MXPA97003451A - Modifiers of growth of crystals for profile pigments - Google Patents

Abstract

The present invention relates to a pigment composition comprising a coprecipitated mixture, comprising: a) from 60 to 95 weight percent of a perylene pigment having the formula: wherein R1 and R2 are independently C1-C6 alkyl , C5-C7 cycloalkyl, C7-C16 aralkyl or C6-C10 aryl, and b) from 5 to 40 weight percent of a polycyclic aromatic compound containing at least five aromatic rings, at least one of said aromatic rings being substituted with one or more groups

Description

MODIFIERS OF GLASS GROWTH FOR PERILENE PIGMENTS BACKGROUND OF THE INVENTION This invention relates to a pigment composition comprising co-precipitated mixtures of perylene pigments and polycyclic aromatic compounds. Perylene pigments are known, for example, from the work of. Herbst and K. Hunger, Industrial Orqanic Pigments (New York: VCH Editors, Inc. 1993), pages 9 and 467-475; see also H. Zollinger, Color Chemistry (VCH Verlagsgesellschaft, 1973), pages 227-228 and 297-298, and M.A. Perkins, "Piridines and Piridones" in The Chemistry? of Synthetic Dyes and Pigments, ed. HE HAS. Lubs (Malabar, Florida: Robert E. Krieger Publishing Company, 1955), pages 481-482. Perylene pigments typically exhibit a high dye strength combined with excellent light and environmental fastness. However, improved color properties would provide technical and commercial advantages. It has now been found that mixtures of co-precipitated perylene pigment with certain polycyclic aromatic compounds, in particular certain antantrones, provide enhanced transparency and depth not found in untreated perylenes. Although conventional blends with the polycyclic aromatic pigment 4, 8-dibromoantantrone (ie, Pigment Red 168) have been described as being useful for altering the hue of the perylenenetetracarboxylic acid pigments (eg, Herbst and K. Hunger, Industrial Orqanic Piqments). (New York: VCH Editors, Inc., 1993), page 511), co-precipitated mixtures of the type described herein have not been published before.

COMPENDIUM OF THE INVENTION This invention relates to a pigment composition comprising a co-precipitated mixture consisting of: (a) about 60 to about 95 weight percent (preferably 75 to 90 weight percent) of a perylene pigment having the formula (I) where R1 and R2 are independently C1-C6 alkyl, C5-C7 cycloalkyl, C.-C16 aralkyl, or C6-C? and (b) about 5 to about 40 weight percent (preferably 10 to 25 weight percent) of a polycyclic aromatic compound, preferably a polycyclic aromatic compound selected from the group consisting of (i) an antantrone having the formula (II) wherein X1 and X2 are independently hydrogen, halogen, C1-C6 alkyl, C-C6 alkoxy, C7-C16 aralkyl, or C6-C10 aryl, (ii) a quinacridone having the formula (III) (III) wherein Y1 and Y2 are independently hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy, C7-C16 aralkyl, or C6-C10 aryl, (iii) a flavantrone having the formula (IV) where Z1 and Z2 are independently hydrogen, halogen, C1-C6 alkyl, C6-C6 alkoxy, C7-C16 aralkyl, or C6-C10 aryl, and (iv) mixtures thereof. This invention further relates to a process for preparing such pigment compositions comprising (1) acid-plating or swelling with acid of a mixture consisting of: (a) about 60 to about 95% by weight (preferably 75 to 90 percent by weight) weight percent) of a perylene pigment of formula (I), (b) about 5 to about 40 weight percent (preferably 10 to 25 weight percent) of a polycyclic aromatic compound, preferably a polycyclic aromatic compound of formula (II), formula (III), or formula (IV), or a mixture thereof, and (c) about 5 to about 25 parts by weight (preferably 9 to 15 parts by weight), with respect to the total of components (a ) and (b), of a strong acid (preferably concentrated sulfuric acid); (2) submerging the mixture of step (1) by adding said mixture to about 0.5 to about 100 parts by weight (preferably 1.5 to 5 parts by weight), for each part of said mixture, of a liquid in which the pigment is substantially insoluble (preferably water) (preferably at a temperature of about 0 to about 60 ° C), thereby precipitating the pigment composition; (2) isolation of the pigment composition; (4) optionally, conditioning the pigment composition DETAILED DESCRIPTION OF THE INVENTION Suitable perylene pigments (a) include any of the known perylene pigments within the definition of formula (I), but preferred perylenes are symmetrical compounds in which R1 and R2 are identical. Particularly preferred perylene pigments are those in which R1 and R2 are identical Cj-C8 alkyl groups, more preferably methyl groups (ie, Pigment Red 179 of the Color Index). Other suitable perylene pigments include those in which R1 and R2 are hydrogen (ie, Pigment Violet 29 of the IC), various araliphatic groups (eg Pigment Black 31 and 32 of the IC)), or various aryl groups (eg. Pigment Red 123, 149, 178 and 190 of I.C.). For example, W. Herbst and K. Hunger, Industrial Orqanic Piq ents (New York: VCH editors, Inc. 1993), p. 470-475.

Suitable polycyclic aromatic compounds (b) are fused ring aromatic systems containing at least five rings (preferably five to ten rings), at least one of which is substituted with one or more keto groups (preferably two keto groups such as characteristic of quinones or analogues and derivatives thereof). Among the examples of polycyclic aromatic compounds Suitable (b) include antantrones, quinacridones, and flavantrones. It is also possible, although much less preferred, to use mixtures of various polycyclic aromatic compounds. Preferred antantrones are compounds of formula (II) wherein X1 and X2 are independently hydrogen or halogen, particularly those in which X1 and X2 are both the same halogen, more preferably bromine (ie, 4,8-dibromo-antantrone, or Pigmento Rojo 168 of the IC, also formerly known as Bright Orange of Indanthrene RK). For example, W. Herbst and K. Hunger, Industrial Orqanic Piqments (New York: VCH Editors, Inc., 1993), pages 509-511; see also H. Zollinger, Color Chemistry (VCH Verlagsgesellschaft, 1973), page 225 and M.S. Whelen, "Anthanthrones" in The Chemistry of Synthetic Dves and Piqments, ed H.A. Lubs (Malabar, Florida: Robert E. Krieger Publishing Company, 1955), pages 444-446. The preferred quinacridones are 2,9-disubstituted quinacridones of formula (Illa) (Illa) wherein Y1 and Y2 are independently hydrogen or halogen, particularly those in which Y1 and Y2 are both the same halogen, more preferably chlorine (ie, 2,9-dichloroquinacridone). For example, W. Herbst and K. Hunger, Industrial Orqanic Piqments (New York: VCH Editors, Inc., 1993), pages 447-463; see also H. Zollinger, Color Chemistrv (VCH Verlagsgessellschaft, 1973), pages 236-240.

A preferred flavantrone is unsubstituted flavantrone of the formula (IVa) (also known as Amarillo Tina or Pigmento Amarillo 24 of the I.C.). For example, W. Herbst and K. Hunger, Industrial Orqanic Piqments (New York: VCH Editors, Inc., 1993), pages 501-503 and 504-505; see also H. Zollinger, Color Chemistry (VCH Verlagsgesellschaft, 1973), pages 237 and 296. As used herein, the term "Cj-C8 alkyl" refers to straight or branched chain aliphatic hydrocarbon groups having 1 to 2 carbon atoms. to 6 carbon atoms. Examples of C 1 -C 6 alkyl are methyl, ethyl, propyl, butyl, pentyl, hexyl, and their isomeric forms. The term "C5-C7 cycloalkyl" refers to cycloaliphatic hydrocarbon groups having from 5 to 7 carbon atoms. Examples of cycloalkyl of c5 ~ c are cyclopentyl, cyclohexyl and cycloheptyl. The term "aralkyl of C.-C" refers to C ^ Cg alkyl substituted with C6-C10 aryl of so that the total number of carbon atoms is 7 to 16. Examples of C7-C16 aralkyl are benzyl, phenethyl, and naphthylmethyl. The term "C6-C10 aryl" refers to phenyl and 1- or 2-naphthyl. As used herein, the term "aryl" also refers to alkyl substituted aryl groups, alkoxy, halogen, hydroxy, alkoxycarbonyl, aryloxycarbonyl, cyano, nitro, and other known groups. The term "C 1 -C 6 alkoxy" refers to straight or branched chain alkyloxy groups having from 1 to 6 carbon atoms. Examples of C1-C6 alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy and isomeric forms thereof. Examples of suitable halogen include fluorine, chlorine, bromine and iodine. The pigment compositions of the invention are first prepared by acid-staining or swelling with acid of a mixture of the perylene pigment of formula (I) and the polycyclic aromatic compound of formula (II) in the specified amount of a strong acid, preferably a mineral acid such as concentrated sulfuric acid (i.e., 96-98%), oleum, chlorosulfonic acid, or mixtures thereof. The term "acid swelling" is generally used to refer to a process in which an acid solution containing protonated pigment is formed, while the term "swelling with acid" generally refers to a process in which a swelling is formed. protonated pigment suspension. The process of step (1), of course, includes a continuous range from completely dissolved pigment to almost completely undissolved. However, an essentially complete solution in strong acid is generally preferred. The amount of strong acid used in step (1) is selected so as to ensure the formation of an acid solution or suspension in a reasonable period of time. Although step (1) can be carried out more rapidly by heating the acid mixture (e.g. to about 50 ° C), it is generally preferred to use temperatures of 35 ° C or below this temperature to minimize the degradation of the pigment components. Regardless of which variant is used in step (1), the strongly acidic mixture (ie, "immersed") is then precipitated in step (2) by adding the strongly acidic mixture to a liquid in which the The pigment is substantially insoluble, thus forming a co-precipitated mixture according to the invention. Submersion in water is preferred, but it is also possible to use lower aliphatic alcohols (especially methanol) or other known water miscible organic solvents, preferably in a mixture with water. Although it is possible to add the submersion liquid to the acid melt (e.g., U.S. Patent 3,265,699), the present invention is preferably carried out by addition of the acid melt to the solvent (compare U.S. Patent 4,100,162). The temperature at which the submersion is carried out is not critical, in general, although the temperature of the submersion liquid is usually between about 5 ° C and about 65 ° C. Generally, lower temperatures give pigments that have smaller particle sizes. However, since the time of the process cycle (due to manufacturing costs) is also very important, a shorter submersion time is preferable. The submerged pigment is then isolated in step (3) using methods known in the art, such as filtration, and then dried if desired. Other recovery methods known in the art, such as centrifugation or even a simple decanting, are also suitable. The resulting co-precipitated pigment compositions do not appear as solid solutions (as determined by X-ray crystallography) but instead appear in the form of crystalline or partially crystalline particles containing "domains" of the perylene pigment and aromatic compound polycyclic Although the presence of domains of solid solution in small amounts, the unique properties of the pigment compositions of the invention do not depend on these domains. The pigment obtained in step (3) can be conditioned in an optional step (4) using methods known in the art, such as solvent or mill treatment in combination with solvent treatment. The final particle size of the pigment can be controlled by varying the post-treatment method. For example, the pigments can be made more transparent by reducing the particle size or more opaque by increasing the particle size. Suitable grinding methods include dry grinding methods such as sand grinding, ball milling and the like, with and without additives, or wet grinding methods such as salt kneading, pearl grinding and the like, in water or organic solvents, with or without additives. The dyeing strength and transparency of the pigment can be affected by the solvent treatment carried out by heating a pigment dispersion frequently in the presence of additives, in a suitable solvent. Suitable solvents include organic solvents, such as alcohols, esters, ketones and aliphatic and aromatic hydrocarbons and derivatives thereof, and inorganic solvents, such as water. Suitable additives include compositions that decrease or prevent flocculation, increase the dispersion stability of the pigment and reduce the viscosity of the coating, such as polymeric dispersants (or surfactants). For example, U.S. Patents 4,455,173; 4,758,665; 4,844,742; 4,895,948; and 4,895,949. Once the pigment has been isolated and optionally conditioned, this pigment can be further mixed (preferably by dry blending) with one or more pigment derivatives known in the art. Due to its stability to light and properties of With the migration, the pigment compositions of the present invention are suitable for many different pigment applications. For example, the pigments prepared according to the invention can be used as a colorant (or as one of two or more colorants) for pigmented systems with high light fastness. Examples include mixtures pigmented with other materials, pigment formulations, paints, printing ink, colored paper, or colored macromolecular materials. The term "mixtures with other materials" is understood to include, for example, mixtures with inorganic white pigments, such as titanium dioxide (rutile) or cement, or other inorganic pigments. Examples of pigment formulations include pastes discarded with organic liquids or pastes and dispersions with water, dispersants and, if appropriate, preservatives. Examples of paints in which the pigments of this invention may be used include, for example, physical or oxidative drying lacquers, stoving enamels, reactive paints, two-component paints, solvent paints or water paints, paints of emulsion for resistant coatings to the bad weather, and paintings to the temple. Printing inks include those known for use on paper, textiles and tinplate. Suitable macromolecular substances include those of natural origin, such as rubber; those obtained by chemical modification, such as acetyl cellulose, cellulose butyrate, or viscose; or those produced synthetically, such as polymers, polyaddition products, and polycondensates. Examples of synthetically produced macromolecular substances include plastic materials, such as polyvinyl chloride, polyvinyl acetate, and polyvinyl propionate; polyolefins, such as polyethylene and polypropylene; high molecular weight polyamides; polymers and copolymers of acrylates, methacrylates, acrylonitrile, acrylamide, butadiene, or styrene; polyurethanes; and polycarbonates. These Pigmented materials with the pigment compositions of the present invention may have any molding or shape that is desired. The pigments prepared according to this invention are very resistant to water, resistant to oils, resistant to acids, resistant to lime, resistant to alkalis, resistant to solvents, stable to overcoat, stable to overcoat of spray, stable to sublimation, thermo-resistant and resistant to vulcanization, still giving a good dyeing performance and being easily dispersible. The following examples further illustrate in more detail the preparation of the compositions of this invention. The invention, which is presented in the following description is not limited in its spirit or scope by these examples. Those skilled in the art will understand that variations in the conditions and processes of the following preparative procedures can be made to prepare these compositions. Unless stated otherwise, all temperatures are in degrees Celsius and all percentages are by weight.

EXAMPLES Coloristic properties were evaluated using a water-based coating system / solvent-clear coating. Aqueous dispersions were prepared using a 12.4% mixture of acrylic resin AROLONR 559-G4-70 (Reichhold Chemicals, Inc., Research Triangle Park, North Carolina), 3.2% hyperdispersant SOLSPERSER 27000 (Zeneca, Inc. ilmington, Delaware), 1.6% 2-amino-2-methyl-1-propanol (Angus Chemical, Buffalo Grove, Illinois), and 18% pigment, which gave a pigment-to-binder ratio of 18:12 and a total solids content of 30%. The ratio of pigment to binder 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, West Patterson, New Jersey), which gave a total solids content of 50%. Mass tone and transparency measurements were made using films applied at a wet film thickness of 76 μm and 38 μm, respectively, and allowed to stand at room temperature for fifteen 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) and 20% melamine / formaldehyde resin CYMELR 325 at a total solids level of 57% on the base layer a a wet film thickness of 76 μm followed by standing at room temperature for fifteen minutes and at 121 ° C for fifteen minutes. Low-tone dye paint was prepared from the above-described reduced aqueous dispersions having a pigment-to-binder ratio of 10:40 by the addition of more acrylic resin AR0L0NR 559-G4-70, melamine / formaldehyde resin CYMELR 325, and 35% white dispersion TINT-AYDR CW-5003 (Daniel Products Company, Jersey City, New Jersey), which gave a pigment-to-binder ratio of 1: 1.1, a total solids content of 55% and a Ti02 ratio a pigment of 90:10. Color measurements were made using films applied at a wet film thickness of 38 μm and allowed to stand at room temperature for fifteen minutes and at 100 ° C for five minutes. Transparent layers were then applied and oven-dried as described above. Metal paints were prepared from the dispersion described above having a pigment to binder ratio of 18:12 using a water dispersible aluminum pigment (available as HYDRO PASTER 8726 from Silberline Manufacturing Co., Inc., Tamaqua, Pennsylvania) , AROLONR 559-G4-70 acrylic resin, and CYMELR 325 melamine / formaldehyde resin in amounts that provided a pigment-to-binder ratio of 1: 2, an aluminum to pigment ratio of :80, and a total solids content of 43%. Color measurements were made using films applied at 38 μm wet film thickness and oven dried as described above. Transparent layers were then applied and oven dried as described above. Differences in tonality and chromaticity of the bulk tone, subtone and metallic paints were measured using a Chroma Sensor CS-5 (Datacolor International, Lawrenceville, New Jersey).

EXAMPLE 1 Example 1 illustrates the preparation of a pigment composition of the invention containing 80% by weight of a perylene pigment and 20% by weight of an antantrone pigment. To 604 g of approximately 99% sulfuric acid (prepared from a mixture of 551 g of 98% commercial sulfuric acid and 100 g of 20% oleum) at 25-30 ° C, 8 g of 4, 8-dibromoantantrone (Pigment red 168 from IC, available as RK Brilliant Orange from Casella AG, Frankfurt, Germany) followed by 32 g of N, N-dimethylperilendiimide (Pigment Red 179 of IC, prepared as described in the patent) American 3,331,847). The mixture was stirred at 25-30 ° C for 17 to 18 hours, then poured into one liter of water at 5-10 ° C, maintaining the temperature at 5-10 ° C with the periodic addition of ice. The mixture was heated to 90 ° C, then maintained at 90-95 ° C for one hour. The resulting precipitate was collected by filtration, washed with water, resuspended in 800 ml of water at a pH of 5.0-6.0, and heated to 80 ° C. The slurry was stirred rapidly for five minutes at 80 ° C with a dispersant mixture containing 1.6 g of SOLSPERSER 24000 (available from Zeneca, Inc. Wilmington, Delaware), 0.5 g of a nonionic surfactant having a HLB equilibrium value of 14 to 15, 0.6 g of glacial acetic acid, and 5.0 g of water and then for an additional fifteen minutes at 80-85 ° C with a mixture of 3.2 g of a 50% aqueous solution of the dehydroabietylamine acetate salt, and 10 ml of water. The pH of the resulting mixture was adjusted to about 8.0 - 8.5 and stirred at 80-85 ° C for 2 hours. The solid component was recovered by filtration, washed with water, and dried in an oven at 60 ° C to give 41.8 g of a pigment composition having a clear, deep red color. The test results are given in Table 1.

EXAMPLE 2 Example 2 illustrates a preparation of a pigment composition containing 75% by weight of a perylene pigment and 25% by weight of an antantrone pigment. To 99% sulfuric acid (prepared from a mixture of 1269 g of 98% commercial sulfuric acid and 231 g of 20% oleum) at 25-30 ° C was added 25 g of 4,8-dibromoanthrinone followed by 75 g of N, N-dimethylperilendiimide. The mixture was stirred at 25-30 ° C for 17 to 18 hours, then poured into 2.5 liters of water at 5-10 ° C, the temperature being maintained at 5-10 ° C for about an hour by periodic addition of ice. The mixture was heated to 80 ° C, then maintained at 80-90 ° C for one hour. The resulting precipitate was collected by filtration, washed with water, resuspended in two. liters of water at a pH of 8-9, and heated to 50 ° C. The slurry was stirred rapidly for fifteen minutes with an emulsion mixture containing 30 g of petroleum distillate, 1.0 g of an anionic sulfosuccinate surfactant, and 100 g of water. The pH was adjusted to about 3.0-3.5 with dilute aqueous sulfuric acid and stirred at 50 ° C for four hours. A mixture of 16 g of a 50% aqueous solution of the dehydroabietylamine acetate salt and 100 ml of water was added, and the resulting mixture was stirred at about 50 ° C for fifteen minutes. After adjusting the pH to about 8.5-9.5, the mixture was stirred at about 50 ° C for one hour. The solid component was collected by filtration, washed with water, dried at 60 ° C, triturated and sieved through 80 mesh screen to give 106.5 g of a pigment composition having a dark red color. . The results of the test are shown in Table 1.

EXAMPLE 3 (comparison) Example 3 illustrates the preparation of a comparison perylene pigment that does not contain antantrone pigment. The resulting pigment was used as a standard for the pigments of Examples 1 and 2 (see Table 1) and a direct comparison for Examples 4-6 (see Table 2). To 440 g of 98% commercial sulfuric acid was added 40 g of N, N-dimethylperilendiimide. The mixture was heated to 40 ° C, maintained at 40-45 ° C for four hours, stirred at room temperature for 12 to 14 hours, and then poured into 800 ml of water at 5-10 ° C, maintaining the temperature at 5-10ßC by periodic addition of ice. The mixture was then stirred for approximately thirty minutes at 5-15 ° C, heated to 60 ° C, and stirred for an additional thirty minutes. The resulting precipitate was collected by filtration, washed with water, resuspended in 400 ml of water at a pH of 6.5-7.5. The slurry was then stirred rapidly at room temperature for fifteen minutes with an emulsion mixture containing 12.0 g of petroleum distillate, 0.4 g of anionic sulfosuccinate surfactant, and 40 g of water, then subjected to 110 ° C in autoclave for two hours. The autoclave mixture was poured into 800 ml of water at a pH of 4-5. A mixture of 6.4 g of a 50% aqueous solution of the dehydroabietylamine acetate salt and 20 ml of water was added, and the resulting mixture was stirred at 80 ° C for fifteen minutes. After adjusting the pH to about 8.5-9.0, the mixture was stirred at 80-85 ° C for one hour, then cooled to a temperature of less than 70 ° by the addition of water. The solid component was collected by filtration, washed with water, and dried 60 ° C to give 40.3 g of a pigment having lower color properties when compared to pigment compositions prepared according to the invention.

TABLE 1 Color Properties ^ for Examples 1 and 2 (1) The color properties are with respect to the comparison pigment of Example 3 EXAMPLES 4-6 Examples 4-6 of the invention were carried out following the method of Comparative Example 3 except for the use of mixtures of N, N-dimethylperilendiimide and 4,8-dibromoanthrone in the amounts shown in Table 2 The test results (in relation to the comparison pigment of Example 3) are also shown in Table 2.

EXAMPLE 7 (comparison) 10 Example 7 illustrates the preparation of a comparative dry mixed composition containing 80% by weight of a perylene pigment and 20% by weight of an antantrone pigment.

The procedure of Example 3 was repeated except that 4, 8-dibromoantantrone was used in place of N, N-dimethylperilendiimide. A 1.8 g portion of the resulting orange pigment was mixed dry with 16.2 g of perylene pigment from Comparative Example 3. The resulting dry mixture exhibited inferior color properties when compared to pigment compositions prepared according to Examples 4-6 of the invention. The test results are shown in Table 2. TABLE 2 Quantities and color properties ^ for Examples 4-7 Cantj .dades Color properties (1) Example Perylene Antantrone Tone TransSubSub% massive parentono tone inten¬ ? C (C? C? C? Sity? A) tone (made massive subtone 4 38 g 95% g 5% -0.01 equal 0.63 0.81 102.11 36 g 90% 4 g 10% -2.46 higher 0.90 2.23 111.33 6 32 g 80% 8 g 20% -2.17 greater 1.43 3.17 106.27 7 (comp) 16, 2g 90% l, 8g 10% 0.99 equal 0.19 0.87 96.23 (i) The color properties are with respect to the comparison pigment of Example 3 EXAMPLE 8 Example 8 illustrates the preparation of a pigment composition of the invention containing 90% by weight of a perylene pigment and 10% by weight of a quinacridone pigment. To 440 g of 98% commercial sulfuric acid was added 36 g of N, N-dimethylperilendiimide. The mixture was heated to 40 ° C, maintained at 40-45 ° C for four hours and stirred at room temperature for 12 to 14 hours.To this mixture was added 4 g of a crude dichloroquinacridone prepared according to the method described in US Pat. No. 3,257,405 The resulting mixture was stirred at room temperature for one hour and then poured into 900 ml of water at 5-10 ° C., maintaining the temperature by periodic addition of ice. The mixture was then stirred for about thirty minutes at 5-10 ° C, heated to 60 ° C, and stirred for an additional thirty minutes. The resulting precipitate was collected by filtration, washed with water, resuspended in 450 ml of water at a pH of 6.5-7.5. The slurry was stirred rapidly at room temperature for fifteen minutes with an emulsion mixture containing 12.0 g of petroleum distillate, 0.4 g of an anionic sulfosuccinate surfactant, and 20 g of water, then autoclaved. at 110-115 ° C for two hours. The autoclave mixture was poured into 800 ml of water at a pH of less than 6. A mixture of 4.8 g of a 50% aqueous solution of the dehydroabietylamine acetate salt and 20 ml of water was added, and the mixture The resulting mixture was stirred at 80-85 ° C for fifteen minutes, then the pH was adjusted to approximately 9.0-9.5, the mixture was stirred at 80-85 ° C for an additional fifteen minutes, then cooled to a temperature of less than 70 ° C by addition of water The solid component was collected by filtration, washed with water and dried at 60 ° C to give an intense red pigment.The test results are shown in Table 3.

EXAMPLE 9 Example 9 illustrates the preparation of a pigment composition of the invention containing 90% by weight of a perylene pigment and 10% by weight of a flavantrone pigment. To 500 g of 98% commercial sulfuric acid was added 5 g of flavantrone (available as Tina Yellow 1 from I.C., from Aceto Chemicals) followed by 45 g of N, N-dimethylperilendiimide. The mixture was heated to 40 ° C, kept at 40-45 ° C for four hours, stirred at room temperature for 12-14 hours, and then added dropwise to one liter of water at 5-10 ° C. the temperature was maintained by periodic addition of ice, the mixture was then stirred for thirty minutes at 5-15 ° C, heated to 60 ° C, and stirred for an additional thirty minutes.The resulting precipitate was collected by filtration, washed with water, and divided into two equal portions, each of which was resuspended in 500 ml of water. (A) One of the portions of the resulting slurry was adjusted to pH 11.0-11.5, it was heated to 45 ° C and stirred at 45-50 ° C for two hours with an emulsion mixture containing 7.5 g of petroleum distillate, 0.1 g of an anionic sulfosuccinate surfactant and 10 g of water. After adjusting the pH to 4.0-5.0, a mixture of 4.0 g of a 50% aqueous solution of the dehydroacetate salt was added. bethylamine and 10 ml of water and the resulting mixture was stirred at 45-50 ° C for 30 minutes. Once the pH had been adjusted to 8.5-9.0, the mixture was stirred at 45-50 ° C for an additional fifteen minutes. The solid component was collected by filtration, washed with water, and dried at 60 ° C to give 24.4 g of a yellowish red pigment. The results of the test are given in Table 3.

(B) The second portion of the slurry described above was adjusted to pH 11.5-12.0, after which 25 g of a commercial sodium hypochlorite solution was added. The resulting mixture was stirred at 90 ° C for one hour, then cooled to 45 ° C and stirred at 45-50 ° C for two hours with an emulsion mixture containing 7.5 g of petroleum distillate, 0, 1 g of an anionic sulfosuccinate surfactant and 10 g of water.

After adjusting the pH to 4.0-5.0, a mixture of 4.0 g of a 50% aqueous solution of the dehydroabietylamine acetate salt and 10 ml of water was added and the resulting mixture was stirred at 45.degree. 50ßC for thirty minutes. After adjusting the pH to 8.5-9.0, the mixture was stirred at 45-50 ° C for fifteen minutes. The solid component was collected by filtration, washed with water and dried at 60 ° C to give 22.8 g of a yellowish red pigment. The test results are shown in Table 3.

TABLE 3 Color Properties ^ for Examples 8 and 9 (1) The color properties are in relation to the comparison pigment of Example 3

Claims (14)

1. CLAIMS 1. A pigment composition comprising a co-precipitated mixture consisting of (a) 60 to 95 weight percent of a perylene pigment having the formula wherein R 1 and R 2 are independently C 1 -C 6 alkyl, C 5 -C 7 cycloalkyl, C 7 -C 16 aralkyl, or C 6 -C 0 aryl; and (b) 5 to 40 weight percent of a polycyclic aromatic compound.
2. 2. A pigment composition according to claim 1 wherein the polycyclic aromatic compound is (i) an antantrone having the formula wherein X1 and X2 are independently hydrogen, halogen, C6-C6 alkyl, C6-C6-aralkyl, C7-C1g alkoxy, or C6-Cl-aryl? (ii) a quinacridone that has the formula wherein Y1 and Y2 are independently hydrogen, halogen, Cj-C8 alkyl, C ^ Cg alkoxy, C7-C16 aralkyl, or C6-C10 aryl, (ii) a flavantrone having the formula wherein Z1 and Z2 are independently hydrogen, halogen, C1-C6 alkyl, Cj-C8 alkoxy, C7-C16 aralkyl, or C6-C10 aryl
3. 3. A pigment composition according to claim 1 wherein the co-precipitated mixture it comprises 75 to 90 weight percent perylene pigment (a) and 10 to 25 weight percent aromatic polycyclic compound (b).
4. 4. A pigment composition according to claim 1 wherein the polycyclic aromatic compound is an antantrone having the formula where X1 and X2 are, independently, hydrogen or halogen.
5. 5. A pigment composition according to claim 1 wherein the polycyclic aromatic compound is 4,8-dibromoantantrone.
6. 6. A pigment composition according to claim 1 wherein the polycyclic aromatic compound is a 2,9-disubstituted quinacridone having the formula where Y1 and Y2 are independently hydrogen or halogen.
7. 7. A composition according to claim 1 wherein the polycyclic aromatic compound is 2,9-dichloroquinacridone.
8. 8. A pigment composition according to claim 1 wherein the polycyclic aromatic compound is unsubstituted flavantrone having the formula
9. 9. A process for preparing a pigment composition according to claim 1 comprising (1) acid-swelling or swelling with acid a mixture comprising (a) 60 to 95 percent of a perylene pigment having the formula wherein R 1 and R 2 are independently C 1 -C 8 alkyl, C 5 -C 7 cycloalkyl, C 7 -C 16 aralkyl, or C 1 -C 10 aryl; and (b) 5 to 40 weight percent of a polycyclic aromatic compound; and (c) 5 to 25 parts by weight, relative to the total of components (a) (b), of a strong acid; (2) submerging the mixture of step (1) by adding said mixture to about 0.5 to about 100 parts by weight for each part of said mixture, of a liquid in which the pigment is substantially insoluble, with what precipitates the pigment composition; (3) isolation of the pigment composition; (4) optionally, conditioning the pigment composition.
10. 10. A process according to claim 9 wherein the polycyclic aromatic compound is (i) an antantrone having the formula where X1 and X2 are independently hydrogen, halogen, C 1 -C 8 alkyl, C 1 Cg alkoxy, C 7 -C 16 aralkyl, or C 6 -C 10 aryl, (ii) a quinacridone having the formula wherein Y1 and Y2 are independently hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy, C7-C16 aralkyl, or C6-C10 aryl, or (iü) a flavantrone having the formula wherein Z1 and Z2 are independently hydrogen, halogen, C1-C6 alkyl, C1-C6 alkoxy, C7-C16 aralkyl, or C6-C10 aryl.
11. 11. A process according to claim 9 wherein the mixture used in step (1) comprises 75 to 90 weight percent perylene pigment (a) and 10 to 25 weight percent polycyclic aromatic compound (b).
12. 12. A process according to claim 9 wherein the strong acid used in step (1) is concentrated sulfuric acid, oleum, or a mixture thereof.
13. 13. A process according to claim 9 wherein in step (1) 9 to 15 parts by weight, based on the total of components (a) and (b), of a strong acid are used.
14. 14. A process according to step 9 wherein the liquid used in the submersion step (2) is water.