SILANE QUINACRIDONE DYES, COMPOSITE PIGMENTS OBTAINABLE THEREFROM, AND PROCESSES FOR PREPARING THE SAME

Abstract: There are described silane quinacridone dyes, compo­ site pigments obtainable therefrom by grafting onto an inorganic substrate or support, and processes for preparing the same. The dyes have the general formula: wherein X is an -SO₂NHR group, where R is an alkyl group, linear or branched, having from 1 to 6 carbon atoms, a cycloalkyl group, or a phenyl optionally substituted by one or more halogens or alkyl or alkoxy groups having from 1 to 6 carbon atoms; Y and Z indicate a silane group having the formula: wherein R₁ is an alkoxy group (C₁-C₂); R₂ is an alkyl group (C₁-C₄) or a phenyl group; n is 3, 4 or 5; q is 0 or 1; p and m are integers such that when q is 1, p is 2 and m is 0, 1 or 2 and when q is 0, p is 3 and m is 0, 1, 2 or 3; W indicates an -SO₃H group; a, b and c are 0 or 1, selected such that the sum a + b + c is equal to 1. The composite pigments obtained from said dyes are used in paints, air enamels and stove enamels, in the pigmentation of plastics and in printing inks.

Description: The present invention relates to quinacridone dyes containing, in chemical combination, at least one silane group, to the corresponding composite pigments obtainable therefrom by association with a solid inorganic substrate or support, and to processes for preparing such silane quinacridone dyes and corresponding composite pigments. Whenever used in the following description, the term "composite pigment" means a pigmentary material comprising a quinacridone dye containing at least one silane group, associated with an inorganic solid substrate or support. The association of the quinacridone dye containing at least one silane group, or, briefly, silane quinacridone dye, with the solid substrate or support, impacts a pigmentary nature to the dye. Such association is obtained by the formation of chemical bonds (grafting) between the silane portion of the dye and the inorganic substrate or support. Composite pigments are already known from GB-A- 2 113 704. According to this reference a pigment is obtained by grafting, onto an inorganic pigment, a quinophthalonic-silanic dye which does not exhibit, per se , any pigmentary characteristic. The pigmentary features of the composite product are entirely bound to the inorganic component, which becomes coloured or dyed because of the properties of the used silanic "dye". The document JP-A- 82,73029 disclosed a composite pigment where a quinacridonic component is coupled to an inorganic inert support (e.g. silica); silanes are used as "coupling agents." This prior art composite pigment is in fact a purely physical mixture, characterized by the absence of any chemical bond of the quinacridone either with silica or with the silanic agent, which merely affects, as is known, the silica particles, thus supplying same silica with physical compatibility with respect to the organic component, namely to (not-modified) quinacridones. An aim of the present invention is to provide silane quinacridone dyes, insoluble in water, capable of providing composite pigments having high pigmentary properties. Further aims of the invention are the preparation of the above said dyes and pigments by simple and economic methods. The present invention in one aspect provides quinacridone dyes containing at least one silane group having the formula: wherein X is an SO₂ NHR group, where R is an alkyl group, linear or branched, having from 1 to 6 carbon atoms, a cycloalkyl group, a phenyl group optionally substituted by one or more halogens or alkyl or alkoxy groups having from 1 to 6 carbon atoms; Y and Z indicate a silane group having the formula where R₁ is an alkoxy group having 1 or 2 carbon atoms; R₂ is an alkyl group having from 1 to 4 carbon atoms, or a phenyl group; n is 3, 4 or 5; q is 0 or 1; p and m are integers such that when q is 1, p is 2 and m is 0, 1 or 2 and when q is 0, p is 3 and m is 0, 1, 2 or 3; W is an -SO₃H group; a,b and c are 0 or 1, selected such that the sum a + b + c is equal to 1. Such compounds according to the invention may be prepared, according to another aspect of the invention, by a process comprising reacting a quinacridone sulphochloride having the formula: with a silane compound having the formula wherein R₁, R₂, m, n, p and q are as defined above, in a molar ratio of silane compound (III): sulphochloride (II) of at least 1, and optionally with a compound having the formula: H₂N - R (IV) wherein R is as defined above, utilizing at least one mole of silane compound (III) and at least one mole of amine (IV) for each mole of sulphochloride (II), in a reaction medium comprising water and/or an organic solvent, at a temperature from 5°C to the reflux temperature of the reaction medium, for 1 to 12 hours. In practice, when it is desired to obtain essentially the dyes of formula (I) wherein b is 1, a molar ratio of silane compound (III): sulphochloride (II) of at least 2 must be used; when it is desired to obtain the dyes of formula (I) wherein c is 1, a substantially equimolar ratio of compound (III): sulphochloride (II) is used; when it is desired to obtain the dyes of formula (I) wherein a is 1, substantially equimolar ratios of the compounds (III): (II): (IV) are used. The reaction can be optionally conducted in the presence of a hydrochloric acid-acceptor compound such as Na₂CO₃, NaHCO₃, triethylamine or pyridine. The reaction can be carried out in aqueous suspension, in organic solvents or in mixtures of water and organic solvents miscible with water. As water miscible organic solvents there may be utilized, for example, dimethylformamide, dioxane, acetonitrile, pyridine, and triethylamine, and as water-immiscible solvents there may be utilized, for example, xylene, nitrobenzene, and dichlorobenzene. The quinacridone sulphochloride having the formula (II) can be prepared according to essentially conventional methods, for example by treating quinacridone with chlorosulphonic acid at a temperature from 5°C to 120°C for 1 to 4 hours. Silane compounds of formula (III), which have proved to be particularly suitable, are those derived from amino-alkoxy-silanes, such as, for example, γ-aminopropyl-triethoxysilane, δ-aminobutyl-triethoxysilane, δ-aminobutyl-phenyl-diethoxysilane, and γ-aminopropyl-methyl-diethoxysilane. Such amino-alkoxy silanes are known compounds which are commercially available. However, they can be prepared. according to conventional techniques, for example by reacting the correspondent chloro-alkoxy-silanes with aliphatic amines. The amines of formula (IV) which can be used are for example methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine and their branched isomers, aniline, cyclohexylamine, ortho-, meta- and para- toluidines, anisidines or chloro-anilines, 2,4 and 3,5-xylidines, dianisidines or dichloroanilines, 2-methyl-4-chloroaniline, and 2,5-dimethoxy-4-chloroaniline. The silane quinacridone dyes of formula (I) possess good pigmentary properties, such as good stability to solvents, and when used in stove enamels they give products having high tinting strength, with red shades, particularly pure and bright, good general resistance and excellent photostability. The silane quinacridone dyes of formula (I), since they contain in their molecules silanol groups and/or alkoxyl groups hydrolyzable to silanol groups -Si(OH)₃, are capable of self-condensation reactions between the silanol groups, as well as of chemical reaction with surface hydroxyl groups of suitable inorganic substrates or supports, which condense with those of the dyes, thus forming stable chemical bonds (grafting) between the dye and the substrate, giving rise to a composite product having excellent pigmentary characteristics. The aforesaid dyes are therefore preferably utilized in the preparation of composite pigments, according to another aspect of the present invention, comprising silane quinacridone dyes of formula (I) grafted onto an inorganic substrate or support. The silane dyes of formula (I) which have proved to be particularly suitable for preparing composite pigments are those in which c is 0, q is 0, and when b is 1, Y is the same as Z. Inorganic substrates or supports particularly suitable for imparting pigmentary properties to the silane quinacridone dyes of formula (I) are the following: TiO₂, in its gel, semicrystalline, rutile or anatase forms, also of the commercial type, which can carry surface coatings comprising mixtures containing one or more oxides selected from SiO₂, Al₂O₃, TiO₂; moreover it is possible to employ physical (mechanical) mixtures of TiO₂ with SiO₂ and/or Al₂O₃, as well as SiO₂ and/or Al₂O₃, such substrates of supports being finely particulated. Due to their superior characteristics, it is preferable to employ mixed substrates of TiO₂, SiO₂ and/or Al₂O₃ prepared by precipitation of SiO₂ and/or Al₂O₃, also as alumino-silicates onto crystalline TiO₂ particles, according to conventional methods. In relation to the desired uses, hiding degree or power or tinting strength, the above said substrates or supports may also be utilized in mixtures with each other. The specific surface area of such substrates or supports may vary within wide limits, from 5 to 500 m²/g, preferably from 10 to 200 m²/g. Due to their excellent properties, the composite pigments particularly preferred are those containing the silane quinacridone dye of formula (I) in grafted form in amounts from 10 to 50% by weight. According to a yet further aspect of the invention, a process for preparing the composite pigments comprising the silane quinacridone dyes (I) grafted on the inorganic substrates or supports comprises reacting the selected substrate or support with the silane dye (I), in a reaction medium comprising water and/or an inert organic solvent, at a temperature from 20°C to the reflux temperature of the reaction medium, and separating the resulting product by filtration, followed by washing and drying. Such treatment can be advantageously carried out by grinding the silane dye with the substrate or support in the reaction medium, either at room temperature or in a hot reactor for a time period of 2 to 12 hours, according to the reaction temperature used. Particularly advantageous results are obtained if the composite pigment, after its separation by filtration, is subjected to a dry heat treatment in an oven for 4-8 hours at 60-110°C, prior to the washing, which washing is accomplished in order to remove the non-grafted silane dye. The inert organic solvents employed can be for example the aliphatic hydrocarbons (n-heptane), their chlorinated derivatives (tetrachloroethane), alicyclic and aromatic hydrocarbons and their derivatives (benzene, toluene, xylenes, nitrobenzene, chlorobenzenes), alkyl or aryl ethers and ketones (N-methyl-pyrrolidone, diphenylether), oxides (dioxane), amides (dimethylformamide), nitriles (acetonitrile), and sulphoxides (dimethylsulphoxide). The preparation process of the present invention has proved particularly suitable for obtaining deeply coloured pigments, having a high tinting strength, even in the presence of inorganic substrates or supports having a low specific surface area, such as for example highly hiding TiO₂. The composite pigments according to the present invention can have a composition varying over a wide range, depending on the nature, granulometry and specific surface area of the substrate particles and in relation to the desired tinting strength of the pigment. Granulometric analysis of a composite pigment according to the invention indicates that the organic portion is essentially distributed on the surface of the inorganic substrate particles. X-ray diffractometric analysis indicates that the composite pigment particles exhibit the crystallinity which is characteristic of the substrate, while the grafted quinacridone coating is of an amorphous nature. The quinacridone pigments of the present invention, due to their composite nature obtained by chemical bonds between the silane organic component and the inorganic component, do not give rise to crystallization phenomena, nor do they change their crystalline form in the presence of aromatic solvents even if hot treated. Moreover, pigmentary compositions based on solvents do not cause sedimentation phenomena, not even after prolonged storage. The composite pigments, both in their highly hiding and transparent forms, exhibit excellent pigmentary properties, are insoluble in common organic and aqueous solvents, possess excellent resistance to migration in polyvinylchloride (PVC), to overpainting in alkyd stove enamels and to acid or alkaline treatments. They have excellent photostability and very good tinting strength, are stable to heat both when obtained in transparent form and at ever increasing degrees of hiding power. They are therefore advantageously utilized in painting products, in air and stone enamels, in the pigmentation of plastic materials, such as PVC, polystyrene, polyethyleneterephthalate, etc., and in printing inks, according to conventional applicative techniques, to obtain particularly pure and bright red-coloured products. The mechanical and/or heat treatments employed in such conventional techniques do not substantially modify the pigmentary characteristics of the composite pigments of the present invention. The composite pigments have the considerable advantage of being composed of an inorganic substrate or support of low cost, capable of imparting excellent pigmentary characteristics, in particular the desired degree of hiding power or transparence, excellent resistance to solvents, stability to crystallization and a non-flocculating nature, on which is grafted a silane quinacridone dye having good photostability, high tinting strength, and pure and bright shades. In general, the composite pigments according to the invention may be suitably used for colouring paints, air and stove enamels, printing inks, and plastics materials. The invention will be further described with reference to the following illustrative examples. In the examples, all parts and percentages, unless otherwise specified, are by weight. EXAMPLE 1 200 ml of chlorosulphonic acid, placed in a reactor, in anhydrous ambient, and cooled at 5°-10°C, were gradually additioned, in 1.5 hours, with 20 parts of beta-quinacridone, then the mixture was gradually heated in one hour up to 80°C and maintained at this temperature for 3 hours. The mixture was cooled at 70°C-75°C and 12 ml of thionyl chloride were added in 15 minutes, then the temperature was raised again to 80°C and the reaction mixture was maintained at this temperature for 2 more hours. The mass was cooled at 5°-10°C, 800 ml of acetone were added, then the reaction medium was filtered, washed with acetone until the liquid became colourless, then with water and ice, with acetone again and finally it was pump-dried by vacuum suction. 16.49 parts (0.0225 moles) of the sulphochloride derivative thus obtained, 4 parts of water, 100 ml of triethylamine and 11 parts (0.05 moles) of γ-aminopropyl-triethoxysilane were reacted at 50°C for 3.5 hours. The reaction mass, hot filtered, gave a cake which was twice treated with 200 parts of water, 600 ml of acetone and 50 ml of 30% ammonium hydroxide. After filtration the cake was treated again with 200 parts of water, 200 parts of 30% NH₄OH and 100 ml of dimethylformamide and maintained at 50°C for 1 hour. The mixture was filtered and the cake was treated with a 50%/50% mixture of water and dimethylformamide at 80°-90°C, the aqueous mixture was filtered again, repeatedly washed with water, then with methanol and was finally dried in the air. A friable intensely red-coloured powder was obtained which, upon elemental analysis, gave the following results: % C = 44; % H = 4.4; % N = 7.62; % S = 8.5; %Si = 7.5. The powder, subjected to infrared spectrographic analysis, revealed the bands characteristic of the ≡Si(OH) silanolic groups in the area at 3450 cm⁻¹ and in the area between 1000 and 1200 cm⁻¹ and the bands characteristic of the sulphonamidic groups (-SO₂-NH-) in the area between 1300 and 1500 cm⁻¹. The analytical and spectroscopic analyses essentially corresponded to a dye having the formula: This dye can also be partially present in oligomeric form, by the formation of≡Si-O-Si≡siloxanic bonds between the -Si(OH)₃ silanolic functions present in the molecule. EXAMPLE 2 12.22 parts (0.024 moles) of the quinacridone sulphochloride derivative obtained in example 1 were reacted with 0.65 parts (0.011 moles) of n-propylamine in 90 ml of triethylamine for 2 hours at room temperature and then for 0.5 hours at 35°-40°C. 3.12 parts (0.014 moles) of γ-aminopropyl-triethoxysilane were subsequently added; the temperature was brought to 55°-60°C and the reaction medium was maintained at this temperature for 2.5 hours. The reaction medium was hot filtered and subsequently washed and dried as described in example 1. A friable deeply red coloured powder was obtained which, upon elemental analysis, gave the following results % C = 48; % H = 4.3; % N = 8.5; % S = 10; % Si = 5. Infrared analysis revealed the same characteristic bands as found for the powder of example 1. The analytical and spectroscopic analyses essentially corresponded to a dye having the formula: This dye can also be partially present in oligomeric form. EXAMPLE 3 By operating in conditions similar to those described in example 2, but employing 1.11 parts of aniline, instead of n-propylamine, and 3.3 parts of γ-aminopropyl-triethoxysilane, a deeply red coloured powder was obtained which, upon elemental analysis, gave the following results. %C = 51; % H = 4; % N = 8.4; % S = 10.1; % Si = 4. The analytical and spectroscopic analyses essentially corresponded to a dye having the formula: This dye can also be partially present in oligomeric form. EXAMPLE 4 A silanated quinacridone composite pigment was prepared by using a mixed inorganic substrate of TiO₂, SiO₂ and Al₂O₃, prepared as follows: 100 parts of TiO₂ were dispersed under mechanical stirring in 1 litre of water and the dispersion was then heated to 60°C. After 15-minute stirring, 210 ml of a sodium silicate solution (titre: 365.47 parts/l of SiO₂) were added and successively, in 3 hours, 200 ml of an aluminium sulphate solution (titre: 60 parts/l of Al₂O₃) were added. Addition was stopped when the pH of the slurry reached a value of 6. Stirring was continued for 1 hour, then the product was filtered, washed with water to remove soluble salts and finally dried at a temperature of 70°C. The dry product was crushed and then ground in an automatic mortar. A white powder having the following composition was obtained: % TiO₂ = 43.4; % SiO₂ = 35.1; % Al₂O₃ = 7.15; % H₂O = 14.35; its specific surface area, determined by a "Sorptometer" was 120 m²/g, actual specific weight = 2.74 g/ml, apparent specific weight = 0.69 g/cc: % porosity = 7.45 and total porosity = 1.06 ml/g. 2 parts of the substrate thus obtained and 1 part of the dye obtained according to example 1 were wet-ground for 12 hours in xylene, then filtered and the cake obtained was hot treated overnight at 110°C, then hot washed with xylene, dimethylformamide, methanol and finally dried. A particularly bright deeply red coloured powder was obtained which, upon elemental analysis, was found to consist of 68% of inorganic ashes. This powder proved particularly stable to treatments, even under hot conditions, with organic solvents and with water. In applications such as alkyd stove enamels and polyvinylchloride, it provided bright red-coloured products having high hiding power, excellent tinting strength, resistance to overpainting, and to migration and light, both in mass and when diluted with TiO₂. The powdery composite pigment, subject to X-ray diffractometric analysis, under CuKα 1.5418 radiation, proved to be formed by particles having the crystallinity characteristic of rutile TiO₂, while SiO₂, Al₂O₃ and the silanic quinacridone coating was found to be amorphous. Due to the amorphous nature of the silanic quinacridone coating, the composite pigment proved particularly stable and not subject to crystallization phenomena deriving from changes of crystalline form due, for instance, to hot treatments with solvents such as xylene, dimethylformamide and dichlorobenzene. The pigment subjected to the abovesaid treatments did not change its shade. Due to its composite nature, the pigment did not present sedimentation phenomena, due to demixing of the components, in formulations with TiO₂ such as those employed for the stove enamels. EXAMPLE 5 One part of the dye obtained as described in example 1 was introduced into a reactor with 70 parts of water, 1 part of TiO₂ and 2.1 ml of sodium silicate (titre: 365.47 parts/1 of SiO₂). The suspension was heated to 60°C and, under stirring, additioned in 3 hours with 2 ml of aluminium sulphate solution (titre: 60 parts/1 of Al₂O₃), maintained at 60°C for 1 hour and then cooled at room temperature. After filtration, the cake obtained was washed with water to neutral pH, dried in an oven at 110°C for one night, then repeatedly washed with hot water and finally dried. A bright deeply red-coloured powder was obtained which, upon elemental analysis, was found to consist of 67.5% of inorganic ashes. The product exhibited applicative properties, solidity, hiding power, tinting strength and diffractometric characteristics similar to those of the pigment obtained according to example 4. Similarly to the pigment of example 4, the pigment did not exhibit the crystallization phenomena and consequently did not change its shade when hot-treated with solvents, nor did it exhibit the demixing phenomenon of the components, in formulations with TiO₂. EXAMPLE 6 One part of the dye obtained as described in the example 1 was introduced into a reactor with 70 parts of water, and 4.2 ml of sodium silicate solution (titre: 365.47 parts/l of SiO₂). The suspension was heated to 60°C and, under stirring, additioned in 3 hours with 4 ml of aluminium sulphate solution (titre: 60 parts/l of Al₂O₃), maintained at 60°C for 1 hour and then cooled at room temperature. After filtration, the cake obtained was washed with water to neutral pH, dried in an oven at 110°C for one night, then repeatedly washed with hot water and finally dried. A particularly bright red-coloured powder was obtained which, upon elemental analysis, was found to consist of 67.5% of inorganic ashes. Upon X-ray analysis, the composite pigment was found to consist of amorphous particles. In applications such as in stove enamels and in polyvinylchloride, the powder gave products of a bright red shade, perfectly transparent, having excellent solidity and photostability and free from crystallinization phenomena and demixing in formulations with TiO₂. EXAMPLES 7-16 By operating according to the procedures described in examples 4, 5 and 6 and employing the silanated quinacridone dyes described in examples 1, 2, 3 in combination with the inorganic substrates given in Table 1, 10 red pigments with slight shade differences were prepared, having different hiding power or transparency degrees and with characteristics of stability similar to those of the products obtained in examples 4, 5 and 6. EXAMPLE 17 (application in PVC) In a rotary arm mixer there were mixed, at 70°C: 1.0 parts of the pigment obtained according to example 4, previously ground, 100 parts of powdered polyvinylchloride (PVC), 1.5 parts of calcium stearate for exerting a complexing and stabilizing action, 3.0 parts of epoxidized soybean oil, 0.5 parts of lubricant (mixture of glycerides from C₁₆ to C₃₆). 2.0 parts of TiO₂. The resulting mixture was then treated at 180°C in a three-roll refiner until complete dispersion of the pigment occurred, in order to obtain a sheet exhibiting a bright red colour, having excellent hiding power, good colour brightness, good photostability, good tinting strength, good stability to heat and excellent stability to migration. EXAMPLE 18 (application in enamels) 5.0 parts of the pigment obtained according to example 4 were mixed by grinding with 95.0 parts of a fluid carrier having the following composition: 22% of alkyd resin, 19% of melamine resin, 59% of xylene. Homogenization was accomplished in a ball mill by grinding the mixture in the presence of porcelain balls having a diameter of 10 mm, for a time of 24 hours. The resulting enamel was applied onto the surface to be painted, allowed to dry overnight and then was placed in an oven at 120°-125°C for 30 minutes. A bright red-coloured paint with excellent hiding power, photostability and stability to overpainting and good tinting strength was obtained. In order to obtain a paint of a lighter shade and having higher hiding power, 1 part of the enamel obtained as hereinabove described was further diluted with 9 parts of a white synthetic stove enamel (10% of TiO₂) having the following composition: 30% of alkyd resin, 27% of melamine resin, 33% of xylene, 10% of TiO₂. Homogenization was carried out in a ball mill by grinding the mixture in the presence of porcelain balls having a diameter of 10 mm for a time period of 24 hours. The cut enamel so obtained was applied onto the surface to be painted; it was allowed to dry overnight and then was maintained in an oven at 120°-125°C for 30 minutes. A light red-coloured paint of pure shade having excellent general stabilities and high hiding power was obtained.

Claims: A quinacridone dye containing at least one silane group, characterized by having the formula: wherein X is an -SO₂NHR group, where R is an alkyl group, linear or branched, having from 1 to 6 carbon atoms, a cycloalkyl group, or a phenyl group optionally substituted by one or more halogens or alkyl or alkoxy groups having from 1 to 6 carbon atoms; Y and Z are each a silane group having the formula: where R₁ is an alkoxy group having 1 or 2 carbon atoms; R₂ is an alkyl group having from 1 to 4 carbon atoms, or a phenyl group; n is 3, 4 or 5; q is 0 or 1; and p and m are integers such that when q is 1, p is 2 and m is 0, 1 or 2 and when q is 0, p is 3 and m is 0, 1, 2 or 3; W is an -SO₃H group; a, b and c are 0 or 1, selected such that the sum a + b + c is equal to 1. A silane quinacridone dye as claimed in claim 1, characterized in that c is 0, q is 0, and when b is 1, Y is the same as Z. A process for preparing a quinacridone dye according to claim 1, characterized in that a quinacridone sulphochloride having the formula: is reacted with a silane compound having the formula: wherein R₁, R₂, m, n, p and q are as defined in claim 1, in a molar ratio of silane compound (III): sulphochloride (II) of at least 1, and optionally with an amine compound having the formula: H₂N-R (IV) wherein R is as defined in claim 1, utilizing at least one mole of silane compound (III) and at least 1 mole of amine (IV) for each mole of sulphochloride (II), in a reaction medium comprising water and/or an organic solvent, at a temperature from 5°C to the reflux temperature of the reaction medium, for 1 to 12 hours. A process as claimed in claim 3, characterized in that the reaction is carried out in the presence of a hydrochloric acid-acceptor compound. A process as claimed in claim 4, characterized in that the hydrochloric acid-acceptor compound is selected from Na₂CO₃, NaHCO₃, triethylamine and pyridine. A process as claimed in any of claims 3 to 5, characterized in that the organic solvent is selected from dimethylformamide, dioxane, acetonitrile, pyridine, triethylamine, xylene, nitrobenzene and dichlorobenzene. A process as claimed in any of claims 3 to 6, characterized in that the amino-alkoxysilane of formula (III) is selected from γ-aminopropyl-triethoxysilane, δ-aminobutyl-phenyl-diethoxysilane, γ-aminopropyl-methyl-diethoxysilane, and δ-aminobutyl-triethoxysilane. A process as claimed in any of claims 3 to 7, characterized in that the amine of formula (IV) is selected from methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine and their branched isomers, cyclohexylamine, aniline, ortho-, meta-, and para-toluidines, chloroanilines or anisidines, 2,4- or 3,5-xylidines, dianisidines or dichloroanilines, 2-methyl-4-chloroaniline, 2,5-dimethoxy-4-chloroaniline. A composite pigment, characterized by comprising a silane quinacridone dye as claimed in claim 1 or 2, grafted onto a solid inorganic substrate or support. A composite pigment as claimed in claim 9, characterized in that the inorganic substrate or support is selected from TiO₂ gel, semicrystalline TiO₂, rutile TiO₂ and anatase TiO₂; mixtures of TiO₂ with SiO₂ and/or Al₂O₃; SiO₂ and/or Al₂O₃; and mixtures thereof; the said substrate or support being finely particulated and having a specific surface area of from 5 to 500 m²/g. A composite pigment as claimed in claim 9 to 10, characterized by containing from 10 to 50% by weight of silane quinacridone dye in grafted form. A process for preparing a composite pigment according to claim 9, characterized by comprising reacting the inorganic substrate or support with a silane quinacridone dye of formula (I) in a reaction medium comprising water and/or an inert organic solvent, at a temperature from 20°C to the reflux temperature of the reaction medium, and separating the pigment by filtration followed by washing and drying . A process as claimed in claim 12, characterized in that the reaction is carried out by grinding the silane dye with the substrate or support in the presence of the reaction medium either at room temperature or in a hot reactor, for a time period from 2 to 12 hours. A process as claimed in claim 12 or 13, characterized in that the composite pigment, separated by filtration, is subjected to a dry thermal treatment in an oven at 60°C-110°C for 4-8 hours before washing. A paint, air enamel, stove enamel, printing ink, or plastics mateial, when coloured with a composite pigment as claimed in any of claims 9 to 11.

Inventors: CARLINI, FILIPPO MARIA, MARRACCINI, ANTONIO, PASQUALE, ANTONIO, PONTEVIVO, MICHELE
Applicants: MONTEDISON S.P.A.
Application year: 1984
Main classification: C09B48
IPC codes: C09B62, C09B48, C09B67, C09B69