Perylene-3, 4, 9, 10-tetracarboxylic acid N, N'-bis-methylimide of the formula has been known as a pigment for many years. The pigment is manufactured by reacting perylene-3, 4,9, 1 0-tetracarboxylic acid dianhydride with methylamine (method 1, see for example US-4, 153,602) ; by methylating perylene-3, 4,9, 10- tetracarboxylic acid diimide in the presence of an alkali, for example with methyl chloride (see GB-923,721) or dimethyl sulfate or carbonate (method 2); or by fusing naphthalic acid N-methylimide with an alkali metal hydroxide (method 3, see ,, DE-276, 357).

Depending on the process of manufacture, the crude pigments give pigmentary forms that produce red or dull reddish brown hues.

According to US-4,189, 582, the disclosure of which is incorporated by reference, red pigments of perylene-3, 4,9, 10-tetracarboxylic acid N, N'-bis-methylimide are only obtained when the pigment has been manufactured by method 1. In contrast, methods 2 and 3 always give dull reddish brown products which even after comminution and finishing, for example by the processes described in DE-1,272, 270 (= GB 923,721), give only dull reddish brown pigments.

Now, surprisingly, it has been found that comminution of a mixture comprising perylene-3, 4,9, 10-tetracarboxylicacid N, N'-bis-methylimide produced by methylation of perylenetetracarboxylic imide with an alkylating agent (above

method 2) and perylene-3, 4,9, 10-tetracarboxylic acid N, N'-bis-methylimide produced by the condensation of perylenetetracarboxylic anhydride with methyl- amine (above method 1), in the presence of dimerized rosin, produces a tinctorially valuable pigmentary form of perylene-3, 4,9, 10-tetracarboxylic acid N, N'-bis-methyl- imide having a transparent clean yellowish shade of said red perylene pigment.

Hence, one aspect of the present invention is a process for the manufacture of a pigmentary form of perylene-3, 4,9, 10-tetracarboxylic acid N, N'-bis-methylimide having a transparent clean yellowish shade, which comprises comminution of a mixture comprising perylene-3, 4,9, 10-tetracarboxylic acid N, N'-bis-methylimide produced by methylation of perylenetetracarboxylic imide with an alkylating agent (method 2) and perylene-3, 4,9, 10-tetracarboxylic acid N, N'-bis-methylimide produced by the condensation of perylenetetracarboxylic anhydride with methylamine, (method 1), in the presence of dimerized rosin.

Another aspect of the present invention is a pigmentary form of perylene-3, 4,9, 10- tetracarboxylic acid N, N'-bis-methylimide having a transparent clean yellowish shade, which is produced by a process which comprises comminution of a mixture comprising perylene-3, 4,9, 10-tetracarboxylic acid N, N'-bis-methylimide produced by methylation of perylenetetracarboxylic imide with an alkylating agent (method 2) and perylene-3, 4,9, 10-tetracarboxylic acid N, N'-bis-methylimide produced by the condensation of perylenetetracarboxylic anhydride with methylamine (method 1), in the presence of dimerized rosin.

Comminution of a mixture comprising perylene-3, 4,9, 10-tetracarboxylic acid N, N'- bis-methylimide produced by methods 1 and 2 in the presence of dimerized rosin can be carried out by a variety of techniques which are known in the pigments art, for example by wet milling and by salt attrition. Conveniently pigment crudes are employed. Wet milling of perylene is described in US-6,154, 361.

The ratio of perylene-3, 4,9, 10-tetracarboxylic acid N, N'-bis-methylimide produced by method 1 to that produced by method 2 can vary considerably. Preferred ratios are 35-90 parts by weight of perylene-3, 4,9, 10-tetracarboxylic acid N, N'-bis-methyl-

imide produced by method 1 to 65-10 parts by weight of perylene-3, 4,9, 10-tetra- carboxylic acid N, N'-bis-methylimide produced by method 2, in particular 40-70 parts produced by method 1 to 60-30 parts produced by method 2 and especially 45-60 parts produced by method 1 to 55-40 parts produced by method 2.

In one preferred embodiment, comminution of the mixture is carried out by salt attrition. Salt attrition of perylene-3, 4,9, 10-tetracarboxylic acid N, N'-bis-methylimide is known for example from US-5,145, 964 and US-6,235, 099.

According to the present invention, suitably 2 to 15 parts of salt, conveniently 6 to 12 parts of salt, in particular 8 to 10 parts of salt, by weight per part of the pigment mixture, are employed for the salt attrition. The salt should be sufficiently soluble (for example in water) so that it can be removed from the final pigment by washing with a reasonable amount of water or other solvent. Salts suitable for use in this invention include, for example, sodium chloride, calcium chloride, sodium sulfate, sodium formate, sodium acetate or any other organic or inorganic salt with or without crystal water, in particular alkali and earth alkali salts. The preferred grinding auxiliaries are sodium chloride, sodium formate and sodium acetate.

Additionally the attrition mixture advantageously contains from 1 to 2 parts by weight of a water-soluble alcohol such as a lower (Ci-Ce) alcohol, ethylene or propylene glycol, diethyleneglycol or, preferably, glycerin, plus a small amount of a base, for example 0.005 to 0.05 parts, especially 0.01 to 0.04 parts by weight of a base such as an alkali metal hydroxide, for example sodium or potassium hydroxide, per part of the pigment mixture.

The attrition mixture additionally contains from 0.02 to 0.4 parts by weight of dimerized rosin, in particular 0.06 to 0.25 parts and especially 0.1 to 0.2 parts by weight per part of the pigment mixture.

Surprisingly, the inclusion of dimerized rosin during the attrition process not only affords a Pigment Red 179 product with superior transparency and color properties but also with superior rheological properties in solvent borne OEM paints.

Typically the comminution of the mixture is carried out for 3 to 18 hours, in particular for 5 to 16 hours and especially for 8 to 12 hours. The temperature rises as the attrition proceeds, typically eventually reaching a range of about 88 to 105°C after several hours. Temperatures above about 110°C are preferably avoided.

After completion of the attrition, the mixture is for example drowned into water to dissolve the salt and alcohol, isolated by filtration, washed with water, suspended in water and acidified to a pH of less than 1.0 with 35-36% HCI, recovered by filtration, washed with water, dispersed in deionized water to afford a suspension, typically about a 15 g/100 ml suspension, and spray dried to afford a dry finished product. This product can then be blended by micropulverizing using conventional equipment, for example a hammer mill.

Analysis indicates that the dimer rosin is substantially retained in the product.

The pigments obtainable in accordance with the present invention are notable for their outstanding coloristic and rheological properties, especially for outstanding rheology, high flocculation stability, high transparency, ease of dispersion, good gloss properties, high color strength, excellent solvent fastness and fastness to overcoating, as well as very good weather fastness. They are suitable for use in both solventbome and aqueous systems.

Thus another aspect of the present invention is a perylene-3, 4,9, 1 0-tetracarboxylic acid N, N'-bis-methylimide pigment having a transparent clean yellowish shade, , which is produced by a process which comprises comminution of a mixture comprising perylene-3, 4,9, 10-tetracarboxylic acid N, N'-bis-methylimide produced by methylation of perylenetetracarboxylic imide with an alkylating agent (method 2) and perylene-3, 4,9, 10-tetracarboxylicacid N, N'-bis-methylimide produced by the condensation of perylenetetracarboxylic anhydride with methylamine (method 1), in the presence of dimerized rosin.

Preferably said pigment is produced by a process which comprises comminution of a mixture comprising 65-10 parts by weight of perylene-3, 4,9, 10-tetracarboxylic

acid N, N'-bis-methylimide produced by methylation of perylenetetracarboxylic imide with an alkylating agent (method 2) and 35-90 parts by weight of perylene-3, 4,9, 10- tetracarboxylic acid N, N'-bis-methylimide produced by the condensation of perylenetetracarboxylic anhydride with methylamine (method 1), in the presence of from 0.02 to 0.4 parts by weight of dimerized rosin.

The inventive perylene pigment is particularly suitable for preparing coatings conventionally employed in the automobile industry, especially in acrylic/melamine resin, alkyd/melamine resin or thermoplastic acrylic resin systems, as well as in aqueous based coating systems.

When applied in solvent borne paints, the product of the above invention affords a very transparent coating that exhibits an attractive clean yellow shade of red compared to most other Pigment Red 179 products. In addition, it readily disperses into the currently preferred OEM paint systems due to its superior rheological properties. As a consequence, paint dispersions with higher pigment loadings can be produced, thus providing extra value in use for the customer.

The inventive pigment shows excellent pigment properties and may be applied alone or in the presence of other pigments or dyes in multicoat, such as basecoaUclearcoat, as well as monocoat automotive or industrial paint and ink systems.

High molecular weight organic materials that are used in heat-curable coatings or cross-linked, chemically-reactive coatings, may also be colored with the inventive pigment. The pigmented, high molecular weight organic materials prepared according to the present invention are especially useful in stoving finishes which contain customary binders and which are reactive at high temperature. These stoving finishes can be obtained from solvent or aqueous or powder paint systems known in the art. Examples of pigmented, high molecular weight organic materials which are used in coatings include acrylic, alkyd, epoxy, phenolic, melamine, urea, polyester, polyurethane, blocked isocyanate, benzoguanamine or cellulose ester resins, or combinations thereof. The pigmented, high molecular weight organic

materials prepared according to the present invention are also useful as air-drying or physically-drying coatings.

The perylene compounds of the invention are also suitable as colorants in powders and powder coating materials, especially in triboelectrically or electrokinetically sprayable powder coating materials which are used to coat the surfaces of articles made, for example, of metal, wood, plastic, glass, ceramic, concrete, textile material, paper or rubber (J. F. Hughes,"Electrostatics Powder Coating"Research Studies, John Wiley & Sons, 1984).

Typical powder coating resins employed are epoxy resins, carboxyl-and hydroxyl- containing polyester resins, polyurethane resins and acrylic resins, together with customary hardeners. Combinations of resins are also used. For example, epoxy resins are frequently employed in combination with carboxyl-and hydroxyl- containing polyester resins. Typical hardener components (depending on the resin system) are, for example, acid anhydrides, imidazoles and also dicyandiamide and its derivatives, blocked isocyanates, bisacylurethanes, phenolic and melamine resins, triglycidyl isocyanurates, oxazoline and dicarboxylic acids.

. p,., The pigments prepared in accordance with the invention can be used for pigmen- ting (coloring in the mass) organic materials of natural or synthetic origin, generally with a high molecular weight, preferably in the range from 103 to 10$ g/mol.

Examples of high molecular weight organic materials which can be pigmented with said pigments are cellulose ethers and cellulose esters, such as ethylcellulose, nitrocellulose, cellulose acetate or cellulose butyrate, natural resins and synthetic resins, such as addition-polymerization resins or condensation resins, examples being amino resins, especially urea-formaldehyde and melamine-formaldehyde resins, alkyd resins, acrylic resins, phenolic resins, polycarbonates, polyolefins, such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylo- nitrile, polyacrylates, polyamides, polyurethanes or polyesters, rubber, casein, silicone and silicone resins, individually or in mixtures.

Thus, the present invention relates to a method of coloring a high molecular weight organic material which comprises incorporating an effective pigmenting amount of the inventive perylene pigment into the high molecular weight organic material and to a composition comprising a high molecular weight organic material and an effective pigmenting amount of the inventive perylene pigment.

An effective pigmenting amount is any amount suitable to provide the desired color in the high molecular weight organic material. In particular, the inventive pigment is used in an amount of 0.01 to 30% by weight, preferably 0.1 to 10% by weight, based on the weight of the high molecular weight organic materiat to be pigmented.

The pigment concentration can also be higher and reach for example up to 70% by weight in masterbatches.

It is irrelevant whether the high molecular weight organic compounds referred to are in the form of plastic masses, melts, spinning solutions, varnishes, paints or printing inks.

The perylene pigments according to the invention are suitable as colorants in electrophotographic toners and developers, such as one-or two-component powder toners (also called one-or two-component developers), magnetic toners, liquid toners, polymerization toners and specialty toners.

Typical toner binders are addition polymerization, polyaddition and polyconden- sation resins, such as styrene, styrene-acrylate, styrene-butadiene, acrylate, polyester and phenol-epoxy resins, polysulfones, polyurethanes, individually or in combination, and also polyethylene and polypropylene, which may include further constituents, such as charge control agents, waxes or flow assistants, or may be modified subsequently with these additives.

Furthermore, the perylene according to the invention are suitable for use as colorants in inkjet inks on either an aqueous or nonaqueous basis and in those inks which operate in accordance with the hotmelt technique.

The following examples describe certain embodiments of this invention, but the invention is not limited thereto. It should be understood that numerous changes to the disclosed embodiments can be made in accordance with the disclosure herein without departing from the spirit or scope of the invention. These examples are therefore not meant to limit the scope of the invention. Rather, the scope of the invention is to be determined only by the appended claims and their equivalents. In these examples all parts given are by weight unless otherwise indicated.

Example 1: An attrition mixture is prepared comprising the following proportions of the following components: Parts w/w Crude # 1 + Crude # 2: (0.50 + 0.50) 1.00 Polypale dimerized rosin 0.15 Potassium hydroxide 0.02 Glycerol 1.64 Sodium chloride 9.0 », N Crude #1 is perylene-3, 4,9, 1 0-tetracarboxylic acid N, N'-bis-methylimide produced by the condensation of perylenetetracarboxylic anhydride (PTCA) with methylamine (described above as method 1) and Crude #2 is perylene-3, 4,9, 1 0-tetracarboxylic acid N, N'-bis-methylimide produced by methylation of perylenetetracarboxylic imide (PTCI) with an alkylating agent (described above as method 2). Polypale dimerized rosin is a product of Eastman Chemical Company.

The attrition is performed in a laboratory mix-muller or kneader at 80-90°C for 5 hours. At the completion of the attrition the mixture is drowned into water at 95- 100°C with efficient agitation to dissolve the salt and glycerol. After 6 hours the product is recovered by filtration. The filtercake is washed with water until the conductivity of the effluent is equivalent to that of the wash water. The washed filtercake is suspended in water at ambient temperature and a solution of HCI (35-36%) is added until the mixture has a pH <1.0. After agitating the mixture for

2 hours the product is recovered by filtration. The filtercake is washed with water until the effluent pH and conductivity values are equivalent to those of the wash water.

The washed filtercake is then dispersed in deionized water to afford a suspension with a concentration of 15% (w/v). The latter is now pumped through a spray dryer to afford a dry finished product. Analysis indicates that the dimer rosin is substantially retained in the product.

Example 2 : Various pigments are prepared analogously to Example 1. After micropulverizing in a hammer mill or similar apparatus, the pigment powders are incorporated into standard tinted paint formulations and applied to panels. The results are shown below.

Transparency Ratio (TR) relative to standard in masstone; tint strength and color values compared to standard 1 in tinted paint Example Attritionconditions Transp. Ratio 2 Tinl TintA'Tint/\Bt # AE*Sp,/DE*sta 50 : 50 #1 : #2, 5. 0 h, 1 glycerol/2% KOH, 0. 91 107. 00 0. 62-0. 77 15% PP3. crude #2, 2. 5 h, 1. 16 88. 89-1. 78-1. 12 glycerol/2% KOH. 3 I crude #1, 2. 5 h, 2. 21 79. 93 1. 52-0. 93 glycerol/2% KOH : 40 : 60 #1 : #2, 2. 5h, 1. 23 89. 43-0. 73-0. 60 glycerol/2% KOH. 40 : 60 #1 : #2, 2. 5 h, 5 glycerol/2% KOH, 0. 92 95. 70-0. 89 0. 12 10% PP3. 50 : 50 #1 : #2, 5. 0 h, 6 glycerol/2% KOH, 0. 95 99. 83 0. 44-1. 66 10% PP3.

Paliogene Red L 3875, a commercially available Pigment Red 179 from BASF.

2 The product is more transparent than standard when TR < 1. 0, more opaque when TR > 1.0 3 PP = Polypale dimerized rosin, a product of Eastman Chemical Company.

As can be seen from the table, the best combination of Transparency Ratio (TR) relative to standard in masstone; and tint strength and color values is obtained with the product of Example 1. The products of examples 1,5 and 6 have surprisingly better transparency and higher tinting strength than those of examples 2,3 and 4.