Title of Invention	WATER-SOLUBLE GRANULES OF PHTHALOCYANINE COMPOUND
Abstract	Water-soluble granules of phthalocyanine compounds comprising a) from 2 to 50 % by weight of a water-soluble phthalocyanine compound, b) from 10 to 95 % by weight of an anionic dispersing agent, c) from 0 to 25 % by weight of a water-soluble organic polymer, d) from 0 to 10 % by weight of a further additive and e) from 3 to 15 % by weight of water, based on the total weight of the granules, are described. The granules are suitable especially as additives to washing agents for textile materials.

Title of Invention

WATER-SOLUBLE GRANULES OF PHTHALOCYANINE COMPOUND

Abstract

Water-soluble granules of phthalocyanine compounds comprising a) from 2 to 50 % by weight of a water-soluble phthalocyanine compound, b) from 10 to 95 % by weight of an anionic dispersing agent, c) from 0 to 25 % by weight of a water-soluble organic polymer, d) from 0 to 10 % by weight of a further additive and e) from 3 to 15 % by weight of water, based on the total weight of the granules, are described. The granules are suitable especially as additives to washing agents for textile materials.

Full Text	The present invention relates to water-soluble granules of phthalocyanine compounds, to a method of produC1ng them, and to the use thereof in washing agent preparations. Water-soluble phthalocyanine dyes, espeC1ally zinc and aluminium phthalocyanine-sulfonates, are frequently used as photoactivators in washing agent preparations. In view of the fact that such photoactivators dissolve too slowly in water, problems often arise, espeC1ally when there is inadequate mixing of the washing liquor, because the coloured photoactivators stain the laundry. Solid microcapsules of phthalocyanine photoactivators that contain at least 38 % of an encapsulating material havealready been described in EP-B-0 333 270 but those microcapsules are also not able to satisfy all of the consumer"s requirements in terms of dissolving behaviour and staining of the laundry. It has now been found that, surprisingly, granules comprising a water-soluble phthalocyanine compound, an anionic dispersing agent and a maximum of 25 % by weight of an organic polymer are distinguished by a high rate of dissolution in water, with the result that the problems mentioned above are substantially or entirely eliminated. A further advantage of such granules is that, even in the case of prolonged contact with a non-ionic surfactant, the phthalocyanine compound is not dissolved out of the granules and the laundry is not stained. The present invention accordingly relates to water-soluble granules of phthalocyanine compounds comprising a) from 2 to 50 % by weight of a water-soluble phthalocyanine compound, b) from 10 to 95 % by weight of an anionic dispersing agent, c) from 0 to 25 % by weight of a water-soluble organic polymer, d) from 0 to 10 % by weight of a further additive and e) from 3 to 15 % by weight of water, based on the total weight of the granules. J There come into consideration as the phthalocyanine compound for the granules according to the invention phthalocyanine complexes having a di-, tri- or tetra-valent metal (complexes having a d° or d 10configuration) as the central atom. Such complexes are espeC1ally water- soluble Zn, Fe(ll), Ca, Mg, Na, K, Al, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(lll), Zr(IV), In(lll), if Sn(IV) and Hf(VI) phthalocyanines, aluminium phthalocyanine and zinc phthalocyanine being I] espeC1ally preferred. Advantageously, the composition according to the invention comprises a phthalocyanine compound of formula wherein PC is the phthalocyanine ring system; Me is Zn, Fe(ll), Ca, Mg, Na, K, AI-Z1, Si(IV), P(V), Ti(l\/), Ge(IV), Cr(VI), Ga(lll). Zr(IV), Re is branched or unbranched C1-Csalkylene; or 1,3- or 1,4-phenylene; X2 is -NH-; or -N-d-C5alkyl-; X3* is a group of the formula and in the above formulae R7 and R8 are each independently of the other C1-Cealkyl; R9 is C1-CealkyI; Cs-C/cycioalkyI; or NR11R12; R10 and R11 are each independently of the other C1-CealkyI; R12 and Ri3 are each independently of the other hydrogen or C1-CsalkyI; Ri4 and R15 are each independently of the other unsubstituted C1-CealkyI or C1-CealkyI substituted by hydroxy, cyano, carboxy, C1-Cealkoxycarbonyl, CrCealkoxy, phenyl, naphthyl or by pyridyl; u is from 1 to 6; Ai is the balance of an aromatic 5- to 7-membered nitrogen heterocycle which may contain one or two further nitrogen atoms as ring members, and Bi is the balance of a saturated 5- to 7-membered nitrogen heterocycle which may contain 1 or 2 further nitrogen, oxygen and/or sulfur atoms as ring members; Q2 is hydroxy; CrC22alkyl; branched C4-C22alkyl; C2-C22alkenyl; branched C4-C22alkenyl or a mixture thereof; C1-C22alkoxy; a sulfo or carboxyl radical; a radical of the formula I B2 is hydrogen; hydroxy; C1-CaoalkyI; C1-Caoalkoxy; -CO2H; -CH2COOH; SO3Mr; -OSO3M/; -PO3; Mi; -Poem’s; or a mixture thereof; B3 is hydrogen; hydroxy; -COOH; -SO2iVI/; -Sao’s/; or C1-C6all Ml is a water-soluble cation; Ti is -0-; or -NH-; Xi and X4 are each independently of the other -0-; -NH-; or -N-C1-Csaikyl; R16 and R17 are each independently of the other hydrogen, a sulfo group or a salt thereof, a carboxyl group or a salt thereof, or a hydroxyl group, at least one of the radicals R16 and R17 being a sulfo or carboxyl group or a salt thereof, Y2 is -0-, -S-, -NH- or -N-C1-CsalkyI; R18 and Ri9 are each independently of the other hydrogen, C1-CealkyI, hydroxy-C1-Cealkyl, cyano-C1-CealkyI, sulfo-CycioalkyI, carboxy or halo-C1-CealkyI; unsubstituted phenyl; or phenyl substituted by halogen, C1-C4alkyl or C1-C4alkoxy, sulfo or by carboxy; or R18 and Ri9, together with the nitrogen atom to which they are bonded, form a saturated 5-or 6-membered heterocyclic ring that may in addition contain a further nitrogen atom or an oxygen atom as ring member; All ot the adore-mentioned nitrogen neterocycles may In addition be substituted by alky! groups, either at a carbon atom or at a further nitrogen atom located in the ring, in which case the methyl group is preferred as alkyl group. As in formula (1a) denotes, as countering to the positive charge of the remainder of the molecule, any desired anion. It is generally introduced by the preparation process (quaternisation), in which case it Is preferably a halogen ion, an alkyl sulfate ion or an aryl sulfate ion. Among the aryl sulfate ions mention should be made of the phenylsulfonate, p-tolylsulfonate and p-chlorophenylsulfonate ions. It is also possible, however, for any other anion to function as the anion, since the anions can readily be interchanged in known manner; As’ may also be a sulfate, sulfite, carbonate, phosphate, nitrate, acetate, oxalate, citrate or lactate ion or another anion of an organic carboxylic acid. In the case of mono¬valent anions, the index s is equal to r. In the case of polyvalent anions, s assumes a value C1-C6AlkyI and C1-C6alkoxy are straight-chain or branched alkyl and alkoxy radicals, respectively, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl or hexyl and methoxy, ethoxy, n-priory, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy, tert-amyloxy or hexyloxy, respectively. C2-C22Alkenyl is, for example, ally, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl. Preferred phthalocyanine compounds of formula (1a) for the granules according to the invention correspond to formula Me, q, PC, X2, X3 and Re are as defined for formula (1a); M is hydrogen, or an alkali metal, ammonium or amine salt ion; and the sum of the numbers ri and TZ is from 1 to 4, and As" exactly balances the positive charge of the remainder of the molecule, and correspond especially to formula in which formulae R7 and Rs are each independently of the other unsubstituted Ci-C4alkyl or Ci-C4alkyl substituted by hydroxy, cyano, halogen or by phenyl; R9 is R7; cyclohexyl or amino; R11 is Ci-C4alkyl; R21 is Ci-C4alkyl; Ci-C4alkoxy; halogen, carboxy, Ci-C4alkoxycarbonyl or hydroxy; and A" is a halide, alkyl sulfate or aryl sulfate ion; wherein the radicals -S02NHR"6-X3""^A" may be identical or different. Further phthalocyanine compounds that can be used in accordance with the invention correspond to formula wherein PC is the phthalocyanine ring system; Me is Zn, Fe(ll), Ca, Mg, Na, K, AI-Z1, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(ill), Zr(IV), In(lll), Sn(IV) or Hf(VI); Zi is a halide, sulfate, nitrate, acetate or hydroxy ion; Y3" is hydrogen, an alkali metal ion or an ammonium ion; and r is any number from 1 to 4. Special preference is given to those phthalocyanine compounds of formula (4) wherein Me isZn or AI-Z1; and Zi is a halide, sulfate, nitrate, acetate or hydroxy ion. Further phthalocyanine compounds of interest that can be used in accordance with the invention correspond to formula wherein PC, Me and q are as defined for formula (4); R17" and Ris" are each independently of the other hydrogen, phenyl, sulfophenyl, carboxyphenyl, Ci-CealkyI, hydroxy-C1-CealkyI, cyano-CrCealkyl, sulfo-C1-CealkyI, carboxy-C1-C6alkyI or halo-CrCealkyl or, together with the nitrogen atom, form a morpholine ring; q" is an integer from 2 to 6; and r is a number from 1 to 4; Further phthalocyanine compounds of interest that can be used in accordance with the invention correspond to formula wherein PC, Me and q are as defined for formula (4); Y"3 is hydrogen, an alkali metal ion or an ammonium ion; q" is an integer from 2 to 6; R17" and Rie" are each independently of the other hydrogen, phenyl, sulfophenyl, carboxyphenyl, Ci-CealkyI, hydroxy-Ci-CealkyI, cyano-CrCealkyI, sulfo-CrCealkyl, carboxy-Ci-CealkyI or halo-Ci-CealkyI or, together with the nitrogen atom, form a morpholine ring, m" is 0 or 1; and r and ri are each independently of the other any number from 0.5 to 3.5, the sum r +ri being a minimum of 1 and a maximum of 4. Where the central atom Me in the phthalocyanine ring is Si(IV), the phthalocyanines used in accordance with the invention may contain, in addition to the substituents on the phenyl nucleus of the phthalocyanine ring, also axial substituents (= R24). Such phthalocyanines correspond, for example, to formula Especially preferred as phthalocyanlne compound are compounds such as those commercially available and used in washing agents. Usually, the anionic phthalocyanlne compounds are in the form of alkali metal salts, especially sodium salts. Preferred formulations of the granules contain from 4 to 30 % by weight, especially from 5 to / 20 % by weight, of phthalocyanlne compound, based on the total weight of the granules. I it will be understood that it is also possible to use mixtures of two or more phthalocyanlne compounds instead of a single, homogeneous phthalocyanlne compound. The anionic dispersing agents used are, for example, the commercially available water-soluble anionic dispersing agents for dyes, pigments etc.. The following products, especially, come into consideration: condensation products of aromatic sulfonic acids and formaldehyde, condensation products of aromatic sulfonic acids with unsubstituted or chlorinated diphenylene or diphenyl oxides and optionally form- ; aldehyde, (mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerised organic sulfonic acids, sodium salts of polymerised alkylnaphthalenesulfonic acids, sodium salts of Ah polymerised alkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkyl polyglycol i ^ ether sulfates, polyalkylated polynuclear arylsulfonates, methylene-linked condensation \| I products of arylsulfonic acids and hydroxyarylsulfonic acids, sodium salt of dally- \| I sulfosuccinic acid, sodium salts of alkyl diglycol ether sulfates, sodium salts of poly- i naphthalenemethanesulfonates, jigno- or oxyligno-sulfonates or heterocyclic polysulfonic \| acids. The dispersing agents may be used individually or in the form of a mixture of two or more dispersing agents. Especially suitable anionic dispersing agents are condensation products of naphthalene- \ , l sulfonic acids with formaldehyde, sodium salts of polymerised organic sulfonic acids, 1 v vv " (mono-/di-)alkylnaphthalenesulfonates, polyalkylated polynuclear aryl sulfonates, sodium h " salts of polymerised alkylbenzenesulfonic acid, lignosulfonates, oxylignosulfonates and U condensation products of naphthalenesulfonic acid with a polychloromethyldiphenyl. Preferably, the granules according to the invention contain from 40 to 90 % by weight, / ^" ^^ ^ "^ especially from 50_to.S£L% by weight, of anionic dispersing agent. "l In addition to the water-soluble phthalocyanine compound and the anionic dispersing agent, the granules according to the invention may comprise a water-soluble organic polymer. Such polymers may be used individually or in the form of a mixture of two or more polymers. Preferably, such a polymer is added for the purpose of improving the mecjianic stability of the granules and/or when, during later use of the granules in a washing agent, the phthalo¬cyanine compound is to be prevented from being dissolved out of the granules by a non-ionic surfactant. There come into consideration as water-soluble polymers, for example, gelatin, poly-acrylates, polymethacrylates, copolymers of ethyl acetate, methyl methacrylate and methacrylic acid (ammonium salt), polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, copolymers of vinylpyrrolidone with long-chained a-olefins, poly(vinylpyrrolidone/dimethyl-aminoethyl methacrylates), copolymers of vinylpyrrolidone/dimethylaminopropyl methacrylamides, copolymers of vinylpyrrolidone/dimethylaminopropyl acrylamides, quaternised copolymers of vinylpyrrolidones and dimethylaminoethyl methacrylates, terpolymers of vinylcaprolactam/vinylpyrrolldone/dimethylaminoethyl methacrylates, copolymers of vinylpyrrolidone and methacrylamidopropyl-trimethylammonium chloride, terpolymers of caprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates, copolymers of styrene and acrylic acid, polycarboxylic acids, polyacrylamides, carboxymethylcellulose, hydroxymethylcellulose, polyvinyl alcohols, polyvinyl acetate, hydrolysed polyvinyl acetate, copolymers of maleic acid with unsaturated hydrocarbons, and mixed polymerizations products of the mentioned polymers. Of those organic polymers, carboxymethylcellulose, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates, copolymers of vinylpyrrolidone and vinyl acetate, and also polyacrylates and polymethacrylates, are especially preferred. The organic polymers are used in an amount of from 0 to 25 % by weight, preferably from 5 to 20 % by weight and, especially, from 8 to 18 % by weight, based on the total weight of the granules. The granules according to the invention may comprise further additives, for example wetting agents, water-insoluble or water-soluble dyes or pigments, and also dissolution accelerators and optical brighteners. Such additives are present in an amount of from 0 to 10 % by weight, based on the total weight of the granules. The granules according to the invention are produced, for example, in the following manner: first of all an aqueous solution of the phthalocyanine dye is prepared, the anionic dispersing agent and, if desired, further additives are added thereto, and the mixture is stirred, where appropriate with heating, until a homogeneous solution is obtained. The solids content of the solution should preferably be at least 30 % by weight, especially from 40 to 50 % by weight, based on the total weight of the solution. The viscosity of the solution is preferably less than 200 mPas. The aqueous solution comprising the phthalocyanine dye and the anionic dispersing agent is then subjected to a drying step in which all water, with the exception of a residual amount, is removed, solid particles (granules) simultaneously being formed. Known methods are suitable for producing the granules from the aqueous solution. In principle, both continuous methods and discontinuous methods are suitable. Continuous methods are preferred, especially spray-drying and fluidized bed granulation processes. Especially suitable are spray-drying processes in which the active ingredient solution is sprayed into a chamber with circulating hot air. The atomization of the solution is carried out using unitary or binary nozzles or is brought about by the spinning effect of a rapidly rotating disc. In order to increase the particle size, the spray- drying process may be combined with an additional agglomeration of the liquid particles with solid nuclei in a fluidized bed that forms an integral part of the chamber (so-called fluidized spray dryer). The fine particles ( During the granulation step, the water can rapidly be removed from the solutions comprising phthalocyanine compound, anionic dispersing agent and possibly organic polymer and further additives, and it is expressly intended that agglomeration of the droplets forming in the atomising cone, i.e. the agglomeration of droplets with solid particles, will take place. If necessary, the granules formed in the spray-dryer are removed in a continuous process, for example by a sieving operation. The fines and the oversize particles are either recycled directly to the process (without being rediscover) or are dissolved in the liquid active ingredient formulation and subsequently granulated again. The granules according to the invention are resistant to abrasion, low in dust, free-flowing and can readily be metered. They are distinguished in particular by very rapid solubility in water. They are used especially in washing agent formulations. They may be added in the desired concentration of the phthalocyanine compound directly to a washing agent formulation. The present invention relates also to that use. Where the dark appearance of the granules in the washing agent is to be suppressed, this can be achieved, for example, by embedding the granules in a droplet of a whitish moldable substance ("water-soluble wax") or, preferably, by encapsulating the granules in a melt consisting, for example, of a water-soluble wax, as described in EP-B-0 323 407 B1, a white solid (e.g. titanium dioxide) being added to the melt in order to reinforce the masking effect of the capsule. The present invention accordingly relates also to washing agent formulations comprising I) from 5 to 70 % A) of an anionic surfactant and/or B) of a non-ionic surfactant, II) from 5 to 50 % C) of a builder substance, III) from 1 to 12 % D) of a peroxide and, where appropriate, a catalyst and IV) from 0.01 to 1 % E) of granules according to the invention, the percentages in each case being percentages by weight, based on the total weight of the washing agent. Preference is given to washing agent formulations comprising I) from 5 to 70 % A) of an anionic surfactant and/or B) of a non-ionic surfactant, II) from 5 to 40 % C) of a builder substance, III) from 1 to 12 % D) of a peroxide and, where appropriate, a catalyst and IV) from 0.01 to 0.5 % E) of granules according to the invention, the percentages in each case being percentages by weight, based on the total weight of the washing agent. The washing agent may be in solid or liquid form, for example in the form of a liquid non¬aqueous washing agent containing not more than 5 % by weight, preferably from 0 to 1 % by weight, of water, and may have as base a suspension of a builder substance in a non-ionic surfactant, for example as described in GB-A-2 158 454. Preferably, however, the washing agent is in the form of a powder or granules, which can be produced, for example, by first of all preparing a starting powder by spray-drying an aqueous suspension containing all of the components listed above with the exception of components D) and E), and then adding the dry components D) and E) and mixing everything together. It is also possible to start with an aqueous suspension that contains components A) and C), but not component B) or only some of component B). The suspension is spray-dried, then component E) is mixed with component B) and the mixture is added to the suspension, and subsequently component D) is admixed dry. Preferably, the components are mixed with one another in such amounts that a solid compact washing agent in the form of granules is obtained that has a specific weight of at least 500 g/l. In another preferred embodiment, the production of the washing agent is carried out in three steps. In the first step a mixture of anionic surfactant (and, where appropriate, a small amount of non-ionic surfactant) and builder substance is prepared. In the second step that mixture is sprayed with the major portion of the non-ionic surfactant and then, in the third step, peroxide, where appropriate catalyst, and the granules according to the invention are added. That method is usually carried out in a fluidized bed. In a further preferred embodiment, the individual steps are not carried out completely separately, so that there is a certain amount of overlap between them. Such a method is usually carried out in an extruder, in order to obtain granules in the form of mega pearls. The anionic surfactant A) may be, for example, a sulfate, sulfonates or carboxyl ate surfactant or a mixture of those surfactants. Preferred sulfates are those having from 12 to 22 carbon atoms in the alkyl radical, where appropriate in combination with alkyl ethoxysulfates having from 10 to 20 carbon atoms in the alkyl radical. Preferred sulfonates are, for example, alkylbenzenesulfonates having from 9 to 15 carbon atoms in the alkyl radical and/or alkyl naphthalenesulfonates having from 6 to 16 carbon atoms in the alkyl radical in question. The cation in the anionic surfactant is preferably an alkali metal cation, especially sodium. Preferred carboxylates are alkali metal sarcosinates of the formula R-C0-N(R1)-CH2C00M\ wherein R is alkyl or alkenyl having from 8 to 18 carbon atoms in the alkyl or alkenyl radical, R1 is C1-C4alkyl and M1 is an alkali metal. The non-ionic surfactant B) may be, for example, a condensation product of from 3 to 8 mols of ethylene oxide with 1 mol of primary alcohol that contains from 9 to 15 carbon atoms. There come into consideration as builder substance C), for example, alkali metal phosphates, especially tripolyphosphates, carbonates or hydrogen carbonates, especially the sodium salts, silicates, aluminium silicates, polycarboxylates, polycarboxylic acids. organic phosphonates, aminoalkylenepoly(alkylenephosphonates) or mixtures of those compounds. Especially suitable silicates are sodium salts of crystalline silicates having layered structures of the formula NaHSit02t+i.pH20 or Na2Sif02t+i.pH20, wherein t is a number from 1.9 to 4 and p is a number from 0 to 20. Among the aluminium silicates, preference is given to those obtainable commercially under the names zeolite A, B, X and HS, and also to mixtures comprising two or more of those components. Among the polycarboxylates, preference is given to polyhydroxycarboxylates, especially citrates, and acrylates and also copolymers thereof with malefic anhydride. Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylenediamine dissociated either in racemes form or in the enantiomerically pure S,S form. Phosphonates or aminoalkylenepoly(alkylenephosphonates) that are especially suitable are alkali metal salts of 1-hydroxyethane-1,1-diphosphonlc acid, nitrilotris(methylenephos-phonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepenta-methylenephosphonic acid. There come into consideration as the peroxide component D), for example, the organic and inorganic peroxides known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 10 to 95°C. The organic peroxides are, for example, mono- or poly-peroxides, especially organic piracies or salts thereof, such as phthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanoic diacid, diperoxynonanoic diacid, diperoxydecanoic dyadic, diperoxy-phthalic acid or salts thereof. Preferably, however, inorganic peroxides are used, such as, for example, per sulfates, per borates, percarbonates and/or per silicates. It will be understood that mixtures of inorganic and/or organic peroxides can also be used. The peroxides may be in a variety of crystalline forms and have different water contents, and they may also be used together with other inorganic or organic compounds in order to improve their storage stability. The peroxides are added to the washing agent preferably by mixing the components, for example using a screw metering system and/or a fluidized bed mixer. The washing agents may comprise, in addition to the combination according to the invention, one or more optical brighteners, for example from the class bis-triazinylamino-stilbenedisulfonic acid, bis-triazolylstiibenedisuifonic acid, bis-styrylbiphenyl or bis-benzo-furanylbiphenyl, a bis-benzoxalyl derivative, bis-benzimidazolyl derivative or coumarone derivative or a pyrazoline derivative. The washing agent may also comprise suspending agents for dirt, e.g. sodium carboxy-methylcellulose, pH regulators, e.g. alkali metal or alkaline earth metal silicates, foam regulators, e.g. soap, salts for regulating the spray-drying and the granulating properties, e.g. sodium sulfate, perfumes and, optionally, antistatic agents and softeners, enzymes, such as amylase, bleaches, pigments and/or toning agents. It will be understood that such constituents must be stable towards the bleaching agent used. Further preferred additives to the washing agents according to the invention are polymers which, during the washing of textiles, prevent staining caused by dyes in the washing liquor which have been released from the textiles under the washing conditions. Such polymers are preferably polyvinylpyrrolidones which, where appropriate, have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range from 5000 to 60 000, more especially from 10 000 to 50 000. Such polymers are preferably used in an amount of from 0.05 to 5 % by weight, especially from 0.2 to 1.7% by weight, based on the total weight of the washing agent. In addition, the washing agents according to the invention may also comprise so-called perborate activators, such as, for example, TAED or TAGU. Preference is given to TAED, which is preferably used in an amount of from 0.05 to 5 % by weight, especially from 0.2 to 1.7 % by weight, based on the total weight of the washing agent. Accordingly, the present invention provides a water-soluble granules of a phthalocyanine compound comprising a) from 2 to 50 % by weight of a water-soluble phthalocyanine compound, b) from 10 to 95 % by weight of an anionic dispersing agent, c) from 0 to 25 % by weight of a water-soluble organic polymer, d) from 0 to 10 % by weight of a wetting agent, water-insoluble, water-soluble dye or pigment, or dissolution accelerator or optical brightener, wherein components (a) to (d) are as herein described, and e) from 3 to 15 % by weight of water, based on the total weight of the granules. Accordingly, the present invention also provides a method of producing the granules such as herein described, wherein first of all an aqueous solution of the phthalocyanine dye is prepared in a known manner the anionic dispersing agent and, optional, a wetting agent, water-insoluble, water-soluble dye or pigment, or dissolution accelerator or optical brightener, and, optional, a water-soluble organic polymer, are added thereto, the mixture is stirred until a homogeneous solution is obtained, and the aqueous solution is then subjected to a drying step in which all water, with the exception of a residual amount, is removed, solid particles (granules) simultaneously being formed. The following Examples serve to illustrate the invention without limiting the invention thereto. Parts and percentages relate to weight, unless specified otherwise. Example 1: 725 g of an aqueous solution of a zinc phthalocyanine compound (sodium salt of zinc phthalocyanine, containing 3 or 4 sulfo groups) having a solids content of 20 % by weight are introduced into a glass beaker. 3010 g of an aqueous solution containing 40 % by weight of an anionic dispersing agent (condensation product of naphthalenesulfonic acid and formaldehyde) are added to the first solution. The phthalocyanine/dispersing agent mixture having a solids content of approximately 34 % by weight is homogenised by stirring at 25°C for 1 hour. The solution is then spray-dried in a spray dryer equipped with a unitary nozzle. The exhaust air temperature is 105°C at a feed air temperature of 195°C. Free-flowing granules having an average particle size of 50 [jm and a residual water content of 7 % are obtained. The granules produced in that manner contain 10 % zinc phthalocyanine. Examples 2 to 7: Granules having the following compositions are produced according to the same procedure: the phthalocyanines in Examples 2 to 48 each contain 3 or 4 sulfo groups and are in the form of sodium salts. Example 8: 880 g of an aqueous solution of an aluminium phthalocyanine compound (sodium salt of aluminium phthalocyanine, containing 3 or 4 sulfo groups) having a solids content of 25 % by weight are introduced into a glass beaker and diluted with 1460 g of deionised water. The solution is heated to 45""C and a dry, pulverulent anionic dispersing agent (condensation product of formaldehyde with naphthalenesulfonic acid) is introduced in portions into the heated solution. The dispersing-agent-containing phthalocyanine solution is then stirred at 45°C for 2 hours in order that the dispersing agent is completely dissolved. The finished phthalocyanine/dispersing agent solution having a solids content of 45 % is granulated while still warm in a bench fluidized spray dryer. In the first phase of that granulation procedure, the nuclei are formed in the fluidized bed ( 95°C). Once enough nuclei are present in the fluidized bed for the granulation, the bed temperature is reduced to approximately 50°C in order to initiate the granulation process. The granulation of the entire phthalocyanine solution is carried out at a fluidized bed temperature of from 48 to 51 °C. The granules discharged from the granulator have a residual moisture content of approximately 14 % by weight and are then dried to the desired value of 9 % by weight in a continuously operating fluidized bed with air at a temperature of 75°C. The free-flowing granules have an average particle size of 160 pm and contain 10 % by weight aluminium phthalocyanine compound. Example 15: The preparation of the phthalocyanine solution and the typical formulations of the phthalocyanine granules correspond to Examples 1 to 7. Unlike Example 1, the granulation is carried out in a spray dryer in which the fines produced during the process are continuously separated from the waste gas flow and are conveyed directly by a gas flow into the atomizing cone of the nozzle. The resulting granules have the same properties as those already described in Example 1. Their average particle size is 112 \|jm, so that they are obtained in a substantially coarser particle size than in Example 1. The product from this Example contains substantially less fine dust (max. 4.5 % of particles Example 16: 512 g of an anionic dispersing agent (condensation product of formaldehyde with naphthalenesulfonic acid) and 1000 g of a further anionic dispersing agent (methylene-lini The ground product is subsequently introduced Into a laboratory fluidized bed granulator (STREA-1; Aeromatic AG, Bubendorf, Switzerland) as granulation nuclei. The nuclei are fluidized with the hot air (approximately eS"C) flowing into the granulator through the perforated base. The phthalocyanine solution is then sprayed continuously into the fluidized bed using a binary nozzle. After approximately 90 minutes, the granulation (metering in of the phthalocyanine solution) is terminated. Once the granulation is concluded the granules are dried in the same equipment, with air at a temperature of 80""C, to a residual water content of 5 % by weight. The particles are then discharged and the fines are removed by sieving. The average particle size is 380 pm. Examples 17 to 22: Granules having the following compositions are produced according to the same procedure as that in Example 16: Example 23: 826 g of a pulverulent dispersing agent (condensation product of formaldehyde with naphthalenesulfonic acid) are stirred into and dissolved in 1073 g of an aqueous solution of the zinc phthalocyanine compound from Example 1 having a solids content of 11 % by weight. The aqueous phthalocyanine solution is stirred for 1 hour in order that the dispersing agent is completely dissolved. In a glass beaker, 177 g of a water-soluble polyacrylamide (MW=200 000) are dissolved in 700 g of deionised water by heating the solution to a maximum of 50°C. Once the polymer has dissolved completely, the phthalocyanine solution is added with stirring. The preparation is stirred for one hour and then filtered through a filter having a pore size of 0.5 μ m. The filtrate is granulated in a spray dryer in which the fines produced during the process are continuously separated from the exhaust gas flow and conveyed directly by a gas flow into the spray cone of the nozzle. The granules are free-flowing and have an average particle size of 105μm. The fines (particle size The granules are completely soluble in water within a period of less than 2 minutes. When stored in a non-ionic surfactant, no dissolving out of the phthalocyanine compound is detected even after several days. Examples 24 to 34: The formulations listed in the following Table are produced analogously to Example 23 and, after spray-drying, result in granules having the same properties in terms of particle size, solubility in water and non-ionic surfactants as the granules according to Example 23. Examples 35 to 53: The formulations listed in the following Table are obtained by first of all preparing aqueous solutions of the components and then granulating those solutions in a fluidized spray dryer. As already described in Example 8, in the first phase of the granulation procedure the equipment is operated as a spray dryer in order to produce in the fluidized bed the nuclei necessary for the granulation (Tfeedair=210°C, Tbed=115°C). Once enough nuclei are present in the fluidized bed for the granulation, the bed temperature is reduced to approximately 65°C in order to initiate the granulation process. The granulation of the phthalocyanine solution is carried out at a fluidized bed temperature of from 60 to 68°C. The granules discharged from the granulator have a residual moisture content of approximately 12 % by weight and are then dried to the formulation-specific desired value (see following Table) in a continuously operating fluidized bed into which air at a temperature of 85°C is fed. Irrespective of the formulation in question, the granules are free-flowing, are rapidly dissolved in water and are not visibly soluble in non-ionic surfactants for a period of days. Example 54: The formulations listed in Examples 45 to 51 are granulated in a fluidized bed granulator (STREA-1, Aeromatic AG) instead of in the fluidized spray dryer. For that purpose, as explained in Example 16 some of the phthalocyanine solution is dried and ground separately and used as nuclei in the granulating procedure. The granules obtained from the fluidized bed granulation have an average particle size of from 250 to 480μm. The average particle size varies within that range according to the composition of the formulation. WE CLAIM: 1. Water-soluble granules of a phthalocyanine compound comprising a) from 2 to 50 % by weight of a water-soluble phthalocyanine compound, b) from 10 to 95 % by weight of an anionic dispersing agent, c) from 0 to 25 % by weight of a water-soluble organic polymer, d) from 0 to 10 % by weight of a wetting agent, water-insoluble, water-soluble dye or pigment, or dissolution accelerator or optical brightener, wherein components (a) to (d) are as herein described, and e) from 3 to 15 % by weight of water, based on the total weight of the granules. 2. The granules according to claim 1 comprising from 4 to 30 % by weight of phthalocyanine compound. 3. The granules according to claim 2 comprising from 5 to 20 % by weight of phthalocyanine compound. 4. The granules according to anyone of claims 1 to 3 comprising from 40 to 90 % by weight of anionic dispersing agent. 5. The granules according to claim 4 comprising from 50 to 90 % by weight of anionic dispersing agent. 6. The granules according to anyone of claims 1 to 5 comprising from 5 to 20 % by weight of organic polymer. 7. The granules according to claim 6 comprising from 8 to 18 % by weight of organic polymer. 8. The granules according to anyone of claims 1 to 7 comprising as phthalocyanine compound a water-soluble Zn, Fe(II), Ca, Mg, Na, K, AI, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) or Hf(VI) phthalocyanine compound. t is 0 or 1; and in the above formulae R7 and R6 are each independently of the other C1-CealkyI; R9 is C1-CealkyI; Cs-CycycloalkyI; or NR11R12; Rio and Rn are each independently of the other CrCsalkyl; R12 and R13 are each independently of the other hydrogen or C1-CsalkyI; R14 and R15 are each independently of the other unsubstituted C1-C6alkyl or C1-CealkyI substituted by hydroxy, cyano, carboxy, C1-C6alkoxycarbonyl, C1-Cealkoxy, phenyl, naphthyl or by pyridyl; u is from 1 to 6; Ai is the balance of an aromatic 5- to 7-membered nitrogen heterocycle which may contain one or two further nitrogen atoms as ring members, and Bi is the balance of a saturated 5- to 7-membered nitrogen heterocycle which may contain 1 or 2 further nitrogen, oxygen and/or sulfur atoms as ring members; Q2 is hydroxy; C1-C22alkyI; branched C4-C22alkyl; C2-C22alkenyl; branched C4-C22alkenyl or a mixture thereof; C1-C22alkoxy; a sulfo or carboxyl radical; a radical of the formula in which formulae Bz is hydrogen; hydroxy; C1-CaoalkyI; C1-Caoalkoxy; -CO2H; -CH2COOH; SO3M/; Mi; -Opium; or a mixture thereof; M is hydrogen; or an alkali metal ion or ammonium ion; Z2 is a chlorine, bromine, alkyl sulfate or aurally sulfate ion; a is 0 or 1; b is from 0 to 6; c is from 0 to 100; d isO;or1; e is from 0 to 22; V is an integer from 2 to 12; w is 0 or 1; and A is an organic or inorganic anion, and s in the case of monovalent anions A" is equal to r and in the case of polyvalent anions is and wherein the phthalocyanine ring system may also comprise further solubilising groups. 10. Granules according to)claim 9 comprising a phthalocyanine compound of formula R21 is C1-C4alkyl; C1-C4alkoxy; halogen, carboxy, C1-C4alkoxycarbonyl or hydroxy; and A" is a halide, alkyl sulfate or aryl sulfate ion; wherein the radicals -SO2NHR6-Xs"^A" may be identical or different. \11. Granules according to fclaim 10 comprising a phthalocyanine compound of formula wherein PC is the phthalocyanine ring system; Me is Zn, Fe(ll), Ca, Mg, Na, K, Al-Z,, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(lll). Zr(IV), In(lll), Sn(IV)orHf(VI); Zi is a halide, sulfate, nitrate, acetate or hydroxy ion; " is hydrogen, an alkali metal ion or an ammonium ion; and . r is any number from 1 to 4. Granules according to claim 11 comprising a phthalocyanine compound of formula (4) wherein Me isZn or AI-Z1; and Z1 is a halide, sulfate, nitrate, acetate or hydroxy ion. 13. Granulesrdccording claim 10 comprising a phthalocyanine compound of formula wherein PC, Me and q are as defined for formula (4); R17" and R18" are each independently of the other hydrogen, phenyl, sulfophenyl, carboxyphenyl, C1-CalkyI, hydroxy-C1-Cgalkyl, cyano-C1-CealkyI, sulfo-C1-Cealkyl, carboxy-CrCealkyl or halo-CrC6alkyl or, together with the nitrogen atom, form a morpholine ring; q" is an integer from 2 to 6; and wherein PC, Me and q are as defined for formula (4); Y"3 is hydrogen, an ali q" is an integer from 2 to 6; R17" and RIB" are each independently of the other hydrogen, phenyl, sulfophenyl, carboxy-phenyl, C1-CealkyI, hydroxy-CrCealkyl, cyano-C1-CealkyI, sulfo-C1-CealkyI, carboxy-C1-Cealkyl or halo-C1-CealkyI or, together with the nitrogen atom, form a morpholine ring, m" is 0 or 1; and r and ri are each independently of the other any number from 0.5 to 3.5, the sum r +ri being a minimum of 1 and a maximum of 4. 15. Granules according to claim 10 comprising a phthalocyanine compound of formula 16. Granules accord any one of claims 1 to 15 comprising as anionic dispersing agent a condensation product from the following group: condensation products of aromatic sulfonic acids and formaldehyde, condensation products of aromatic sulfonic acids with unsubstituted or chlorinated diphenylene or biphenyl oxides and optionally formaldehyde, (mono-/di-)-alkylnaphthalenesulfonates, sodium salts of polymerised organic sulfonic acids, sodium salts of polymerised alkylnaphthalenesulfonic acids, sodium salts of polymerised alkyl benzene-sulfonic acids, alkylarylsulfonates, sodium salts of alkyl polyglycol ether sulfates, polyalkylated polynuclear arylsulfonates, methylene-linked condensation products of arylsulfonic acids and hydroxyarylsulfonic acids, sodium salt of dialkylsulfosuccinic acid, sodium salts of alkyl diglycol ether sulfates, sodium salts of polynaphthalenemethane-sulfonates, ligno- or oxyligno-sulfonates or heterocyclic polysulfonic acids. 17. Granules according to claim 16 comprising as anionic dispersing agent a condensation product from the following group: condensation products of naphthalenesulfonic acids with formaldehyde, sodium salts of polymerised organic sulfonic acids, (mono-/di-)alkyl-naphthalenesulfonates, polyalkylated polynuclear arylsulfonates, sodium salts of polymerised alkylbenzenesulfonic acid, lignosulfonates, oxylignosulfonates and condensation products of naphthalenesulfonic acid with a polychloromethyldiphenyl. 18. Granules one of claims 1 to 17 comprising as water-soluble polymer a compound from the following group: gelatin, polyacrylates, polymethacrylates, polyvinyl¬ pyrrolidones, vinylpyrrolidones, vinyl acetates, copolymers of vinylpyrrolidone with long- chained a-olefins, poly(vinylpyrrolidone/dimethylaminoethyl methacrylates), copolymers of vinylpyrrolidone/dimethylaminopropyl methacrylamides, copolymers of vinylpyrrolidone/- dimethylaminopropyl acrylamides, quatemised copolymers of vinylpyrrolidones and dimethylaminoethyl methacrylates, terpolymers of vinylcaprolactam/vinylpyrrolidone dimethylaminoethyl methacrylates, copolymers of vinylpyrrolidone and methacrylamido-propyl-trimethylammonium chloride, terpolymers of caprolactam/vinylpyrrolidone/dimethyl-amino ethyl methacrylates, copolymers of styrene and acrylic acid, polycarboxylic acids, poly-acrylamides, carboxymethylcellulose, hydroxymethylcellulose, polyvinyl alcohols, polyvinyl acetate, hydrolysed polyvinyl acetate, copolymers of maleic acid with unsaturated hydro¬carbons, and mixed polymerizations products of the mentioned polymers. 19. The granules according to claim 18 comprising as water-soluble polymer a compound from the following group: carboxymethylcellulose, polyacrylamides, polyvinyl alcohols, polyvinyl¬pyrrolidones, gelatin, hydrolysed polyvinyl acetates, copolymers of vinylpyrrolidone and vinyl acetate, and also polyacrylates and polymethacrylates. 20. A method of producing the granules according to claim 1, wherein first of all an aqueous solution of the phthalocyanine dye is prepared in a known manner the anionic dispersing agent and, optional, a wetting agent, water-insoluble, water-soluble dye or pigment, or dissolution accelerator or optical brightener, and, optional, a water-soluble organic polymer, are added thereto, the mixture is stirred until a homogeneous solution is obtained, and the aqueous solution is then subjected to a drying step in which all water, with the exception of a residual amount, is removed, solid particles (granules) simultaneously being formed. 21. The method according to claim 20, wherein the removal of water is effected by spray-drying. 22. The method according to claim 21, wherein the removal of water is effected by spray-drying with direct return of the fine particles of solid to the spraying zone. 23. The method according to claim 20, wherein the removal of water is carried out in a fluidized bed dryer. 24. The method according to claim 20, wherein the removal of water is carried out in a fluidized bed .

Full Text

The present invention relates to water-soluble granules of phthalocyanine compounds, to a method of produC1ng them, and to the use thereof in washing agent preparations.
Water-soluble phthalocyanine dyes, espeC1ally zinc and aluminium phthalocyanine-sulfonates, are frequently used as photoactivators in washing agent preparations. In view of the fact that such photoactivators dissolve too slowly in water, problems often arise, espeC1ally when there is inadequate mixing of the washing liquor, because the coloured photoactivators stain the laundry.
Solid microcapsules of phthalocyanine photoactivators that contain at least 38 % of an encapsulating material havealready been described in EP-B-0 333 270 but those microcapsules are also not able to satisfy all of the consumer"s requirements in terms of dissolving behaviour and staining of the laundry.
It has now been found that, surprisingly, granules comprising a water-soluble phthalocyanine compound, an anionic dispersing agent and a maximum of 25 % by weight of an organic polymer are distinguished by a high rate of dissolution in water, with the result that the problems mentioned above are substantially or entirely eliminated. A further advantage of such granules is that, even in the case of prolonged contact with a non-ionic surfactant, the phthalocyanine compound is not dissolved out of the granules and the laundry is not stained.
The present invention accordingly relates to water-soluble granules of phthalocyanine compounds comprising
a) from 2 to 50 % by weight of a water-soluble phthalocyanine compound,
b) from 10 to 95 % by weight of an anionic dispersing agent,

c) from 0 to 25 % by weight of a water-soluble organic polymer,
d) from 0 to 10 % by weight of a further additive and
e) from 3 to 15 % by weight of water, based on the total weight of the granules. J
There come into consideration as the phthalocyanine compound for the granules according to the invention phthalocyanine complexes having a di-, tri- or tetra-valent metal (complexes having a d° or d 10configuration) as the central atom. Such complexes are espeC1ally water-

soluble Zn, Fe(ll), Ca, Mg, Na, K, Al, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(lll), Zr(IV), In(lll), if Sn(IV) and Hf(VI) phthalocyanines, aluminium phthalocyanine and zinc phthalocyanine being I] espeC1ally preferred.
Advantageously, the composition according to the invention comprises a phthalocyanine compound of formula

wherein
PC is the phthalocyanine ring system;
Me is Zn, Fe(ll), Ca, Mg, Na, K, AI-Z1, Si(IV), P(V), Ti(l\/), Ge(IV), Cr(VI), Ga(lll). Zr(IV),

Re is branched or unbranched C1-Csalkylene; or 1,3- or 1,4-phenylene; X2 is -NH-; or -N-d-C5alkyl-; X3* is a group of the formula

and in the above formulae
R7 and R8 are each independently of the other C1-Cealkyl;
R9 is C1-CealkyI; Cs-C/cycioalkyI; or NR11R12;
R10 and R11 are each independently of the other C1-CealkyI;
R12 and Ri3 are each independently of the other hydrogen or C1-CsalkyI;
Ri4 and R15 are each independently of the other unsubstituted C1-CealkyI or C1-CealkyI
substituted by hydroxy, cyano, carboxy, C1-Cealkoxycarbonyl, CrCealkoxy, phenyl,
naphthyl or by pyridyl; u is from 1 to 6; Ai is the balance of an aromatic 5- to 7-membered nitrogen heterocycle which may
contain one or two further nitrogen atoms as ring members, and Bi is the balance of a saturated 5- to 7-membered nitrogen heterocycle which may
contain 1 or 2 further nitrogen, oxygen and/or sulfur atoms as ring members; Q2 is hydroxy; CrC22alkyl; branched C4-C22alkyl; C2-C22alkenyl; branched C4-C22alkenyl
or a mixture thereof; C1-C22alkoxy; a sulfo or carboxyl radical; a radical of the formula

I
B2 is hydrogen; hydroxy; C1-CaoalkyI; C1-Caoalkoxy; -CO2H; -CH2COOH; SO3Mr; -OSO3M/; -PO3; Mi; -Poem’s; or a mixture thereof;
B3 is hydrogen; hydroxy; -COOH; -SO2iVI/; -Sao’s/; or C1-C6all Ml is a water-soluble cation;
Ti is -0-; or -NH-;
Xi and X4 are each independently of the other -0-; -NH-; or -N-C1-Csaikyl;
R16 and R17 are each independently of the other hydrogen, a sulfo group or a salt thereof, a carboxyl group or a salt thereof, or a hydroxyl group, at least one of the radicals R16 and R17 being a sulfo or carboxyl group or a salt thereof,
Y2 is -0-, -S-, -NH- or -N-C1-CsalkyI;
R18 and Ri9 are each independently of the other hydrogen, C1-CealkyI, hydroxy-C1-Cealkyl, cyano-C1-CealkyI, sulfo-CycioalkyI, carboxy or halo-C1-CealkyI; unsubstituted phenyl; or phenyl substituted by halogen, C1-C4alkyl or C1-C4alkoxy, sulfo or by carboxy; or R18 and Ri9, together with the nitrogen atom to which they are bonded, form a saturated 5-or 6-membered heterocyclic ring that may in addition contain a further nitrogen atom or an oxygen atom as ring member;

All ot the adore-mentioned nitrogen neterocycles may In addition be substituted by alky! groups, either at a carbon atom or at a further nitrogen atom located in the ring, in which case the methyl group is preferred as alkyl group.
As in formula (1a) denotes, as countering to the positive charge of the remainder of the molecule, any desired anion. It is generally introduced by the preparation process (quaternisation), in which case it Is preferably a halogen ion, an alkyl sulfate ion or an aryl sulfate ion. Among the aryl sulfate ions mention should be made of the phenylsulfonate, p-tolylsulfonate and p-chlorophenylsulfonate ions. It is also possible, however, for any other anion to function as the anion, since the anions can readily be interchanged in known manner; As’ may also be a sulfate, sulfite, carbonate, phosphate, nitrate, acetate, oxalate, citrate or lactate ion or another anion of an organic carboxylic acid. In the case of mono¬valent anions, the index s is equal to r. In the case of polyvalent anions, s assumes a value C1-C6AlkyI and C1-C6alkoxy are straight-chain or branched alkyl and alkoxy radicals, respectively, such as, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl or hexyl and methoxy, ethoxy, n-priory, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy, tert-amyloxy or hexyloxy, respectively.
C2-C22Alkenyl is, for example, ally, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.
Preferred phthalocyanine compounds of formula (1a) for the granules according to the invention correspond to formula

Me, q, PC, X2, X3 and Re are as defined for formula (1a);
M is hydrogen, or an alkali metal, ammonium or amine salt ion;
and the sum of the numbers ri and TZ is from 1 to 4, and
As" exactly balances the positive charge of the remainder of the molecule,
and correspond especially to formula

in which formulae
R7 and Rs are each independently of the other unsubstituted Ci-C4alkyl or Ci-C4alkyl
substituted by hydroxy, cyano, halogen or by phenyl; R9 is R7; cyclohexyl or amino; R11 is Ci-C4alkyl;
R21 is Ci-C4alkyl; Ci-C4alkoxy; halogen, carboxy, Ci-C4alkoxycarbonyl or hydroxy; and A" is a halide, alkyl sulfate or aryl sulfate ion; wherein the radicals -S02NHR"6-X3""^A" may be identical or different.
Further phthalocyanine compounds that can be used in accordance with the invention correspond to formula

wherein
PC is the phthalocyanine ring system;
Me is Zn, Fe(ll), Ca, Mg, Na, K, AI-Z1, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(ill), Zr(IV),
In(lll), Sn(IV) or Hf(VI); Zi is a halide, sulfate, nitrate, acetate or hydroxy ion;
Y3" is hydrogen, an alkali metal ion or an ammonium ion; and r is any number from 1 to 4.
Special preference is given to those phthalocyanine compounds of formula (4) wherein
Me isZn or AI-Z1; and
Zi is a halide, sulfate, nitrate, acetate or hydroxy ion.
Further phthalocyanine compounds of interest that can be used in accordance with the invention correspond to formula

wherein
PC, Me and q are as defined for formula (4);
R17" and Ris" are each independently of the other hydrogen, phenyl, sulfophenyl,
carboxyphenyl, Ci-CealkyI, hydroxy-C1-CealkyI, cyano-CrCealkyl, sulfo-C1-CealkyI, carboxy-C1-C6alkyI or halo-CrCealkyl or, together with the nitrogen atom, form a morpholine ring;
q" is an integer from 2 to 6; and
r is a number from 1 to 4;

Further phthalocyanine compounds of interest that can be used in accordance with the invention correspond to formula

wherein
PC, Me and q are as defined for formula (4);
Y"3 is hydrogen, an alkali metal ion or an ammonium ion;
q" is an integer from 2 to 6;
R17" and Rie" are each independently of the other hydrogen, phenyl, sulfophenyl,
carboxyphenyl, Ci-CealkyI, hydroxy-Ci-CealkyI, cyano-CrCealkyI, sulfo-CrCealkyl, carboxy-Ci-CealkyI or halo-Ci-CealkyI or, together with the nitrogen atom, form a morpholine ring,
m" is 0 or 1; and
r and ri are each independently of the other any number from 0.5 to 3.5, the sum r +ri being
a minimum of 1 and a maximum of 4.
Where the central atom Me in the phthalocyanine ring is Si(IV), the phthalocyanines used in accordance with the invention may contain, in addition to the substituents on the phenyl nucleus of the phthalocyanine ring, also axial substituents (= R24). Such phthalocyanines correspond, for example, to formula

Especially preferred as phthalocyanlne compound are compounds such as those commercially available and used in washing agents. Usually, the anionic phthalocyanlne compounds are in the form of alkali metal salts, especially sodium salts.
Preferred formulations of the granules contain from 4 to 30 % by weight, especially from 5 to /
20 % by weight, of phthalocyanlne compound, based on the total weight of the granules. I
it will be understood that it is also possible to use mixtures of two or more phthalocyanlne compounds instead of a single, homogeneous phthalocyanlne compound.
The anionic dispersing agents used are, for example, the commercially available water-soluble anionic dispersing agents for dyes, pigments etc..
The following products, especially, come into consideration: condensation products of
aromatic sulfonic acids and formaldehyde, condensation products of aromatic sulfonic acids with unsubstituted or chlorinated diphenylene or diphenyl oxides and optionally form- ;
aldehyde, (mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerised organic
sulfonic acids, sodium salts of polymerised alkylnaphthalenesulfonic acids, sodium salts of Ah
polymerised alkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkyl polyglycol i ^
ether sulfates, polyalkylated polynuclear arylsulfonates, methylene-linked condensation |
I
products of arylsulfonic acids and hydroxyarylsulfonic acids, sodium salt of dally- |
I
sulfosuccinic acid, sodium salts of alkyl diglycol ether sulfates, sodium salts of poly- i
naphthalenemethanesulfonates, jigno- or oxyligno-sulfonates or heterocyclic polysulfonic |
acids.

The dispersing agents may be used individually or in the form of a mixture of two or more dispersing agents.
Especially suitable anionic dispersing agents are condensation products of naphthalene- \ , l
sulfonic acids with formaldehyde, sodium salts of polymerised organic sulfonic acids, 1 v *vv "* (mono-/di-)alkylnaphthalenesulfonates, polyalkylated polynuclear aryl sulfonates, sodium h " salts of polymerised alkylbenzenesulfonic acid, lignosulfonates, oxylignosulfonates and U condensation products of naphthalenesulfonic acid with a polychloromethyldiphenyl.
Preferably, the granules according to the invention contain from 40 to 90 % by weight, / ^" ^^ ^ "^
especially from 50_to.S£L% by weight, of anionic dispersing agent. "l
In addition to the water-soluble phthalocyanine compound and the anionic dispersing agent, the granules according to the invention may comprise a water-soluble organic polymer. Such polymers may be used individually or in the form of a mixture of two or more polymers. Preferably, such a polymer is added for the purpose of improving the mecjianic stability of the granules and/or when, during later use of the granules in a washing agent, the phthalo¬cyanine compound is to be prevented from being dissolved out of the granules by a non-ionic surfactant.
There come into consideration as water-soluble polymers, for example, gelatin, poly-acrylates, polymethacrylates, copolymers of ethyl acetate, methyl methacrylate and methacrylic acid (ammonium salt), polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, copolymers of vinylpyrrolidone with long-chained a-olefins, poly(vinylpyrrolidone/dimethyl-aminoethyl methacrylates), copolymers of vinylpyrrolidone/dimethylaminopropyl methacrylamides, copolymers of vinylpyrrolidone/dimethylaminopropyl acrylamides, quaternised copolymers of vinylpyrrolidones and dimethylaminoethyl methacrylates, terpolymers of vinylcaprolactam/vinylpyrrolldone/dimethylaminoethyl methacrylates, copolymers of vinylpyrrolidone and methacrylamidopropyl-trimethylammonium chloride, terpolymers of caprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates, copolymers of styrene and acrylic acid, polycarboxylic acids, polyacrylamides, carboxymethylcellulose, hydroxymethylcellulose, polyvinyl alcohols, polyvinyl acetate, hydrolysed polyvinyl acetate, copolymers of maleic acid with unsaturated hydrocarbons, and mixed polymerizations products of the mentioned polymers.

Of those organic polymers, carboxymethylcellulose, polyacrylamides, polyvinyl alcohols, polyvinylpyrrolidones, gelatin, hydrolysed polyvinyl acetates, copolymers of vinylpyrrolidone and vinyl acetate, and also polyacrylates and polymethacrylates, are especially preferred.
The organic polymers are used in an amount of from 0 to 25 % by weight, preferably from 5 to 20 % by weight and, especially, from 8 to 18 % by weight, based on the total weight of the granules.
The granules according to the invention may comprise further additives, for example wetting agents, water-insoluble or water-soluble dyes or pigments, and also dissolution accelerators and optical brighteners. Such additives are present in an amount of from 0 to 10 % by weight, based on the total weight of the granules.
The granules according to the invention are produced, for example, in the following manner: first of all an aqueous solution of the phthalocyanine dye is prepared, the anionic dispersing agent and, if desired, further additives are added thereto, and the mixture is stirred, where appropriate with heating, until a homogeneous solution is obtained. The solids content of the solution should preferably be at least 30 % by weight, especially from 40 to 50 % by weight, based on the total weight of the solution. The viscosity of the solution is preferably less than 200 mPas.
The aqueous solution comprising the phthalocyanine dye and the anionic dispersing agent is then subjected to a drying step in which all water, with the exception of a residual amount, is removed, solid particles (granules) simultaneously being formed. Known methods are suitable for producing the granules from the aqueous solution. In principle, both continuous methods and discontinuous methods are suitable. Continuous methods are preferred, especially spray-drying and fluidized bed granulation processes.
Especially suitable are spray-drying processes in which the active ingredient solution is sprayed into a chamber with circulating hot air. The atomization of the solution is carried out using unitary or binary nozzles or is brought about by the spinning effect of a rapidly rotating disc. In order to increase the particle size, the spray- drying process may be combined with an additional agglomeration of the liquid particles with solid nuclei in a fluidized bed that forms an integral part of the chamber (so-called fluidized spray dryer). The fine particles

( During the granulation step, the water can rapidly be removed from the solutions comprising phthalocyanine compound, anionic dispersing agent and possibly organic polymer and further additives, and it is expressly intended that agglomeration of the droplets forming in the atomising cone, i.e. the agglomeration of droplets with solid particles, will take place.
If necessary, the granules formed in the spray-dryer are removed in a continuous process, for example by a sieving operation. The fines and the oversize particles are either recycled directly to the process (without being rediscover) or are dissolved in the liquid active ingredient formulation and subsequently granulated again.
The granules according to the invention are resistant to abrasion, low in dust, free-flowing and can readily be metered. They are distinguished in particular by very rapid solubility in water. They are used especially in washing agent formulations. They may be added in the desired concentration of the phthalocyanine compound directly to a washing agent formulation. The present invention relates also to that use.
Where the dark appearance of the granules in the washing agent is to be suppressed, this can be achieved, for example, by embedding the granules in a droplet of a whitish moldable substance ("water-soluble wax") or, preferably, by encapsulating the granules in a melt consisting, for example, of a water-soluble wax, as described in EP-B-0 323 407 B1, a white solid (e.g. titanium dioxide) being added to the melt in order to reinforce the masking effect of the capsule.
The present invention accordingly relates also to washing agent formulations comprising
I) from 5 to 70 % A) of an anionic surfactant and/or B) of a non-ionic surfactant,
II) from 5 to 50 % C) of a builder substance,
III) from 1 to 12 % D) of a peroxide and, where appropriate, a catalyst and
IV) from 0.01 to 1 % E) of granules according to the invention,

the percentages in each case being percentages by weight, based on the total weight of the washing agent.
Preference is given to washing agent formulations comprising
I) from 5 to 70 % A) of an anionic surfactant and/or B) of a non-ionic surfactant,
II) from 5 to 40 % C) of a builder substance,

III) from 1 to 12 % D) of a peroxide and, where appropriate, a catalyst and
IV) from 0.01 to 0.5 % E) of granules according to the invention,
the percentages in each case being percentages by weight, based on the total weight of the washing agent.
The washing agent may be in solid or liquid form, for example in the form of a liquid non¬aqueous washing agent containing not more than 5 % by weight, preferably from 0 to 1 % by weight, of water, and may have as base a suspension of a builder substance in a non-ionic surfactant, for example as described in GB-A-2 158 454.
Preferably, however, the washing agent is in the form of a powder or granules, which can be produced, for example, by first of all preparing a starting powder by spray-drying an aqueous suspension containing all of the components listed above with the exception of components D) and E), and then adding the dry components D) and E) and mixing everything together.
It is also possible to start with an aqueous suspension that contains components A) and C), but not component B) or only some of component B). The suspension is spray-dried, then component E) is mixed with component B) and the mixture is added to the suspension, and subsequently component D) is admixed dry.
Preferably, the components are mixed with one another in such amounts that a solid compact washing agent in the form of granules is obtained that has a specific weight of at least 500 g/l.
In another preferred embodiment, the production of the washing agent is carried out in three steps. In the first step a mixture of anionic surfactant (and, where appropriate, a small amount of non-ionic surfactant) and builder substance is prepared. In the second step that

mixture is sprayed with the major portion of the non-ionic surfactant and then, in the third step, peroxide, where appropriate catalyst, and the granules according to the invention are added. That method is usually carried out in a fluidized bed.
In a further preferred embodiment, the individual steps are not carried out completely separately, so that there is a certain amount of overlap between them. Such a method is usually carried out in an extruder, in order to obtain granules in the form of mega pearls.
The anionic surfactant A) may be, for example, a sulfate, sulfonates or carboxyl ate surfactant or a mixture of those surfactants.
Preferred sulfates are those having from 12 to 22 carbon atoms in the alkyl radical, where appropriate in combination with alkyl ethoxysulfates having from 10 to 20 carbon atoms in the alkyl radical.
Preferred sulfonates are, for example, alkylbenzenesulfonates having from 9 to 15 carbon atoms in the alkyl radical and/or alkyl naphthalenesulfonates having from 6 to 16 carbon atoms in the alkyl radical in question.
The cation in the anionic surfactant is preferably an alkali metal cation, especially sodium.
Preferred carboxylates are alkali metal sarcosinates of the formula R-C0-N(R1)-CH2C00M\ wherein R is alkyl or alkenyl having from 8 to 18 carbon atoms in the alkyl or alkenyl radical, R1 is C1-C4alkyl and M1 is an alkali metal.
The non-ionic surfactant B) may be, for example, a condensation product of from 3 to 8 mols of ethylene oxide with 1 mol of primary alcohol that contains from 9 to 15 carbon atoms.
There come into consideration as builder substance C), for example, alkali metal phosphates, especially tripolyphosphates, carbonates or hydrogen carbonates, especially the sodium salts, silicates, aluminium silicates, polycarboxylates, polycarboxylic acids.

organic phosphonates, aminoalkylenepoly(alkylenephosphonates) or mixtures of those compounds.
Especially suitable silicates are sodium salts of crystalline silicates having layered structures of the formula NaHSit02t+i.pH20 or Na2Sif02t+i.pH20, wherein t is a number from 1.9 to 4 and p is a number from 0 to 20.
Among the aluminium silicates, preference is given to those obtainable commercially under the names zeolite A, B, X and HS, and also to mixtures comprising two or more of those components.
Among the polycarboxylates, preference is given to polyhydroxycarboxylates, especially citrates, and acrylates and also copolymers thereof with malefic anhydride.
Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and ethylenediamine dissociated either in racemes form or in the enantiomerically pure S,S form.
Phosphonates or aminoalkylenepoly(alkylenephosphonates) that are especially suitable are alkali metal salts of 1-hydroxyethane-1,1-diphosphonlc acid, nitrilotris(methylenephos-phonic acid), ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepenta-methylenephosphonic acid.
There come into consideration as the peroxide component D), for example, the organic and inorganic peroxides known in the literature and available commercially that bleach textile materials at conventional washing temperatures, for example at from 10 to 95°C.
The organic peroxides are, for example, mono- or poly-peroxides, especially organic piracies or salts thereof, such as phthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanoic diacid, diperoxynonanoic diacid, diperoxydecanoic dyadic, diperoxy-phthalic acid or salts thereof.
Preferably, however, inorganic peroxides are used, such as, for example, per sulfates, per borates, percarbonates and/or per silicates. It will be understood that mixtures of

inorganic and/or organic peroxides can also be used. The peroxides may be in a variety of crystalline forms and have different water contents, and they may also be used together with other inorganic or organic compounds in order to improve their storage stability.
The peroxides are added to the washing agent preferably by mixing the components, for example using a screw metering system and/or a fluidized bed mixer.
The washing agents may comprise, in addition to the combination according to the invention, one or more optical brighteners, for example from the class bis-triazinylamino-stilbenedisulfonic acid, bis-triazolylstiibenedisuifonic acid, bis-styrylbiphenyl or bis-benzo-furanylbiphenyl, a bis-benzoxalyl derivative, bis-benzimidazolyl derivative or coumarone derivative or a pyrazoline derivative.
The washing agent may also comprise suspending agents for dirt, e.g. sodium carboxy-methylcellulose, pH regulators, e.g. alkali metal or alkaline earth metal silicates, foam regulators, e.g. soap, salts for regulating the spray-drying and the granulating properties, e.g. sodium sulfate, perfumes and, optionally, antistatic agents and softeners, enzymes, such as amylase, bleaches, pigments and/or toning agents. It will be understood that such constituents must be stable towards the bleaching agent used.
Further preferred additives to the washing agents according to the invention are polymers which, during the washing of textiles, prevent staining caused by dyes in the washing liquor which have been released from the textiles under the washing conditions. Such polymers are preferably polyvinylpyrrolidones which, where appropriate, have been modified by the incorporation of anionic or cationic substituents, especially those having a molecular weight in the range from 5000 to 60 000, more especially from 10 000 to 50 000. Such polymers are preferably used in an amount of from 0.05 to 5 % by weight, especially from 0.2 to 1.7% by weight, based on the total weight of the washing agent.
In addition, the washing agents according to the invention may also comprise so-called perborate activators, such as, for example, TAED or TAGU. Preference is given to TAED, which is preferably used in an amount of from 0.05 to 5 % by weight, especially from 0.2 to 1.7 % by weight, based on the total weight of the washing agent.

Accordingly, the present invention provides a water-soluble granules of a phthalocyanine compound comprising a) from 2 to 50 % by weight of a water-soluble phthalocyanine compound, b) from 10 to 95 % by weight of an anionic dispersing agent, c) from 0 to 25 % by weight of a water-soluble organic polymer, d) from 0 to 10 % by weight of a wetting agent, water-insoluble, water-soluble dye or pigment, or dissolution accelerator or optical brightener, wherein components (a) to (d) are as herein described, and e) from 3 to 15 % by weight of water, based on the total weight of the granules.
Accordingly, the present invention also provides a method of producing the granules such as herein described, wherein first of all an aqueous solution of the phthalocyanine dye is prepared in a known manner the anionic dispersing agent and, optional, a wetting agent, water-insoluble, water-soluble dye or pigment, or dissolution accelerator or optical brightener, and, optional, a water-soluble organic polymer, are added thereto, the mixture is stirred until a homogeneous solution is obtained, and the aqueous solution is then subjected to a drying step in which all water, with the exception of a residual amount, is removed, solid particles (granules) simultaneously being formed.

The following Examples serve to illustrate the invention without limiting the invention thereto. Parts and percentages relate to weight, unless specified otherwise.
Example 1: 725 g of an aqueous solution of a zinc phthalocyanine compound (sodium salt of zinc phthalocyanine, containing 3 or 4 sulfo groups) having a solids content of 20 % by weight are introduced into a glass beaker. 3010 g of an aqueous solution containing 40 % by weight of an anionic dispersing agent (condensation product of naphthalenesulfonic acid and formaldehyde) are added to the first solution. The phthalocyanine/dispersing agent mixture having a solids content of approximately 34 % by weight is homogenised by stirring at 25°C for 1 hour. The solution is then spray-dried in a spray dryer equipped with a unitary nozzle. The exhaust air temperature is 105°C at a feed air temperature of 195°C. Free-flowing granules having an average particle size of 50 [jm and a residual water content of 7 % are obtained. The granules produced in that manner contain 10 % zinc phthalocyanine.
Examples 2 to 7: Granules having the following compositions are produced according to the same procedure: the phthalocyanines in Examples 2 to 48 each contain 3 or 4 sulfo groups and are in the form of sodium salts.

Example 8: 880 g of an aqueous solution of an aluminium phthalocyanine compound (sodium salt of aluminium phthalocyanine, containing 3 or 4 sulfo groups) having a solids content of 25 % by weight are introduced into a glass beaker and diluted with 1460 g of deionised water. The solution is heated to 45""C and a dry, pulverulent anionic dispersing agent (condensation product of formaldehyde with naphthalenesulfonic acid) is introduced in portions into the heated solution. The dispersing-agent-containing phthalocyanine solution is then stirred at 45°C for 2 hours in order that the dispersing agent is completely dissolved.
The finished phthalocyanine/dispersing agent solution having a solids content of 45 % is granulated while still warm in a bench fluidized spray dryer. In the first phase of that granulation procedure, the nuclei are formed in the fluidized bed (

95°C). Once enough nuclei are present in the fluidized bed for the granulation, the bed temperature is reduced to approximately 50°C in order to initiate the granulation process. The granulation of the entire phthalocyanine solution is carried out at a fluidized bed temperature of from 48 to 51 °C. The granules discharged from the granulator have a residual moisture content of approximately 14 % by weight and are then dried to the desired value of 9 % by weight in a continuously operating fluidized bed with air at a temperature of 75°C.
The free-flowing granules have an average particle size of 160 pm and contain 10 % by weight aluminium phthalocyanine compound.

Example 15: The preparation of the phthalocyanine solution and the typical formulations of the phthalocyanine granules correspond to Examples 1 to 7. Unlike Example 1, the granulation is carried out in a spray dryer in which the fines produced during the process are continuously separated from the waste gas flow and are conveyed directly by a gas flow into the atomizing cone of the nozzle. The resulting granules have the same properties as those already described in Example 1. Their average particle size is 112 |jm, so that they are obtained in a substantially coarser particle size than in Example 1. The product from this Example contains substantially less fine dust (max. 4.5 % of particles Example 16: 512 g of an anionic dispersing agent (condensation product of formaldehyde with naphthalenesulfonic acid) and 1000 g of a further anionic dispersing agent (methylene-lini The ground product is subsequently introduced Into a laboratory fluidized bed granulator (STREA-1; Aeromatic AG, Bubendorf, Switzerland) as granulation nuclei. The nuclei are fluidized with the hot air (approximately eS"C) flowing into the granulator through the perforated base. The phthalocyanine solution is then sprayed continuously into the fluidized bed using a binary nozzle. After approximately 90 minutes, the granulation (metering in of the phthalocyanine solution) is terminated. Once the granulation is concluded the granules are dried in the same equipment, with air at a temperature of 80""C, to a residual water content of 5 % by weight.
The particles are then discharged and the fines are removed by sieving. The average particle size is 380 pm.
Examples 17 to 22: Granules having the following compositions are produced according to the same procedure as that in Example 16:

Example 23: 826 g of a pulverulent dispersing agent (condensation product of formaldehyde with naphthalenesulfonic acid) are stirred into and dissolved in 1073 g of an aqueous solution of the zinc phthalocyanine compound from Example 1 having a solids content of 11 % by weight. The aqueous phthalocyanine solution is stirred for 1 hour in order that the dispersing agent is completely dissolved.
In a glass beaker, 177 g of a water-soluble polyacrylamide (MW=200 000) are dissolved in 700 g of deionised water by heating the solution to a maximum of 50°C. Once the polymer has dissolved completely, the phthalocyanine solution is added with stirring. The preparation is stirred for one hour and then filtered through a filter having a pore size of 0.5 μ m.
The filtrate is granulated in a spray dryer in which the fines produced during the process are continuously separated from the exhaust gas flow and conveyed directly by a gas flow into the spray cone of the nozzle. The granules are free-flowing and have an average particle

size of 105μm. The fines (particle size The granules are completely soluble in water within a period of less than 2 minutes. When stored in a non-ionic surfactant, no dissolving out of the phthalocyanine compound is detected even after several days.
Examples 24 to 34: The formulations listed in the following Table are produced analogously to Example 23 and, after spray-drying, result in granules having the same properties in terms of particle size, solubility in water and non-ionic surfactants as the granules according to Example 23.

Examples 35 to 53: The formulations listed in the following Table are obtained by first of all preparing aqueous solutions of the components and then granulating those solutions in a fluidized spray dryer.
As already described in Example 8, in the first phase of the granulation procedure the equipment is operated as a spray dryer in order to produce in the fluidized bed the nuclei necessary for the granulation (Tfeedair=210°C, Tbed=115°C). Once enough nuclei are present in the fluidized bed for the granulation, the bed temperature is reduced to approximately

65°C in order to initiate the granulation process. The granulation of the phthalocyanine solution is carried out at a fluidized bed temperature of from 60 to 68°C. The granules discharged from the granulator have a residual moisture content of approximately 12 % by weight and are then dried to the formulation-specific desired value (see following Table) in a continuously operating fluidized bed into which air at a temperature of 85°C is fed. Irrespective of the formulation in question, the granules are free-flowing, are rapidly dissolved in water and are not visibly soluble in non-ionic surfactants for a period of days.

Example 54: The formulations listed in Examples 45 to 51 are granulated in a fluidized bed granulator (STREA-1, Aeromatic AG) instead of in the fluidized spray dryer. For that purpose, as explained in Example 16 some of the phthalocyanine solution is dried and ground separately and used as nuclei in the granulating procedure.
The granules obtained from the fluidized bed granulation have an average particle size of from 250 to 480μm. The average particle size varies within that range according to the composition of the formulation.

WE CLAIM:
1. Water-soluble granules of a phthalocyanine compound comprising
a) from 2 to 50 % by weight of a water-soluble phthalocyanine compound,
b) from 10 to 95 % by weight of an anionic dispersing agent,
c) from 0 to 25 % by weight of a water-soluble organic polymer,
d) from 0 to 10 % by weight of a wetting agent, water-insoluble, water-soluble dye or pigment, or dissolution accelerator or optical brightener, wherein components (a) to (d) are as herein described, and
e) from 3 to 15 % by weight of water, based on the total weight of the granules.
2. The granules according to claim 1 comprising from 4 to 30 % by weight of phthalocyanine
compound.
3. The granules according to claim 2 comprising from 5 to 20 % by weight of phthalocyanine
compound.
4. The granules according to anyone of claims 1 to 3 comprising from 40 to 90 % by weight of
anionic dispersing agent.
5. The granules according to claim 4 comprising from 50 to 90 % by weight of anionic dispersing agent.
6. The granules according to anyone of claims 1 to 5 comprising from 5 to 20 % by weight of organic polymer.

7. The granules according to claim 6 comprising from 8 to 18 % by weight of organic polymer.
8. The granules according to anyone of claims 1 to 7 comprising as phthalocyanine compound a water-soluble Zn, Fe(II), Ca, Mg, Na, K, AI, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) or Hf(VI) phthalocyanine compound.

t is 0 or 1;
and in the above formulae
R7 and R6 are each independently of the other C1-CealkyI;
R9 is C1-CealkyI; Cs-CycycloalkyI; or NR11R12;
Rio and Rn are each independently of the other CrCsalkyl;
R12 and R13 are each independently of the other hydrogen or C1-CsalkyI;
R14 and R15 are each independently of the other unsubstituted C1-C6alkyl or C1-CealkyI
substituted by hydroxy, cyano, carboxy, C1-C6alkoxycarbonyl, C1-Cealkoxy, phenyl,
naphthyl or by pyridyl; u is from 1 to 6;

Ai is the balance of an aromatic 5- to 7-membered nitrogen heterocycle which may contain one or two further nitrogen atoms as ring members, and
Bi is the balance of a saturated 5- to 7-membered nitrogen heterocycle which may contain 1 or 2 further nitrogen, oxygen and/or sulfur atoms as ring members;
Q2 is hydroxy; C1-C22alkyI; branched C4-C22alkyl; C2-C22alkenyl; branched C4-C22alkenyl or a mixture thereof; C1-C22alkoxy; a sulfo or carboxyl radical; a radical of the formula

in which formulae
Bz is hydrogen; hydroxy; C1-CaoalkyI; C1-Caoalkoxy; -CO2H; -CH2COOH; SO3M/;
Mi; -Opium; or a mixture thereof;

M is hydrogen; or an alkali metal ion or ammonium ion;
Z2 is a chlorine, bromine, alkyl sulfate or aurally sulfate ion;
a is 0 or 1;
b is from 0 to 6;
c is from 0 to 100;
d isO;or1;
e is from 0 to 22;
V is an integer from 2 to 12;
w is 0 or 1; and
A is an organic or inorganic anion,
and

s in the case of monovalent anions A" is equal to r and in the case of polyvalent anions is and wherein the phthalocyanine ring system may also comprise further solubilising groups.
10. Granules according to)claim 9 comprising a phthalocyanine compound of formula

R21 is C1-C4alkyl; C1-C4alkoxy; halogen, carboxy, C1-C4alkoxycarbonyl or hydroxy; and
A" is a halide, alkyl sulfate or aryl sulfate ion;
wherein the radicals -SO2NHR6-Xs"^A" may be identical or different.
\11. Granules according to fclaim 10 comprising a phthalocyanine compound of formula

wherein
PC is the phthalocyanine ring system;
Me is Zn, Fe(ll), Ca, Mg, Na, K, Al-Z,, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(lll). Zr(IV),
In(lll), Sn(IV)orHf(VI); Zi is a halide, sulfate, nitrate, acetate or hydroxy ion;
" is hydrogen, an alkali metal ion or an ammonium ion; and
. r is any number from 1 to 4.
Granules according to claim 11 comprising a phthalocyanine compound of formula (4) wherein
Me isZn or AI-Z1; and Z1 is a halide, sulfate, nitrate, acetate or hydroxy ion.
13. Granulesrdccording claim 10 comprising a phthalocyanine compound of formula

wherein
PC, Me and q are as defined for formula (4);
R17" and R18" are each independently of the other hydrogen, phenyl, sulfophenyl,
carboxyphenyl, C1-CalkyI, hydroxy-C1-Cgalkyl, cyano-C1-CealkyI, sulfo-C1-Cealkyl, carboxy-CrCealkyl or halo-CrC6alkyl or, together with the nitrogen atom, form a morpholine ring;
q" is an integer from 2 to 6; and

wherein
PC, Me and q are as defined for formula (4);
Y"3 is hydrogen, an ali q" is an integer from 2 to 6;
R17" and RIB" are each independently of the other hydrogen, phenyl, sulfophenyl, carboxy-phenyl, C1-CealkyI, hydroxy-CrCealkyl, cyano-C1-CealkyI, sulfo-C1-CealkyI, carboxy-C1-Cealkyl or halo-C1-CealkyI or, together with the nitrogen atom, form a morpholine ring,
m" is 0 or 1; and
r and ri are each independently of the other any number from 0.5 to 3.5, the sum r +ri being
a minimum of 1 and a maximum of 4.
15. Granules according to claim 10 comprising a phthalocyanine compound of formula

16. Granules accord any one of claims 1 to 15 comprising as anionic dispersing agent a condensation product from the following group: condensation products of aromatic sulfonic acids and formaldehyde, condensation products of aromatic sulfonic acids with unsubstituted or chlorinated diphenylene or biphenyl oxides and optionally formaldehyde, (mono-/di-)-alkylnaphthalenesulfonates, sodium salts of polymerised organic sulfonic acids, sodium salts of polymerised alkylnaphthalenesulfonic acids, sodium salts of polymerised alkyl benzene-sulfonic acids, alkylarylsulfonates, sodium salts of alkyl polyglycol ether sulfates, polyalkylated polynuclear arylsulfonates, methylene-linked condensation products of arylsulfonic acids and hydroxyarylsulfonic acids, sodium salt of dialkylsulfosuccinic acid, sodium salts of alkyl diglycol ether sulfates, sodium salts of polynaphthalenemethane-sulfonates, ligno- or oxyligno-sulfonates or heterocyclic polysulfonic acids.
17. Granules according to claim 16 comprising as anionic dispersing agent a condensation product from the following group: condensation products of naphthalenesulfonic acids with formaldehyde, sodium salts of polymerised organic sulfonic acids, (mono-/di-)alkyl-naphthalenesulfonates, polyalkylated polynuclear arylsulfonates, sodium salts of polymerised alkylbenzenesulfonic acid, lignosulfonates, oxylignosulfonates and condensation products of naphthalenesulfonic acid with a polychloromethyldiphenyl.
18. Granules one of claims 1 to 17 comprising as water-soluble polymer a
compound from the following group: gelatin, polyacrylates, polymethacrylates, polyvinyl¬
pyrrolidones, vinylpyrrolidones, vinyl acetates, copolymers of vinylpyrrolidone with long-
chained a-olefins, poly(vinylpyrrolidone/dimethylaminoethyl methacrylates), copolymers of
vinylpyrrolidone/dimethylaminopropyl methacrylamides, copolymers of vinylpyrrolidone/-

dimethylaminopropyl acrylamides, quatemised copolymers of vinylpyrrolidones and dimethylaminoethyl methacrylates, terpolymers of vinylcaprolactam/vinylpyrrolidone dimethylaminoethyl methacrylates, copolymers of vinylpyrrolidone and methacrylamido-propyl-trimethylammonium chloride, terpolymers of caprolactam/vinylpyrrolidone/dimethyl-amino ethyl methacrylates, copolymers of styrene and acrylic acid, polycarboxylic acids, poly-acrylamides, carboxymethylcellulose, hydroxymethylcellulose, polyvinyl alcohols, polyvinyl acetate, hydrolysed polyvinyl acetate, copolymers of maleic acid with unsaturated hydro¬carbons, and mixed polymerizations products of the mentioned polymers.
19. The granules according to claim 18 comprising as water-soluble polymer a compound from the following group: carboxymethylcellulose, polyacrylamides, polyvinyl alcohols, polyvinyl¬pyrrolidones, gelatin, hydrolysed polyvinyl acetates, copolymers of vinylpyrrolidone and vinyl acetate, and also polyacrylates and polymethacrylates.
20. A method of producing the granules according to claim 1, wherein first of all an aqueous solution of the phthalocyanine dye is prepared in a known manner the anionic dispersing agent and, optional, a wetting agent, water-insoluble, water-soluble dye or pigment, or dissolution accelerator or optical brightener, and, optional, a water-soluble organic polymer, are added thereto, the mixture is stirred until a homogeneous solution is obtained, and the aqueous solution is then subjected to a drying step in which all water, with the exception of a residual amount, is removed, solid particles (granules) simultaneously being formed.
21. The method according to claim 20, wherein the removal of water is effected by spray-drying.
22. The method according to claim 21, wherein the removal of water is effected by spray-drying with direct return of the fine particles of solid to the spraying zone.
23. The method according to claim 20, wherein the removal of water is carried out in a fluidized bed dryer.
24. The method according to claim 20, wherein the removal of water is carried out in a fluidized bed .

Documents:

0562-mas-1999 abstract-duplicate.pdf

0562-mas-1999 abstract.pdf

0562-mas-1999 claims-duplicate.pdf

0562-mas-1999 claims.pdf

0562-mas-1999 correspondence-others.pdf

0562-mas-1999 correspondence-po.pdf

0562-mas-1999 description (complete)-duplicate.pdf

0562-mas-1999 description (complete).pdf

0562-mas-1999 form-1.pdf

0562-mas-1999 form-19.pdf

0562-mas-1999 form-26.pdf

0562-mas-1999 form-4.pdf

0562-mas-1999 form-6.pdf

0562-mas-1999 others.pdf

0562-mas-1999 petition.pdf

« Previous Patent

Next Patent »

Patent Number

214413

Indian Patent Application Number

562/MAS/1999

PG Journal Number

13/2008

Publication Date

31-Mar-2008

Grant Date

12-Feb-2008

Date of Filing

17-May-1999

Name of Patentee

CIBA SPECIALTY CHEMICALS HOLDING INC

Applicant Address

KLYBECKSTRASSE 141, 4057 BASEL,

Inventors:

#	Inventor's Name	Inventor's Address
1	PETR KVITA	TSCHAPPERLIRING 10, 4153 REINACH,
2	PIERRE DREYER	RUE DE I'ALMA 2, 68740 BLODELSHEIM,

PCT International Classification Number

C11 D 3/00

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	98810459.2	1998-05-18	EUROPEAN UNION