EP0959123B1 - Granules de composés de phthalocyanine solubles dans l'eau - Google Patents

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

Info

Publication number
EP0959123B1
EP0959123B1 EP19990810412 EP99810412A EP0959123B1 EP 0959123 B1 EP0959123 B1 EP 0959123B1 EP 19990810412 EP19990810412 EP 19990810412 EP 99810412 A EP99810412 A EP 99810412A EP 0959123 B1 EP0959123 B1 EP 0959123B1
Authority
EP
European Patent Office
Prior art keywords
alkyl
formula
weight
hydroxy
granules according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19990810412
Other languages
German (de)
English (en)
Other versions
EP0959123A1 (fr
Inventor
Petr Kvita
Pierre Dreyer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Schweiz AG
Ciba SC Holding AG
Original Assignee
Ciba Spezialitaetenchemie Holding AG
Ciba SC Holding AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Spezialitaetenchemie Holding AG, Ciba SC Holding AG filed Critical Ciba Spezialitaetenchemie Holding AG
Priority to EP19990810412 priority Critical patent/EP0959123B1/fr
Publication of EP0959123A1 publication Critical patent/EP0959123A1/fr
Application granted granted Critical
Publication of EP0959123B1 publication Critical patent/EP0959123B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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 primarily 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) or (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 already be sufficient, in general that of 0.001 to 1 g / l is appropriate.
  • Halogen means fluorine, bromine or especially chlorine.
  • groups come into consideration above all The group is preferred As heterocyclic rings in the group the groups mentioned above can also be considered, only the binding to the residual substituents 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 heterocytes mentioned above can also be substituted by alkyl groups, either on a carbon atom or on another nitrogen atom in the ring.
  • 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, phenyl sulfonate, p-tolyl sulfonate and p-chlorophenyl sulfonate are mentioned.
  • a s - ie can also be a sulfate, sulfite, carbonate, phosphate, nitrate, acetate, oxalate, citrate, lactate ion or another anion represent an organic carboxylic acid.
  • the index s is equal to r for monovalent anions.
  • r assumes a value ⁇ r, whereby depending on the conditions it must be such that it just compensates for the positive charge of the residual moiety.
  • 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.
  • 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. 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, Na 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 dialky
  • 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 pyrroli
  • organic polymers are carboxymethyl cellulose, polyacrylamides, Polyvinyl alcohols, polyvinyl pyrrolidones, gelatins, 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.
  • the 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.
  • aqueous solution containing the phthalocyanine dye and the anionic Dispersant is then all in one drying step except for a residual amount Extracted 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 enlarge 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".
  • 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 Na 2 Si 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 is 20.
  • 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 Fluidized 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 bisbenzofuranylbiphenyl, 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 bisbenzofuranylbiphenyl, 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, z. B. soap, salts for controlling spray drying and granulating properties
  • z. B. sodium sulfate e.g. B. sodium carboxymethyl cellulose
  • pH regulators e.g. B. alkali or alkaline earth metal silicates
  • foam regulators e.g. B. alkali or alkaline earth metal silicates
  • z. B. soap e.g. sodium sulfate
  • fragrances e.g. B. sodium sulfate
  • antistatic agents and fabric softeners e.g. B. sodium sulfate
  • 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 from 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.
  • Aluminiumphtalocyanin 15 Formaldehyde condensation product with naphthalenesulfonic acid 80 5% by weight 3 zinc phthalocyanine 5 Na salt polymerized alkylnaphthalenesulfonic acid 86 9% by weight 4 zinc phthalocyanine 20
  • zinc phthalocyanine 9 Formaldehyde condensation product with naphthalenesulfonic acid 82 9% by weight 7 zinc phthalocyanine 10
  • 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.
  • the granulate contains about 14% by weight residual moisture at the discharge of the granulator 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% by weight. %. 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 10 zinc phthalocyanine 10 Formaldehyde condensation product with naphthalenesulfonic acid 85 5% by weight 11 aluminum phthalocyanine 6 Naphthalenesulfonic acid Na salt condensed with formaldehyde 86 8% by weight 12 aluminum phthalocyanine 12 Condensation product of sulfonated naphthalene with a polychloromethyldiphenyl mixture 82 4% by weight 13 aluminum phthalocyanine 18 Di-naphthylmethanesulfonic acid, sodium salt 77 5% by weight 14 aluminum phthalocyanine 14 Sodium lignosulfate dinaphthylmethanesulfonic acid 36
  • Example 15 The preparation of the phthalocyanine solution and the typical formulations of the phthalocyanine granules correspond to Examples 1 to 7. In contrast to Example 1, 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 ⁇ m, 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 ⁇ m, 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 mixed 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 Plant 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 17 Aluminiumphthpalocyanin 6 Oxylignin sulfonate sodium salt 84 10% by weight 18 zinc phthalocyanine 10 Formaldehyde condensation product with naphthalenesulfonic acid 85 5% by weight 19 aluminum phthalocyanine 17 Alkyl polyglycol ether sulfate Na salt 79 4% by weight 20 aluminum phthalocyanine 9 sodium lignosulfonate 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 detach even after several days of the phthalocyanine compound.
  • Examples 24 to 34 The formulations listed in the following table 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.
  • 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 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.
  • 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 a medium grain size between 250 and 480 ⁇ m.
  • the average grain size varies in this area with the Composition of the formulation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (26)

  1. Granulés hydrosolubles de composés de phtalocyanine renfermant
    a) de 2 à 50 % en masse d'un composé de phtalocyanine hydrosoluble,
    b) de 10 à 95 % en masse d'un dispersant anionique,
    c) de 0 à 25 % en masse d'un polymère organique hydrosoluble,
    d) de 0 à 10 % en masse d'un autre additif et
    e) de 3 à 15 % en masse d'eau, par rapport au poids total du granulé.
  2. Granulés selon la revendication 1, caractérisés en ce qu'ils présentent une teneur de 4 à 30 % en masse en composé de phtalocyanine.
  3. Granulés selon la revendication 2, caractérisés en ce qu'ils présentent une teneur de 5 à 20 % en masse en composé de phtalocyanine.
  4. Granulés selon l'une des revendications 1 à 3, caractérisés en ce qu'ils présentent une teneur de 40 à 90 % en masse en dispersant anionique.
  5. Granulés selon la revendication 4, caractérisés en ce qu'ils présentent une teneur de 50 à 90 % en masse en dispersant anionique.
  6. Granulés selon l'une des revendications 1 à 5, caractérisés en ce qu'ils présentent une teneur de 5 à 20 % en masse en polymère organique.
  7. Granulés selon la revendication 6, caractérisés en ce qu'ils présentent une teneur de 8 à 18 % en masse en polymère organique.
  8. Granulés selon l'une des revendications 1 à 7, caractérisés en ce qu'ils renferment en tant que composé de phtalocyanine un composé hydrosoluble de phtalocyanine de 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) ou Hf (VI).
  9. Granulés selon la revendication 8, caractérisés en qu'ils renferment un composé de phtalocyanine de formule
    Figure 00530001
    où
    PC
    représente le système cyclique de phtalocyanine ;
    Me
    représente Zn, Fe(II), Ca, Mg, Na, K, Al-Z1, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) ou Hf(VI) ;
    Z1
    représente un ion halogénure, sulfate, nitrate, acétate ou hydroxy ;
    q
    vaut 0,1 ou 2 ;
    r
    va de 1 à 4 ;
    Q1
    représente un groupe sulfo ou carboxyle ; ou un reste de formule
    Figure 00530002
    où
    R6
    représente un reste alkylène en C1-C8 linéaire ou ramifié ; ou 1,3- ou 1,4-phénylène ;
    X2
    représente un groupe -NH-; ou -N-alkyle en C1-C5 ;
    X3 +
    représente un groupe de formule
    Figure 00530003
    dans le cas où R6 = alkylène en C1-C8, également un groupe de formule
    Figure 00530004
    Y1 +
    représente un groupe de formule
    Figure 00530005
    t
    vaut 0 ou 1;
    dans les formules ci-dessus
    R7 et R8
    indépendamment l'un de l'autre représentent un groupe alkyle en C1-C6 ;
    R9
    représente un groupe alkyle en C1-C6 ; cycloalkyle en C5-C7 ; ou NR11R12 ;
    R10 et R11
    indépendamment l'un de l'autre représentent un groupe alkyle en C1-C5 ;
    R12 et R13
    indépendamment l'un de l'autre représentent un atome d'hydrogène ou un groupe alkyle en C1-C5 ;
    R14 et R15
    indépendamment l'un de l'autre représentent un groupe alkyle en C1-C6 non substitué ou substitué par des substituants hydroxy, cyano, carboxy, carbalkoxy en C1-C6, alkoxy en C1-C6, phényle, naphtyle ou pyridyle ;
    u
    va de 1 à 6 ;
    A1
    est le complément d'un hétérocycle azoté aromatique de 5 à 7 chaínons, qui peut éventuellement présenter encore un ou deux autres atomes d'azote en tant que chaínons du cycle, et
    B1
    est le complément d'un hétérocycle azoté saturé de 5 à 7 chaínons, qui peut éventuellement présenter encore 1 à 2 atomes d'azote, d'oxygène et/ou de soufre en tant que chaínons du cycle ;
    Q2
    représente un groupe hydroxy ; alkyle en C1-C22 ; alkyle en C4-C22 ramifié ; alcényle en C2-C22 ; alcényle en C4-C22 ramifié et leurs mélanges ; alkoxy en C1-C22 ; un reste sulfo ou carboxyle ; un reste de formule
    Figure 00540001
    Figure 00540002
    -SO2(CH2)v-OSO3M; -SO2(CH2)v-SO3M;
    Figure 00550001
    Figure 00550002
    Figure 00550003
    Figure 00550004
    un reste alkoxy ramifié de formule
    Figure 00550005
    Figure 00550006
    une unité alkyloxyéthylène de formule -(T1)d-(CH2)b(OCH2CH2)a-B3 ou un ester de formule COOR23
    où
    B2
    représente un atome d'hydrogène ; un groupe hydroxy ; alkyle en C1-C30 ; alkoxy en C1-C30 ; -CO2H ; -CH2COOH ; SO3 -M1 + ; -OSO3 -M1 + ; -PO3 2- : M1 ; -OPO3 2-M1 ; et leurs mélanges ;
    B3
    représente un atome d'hydrogène ; un groupe hydroxy ; -COOH ; SO3 -M1 + ; -OSO3 -M1 + : alkoxy en C1-C6 ;
    M1
    est un cation hydrosoluble ;
    T1
    représente un groupe -O- ; ou -NH- ;
    X1 et X4
    indépendamment l'un de l'autre représentent -O- ; -NH- ; ou N-alkyle en C1-C5 ;
    R16 et R17
    indépendamment l'un de l'autre représentent un atome d'hydrogène, le groupe sulfo et ses sels, le groupe carboxyle et ses sels ou le groupe hydroxyle, au moins un des restes R16 et R17 représente un groupe sulfo ou carboxyle ou leurs sels,
    Y2
    représente un groupe -O-, -S-, -NH- ou N-alkyle en C1-C5 ;
    R18 et R19
    indépendamment l'un de l'autre représentent un atome d'hydrogène, un groupe alkyle en C1-C6, hydroxyalkyle en C1-C6, cyanoalkyle en C1-C6, sulfoalkyle en C1-C6, carboxy ou halogénoalkyle en C1-C6 ; phényle non substitué ou substitué par un substituant halogène, alkyle en C1-C4ou alkoxy en C1-C4, sulfo ou carboxy ; ou R18 et R19 conjointement avec l'atome d'azote auquel ils sont liés forment un cycle hétérocyclique saturé de 5 ou 6 chaínons, qui peut présenter de plus un atome d'azote ou un atome d'oxygène comme chaínon du cycle ;
    R20 et R21
    indépendamment l'un de l'autre représentent un reste alkyle en C1-C6 ou arylalkyle en C1-C6 ;
    R22
    représente un atome d'hydrogène ; ou un groupe alkyle en C1-C6 non substitué ou substitué par des substituants halogène, hydroxy, cyano, phényle, carboxy, carbalkoxy en C1-C6 ou alkoxy en C1-C6 ;
    R23
    représente un groupe alkyle en C1-C22, alkyle en C4-C22 ramifié, alcényle en C1-C22 ou alcényle en C4-C22 ramifié ; glycol en C3-C22 ; alkoxy en C1-C22 ; alkoxy en C4-C22 ramifié ; et leurs mélanges ;
    M
    représente un atome d'hydrogène ; ou un ion métal alcalin ou ammonium,
    Z2
    représente un ion chlore, brome, alkyl- ou aralkyl-sulfate ;
    a
    vaut 0 ou 1 ;
    b
    va de 0 à 6 ;
    c
    va de 0 à 100 ;
    d
    vaut 0 ; ou 1 ;
    e
    va de 0 à 22 ;
    v
    est un entier de 2 à 12 ;
    w
    vaut 0 ou 1 ; et
    A
    est un anion organique ou inorganique,
    et
    s
    dans le cas d'anions monovalents A- est r et dans le cas d'anions multivalents est ≤r, As - devant compenser la charge positive ; lorsque r ≠ 1, les restes Q1 peuvent être identiques ou différents,
    et le système cyclique de phtalocyanine peut présenter également d'autres groupes solubilisants.
  10. Granulés selon la revendication 9, caractérisés en ce qu'ils renferment un composé de phtalocyanine de formule
    Figure 00570001
    où
    Me, q, PC, X2, X3 et R6
    possèdent la signification donnée à la formule (la),
    M
    représente un atome d'hydrogène, un ion métal alcalin, un ion ammonium ou sel d'amine :
    et la somme des nombres r1 et r2 va de 1 à 4 et
    As -
    compense exactement la charge positive de la molécule du reste,
    ou de formule
    Figure 00570002
    où
    Me, q et PC
    possèdent la signification donnée à la formule (la),
    R6'
    représente un groupe alkylène en C2-C6 ;
    r1
    est un nombre de 1 à 4 ;
    X3'
    représente un groupe de formule
    Figure 00580001
    où
    R7 et R8
    indépendamment l'un de l'autre représentent un groupe alkyle en C1-C4 non substitué ou substitué par des substituants hydroxy, cyano, halogène ou phényle ;
    R9
    représente R7 ; un groupe cyclohexyle ou amino ;
    R11
    représente un groupe alkyle en C1-C4 ;
    R21
    représente un groupe alkyle en C1-C4 ; alkoxy en C1-C4 ; halogène, carboxy, carbalkoxy en C1-C4 ou hydroxy ; et
    A'
    représente un ion halogénure, alkylsulfate ou arylsulfate ;
    les restes -SO2NHR' 6-X3 '+A- peuvent être identiques ou différents.
  11. Granulés selon la revendication 10, caractérisés en ce qu'ils renferment un composé de phtalocyanine de formule
    Figure 00580002
    PC
    représente le système cyclique phtalocyanine ;
    Me
    représente Zn, Fe(II), Ca, Mg, Na, K, Al-Z1, Si(IV), P(V), Ti(IV), Ge(IV), Cr(VI), Ga(III), Zr(IV), In(III), Sn(IV) ou Hf(VI) ;
    Z1
    représente un ion halogénure, sulfate, nitrate, acétate ou hydroxy ;
    q
    vaut 0 ; 1 ; ou 2 ;
    Y3'
    représente un atome d'hydrogène ; un ion métal alcalin ou ammonium ; et
    r
    est un nombre quelconque de 1 à 4.
  12. Granulés selon la revendication 11, caractérisés en ce qu'ils renferment un composé de phtalocyanine de formule (4), où Me représente Zn ou Al-Z1 ; et
    Z1
    représente un ion halogénure, sulfate, nitrate, acétate ou hydroxy.
  13. Granulés selon la revendication 10, caractérisés en ce qu'ils renferment un composé de phtalocyanine de formule
    Figure 00590001
    où
    PC, Me et q
    possèdent la signification donnée à la formule (4) ;
    R17' et R18'
    indépendamment l'un de l'autre représentent un atome d'hydrogène, un groupe phényle, sulfophényle, carboxyphényle, alkyle en C1-C6, hydroxyalkyle en C1-C6, cyanoalkyle en C1-C6, sulfoalkyle en C1-C6, carboxyalkyle en C1-C6 ou halogénoalkyle en C1-C6 ou conjointement avec l'atome d'azote le cycle morpholine ;
    q'
    est un entier de 2 à 6 ; et
    r
    est nombre de 1 à 4 ;
    dans le cas où r>1, les restes
    Figure 00590002
    présents dans la molécule, peuvent être identiques ou différents.
  14. Granulés selon la revendication 10, caractérisés en ce qu'ils renferment un composé de phtalocyanine de formule
    Figure 00590003
    où
    PC, Me et q
    possèdent la signification donnée à la formule (4) ;
    Y3'
    représente un atome d'hydrogène, un ion métal alcalin ou ammonium ;
    q'
    est un entier de 2 à 6 ;
    R17' et R18'
    indépendamment l'un de l'autre représentent un atome d'hydrogène, un groupe phényle, sulfophényle, carboxyphényle, alkyle en C1-C6, hydroxyalkyle en C1-C6, cyanoalkyle en C1-C6, sulfoalkyle en C1-C6, carboxyalkyle en C1-C6 ou halogénoalkyle en C1-C6 ou conjointement avec l'atome d'azote le cycle morpholine ;
    m'
    vaut 0 ou 1 ; et
    r et r1
    indépendamment l'un de l'autre sont un nombre quelconque de 0,5 à 3,5, la somme de r+r1 est au moins égale à 1, mais au maximum égale à 4.
  15. Granulés selon la revendication 10, caractérisés en ce qu'ils renferment un composé de phtalocyanine de formule
    Figure 00600001
    où
    R24
    représente un groupe hydroxy ; alkyle en C1-C22 ; alkyle en C4-C22 ramifié ; alcényle en C1-C22 ; alcényle en C4-C22 ramifié et leurs mélanges ; alkoxy en C1-C22 ; un reste sulfo ou carboxyle ; un reste de formule
    Figure 00610001
    Figure 00610002
    -SO2(CH2)-OSO3M;-SO2(CH2)-SO3M;
    Figure 00610003
    Figure 00610004
    Figure 00610005
    Figure 00610006
    un reste alkoxy
    Figure 00610007
    ramifié de formule
    Figure 00610008
    une unité alkyloxyéthylène de formule -(T1)d-(CH2)b(OCH2CH2)a-B3 ou un ester de formule COOR23 ; et
    U
    représente un groupe [Q1]r +As - ; ou Q2 ; R16, R17, R18, R19, R20, R21, R22, R23, B2, B3, M, M1, Q1, Q2, As, T1, X1, Y2, Z2, a, b, c, d, e, r, v et w possèdent les significations données à la formule (1a) et (1b).
  16. Granulés selon l'une des revendications 1 à 15, caractérisés en ce qu'ils renferment en tant que dispersant anionique un produit de condensation pris dans le groupe suivant : les produits de condensation d'acides sulfoniques aromatiques sur le formaldéhyde, les produits de condensation d'acides sulfoniques aromatiques sur des oxydes de diphényle ou des diphényles éventuellement chlorés et éventuellement le formaldéhyde, les (mono/di-)alkylnaphtalènesulfonates, les sels de Na d'acides sulfoniques organiques polymérisés, les sels de Na d'acide alkylnaphtalènesulfonique polymérisé, les sels de Na d'acide alkylbenzènesulfonique polymérisé, les alkylarylsulfonates, les sels de Na d'éthersulfates d'alkylpolyglycols, les arylsulfonates polynucléaires polyalkylés, les produits de condensation d'acides arylsulfoniques et d'acides hydroxyarylsulfoniques reliés par des groupes méthylène, le sel de Na d'acide dialkylsulfosuccinique, les sels de Na d'éthersulfates d'alkyldiglycols, les sels de Na de polynaphtalèneméthanesulfonates, les ligno- ou oxylignosulfonates ou les acides polysulfoniques hétérocycliques.
  17. Granulés selon la revendication 16, caractérisés en ce qu'ils renferment en tant que dispersant anionique un produit de condensation du groupe suivant comprenant : les produits de condensation d'acides naphtalènesulfoniques sur le formaldéhyde, les sels de Na d'acides sulfoniques organiques polymérisés, les (mono/di-)alkylnaphtalènesulfonates, les arylsulfonates polynucléaires polyalkylés, les sels de Na d'acide alkylbenzènesulfonique polymérisé, les lignosulfonates, les oxylignosulfonates et les produits de condensation d'acide naphtalènesulfonique sur un polychlorométhyldiphényle.
  18. Granulés selon l'une des revendications 1 à 17, caractérisés en ce qu'ils renferment en tant que polymère hydrosoluble un composé pris dans le groupe suivant : la gélatine, les polyacrylates, les polyméthacrylates, les polyvinylpyrrolidones, les vinylpyrrolidones, les acétates de vinyle, les copolymères de vinylpyrrolidone avec des α-oléfines à chaíne longue, les poly(vinylpyrrolidone/diméthylaminoéthylméthacrylates), des copolymères de vinylpyrrolidone/diméthylaminopropylméthacrylamides, les copolymères de vinylpyrrolidone/diméthylamino-propylacrylamides, les copolymères quaternisés de vinylpyrrolidones et de diméthylaminoéthylméthacrylates, les terpolymères de vinylcaprolactame/vinympyrrolidone/diméthylaminoéthylméthacrylates, les copolymères de vinylpyrrolidone et de chlorure de méthacrylamidopropyl-triméthylammonium, des terpolymères de caprolactame/vinylpyrrolidone/diméthylaminoéthylméthacrylates, les copolymères de styrène et d'acide acrylique, les acides polycarboxyliques, les polyacrylamides, la carboxyméthylcellulose, l'hydroxyméthylcellulose, les poly-(alcools vinyliques), le poly(acétate de vinyle) éventuellement saponifié, les copolymères d'acide maléique avec des hydrocarbures insaturés ainsi que les copolymères des polymères précités.
  19. Granulés selon la revendication 18, caractérisés en ce qu'ils renferment en tant que polymère hydrosoluble un composé pris dans le groupe suivant : la carboxyméthylcellulose, les polyacrylamides, les poly(alcools vinyliques), les polyvinylpyrrolidones, la gélatine, les poly(acétates de vinyle) saponifiés, les copolymères de polyvinylpyrrolidone et d'acétate de vinyle, ainsi que les polyacrylates et polyméthacrylates.
  20. Procédé pour la préparation des granulés selon la revendication 1, caractérisé en ce qu'on prépare d'abord une solution aqueuse du colorant de phtalocyanine, on lui ajoute un dispersant anionique et éventuellement d'autres matières d'addition et on agite jusqu'à l'obtention d'une solution homogène et ensuite on soutire la totalité de l'eau à la solution aqueuse dans une étape de séchage jusqu'à l'obtention d'une quantité résiduelle, pendant qu'il se forme, simultanément, des particules solides (granulés).
  21. Procédé selon la revendication 20, caractérisé en ce qu'on soutire l'eau par séchage par pulvérisation.
  22. Procédé selon la revendication 21, caractérisé en ce qu'on soutire l'eau par séchage par pulvérisation avec un recyclage direct des particules fines de la matière solide à la zone de pulvérisation.
  23. Procédé selon la revendication 20, caractérisé en ce qu'on soutire l'eau dans un Fluidized Bed Dryer.
  24. Procédé selon la revendication 20, caractérisé en ce qu'on soutire l'eau dans un lit turbulent granulateur.
  25. Formulations de détergents, renfermant
    I) 5-70 % de A) un agent de surface anionique et/ou de B) un agent de surface non ionique,
    II) 5-50 % de C) une substance active détergente,
    III) 1-12 % de D) un peroxyde et éventuellement un catalyseur et
    IV) 0,01-1 % de E) un granulé selon la revendication 1,
    les indications en pourcentages sont les pour cents en masse, par rapport au poids total du détergent.
  26. Formulations de détergents selon la revendication 25, renfermant
    I) 5-70 % de A) un agent de surface anionique et/ou de B) un agent de surface non ionique,
    II) 5-40 % de C) une substance active détergente,
    III) 1-12 % de D) un peroxyde et éventuellement un catalyseur et
    IV) 0,01-0,5 % de E) un granulé selon la revendication 1,
    les indications en pourcentages sont les pour cents en masse, par rapport au poids total du détergent.
EP19990810412 1998-05-18 1999-05-10 Granules de composés de phthalocyanine solubles dans l'eau Expired - Lifetime EP0959123B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP19990810412 EP0959123B1 (fr) 1998-05-18 1999-05-10 Granules de composés de phthalocyanine solubles dans l'eau

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
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

Publications (2)

Publication Number Publication Date
EP0959123A1 EP0959123A1 (fr) 1999-11-24
EP0959123B1 true EP0959123B1 (fr) 2004-07-28

Family

ID=26151930

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19990810412 Expired - Lifetime EP0959123B1 (fr) 1998-05-18 1999-05-10 Granules de composés de phthalocyanine solubles dans l'eau

Country Status (1)

Country Link
EP (1) EP0959123B1 (fr)

Families Citing this family (6)

* 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
KR101136843B1 (ko) * 2002-09-04 2012-05-25 시바 홀딩 인코포레이티드 수용성 과립을 포함하는 배합물
EP1877532A1 (fr) * 2005-05-04 2008-01-16 Ciba Specialty Chemicals Holding Inc. Granules de phtalocyanine encapsules
JP2010523783A (ja) * 2007-04-13 2010-07-15 ビーエーエスエフ ソシエタス・ヨーロピア 有機顔料の調製方法
BR112014024456A2 (pt) 2012-04-03 2017-07-25 Basf Se composição, grânulos, composição de agente de lavagem, e, processo para a preparação dos grânulos.
CN112105173B (zh) * 2020-09-21 2022-01-18 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

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4394125A (en) * 1980-09-09 1983-07-19 Ciba-Geigy Corporation Process for bleaching textiles and for combating micro-organisms with sulfonated phthalocyanine of aluminum or zinc and containing halogen or cyano substituents as photoactivator
CH657864A5 (de) * 1984-02-17 1986-09-30 Ciba Geigy Ag Wasserloesliche phthalocyaninverbindungen und deren verwendung als photoaktivatoren.
CH659082A5 (en) * 1984-04-09 1986-12-31 Ciba Geigy Ag Detergent powder additives in the form of speckles
ATE146508T1 (de) * 1990-11-02 1997-01-15 Zeneca Ltd Polysubstituierte phthalocyanine
DE69515318D1 (de) * 1994-08-30 2000-04-06 Procter & Gamble Mittels chelatbildnern verbessertes photobleichen
US5916481A (en) * 1995-07-25 1999-06-29 The Procter & Gamble Company Low hue photobleaches
NZ331196A (en) * 1997-08-15 2000-01-28 Ciba Sc Holding Ag Water soluble fabric softener compositions comprising phthalocyanine, a quaternary ammonium compound and a photobleaching agent

Also Published As

Publication number Publication date
EP0959123A1 (fr) 1999-11-24

Similar Documents

Publication Publication Date Title
DE60305509T2 (de) Formulierungen enthaltend wasserlösliche granulate
DE60033522T2 (de) Wasserlösliche granulate von mangankomplexen vom salentyp
US6291412B1 (en) Water-soluble granules of phthalocyanine compounds
DE602004004904T2 (de) Nuancierungsmittel
AT396246B (de) Koerniges waschmitteladditiv, verfahren zu seiner herstellung und waschmittel, das das additiv enthaelt
DE60304200T2 (de) Verwendung von metallkomplexverbindungen als oxidationskatalysatoren
JP4823909B2 (ja) 漂白触媒を含む安定な粒子状組成物
EP2417240B1 (fr) Granulés d'agent de blanchiment à revêtement actif
EP1913124B1 (fr) Procede pour realiser des granulats de catalyseur de blanchiment
JP2008540715A (ja) カプセル化フタロシアニン粒質物
DE60306672T2 (de) Verwendung von metallkomplexverbindungen als oxidationskatalysatoren
EP0959123B1 (fr) Granules de composés de phthalocyanine solubles dans l'eau
EP1543099A1 (fr) Procede de coloration de carbonate de sodium et utilisation du carbonate de sodium colore dans des formulations de produits de lavage et de nettoyage
MXPA99004544A (es) Granulados de compuestos de ftalocianina solubles en agua
DE10222386A1 (de) Bleichaktivatorkörnchen und Bleichmittelzusammensetzung
DE102007026216A1 (de) Feste Partikel von hydrophoben Bleichaktivatoren

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB GR IT LI NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20000418

AKX Designation fees paid

Free format text: AT BE CH DE ES FR GB GR IT LI NL PT SE

17Q First examination report despatched

Effective date: 20021108

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040728

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59910042

Country of ref document: DE

Date of ref document: 20040902

Kind code of ref document: P

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20040813

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20041028

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20041028

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2226324

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050531

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20050429

BERE Be: lapsed

Owner name: *CIBA SPECIALTY CHEMICALS HOLDING INC.

Effective date: 20050531

BERE Be: lapsed

Owner name: *CIBA SPECIALTY CHEMICALS HOLDING INC.

Effective date: 20050531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041228

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: CIBA HOLDING INC.

Free format text: CIBA SPECIALTY CHEMICALS HOLDING INC.#KLYBECKSTRASSE 141#4057 BASEL (CH) -TRANSFER TO- CIBA HOLDING INC.#KLYBECKSTRASSE 141#4057 BASEL (CH)

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20100531

Year of fee payment: 12

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110531

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20110531

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20160531

Year of fee payment: 18

Ref country code: ES

Payment date: 20160627

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20160523

Year of fee payment: 18

Ref country code: FR

Payment date: 20160526

Year of fee payment: 18

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20160729

Year of fee payment: 18

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 59910042

Country of ref document: DE

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20170510

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20180131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171201

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170510

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170510

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170531

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20180703

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170511