, 7-amino-4-hydroxy-2-naphthalenesulfonic acid, aminophenylboronic acid, aminophenylphosphonic acid, and menylic acid. It is not limited.

The organic group may 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 salt thereof; It may be a substituted or unsubstituted (polysulfo) naphthyl group or a salt thereof. One example of a sulfophenyl group is a hydroxysulfophenyl group or a salt thereof.

Particular organic groups having ionic functional groups that form anions are p-sulfophenyl and 4-hydroxy-3-sulfophenyl.

Amines represent examples of ionic functional groups that form cationic groups, and may be bound to the same organic groups as described above for ionizable groups that form anions. For example, amines can be protonated in acidic media to form ammonium groups. Preferably, the organic group having an amine substituent has a pKb of less than 5. In addition, quaternary ammonium groups (-NR ₃ ⁺⁾ and quaternary phosphonium nyumgi (-PR ₃ ⁺⁾ represents an example of a cationic group, the same organic groups as described above for groups that can be ionized to form an anionic Can be combined. Preferably, the organic group contains an aromatic group such as a phenyl or naphthyl group and a quaternary ammonium or quaternary phosphonium group. In addition, quaternary cyclic amines and quaternary aromatic amines can be used as the organic group. Therefore, N-substituted pyridinium compounds such as N-methyl-pyridyl can be used in this respect. Examples of the organic group is _{3-C 5 H 4 N (} C 2 H 5) + X -, C 6 H 4 NC 5 H 5 + X -, C 6 H 4 COCH 2 N (CH 3) 3 + X -, _{C 6 H 4 COCH 2 (NC} 5 H 5) + X -, 3-C 5 H 4 N (CH 3) + X -, C 6 H 4 N (CH 3) 3 + X - and C ₆ H ₄ CH ₂ N (CH ₃ ) ₃ ⁺ X ⁻ , wherein X ⁻ is a halide or an anion derived from an inorganic or organic acid.

Additional optional functional groups that may be present on the organic group are R, OR, COR, COOR, OCOR, halogen, CN, NR ₂ , SO ₂ NR (COR), SO ₂ NR ₂ , CR (COR), CONR ₂ , NO ₂ , SO ₃ M, SO ₃ NR ₄ and N = NR ′. R is independently hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl (branched or unbranched), C ₃ -C ₂₀ substituted or unsubstituted alkenyl, (C ₂ -C ₄ alkyleneoxy) _X R '' Or substituted or unsubstituted aryl. R 'is independently hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl (branched or unbranched) or substituted or unsubstituted aryl. R '' is hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, C ₁ -C ₂₀ substituted or unsubstituted alkanoyl or substituted or unsubstituted aro It is work. M is H, Li, Na, Cs, or K. The integer x is 1-40 and preferably 2-25.

Another example of an organic group is an aromatic group of formula A _y Ar-, which corresponds to the primary amine of formula A _y ArNH ₂ . In this formula, the variables have the following meanings: Ar is an aromatic radical selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, pyridinyl and triazinyl, and A is the functional group described above Is a substituent on an aromatic radical independently selected from or A is a straight, branched or cyclic hydrocarbon radical (preferably containing from 1 to 20 carbon atoms) substituted or unsubstituted with one or more such functional groups, and y is When Ar is phenyl, it is an integer from 1 to 5, when Ar is naphthyl, it is an integer from 1 to 7, when Ar is anthracenyl, phenanthrenyl or biphenyl, it is an integer from 1 to 9, and Ar is a pyri Dinyne, an integer from 1 to 4, or when Ar is triazinyl, an integer of 1 or 2. When A is a (C ₂ -C ₄ alkyleneoxy) xR '' group, it is preferably a polyethoxylate group, a polypropoxylate group or a random or block mixture of the two.

Other examples of modified carbon products include carbon and bonded organic groups having a) aromatic groups or C ₁ -C ₁₂ alkyl groups and b) at least one group of the formula SO ₂ NR ₂ or SO ₂ NR (COR). R is independently hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, (C ₂ -C ₄ alkyleneoxy) _X R ′ or substituted or unsubstituted Aryl. R 'is hydrogen, C ₁ -C ₂₀ substituted or unsubstituted alkyl, C ₃ -C ₂₀ substituted or unsubstituted alkenyl, C ₁ -C ₂₀ substituted or unsubstituted alkanoyl, substituted or unsubstituted aroyl And x is 1 to 40. The aromatic groups are pC ₆ H ₄ SO ₂ NH ₂ , pC ₆ H ₄ SO ₂ NHC ₆ H ₁₃ , pC ₆ H ₄ SO ₂ NHCOCH ₃ , pC ₆ H ₄ SO ₂ NHCOC ₅ H ₁₁ and pC ₆ H ₄ SO ₂ NHCOC ₆ H ₅ .

As described above, the modified carbon product is useful in non-aqueous ink formulations. Accordingly, the present invention relates to a suitable solvent and a) substituted or unsubstituted aromatic or C ₁ -C ₁₂ alkyl groups and b) one or more ionic groups, one or more ionizable groups, or ionic groups and ionizable groups Provided is an improved ink composition containing a modified carbon product having a bound organic group comprising a mixture. Other known ink additives may be mixed in the ink formulation. It is also within the scope of the present invention to use ink formulations containing mixtures of unmodified carbon and modified carbon products.

Generally, the ink contains colorants or pigments and solvents to control the viscosity or dryness. The ink may optionally further include a vehicle or varnish and / or additives that act as a carrier during printing to improve printability, dryness, and the like. A general discussion of the nature, preparation and use of inks can be found in The Printing Manual, 5th Ed., R. H. Leach, et al., Eds. (Chapman & Hall, 1993).

The modified carbon product of the present invention can be mixed into the ink formulation as a predispersion or solid using standard techniques. The use of the modified carbon product of the present invention can reduce the viscosity of the formulation to provide significant benefits and cost savings. It may also allow for greater loading of carbon compounds in the formulation. In addition, the grinding time can also be reduced. In addition, the modified carbon products of the present invention can provide improved spraying, blue shade and gloss.

The modified carbon product may also be used in non-aqueous coating compositions such as paints or finishes. Accordingly, embodiments of the present invention are coating compositions containing suitable solvents and modified carbon products of the present invention. Other conventional coating additives may be mixed in non-aqueous coating compositions such as binders.

Non-aqueous coating formulations vary widely depending on the conditions and needs of the end use. Generally, the coating system contains up to 30% by weight of carbon. The resin content varies widely, up to almost 100% or less. Examples include acrylics, alkyds, urethanes, epoxies, celluloses and the like. The solvent content can vary from 0 to 80%. Examples include aromatic hydrocarbons, aliphatic hydrocarbons, alcohols, polyalcohols, ketones, esters and the like. Two other common additives are fillers and modifiers. Examples of fillers are other colored pigments (eg TiO ₂ , phthalo blue, etc.), clays, talc, silica and carbonates. Fillers may be added up to 60% depending on the end use needs. Examples of modifiers are flow and leveling agents and fungicides which are generally applied at less than 5%. The modified carbon product of the present invention can be mixed into the non-aqueous coating composition as a predispersion or a solid using standard techniques.

Examples of non-aqueous media for mixing compositions containing modified carbon products of the present invention include, but are not limited to, melamine-acrylic resins, melamine-alkyd resins, urethane-hard alkyd resins, urethane-hard acrylic resins, and the like. Do not. In addition, the modified carbon products of the present invention can also be used in aqueous emulsion paints. In this type of paint, there is a non-aqueous portion containing the pigment, which is dispersed in the aqueous paint. Thus, the modified carbon product of the present invention can be used as part of the non-aqueous portion dispersed in the aqueous emulsion paint.

Modified carbon products of the present invention are also useful in aqueous inks and coating formulations. Aqueous includes a mixture of water and other water miscible or water dispersible materials, such as alcohols. Accordingly, the present invention provides an aqueous ink composition comprising water and a modified carbon product according to the present invention. Other known aqueous ink additives may be mixed into the aqueous ink formulation. As described above, the ink may consist of the various components described above. In addition, various aqueous ink compositions are described, for example, in US Pat. Nos. 2,833,736, all of which are incorporated herein by reference; 3,607,813; US Pat. 4,104,833; 4,104,833; 4,308,061; 4,308,061; 4,770,706 and 5,026,755, all of which are incorporated herein by reference.

The modified carbon product of the present invention can be mixed into the aqueous ink formulation as a predispersion or as a solid using standard techniques.

Flexo printing inks represent a group of aqueous ink compositions. Flexographic printing inks generally comprise a colorant, a binder and a solvent. The modified carbon product of the present invention may be useful as a flexographic printing ink colorant. The modified carbon product of the present invention can be used in aqueous newspaper inks. For example, the aqueous newspaper ink composition may comprise water, modified carbon products of the invention, resins and conventional additives such as antifoam additives or surfactants.

In addition, the modified carbon products of the present invention can be used in aqueous coating compositions such as paints or finishes. Accordingly, embodiments of the present invention relate to improved aqueous coating compositions comprising water, resins and modified carbon products according to the present invention. Other known aqueous coating additives may be mixed into the aqueous coating composition [eg, McGraw-Hill Encyclopedia of Science & Technology, 5th edition (McGraw-Hill, 1982) and US Pat. No. 5,051,464, 5,319,044. 5,204,404, 5,051,464, 4,692,481, 5,356,973, 5,314,945, 5,266,406 and 5,266,361, all of which are incorporated herein by reference. Included). In addition, the aqueous compositions of the present invention may also comprise further other colored pigments (eg, TiO ₂ and phthalo blue, etc.), clays, talc, silica and carbonates. The modified carbon product of the present invention can be mixed into the aqueous coating composition as a predispersion or as a solid using standard techniques.

Inks or coatings can be used for a variety of purposes. Preferably, in the aqueous inks and coatings of the present invention, the modified carbon product is present in an amount of up to 20% by weight of the ink or coating. It is also within the scope of the present invention to use aqueous or non-aqueous inks or coating formulations containing a mixture of modified carbon products and unmodified carbon of the present invention. Conventional additives as discussed below may be added to the dispersion to further improve the properties of the aqueous ink or coating.

The modified carbon product of the present invention may also be used in ink jet inks, in which the ink formulations can be based on solvents, water, or aqueous emulsions.

Finally, the present invention also relates to other non-aqueous inks and coating formulations. In these formulations, a suitable solvent is present with the modified carbon product of the present invention. For these formulations, the modified carbon product comprises carbon in which one or more organic groups are bonded, wherein the organic groups are a) one or more aromatic groups or C ₁ -C ₁₂ alkyl groups, and b) one or more ionic groups, one or more ionizable Groups, or mixtures of ionic groups and groups that can be ionized. Aromatic groups are bonded directly to carbon, and the amount of organic groups present on carbon is not limited. The various additional components described above in relation to the non-aqueous inks and coating formulations here apply equally here, as well as the amounts of the various components except for the amount of organic groups on carbon without upper or lower limits apply here. The above discussion and examples of organic groups apply equally here.

The following examples are intended to illustrate the claimed invention and not to limit it.

BET nitrogen surface area was obtained using ASTM D-4820. CTAB area values were obtained using ASTM D-2414. Optical properties of the ink and coating films were measured using the following instruments: L ^* a ^* b ^* values were measured using Hunter Lab Scan 6000 on a 10 degree D65 CIELAB color space instrument; Optical density was measured using a MacBeth RD918 density meter; Gloss was measured using a BYK Gardner Model 4527 glossmeter.

Nitrogen and external surface area (t-area) were measured according to the sample preparation and measurement procedure described in ASTM D-3037. For this measurement, the nitrogen adsorption isotherm was extended to 0.55 relative pressure. The relative pressure is a value obtained by dividing the pressure P by the saturation pressure (Po, the pressure at which nitrogen is condensed). Adsorption layer thickness (t, Å) was calculated using the following formula:

t = 0.88 (P / Po) ² + 6.45 (P / Po) + 2.98

The volume of adsorbed nitrogen (v) was then plotted against t ₁ and then straightened through data points for t values between 3.9 and 6.2 kPa. The t-area was then determined from the slope of the straight line as follows:

t-area (㎡ / g) = 15.47 × slope

The sulfur content on the carbon black product was measured by burning the Soxhlet of each sample followed by combustion analysis. Bound sulfur (mmol) was determined by the difference from the analysis of untreated carbon black.

<Example 1>

Preparation of Carbon Black Product with Diazonium Produced During Reaction

Sulfanic acid (3.0 g) was added to 900 mL deionized water and the mixture was heated to 70-90 ° C. To this solution was added carbon black (100 g) having a CTAB surface area of 350 m 2 / g, a t-area of 366 m 2 / g and a DBPA of 120 ml / 100 g. The mixture was stirred well to wet all the carbon blacks. A solution of 1.2 g sodium nitrite in 1.0 mL deionized water was added to the carbon black slurry. Within seconds, the gas was released. The mixture was heated to suspend and the mixture was cooled to ambient temperature with continued stirring. The product was isolated by evaporating the solution to 70-100 ° C. in an oven. The product had a bound pC ₆ H ₄ -SO ₃ Na group.

Alternatively, the slurry may be filtered in a Buchner funnel and the solids washed with deionized water to isolate the product.

<Example 2>

Preparation of Carbon Black Products Having Different Amounts of Bonding Groups

Using the amounts of reagents listed in the table below, the procedure of Example 1 was repeated using carbon black having a CTAB surface area of 350 m 2 / g, a t-area of 366 m 2 / g and a DBPA of 120 ml / 100 g. :

Example Sulfanic acid (g) g NaNO ₂ / g H ₂ O Carbon black (g) 2a 7.0 2.8 / 3 100 2b 15.0 6.0 / 6 100

<Example 3>

Preparation of Carbon Black Products Using Pin Pelletizers

An 8 inch diameter pin pelletizer was charged with 300 g of carbon black and 15 g of sulfanic acid having a CTAB surface area of 350 m 2 / g, a t-area of 366 m 2 / g and a DBPA of 120 ml / 100 g. The pelletizer was operated at 150 rpm for 1 minute. A solution of deionized water (280 mL) and sodium nitrite (5.98 g) was added and the pelletizer was run at 250 rpm for 2 minutes. The pelletizer was stopped, the shaft and pins discarded, and the pelletizer was run for an additional 3 minutes at 650 rpm. 4-sulfobenzenediazonium hydroxide salt was formed during the reaction and reacted with carbon black. The product was discharged from the pelletizer and dried in the oven to 70-100 ° C. in the oven. The product had a bound pC ₆ H ₄ -SO ₃ Na group. Analysis of Soxhlet extract samples for sulfur content indicates that the product has 0.15 mequiv./g of bound sulfonate groups, or 0.43 micromol / m 2 of bound sulfonate groups.

<Example 4>

Preparation of Carbon Black Product

A solution of the diazonium salt of 4-aminosalicylic acid was prepared as follows. 57.4 g of 4-aminosalicylic acid was added to 550 mL of deionized water. The mixture was cooled in an ice bath and 93.75 mL concentrated hydrochloric acid was added. To this cold mixture was added a solution of 25.9 g of sodium nitrite in 50 mL of deionized water. The mixture became dark in color and some gas was released. This solution was calculated to contain 0.038 g of diazonium of 4-aminosalicylic acid per gram of solution.

233.2 g of 4-aminosalicylic acid diazonium solution was added to a well stirred slurry of carbon black (200 g) having a CTAB surface area of 350 m 2 / g and 120 ml / 100 g of DBPA in 1.8 L of deionized water cooled in an ice bath. The gas was released. Stirring was continued until no further gas evolution was observed. The slurry was vacuum filtered and washed with deionized water. The wet cake was dried at 75 ° C. in an oven. The product had a bound pC ₆ H _3- (2-OH) -COOH group.

Example 5

Preparation of Carbon Black Product

4-aminosalicylic acid diazonium as prepared in Example 4 in a well stirred slurry of carbon black (200 g) having a CTAB surface area of 350 m 2 / g and a DBPA of 120 ml / 100 g in 1.8 L of deionized water cooled in an ice bath. 1168 g of solution was added. The gas was released. Stirring was continued until no further gas evolution was observed. The slurry was vacuum filtered and washed with deionized water. The wet cake was dried at 75 ° C. in an oven. The product had a bound pC ₆ H _3- (2-OH) -COOH group.

<Example 6>

Preparation of Carbon Black Product

A solution of the diazonium salt of 4-aminobenzoic acid was prepared as follows. 89.1 g of 4-aminobenzoic acid was added to 925 mL of deionized water. The mixture was cooled in an ice bath and 162.5 ml of concentrated hydrochloric acid was added. Acetone (50 mL) was added to completely dissolve 4-aminobenzoic acid. To this cold mixture was added a solution of 44.9 g of sodium nitrite in 100 mL of deionized water. The color of the mixture darkened and some gas was released. This solution was calculated to contain 0.061 g of diazonium of 4-aminobenzoic acid per gram of solution.

131 g of 4-aminobenzoic acid diazonium solution was added to a well stirred slurry of carbon black (200 g) having 350 m 2 / g CTAB surface area and 120 ml / 100 g DBPA in 1.8 L of deionized water cooled in an ice bath. . The gas was released. Stirring was continued until no further gas evolution was observed. The slurry was vacuum filtered and washed with deionized water. The wet cake was dried at 75 ° C. in an oven. The product had a bound pC ₆ H ₄ -COOH group. The product had 90% 325 mesh residue.

<Example 7>

Preparation of Carbon Black Products Having Different Amounts of Bonding Groups

Using the diazonium solution prepared in Example 6, carbon blacks with CTAB surface area of 350 m 2 / g and DBPA of 120 ml / 100 g were functionalized with various amounts of phenyl carboxylate groups. The amount used is shown in the table below. The procedure used was similar to Example 6.

Example Amount of diazonium solution Amount of carbon black 325 mesh residue 7a 263 g 200 g 63.7% 7b 394 g 200 g 3.9% 7c 656 g 200 g 4.0%

<Example 8>

Preparation of Carbon Black Product in Pin Pelletizers

This procedure was performed similarly to Example 3 using 300 g of carbon black and 24 g of 4-aminobenzoic acid having a CTAB surface area of 350 m 2 / g and a DBPA of 120 ml / 100 g. The pelletizer was operated at 500 rpm for 1 minute. A solution of deionized water (300 mL) and sodium nitrite (12.1 g) was added and the pelletizer was operated at 1100 rpm for 2-3 minutes. The product was withdrawn from the pelletizer and dried at 70-100 ° C. in an oven. The product had a bound pC ₆ H ₄ -COONa group.

Example 9

Preparation of Carbon Black Product

This example is another method for preparing a product similar to the product of Example 6. The product of Example 8 (150 g) was slurried in 500 mL of deionized water. 21.9 mL of concentrated hydrochloric acid was added to this slurry. After stirring for 30 minutes, the slurry was filtered, washed with deionized water and the wet cake was dried at 75 ° C. The product had a bound pC ₆ H ₄ -COOH group.

<Example 10>

Preparation of Carbon Black Product

This process is similar to Example 1 except using carbon oxide black having a nitrogen surface area of 560 m 2 / g, DBPA of 90 ml / 100 g and a volatile content of 9.5%. The amount of reagent used for each treatment level is shown in the table below. Carbon black was a 10% slurry in deionized water.

Example Sulfanic acid (g) g NaNO ₂ / g H ₂ O Carbon black (g) Combined S (mmol) / g Products 10a 6.0 2.4 / 3 200 0.162 10b 10.0 4.0 / 5 200 0.237 10c 20.0 8.0 / 8 200 0.496 10d 30.0 12.0 / 12 200 0.670 10e 50.0 19.9 / 20 200 1.00

<Example 11>

Preparation of Carbon Black Product

Carbon black with t-area of 93 m 2 / g and DBPA of 55 ml / 100 g was used and the procedure of Example 3 was used. The amount of reagent used is shown in the table below.

Carbon Source (Example Number) Carbon black (g) Sulfanic acid (g) NaNO ₂ (g) Deionized water (ml) Combined S (mmol) / g Products Combined S (μmol) / ㎡ Products 11a 400 0 0 215 0 0 11b 400 4 1.6 215 0.041 0.44 11c 400 8 3.2 215 0.084 0.90 11d 400 20 8.0 215 0.193 2.08

These products had a bound pC ₆ H ₄ -SO ₃ Na group. Each sample was Soxhlet extracted (ethanol) and the sulfur content was analyzed. The results are shown in the table with the corresponding bond amounts / m 2.

The pellets produced in this process were ground on a 20.3 cm (8 inch) jet mill (Sturtevant, Boston, Mass.) To convert the pellets into a "fluffy" type product. This process is described in Perry's Chemical Engineers' Handbook , 6th edition, published by RH Perry and D. Green, pp. 8-46. These polished materials were used in Example 18.

<Example 12>

Preparation of Carbon Black Product

This process describes the preparation of carbon black products under continuous operating conditions. 25 parts / hour of sulfanilic acid and 10 parts / hour of sodium nitrite as an aqueous solution in a pin mixer operating continuously at a speed of 100 parts / hour with carbon black having a CTAB surface area of 350 m 2 / g and 120 mL / 100 g of DBPA; Filled together. The resulting material was dried to yield a carbon black product having bound pC ₆ H ₄ SO ₃ Na groups. Analysis of Soxhlet extracted (ethanol) samples for sulfur content indicates that the product has 0.95 mequiv./g of bound sulfonate groups, or 2.7 micromol / m 2 of bound sulfonate groups.

Example 13

Use of Carbon Black Products in Coating Compositions

This example illustrates the use of carbon black products in thermosetting acrylic compositions. The standard material was carbon black with a CTAB surface area of 350 m ² / g and DBPA of 120 ml / 100 g without any additional treatment. The materials evaluated here were prepared in Examples 1, 2a, 2b and 12.

The coating composition was prepared as follows. 2.1 kg ¼ "steel balls, 3.3 kg ½" steel balls, 282 g grinding masterbatch [64 parts of ACRYLOID AT400 resin, 30 minutes n-butanol] in a 0.5 gallon (1.893 L) steel ball mill , 6 parts of methyl-n-amyl ketone] and 30 g of carbon black were charged. The wheat ego was spun at 44 rpm on an ego roll mill (Paul O. Abbe model 96806 or equivalent) operating at 82 rpm for the designated time. Each mill comprising 249 g of AT-400 resin was first reduced and spun on an ego mill for 1 hour to prepare the finished coating composition. The second reduction was 33 parts of AT-400 resin, 35.3 parts of CYMEL 303 melamine-formaldehyde resin, 7.2 parts of methyl-n-methyl ketone, 2-ethoxyethyl acetate [Cellosolve Acetate-Union Carbide ( Union Carhide) 8.5 parts, CYCAT 4040 (acid catalyst of toluenesulfonic acid and isopropanol), 1.8 parts of a mixture of 0.3 parts of fluoride FC431 additive and 14 parts of n-butanol were added and ground for 1 hour. Was performed.

Acryloid is a registered trademark of resin marketed by Rohm and Haas, Philadelphia, Pennsylvania, USA. Simel and Seacat are registered trademarks of product marketed by Cytec Industries, West Paterson, NJ. Fluorad, is a registered trademark of Additives, commercially available from 3M, St. Paul, Minn., USA.

Optical properties were measured on a 3 mil film in a sealed Reneta chart which was air dried for 30 minutes and then baked at 250 ° C. for 30 minutes. Hunter colorimeters were used to measure L *, a * and b * values. Optical density was measured with a MacBeth RD918 density meter. Gloss was measured with a BYK Gardner Model 4527 glossmeter. Viscosity was measured in units of Krebs on a Brookfield KU-1 viscometer.

Thermosetting acrylic formulations were prepared by grinding in a ball mill for 27 hours according to the general method described. A 3 mil thick stretch was prepared and the optical properties evaluated. The results are summarized in the table below.

Carbon Source (Example Number) Optical density L ^* a ^* b ^* Gloss (60 °) Viscosity Standard material 2.76 1.55 0.02 0.02 89.9 107 One 2.81 1.29 -0.05 -0.12 92.0 105 2a 2.75 1.44 0.03 -0.06 90.0 98 2b 2.71 1.46 -0.06 0.15 87.5 91 12 2.77 1.40 0.02 0.12 81.3 82

As the treatment level increased, the viscosity of the composition decreased. All optical properties peaked at lower levels, and coatings made using the carbon black product from Example 1 treated with 3 wt% sulfanilic acid diazonium salt had higher optical density than all other materials, and Sprayed, darker blue, and more glossy. These samples were weight corrected with an equivalent amount of carbon black in each formulation for treatment.

<Example 14>

Carbon black product treated with various levels of salicylic acid used in thermoset acrylic formulations

The carbon black products prepared in Examples 4 and 5 were milled for 18 and 42 hours and then evaluated in the thermosetting acrylic composition according to the general method of Example 13. The results are summarized in the table below. In this example, the same amount of carbon black product was used for each formulation. The standard material was carbon black with a CTAB surface area of 350 m ² / g and DBPA of 120 ml / 100 g without any additional treatment.

Carbon Source (Example Number) Crushing time (hours) Optical density L ^* a ^* b ^* Gloss (60 °) Viscosity Standard material 18 2.82 1.35 -0.15 0.03 93.0 93 Standard material 42 2.82 1.24 -0.07 -0.27 91.2 101 4 18 2.87 1.16 -0.14 -0.16 93.7 97 4 42 2.94 1.02 -0.04 -0.41 92.8 103 5 18 2.85 1.25 -0.16 -0.18 92.2 94 5 42 2.86 1.10 0.03 -0.36 92.5 98

At each milling time, the lower treatment, i.e., the material of Example 4, had a greater optical density, spraying degree (L ^* ), darker blue than the untreated standard material or the higher treated material (Example 5). And more glossy.

<Example 15>

Carbon black products treated with various levels of 4-aminobenzoic acid used in thermoset acrylic formulations

Carbon black products prepared according to Examples 6, 7a and 7b were evaluated in thermoset acrylic formulations as described in Example 13. The optical properties of the coatings prepared after grinding for 27 hours are shown in the table below. Each formulation contained 30 g of carbon black product. The standard material was carbon black with a CTAB surface area of 350 m ² / g and DBPA of 120 ml / 100 g without any additional treatment.

Carbon Source (Example Number) Optical density L ^* a ^* b ^* Gloss (60 °) Viscosity Standard substance ** 2.82 1.58 -0.06 0.17 91.6 94 6 3.09 0.88 -0.15 -0.26 91.7 100 7a 3.19 0.75 -0.04 -0.22 96.5 91 7b 3.22 0.75 -0.06 -0.22 98.0 88 7c 3.20 0.74 -0.10 -0.20 98.4 85 ** Sample prepared after grinding for 42 hours

In this example in which the benzoic acid group was bonded, Example 7a treated with 8% by weight of 4-aminobenzoic acid diazonium salt was sufficient to show improved optical properties than standard material, untreated material or carbon black. Higher treatment levels did not significantly improve coating properties.

<Example 16>

Performance of surface treated carbon black products further functionalized with varying amounts of sulfanilic acid diazonium salts

The carbon black products prepared in Examples 10a-10e (3, 5, 10, 15, 25 wt% of sulfanyl diazonium, respectively) were evaluated in thermosetting acrylic formulations as described in Example 13. The optical properties of the coatings prepared after grinding for 27 hours are shown in the table below. Each formulation contained the same amount of carbon black. The standard material was surface treated carbon black with a nitrogen surface area of 560 m ² / g, 90 mL / 100 g of DBPA and a 9.5% content of volatiles.

Carbon Source (Example Number) Optical density L ^* a ^* b ^* Gloss (60 °) Viscosity Standard material 2.68 1.74 -0.07 0.11 88.8 92 10a 2.95 1.32 -0.01 0.14 93.7 89 10b 2.88 1.12 -0.11 -0.19 86.5 98 10c 2.84 1.21 -0.08 -0.10 76.9 102 10d 2.85 1.24 -0.07 -0.06 84.0 99 10e 2.81 1.34 -0.03 -0.08 90.1 97

Oxidized carbon black products bound with sulfonate groups showed greater optical density, sprayability, and deeper blue than untreated standard materials. Sealing Example 10b (5 wt% treatment) sprayed better than the other materials and was darker blue.

<Example 17>

Carbon Black Products Treated with Various Levels of Sulfanic Acid Used in Urethane Cured Acrylic Formulations

This example illustrates the use of the carbon black product in acrylic enamel formulations. Carbon black products from Examples 3 and 12 were used in the following compositions. This carbon black product was ground in a small steel mill (2-1 / 16 "high by 2-3-3" diameter) on a paint shaker. Each mill consists of 200 g of 3/16 "chrome steel balls, 2.19 g of carbon composition, and a mixture of 80/20 DMR-499 acrylic mixed enamel (PPG Finishes, Strongsville, OH) and xylene The mixture was ground for 50 minutes The samples were evaluated on a Hegman gauge 23.3 g of DMR-499, 17.3 g of xylene and DXR-80 urethane hardener [Strongsville, Ohio, USA] Product PPG Finishes] 1.4 g was added to the mill and shaken for 15 minutes to prepare the final formulation A 3 mil thick stretch of the finished formulation was prepared on a sealed Renetta chart. Dry then bake for 30 minutes at 140 ° F. 60 ° C. Optical properties were measured as described in Example 13.

The standard material was carbon black with a CTAB surface area of 350 m ² / g and DBPA of 120 ml / 100 g without any additional treatment. Optical properties and Hegman grinding are shown in the table below. Hegman values were measured on a Hegman gauge dense with 5 "sand" particles.

Carbon Source (Example Number) Optical density L ^* a ^* b ^* Gloss (60 °) Hegman crushing in 50 minutes Standard material 2.83 1.23 0.08 0.05 52.3 4.0 3 3.08 0.70 -0.04 -0.27 88.0 6.6 12 2.79 1.41 0.17 -0.03 92.5 6.2

For this composition, the wetting of the standard product was incomplete, as evidenced by very low gloss and Hegman gauge recordings. Carbon from Example 12 was weight corrected for throughput on carbon (2.66 g). The product of Example 3 (5 wt% sulfanilic acid diazonium salt treatment) showed better optical density, sprayability and blue tone values compared to standard and higher treated materials.

Example 18

Evaluation of Carbon Black Products in Glossy Ink Formulations

The carbon black products of Examples 11a-11d were evaluated in standard thermoset gloss ink formulations prepared on 3-roll mills. The performance of 11b-11d was compared with the control sample (Example 11a).

A carbon black sample was prepared by grinding by mixing 15 g of carbon black by hand on a 3-roll mill with 35 g of a grinding masterbatch. Samples were corrected for the throughput used (11a, 15.0 g; 11b, 15.2 g; 11c, 15.3 g; 11d, 15.8 g). The masterbatch consists of 9 parts of LV-3427XL (thermosetting milling vehicle, Lowter International, Northbrook, Illinois) for 1 part of MAGIESOL 47 oil. 50 g of this mixture were ground on a Kent 3-roll mill operating at 70 ° F. (21.11 ° C.). Samples were mixed down with the same amount of grinding masterbatch and then applied to a NIPRI produced grinding system to assess grinding. As a rule, the standard material was passed through the mill for 4 hours. If the grind gauge record was greater than 20 microns, an additional pass was made. The milled material is mixed with the same amount of descent masterbatch [3 parts of LV3427XL, 12 parts of LV6025 (thermoset gel vehicle, rotor International), 5 parts of marsole 47 oil] and passed through a 3-roll mill for 1 hour. The finished ink was prepared.

Majisol is a registered trademark of oil sold by Magie Brothers, Franklin Park, Illinois, USA.

The fineness and viscosity measurements of the resulting ink's grinding data are shown in the table below. The values in the grinding data table were microns as measured on the G-2 grinding gauge, indicating the level at which 5 scratch / 10 scratching / 5 defective particles were detected on the gauge. Steel Bar Laray Viscosity was measured according to ASTM Method D-4040-91 at 25 ° C. using a TMI 95-15-00 Testing Machines Inc., and vertical glass plate flow was measured using a glass plate. After standing for 0, 30, and 60 minutes before standing, the vertical glass plate was measured as a distance of 0.5 cc (0.5 mL) of ink sample moving down, and the development characteristics were measured using a Toyoseiki Testing Machine Inc. It was measured as described in Japanese Industrial Standard Lithography and Letterpress Test Method (JIS K5701-4.1.2).

Properties / Samples 11a 11b 11c 11d Carbon black properties Ink Manufacturing Grinding Substrate (5 Scratch / 10 Scratch / Sand) 1 pass 6/0/46 0/0/27 0/0/24 0/0/24 2 passes 0/0/24 0/0/14 0/0/22 0/0/20 3 passes 0/0/20 0/0/13 0/0/12 0/0/17 4 passes 0/0/16 0/0/8 0/0/12 0/0/18 Ink Properties Steel Bar Laray Viscosity Viscosity at 2500 s ^-1 66.7 64.6 61.7 58.2 Yield at 2.5 sec ^-1 is (dyne / cm) 507 553 533 490 Vertical Glass Flow (mm) Not cured 20 minutes 85 125 105 11 540 minutes 95 155 132 14 460 minutes 105 175 145 167 30 minutes Cure 20 minutes 43 98 85 9540 minutes 56 126 109 11960 minutes 61 145 126 139 60 minutes curing 20 minutes 26 95 79 8 640 minutes 42 125 102 11 560 minutes 48 143 120 135 Measurement system characteristics Slope (mm) 8.6 9.8 9.3 9.2 Intercept (mm) 23.9 23.3 24.9 25.6 Yield is (dyne / cm ² ) 128.4 113.3 116.0 114.1

       These data indicate how the treatment modifies the rheology of the ink composition. In this case, increasing the treatment level slightly reduced the Laray viscosity, but significantly increased the flow (vertical glass plate flow). Remaining flow after 1 hour of curing time indicates that this ink composition will flow more consistently with time. This is particularly useful in offset inks.

In addition, the development meter slope is an indicator of flowability, but not under different shear conditions (higher values corresponding to larger flows). The development meter slice is an indicator of the plastic viscosity of the sample.

Optical properties for the inks made from carbon black products 11b-11d and standard carbon black 11a were determined from prints made using RNA-42 Printability Tester (Research North America Inc.) and shown in the table below. Values for 1.0 and 2.0 micron film thicknesses were calculated from the regression of data from prints made beyond the film thickness range.

Optical Properties of 1 Micron Films Prepared from Samples 11a-11d

Example OD L ^* a ^* b ^* Polished 60 ° 11a 1.47 19.9 1.94 5.87 45.3 11b 1.37 23.23 1.93 6.18 45.1 11c 1.38 23.67 1.79 5.72 42.3 11d 1.20 31.10 1.63 5.84 38.6

Optical Properties of 2 Micron Films Prepared from Samples 11a-11d

Example OD L * a * b * Polished 60 ° 11a 2.28 2.93 0.68 0.75 49.1 11b 2.24 3.16 0.94 1.33 46.8 11c 2.08 5.41 1.53 2.67 48.1 11d 2.10 4.30 0.95 1.39 39.7

These data indicate that the optical properties are somewhat reduced when increasing the level of processing. Example 11b combines improved rheology (when used with offset inks) and very good dispersibility with minimal loss of optical properties.

Example 19

Preparation of Carbon Black Product

The method of Example 3 where the carbon black had a t-area of 93 m ² / g and a DBPA of 55 mL / 100 g was used. The amount of reagent used is shown in the table below.

Example number Carbon black (g) Para-aminobenzoic acid NaNO ₂ (g) Deionized Water (mL) 19a 400 0 0 220 19b 400 4 2.01 220 19c 400 8 4.01 220 19d 400 20 10.0 220

These products bound pC ₆ -H ₄ -CO ₂ Na groups.

The pellets prepared from this method were dried and then ground using a 20.3 cm (8 inch) jet mill (Strurtvant, Boston, USA) to convert the pellets into a product of 'floppy' form. This method is described in Perry's Chemical Engineers' Handbook, 6th Ed., RH Perry and D. Green Eds., Page 8-46, which is incorporated herein by reference. Used in Example 20.

Example 20

Evaluation of Carbon Black Products in Glossy Ink Formulations

The carbon black products of Examples 19a through 19d were evaluated in standard thermosetting gloss ink formulations made on a 3-roll mill, as described in Example 18. Carbon black product 19a was used as a control. Throughput 19a, 15.0 g used; 19b, 15.2 g; 19c, 15.3 g; 19d, 15.8 g of the sample was weight corrected.

The milling fineness data and viscosity measurements of the resulting inks are shown in the table below. The term "hangback" indicates that carbon black was not evenly mixed in the resin during the first mill pass.

Properties / Samples 19a 19b 19c 19d Carbon black properties Ink Manufacturing Grinding Substrate (5 Scratch / 10 Scratch / Sand) 1 pass 10/6/46 Hangback Hangback Hangback 2 passes 6/4/34 0/0/32 0/0/30 0/0/30 3 passes 5/0/26 0/0/26 0/0/12 0/0/24 4 passes 0/0/20 0/0/10 0/0/21 Ink Properties Steel Bar Laray Viscosity Viscosity at 2500 s ^-1 71.7 71.8 77.0 75.5 Yield at 2.5 seconds ^-1 (dyne / cm) 832 655 715 785 Vertical glass flow (mm) Not cured 20 minutes 110 105 125 11 940 minutes 133 122 160 15 160 minutes 145 130 179 175 30 minutes Curing 20 minutes 78 55 105 9440 minutes 100 70 137 12 960 minutes 115 78 155 150 60 minutes Curing 20 minutes 68 35 100 9 240 minutes 90 43 135 12660 minutes 102 49 150 146 Measurement system characteristics Slope (mm) 8.9 8.7 9.0 7.2 Interceptor (mm) 29.1 30.0 28.6 29.7 Yield (dyne / cm ² ) 94.3 107.9 102.3 96.2

These data indicate how treatment modifies the rheology of the ink formulation. In this case, increasing the treatment level significantly increased the flow (vertical glass plate flow). Remaining flow after the 1 hour curing time indicated that this ink composition would flow more consistently with time. This is particularly useful in offset inks. In addition, the carbon black of Example 19c was dispersed in ink at a faster rate than Control Example 19a.

Further, the development meter slope is an indicator of fluidity but not under different shear conditions (higher values corresponding to larger flows). The development meter slice is an indicator of the plastic viscosity of the sample.

The optical properties of the inks made from control carbon black 19a and the carbon black products 19b to 19d were measured as described in Example 18. Values for 1.0 and 2.0 micron film thicknesses were calculated from data regression from prints made beyond the film thickness range.

Optical Properties of 1 Micron Films Prepared from Samples 19a-19d

Example OD L ^* a ^* b ^* Gloss (60 °) 19a 1.40 24.5 1.18 3.67 36.7 19b 1.54 19.53 1.81 5.38 41.9 19c 1.34 25.16 1.80 5.71 42.7 19d 1.17 28.40 1.32 4.32 31.4

Optical Properties of 2 Micron Films Prepared from Samples 19a through 19d

Example OD L ^* L ^* L ^* Gloss (60 °) 19a 2.14 5.12 0.83 1.53 44.8 19b 2.25 3.47 0.75 0.92 49.9 19c 2.13 4.86 1.32 2.42 42.1 19d 1.85 9.37 1.21 2.85 31.7

These data indicate that when increasing throughput, the optical properties are somewhat reduced. Example 19 c had improved rheology (when used with offset inks), very good dispersibility and optical properties comparable to the control.

Example 21

Preparation of Carbon Black Product

Carbon black products with different amounts of bound groups were prepared under continuous process conditions. 100 parts / hour of carbon black with a t-area of 342 m ² / g and DBPA of 106 mL / 100 g were charged to a continuously running fin mixer. The amounts of sulfanilic acid, sodium nitrite and water used in each example are shown in the table below. The resulting material was dried to yield a carbon black product having combined pC ₆ H ₄ SO ₃ Na groups. The amount of bound groups was determined by analysis of Soxhlet extracted samples of each product against sulfur content. The results are shown in the table.

Carbon Source (Example Number) Sulfanic acid (parts / hour) NaNO ₂ (parts / hour) Deionized Water (parts / hour) Bound S mmol / product g Bound S mmol / product m ² 21a 3 1.2 115 0.15 0.44 21b 5 2 115 0.18 0.52 21c 7 2.8 115 0.28 0.82 21d 9 3.6 115 0.34 1.0 21e 15 6.0 115 0.54 1.6

<Example 22>

Carbon black products treated with varying amounts of sulfanilic acid used in urethane cured acrylic formulations

This example was performed as described in Example 17. The carbon black products of Examples 21a-21e were used in the composition. In each example the milling time was 60 minutes.

Carbon Source (Example Number) Optical density L ^* a ^* b ^* Gloss (60 ℃) Hegman crush in 60 minutes 21a 2.98 0.95 -0.01 -0.05 82.1 6.1 21b 2.94 0.99 0.01 -0.08 81.5 6.8 21c 3.20 0.69 -0.08 -0.28 88.8 6.8 21d 3.28 0.48 -0.07 -0.14 90.8 7.3 21e 2.92 0.89 0.01 -0.09 89.0 7.0

In this formulation, improved optical density, sprayability and gloss were found for the product of Example 21d. Carbon products having higher or lower levels of bound organic groups did not exhibit the coloring properties of the coating.

<Example 23>

Preparation of Carbon Black Product

This process describes the preparation of carbon black products under continuous process conditions. 100 parts / hour of carbon black having a CTAB-surface area of 361 m ² / g and DBPA of 117 mL / 100 g was added to a pin mixer operating continuously with 9 parts / hour of sulfanilic acid and 3.8 parts / hour of sodium nitrite as an aqueous solution. Filled. The resulting material was dried to yield a pelletized carbon black product having pC ₆ H ₄ SO ₃ Na groups. Analysis of samples extracted overnight with 90% ethanol in a Soxhlet extractor showed that the product had 0.35 mmol / g of bound sulfonate groups or 0.97 micromol / m ² bound sulfonate groups. The product sample was ground using a 10.15 cm (4 inch) jet mill at 3 lbs / hour to obtain a floppy material.

<Example 24>

Use of Carbon Black Products in Coating Compositions

This example illustrates the use of a carbon black product in a thermoset acrylic composition containing another pigment. Standard carbon blacks were surface treated carbon blacks with a nitrogen surface area of 560 m ² / g, DBPA 100 mL / 100 g and 9.5% volatile content. The materials evaluated in this example were prepared in Example 23.

The coating composition was prepared as follows.

Composition A: A quarter container was charged with 15.1 g of carbon black, 238.4 g of acryloid AT400 resin, 23.6 g of butyl acetate, 23.6 g of ethyl glycol monomethyl ether acetate, and 11.8 g of xylene, and mixed at 6000 rpm using an impeller mixer. A mill substrate was prepared by adding 900 g of a # 550 steel shot and grinding the mixture in a shot mill until a Hegman grind of 7.5 was obtained. The relaxation vehicle was prepared by rolling 564.4 g of acryloid AT400 resin, 260 g of Simel 325 melamineformaldehyde resin, 27 g of butyl acetate, 27 g of ethylene glycol monoethyl ether and 13.5 g of xylene in a gallon can for 1 hour. A mixture of mill substrate (200 parts) and 255 parts of relaxation vehicle were mixed for 15 minutes at 3000 rpm using an impeller mixer.

Composition B: A 0.5 gallon ceramic ball mill was charged with 2 kg of 20 mm ceramic medium, 204 g of acryloid AT400 resin, 356 g of Dupont R900 TiO ₂ , 16 g of butyl acetate and 16 g of ethylene glycol monomethyl ether acetate and 8 g of xylene. The wheat ego was spun for 4 hours on an ego roll mill running at 82 rpm until a Hegman crush of 7.5 was obtained. Additional 241 g of acryloid AT400 resin, 88.9 g of Cimell 325 melamine-formaldehyde resin, 18.3 g of butyl acetate, 18.3 g of ethylene glycol monomethyl ether acetate and 9.2 g of xylene were added and the mixture was further added on a ball mill for 4 hours. Rolling.

Composition C: Blends of Composition A and Composition B were mixed on a paint shaker for 30 minutes.

Stretches of samples of composition C were prepared on a glass plate using a 6-mill bird applicator, flowed out at room temperature for 5-10 minutes, and cured at 100 ° C. for 25 minutes at open. L ^* , a ^* , b ^* values were measured. As can be seen in the table below, the pelletized floppy carbon black product of Example 23 showed greater coloring than the control black. In the preparation of Composition A, when all the carbon samples were ground for 40 minutes, similar results were obtained for the pelletized material, but not for the floppy material.

Carbon product Composition A (part) Composition B (part) % Carbon Black in Composition C Sample tested L ^* a ^* b ^* contrast 20 20 1.06 3 50.25 -1.29 -2.98 Example 23 ^a 20 20 1.06 2 37.76 -1.06 -2.50 Example 23 ^* 12.5 20 0.82 One 44.38 -1.14 -2.49 Example 23 ^b 20 20 1.06 3 49.60 -1.50 -4.44 ^a = pelleted, ^b = floppy

<Example 25>

Preparation of Carbon Black Product

This process describes the preparation of carbon black products under continuous process conditions. 100 parts / hour of carbon black having a CTAB surface area of 361 m ² / g and DBPA of 117 mL / 100 g was charged to a pin mixer running continuously with sulfanilic acid and sodium nitrite as an aqueous solution. A portion of the resulting material was dried to yield a carbon black product having bound pC ₆ H ₄ SO ₃ Na groups. The concentration of pC ₆ H ₄ SO ₃ Na group was determined from sulfur analysis of the sample extracted with methanol overnight in a Soxhlet extractor.

Example Sulfanic acid (parts / hour) NaNO ₂ (parts / hour) Water (parts / hour) Combined C ₆ H ₄ SO ₃ Na μmol / g Combined C ₆ H ₄ SO ₃ Na μmol / m ² 325% mesh residue 25a 25.4 10.0 75 1220 3.38 0.05 25b 20.1 8.1 75 940 2.60 0.02 25c 18 7.0 75 860 2.38 0.58 25d 16.6 6.6 75 800 2.22 1.24 25e 14.9 5.9 75 680 1.88 1.99

Example 26

Use of Carbon Black Products in Coating Compositions

This example illustrates the use of the carbon black product of Example 25 in an aqueous thermoset acrylic composition. The coating composition was prepared as follows:

Composition A: Water (57.8 g), Patco 845 release agent and 3.4 g of dimethylethanolamine were mixed for 5 minutes using a low shear stress mixer. Cargill 17-8241 acrylic resin (34.4 g) and 4.3 g of SURPYNOL CT136 surfactant were added and the composition was further mixed for 10 minutes using a low shear stress mixer. The Patco 845 Release Agent is commercially available from American Ingridient Co. of Kansas City, Missouri. Cargill 17-7241 acrylic resin is commercially available from Cargill, Minneapolis, Minnesota, USA. Sulfinol CT136 is a registered trademark of Air Products and Chemicals, Allentown, PA.

Composition B: Water (68.5 g), Cargill 17-7241 acrylic resin 23.0 g, dimethyl ethanolamine 2.7 g, Cargill 23-2347 melamine resin 5.4 g and BYK-306 surfactant 0.3 g using a low shear stress mixer Mix further for 10 minutes. Cargill 23-2347 melamine resin is commercially available from Cargill, Minneapolis, Minnesota, USA. BYK-306 is a registered trademark of Surfactant manufactured and marketed by BYK-Chemie USA, Wallingford, USA.

Composition C: The carbon black product was added to water and stirred for about 15 minutes under low shear stress to prepare a 10% dispersion of the carbon black product of Example 25. Composition A (3.2 g) was added to 2.5 g of the carbon black product dispersion and mixed for 15 minutes using a magnetic stirrer. Composition B (19.3 g) was added and the resulting material was further mixed using a magnetic stirrer for 15 minutes. The coating composition was left overnight before use.

This coating was stretched on lenetta paper using a 3-mil bird applicator and dried at 163 ° C. for 15 minutes. The table below shows that when using a carbon black product having a reduced treatment level, a coating with improved spraying degree was obtained.

Carbon Source (Example Number) Bond C ₆ H ₄ SO ₃ Na μmol / m ² L ^* a ^* b ^* 25a 3.38 1.81 -0.16 -0.03 25b 2.60 1.55 -0.02 0.01 25c 2.38 1.30 0.03 0.02 25d 2.22 1.16 0.04 0.06 25e 1.88 1.19 -0.03 0.03

Other embodiments of the present invention will be apparent to those of ordinary skill in the art in view of the detailed description and examples of the disclosed invention. The detailed description and examples of the invention are intended to be considered merely as examples with the true scope and spirit of the invention as indicated by the following claims.

Claims (43)

One or more organic groups comprising (a) one or more aromatic groups or C ₁ -C ₁₂ alkyl groups, and (b) one or more ionic groups, one or more ionizable groups, or a mixture of ionic and ionizable groups includes carbon which is bonded, wherein the organic group or the CTAB of the carbon concentration or the modified carbon product of about 0.10 to about 2.7 micromoles per m ² of carbon used based on the t- area exceeding about 5% by weight residue value Present in an amount having a modified carbon product. The product of claim 1 wherein the concentration of organic groups per m ² carbon used is based on CTAB or the t-region of carbon between about 0.4 and about 2.5 micromolar. The product of claim 1, wherein the ionic group or ionizable group is a carboxylic acid or salt thereof. The product of claim 1, wherein the ionic group or ionizable group is sulfonic acid or a salt thereof. The product according to claim 1, wherein the organic group is a sulfophenyl group or a salt thereof. The product of claim 1, wherein the organic group is p-sulfophenyl or a salt thereof. The product of claim 1, wherein the organic group is pC ₆ H ₄ SO ₃ Na. The product according to claim 1, wherein the organic group is a carboxyphenyl group or a salt thereof. The product according to claim 1, wherein the organic group is a p-carboxyphenyl group or a salt thereof. The product of claim 1, wherein the organic group is a pC ₆ H ₄ CO ₂ H group. The product of claim 1, wherein the ionic group or ionizable group is a quaternary ammonium salt. The method of claim 1, wherein the organic group is _{3-C 5 H 4 N (} C 2 H 5) + X -, C 6 H 4 NC 5 H 5 + X -, C 6 H 4 COCH 2 N (CH 3) 3 + ^{_{X -, C 6 H 4 COCH}} 2 (NC 5 H 5) + X -, 3-C 5 H 4 N (CH 3) + X -, C 6 H 4 N (CH 3) 3 + X - , and C ₆ H ₄ CH ₂ N (CH ₃ ) ₃ ⁺ X ⁻ , wherein X ⁻ is a halide or an anion derived from an inorganic or organic acid. The method of claim 12, wherein the organic group is _{C 6 H 4 NC 5 H 5} + X - or _{C 6 H 4 N (CH 3} ) 3 + X - in the product. The product according to claim 1, wherein the organic group is a carboxy-hydroxy phenyl group or a salt thereof. The product of claim 1, wherein the organic group is 4-carboxy-3-hydroxy phenyl. The product of claim 1 wherein the carbon is carbon black, graphite, carbon fiber, glassy carbon, fine carbon, activated charcoal, activated carbon, or mixtures thereof. The product of claim 16, wherein the carbon is carbon black. The product according to claim 1, wherein the aromatic ring of the aromatic group is an aryl group. The product according to claim 1, wherein the aromatic ring of the aromatic group is a heteroaryl group. The organic group of claim 1, wherein the organic group is R, OR, COR, COOR, OCOR, halogen, CN, NR ₂ , SO ₂ NR (COR), SO ₂ NR ₂ , NR (COR), CONR ₂ , NO ₂ , SO ₃ M, SO ₃ NR ₄ , and N = NR ′ wherein R is independently hydrogen, substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₃ -C ₂₀ alkenyl, (C _2- C ₄ alkyleneoxy) _x R ″, or substituted or unsubstituted aryl; R ′ is independently hydrogen, substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted aryl; R ″ is hydrogen , Substituted or unsubstituted C ₁ -C ₂₀ alkyl, or substituted or unsubstituted C ₃ -C ₂₀ alkenyl, substituted or unsubstituted C ₁ -C ₂₀ alkanoyl, or substituted or unsubstituted aroyl; M is H, Li, Na, Cs, or K; x is an integer from 1 to 40. The product of claim 1, wherein the aromatic carbon of the formula is further bonded to the carbon of the modified carbon product. A _y Ar- Where Ar is an aromatic radical selected from the group consisting of phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, pyridinyl and triazinyl; A is hydrogen or R, OR, COR, COOR, OCOR, halogen, CN, NR ₂ , SO ₂ NR ₂ , SO ₂ NR (COR), NR (COR), CONR ₂ , NO ₂ , SO ₃ M, SO ₃ NR ₄ , and N = NR ′ is a functional group selected from the group consisting of; Linear, branched, or cyclic hydrocarbon radicals unsubstituted or substituted with one or more of the above functional groups; R is independently hydrogen, substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted C ₃ -C ₂₀ alkenyl, (C ₂ -C ₄ alkyleneoxy) _x R ″, or substituted or unsubstituted Aryl; R 'is hydrogen, substituted or unsubstituted C ₁ -C ₂₀ alkyl, substituted or unsubstituted aryl; R ″ is hydrogen, substituted or unsubstituted C ₁ -C ₂₀ alkyl, or substituted or unsubstituted C ₃ -C ₂₀ alkenyl, substituted or unsubstituted C ₁ -C ₂₀ alkanoyl, or substituted or unsubstituted Aroyl; x is 1 to 40, M is H, Li, Na, Cs, or K; y is an integer of 1 to 5 when Ar is phenyl, an integer of 1 to 7 when Ar is naphthyl, an integer of 1 to 9 when Ar is anthracenyl, phenanthrenyl, or biphenyl, or Ar is pyridi It is an integer of 1 to 4 when it is Neal, or an integer of 1 to 2 when Ar is triazinyl. A non-aqueous coating composition comprising a non-aqueous solvent and the modified carbon product of claim 1. A nonaqueous ink composition comprising a nonaqueous vehicle and the modified carbon product of claim 1. An aqueous coating composition comprising water and the modified carbon product of claim 1. An aqueous ink composition comprising water and the modified carbon product of claim 1. a carbon bound to at least one organic group comprising (a) at least one aromatic group and (b) at least one ionic group, at least one ionizable group, or a mixture of ionic groups and ionizable groups, A non-aqueous ink or coating composition comprising a modified carbon product and a non-aqueous solvent or vehicle in which at least one aromatic group of the organic group is bonded directly to carbon. A method of increasing the flow of ink as measured by glass plate flow, comprising incorporating the modified carbon product of claim 1 into the ink. A coating composition comprising a water or non-aqueous solvent, the modified carbon product of claim 1 and colored pigments other than carbon black. A coating composition comprising a water or non-aqueous solvent, the modified carbon product of claim 2 and colored pigments other than carbon black. A coating composition comprising a water or non-aqueous solvent, the modified carbon product of claim 3 and colored pigments other than carbon black. A coating composition comprising a water or non-aqueous solvent, the modified carbon product of claim 4 and colored pigments other than carbon black. A coating composition comprising a water or non-aqueous solvent, the modified carbon product of claim 5 and colored pigments other than carbon black. A coating composition comprising a water or non-aqueous solvent, the modified carbon product of claim 6 and colored pigments other than carbon black. A coating composition comprising a water or non-aqueous solvent, the modified carbon product of claim 7 and colored pigments other than carbon black. A coating composition comprising a water or non-aqueous solvent, the modified carbon product of claim 8 and colored pigments other than carbon black. A coating composition comprising a water or non-aqueous solvent, the modified carbon product of claim 10 and colored pigments other than carbon black. A coating composition comprising a water or non-aqueous solvent, the modified carbon product of claim 11 and colored pigments other than carbon black. A coating composition comprising a water or non-aqueous solvent, the modified carbon product of claim 12 and colored pigments other than carbon black. A coating composition comprising a water or non-aqueous solvent, the modified carbon product of claim 17 and a colored pigment other than carbon black. A coating composition comprising a water or non-aqueous solvent, the modified carbon product of claim 20 and colored pigments other than carbon black. A coating composition comprising a water or non-aqueous solvent, the modified carbon product of claim 21 and a colored pigment other than carbon black. The coating composition of claim 26 further comprising a colored pigment in addition to carbon. A coating composition comprising water or a non-aqueous solvent, the modified carbon product of claim 1 and clay, talc, silica, or carbonate.