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EP0959123A1 - Granules de composés de phthalocyanine solubles dans l'eau - Google Patents

Granules de composés de phthalocyanine solubles dans l'eau Download PDF

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Publication number
EP0959123A1
EP0959123A1 EP99810412A EP99810412A EP0959123A1 EP 0959123 A1 EP0959123 A1 EP 0959123A1 EP 99810412 A EP99810412 A EP 99810412A EP 99810412 A EP99810412 A EP 99810412A EP 0959123 A1 EP0959123 A1 EP 0959123A1
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EP
European Patent Office
Prior art keywords
alkyl
formula
contain
weight
phthalocyanine
Prior art date
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Granted
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EP99810412A
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German (de)
English (en)
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EP0959123B1 (fr
Inventor
Petr Kvita
Pierre Dreyer
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BASF Schweiz AG
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Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
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Priority to EP19990810412 priority Critical patent/EP0959123B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0063—Photo- activating compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/168—Organometallic compounds or orgometallic complexes

Definitions

  • the present invention relates to water-soluble granules of phthalocyanine compounds, a process for their preparation and their use in detergent preparations.
  • Water-soluble phthalocyanine dyes especially zinc and aluminum phthalocyanine sulfonates, are often used as photoactivators in detergent preparations. Because of the slow dissolution rate of these photoactivators, step into water often problems, especially if the wash liquor is insufficiently mixed, because the colored photoactivators stain the laundry.
  • microcapsules of phthalocyanine photoactivators are already in EP-B-0 333 270 described which contain at least 38% of an encapsulation material. This too However, microcapsules are not yet capable of dissolving and soiling the Linen to meet all consumer needs.
  • Suitable phthalocyanine compounds for the granules according to the invention are phthalocyanine complexes with di-, tri- and tetravalent metals (complexes with ad 0 and d 10 configuration) as the central atom. It is mainly a water-soluble Zn, Fe (II), Ca, Mg, Na, K, Al, Si (IV), P (V), Ti (IV), Ge (IV), Cr (VI), Ga (III), Zr (IV), In (III), Sn (IV) or Hf (VI) phthalocyanine, with aluminum and zinc phthalocyanines being particularly preferred.
  • the number of substituents Q 1 and Q 2 in formula (1a) and (1b), which may be the same or different, is between 1 and 8, and, as is customary in the case of phthalocyanines, it does not have to be an integer (degree of substitution) . If other non-cationic substituents are also present, the sum of the latter and the cationic substituents is between 1 and 4.
  • the minimum number of substituents that must be present in the molecule depends on the water solubility of the resulting molecule. Sufficient water solubility is given when enough phthalocyanine compound goes into solution to cause photodynamically catalyzed oxidation on the fiber. A solubility of 0.01 mg / l may be sufficient, in general that of 0.001 to 1 g / l is appropriate.
  • Halogen means fluorine, bromine or especially chlorine.
  • the group is preferred
  • heterocyclic rings in the group the groups mentioned above are also suitable, with only the binding to the residual substituents taking place via a carbon atom.
  • phenyl, naphthyl and aromatic hetero rings can be substituted by one or two further radicals, for example by C 1 -C 6 alkyl, C 1 -C 6 alkoxy, halogen carboxy, carb-C 1 -C 6 - Alkoxy, hydroxy, amino, cyano, sulfo, sulfonamido etc.
  • All of the nitrogen heterocycles mentioned above can still be by alkyl groups be substituted, either on a carbon atom or on another in the ring located nitrogen atom.
  • Preferred as the alkyl group is the methyl group.
  • a - s in formula (1a) means any anion as a counterion to the positive charge of the residual molecule. It is generally introduced through the manufacturing process (quaternization). It then preferably means a halogen ion, an alkyl sulfate or an aryl sulfate ion. Of the aryl sulfate ions, the phenyl sulfonate, p-tolyl sulfonate and p-chlorophenyl sulfonate ions are mentioned.
  • any other anion can also act as the anion, since the anions can be easily exchanged in a known manner;
  • a s - can also represent a sulfate, sulfite, carbonate, phosphate, nitrate, acetate, oxalate, citrate, lactate or other anion of an organic carboxylic acid.
  • the index s is r for monovalent anions.
  • r assumes a value ⁇ r, which, depending on the conditions, must be such that it just compensates for the positive charge of the residual molecule.
  • C 1 -C 6 -alkyl and C 1 -C 6 -alkoxy are straight-chain or branched alkyl or alkoxy radicals such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, Isoamyl, tert.amyl or hexyl or methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec.butoxy, tert.butoxy, amyloxy, isoamyloxy, tert.amyloxy or hexyloxy.
  • C 2 -C 22 alkenyl means, for example, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2 -enyl, n-dodec-2-enyl, iso-dodecenyl, n-dodec-2-enyl or n-octadec-4-enyl.
  • R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , B 2 , B 3 , M, M 1 , Q 1 , Q 2 , A s , T 1 , X 1 , Y 2 , Z 2 'a, b, c, d, e, r, v, w have the meanings given in the formulas (1a) and (1b).
  • phthalocyanine compounds are those compounds as they are commercially available and are used in detergents. Usually they are anionic phthalocyanine compounds as alkali salts, especially as sodium salts.
  • Preferred formulations of the granules contain 4 to 30% by weight, in particular 5 to 20 % By weight of phthalocyanine compound, based on the total weight of the granules.
  • the anionic dispersants used are e.g. B. to those in the trade available water-soluble anionic dispersants for dyes, pigments etc.
  • the following products are particularly suitable: Condensation products aromatic sulfonic acids and formaldehyde, condensation products of aromatic Sulfonic acids with optionally chlorinated diphenyls or diphenyl oxides and optionally formaldehyde, (Mono / di) alkylnaphthalenesulfonates, Na salts of polymerized organic sulfonic acids, Na salts polymerized alkyl naphthalene sulfonic acids, sodium salts polymerized Alkylbenzenesulfonic acids, alkylarylsulfonates, sodium salts of alkylpolyglycol ether sulfates, polyalkylated polynuclear arylsulfonates, methylene linked condensation products of Arylsulfonic acids and hydroxyarylsulfonic acids, Na salt of
  • Dispersants can be used individually or as mixtures of two or more Dispersants are used.
  • Particularly suitable anionic dispersants are condensation products from Naphthalenesulfonic acids with formaldehyde, sodium salts of polymerized organic sulfonic acids, (Mono / di) alkylnaphthalenesulfonates, polyalkylated polynuclear arylsulfonates, Na salts of polymerized alkylbenzenesulfonic acid, ligninsulfonates, oxiligninsulfonates and Condensation products of naphthalenesulfonic acid with a polychloromethyl diphenyl.
  • the granules according to the invention preferably contain 40 to 90% by weight, in particular 50 to 90% by weight, of anionic dispersant.
  • the granules according to the invention can contain a water-soluble organic polymer. These polymers can be used individually or as mixtures of two or more polymers. Such a polymer is preferably added to improve the mechanical stability of the granules and / or if, when the granules are subsequently used in the detergent, the dissolution of the phthalocyanine compound from the granules is to be suppressed by a nonionic surfactant.
  • water-soluble polymers such as gelatin, polyacrylates, polymethacrylates, Copolymers of ethyl acetate, methyl methacrylate and methacrylic acid (ammonium salt), Polyvinylpyrrolidone, vinylpyrrolidone, vinyl acetate, copolymers of vinylpyrrolidone with long chain ⁇ -olefins, poly (vinyl pyrrolidone / dimethylaminoethyl methacrylate), copolymers of vinyl pyrrolidone / dimethylaminopropyl methacrylamides, copolymers of Vinylpyrrolidone / dimethylaminopropylacrylamiden, quaternized copolymers of Vinyl pyrrolidones and dimethylaminoethyl methacrylates, terpolymers of Vinylcaprolactam, vinylpyrrolidone / dimethylaminoethyl methacrylates, copolymers of Vinyl pyrrolactam
  • organic polymers are carboxymethyl cellulose, polyacrylamides, Polyvinyl alcohols, polyvinyl pyrrolidones, gelatine, saponified polyvinyl acetates, copolymers Vinylpyrrolidone and vinyl acetate as well as polyacrylates and polymethacrylates in particular prefers.
  • the organic polymers are used in an amount of 0 to 25% by weight, preferably 5 to 20% by weight and in particular 8 to 18% by weight, based on the total weight of the Granules.
  • the granules according to the invention can contain further additives, for example Wetting agents, water-insoluble or water-soluble dyes or pigments as well Solution accelerators and optical brighteners. These additives are in an amount from 0 to 10% by weight, based on the total weight of the granules, is present.
  • the granules according to the invention are produced, for. B. in the following way: Man first produces an aqueous solution of the phthalocyanine dye, adds this the anionic dispersant and, if appropriate, other additives, and stirring, if necessary with heating, until a homogeneous solution is obtained.
  • Solids content of the solution should preferably be at least 30% by weight, especially 40 to 50 % By weight, based on the total weight of the solution.
  • the viscosity of the solution is preferably below 200 mPas.
  • the aqueous solution containing the phthalocyanine dye and the anionic Dispersant is then all in one drying step except for a residual amount Removed water, at the same time solid particles (granules) are formed.
  • Known methods are suitable for producing the granules from the aqueous solution. In principle, both processes with a continuous and with a are suitable discontinuous process control. Continuous processes are preferred, in particular spray drying and fluidized bed granulation processes used.
  • Spray drying processes in which the active ingredient solution is divided into a Chamber is sprayed with circulating hot air.
  • the solution is atomized with 1-fabric or 2-fabric nozzles or through the swirl effect of a rapidly rotating disc.
  • the spray drying process can be used to increase the particle size with a additional agglomeration of the liquid particles with solid germs in one in the Chamber integrated fluidized bed can be combined (so-called Fluidized Spray Dryer). From fine particles ( ⁇ 100 ⁇ m) created by a conventional spray drying process can optionally after separation from the exhaust gas stream without further Treatment as germs directly in the spray cone of the atomizer of the spray dryer Agglomeration with the liquid drops of the active ingredient are supplied.
  • the granules formed in the spray dryer become continuous working processes, e.g. separated by a sieving process.
  • the fines and the oversize is either directly recycled (without intermediate dissolving) or in dissolved the liquid active ingredient formulation and then granulated again.
  • the granules according to the invention are abrasion-resistant, low-dust, free-flowing and easy to dose. They are particularly characterized by their very rapid solubility in water. she are used primarily in detergent formulations. You can in the one you want Concentration of the phthalocyanine compound added directly to a detergent formulation become. This use is another object of the present invention represents.
  • the detergent can be in solid or liquid form, for example as a liquid, non-aqueous detergent containing not more than 5, preferably 0 to 1% by weight Water, and as a basis a suspension of a builder in a nonionic Have surfactant, e.g. B. as described in GB-A-2,158,454.
  • the detergent is preferably in the form of a powder or granules.
  • aqueous slurry which is the Components A) and C), which component B) does not or only partially contains.
  • the Slurry is spray dried, then component E) with component B) mixed and added and then component D) is added dry.
  • the components are preferably mixed with one another in such amounts that you get a solid compact detergent as granules with a specific weight of at least 500 g / l.
  • the production of the detergent is carried out in three stages.
  • a mixture of anionic surfactant, (and possibly a small amount of nonionic surfactant) and builder manufactured In the second stage, this mixture becomes nonionic with the bulk Sprayed surfactant and in the third stage then peroxide, possibly catalyst and added the granules according to the invention. This procedure is commonly used in a fluid bed.
  • the individual stages are not Completely separate, so there is some overlap between them. This process is usually carried out in an extruder to form granules to get from "Megaperls".
  • the anionic surfactant A) can, for. B. a sulfate, sulfonate or carboxylate surfactant or be a mixture of these.
  • Preferred sulfates are those with 12-22 carbon atoms in the alkyl radical, optionally in combination with Alkyl ethoxy sulfates, the alkyl radical of which has 10-20 C atoms.
  • Preferred sulfonates are e.g. B. Alkylbenzenesulfonates with 9 - 15 carbon atoms in the alkyl radical and / or alkylnaphthalenesulfonates with 6 to 16 carbon atoms in the respective alkyl radical.
  • the cation in the anionic surfactants is preferably an alkali metal cation, especially sodium.
  • Preferred carboxylates are alkali metal sarcosinates of the formula R-CO-N (R 1 ) -CH 2 COOM 1 , in which R is alkyl or alkenyl having 8-18 C atoms in the alkyl or alkenyl radical, R 1 is C 1 -C 4 alkyl and M. 1 means an alkali metal.
  • alkali metal phosphates especially tripolyphosphates, Carbonates or bicarbonates, in particular their sodium salts, silicates, Aluminum silicates, polycarboxylates, polycarboxylic acids, organic phosphonates, Aminoalkylene poly (alkylene phosphonates) or mixtures of these compounds.
  • Particularly suitable silicates are sodium salts of crystalline layered silicates of the formula NaHSi t O 2t + 1- pH 2 O or Na2Si t O 2t + 1- pH 2 O, where t is a number between 1.9 and 4 and p is a number between 0 and 20 is.
  • the aluminum silicates are commercially available under the names Zeolit A, B, X and HS available preferably as well as mixtures containing two or more of these Components.
  • polycarboxylates are the polyhydroxycarboxylates, in particular Citrates, and acrylates and their copolymers with maleic anhydride.
  • Preferred polycarboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid and Ethylene diamine disuccinate both in racemic form and the enantiomerically pure S, S form.
  • Particularly suitable phosphonates or aminoalkylene poly (alkylene phosphonates) are Alkali metal salts of 1-hydroxyethane-1,1-diphosphonic acid, nitrilotris (methylenephosphonic acid), Ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid.
  • peroxide component D) z. B those known in the literature and in the market Available organic and inorganic peroxides in question, the textile materials usual washing temperatures, for example at 10 to 95 ° C.
  • the organic peroxides are, for example, mono- or polyperoxides, especially organic peracids or their salts, such as phthalimidoperoxycaproic acid, Peroxybenzoic acid, diperoxydodecanedioic acid, diperoxynonanedioic acid, Diperoxydecanedioic acid, diperoxyphthalic acid or their salts.
  • organic peracids or their salts such as phthalimidoperoxycaproic acid, Peroxybenzoic acid, diperoxydodecanedioic acid, diperoxynonanedioic acid, Diperoxydecanedioic acid, diperoxyphthalic acid or their salts.
  • inorganic peroxides such as, for. B. persulfates, Perborates, Percarbonates and or Persilikate.
  • inorganic peroxides such as, for. B. persulfates, Perborates, Percarbonates and or Persilikate.
  • the Peroxides can be in different crystal forms and with different Water content is present and they can also be combined with other inorganic or organic compounds are used to improve their storage stability.
  • the peroxides are preferably added to the detergent by mixing the Components, e.g. B. with the help of a screw dosing system and / or one Fluid bed mixer.
  • the detergents can contain one or contain several optical brighteners, for example from the class bis-triazinylaminostilbene-disulfonic acid, Bis-triazolyl-stilbene-disulfonic acid, bis-styryl-biphenyl or bis-benzofuranylbiphenyl, a bis-benzoxalyl derivative, bis-benzimidazolyl derivative, coumarin derivative or a pyrazoline derivative.
  • optical brighteners for example from the class bis-triazinylaminostilbene-disulfonic acid, Bis-triazolyl-stilbene-disulfonic acid, bis-styryl-biphenyl or bis-benzofuranylbiphenyl, a bis-benzoxalyl derivative, bis-benzimidazolyl derivative, coumarin derivative or a pyrazoline derivative.
  • the detergent suspending agent for dirt e.g. B. sodium carboxymethyl cellulose
  • pH regulators e.g. B. alkali or alkaline earth metal silicates
  • foam regulators e.g. B. soap
  • salts for controlling spray drying and granulating properties e.g. B. sodium sulfate, fragrances and optionally, antistatic agents and fabric softeners, enzymes, such as amylase, bleach, pigments and / or shading agents.
  • enzymes such as amylase, bleach, pigments and / or shading agents.
  • polymers which Soiling when washing textiles from those in the wash liquor Dyes that have detached from the textiles under washing conditions prevent. It is preferably polyvinylpyrrolidone, which, if appropriate are modified by incorporation of anionic or cationic substituents, especially those with a molecular weight in the range of 5000 to 60,000 all from 10,000 to 50,000. These polymers are preferably used in an amount of 0.05 up to 5% by weight, especially 0.2 to 1.7% by weight, based on the total weight of the Detergent used.
  • the detergents according to the invention can also contain so-called perborate activators, such as. TAED or TAGU included.
  • perborate activators such as. TAED or TAGU included.
  • TAED which is preferably in one Amount of 0.05 to 5% by weight, especially 0.2 to 1.7% by weight, based on the Total weight of the detergent is used.
  • Example 1 725 g of an aqueous solution of a zinc phthalocyanine compound (sodium salt of zinc phthalocyanine, containing 3 to 4 sulfo groups) with a solids content of 20% by weight are placed in a beaker. 3010 g of an aqueous solution containing 40% by weight of an anionic dispersant (condensate of naphthalene sulfonic acid and formaldehyde) are added to this solution. The phthalocyanine / dispersant mixture with a solids content of approx. 34% by weight is homogenized by stirring at 25 ° C. for 1 hour. The solution is then spray dried in a spray dryer equipped with a 1-component nozzle.
  • a zinc phthalocyanine compound sodium salt of zinc phthalocyanine, containing 3 to 4 sulfo groups
  • an anionic dispersant condensate of naphthalene sulfonic acid and formaldehyde
  • the exhaust air temperature is 105 ° C with a supply air temperature of 195 ° C.
  • a flowable granulate with an average grain size of 50 ⁇ m and a residual water content of 7% is obtained.
  • the granules thus produced contain 10% of the zinc phthalocyanine.
  • Examples 2 to 7 Granules having the following composition are produced by the same process:
  • the phthalocyanines in Examples 2 to 48 each contain 3-4 sulfo groups and are present as sodium salts.
  • Example No. Dye% by weight Anionic dispersant% by weight Residual moisture granules 2nd Aluminum phthalocyanine 15 Formaldehyde condensation product with naphthalenesulfonic acid 80 5% by weight 3rd Zinc phthalocyanine 5 Na salt polymerized alkylnaphthalenesulfonic acid 86 9% by weight 4th Zinc phthalocyanine 20
  • Zinc phthalocyanine 9 Formaldehyde condensation product with naphthalenesulfonic acid 82 9% by weight 7
  • Zinc phthalocyanine 10 Formalde
  • Example 8 880 g of an aqueous solution of an aluminum phthalocyanine compound (Na salt of aluminum phthalocyanine, containing 3 to 4 sulfo groups) with a solids content of 25% by weight are placed in a beaker and diluted with 1460 g of deionized water. The solution is warmed to 45 ° C. and a dry powdery anionic dipergator (formaldehyde condensation product with naphthalene sulfonic acid) is introduced into the heated solution in portions. The dispersant-containing phthalocyanine solution is further stirred at 45 ° C. for 2 hours so that the dispersant is completely dissolved.
  • an aluminum phthalocyanine compound Na salt of aluminum phthalocyanine, containing 3 to 4 sulfo groups
  • the finished phthalocyanine / dispersant solution with a solids content of 45% is granulated warm in a Bench Fluidized Spray Dryer.
  • the entire phthalocyanine solution was granulated at a fluidized bed temperature of 48-51 ° C. At the discharge of the granulator, the granulate contains about 14% by weight of residual moisture and is then dried in a continuously working fluid bed with air at 75 ° C. to the setpoint of 9% by weight.
  • the free-flowing granulate has an average grain size of 160 ⁇ m and contains 10 wt. %. the aluminum phthalocyanine compound.
  • Examples 9 to 14 Granules with the following composition are produced by the same process: Example No. Dye% by weight Anionic dispersant% by weight Residual moisture granules 9
  • Zinc phthalocyanine 14 Dialkylnaphthalenesulfonate Na salt 80 6% by weight 10th Zinc phthalocyanine 10
  • Aluminum phthalocyanine 6 Naphthalenesulfonic acid Na salt condenses 86 with formaldehyde 8% by weight 12th Aluminum phthalocyanine 12
  • Aluminum phthalocyanine 18 Di-naphthylmethanesulfonic acid, Na salt 77 5% by weight 14
  • Aluminum phthalocyanine 14 Sodium lignosulfate 36 Dinap
  • Example 15 The preparation of the phthalocyanine solution and the typical formulations of the phthalocyanine granules correspond to Examples 1 to 7.
  • the granulation takes place in a spray dryer in which the fine particles formed in the process are continuously separated from the exhaust gas stream and directly with a gas stream into the spray cone of the nozzle.
  • the resulting granules have the same properties as described in Example 1.
  • Their average grain size is 112 pm, which means that they are much coarser than in Example 1.
  • the product from this example contains significantly less fine dust (max. 4.5% grains ⁇ 20 pm, compared to 15% by weight in Example 1).
  • Example 16 512 g of an anionic dispersant (formaldehyde condensation product with naphthalenesulfonic acid) and 1000 g of another anionic dispersant (methylene-linked condensation product of arylsulfonic acids and hydroxyarylsulfonic acids) are made in 1980 g of a 10% aqueous solution of the zinc phthalocynine compound from Example 1, which is based on 50 ° C was heated, dissolved in succession. The aqueous phthalocyanine formulation is stirred for a further 3 hours so that all components are completely dissolved. Then part of the phthalocyanine solution is dried under vacuum for 48 hours and the dry material is then ground in a grater.
  • an anionic dispersant formaldehyde condensation product with naphthalenesulfonic acid
  • another anionic dispersant methylene-linked condensation product of arylsulfonic acids and hydroxyarylsulfonic acids
  • the ground product is processed in a laboratory fluid bed granulator (STREA-1; Aeromatic AG, Bubendorf, Switzerland) as pelletizing seeds.
  • the germs are with the in the The granulator is whirled up by warm air flowing in through the sieve bottom (approx. 65 ° C).
  • the fluidized bed is now continuously the phthaocyanin solution with a two-component nozzle sprayed.
  • the granulation metering in of the phthalocyanine solution
  • the granules are in the same System with 80 ° C warm air dried to the residual water content of 5% by weight. The particles are then discharged and the fine particles are screened off.
  • the middle Grain size is 380 ⁇ m.
  • Examples 17 to 22 Granules having the following composition are produced by the same method as in Example 16: Example No. Dye% by weight Anionic dispersant% by weight Residual moisture granules 17th Aluminum phthalocyanine 6 Oxylignin sulfonate Na salt 84 10% by weight 18th Zinc phthalocyanine 10 Formaldehyde condensation product with naphthalenesulfonic acid 85 5% by weight 19th Aluminum phthalocyanine 17 Alkyl polyglycol ether sulfate Na salt 79 4% by weight 20th Aluminum phthalocyanine 9 Sodium lignosulfate 82 9% by weight 21 Zinc phthalocyanine 15 Condensation product of sulfonated naphthalene with a polychloromethyldiphenyl mixture 77 8% by weight 22 Aluminum phthalocyanine 10 Lignin sulfonate 85 5% by weight
  • EXAMPLE 23 826 g of a powdery dispersant (formaldehyde condensation product with naphthalene sulfonic acid) are stirred into and dissolved in 1073 g of an aqueous solution of the zinc phthalocyanine compound from Example 1 with a solids content of 11% by weight. The aqueous phthalocyanine solution is stirred for 1 hour so that the dispersant is completely dissolved.
  • a powdery dispersant formaldehyde condensation product with naphthalene sulfonic acid
  • the filtrate is granulated in a spray dryer in which the resulting in the process Fine particles are continuously separated from the exhaust gas flow and directly with a gas flow in the spray cone of the nozzle.
  • the granules are free flowing and have one average grain size of 105 ⁇ m.
  • the fine fraction (grain size ⁇ 20 ⁇ m) is 6.2%.
  • the Fraction ⁇ 50 ⁇ m is separated from Gutkom using an air jet sieve.
  • the granules are completely soluble in water in less than 2 minutes. At Storage in a nonionic surfactant will not dissolve even after several days of the phthalocyanine compound.
  • Examples 24 to 34 The formulations listed in the table below are prepared analogously to Example 23 and, after spray drying, give granules with the same properties with respect to particle size, solubility in water and nonionic surfactants as the granulate according to Example 23.
  • Dispersant wt% Water soluble polymer wt% Residual moisture granules 24th Aluminum phthalocyanine 7 Oxylignin sulfonate sodium salt) 73 low-viscosity Na carboxymethyl cellulose 12 8% by weight 25th Zinc phthalocyanine 10 Formaldehyde condensation product with naphthalenesulfonic acid 70 water-soluble polyacrylamide with MW 200000 15 5% by weight 26 Aluminum phthalocyanine 12 Alkyl polyglycol ether sulfate Na salt 71 Polyvinyl alcohol 13 4% by weight 27 Aluminum phthalocyanine 15 Sodium lignin sulfonate 58 Polyvinyl pyrrolidone 18 9% by weight 28 Zinc phthalocyanine 12 Condensation product of sulfonated naphthalene with a polychloromethyldiphenyl mixture 72 Saponified polyvinyl acetate 10 6% by weight 29 Aluminum phthalocyanine 10 Sodium
  • Examples 35 to 53 The formulations listed in the following table are obtained by first preparing aqueous solutions of the components and then granulating them in a Fluidized Spray Dryer.
  • the phthalocyanine solutions are granulated at a fluidized bed temperature of 60-68 ° C.
  • the granulate contains approx. 12% by weight of residual moisture at the discharge of the granulator and is then dried to the formulation-specific setpoint (see table below) in a continuously working fluid bed to which 85 ° C warm air is fed.
  • the granulate is free-flowing regardless of the formulation, can be quickly dissolved in water and is visually insoluble in non-ionic surfactants for days.
  • Zinc phthalocyanine 10 Oxylignin sulfonate Na salt 75 low-viscosity carboxymethyl cellulose 10 5% by weight 36
  • Zinc phthalocyanine 11 Di-naphthylmethanesulfonic acid, Na salt 73
  • Zinc phthalocyanine 10 Formaldehyde
  • 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 this purpose, as shown in Example 16, part of the phthalocyanine solution is dried and ground separately and used as seeds in the granulation process.
  • STREA-1 fluidized bed granulator
  • the granules obtained from the fluidized bed granulation have an average grain size between 250 and 480 ⁇ m.
  • the average grain size varies in this area with the Composition of the formulation.

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EP19990810412 1998-05-18 1999-05-10 Granules de composés de phthalocyanine solubles dans l'eau Expired - Lifetime EP0959123B1 (fr)

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EP98810459 1998-05-18
EP98810459 1998-05-18
EP19990810412 EP0959123B1 (fr) 1998-05-18 1999-05-10 Granules de composés de phthalocyanine solubles dans l'eau

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004022693A1 (fr) * 2002-09-04 2004-03-18 Ciba Specialty Chemicals Holding Inc. Formulations comprenant des granules hydrosolubles
WO2006117301A1 (fr) * 2005-05-04 2006-11-09 Ciba Specialty Chemicals Holding Inc. Granules de phtalocyanine encapsules
DE10020767B4 (de) * 2000-04-27 2008-12-04 Rudolf Weber Textilwaschmittel mit Niedrigtemperaturbleiche
WO2008125628A3 (fr) * 2007-04-13 2009-04-09 Basf Se Procédé de mise en forme de pigments organiques
WO2013150000A1 (fr) * 2012-04-03 2013-10-10 Basf Se Compositions comprenant des granulés de phtalocyanines
CN112105173A (zh) * 2020-09-21 2020-12-18 广东硕成科技有限公司 一种用于软板孔金属化的碳纳米组合物及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0047716A2 (fr) * 1980-09-09 1982-03-17 Ciba-Geigy Ag Procédé pour blanchir des matières textiles et pour combattre les microorganismes
EP0153278A2 (fr) * 1984-02-17 1985-08-28 Ciba-Geigy Ag Composés phtalocyaniniques aquasolubles et leur utilisation comme photoactivateurs
CH659082A5 (en) * 1984-04-09 1986-12-31 Ciba Geigy Ag Detergent powder additives in the form of speckles
WO1996006906A1 (fr) * 1994-08-30 1996-03-07 The Procter & Gamble Company Agent de photoblanchiment ameliore par l'adjonction d'un chelatant
WO1997005202A1 (fr) * 1995-07-25 1997-02-13 The Procter & Gamble Company Agents de photoblanchiment faiblement teintes
US5847114A (en) * 1990-11-02 1998-12-08 Zeneca Limited Poly-substituted phthalocyantines
EP0899325A2 (fr) * 1997-08-15 1999-03-03 Ciba SC Holding AG Composition adoucissante pour textiles

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0047716A2 (fr) * 1980-09-09 1982-03-17 Ciba-Geigy Ag Procédé pour blanchir des matières textiles et pour combattre les microorganismes
EP0153278A2 (fr) * 1984-02-17 1985-08-28 Ciba-Geigy Ag Composés phtalocyaniniques aquasolubles et leur utilisation comme photoactivateurs
CH659082A5 (en) * 1984-04-09 1986-12-31 Ciba Geigy Ag Detergent powder additives in the form of speckles
US5847114A (en) * 1990-11-02 1998-12-08 Zeneca Limited Poly-substituted phthalocyantines
WO1996006906A1 (fr) * 1994-08-30 1996-03-07 The Procter & Gamble Company Agent de photoblanchiment ameliore par l'adjonction d'un chelatant
WO1997005202A1 (fr) * 1995-07-25 1997-02-13 The Procter & Gamble Company Agents de photoblanchiment faiblement teintes
EP0899325A2 (fr) * 1997-08-15 1999-03-03 Ciba SC Holding AG Composition adoucissante pour textiles

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10020767B4 (de) * 2000-04-27 2008-12-04 Rudolf Weber Textilwaschmittel mit Niedrigtemperaturbleiche
WO2004022693A1 (fr) * 2002-09-04 2004-03-18 Ciba Specialty Chemicals Holding Inc. Formulations comprenant des granules hydrosolubles
US8080511B2 (en) 2002-09-04 2011-12-20 Basf Se Formulations comprising water-soluble granulates
WO2006117301A1 (fr) * 2005-05-04 2006-11-09 Ciba Specialty Chemicals Holding Inc. Granules de phtalocyanine encapsules
WO2008125628A3 (fr) * 2007-04-13 2009-04-09 Basf Se Procédé de mise en forme de pigments organiques
WO2013150000A1 (fr) * 2012-04-03 2013-10-10 Basf Se Compositions comprenant des granulés de phtalocyanines
US9534192B2 (en) 2012-04-03 2017-01-03 Basf Se Phthalocyanine-containing granules to decrease phthalocyanine deposition on textiles
CN112105173A (zh) * 2020-09-21 2020-12-18 广东硕成科技有限公司 一种用于软板孔金属化的碳纳米组合物及其制备方法

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