MXPA97000753A - Preparation of aqueous coating systems contain ftalocian - Google Patents

Abstract

The present invention relates to a phthalocyanine pigment formulation, which is dispersed in water, consisting essentially of a mixture of: a) 60 to 99.5% by weight, based on the total amount of components a) and b), of a metal phthalocyanine conditioned pigment, and b) 0.5 to 40% by weight, based on the total amount of components a) and b), of a water insoluble sulfonated phthalocyanine, having the formula: Pc (SO3R) x where Pc represents a part of phthalocyanine, R is H or M, wherein M is a monovalent metal, divalent metal, trivalent metal or ammonium cation, and X is from about 0.2 to about 4, wherein the pigment (a) of metal phthalocyanine is conditioned before being mixed with the insoluble sulfonated phthalocyanine (b) on

Description

PREPARATION OF AQUEOUS COATING SYSTEMS CONTAINING FTALOCIANIN BACKGROUND OF THE INVENTION This invention relates to an aqueous-based coating system containing phthalocyanine pigments and certain sulfonated copper phthalocyanines. The solvent-based pigment systems in which various pigments are dispersed in an organic liquid are already known systems. When preparing phthalocyanine pigment dispersions, it is generally necessary to include various additives, particularly ionic surfactants, to maintain a stable dispersion. For example, US Patent 4,057,436 and T. Schauer and L. Dulog, "Einflussfaktoren bei der Bestimmung der Teilchengrossen von Pigmenten" (Factors influencing the determination of pigment particle size) in Farbe + Lacke, 97, 665- 669 (1991). Sulfonated copper phthalocyanines have been described as particularly useful dispersing agents for solvent-based phthalocyanine pigment dispersions used in coatings and inks (e.g. U.S. Patents 2,526,345, 3,754,958, 4,152,171, 4,709,021 and 4,726. 847 and British Patent 1,502,884, see also JF Santimauro, "An Introduction to Copper Phthalocyanine Pigments" (Introduction to copper phthalocyanine pigments) in Dyestuffs 43, 158-163 (1960)) and have been described as useful for imparting stability thermal to quinacridone pigments used in plastics (e.g., U.S. Patent 5,362,780) but have not been previously described for use in aqueous-based pigment systems. Water-based pigment systems can provide both environmental and economic advantages over solvent-based pigment systems. However, as with solvent-based systems, it is generally necessary to include various additives to provide adequate dispersions of phthalocyanine pigments. For example, R. Craft, "Mechanisms of Pigment Dispersion Stabilization in Water-borne Coatings" (Mechanisms of stabilization of pigment dispersions in water-based coatings) in Modern Paint and Coatings, pages 38-43 (March, 1991). For example, U.S. Patent 4,239,549 describes the use of certain alkylarylsulfonic acids to provide water-dispersible phthalocyanine pigment formulations, and European Patent Application 430,875 describes the use of certain sulfonated pyrrolopyrrole derivatives and quinacridone to provide dispersible formulations in water containing pyrrolopyrrole and quinacridone pigments, respectively. Although US Patent 3,754,958 discloses amine-containing pigment preparations which may also contain water, only solvent-based applications are described. Stable aqueous dispersions containing mixtures of sulfonated phthalocyanine copper phthalocyanines such as those prepared according to the present invention have not been previously described. It has now been found that it is possible to prepare stable water-dispersible phthalocyanine pigment formulations by surface treatment of phthalocyanine pigments conditioned with certain sulfonated copper phthalocyanines.

COMPENDIUM OF THE INVENTION This invention relates to a phthalocyanine pigment formulation dispersible in water comprising a mixture of (a) about 60 to about 99.5% by weight (preferably 90 to 98% by weight), based on the total amount of components (a) and (b), of a conditioned metal phthalocyanine pigment (preferably a copper phthalocyanine pigment), preferably having an average particle size from about 0.2 to about 0.3 μm, and (b) from about 0.5 to about 40% by weight, based on the total amount of components (a) and (b), of a sulfonated phthalocyanine insoluble in water ( preferably a sulfonated metal phthalocyanine, more preferably a sulfonated copper phthalocyanine) having the formula Pc (S02OR) x (I) where Pe represents a phthalocyanine radical (preferably a metal phthalocyanine radical, more preferably a phthalocyanine copper radical); R is H or M, where M is a monovalent metal, divalent metal, trivalent metal, or ammonium cation, and x is from about 0.2 to about 4 (preferably 1 to 1.8). This invention further relates to an aqueous coating system comprising (1) about 10 to about 30 weight percent (preferably 15 to 20 weight percent) of a water dispersible phthalocyanine pigment formulation of the invention, and (2) a water dispersible coating binder.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates in general to water-based coating systems containing metallic phthalocyanine pigments and certain sulfonated phthalocyanines. The preferred metal phthalocyanine pigments of component (a) are copper phthalocyanines. However, other phthalocyanines containing metal, such as those based on cobalt, iron, nickel and other metals of this type known in the art can also be used. In addition, the metal phthalocyanine pigments of the present invention may be partially substituted on the ring (eg, with 1 to 16 chloro substituents, Ci-Cr alkyl, C6-C6 alkoxy, or other typical pigment substituents > of phthalocyanine) or they can be unsubstituted. The sulfonated phthalocyanines used as a component (b) are preferably free water-insoluble sulfonic acids having the general formula Pc (S02OH) x in which Pe is phthalocyanine radical (more preferably a metal phthalocyanine radical) and x is from about 0.2 to about 4. Without However, water insoluble salts having the general formula Pc (S02OM) x in which M is an alkaline cationic metal, alkaline earth metal, zinc, aluminum or RaRbRcRdN + are also suitable (where Ra, Rb, Rc and Rd are, independently, Ci-Ciß alkyl, phenyl, or phenyl substituted with C? -C6 alkyl, C? -C6 alkoxy, halogen, nitro, aryl, amino, amido, carboxyl, or other known substituents). It is also possible, although much less preferred, to use sulfonamides having the general formula Pe (S02NReRf) x (in which Re and Rf can be C? -C6 alkyl, C? -C6 alkoxy, halogen, nitro, aryl, aminoalkyl, or other known substituents), optionally in admixture with components of formula (I). Although it is also not generally preferred, mainly for economic reasons, the phthalocyanine radical may be substituted on the ring, for example with chlorine, alkyl, alkoxy, or other known substituents. It is also possible to use sulfonated phthalocyanines of formula (I) in which the phthalocyanine radical Pe is free of metal. Component (b) is preferably sulfonated copper phthalocyanine. Preferred sulfonated copper phthalocyanines in particular include so-called monosulfonated copper phthalocyanines having the formula Pc (S02OR) x in which Pe represents a copper phthalocyanine radical (including ring-substituted derivatives); R is H or, in general less preferably, M, where M is a monovalent, divalent or trivalent metal cation or an ammonium ion as described above; and x is from about 1 to about 1.8. Although these compounds must, of course, be insoluble in water, salts of even alkali metal and alkaline earth metal can be used provided they exhibit the requisite insolubility. Disulfonated copper phthalocyanines, on the other hand, are generally inadequate, due at least in part to their greater water solubility in general. A preferred sulfonated copper phthalocyanine in particular is that represented by the formula Pc (S02OR) x wherein x is about 1.7 and is marketed by Fabricolor, Paterson, New Jersey. The crude phthalocyanine pigments are usually prepared by a reaction of phthalic anhydride or derivative thereof, urea, and a metal source, or by reaction of phthalonitrile or a derivative thereof and a metal source in an organic solvent. The resulting phthalocyanine particles, however, undergo crystal growth during the preparation and have an axis greater than about 10 to about 200 μm. These metal phthalocyanines have little or no color value as a pigment for use in inks, coating compositions, plastics and the like. For this reason, crude metal phthalocyanine should be conditioned by methods known in the art, such as grinding and / or solvent treatment methods, to obtain a high color index. The conditioned pigments typically have particle sizes of about 0.01 to about 0.5 μm and suitable crystal forms. Phthalocyanine pigments (a) (i) according to the present invention, however, should preferably have average particle sizes of from about 0.2 to about 0.3 μm. The phthalocyanine pigments (a) are preferably conditioned before adding the sulfonated phthalocyanine component (b), but the two components can also be mixed before the conditioning step. For example, the pigment component (a) can be mixed using known methods with at least a portion of the specified amount of component (b) before conditioning. Suitable mixing methods include dry grinding or, if wet grinding or solvent conditioning treatment, a simple solvent treatment, optionally at elevated temperatures. Regardless of whether the components are mixed before or after the conditioning process, it is possible to use essentially any method normally employed for phthalocyanine conditioning. Suitable grinding methods for conditioning the phthalocyanine pigments include dry grinding methods, such as grinding with sand, grinding with balls and the like, with or without additives, or wet grinding operations such as salt kneading, grinding with pellets, and the like, in water or organic solvents (such as alcohols or esters), with or without additives. After the grinding step is completed, an optional solvent treatment can be used, generally at temperatures between about 10 ° C and about 200 ° C. This treatment with solvent is preferably carried out at elevated temperatures, such as 60 ° C to 145 ° C. Suitable solvents for an optional solvent treatment include water, inorganic acids, such as sulfuric or phosphoric acid, adjusted to suitable concentration; organic acids, such as formic acid or acetic acid; and various organic solvents such as alcohols (for example methanol, ethanol or ethylene glycol), cyclic or open chain ethers (for example dioxane, tetrahydrofuran, monoalkyl or dialkyl ethers of ethylene glycol, and oligo- or polyglycol ethers); ketones (for example, acetone or methyl ethyl ketone), aromatics (for example, toluene, xylene, chlorobenzene, nitrobenzene, or chloronaphthalene), esters (for example, methyl benzoate, dimethyl phthalate, dimethyl succinate or methyl salicylate) , and amides (e.g., formamide, dimethylformamide, or N-methylpyrrolidone). Frequently, it is advantageous to use mixtures of these solvents. Suitable solvents for direct conditioning of the solvent include inorganic acids such as sulfuric or phosphoric acid. The ionic strength and amount of acid can be adjusted so that the pigment dissolves.

When concentrated acids such as sulfuric acid are used, about 6 to 10 times by weight of acid is typically employed relative to the amount of pigment. The acid treated pigment is precipitated from the acidic liquid solution by the addition of water ("acid paste formation") or, in an optional method, the acidity is adjusted in such a way that acid salts are formed, so that in the suspension the transformation to a solution takes place ("acid swelling"). Other suitable solvents, although generally less preferred, which are used for this solvent treatment include organic acids such as formic or acetic acid; alcohols such as methanol, ethanol or ethylene glycol; ethers such as dioxane, tetrahydrofuran, ethylene glycol monoethyl or diethyl ether, or oligo or polyglycolyl ethers; ketones, such as acetone or methyl ethyl ketone; aromatics, such as toluene, xylene, chlorobenzene, nitrobenzene, or chloronaphthalene; esters, such as methyl benzoate, dimethyl phthalate, or methyl salicylate; and amides, such as formamide, dimethylformamide, or N-methylpyrrolidone. The pigments used in the process of the invention can be further treated using known methods. This post-treatment can be carried out in conditions similar to those described above for the optional treatment with solvent used after grinding. The dyeing strength and transparency of the pigment can be affected by post-treatment variation. In a preferred grinding procedure, a copper phthalocyanine pigment is introduced into a ball mill and crushed wet or dry and the ground pigment is then treated with methyl benzoate in an aqueous paste typically diluted at 30-145 ° C. The use of methyl salicylate or methyl phthalate in place of methyl benzoate is also suitable. If desired, the ester solvent can then be hydrolysed with dilute caustic material. The resulting product is then collected, washed and dried by methods well known in the art. In another preferred milling method, a copper phthalocyanine pigment is added to water to make a slurry which is then passed through a bead mill, for example glass or zirconium silicate pellets and centrifuged at high speed. The pigment paste is separated from the pellets and heated, typically at 30 to 145 ° C, before isolation. In a preferred solvent conditioning process, a copper phthalocyanine is added to an excess (for example 10 parts by weight of the mixed pigments) of concentrated sulfuric acid and stirred, preferably at room temperature, until the solution is complete . The solution can precipitate by slow pouring of the acidic liquid solution in cold water while stirring at the same time. The resulting precipitate is filtered and preferably washed until it is acid free. When the acid precipitation method is used, it is generally preferred to carry out a post-treatment of the resulting pressed cake, for example, by preparing a slurry in water and heating, typically between 30 and 145 ° C, before the isolation. In another preferred method of solvent conditioning, a copper phthalocyanine is added to 65 to 80% sulfuric acid, during which process the pigment swells. The swollen pigment can be precipitated by pouring it in cold water and stirring. The resulting precipitate can then be subjected to post-treatment and isolated as described above. Regardless of the conditioning method used, the phthalocyanine pigment of conditioned metal preferably has a mean particle size of about 0.2 to about 0.3 μm. If the sulfonated copper phthalocyanine component is not added before conditioning (or if only a portion of the sulfonated copper phthalocyanine component is added), the conditioned phthalocyanine pigment is intimately mixed with the sulfonated metal phthalocyanine component (b) using known, preferably dry milled, to obtain the specified relative amounts. The aqueous coating systems according to the invention can be prepared by mixing water-dispersible phthalocyanine pigment formulations of the invention with suitable water-dispersible coating binders known in the art. Although the specific type of binder is not generally critical as long as it is dispersible in water, preferred binders include known water-dispersible homopolymers or copolymers of olefinically unsaturated monomers (especially (meth) -acrylic binders, either as free acids or as the corresponding alkyl or hydroxyalkyl esters), polyester binders, polyurethane binders, and combinations thereof. Suitable coating systems contain about 10 to about 30 weight percent (preferably 15 to 20 weight percent) of the pigment formulation, with the balance being the binder, known fillers and other additives, and water. The water-based coating systems according to the present invention are suitable for use in many coating applications where pigmented coatings are desired. The following examples further illustrate details of preparation and use of the compositions of this invention. The invention described in the foregoing is not limited in its spirit or scope by these examples. Those skilled in the art will readily understand that known variations of the conditions and processes of the following preparative procedures can be made to prepare these compositions. Unless otherwise indicated, all temperatures are in degrees Celsius and all parts and percentages are parts by weight and percentages by weight, respectively.

EXAMPLES Examples 1-7 Examples 1-7 illustrate the preparation of copper phthalocyanine pigments in the presence and absence of sulfonated copper phthalocyanine additive. The coloring properties were determined using an aqueous based layer / clear solvent based layer system. Aqueous dispersions were prepared using a mixture of 12.4% acrylic resin AROLONR 559-G4-70 (Reichhold Chemicals, Inc.), 3.2% hyperdispersant SOLSPERSE 27000 (Zeneca, Inc.), 1.6% of 2 -amino-2-methyl-l-propanol (Angus Chemical), and 18% pigment, which gave a pigment-to-binder ratio of 18:12 and a total solids content of 30%. The pigment-to-binder ratio was then reduced to 10:40 with additional acrylic resin AROLONR 559-G4-70 (total amount 26%) and 25% melamine / formaldehyde resin CYMELR 325 (Cytec Industries), which gave a total content of 50% solids. Mass tone and transparency measurements were made using films applied at wet film thicknesses of 76 μm and 38 μm, respectively, and allowed to stand at room temperature for 15 minutes and at 100 ° C for five minutes. Transparent layers were then applied containing a mixture of 80% alkyd resin AROPLAZR 1453-X-50 (Reichhold Chemicals, Inc.) and 20% melamine / formaldehyde resin CYMELR325 at a total solids level of 57% on the Base coat at a wet film thickness of 76 μm allowing to stand at room temperature for 15 minutes and at 121 ° C for fifteen minutes. Sub-tone dye paints were prepared from the above-described reduced aqueous dispersions having a pigment-to-binder ratio of 10:40 by addition addition of acrylic resin AROLONR 559-G4-70, melamine / formaldehyde resin CYMELR 325 and 35% white dispersion TINT-AYDR CW-5003 (Daniel Products Company), which gave a pigment-to-binder ratio of 1: 1.1, a total solids content of 55% and a Ti02 to pigment ratio of 90 : 10 The color measurements were made using films applied at a wet film thickness of 38 μm and allowed to stand at room temperature for 15 minutes and at 100 ° C for five minutes. Transparent layers were then applied and baked as described above. Metallic paints were prepared from the dispersion described above with a pigment-to-binder ratio of 18:12 using an aluminum pigment dispersible in water. (marketed as HYDRO-PASTER 8726 by Silberline Manufacturing Co., Inc.), AROLONR 559-G4-70 acrylic resin, and CYMELR 325 formaldehyde melamine resin in amounts that provided a pigment-to-binder ratio of 1: 2, aluminum to pigment ratios of 20:80 and 80: 20, and a total solids content of 43%. The color measurements were made using films applied at a wet film thickness of 38 μm and baking as described above. The transparent layers were then applied and baked as described above. The intensity of the reflective color in the CIELAB measuring system was determined for each test sample using an ACS-1800 color calculator (for inks) and a X-Rite MA58 Multi-Angle spectrophotometer (metallic). In the CIELAB system the term H refers to the nuance; the term C refers to chroma, an indication of color saturation and is calculated as the square root of the sum of squares of a * and b *; the term L refers to clarity, for which a higher value is a lighter color and a lower value is a darker color; and the term E refers to the total color difference. The results are expressed in terms of the difference (ie, delta values) between the corresponding H, C, L and E values of the transparent layers prepared using pigments containing sulfonated copper phthalocyanine additive and the corresponding pigment values of Comparison prepared in the absence of sulfonated copper phthalocyanine additive. Example 1 100 parts of a copper phthalocyanine with a chlorine content of 16% ("copper tetrachloro phthalocyanine") sold by Sanyo Color Works were introduced, Ltd. (Japan) and a small amount of a solvent containing hydroxy in a ball mill containing 3000 parts of steel balls as grinding elements. The capacity of the ball mill was such that it constituted 60% of the total when it was fully loaded. The mill was turned for 48 hours. The powder was discharged from the mill through a sieve that retained the grinding elements. The powder ground with the balls was added to the water (4 times the weight of the pigment) and stirred until it was thoroughly moistened. The moistened powder was treated with methyl benzoate (80% by weight of the pigment powder), then heated to 85-90 ° C and maintained at that temperature for 12 hours. After the batch was cooled, the methyl benzoate was hydrolysed using 50% aqueous sodium hydroxide at 90 ° C for about 4 hours. The resulting mixture was cooled, filtered, washed with water, and dried to obtain a conditioned pigment having a blue hue. A sulfonated copper phthalocyanine having a sulfonation ratio of about 1.71, marketed as a pressed cake by Fabricolor (Paterson, New Jersey), was dried at about 80 ° C until the humidity was constant (two to four days) ). A 5 gram portion of the dry sulfonated copper phthalocyanine was mixed dry with 100 grams of each conditioned pigment and mixed by mechanical means. The resulting mixtures were discharged from the mixer as water-dispersible pigments which were used to prepare water-based paints having a blue hue. The metallic paints prepared according to the invention showed deep displacement and neutral detachment. Water-based comparison paints prepared in the same manner but in the absence of sulfonated copper phthalocyanine had a blue hue but exhibited a lower intensity, a lighter mass tone, slightly less transparency and, for metal paints, lower displacement and detachment. The color properties are shown in the Table.

Table Color properties of the aqueous dispersions of Example 1 (for comparison pigments not containing sulfonated copper phthalocyanine) Intensity (%)? H? C? L? E Comments (at 610 nm) Non-metallic la) 120 -0.03 0.38 0.05 0.38 Brighter stroke Metallic l (b) angle of 25c -1.25 1.48 5.24 5.59 Green, bright, clear angle 45c 0.26 -0.74 1.02 1.29 Reddish, slightly matt, clear angle of 75 ° C 1.78 -1.06 -1.16 2.37 Red, matt, dark Path Id) 3, 03 -6.40 Darker Metallic 2 | C > angle of 25 ° 0.00 1.42 2.24 2.65 Brilliant, clear angle of 45 ° 0.02 0.55 0.01 0.55 Slightly bright angle of 75 ° C 0.42 -0.75 - 1,96 2,14 Reddish stroke, slightly matt dark Distance ldl 0,42 -4,20 Darker (a) Non-metallic paint that does not contain aluminum (b) Metallic paint 1 containing aluminum and pigment in a weight ratio of 20:80 (c) Metallic paint 2 containing aluminum and pigment in a weight ratio of 80:20 (d) Displacement values calculated using the formulas? H75 «-? H25 ° and? 75 ° -? I 2S ° Example 2 The procedure of Example 1 was repeated, except that a copper phthalocyanine with a chlorine content of 5.7% by weight ("copper monochloro phthalocyanine") sold by Sanyo Color Works, Ltd. (Japan) was used. instead of copper phthalocyanine tetrachloride. The conditioned pigment, which exhibited a reddish blue hue, provided non-metallic and metallic water-based paints that had a reddish-blue hue when applied to a substrate and dried. A comparison water-based paint was prepared in the same manner but without sulfonated copper phthalocyanine which provided a painted surface which had a reddish-blue tone but less intensity, lighter bulk tone, less transparency and, for metallic paints lower displacement and detachment. EXAMPLE 3 One hundred parts of Green Pigment 7 having a chlorine content of 48% by weight were conditioned as in Example 1. The conditioned pigment, which had a greenish hue, led to water-based metallic and non-metallic paints that They had a greenish tint when applied to a substrate and dried. A comparison water-based paint prepared in the same manner but without sulfonated copper phthalocyanine provided a painted surface that had a greenish tone but a lower intensity, lighter bulk tone, less transparency and, for metallic paints, lower offset and detachment EXAMPLE 4 50 parts of crude Pigment Green 7 with a chlorine content of 48% by weight and 50 parts of a copper tetrachloro phthalocyanine with a chlorine content of 16% by weight were mixed and the mixture was conditioned as in Example 1 The conditioned pigment, which had a blue-green hue, gave metallic or non-metallic water-based paints that had a blue-green hue when applied to a substrate and dried. A water-based comparison paint prepared in the same way but without copper sulfide phthalocyanine, nothing provided a painted surface that had a blue-green hue but a lower intensity, lighter mass tone, less transparency and, for metallic paints, lower displacement and detachment. Example 5 A copper phthalocyanine without crude chlorine was introduced (125 g) marketed by Toyo Ink Inc. (Japan) as "Phtalo Blue Crude CPC Grade No. 4"in a ball mill containing 3000 grams of steel balls as crushing elements. The capacity of the ball mill was such that it was 60% full when fully loaded. The mill was rotated for 48 hours, after which the resulting powder was discharged through a sieve that retained the grinding elements. The powder milled with the balls was added to water (four times the weight of the pigment) and stirred until it was thoroughly dispersed. The moistened powder was then treated with dimethyl succinate (60 wt.% Pigment powder), was then heated to 85 ° C and maintained at that temperature for eight hours. The treated pigment was cooled and the dimethyl succinate was hydrolyzed using 50% aqueous sodium hydroxide at 85 ° C for two hours. The resulting mixture was cooled, filtered, washed with water and dried to give a conditioned pigment with a blue-green hue. The conditioned pigment, after being mixed with sulfonated copper phthalocyanine and dispersed in aqueous medium, gave water-based metallic and non-metallic paints having a blue-greenish tint when applied to a substrate and dried. A comparison water-based paint prepared in the same manner but in the absence of sulfonated copper phthalocyanine provided a painted surface that had a blue-green hue but a lower intensity, lighter bulk, less transparency and, for metal paints, lower displacement and detachment.

EXAMPLE 6 The procedure of Example 5 was repeated, except that the chloro-free phthalocyanine was replaced with a mixture of 30% by weight of monochlorinated copper phthalocyanine (marketed by Sanyo Color Works) and 70% by weight of free copper phthalocyanine of chlorine (commercialized by Toyo Ink Inc.). The conditioned pigment, which had a reddish-blue hue, provided metallic and non-metallic paints that showed a reddish-blue hue when applied to a substrate and dried. An aqueous-based comparison paint was prepared in the same manner but without sulfonated copper phthalocyanine which provided a painted surface which had a reddish-blue tone but a lower intensity, lighter bulk, less transparency and, for metallic paints, lower displacement and detachment. Example 7 The procedure of Example 6 was repeated except that the chloro-free phthalocyanine was replaced with a crude cobalt phthalocyanine (marketed by Bayer AG, Germany). The cobalt-conditioned phthalocyanine pigment, which had an intense and uniform turquoise hue, provided water-based metallic and non-metallic paints that showed a turquoise hue when applied to a substrate and dried. A comparison water-based paint prepared in the same manner but in the absence of sulfonated copper phthalocyanine provided a painted surface that had a turquoise hue but lower intensity, lighter bulk tone, less transparency and, for metallic paints, lower offset and detachment.

Claims (3)

1. CLAIMS 1. A phthalocyanine pigment formulation dispersible in water comprising a mixture of (a) 60 to 99.5% by weight, based on the total amount of components (a) and (b), of a metal phthalocyanine pigment conditioning, and (b) 0.5 to 40% by weight, based on the total amount of components (a) and (b), of a sulfonated phthalocyanine insoluble in water having the formula
2. Pc (S02OR) x (I) where Pe represents a phthalocyanine radical; R is H or M, where M is a monovalent metal, a divalent metal, a trivalent metal, or ammonium cation, and x is from about 0.2 to about 4. 2. A phthalocyanine pigment formulation dispersible in water according to the claim 1 wherein the metal phthalocyanine pigment (a) is a copper phthalocyanine pigment or a substituted derivative in the ring thereof.
3. 3. A water-dispersible phthalocyanine pigment formulation according to claim 1 wherein the sulfonated phthalocyanine (b) is a sulfonated metal phthalocyanine. . A water-dispersible phthalocyanine pigment formulation according to claim 1 wherein the sulfonated phthalocyanine (b) is a sulfonated copper phthalocyanine. 5. A water-dispersible phthalocyanine pigment formulation according to claim 1 wherein the sulfonated phthalocyanine (b) is a sulfonated copper phthalocyanine having the formula Pc (S02OR) x where Pe is a phthalocyanine radical of copper; R is H or M, where M is a monovalent, divalent or trivalent metal cation, or an ammonium ion, and x is from about 1 to about 1.8. 6. A water-dispersible phthalocyanine pigment formulation according to claim 1 wherein the sulfonated phthalocyanine (b) is a sulfonated copper phthalocyanine having the formula Pc (S02OH) x where Pe is a phthalocyanine radical of copper; and x is from about 1 to about 1.8. 7. A water-dispersible phthalocyanine pigment formulation according to claim 1 wherein the sulfonated phthalocyanine (b) is a sulfonated copper phthalocyanine having the formula Pc (S02OM) x where Pe is a copper phthalocyanine radical M is an alkali metal, alkaline earth metal, zinc, aluminum or RaRbRcRdN + cation (where Ra, Rb, Rc and Rd are, independently, C-alkyl) C? 8, .. phenyl, or substituted phenyl); and x is from about 1 to about 1.8. 8. An aqueous coating system comprising (1) about 10 to about 30 weight percent of water dispersible phthalocyanine pigment formulation according to claim 1, and (2) a water dispersible coating binder. 9. An aqueous coating system according to claim 8 wherein the Water-dispersible Coating binder is a homopolymer or copolymer of olefinically unsaturated monomers, a polyester binder, a polyurethane binder, or a combination thereof. 10. An aqueous coating system according to claim 8 wherein the water dispersible coating binder is an acrylic binder.