EP1106678A2 - Granules de surfactant nonionique et procédé d'obtention - Google Patents

Granules de surfactant nonionique et procédé d'obtention Download PDF

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Publication number
EP1106678A2
EP1106678A2 EP00126126A EP00126126A EP1106678A2 EP 1106678 A2 EP1106678 A2 EP 1106678A2 EP 00126126 A EP00126126 A EP 00126126A EP 00126126 A EP00126126 A EP 00126126A EP 1106678 A2 EP1106678 A2 EP 1106678A2
Authority
EP
European Patent Office
Prior art keywords
granules
acid
preferred
nonionic surfactants
polymers
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.)
Granted
Application number
EP00126126A
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German (de)
English (en)
Other versions
EP1106678A3 (fr
EP1106678B1 (fr
Inventor
Wilfried Dr. Rähse
Georg Dr. Assmann
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP1106678A2 publication Critical patent/EP1106678A2/fr
Publication of EP1106678A3 publication Critical patent/EP1106678A3/fr
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Publication of EP1106678B1 publication Critical patent/EP1106678B1/fr
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • 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
    • C11D3/18—Hydrocarbons
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C11D3/2079—Monocarboxylic acids-salts thereof
    • 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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides

Definitions

  • the present invention relates to granules containing nonionic surfactants and a Manufacturing process for such granules and detergents and / or cleaning agents contain such granules.
  • Detergents and cleaning agents contain to increase their washing and Cleaning performance, especially against dust / skin grease stains, nonionic surfactants.
  • nonionic surfactants are included Liquid at room temperature, which makes it difficult to incorporate them into powdery media.
  • the liquid nonionic surfactants are usually in the form of so-called compounds, which are usually used with wet granulation Zeolite or other solid detergent builder as well as granulating liquid getting produced.
  • the nonionic surfactants are applied to the zeolite upset.
  • Commonly used zeolites are zeolite A, X and P.
  • a limitation of the Proportion of nonionic surfactant in the compound forms the absorption capacity of the Zeolite, if the content is too high, the particles produced are no longer flowable. These products are therefore for processing and for direct use in powdery products not suitable.
  • nonionic surfactants Another disadvantage of nonionic surfactants is their tendency to gel. For Avoiding gel formation and increasing solubility are known from the prior art Technique some process for making solid detergent particles, the non-ionic Contain surfactants, known.
  • DE-A-41 24 701 describes a process for the production of solid washing and cleaning agents discloses, wherein solid and liquid detergent raw materials under simultaneous or subsequent shaping and possibly drying.
  • fixed Ingredients are anionic surfactants, builder substances and alkalizing agents and as liquid components non-ionic surfactants used.
  • the liquid nonionic surfactants are mixed with a Structure breaker mixed in a weight ratio of 10: 1 to 1: 1.
  • Structural breakers are polyethylene glycol or polypropylene glycol, sulfates and / or Disulfates of polyethylene glycol or polypropylene glycol; Sulfosuccinates and / or Disulfosuccinate from polyethylene glycol or polypropylene glycol or mixtures of used this.
  • a builder component which is a crystalline sheet silicate of the general formula NaMSi x O 2x + 1 ⁇ H 2 O, where M is sodium or hydrogen, x is a number of 1 , 9 to 4 and y is a number from 0 to 20, and contains an impregnating agent.
  • the builder component contains at least 60% by weight, based on the impregnated builder component, of crystalline layered silicates in granular form with bulk densities above 650 g / l.
  • the impregnating agent is preferably selected from ethoxylated nonionic surfactants, mixtures of nonionic and anionic surfactants, pasty aqueous nonionic surfactants and / or anionic surfactants, silicone oils and paraffin oils.
  • European patent application 0 799 884 describes a mixture of ethoxylated nonionic surfactants and alkyl polyglycosides, which is applied to a carrier material in order to produce surfactant granules.
  • Zeolite A, zeolite P and NaCO 3 are mentioned as carrier materials.
  • WO 97/03165 describes a process for the production of alkyl polyglycoside granules described.
  • the alk (en) yl polyglycosides and / or fatty acid N-alkyopolyhydroxyalkylamides are granulated in the presence of zeolites and / or water glasses.
  • a mixture of alkyl polyglycosides and ethoxylated fatty alcohols used.
  • the present invention was therefore based on the object of alternative particles Use in detergents and cleaners to provide a high Have content of liquid nonionic surfactants, in particular more than 20% by weight, however, do essentially without water-insoluble carrier material and look good suitable for incorporation in detergents or cleaning agents.
  • a first object of the invention are granules Room temperature liquid non-ionic surfactants, which solidify as a carrier material Contain polymer melt, and less than 10 wt .-% inorganic carrier contain.
  • Preferred granules consist of more than 20% by weight, in particular at least 40% by weight of nonionic surfactants which are liquid at room temperature.
  • the nonionic surfactants liquid at room temperature selected from the Nonionic surfactants commonly used in washing and cleaning agents.
  • alkoxylated C 8 -C 18 alcohols should be mentioned in particular here.
  • Ethoxylated, in particular primary alcohols with 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol are preferably used, in which the alcohol radical can be methyl-branched linearly or preferably in the 2-position or linear and methyl-branched radicals in the Can contain mixture, as they are usually present in oxo alcohol residues.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • alkyl polyglycosides can also be used. These compounds have the general formula RO (G) x , in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • Alkoxylated, preferably ethoxylated or ethoxylated and propoxylated alkyl C 8 -C 18 fatty acid esters, N-fatty alkyl amine oxides, polyhydroxy fatty acid amides or mixtures thereof can also be used as further suitable nonionic surfactants.
  • preferred nonionic surfactants are selected from the group consisting of alkoxylated, preferably ethoxylated or ethoxylated and propoxylated C 8 -C 18 alcohols, alkyl polyglycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated C 8 -C 18 fatty acid alkyl esters, N-fatty alkyl amine oxides , Polyhydroxyfatty acid amides or mixtures thereof.
  • alkoxylated, preferably ethoxylated C 8 -C 18 alcohols is particularly preferred.
  • the granules preferably contain a polymer as the polymeric carrier material, which is selected from the group consisting of thermoplastic polymers, polyalkylene oxides, preferably with a melting point above room temperature, natural and synthetic fats, long chain fatty acids, long chain fatty alcohols, paraffins and long chain nonionic surfactants solid at room temperature, preferred polymers are in particular polyalkylene oxides, of which in turn polyethylene glycols with a Molar mass from the range 400 to 10000 g / mol are preferred.
  • a polymer as the polymeric carrier material which is selected from the group consisting of thermoplastic polymers, polyalkylene oxides, preferably with a melting point above room temperature, natural and synthetic fats, long chain fatty acids, long chain fatty alcohols, paraffins and long chain nonionic surfactants solid at room temperature, preferred polymers are in particular polyalkylene oxides, of which in turn polyethylene glycols with a Molar mass from the range 400 to 10000 g / mol are
  • Granules preferred according to the invention are suitable for incorporation into solid Detergent with high bulk densities. For such granules, it is desirable that they both in their bulk density and in their particle size distribution Similar components of the agent. Accordingly, it is preferred if the Particle size distribution is narrow and the granules have a bulk density between 400 and 1000g / l, preferably between 550 and 850 g / l.
  • the granules are constructed such that they have a liquid core of non-ionic surfactants, which from a shell solidified polymer melt is surrounded. Granules with this structure appear again outside as pure polymer granules with the corresponding advantages in terms of storage and Flowability. When dissolving in water, they then put the contained ones non-ionic surfactants free.
  • Another object of the present invention is accordingly a method for Manufacture of granules of non-ionic surfactants, liquid granules for granulation nonionic surfactants polymer melts are used, which are prilled in the gas stream become.
  • Prilling is understood to mean a process in which a melt is sprayed and solidify the drops thus formed.
  • Any organic compounds can be used as polymers, one Melting point (softening point) below its decomposition temperature and the Have decomposition temperature of the nonionic surfactants and which are in the form of their Have melt processed.
  • thermoplastic polymers Polyethylene glycols, preferably with a melting point above room temperature, natural and synthetic fats, long-chain fatty acids, long-chain fatty alcohols, Paraffins and long chain nonionic surfactants. These connections can be used individually Substances or as a mixture can be granulated.
  • Long chain in the sense of this invention are those compounds that have a softening point due to the alkyl radical have above 20 ° C, preferably even above 25 ° C.
  • solid components can be selected from organic and inorganic substances, preferably selected according to the intended use of the granules produced.
  • solid particles are called "nuclei" in submitted to the fluidized bed. With these solid components, or solid particles these are usually substances that perform a carrier function. It is when the granules are used in detergents or cleaning agents should, particularly preferably, if the solid components of finely divided Carriers that also have a builder effect in the wash liquor, are selected.
  • the suitable inorganic carrier components are in particular To count aluminosilicates, alkali sulfates and carbonates.
  • crystalline aluminosilicates - the zeolites - are preferably used.
  • Zeolites A, P, X, Y and mixtures thereof are preferred zeolites as carriers.
  • the use of zeolite A as a carrier is known from numerous publications.
  • zeolite P and the faujasite-type zeolites have an increased oil absorption capacity compared to zeolite A and can therefore be preferred in granules.
  • the zeolite A-LSX described in European patent application EP-A-816 291 which corresponds to a co-crystallizate of zeolite X and zeolite A and in its anhydrous form has the formula (M 2 / n O + M ' 2 / n O) .Al 2 O 3 .zSiO 2 , where M and M' can be alkali or alkaline earth metals and z is a number between 2.1 and 2.6.
  • This product is commercially available under the brand name VEGOBOND AX from CONDEAAugusta SpA.
  • zeolite P it may be preferred to use a zeolite MAP as described in European patent EP-B-380 070.
  • the particle sizes of the zeolites used according to the invention are preferably in the range from 0.1 to 100 ⁇ m, preferably between 0.5 and 50 ⁇ m and in particular between 1 and 30 ⁇ m, each measured using standard particle size determination methods.
  • Organic builder components suitable as carriers are in particular Polycarboxylates.
  • Polycarboxylic acids polycarboxylic acids being understood to mean such carboxylic acids that have more than one acid function.
  • these are Citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, Maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of the polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these, in particular trisodium citrate.
  • polymeric polycarboxylates are also suitable as organic carrier materials. These are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated.
  • Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, can in turn be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
  • mixtures of organic and inorganic carriers are used. Independent of Mixtures of different carriers, or only one carrier component can be used, the carrier content in the granules is below 10% by weight, preferably below 5% by weight.
  • prilling in different equipment.
  • prilling can be done in a conventional manner Prill tower take place, which is less preferred in the sense of the present invention.
  • the melt introduced into a fluidized bed via one or more nozzles it turned out to be proven advantageous when the individual components through the different channels be introduced into a multi-component nozzle.
  • the liquid nonionic surfactants via the inner channel and the polymer melt spray the outer channel of the nozzle. Enveloped when the jet is torn the polymer melt in this process the liquid and the polymer thus formed The outer surface solidifies particularly quickly.
  • the fluidized bed chamber used in the process according to the invention is usually round, the apparatus may be cylindrical, i.e. one in height can have a constant diameter.
  • Such fluidized bed chambers are preferred for whom the spinal zone is conical, extended upwards and only at that subsequent calming zone after a conical transition piece cylindrical is.
  • the process can be carried out regardless of the shape of the fluidized bed apparatus be carried out batchwise or continuously, in the sense of the present However, continuous process control is preferred according to the invention.
  • Fluid bed apparatus is a Jet-Priller® (from GMF Gouda). Allow these attachments either the pre-cooling of ambient air used for prilling and in one preferred embodiment, the circulation of used as process gas Nitrogen, which is fed through a tank of liquid nitrogen.
  • Solids are either pneumatically over Blow lines dusted, adding either before atomization of the melt or takes place simultaneously with it, or added as a mixture with the melt, the mixture of these components either prior to spraying or immediately in the nozzle takes place.
  • the arrangement of the nozzle or nozzles and the spray direction can be any, as long as an essentially even distribution of the liquid components in the fluidized bed.
  • solid components before spraying with the The melt is mixed and then blown into the fluidized bed through a nozzle.
  • Fluidized bed apparatuses used with preference have base plates with dimensions of at least 0.15 m.
  • fluidized bed apparatuses which have a base plate are also suitable have a diameter greater than 5 m.
  • a Conidurboden can Support the swirl effect of the additional air supply.
  • the process according to the invention is preferably carried out at swirl air speeds between 1 and 8 m / s and in particular between 1.2 and 5.5 m / s.
  • the granules are discharged from the fluidized bed via a Size classification of the granules. This classification can be done with a Screening device or by an opposite air flow (classifier air), the is regulated so that only particles from a certain particle size out of the Fluidized bed removed and smaller particles retained in the fluidized bed.
  • the air flowing in from below exposes itself the unheated classifier air and possibly the heated bottom air.
  • the soil air temperature is between 10 and 35 ° C, particularly preferably between 10 and 25 ° C, with particular preference is when the soil air temperature is at least 5 ° C below the softening temperature of organic matter.
  • the soil air temperature is even more than 10 ° C., preferably is even more than 15 ° C below the softening temperature because of its low temperature Temperatures accelerate the solidification of the substances.
  • the temperature of the Vortex air measured about 5 cm above the base plate is preferably also well below the softening temperature of the organic substances.
  • the fluidized air temperature is more than 10 ° C below the softening temperature, especially even more than 15 ° C below the softening temperature of the organic Substance.
  • the fluidized air warms up by absorbing the the heat of fusion released.
  • the Air outlet temperature below the softening temperature of the granulated organic substances.
  • the Air outlet temperature is at least 5 ° C below the softening temperature.
  • process gas nitrogen is used as process gas (soil air)
  • the soil air temperature can are much lower. Process gas temperatures from -196 ° C to are then conceivable 35 ° C, but temperatures below 0 ° C are less preferred, otherwise Problems with the condensation of moisture can occur ..
  • the bulk weights of the resulting granules depend strongly on the Granulation conditions and the added carriers. Usual Bulk weights are in the range 400 to 1000 g / l, in particular bulk weights in the range of 550 to 850 g / l for the use of the granules in washing or Cleaning agents can be preferred.
  • the granules preferably contain no particles with a particle size below 50 ⁇ m, preferably also none Particles with a particle size below 100 microns.
  • Granules preferred according to the invention have ad 50 values between 0.4 and 2.5 mm.
  • the grain fraction which is greater than 1.6 mm is returned. This coarse grain fraction can either be added as a solid component after grinding the fluidized bed or it is melted again and sprayed into the fluidized bed.
  • the granules obtained can still be used and processed further improve, be powdered with an oil absorption component.
  • an oil absorption component By this powdering step with a finely divided component becomes the liquids tied to the surface of the granules, so that the granules are not stored can clump together.
  • the oil absorption component should have an oil absorption capacity of at least 20g / 100g, more suitable at least 50g / 100g, preferably at least 80g / 100g, particularly preferably at least 120g / 100g and in particular at least Have 140g / 100g.
  • the oil absorption capacity is a physical property of a substance that can be determined using standardized methods. For example, the British standard methods BS1795 and BS3483: Part B7: 1982 exist, both of which refer to the ISO 787/5 standard.
  • a balanced sample of the substance in question is placed on a plate and refined flaxseed oil (density: 0.93 gcm -3 ) from a burette is added dropwise. After each addition, the powder is thoroughly mixed with the oil using a spatula, the addition of oil being continued until a paste of smooth consistency is obtained. This paste should flow or run without crumbling.
  • the oil absorption capacity is now the amount of the added oil, based on 100g absorbent and is given in ml / 100g or g / 100g, whereby conversions about the density of the linseed oil are possible without any problems.
  • the oil absorption component preferably has the smallest possible mean Particle size, since the active surface increases with decreasing particle size.
  • Preferred Detergent tablets contain one component with one Oil absorption capacity of at least 20g / 100g, which has an average particle size of less than 50 microns, preferably less than 20 microns and especially less than 10 microns.
  • a large number of substances are suitable as an oil absorption component.
  • zeolite in particular preferably zeolite A, X or P
  • This Powdering agents reduce the stickiness of the moist ones during granulation Granules additionally and thus promote turbulence and cooling or Prilling to the desired product.
  • the particle size of the powdering agent is preferably less than 10 microns and then contain the granules so obtained between 1 and 4% by weight of the powdering agent.
  • this variant can be advantageous; However, implementation of the invention is not absolutely necessary.
  • the granules obtained according to the invention can be processed directly or on the market to be brought.
  • the invention therefore furthermore relates to detergents or cleaning agents which contain granules according to the invention or granules produced according to the invention.
  • washing and cleaning agents according to the invention which are in the form of granules, powder or tablet-shaped solids or other shaped bodies can be present, except the granules according to the invention in principle all known and in such means contain usual ingredients.
  • Preferred agents for the purposes of the invention are granular Agents, especially those obtained by mixing different granules of washing and / or Detergent components are created.
  • the essential ingredients of the detergents according to the invention are primarily called anionic, nonionic, cationic, amphoteric and / or zwitterionic surfactants become.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates, and also disulfonates of the kind obtained, for example, from C 12 -C 18 monoolefins having an end or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
  • the methyl esters of ⁇ -sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and Trieste and their mixtures represent how they are made by Esterification by a monoglycerin with 1 to 3 moles of fatty acid or during the transesterification of triglycerides with 0.3 to 2 moles of glycerol can be obtained.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are particularly preferred from the point of view of washing technology.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
  • sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol ethylene oxide such as 2-methyl branched C 9 -C 11 alcohols with an average of 3.5 mol ethylene oxide (EO) or C 12 - C 18 fatty alcohols with 1 to 4 EO. Because of their high foaming behavior, they are normally used in washing and cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves.
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are fatty acid derivatives of amino acids, for example of N-methyl taurine (tauride) and / or of N-methyl glycine (sarcoside).
  • Soaps for example in quantities, come in particular as further anionic surfactants from 0.2% to 5% by weight.
  • Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, for example coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants can be in the form of their sodium, Potassium or ammonium salts and as soluble salts of organic bases, such as mono-, Di- or triethanolamine.
  • the anionic surfactants are preferably in Form of their sodium or potassium salts, especially in the form of the sodium salts.
  • Anionic surfactants are preferably in amounts in detergents according to the invention from 1% by weight to 35% by weight and in particular in amounts from 5% by weight to 30% by weight contain.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is a glycose unit with 5 or 6C atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (I) in which R 1 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R 3 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 represents a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 5 represents a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an aikoxide as catalyst.
  • nonionic surfactants which either as sole nonionic surfactant or in combination with other nonionic Surfactants, especially together with alkoxylated fatty alcohols and / or Alkyl glycosides used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 Carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as, for example are described in Japanese patent application JP 58/217598 or which preferably according to that in international patent application WO 90/13533 described methods are produced.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it. It is preferred according to the invention if the nonionic surfactants can be used in the form of the granules according to the invention. it However, it can also be preferred if only a part or only certain nonionic Surfactants are introduced into the composition via the granules according to the invention.
  • gemini surfactants can be considered as further surfactants.
  • these groups are usually separated by a so-called “spacer” separated from each other.
  • This spacer is usually a carbon chain that is long should be enough that the hydrophilic groups are sufficiently spaced so that they can act independently of each other.
  • Such surfactants are characterized in generally due to an unusually low critical micelle concentration and the Ability to greatly reduce the surface tension of the water.
  • Gemini surfactants are not only used as “dimers”, but also understood accordingly "trimeric" surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis and Trimer alcohol tris sulfates and ether sulfates. End group capped dimers and trimeric mixed ethers are particularly characterized by their bi- and multifunctionality. The end group-capped surfactants have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes. But can be used also gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides.
  • the agents according to the invention usually contain a builder system consisting of at least one organic and / or inorganic builder.
  • Usable organic builders are, for example, those in the form of their Polycarboxylic acids that can be used are sodium salts, with polycarboxylic acids being such Carboxylic acids are understood that carry more than one acid function.
  • these are citric acid, adipic acid, succinic acid, glutaric acid, Malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not for ecological reasons objectionable, and mixtures of these.
  • Preferred salts are the salts of Polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids and mixtures of these.
  • the acids themselves can also be used.
  • the acids have besides theirs Builder effect typically also the property of an acidifying component and thus also serve to set a lower and milder pH value of Detergents or cleaning agents.
  • Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.
  • the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight have from 2000 to 20,000 g / mol. Because of their superior solubility, can this group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.
  • copolymeric polycarboxylates especially those of Acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
  • Their relative molecular weight, based on free acids, is in general 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 up to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can either be as a powder or as an aqueous Solution are used.
  • the content of the agents in (co) polymeric polycarboxylates is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer contain.
  • allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid
  • Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or the as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.
  • copolymers are those described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 are described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate exhibit.
  • further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors.
  • polymeric aminodicarboxylic acids to name their salts or their precursors.
  • Particular preferred Polyaspartic acids or their salts and derivatives of which in the German Patent application DE-A-195 40 086 discloses that in addition to cobuilder properties also have a bleach-stabilizing effect.
  • polyacetals which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained.
  • Preferred polyacetals will be from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable organic builder substances are dextrins, for example Oligomers or polymers of carbohydrates by partial hydrolysis of starches can be obtained.
  • the hydrolysis can be carried out according to conventional methods, for example acid or enzyme-catalyzed processes are carried out. It is preferably Hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, particularly preferred from 2 to 30, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which a DE out of 100.
  • DE dextrose equivalent
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known from numerous publications.
  • An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • Ethylene diamine disuccinate are other suitable cobuilders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferred in the form of its sodium or magnesium salts used. Also preferred in this context Glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in Zeolite-containing and / or silicate-containing formulations at 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 carbon atoms and at least one Contain hydroxy group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO 95/20029 described.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder. It is preferably used as the sodium salt used, the disodium salt neutral and the tetrasodium salt alkaline (pH 9) responds.
  • Preferred aminoalkane phosphonates are ethylenediamine tetramethylene phosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question.
  • the Class of phosphonates preferably uses HEDP.
  • the aminoalkane phosphonates also have a strong ability to bind heavy metals. Accordingly, it is preferred, especially if the agents also contain bleach, Aminoalkanephosphonate, especially DTPMP to use, or mixtures of the to use the named phosphonates.
  • a preferred inorganic builder is finely crystalline, synthetic and bound water-containing zeolite, preferably zeolite A, X and / or P.
  • Zeolite P is, for example, zeolite MAP (for example Doucil A24 ; Commercial product from Crosfield) is particularly preferred.
  • zeolite MAP for example Doucil A24 ; Commercial product from Crosfield
  • zeolite MAP for example Doucil A24
  • zeolite MAP for example Doucil A24
  • zeolite MAP for example Doucil A24 ; Commercial product from Crosfield
  • Of particular interest is also a cocrystallized sodium / potassium aluminum silicate from zeolite A and zeolite X, which is commercially available as VEGOBOND AX® (commercial product from Condea Augusta SpA).
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 10 to 22% by weight, in particular 15 to 22% by weight, of bound water.
  • Suitable substitutes or partial substitutes for the zeolite are layer silicates of natural and synthetic origin. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Also crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are suitable for the substitution of zeolites or phosphates. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicate Na 2 Si 2 O 5 .yH 2 O are preferred.
  • the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably of 1: 2 to 1: 2.8 and in particular of 1: 2 to 1: 2,6, which are delayed release and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compacting / sealing or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the sodium salts are particularly suitable Orthophosphate, the pyrophosphate and especially the tripolyphosphate.
  • Your salary generally not more than 25% by weight, preferably not more than 20% by weight, each based on the finished product.
  • tripolyphosphates in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances to form one lead to synergistic improvement of secondary washing ability.
  • bleaching agents Of the compounds which serve as bleaching agents and supply H 2 O 2 in water, sodium perborate monohydrate or tetrahydrate and sodium percarbonate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is 0 to 30% by weight and in particular 5 to 25% by weight, advantageously using perborate monohydrate or percarbonate.
  • bleach activators can be incorporated.
  • bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 up to 4 carbon atoms, and / or optionally substituted perbenzoic acid, be used.
  • Substances containing the O- and / or N-acyl groups are suitable mentioned number of carbon atoms and / or optionally substituted benzoyl groups.
  • Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • TAED Tetraacetylethylenediamine
  • bleaching catalysts can be incorporated. These substances are to bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.
  • Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question.
  • Bacterial strains are particularly suitable or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus-derived enzymatic agents.
  • Proteases are preferably from Subtilisin type and in particular proteases obtained from Bacillus lentus, used.
  • enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, in particular, however, cellulase-containing mixtures of particular interest.
  • Peroxidases or oxidases have proven to be suitable in some cases.
  • the Enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
  • components can also be used, which the oil and Grease washability from textiles has a positive effect (so-called soil repellents). This effect is particularly evident when a textile that is already soiled previously several times with a detergent according to the invention that this oil and contains fat-dissolving component, was washed.
  • nonionic cellulose ethers such as Methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and from 1 to 15% by weight of hydroxypropoxyl groups, each based on the nonionic cellulose ether
  • nonionic cellulose ethers such as Methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and from 1 to 15% by weight of hydroxypropoxyl groups, each based on the nonionic cellulose ether
  • those from the prior art Technology known polymers of phthalic acid and / or terephthalic acid or their derivatives in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these.
  • the sulfonated derivatives of are particularly preferred Phthalic acid and terephthalic acid polymers.
  • the detergents and cleaning agents can be used as optical brighteners Contain diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure, instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group wear. Brighteners of the substituted type can also be used Diphenyl styrenes may be present, e.g.
  • Dyes and fragrances are added to detergents and cleaning agents to make the to improve the aesthetic impression of the products and the consumer in addition to the Softness performance a visually and sensory "typical and unmistakable" To provide product.
  • perfume oils or fragrances Fragrance compounds, e.g. synthetic products of the ester, ether, Aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are e.g.
  • ethers include, for example, benzyl ethyl ether, the aldehydes e.g.
  • the linear alkanals with 8-18 C atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal
  • ketones e.g. the Jonone, ⁇ -isomethylionon and methyl cedryl ketone
  • the alcohols anethole citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol
  • to the hydrocarbons mainly include the terpenes like limes and pinene.
  • Mixtures of different fragrances are used, which together make an appealing Generate fragrance.
  • perfume oils can also contain natural fragrance mixtures included as are available from plant sources, e.g. Pine, citrus, jasmine, Patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, Vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, Orange peel oil and sandalwood oil. Usually the content of washing and Detergents on dyes below 0.01% by weight, while fragrances up to 2% by weight can make up the entire wording.
  • the fragrances can be incorporated directly into the washing and cleaning agents but can also be advantageous to apply the fragrances to the carrier, which increase the liability of the perfume on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles.
  • carrier materials have become
  • cyclodextrins have proven to be the cyclodextrin-perfume complexes can also be coated with other auxiliaries.
  • Preferred dyes whose Selection poses no difficulty for the expert possess a high level Storage stability and insensitivity to the other ingredients of the agent and against light as well as no pronounced substantivity towards textile fibers to this not to stain.
  • the bulk density of the advantageously granular washing and / or cleaning agents is preferably at least about 600 g / l, in particular 650 to 1100 g / l. It can however, means are also produced which are lower Have bulk density. In particular, it may be preferred to use the agents to assemble granular individual components in a kind of modular system.

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WO2004069981A2 (fr) * 2003-02-03 2004-08-19 Ciba Specialty Chemicals Holding Inc. Agent de lavage et formulations d'adoucisseur de tissu
WO2006024415A1 (fr) * 2004-09-02 2006-03-09 Henkel Kommanditgesellschaft Auf Aktien Liquides fabriques sous forme solide, pour une utilisation dans des detergents et des nettoyants particulaires

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DE19959915A1 (de) * 1999-12-11 2001-07-05 Henkel Kgaa Niotensidgranulate durch Prillen
DE102005027660A1 (de) * 2005-06-15 2006-12-28 Henkel Kgaa Dosiervorrichtung
JP4633657B2 (ja) * 2005-09-30 2011-02-16 花王株式会社 自動食器洗浄機用洗浄剤組成物
EP3743493B1 (fr) 2018-01-26 2024-07-17 Ecolab Usa Inc. Tensioactifs anioniques liquides solidifiants
WO2019148076A1 (fr) 2018-01-26 2019-08-01 Ecolab Usa Inc. Solidification de tensioactifs d'oxyde d'amine, de bétaïne et/ou de sultaïne liquide à l'aide d'un liant et d'un éventuel un vecteur
EP3743495A1 (fr) 2018-01-26 2020-12-02 Ecolab USA Inc. Solidification de tensioactifs liquides d'oxyde d'amine, de bétaïne et/ou de sultaïne ayant un véhicule
CA3140905A1 (fr) * 2019-06-21 2020-12-24 Ecolab Usa Inc. Compositions tensio-actives non ioniques solides

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US4545917A (en) * 1984-02-09 1985-10-08 Creative Products Resource Associates Ltd. Automatic dishwasher product in solid form
WO1997010326A1 (fr) * 1995-09-14 1997-03-20 The Procter & Gamble Company Procede de fabrication d'une composition detergente haute densite a partir d'une pate de tensioactif contenant un liant non aqueux
US5739094A (en) * 1997-01-17 1998-04-14 The Procter & Gamble Company Free-flowing particulate detergent admix composition containing nonionic surfactant
DE19718664A1 (de) * 1997-05-02 1998-11-05 Clariant Gmbh Verfahren zur Herstellung von lagerstabilen schmutzablösevermögende Polymere (Soil Release Polymere, SRP) enthaltende Granulate und ihre Verwendung zur Herstellung fester Wasch- und Reinigungsmittel
DE19959915A1 (de) * 1999-12-11 2001-07-05 Henkel Kgaa Niotensidgranulate durch Prillen
DE10021113A1 (de) * 2000-05-02 2001-11-15 Henkel Kgaa Partikuläre Compounds, enthaltend nichtionische Tenside

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Publication number Priority date Publication date Assignee Title
US4088431A (en) * 1974-05-07 1978-05-09 Imperial Chemical Industries Limited Melt spinning filter
US4545917A (en) * 1984-02-09 1985-10-08 Creative Products Resource Associates Ltd. Automatic dishwasher product in solid form
WO1997010326A1 (fr) * 1995-09-14 1997-03-20 The Procter & Gamble Company Procede de fabrication d'une composition detergente haute densite a partir d'une pate de tensioactif contenant un liant non aqueux
US5739094A (en) * 1997-01-17 1998-04-14 The Procter & Gamble Company Free-flowing particulate detergent admix composition containing nonionic surfactant
DE19718664A1 (de) * 1997-05-02 1998-11-05 Clariant Gmbh Verfahren zur Herstellung von lagerstabilen schmutzablösevermögende Polymere (Soil Release Polymere, SRP) enthaltende Granulate und ihre Verwendung zur Herstellung fester Wasch- und Reinigungsmittel
DE19959915A1 (de) * 1999-12-11 2001-07-05 Henkel Kgaa Niotensidgranulate durch Prillen
DE10021113A1 (de) * 2000-05-02 2001-11-15 Henkel Kgaa Partikuläre Compounds, enthaltend nichtionische Tenside

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WO2004069981A2 (fr) * 2003-02-03 2004-08-19 Ciba Specialty Chemicals Holding Inc. Agent de lavage et formulations d'adoucisseur de tissu
WO2004069981A3 (fr) * 2003-02-03 2004-10-28 Ciba Sc Holding Ag Agent de lavage et formulations d'adoucisseur de tissu
WO2006024415A1 (fr) * 2004-09-02 2006-03-09 Henkel Kommanditgesellschaft Auf Aktien Liquides fabriques sous forme solide, pour une utilisation dans des detergents et des nettoyants particulaires

Also Published As

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US20010014657A1 (en) 2001-08-16
EP1106678A3 (fr) 2003-06-04
EP1106678B1 (fr) 2006-09-06
ES2270777T3 (es) 2007-04-16
DE50013430D1 (de) 2006-10-19
CA2327968A1 (fr) 2001-06-11
DE19959915A1 (de) 2001-07-05
ATE338811T1 (de) 2006-09-15

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